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WO2025197877A1 - Composition for forming primer film, laminate, method for producing laminate, and method for producing processed semiconductor substrate or electronic device substrate - Google Patents

Composition for forming primer film, laminate, method for producing laminate, and method for producing processed semiconductor substrate or electronic device substrate

Info

Publication number
WO2025197877A1
WO2025197877A1 PCT/JP2025/010327 JP2025010327W WO2025197877A1 WO 2025197877 A1 WO2025197877 A1 WO 2025197877A1 JP 2025010327 W JP2025010327 W JP 2025010327W WO 2025197877 A1 WO2025197877 A1 WO 2025197877A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
electronic device
group
semiconductor substrate
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/010327
Other languages
French (fr)
Japanese (ja)
Inventor
友輝 臼井
貴久 奥野
高広 岸岡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of WO2025197877A1 publication Critical patent/WO2025197877A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • C09D201/00—Coating compositions 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
    • 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
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a composition for forming a primer film, a laminate, a method for manufacturing a laminate, and a method for manufacturing a processed semiconductor substrate or electronic device substrate.
  • wafers Semiconductor wafers (here simply referred to as wafers) before thinning are adhered to a support in preparation for polishing with a polishing device.
  • This adhesion is called temporary adhesion because it must be easily peeled off after polishing.
  • This temporary adhesion must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening.
  • Temporary adhesives proposed for use in such temporary bonding include adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2).
  • the adhesive layer formed from the temporary adhesive must be difficult to peel off from the support or the semiconductor wafer during temporary bonding, while the adhesive layer must be easy to peel off from the support or the semiconductor wafer when the semiconductor wafer is peeled off from the support.
  • the peeling may occur at the interface between the semiconductor wafer and the adhesive layer (this case is also called device release), or at the interface between the support and the adhesive layer (this case is also called carrier release).
  • the adhesive layer remains (adheres) on the device side of the semiconductor wafer, which raises concerns that cleaning the adhesive layer after peeling will take longer than in the case of device peeling, increasing the process time and placing a greater burden on the device substrate, i.e., the semiconductor wafer. Therefore, device peeling is preferred in order to avoid the above-mentioned concerns.
  • device peeling is preferable from the viewpoint of reducing the amount of adhesive layer residue on the device substrate.
  • carrier peeling may be desired in some cases due to factors such as the adhesive layer used, the type of each substrate that comes into contact with it, or the conditions set in the manufacturing process. Therefore, when peeling the semiconductor wafer from the support, it is convenient to be able to control the location of peeling (peeling interface).
  • the present invention has been made in consideration of the above circumstances, A support substrate; a semiconductor substrate or an electronic device substrate; a laminate including an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
  • the object is to provide a laminate that can control the peeling interface when peeling a semiconductor wafer from a support substrate.
  • the inventors discovered that the above-mentioned problems can be solved by providing a primer film between the adhesive layer and the substrate, which can increase the adhesive strength between the adhesive layer and the substrate, and thus completed the present invention, which has the following gist.
  • a primer coating-forming composition for enhancing the adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction comprising: A primer film-forming composition containing a component that contributes to the hydrosilylation reaction.
  • the primer coating composition according to [1] which contains, as a component contributing to the hydrosilylation reaction, a component selected from the group consisting of a platinum-containing compound, a Si—H group-containing compound, and a vinyl group-containing compound.
  • the adhesive component that cures by a hydrosilylation reaction is Component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; a component (A-2) having an Si—H group;
  • the primer film is a primer film formed from the composition for forming a primer film according to any one of [1] to [5].
  • FIG. 1 is a schematic cross-sectional view of an example of a laminate.
  • FIG. 2 is a schematic cross-sectional view of another example of the laminate.
  • FIG. 3A is a schematic cross-sectional view (part 1) illustrating a method for manufacturing the laminate shown in FIG.
  • FIG. 3B is a schematic cross-sectional view (part 2) illustrating a method for manufacturing the laminate shown in FIG.
  • FIG. 3C is a schematic cross-sectional view (part 3) illustrating a method for manufacturing the laminate shown in FIG. 1 .
  • FIG. 4A is a schematic cross-sectional view (part 1) illustrating a method for manufacturing the laminate shown in FIG. 2 .
  • FIG. 4B is a schematic cross-sectional view (part 2) illustrating a method for manufacturing the laminate shown in FIG.
  • FIG. 4C is a schematic cross-sectional view (part 3) illustrating a method for manufacturing the laminate shown in FIG. 2 .
  • FIG. 4D is a schematic cross-sectional view (part 4) illustrating a method for manufacturing the laminate shown in FIG. 2 .
  • the laminate of the present invention is A support substrate; a semiconductor substrate or an electronic device substrate; a laminate having an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
  • the laminate has a primer film formed on the surface of either the semiconductor substrate or the electronic device substrate, or the support substrate.
  • the primer film is formed from the primer film-forming composition described below.
  • the primer film-forming composition is A composition for enhancing the adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction, the composition containing a component that contributes to the hydrosilylation reaction.
  • a primer layer formed from a primer film-forming composition containing a component that contributes to the hydrosilylation reaction by disposing a primer layer formed from a primer film-forming composition containing a component that contributes to the hydrosilylation reaction on a laminate, it is possible to increase the adhesive strength between the substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that hardens through a hydrosilylation reaction.
  • the adhesive layer is less likely to peel off from the support substrate, semiconductor substrate, or electronic device substrate when temporarily bonded, and when peeling the semiconductor substrate or electronic device substrate from the support substrate, the adhesive layer can be easily peeled off at the interface between the substrate not having the primer film and the adhesive layer.
  • a primer film is formed on the surface of any one of a semiconductor substrate or an electronic device substrate, and a support substrate
  • specific embodiments for forming the primer film include, for example, the following embodiments.
  • a primer coating is formed on the surface of the support substrate.
  • a primer coating is formed on the surface of the support substrate.
  • a primer coating is formed on the surface of the semiconductor substrate.
  • a primer coating is formed on the surface of the semiconductor substrate.
  • a primer coating is formed on the surface of the electronic device substrate.
  • the adhesive strength between the substrate having the primer coating and the adhesive layer is increased by the primer coating, so when an attempt is made to peel the semiconductor substrate from the support substrate, peeling occurs at the interface between the substrate not having the primer coating and the adhesive layer.
  • peeling occurs at the interface between the semiconductor substrate and the adhesive layer.
  • peeling occurs at the interface between the electronic device substrate and the adhesive layer.
  • peeling occurs at the interface between the support substrate and the adhesive layer.
  • peeling carrier peeling
  • the laminate may be in the form of device peeling or carrier peeling, as long as the object of controlling the peeling interface can be achieved.
  • the substrate on which the primer film is to be disposed can be appropriately selected taking into consideration the adhesive layer to be used, the type of each substrate to be in contact with it, or the conditions set in the manufacturing process. However, the following description will be given taking as an example the case of device peeling in which a primer film is formed on the surface of a support substrate.
  • the laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device substrate, and can be suitably used for processing such as thinning a semiconductor substrate or an electronic device substrate (hereinafter, "semiconductor substrate or electronic device substrate” will also be collectively referred to as “semiconductor substrate, etc.”).
  • the semiconductor substrate, etc. is supported by the support substrate while it is being processed, such as thinned, etc. After the semiconductor substrate, etc. is processed, the semiconductor substrate, etc. and the support substrate are separated. After the semiconductor substrate or the like is separated from the support substrate, any residue of the adhesive layer remaining on the semiconductor substrate, electronic device substrate, or support substrate can be removed, for example, with a cleaning composition for cleaning semiconductor substrates or the like.
  • the laminate may include an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate having the primer coating on its surface.
  • This laminate is a device peel-off type laminate.
  • the adhesive layer is provided between the support substrate and the semiconductor substrate or electronic device substrate (such as a semiconductor substrate).
  • the adhesive layer is in contact with, for example, a semiconductor substrate, etc.
  • the adhesive layer is also in contact with, for example, a support substrate having a primer coating formed on its surface.
  • the adhesive layer is formed from an adhesive composition.
  • the thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, but is typically 5 to 500 ⁇ m. From the viewpoint of maintaining film strength, it is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, even more preferably 120 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the adhesive composition according to the present invention contains an adhesive component that cures via a hydrosilylation reaction.
  • the adhesive composition according to the present invention preferably contains an adhesive component and a release agent component.
  • the adhesive composition according to the present invention may contain other components.
  • the release agent component preferably contains polyorganosiloxane.
  • the release agent component preferably contains two or more types of release agent components.
  • the adhesive component is a component that hardens through a hydrosilylation reaction.
  • the component that cures via a hydrosilylation reaction is not particularly limited, but preferably contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter, sometimes referred to as "component (A-1)”), a component having a Si—H group (hereinafter, sometimes referred to as “component (A-2)”), and a platinum group metal catalyst (A-3).
  • the adhesive composition preferably contains component (A-1).
  • the adhesive composition preferably contains component (A-2).
  • the combination of component (A-1), component (A-2), and platinum group metal catalyst (A-3) may be referred to as “curable component (A)” or “component (A).”
  • component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom.
  • the component (A-2) preferably contains a polyorganosiloxane (a2) having Si—H groups.
  • the alkenyl group having 2 to 40 carbon atoms may be substituted.
  • the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
  • the adhesive composition that cures via a hydrosilylation reaction comprises a polysiloxane (A1) containing one or more units selected from the group consisting of siloxane units represented by SiO 2 (Q units), siloxane units represented by R 1 R 2 R 3 SiO 1/2 (M units), siloxane units represented by R 4 R 5 SiO 2/2 (D units), and siloxane units represented by R 6 SiO 3/2 (T units), and a platinum group metal catalyst (A-3).
  • the polysiloxane (A1) contains siloxane units represented by SiO 2 (Q' units), siloxane units represented by R 1 'R 2 'R 3 'SiO 1/2 (M' units), siloxane units represented by R 4 'R 5 'SiO 2/2 (D' units), and siloxane units represented by R 6 'SiO and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T' units) represented by SiO 2 (Q” units), siloxane units (M “ units) represented by R 4 "R 5 "SiO 2/2 (D” units) and siloxane units (T” units) represented by R 6 "SiO 3/2 , and containing at least one unit selected from the group consisting of M" units, D " units and T” units.
  • (a1') is an example of (a1)
  • (a2') is an example of (a2).
  • R 1 to R 6 are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom.
  • substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.
  • R 1 ' to R 6 ' are groups bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, provided that at least one of R 1 ' to R 6 ' is an optionally substituted alkenyl group.
  • substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
  • R 1 ′′ to R 6 ′′ are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, provided that at least one of R 1 ′′ to R 6 ′′ is a hydrogen atom.
  • substituents include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
  • the alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. There are no particular restrictions on the number of carbon atoms, but it is typically 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
  • optionally substituted straight-chain or branched-chain alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, and 4-methyl-n-pentyl.
  • Examples of such groups include, but are not limited to, methyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups.
  • the number of carbon atoms is typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.
  • optionally substituted cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 3,
  • the alkenyl group may be either linear or branched, and although there are no particular limitations on the number of carbon atoms, it is typically 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
  • the optionally substituted linear or branched alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a pentenyl group, and the number of carbon atoms therein is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, an ethenyl group and a 2-propenyl group are particularly preferred.
  • Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.
  • polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl groups contained in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2') undergo a hydrosilylation reaction in the presence of a platinum group metal catalyst (A-3) to form a crosslinked structure and cure. As a result, a cured film is formed.
  • Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying these conditions may be used in combination as polyorganosiloxane (a1').
  • Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).
  • polyorganosiloxane (a1') contains two or more types of polyorganosiloxane
  • combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.
  • Polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. Two or more polyorganosiloxanes satisfying these conditions may be used in combination as polyorganosiloxane (a2').
  • Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M” units), and (Q" units, T" units and M” units).
  • the polyorganosiloxane (a1') is composed of siloxane units in which alkyl and/or alkenyl groups are bonded to the silicon atoms thereof, and the proportion of alkenyl groups in all the substituents represented by R 1 ' to R 6 ' is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R 1 ' to R 6 ' can be alkyl groups.
  • the polyorganosiloxane (a2') is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to the silicon atoms, and the proportion of hydrogen atoms in all the substituents and substituted atoms represented by R 1 '' to R 6 '' is preferably 0.1 to 50.0 mol %, more preferably 10.0 to 40.0 mol %, and the remaining R 1 '' to R 6 '' can be alkyl groups.
  • the molar ratio of alkenyl groups contained in the polyorganosiloxane (a1) to hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.
  • the weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.
  • the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.
  • a GPC apparatus EuSEC, HLC-8320GPC manufactured by Tosoh Corporation
  • GPC column TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation
  • a column temperature 40 ° C.
  • the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, but are typically 10 to 1,000,000 (mPa ⁇ s), and from the perspective of achieving the effects of the present invention with good reproducibility, are preferably 50 to 10,000 (mPa ⁇ s).
  • the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured at 25°C using an E-type rotational viscometer.
  • Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction. Therefore, the curing mechanism is different from, for example, that via silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.
  • Platinum group metal catalyst is a platinum group metal catalyst.
  • platinum-based metal catalysts are catalysts for promoting the hydrosilylation reaction between alkenyl groups and Si—H groups.
  • platinum-based metal catalysts known platinum-based compounds (platinum or compounds containing platinum) can be used. Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.),
  • the alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, but examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred due to the good stability of the resulting platinum-alkenylsiloxane complex.
  • the content of platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).
  • the adhesive component may contain a polymerization inhibitor for the purpose of inhibiting the progress of the hydrosilylation reaction.
  • the polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.
  • the amount of the polymerization inhibitor is not particularly limited, but is, for example, usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.
  • the release agent component is not particularly limited, but from the viewpoint of more suitably achieving the effects of the present invention, polyorganosiloxane is preferred.
  • the polyorganosiloxane used as the release agent component generally does not react with the adhesive component.
  • polyorganosiloxane as a release agent component is a component that does not undergo hydrosilylation reaction.
  • the polyorganosiloxane is not particularly limited, but examples include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.
  • the two or more types of release agent components preferably include two or more types of polyorganosiloxanes.
  • the term "two" in the two or more polyorganosiloxanes refers to, for example, a combination of polydimethylsiloxane and an epoxy group-containing polyorganosiloxane, a combination of polydimethylsiloxane and a phenyl group-containing polyorganosiloxane, or a combination of a phenyl group-containing polyorganosiloxane and an epoxy group-containing polyorganosiloxane. It does not refer to a combination of two epoxy group-containing polyorganosiloxanes that differ in molecular weight, viscosity, type of epoxy group, etc.
  • Examples of the two or more types of release agent components include the following combinations. Combination of polydimethylsiloxane and epoxy group-containing polyorganosiloxane Combination of polydimethylsiloxane and phenyl group-containing polyorganosiloxane Combination of polydimethylsiloxane and carbinol-modified polyorganosiloxane Combination of epoxy group-containing polyorganosiloxane and phenyl group-containing polyorganosiloxane Combination of epoxy group-containing polyorganosiloxane and carbinol-modified polyorganosiloxane Combination of phenyl group-containing polyorganosiloxane and carbinol-modified polyorganosiloxane Among these combinations, the combination of polydimethylsiloxane and epoxy group-containing polyorganosiloxane is preferred as the combination that is most likely to achieve the effects of the present invention.
  • the polydimethylsiloxane contained in the adhesive composition is not particularly limited. Polydimethylsiloxane is a component that does not undergo hydrosilylation reactions.
  • the "polydimethylsiloxane" in the present invention is an unmodified polyorganosiloxane, unlike epoxy group-containing polydimethylsiloxane, phenyl group-containing polydimethylsiloxane, etc., and is a polyorganosiloxane having a methyl group as an organic group bonded to a silicon atom.
  • polydimethylsiloxane examples include, but are not limited to, those represented by formula (M1):
  • n4 represents the number of repeating units and is a positive integer.
  • the weight average molecular weight of the polydimethylsiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000.
  • the dispersity is also not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0.
  • the weight average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane as an adhesive component.
  • the viscosity of polydimethylsiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm 2 /s.
  • epoxy group-containing polyorganosiloxanes examples include those containing siloxane units ( D10 units) represented by R 11 R 12 SiO 2/2 .
  • R11 is a group bonded to a silicon atom and represents an alkyl group
  • R12 is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group
  • specific examples of the alkyl group include those listed above.
  • the epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.
  • Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
  • a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.
  • the epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( D10 units), but may also contain Q units, M units and/or T units in addition to the D10 units.
  • specific examples of the epoxy group-containing polyorganosiloxane include a polyorganosiloxane consisting only of D 10 units, a polyorganosiloxane containing D 10 units and Q units, a polyorganosiloxane containing D 10 units and M units, a polyorganosiloxane containing D 10 units and T units, a polyorganosiloxane containing D 10 units, Q units, and M units, a polyorganosiloxane containing D 10 units, M units, and T units, and a polyorganosiloxane containing D 10 units, Q units, M units, and T units.
  • the epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane with an epoxy value of 0.1 to 5. Its weight average molecular weight is not particularly limited, but is typically 1,500 to 500,000, and is preferably 100,000 or less from the standpoint of suppressing precipitation in the composition.
  • epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).
  • the repeating units thereof may be arranged adjacent to each other to form a block, or may be arranged randomly.
  • the polyorganosiloxane represented by formula (E3) contains both epoxy groups and phenyl groups, and is therefore both an epoxy group-containing polyorganosiloxane and a phenyl group-containing polyorganosiloxane.
  • the epoxy group-containing polyorganosiloxane may or may not contain phenyl groups.
  • the weight average molecular weight of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable peeling, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0.
  • the weight average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane as an adhesive component.
  • the viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 /s.
  • R31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group
  • R32 is a group bonded to a silicon atom and represents a phenyl group
  • specific examples of the alkyl group include those listed above, with a methyl group being preferred.
  • the phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane units ( D30 units), but may also contain Q units, M units and/or T units in addition to the D30 units.
  • phenyl group-containing polyorganosiloxane examples include a polyorganosiloxane consisting only of D30 units, a polyorganosiloxane containing D30 units and Q units, a polyorganosiloxane containing D30 units and M units, a polyorganosiloxane containing D30 units and T units, a polyorganosiloxane containing D30 units, Q units, and M units, a polyorganosiloxane containing D30 units, M units, and T units, and a polyorganosiloxane containing D30 units, Q units, M units , and T units.
  • phenyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).
  • the repeating units thereof may be arranged adjacent to each other to form a block, or may be arranged randomly.
  • Carbinol-modified polyorganosiloxanes are polyorganosiloxanes having hydroxy groups directly bonded to carbon atoms.
  • the carbinol in "carbinol-modified polyorganosiloxanes” is not limited to methanol in the narrow sense, but also includes methanol derivatives.
  • carbinol-modified polyorganosiloxane is carbinol-modified polydimethylsiloxane.
  • the number of hydroxy groups directly bonded to carbon atoms in the carbinol-modified polyorganosiloxane is not particularly limited, and may be one or two or more.
  • the carbinol-modified polyorganosiloxane may have a hydroxy group bonded directly to a carbon atom in a side chain, may have a hydroxy group bonded directly to a carbon atom at one end, or may have hydroxy groups bonded directly to carbon atoms at both ends.
  • the carbinol-modified polyorganosiloxane preferably has a hydroxy group directly bonded to a carbon atom in the side chain. In this case, even if the content of the carbinol-modified polyorganosiloxane is small, the adhesive layer formed from the adhesive composition can be imparted with good releasability.
  • Carbinol-modified polyorganosiloxanes have, for example, groups represented by the following formula (Cg) as groups directly bonded to silicon atoms.
  • R1 represents a group having one or more carbon atoms. * represents a bond bonded to a silicon atom. However, the hydroxy group in formula (Cg) is directly bonded to a carbon atom.
  • the group represented by formula (Cg) may have one hydroxy group directly bonded to a carbon atom, or two or more hydroxy groups. Examples of two or more hydroxy groups include two, three, and four.
  • the number of carbon atoms in R 1 is not particularly limited, and may be, for example, 1 to 30, 1 to 20, or 1 to 10.
  • Examples of the group represented by formula (Cg) include groups represented by the following formulae (Cg-1) to (Cg-4).
  • R 11 represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms.
  • R 12 represents an alkylene group having 1 to 6 carbon atoms
  • R 13 represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a hydroxy group.
  • R 14 represents an alkylene group having 1 to 6 carbon atoms
  • R 15 represents an alkylene group having 1 to 3 carbon atoms
  • m represents an integer of 1 to 10.
  • R 16 to R 18 each independently represent an alkylene group having 1 to 6 carbon atoms.
  • * represents a bond bonded to a silicon atom.
  • the alkylene groups of R 11 to R 18 may be linear, branched, or cyclic.
  • Examples of the group represented by formula (Cg) include the following groups. (In the formula, m1 represents an integer of 2 to 10. * represents a bond bonded to a silicon atom.)
  • the carbinol-modified polyorganosiloxane is represented, for example, by the following formula (CPS-1) or formula (CPS-2).
  • R 51 each independently represents a hydrocarbon group.
  • X 1 represents a group represented by formula (Cg) above.
  • n1 represents an integer of 0 or more.
  • n2 represents an integer of 1 or more.
  • R 52 each independently represents a hydrocarbon group.
  • X 2 represents a group represented by formula (Cg) above.
  • X 3 represents a hydrocarbon group or a group represented by formula (Cg) above.
  • n3 represents an integer of 0 or greater.
  • Examples of the hydrocarbon group for R 51 , R 52 , and X 3 include an alkyl group having 1 to 8 carbon atoms.
  • a methyl group is preferred as the alkyl group having 1 to 8 carbon atoms.
  • the carbinol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a):
  • Cg represents a group represented by formula (Cg) above.
  • n1 represents an integer of 0 or more.
  • n2 represents an integer of 1 or more.
  • X2 represents a group represented by formula (Cg) above.
  • X3 represents a methyl group or a group represented by formula (Cg) above.
  • n3 represents an integer of 0 or greater.
  • the carbinol-modified polyorganosiloxane represented by formula (CPS-1) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a) have a hydroxy group directly bonded to a carbon atom in the side chain.
  • the carbinol-modified polyorganosiloxane represented by formula (CPS-2) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-2a) have hydroxy groups directly bonded to carbon atoms at one end or both ends.
  • the siloxane units represented by —Si(R 51 )(X 1 )—O— may be arranged adjacent to each other to form a block, or may be arranged randomly.
  • the siloxane units represented by —Si(CH 3 )(X 1 )—O— may be arranged adjacent to each other to form a block, or may be arranged randomly.
  • the weight average molecular weight of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of reproducibly realizing the effects of the present invention, it is preferably 5,000 to 50,000.
  • the dispersity is not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of reproducibly realizing suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0.
  • the viscosity of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 100 to 200,000 mm 2 /s.
  • the polyorganosiloxane that is the release agent component (B) may be a commercially available product or may be synthesized.
  • Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, manufactured by Wacker Chemie, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (trade names CMS-227, ECMS-327, EMS-622) manufactured by Gelest, and Shin-Etsu Chemical Co., Ltd.
  • Epoxy group-containing polyorganosiloxanes KF-101, KF-1001, KF-1005, X-22-343
  • epoxy group-containing polyorganosiloxanes DOWSIL BY16-839, DOWSIL8413, DOWSIL8411
  • Dow-Toray Industries, Inc. phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, but are not limited to these.
  • carbinol-modified polyorganosiloxanes include, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, and X-22-4015 manufactured by Shin-Etsu Silicone Co., Ltd.; and DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, and DMS-C27 manufactured by Gelest.
  • Examples include MS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, and MCR-C63; and Dow-Toray Industries, Inc.'s DOWSIL BY 16-201, DOWSIL SF 8427 Fluid, and DOWSIL SF 8428 Fluid.
  • the content of the release agent component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile content of the adhesive composition.
  • the upper limit is not particularly limited, but is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the non-volatile content of the adhesive composition refers to the components other than the solvent in the adhesive composition.
  • the content of polydimethylsiloxane in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the content is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 10% by mass, and particularly preferably 2% by mass to 8% by mass, relative to the adhesive components.
  • the adhesive component here does not include a solvent.
  • the content of the epoxy group-containing polyorganosiloxane in the adhesive composition is not particularly limited, but from the viewpoint of preferably obtaining the effects of the present invention, it is preferably 0.05% by mass to 30% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.2% by mass to 3% by mass, based on the adhesive component.
  • the adhesive component here does not include a solvent.
  • the mass ratio (B-1:B-2) of the polydimethylsiloxane (B-1) to the epoxy group-containing polyorganosiloxane (B-2) in the adhesive composition is not particularly limited, but from the viewpoint of optimally achieving the effects of the present invention, it is preferably 20:1 to 1:10, more preferably 15:1 to 1:7.5, and particularly preferably 15:1 to 5:1.
  • the total ratio of polydimethylsiloxane and epoxy group-containing polyorganosiloxane to the adhesive component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 10% by mass, and particularly preferably 3% by mass to 8% by mass.
  • the adhesive component here does not include a solvent.
  • the adhesive composition may contain a solvent for the purpose of adjusting viscosity, etc.
  • specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specific examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, methylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. These solvents can be used alone or in combination of two or more.
  • the content of the solvent is set appropriately taking into consideration the desired viscosity of the composition, the application method to be used, the thickness of the thin film to be produced, etc., but is typically in the range of approximately 10 to 90% by mass of the entire composition.
  • the viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa ⁇ s at 25°C, and preferably 1,000 to 1,0000 mPa ⁇ s.
  • An example of the adhesive composition used in the present invention can be produced by mixing the adhesive component (A), the release agent component (B), and a solvent.
  • the order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (A) and the release agent component (B) in a solvent, or a method of dissolving a portion of the adhesive component (A) and the remainder of the release agent component (B) in a solvent and then mixing the resulting solutions.
  • heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components.
  • the solvent, solution, etc. used may be filtered using a filter during the production of the adhesive composition or after all of the components have been mixed.
  • the primer coating is formed on the surface of the substrate on the side opposite to the side where a peel interface is desired to form relative to the adhesive layer.
  • the substrate on which the primer film is formed may be a support substrate, a semiconductor substrate, or an electronic device substrate (semiconductor substrate, etc.).
  • the primer coating is formed on the surface of the supporting substrate.
  • the primer coating is formed on the surface of a semiconductor substrate or electronic device substrate (semiconductor substrate, etc.).
  • the primer coating is applied to enhance the adhesive strength between the substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction.
  • the primer film is formed using a primer film-forming composition.
  • the primer coating composition according to the present invention contains a component that further accelerates the hydrosilylation reaction used in forming the adhesive layer, that is, a component that contributes to the hydrosilylation reaction.
  • the composition for forming a primer film has the function of increasing the adhesive strength between a substrate having a primer film on its surface and an adhesive layer, and therefore, in this specification, the composition for forming a primer film is also referred to as an adhesion auxiliary composition.
  • Components that contribute to the hydrosilylation reaction include, for example, compounds selected from the group consisting of platinum-containing compounds, Si-H group-containing compounds, and vinyl group-containing compounds.
  • platinum-containing compound examples include platinum group metals and compounds containing platinum group metals.
  • the platinum-containing compound may be, for example, a supported hydrosilylation catalyst comprising a solid support having a platinum group metal on its surface.
  • supported catalysts include, but are not limited to, platinum on carbon, palladium on carbon, ruthenium on carbon, rhodium on carbon, platinum on silica, palladium on silica, platinum on alumina, palladium on alumina, and ruthenium on alumina.
  • the platinum-containing compound may be, for example, a photoactivatable hydrosilylation catalyst capable of initiating curing upon irradiation and/or heating.
  • a photoactivatable hydrosilylation catalyst refers to, for example, any hydrosilylation catalyst capable of catalyzing a hydrosilylation reaction upon exposure to radiation, particularly those having wavelengths between 150 and 800 nanometers (nm). The suitability of a particular photoactivatable hydrosilylation catalyst for use in the compositions of the present invention can be readily determined through routine experimentation.
  • the photoactivatable hydrosilylation catalyst include platinum(II) ⁇ -diketonate complexes such as platinum(II) bis(2,4-pentanedioate), platinum(II) bis(2,4-hexanedioate), platinum(II) bis(2,4-heptanedioate), platinum(II) bis(1-phenyl-1,3-butanedioate), platinum(II) bis(1,3-diphenyl-1,3-propanedioate), and platinum(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedioate); (h-cyclopentadienyl)trialkylplatinum complexes such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsily
  • the compound containing an Si—H group is not particularly limited as long as it contains an Si—H group, and examples thereof include compounds having a weight average molecular weight (Mw) of 100 or more and 400,000 or less. In addition, compounds containing two or more Si—H groups per molecule are preferred.
  • the compound containing a Si—H group may be a linear compound or a cyclic compound, and is preferably a cyclic compound in terms of solubility in a solvent, for example.
  • vinyl group-containing compound contains a vinyl group, but examples include compounds with a weight average molecular weight (Mw) of 100 or more and 400,000 or less. Furthermore, compounds containing two or more vinyl groups per molecule are preferred.
  • the platinum-containing compound, the Si-H group-containing compound, and the vinyl group-containing compound may be, for example, the adhesive components described in the "Adhesive Components" section of the "Adhesive Composition" above.
  • Preferred embodiments of the component that contributes to the hydrosilylation reaction include, but are not limited to, platinum-containing compounds and Si—H group-containing compounds represented by the following formulae (X-1) to (X-4), which are also used in the following examples.
  • the primer coating composition can be produced, for example, by mixing components that contribute to the hydrosilylation reaction with a solvent.
  • a solvent for example, propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate is used.
  • the method for forming a primer film from the primer film-forming composition is not particularly limited, but examples thereof include a method in which the primer film is formed by applying the primer film-forming composition.
  • the method for applying the primer film-forming composition is not particularly limited, but is usually a spin coating method.
  • the support substrate is not particularly limited as long as it is a member that can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.
  • the shape of the support substrate is not particularly limited, but may be, for example, a disk shape.
  • the disk-shaped support substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat or a notch.
  • the thickness of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 ⁇ m.
  • the diameter of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.
  • An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 ⁇ m.
  • the support substrate used is, for example, a substrate that is optically transparent to the light used.
  • the main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins.
  • the shape of the semiconductor substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped semiconductor substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch.
  • the thickness of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 ⁇ m.
  • the diameter of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.
  • the semiconductor substrate may have bumps, which are protruding terminals.
  • the semiconductor substrate when the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side.
  • bumps are usually formed on the surface on which a circuit is formed.
  • the circuit may be a single layer or a multilayer. There are no particular limitations on the shape of the circuit.
  • the surface opposite to the surface having the bumps (back surface) is the surface to be processed.
  • the material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps.
  • the height, radius and pitch of the bumps are appropriately determined based on the conditions of a bump height of about 1 to 200 ⁇ m, a bump radius of 1 to 200 ⁇ m and a bump pitch of 1 to 500 ⁇ m.
  • materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper.
  • the bumps may be composed of a single component or multiple components. More specifically, alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, may be used.
  • the bump may also have a laminated structure including a metal layer made of at least one of these components.
  • An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 ⁇ m.
  • An electronic device substrate refers to a substrate having an electronic device, and in the present invention, for example, refers to a substrate consisting of a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a substrate consisting of a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.
  • “electronic device” refers to a member that constitutes at least a part of an electronic component.
  • the electronic device is not particularly limited and can be one in which various mechanical structures or circuits are formed on the surface of a semiconductor substrate.
  • the electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member.
  • the electronic device may have a rewiring layer (described later) and/or a semiconductor element or other element sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.
  • FIG. 1 shows a schematic cross-sectional view of an example of a laminate.
  • 1 includes, in this order, a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4.
  • a primer coating 3 is formed on the surface of the support substrate 4.
  • the laminate in FIG. 1 is a device peelable type laminate.
  • FIG. 2 shows a schematic cross-sectional view of another example of the laminate.
  • the laminate of FIG. 2 includes, in order, a support substrate 24, an adhesive layer 22, and an electronic device substrate 26.
  • the electronic device substrate 26 includes a plurality of semiconductor chip substrates 21 and sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .
  • the adhesive layer 22 is provided between the electronic device substrate 26 and the support substrate 24.
  • a primer film 23 is formed on the surface of the support substrate 24.
  • the laminate in FIG. 2 is a device peelable type laminate.
  • the method for producing the laminate of the present invention comprises: A support substrate; a semiconductor substrate or an electronic device substrate; an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate; a primer coating formed on a surface of either the semiconductor substrate or the electronic device substrate, or the support substrate, the method comprising:
  • the method is characterized by including a step of forming a primer film by applying the above-mentioned composition for forming a primer film to the surface of any one of the semiconductor substrate or the electronic device substrate and the support substrate.
  • the method for producing the laminate of the present invention comprises the steps of: Furthermore, a step of applying an adhesive composition for forming the adhesive layer to any one of the semiconductor substrate or the electronic device substrate and the support substrate on which the primer film is not formed; a step of bonding a substrate on which the primer film has been formed and a substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate;
  • the manufacturing method may include the steps of:
  • the method for producing the laminate of the present invention comprises the steps of: Considering that the laminate is particularly a device peel-off type laminate, A step of forming a primer film by applying the above-mentioned composition for forming a primer film to the surface of a support substrate; applying an adhesive composition to a semiconductor substrate or an electronic device substrate to form an adhesive layer;
  • the manufacturing method includes a step of bonding the support substrate on which the primer coating has been formed and the semiconductor substrate or the electronic device substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate.
  • a method for manufacturing a laminate will be described below using the laminate shown in FIG. 1 as an example.
  • An example of the laminate of the present invention can be produced by a method including the following first to fourth steps.
  • First step A step of applying a primer film-forming composition onto a support substrate to form a primer film on the surface of the support substrate.
  • Second step A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer (if necessary, further heating to form an adhesive layer).
  • Third step A step of placing a support substrate having a primer film disposed on its surface on the adhesive coating layer or adhesive layer, and bonding the support substrate having a primer film disposed on its surface and the semiconductor substrate via the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment.
  • Fourth step A step of curing the adhesive coating layer by post-heat treatment to form an adhesive layer.
  • the method for applying the primer film-forming composition is not particularly limited, but is usually a spin coating method.
  • the spin coating conditions are, for example, 1000 rpm for 60 seconds.
  • the method for applying the adhesive composition is not particularly limited, but is usually a spin coating method. Alternatively, a method may be employed in which a coating film is separately formed by a spin coating method or the like to form a sheet-like coating film, and the sheet-like coating film is then attached as an adhesive coating layer.
  • the heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and the like, but is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes.
  • the applied adhesive composition is usually heated.
  • the thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is usually about 5 to 500 ⁇ m, and is appropriately determined so that the final thickness of the adhesive layer falls within the above-mentioned range.
  • the laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment.
  • the treatment conditions to be used, whether heat treatment, decompression treatment, or a combination of both, are determined appropriately taking into consideration various factors such as the type of adhesive composition, film thickness, and desired adhesive strength.
  • the heating temperature is typically determined appropriately from the range of 20 to 160°C, taking into account factors such as removing the solvent from the composition.
  • the temperature is preferably 150°C or lower, more preferably 130°C or lower.
  • the heating time is determined appropriately depending on the heating temperature and type of adhesive, but is typically 30 seconds or longer, preferably 1 minute or longer, to ensure optimal adhesion. However, to prevent deterioration of the adhesive layer and other components, the heating time is typically 10 minutes or shorter, preferably 5 minutes or shorter.
  • the vacuum treatment can be carried out by exposing the adhesive coating layers that come into contact with each other to an air pressure of 10 to 10,000 Pa.
  • the vacuum treatment time is usually 1 to 30 minutes.
  • the load applied in the thickness direction of the semiconductor substrate and support substrate is not particularly limited, as long as it does not adversely affect the semiconductor substrate, support substrate, or layers between them and is a load that can firmly adhere them together, but is usually in the range of 10 to 50,000 N.
  • the post-heating temperature is preferably 120° C. or higher from the viewpoint of realizing a sufficient curing rate, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate and each layer.
  • the post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrates and layers constituting the laminate, and is usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, an oven, etc.
  • the laminate When post-heating is performed using a hot plate, the laminate may be heated with either the semiconductor substrate or the support substrate facing downward, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.
  • post-heat treatment is to realize an adhesive layer that is a more suitable self-supporting film, and in particular to realize suitable curing by the hydrosilylation reaction.
  • FIG. 3A to 3C are diagrams for explaining one embodiment of the manufacturing method of the laminate shown in FIG.
  • a laminate is prepared in which a primer film 3 is formed on a support substrate 4 (FIG. 3A).
  • This laminate can be obtained, for example, by applying a primer film-forming composition onto the support substrate 4 by spin coating.
  • a laminate is prepared in which an adhesive coating layer 2a is formed on the semiconductor substrate 1 (FIG. 3B).
  • This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating it.
  • FIG. 3B are bonded together so that the adhesive coating layer 2a contacts the support substrate 4 via the primer coating 3. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (hot plate, not shown) is placed on the surface of the semiconductor substrate 1 opposite to the surface where the adhesive coating layer 2a contacts, and the adhesive coating layer 2a is heated and hardened by the heating device, converting it into the adhesive layer 2 (Fig. 3C).
  • the laminate shown in FIG. 1 is obtained by the steps shown in FIGS. 3A to 3C.
  • a method for manufacturing a laminate will be described below using the laminate shown in FIG. 2 as an example.
  • An example of the laminate of the present invention can be produced by a method including the following steps 1 (D) to 5 (D).
  • FIG. 4A to 4D are diagrams for explaining one mode of manufacturing the laminate shown in FIG.
  • a laminate is prepared in which a primer film 23 is formed on a support substrate 24 (FIG. 4A). This laminate can be obtained, for example, by applying a primer film-forming composition onto the support substrate 24 by spin coating.
  • a laminate is prepared in which adhesive coating layer 22a is formed on semiconductor chip substrate 21 (FIG. 4B). This laminate can be obtained, for example, by applying an adhesive composition to semiconductor chip substrate 21 and heating it. At this time, adhesive coating layer 22a may be heated to form adhesive layer 22.
  • a heating device (hot plate, not shown) is placed on the surface of the semiconductor chip substrate 21 opposite to the surface where the adhesive coating layer 22a contacts, and the adhesive coating layer 22a is heated and hardened by the heating device to convert it into the adhesive layer 22 (Fig. 4C).
  • Fig. 4C the semiconductor chip substrates 21 fixed on the adhesive layer 22 are sealed with sealing resin 25.
  • the plurality of semiconductor chip substrates 21 temporarily adhered to the support substrate 24 via the adhesive layer 22 are sealed with sealing resin 25.
  • An electronic device substrate 26 having the semiconductor chip substrates 21 and the sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22.
  • the electronic device substrate 26 is a base layer in which the plurality of semiconductor chip substrates are embedded in the sealing resin.
  • the semiconductor chip substrate 21 is sealed using a sealing material.
  • a sealing material for sealing the semiconductor chip substrate 21 a material capable of insulating or sealing a member made of metal or semiconductor is used.
  • a resin composition encapsulating resin
  • the type of encapsulating resin is not particularly limited as long as it can encapsulate and/or insulate metals or semiconductors, but it is preferable to use, for example, an epoxy-based resin or a silicone-based resin.
  • the sealing material may contain other components such as a filler in addition to the resin component. Examples of the filler include spherical silica particles.
  • sealing resin heated to, for example, 130 to 170°C is supplied onto adhesive layer 22 while maintaining a high viscosity, so as to cover semiconductor chip substrate 21, and is compression molded to form a layer made of sealing resin 25 on adhesive layer 22.
  • the temperature condition at this time is, for example, 130 to 170°C.
  • the pressure applied to semiconductor chip substrate 21 is, for example, 50 to 500 N/ cm2 .
  • the use of the laminate according to the present invention makes it possible to provide a method for producing a processed semiconductor substrate or a processed electronic device substrate.
  • the method for producing a processed semiconductor substrate or electronic device substrate of the present invention includes: a fifth step in which the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the laminate of the present invention is processed; a sixth step of separating the semiconductor substrate or the electronic device substrate (semiconductor substrate or the like) processed in the fifth step from a support substrate in a laminate;
  • the present invention is characterized by comprising:
  • the method for producing a processed semiconductor substrate of the present invention includes the following fifth step and the following sixth step.
  • the method for producing a processed electronic device substrate may further include the following seventh step.
  • Fifth step A step of processing the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the laminate of the present invention.
  • Sixth step A step of separating the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) processed in the fifth step from the support substrate.
  • Seventh step A step of cleaning the processed semiconductor substrate or electronic device substrate after the sixth step.
  • the processing performed on the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the fifth step is, for example, processing of the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Thereafter, for example, through-silicon vias (TSVs) are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, for example, before or after this, wafer backside electrodes are formed. During the wafer thinning and TSV process, the wafer is subjected to a heat load of approximately 250 to 350°C while adhered to the support substrate.
  • TSVs through-silicon vias
  • the laminate of the present invention typically has heat resistance to this load.
  • the processing is not limited to the above, and also includes, for example, the implementation of a semiconductor component mounting process when a substrate for mounting a semiconductor component is temporarily bonded to a support substrate to support the substrate.
  • the processing performed on the electronic device substrate in step 5 includes, for example, the grinding step and wiring layer formation step described below.
  • the grinding step is a step of grinding away the resin portion of the sealing resin 25 layer on the electronic device substrate 26 so that a part of the semiconductor chip substrate 21 is exposed.
  • the wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor chip substrate 21 after the grinding step.
  • the wiring layer also called an RDL (Redistribution Layer) is a thin-film wiring body that constitutes wiring connected to a substrate, and may have a single-layer or multi-layer structure.
  • the wiring layer may be, but is not limited to, wiring formed by a conductor (e.g., metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) between dielectrics (e.g. , silicon oxide (SiO x ), photosensitive resins such as photosensitive epoxy, etc.).
  • the wiring layer may be formed, for example, by the following method.
  • a dielectric layer made of silicon oxide (SiO x ), photosensitive resin, or the like is formed on the layer of sealing resin 25.
  • the dielectric layer made of silicon oxide can be formed by, for example, sputtering, vacuum deposition, or the like.
  • the dielectric layer made of photosensitive resin can be formed by applying the photosensitive resin onto the layer of sealing resin 25 by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like.
  • wiring is formed on the dielectric layer using a conductor such as a metal. Examples of methods for forming the wiring include known semiconductor processing techniques such as lithography (e.g., photolithography) and etching. Examples of such lithography include lithography using a positive resist material and lithography using a negative resist material.
  • the method for separating (peeling) the semiconductor substrate or electronic device substrate from the support substrate is not particularly limited.
  • mechanical peeling may be performed using equipment with a sharp part (a so-called debonder).
  • the sharp part is inserted between the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the support substrate, and then the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) is separated from the support substrate.
  • the substrates can be cleaned by spraying the cleaning composition onto the surface of at least one of the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the supporting substrate, or by immersing the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) or the supporting substrate in the cleaning composition. Furthermore, the surface of the processed semiconductor substrate or the like may be cleaned using a removal tape or the like. As an example of cleaning the substrate, a seventh step of cleaning the processed semiconductor substrate or the like may be performed after the sixth step. Examples of detergent compositions used for cleaning include the following.
  • the cleaning composition typically contains a solvent.
  • the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents.
  • lactones include ⁇ -butyrolactone.
  • ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.
  • Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate.
  • Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers (e.g., monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether) or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond.
  • monoalkyl ethers e.g., monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether
  • monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.
  • Examples of cyclic ethers include dioxane.
  • esters examples include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.
  • aromatic organic solvents examples include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, and mesitylene. These may be used alone or in combination of two or more. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.
  • PMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • EL ethyl lactate
  • a mixed solvent of PGMEA and a polar solvent is also preferred.
  • the blending ratio may be appropriately determined taking into consideration the compatibility of PGMEA with the polar solvent, and is preferably within a range of 1:9 to 9:1, and more preferably 2:8 to 8:2.
  • the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2.
  • the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.
  • the mass ratio of PGMEA:(PGME+cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.
  • the cleaning composition may or may not contain salt, but a salt-free composition is preferred in that it will be more versatile when processing semiconductor substrates using the laminate and will help reduce costs.
  • An example of a cleaning composition containing a salt is a cleaning composition containing a quaternary ammonium salt and a solvent.
  • the quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application.
  • Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations, while their counter anions include, but are not limited to, hydroxide ion (OH ⁇ ), halogen ions such as fluoride ion (F ⁇ ), chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodide ion (I ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), and hexafluorophosphate ion (PF 6 ⁇ ).
  • hydroxide ion OH ⁇
  • halogen ions such as fluoride ion (F ⁇ ), chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodide ion (I ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), and hexafluorophosphate i
  • the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.
  • the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.
  • the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.
  • the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.
  • the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.
  • tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.
  • the quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate.
  • the quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more.
  • the amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass based on the detergent composition.
  • the solvent used in combination is not particularly limited, as long as it is suitable for this type of application and dissolves salts such as quaternary ammonium salts.
  • the cleaning composition preferably contains one or more amide solvents.
  • a suitable example of the amide solvent is an acid amide derivative represented by formula (Z).
  • R 0 represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group.
  • R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group.
  • R A and R B are preferably a methyl group or an ethyl group, more preferably both are a methyl group or an ethyl group, and even more preferably both are a methyl group.
  • Examples of acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, and N-ethyl-N-methylisobutyric acid amide.
  • N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, with N,N-dimethylpropionamide being more preferred.
  • the acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.
  • Another example of a preferred amide solvent is a lactam compound represented by formula (Y).
  • R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 102 represents an alkylene group having 1 to 6 carbon atoms.
  • Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group
  • specific examples of the alkylene group having 1 to 6 carbon atoms include, but are not limited to, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
  • lactam compounds represented by formula (Y) include ⁇ -lactam compounds, ⁇ -lactam compounds, ⁇ -lactam compounds, and ⁇ -lactam compounds, which can be used alone or in combination of two or more.
  • the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl- ⁇ -butyrolactam), and in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).
  • the cleaning composition used in the present invention may contain water as a solvent, but from the perspective of avoiding corrosion of the substrate, etc., typically only an organic solvent is intended to be used as the solvent. In this case, however, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent.
  • the water content of the cleaning composition used in the present invention is typically 5% by mass or less.
  • the constituent elements and methodological elements of the above-described steps of the method for manufacturing a processed semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) of the present invention may be modified in various ways without departing from the spirit and scope of the present invention.
  • the method of manufacturing a processed semiconductor substrate or an electronic device substrate (such as a semiconductor substrate) of the present invention may include steps other than those described above.
  • the primer coating composition of the present invention is a primer coating composition for increasing the adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction, and is a composition containing a component that contributes to the hydrosilylation reaction, as described in detail above in the section ⁇ Primer coating composition>> of ⁇ Primer coating>> in (Laminate)>.
  • the adhesive layer which is the target of the primer coating-forming composition for increasing the adhesion to the substrate via the primer coating-forming composition, is as described in the ⁇ Adhesive Layer> section in the above (Laminate).
  • primer film-forming composition (adhesion aid composition)
  • adhesion aid composition To a 100 mL glass container with a lid, 0.01 g of Tetrakis(triphenylphosphine) platinum (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (X-1), 49.995 g of propylene glycol monomethyl ether, and 49.995 g of propylene glycol monomethyl ether acetate were added, and the mixture was stirred for 5 minutes with Stirrer A to obtain a composition for forming a primer film (hereinafter also referred to as an adhesion aid composition).
  • mixture (I) 1.67 g of mixture (I), 157.67 g of a solution prepared by mixing a vinyl group-containing MQ resin (manufactured by Wacker Chemical Co.), a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa ⁇ s (manufactured by Wacker Chemical Co.), and a SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa ⁇ s (manufactured by Wacker Chemical Co.) in a ratio of 51.6:38.9:9.5, and 131.49 g of mixed liquid (II) were added to a 1 L plastic container with a lid, and the mixture was stirred using stirrer B until it became uniform.
  • a vinyl group-containing MQ resin manufactured by Wacker Chemical Co.
  • a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa ⁇ s manufactured by Wacker Chemical Co.
  • Example 1-1 The adhesive auxiliary composition obtained in Preparation Example 1-1 was spin-coated onto a 300 mm silicon wafer (thickness: 775 ⁇ m) as a carrier-side substrate at a rotation speed of 1500 rpm for 60 seconds to form a primer film (also referred to as an adhesive auxiliary coating film) on the silicon wafer as a supporting substrate.
  • the adhesive composition obtained in Preparation Example 2-1 was spin-coated onto a 300 mm silicon wafer (thickness 775 ⁇ m) as the device-side substrate so that the film thickness in the final laminate was 50 ⁇ m, forming an adhesive coating layer on the silicon wafer, which was the semiconductor substrate.
  • the support substrate on which the adhesion auxiliary agent coating film was formed and the semiconductor substrate on which the adhesive coating layer was formed were bonded together so as to sandwich the adhesion auxiliary agent coating film and the adhesive coating layer, and then a laminate was produced by heat treatment at 130° C. for 5 minutes and at 200° C. for 5 minutes.
  • the bonding was performed at a temperature of 23° C., a reduced pressure of 1,000 Pa, and a load of 30 N.
  • Example 1-2 A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-2 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.
  • Examples 1-3 A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-3 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.
  • Examples 1-4 A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-4 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.
  • Example 1-1 A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-5 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.
  • Example 1-2 A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-6 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.
  • Example 1-1 A laminate was obtained in the same manner as in Example 1-1, except that the adhesive auxiliary agent composition obtained in Preparation Example 1-1 was not used and a support substrate on which no adhesive auxiliary agent coating layer was formed was used as the substrate on the carrier side.
  • the primer film-forming composition (adhesion auxiliary composition) of the present invention when used, the adhesive strength of the adhesive composition is improved, interfacial peeling occurs on the device side (semiconductor substrate side) opposite to the support substrate on whose surface the primer film-forming composition (adhesion auxiliary composition) has been applied, and after peeling of the laminate, a film of the adhesive composition remains on the support substrate side on which the primer film-forming composition (adhesion auxiliary composition) has been applied.

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Abstract

The present invention provides, for example, a laminate which comprises a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer that is provided between the semiconductor substrate or the electronic device substrate and the support substrate, and with which it is possible to control the separation interface when a semiconductor wafer is separated from the support substrate.　This laminate comprises a support substrate, a semiconductor substrate or an electronic device substrate, and an adhesive layer that is provided between the semiconductor substrate or the electronic device substrate and the support substrate, wherein: a primer film is formed on a substrate surface of one of the semiconductor substrate, the electronic device substrate, and the support substrate; and the primer film is formed of a composition for forming a primer film for enhancing the adhesion between a substrate and an adhesive layer that is formed of an adhesive composition which contains an adhesive component that is cured by a hydrosilylation reaction, the composition for forming a primer film containing a component that contributes to the hydrosilylation reaction.

Description

プライマー皮膜形成用組成物、積層体、積層体の製造方法、及び加工された半導体基板又は電子デバイス基板の製造方法Primer film-forming composition, laminate, method for manufacturing laminate, and method for manufacturing processed semiconductor substrate or electronic device substrate

　本発明は、プライマー皮膜形成用組成物、積層体、積層体の製造方法、及び加工された半導体基板又は電子デバイス基板の製造方法に関する。 The present invention relates to a composition for forming a primer film, a laminate, a method for manufacturing a laminate, and a method for manufacturing a processed semiconductor substrate or electronic device substrate.

　従来２次元的な平面方向に集積してきた半導体ウエハーは、より一層の集積化を目的に平面を更に３次元方向にも集積（積層）する半導体集積技術が求められている。この３次元積層はシリコン貫通電極（ＴＳＶ：ｔｈｒｏｕｇｈ　ｓｉｌｉｃｏｎ　ｖｉａ）によって結線しながら多層に集積していく技術である。多層に集積する際に、集積されるそれぞれのウエハーは形成された回路面とは反対側（即ち、裏面）を研磨によって薄化し、薄化された半導体ウエハーを積層する。 Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but with the aim of achieving even greater integration, there is a demand for semiconductor integration technology that integrates (stacking) the plane in three dimensions. This three-dimensional stacking is a technology that integrates multiple layers while connecting them using through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are then stacked.

　薄化前の半導体ウエハー（ここでは単にウエハーとも呼ぶ）が、研磨装置で研磨するために支持体に接着される。その際の接着は研磨後に容易に剥離されなければならないため、仮接着と呼ばれる。この仮接着は支持体から容易に取り外されなければならず、取り外しに大きな力を加えると薄化された半導体ウエハーは、切断されたり変形したりすることがあり、その様なことが生じない様に、容易に取り外される。しかし、半導体ウエハーの裏面研磨時に研磨応力によって外れたりずれたりすることは好ましくない。従って、仮接着に求められる性能は研磨時の応力に耐え、研磨後に容易に取り外されることである。 Semiconductor wafers (here simply referred to as wafers) before thinning are adhered to a support in preparation for polishing with a polishing device. This adhesion is called temporary adhesion because it must be easily peeled off after polishing. This temporary adhesion must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary adhesion to become loose or shift due to the polishing stress when the backside of the semiconductor wafer is polished. Therefore, the performance required of temporary adhesion is that it can withstand the stress during polishing and be easily removed after polishing.

　そのような仮接着に用いられる仮接着剤として、ポリジメチルシロキサンを含有する接着剤（特許文献１）、エポキシ変性ポリシロキサンを含有する仮接着剤（特許文献２）などが提案されている。 Temporary adhesives proposed for use in such temporary bonding include adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2).

国際公開第２０１７／２２１７７２号パンフレットInternational Publication No. 2017/221772 国際公開第２０１８／２１６７３２号パンフレットInternational Publication No. 2018/216732

　上述したように、半導体ウエハーと支持体との仮接着においては、仮接着時には仮接着剤から形成される接着剤層は支持体や半導体ウエハーから剥がれにくく、一方、支持体から半導体ウエハーを剥がす際には、接着剤層は支持体や半導体ウエハーから剥がれやすくなっている必要がある。
　ところで、支持体から半導体ウエハーを剥がす際、剥離される場所が、半導体ウエハーと接着剤層との界面である場合（この場合をデバイス剥離（デバイスリリース）ともいう）や、支持体と接着剤層との界面である場合（この場合をキャリア剥離（キャリアリリース）ともいう）がある。
　例えば、剥離がキャリア剥離であった場合、半導体ウエハーのデバイス側に接着剤層が残存している（付着している）ため、デバイス剥離の場合に比べ、剥離後の接着剤層の洗浄が長くなり、工程時間が増加するといった懸念や、半導体ウエハーであるデバイス基板への洗浄負担が大きくなるといった懸念がある。したがって、上述した懸念を生じさせないためには、デバイス剥離の方が好ましい。
　このように、デバイス基板上への接着剤層の残渣を少なくするという観点からはデバイス剥離が好ましいが、一方、使用する接着剤層や、それに接する各基板の種類、あるいは製造工程における設定条件等の理由から、キャリア剥離を望む場合もある。
　そこで、支持体から半導体ウエハーを剥がす際、剥離する場所（剥離界面）がコントロールできると都合がよい。 As described above, in the temporary bonding of a semiconductor wafer and a support, the adhesive layer formed from the temporary adhesive must be difficult to peel off from the support or the semiconductor wafer during temporary bonding, while the adhesive layer must be easy to peel off from the support or the semiconductor wafer when the semiconductor wafer is peeled off from the support.
Incidentally, when peeling the semiconductor wafer from the support, the peeling may occur at the interface between the semiconductor wafer and the adhesive layer (this case is also called device release), or at the interface between the support and the adhesive layer (this case is also called carrier release).
For example, when the peeling is performed by carrier peeling, the adhesive layer remains (adheres) on the device side of the semiconductor wafer, which raises concerns that cleaning the adhesive layer after peeling will take longer than in the case of device peeling, increasing the process time and placing a greater burden on the device substrate, i.e., the semiconductor wafer. Therefore, device peeling is preferred in order to avoid the above-mentioned concerns.
Thus, device peeling is preferable from the viewpoint of reducing the amount of adhesive layer residue on the device substrate. However, carrier peeling may be desired in some cases due to factors such as the adhesive layer used, the type of each substrate that comes into contact with it, or the conditions set in the manufacturing process.
Therefore, when peeling the semiconductor wafer from the support, it is convenient to be able to control the location of peeling (peeling interface).

　本発明は、前記事情に鑑みてなされたものであって、
　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層とを有する積層体において、
　支持基板から半導体ウエハーを剥がす際に剥離界面をコントロールできる積層体を提供することを目的とする。 The present invention has been made in consideration of the above circumstances,
A support substrate;
a semiconductor substrate or an electronic device substrate;
a laminate including an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
The object is to provide a laminate that can control the peeling interface when peeling a semiconductor wafer from a support substrate.

　本発明者らは、前記の課題を解決する為、鋭意検討を行った結果、接着剤層と基板との間に、これら接着剤層と基板との接着力を高めることができるプライマー皮膜を設けることで、前記の課題を解決出来ることを見出し、以下の要旨を有する本発明を完成させた。 As a result of extensive research into solving the above-mentioned problems, the inventors discovered that the above-mentioned problems can be solved by providing a primer film between the adhesive layer and the substrate, which can increase the adhesive strength between the adhesive layer and the substrate, and thus completed the present invention, which has the following gist.

　すなわち、本発明は以下を包含する。
　［１］　ヒドロシリル化反応によって硬化する接着剤成分を含有する接着剤組成物から形成される接着剤層と基板との接着力を高めるためのプライマー皮膜形成用組成物であって、
　前記ヒドロシリル化反応に寄与する成分を含有するプライマー皮膜形成用組成物。
　［２］　前記プライマー皮膜形成用組成物は、前記ヒドロシリル化反応に寄与する成分として、白金を含む化合物、Ｓｉ－Ｈ基を含む化合物、及びビニル基を含む化合物のいずれかから選ばれる成分を含有する、［１］に記載のプライマー皮膜形成用組成物。
　［３］　前記接着剤層を形成する接着剤組成物は、前記接着剤成分と、剥離剤成分とを含有する、［１］又は［２］に記載のプライマー皮膜形成用組成物。
　［４］　前記剥離剤成分が、ポリオルガノシロキサンを含む、［３］に記載のプライマー皮膜形成用組成物。
　［５］　前記ヒドロシリル化反応によって硬化する接着剤成分が、
　　ケイ素原子に結合した炭素原子数２～４０のアルケニル基を有する成分（Ａ－１）と、
　　Ｓｉ－Ｈ基を有する成分（Ａ－２）と、
　　白金族金属系触媒（Ａ－３）と
を含有する、［１］～［４］のいずれかに記載のプライマー皮膜形成用組成物。
　［６］　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層とを有し、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面にプライマー皮膜が形成されており、
　前記プライマー皮膜は、［１］～［５］のいずれかに記載のプライマー皮膜形成用組成物から形成されたプライマー皮膜である、積層体。
　［７］　前記プライマー皮膜は、前記支持基板の表面に形成されている、［６］に記載の積層体。
　［８］　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層と、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面に形成されたプライマー皮膜と、を有する積層体の製造方法であって、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面に、［１］～［５］のいずれかに記載のプライマー皮膜形成用組成物を塗布することによりプライマー皮膜を形成する工程、
を含む積層体の製造方法。
　［９］　さらに、前記プライマー皮膜が形成されていない、前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板に対し、前記接着剤層を形成するための接着剤組成物を塗布する工程、
　前記プライマー皮膜が形成された基板と、前記接着剤組成物が塗布されている基板とを貼り合わせ、その後加熱処理を行うことにより、前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に接着剤層を形成する工程、
を含む、［８］に記載の積層体の製造方法。
　［１０］　支持基板の表面に、［１］～［５］のいずれかに記載のプライマー皮膜形成用組成物を塗布することによりプライマー皮膜を形成する工程、
　半導体基板又は電子デバイス基板に対し、接着剤層を形成するための接着剤組成物を塗布する工程、
　前記プライマー皮膜が形成された前記支持基板と、前記接着剤組成物が塗布されている前記半導体基板又は前記電子デバイス基板とを貼り合わせ、その後加熱処理を行うことにより、前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に接着剤層を形成する工程、
を含む、［９］に記載の積層体の製造方法。
　［１１］　加工された半導体基板又は電子デバイス基板の製造方法であって、
　［６］又は［７］に記載の積層体の前記半導体基板又は前記電子デバイス基板が加工される第５工程と、
　前記第５工程によって加工された前記半導体基板又は前記電子デバイス基板と、前記支持基板とが分離される第６工程と、
を含む、加工された半導体基板又は電子デバイス基板の製造方法。 That is, the present invention includes the following.
[1] A primer coating-forming composition for enhancing the adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction, comprising:
A primer film-forming composition containing a component that contributes to the hydrosilylation reaction.
[2] The primer coating composition according to [1], which contains, as a component contributing to the hydrosilylation reaction, a component selected from the group consisting of a platinum-containing compound, a Si—H group-containing compound, and a vinyl group-containing compound.
[3] The composition for forming a primer coating according to [1] or [2], wherein the adhesive composition forming the adhesive layer contains the adhesive component and a release agent component.
[4] The primer coating composition according to [3], wherein the release agent component contains polyorganosiloxane.
[5] The adhesive component that cures by a hydrosilylation reaction is
Component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom;
a component (A-2) having an Si—H group;
The primer coating composition according to any one of [1] to [4], further comprising a platinum group metal catalyst (A-3).
[6] A support substrate;
a semiconductor substrate or an electronic device substrate;
an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
a primer coating is formed on a surface of any one of the semiconductor substrate or the electronic device substrate and the support substrate;
The primer film is a primer film formed from the composition for forming a primer film according to any one of [1] to [5].
[7] The laminate according to [6], wherein the primer film is formed on the surface of the support substrate.
[8] A support substrate;
a semiconductor substrate or an electronic device substrate;
an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate;
a primer coating formed on a surface of either the semiconductor substrate or the electronic device substrate, or the support substrate, the method comprising:
a step of forming a primer film by applying the primer film-forming composition according to any one of [1] to [5] to a substrate surface of any one of the semiconductor substrate or the electronic device substrate and the support substrate;
A method for producing a laminate comprising the steps of:
[9] Further, a step of applying an adhesive composition for forming the adhesive layer to any one of the semiconductor substrate or the electronic device substrate and the support substrate on which the primer coating is not formed;
a step of bonding a substrate on which the primer film has been formed and a substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate;
The method for producing the laminate according to [8], comprising:
[10] A step of forming a primer film by applying the primer film-forming composition according to any one of [1] to [5] to the surface of a supporting substrate;
applying an adhesive composition to a semiconductor substrate or an electronic device substrate to form an adhesive layer;
a step of bonding the support substrate on which the primer film has been formed and the semiconductor substrate or the electronic device substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate;
The method for producing the laminate according to [9], comprising:
[11] A method for producing a processed semiconductor substrate or electronic device substrate, comprising:
A fifth step in which the semiconductor substrate or the electronic device substrate of the laminate according to [6] or [7] is processed;
a sixth step of separating the semiconductor substrate or the electronic device substrate processed in the fifth step from the support substrate;
1. A method for producing a processed semiconductor substrate or electronic device substrate, comprising:

　本発明によれば、
　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層とを有する積層体において、
　支持基板から半導体ウエハーを剥がす際に剥離界面をコントロールできる積層体を提供することができる。 According to the present invention,
A support substrate;
a semiconductor substrate or an electronic device substrate;
a laminate including an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
It is possible to provide a laminate that allows the separation interface to be controlled when peeling a semiconductor wafer from a support substrate.

図１は、積層体の一例の概略断面図である。FIG. 1 is a schematic cross-sectional view of an example of a laminate. 図２は、積層体の他の一例の概略断面図である。FIG. 2 is a schematic cross-sectional view of another example of the laminate. 図３Ａは、図１に示す積層体の製造方法を説明するための概略断面図である（その１）。FIG. 3A is a schematic cross-sectional view (part 1) illustrating a method for manufacturing the laminate shown in FIG. 図３Ｂは、図１に示す積層体の製造方法を説明するための概略断面図である（その２）。FIG. 3B is a schematic cross-sectional view (part 2) illustrating a method for manufacturing the laminate shown in FIG. 図３Ｃは、図１に示す積層体の製造方法を説明するための概略断面図である（その３）。FIG. 3C is a schematic cross-sectional view (part 3) illustrating a method for manufacturing the laminate shown in FIG. 1 . 図４Ａは、図２に示す積層体の製造方法を説明するための概略断面図である（その１）。FIG. 4A is a schematic cross-sectional view (part 1) illustrating a method for manufacturing the laminate shown in FIG. 2 . 図４Ｂは、図２に示す積層体の製造方法を説明するための概略断面図である（その２）。FIG. 4B is a schematic cross-sectional view (part 2) illustrating a method for manufacturing the laminate shown in FIG. 2 . 図４Ｃは、図２に示す積層体の製造方法を説明するための概略断面図である（その３）。FIG. 4C is a schematic cross-sectional view (part 3) illustrating a method for manufacturing the laminate shown in FIG. 2 . 図４Ｄは、図２に示す積層体の製造方法を説明するための概略断面図である（その４）。FIG. 4D is a schematic cross-sectional view (part 4) illustrating a method for manufacturing the laminate shown in FIG. 2 .

（積層体）
　本発明の積層体は、
　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層とを有している積層体であって、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面にプライマー皮膜が形成されている積層体である。
　前記プライマー皮膜は、以下に記載のプライマー皮膜形成用組成物から形成される。
　前記プライマー皮膜形成用組成物は、
　ヒドロシリル化反応によって硬化する接着剤成分を含有する接着剤組成物から形成される接着剤層と基板との接着力を高めるための組成物であって、前記ヒドロシリル化反応に寄与する成分を含有する。 (Laminate)
The laminate of the present invention is
A support substrate;
a semiconductor substrate or an electronic device substrate;
a laminate having an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
The laminate has a primer film formed on the surface of either the semiconductor substrate or the electronic device substrate, or the support substrate.
The primer film is formed from the primer film-forming composition described below.
The primer film-forming composition is
A composition for enhancing the adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction, the composition containing a component that contributes to the hydrosilylation reaction.

　本発明では、ヒドロシリル化反応に寄与する成分を含有するプライマー皮膜形成用組成物で形成されたプライマー層を積層体に配することで、ヒドロシリル化反応によって硬化する接着剤成分を含有する接着剤組成物から形成される接着剤層と基板との接着力を高めることができる。これにより、該プライマー層を有する積層体は、仮接着時においては、接着剤層が支持基板や半導体基板又は電子デバイス基板から剥がれにくく、一方、支持基板から半導体基板又は電子デバイス基板を剥がす際には、プライマー皮膜を有していない基板と接着剤層との界面において接着剤層を容易に剥がすことができる。 In the present invention, by disposing a primer layer formed from a primer film-forming composition containing a component that contributes to the hydrosilylation reaction on a laminate, it is possible to increase the adhesive strength between the substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that hardens through a hydrosilylation reaction. As a result, in a laminate having this primer layer, the adhesive layer is less likely to peel off from the support substrate, semiconductor substrate, or electronic device substrate when temporarily bonded, and when peeling the semiconductor substrate or electronic device substrate from the support substrate, the adhesive layer can be easily peeled off at the interface between the substrate not having the primer film and the adhesive layer.

　本発明では、「半導体基板又は電子デバイス基板、及び支持基板のいずれかの基板表面にプライマー皮膜を形成する」ことを規定するが、プライマー皮膜を形成する具体的態様として、例えば、以下の態様が挙げられる。
（ａ）半導体基板と支持基板とを有する積層体において、支持基板表面にプライマー皮膜が形成される
（ｂ）電子デバイス基板と支持基板とを有する積層体において、支持基板表面にプライマー皮膜が形成される
（ｃ）半導体基板と支持基板とを有する積層体において、半導体基板表面にプライマー皮膜が形成される
（ｄ）電子デバイス基板と支持基板とを有する積層体において、電子デバイス基板表面にプライマー皮膜が形成される The present invention specifies that "a primer film is formed on the surface of any one of a semiconductor substrate or an electronic device substrate, and a support substrate," and specific embodiments for forming the primer film include, for example, the following embodiments.
(a) In a laminate having a semiconductor substrate and a support substrate, a primer coating is formed on the surface of the support substrate. (b) In a laminate having an electronic device substrate and a support substrate, a primer coating is formed on the surface of the support substrate. (c) In a laminate having a semiconductor substrate and a support substrate, a primer coating is formed on the surface of the semiconductor substrate. (d) In a laminate having an electronic device substrate and a support substrate, a primer coating is formed on the surface of the electronic device substrate.

　例えば、上記（ａ）の態様の場合、プライマー皮膜を有している基板と接着剤層とは、プライマー皮膜により接着力が上がっているため、支持基板から半導体基板を剥がそうとすると、プライマー皮膜を有していない基板と接着剤層との界面で剥離が生じる。つまり、上記（ａ）の態様の場合、半導体基板と接着剤層との界面で剥離（デバイス剥離）が生じる。
　同様に、上記（ｂ）の態様においても、電子デバイス基板と接着剤層との界面で剥離（デバイス剥離）が生じる。
　一方、上記（ｃ）の態様や上記（ｄ）の態様においては、支持基板と接着剤層との界面で剥離（キャリア剥離）が生じる。
　このように、積層体におけるいずれの基板にプライマー皮膜を配するかで、剥離界面をコントロールすることができる。 For example, in the case of the above embodiment (a), the adhesive strength between the substrate having the primer coating and the adhesive layer is increased by the primer coating, so when an attempt is made to peel the semiconductor substrate from the support substrate, peeling occurs at the interface between the substrate not having the primer coating and the adhesive layer. In other words, in the case of the above embodiment (a), peeling (device peeling) occurs at the interface between the semiconductor substrate and the adhesive layer.
Similarly, in the above embodiment (b), peeling (device peeling) occurs at the interface between the electronic device substrate and the adhesive layer.
On the other hand, in the above-mentioned embodiments (c) and (d), peeling (carrier peeling) occurs at the interface between the support substrate and the adhesive layer.
In this way, the peeling interface can be controlled by determining which substrate in the laminate has the primer film disposed on it.

　本発明は、剥離界面のコントロールという目的が達成できれば、積層体の態様として、デバイス剥離であってもキャリア剥離であっても構わない。
　本発明では、プライマー皮膜を配する基板は、使用する接着剤層や、それに接する各基板の種類、あるいは製造工程における設定条件等を考慮して、適宜選択することができる。
　ただし、以下では、支持基板の表面にプライマー皮膜を形成するデバイス剥離の場合を例に挙げ説明することとする。 In the present invention, the laminate may be in the form of device peeling or carrier peeling, as long as the object of controlling the peeling interface can be achieved.
In the present invention, the substrate on which the primer film is to be disposed can be appropriately selected taking into consideration the adhesive layer to be used, the type of each substrate to be in contact with it, or the conditions set in the manufacturing process.
However, the following description will be given taking as an example the case of device peeling in which a primer film is formed on the surface of a support substrate.

　本発明の積層体は、半導体基板又は電子デバイス基板を加工するに際して仮接着するために使用され、半導体基板又は電子デバイス基板（以下、“半導体基板又は電子デバイス基板”をまとめて、“半導体基板等”ともいう）の薄化等の加工に好適に用いることができる。
　半導体基板等に薄化等の加工が施されている間は、半導体基板等は、支持基板に支持されている。他方、半導体基板等の加工後は、半導体基板等と支持基板とは分離される。
　半導体基板等と支持基板とが分離がされた後に、半導体基板や電子デバイス基板、又は支持基板に残る接着剤層の残渣は、例えば、半導体基板等を洗浄するための洗浄剤組成物によって除去することができる。 The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device substrate, and can be suitably used for processing such as thinning a semiconductor substrate or an electronic device substrate (hereinafter, "semiconductor substrate or electronic device substrate" will also be collectively referred to as "semiconductor substrate, etc.").
The semiconductor substrate, etc. is supported by the support substrate while it is being processed, such as thinned, etc. After the semiconductor substrate, etc. is processed, the semiconductor substrate, etc. and the support substrate are separated.
After the semiconductor substrate or the like is separated from the support substrate, any residue of the adhesive layer remaining on the semiconductor substrate, electronic device substrate, or support substrate can be removed, for example, with a cleaning composition for cleaning semiconductor substrates or the like.

　本発明の積層体のより好ましい構成として、
　支持基板と、
　前記支持基板の表面に形成されたプライマー皮膜と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記プライマー皮膜を表面に有する前記支持基板との間に設けられた、接着剤層とを有する、積層体が挙げられる。
　この積層体は、デバイス剥離タイプの積層体である。 As a more preferred configuration of the laminate of the present invention,
A support substrate;
a primer coating formed on the surface of the support substrate;
a semiconductor substrate or an electronic device substrate;
The laminate may include an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate having the primer coating on its surface.
This laminate is a device peel-off type laminate.

　積層体を構成する各構成要件について、以下説明する。 The components that make up the laminate are explained below.

＜接着剤層＞
　接着剤層は、支持基板と、半導体基板又は電子デバイス基板（半導体基板等）との間に設けられる。
　接着剤層は、例えば、半導体基板等と接している。また、接着剤層は、例えば、表面にプライマー皮膜が形成された支持基板と接している。
　接着剤層は、接着剤組成物から形成される。 <Adhesive layer>
The adhesive layer is provided between the support substrate and the semiconductor substrate or electronic device substrate (such as a semiconductor substrate).
The adhesive layer is in contact with, for example, a semiconductor substrate, etc. The adhesive layer is also in contact with, for example, a support substrate having a primer coating formed on its surface.
The adhesive layer is formed from an adhesive composition.

　本発明の積層体が備える接着剤層の厚さは、特に限定されるものではないが、通常５～５００μｍであり、膜強度を保つ観点から、好ましくは１０μｍ以上、より好ましくは２０μｍ以上、より一層好ましくは３０μｍ以上であり、厚膜に起因する不均一性を回避する観点から、好ましくは２００μｍ以下、より好ましくは１５０μｍ以下、より一層好ましくは１２０μｍ以下、更に好ましくは１００μｍ以下である。 The thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, but is typically 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less.

　接着剤組成物から接着剤層を形成する方法については、積層体の製造方法についての説明箇所で、詳しく述べる。 The method for forming an adhesive layer from the adhesive composition will be described in detail in the section explaining the method for manufacturing the laminate.

＜＜接着剤組成物＞＞
　本発明に係る接着剤組成物は、ヒドロシリル化反応によって硬化する接着剤成分を含有する。
　本発明に係る接着剤組成物は、接着剤成分と剥離剤成分とを含有することが好ましい。
　本発明に係る接着剤組成物は、その他の成分を含有していてもよい。 <<Adhesive Composition>>
The adhesive composition according to the present invention contains an adhesive component that cures via a hydrosilylation reaction.
The adhesive composition according to the present invention preferably contains an adhesive component and a release agent component.
The adhesive composition according to the present invention may contain other components.

　剥離剤成分としては、ポリオルガノシロキサンを含むことが好ましい。
　剥離剤成分は、２種類以上の剥離剤成分を含有することが好ましい。 The release agent component preferably contains polyorganosiloxane.
The release agent component preferably contains two or more types of release agent components.

＜＜＜接着剤成分＞＞＞
　接着剤成分としては、ヒドロシリル化反応によって硬化する成分である。
　ヒドロシリル化反応によって硬化する成分としては、特に制限されないが、ケイ素原子に結合した炭素原子数２～４０のアルケニル基を有する成分（以下、「成分（Ａ－１）」と称することがある。）と、Ｓｉ－Ｈ基を有する成分（以下、「成分（Ａ－２）」と称することがある。）と、白金族金属系触媒（Ａ－３）とを含有することが好ましい。 <<<Adhesive components>>>
The adhesive component is a component that hardens through a hydrosilylation reaction.
The component that cures via a hydrosilylation reaction is not particularly limited, but preferably contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter, sometimes referred to as "component (A-1)"), a component having a Si—H group (hereinafter, sometimes referred to as "component (A-2)"), and a platinum group metal catalyst (A-3).

＜＜＜＜成分（Ａ－１）及び成分（Ａ－２）＞＞＞＞
　接着剤組成物は、成分（Ａ－１）を含有することが好ましい。
　接着剤組成物は、成分（Ａ－２）を含有することが好ましい。
　以下、成分（Ａ－１）、成分（Ａ－２）、及び白金族金属系触媒（Ａ－３）の組み合わせを、「硬化する成分（Ａ）」又は「成分（Ａ）」と称することがある。 <<<<Component (A-1) and Component (A-2)>>>>
The adhesive composition preferably contains component (A-1).
The adhesive composition preferably contains component (A-2).
Hereinafter, the combination of component (A-1), component (A-2), and platinum group metal catalyst (A-3) may be referred to as "curable component (A)" or "component (A)."

　成分（Ａ－１）は、本発明の効果を好適に得る観点から、ケイ素原子に結合した炭素原子数２～４０のアルケニル基を有するポリオルガノシロキサン（ａ１）を含有することが好ましい。
　成分（Ａ－２）は、本発明の効果を好適に得る観点から、Ｓｉ－Ｈ基を有するポリオルガノシロキサン（ａ２）を含有することが好ましい。
　ここで、炭素原子数２～４０のアルケニル基は置換されていてもよい。置換基としては、例えば、ハロゲン原子、ニトロ基、シアノ基、アミノ基、ヒドロキシ基、カルボキシル基、アリール基、ヘテロアリール基等が挙げられる。 From the viewpoint of optimally achieving the effects of the present invention, component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom.
From the viewpoint of suitably achieving the effects of the present invention, the component (A-2) preferably contains a polyorganosiloxane (a2) having Si—H groups.
Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

　他の好ましい態様においては、ヒドロシリル化反応によって硬化する接着剤組成物は、ＳｉＯ２で表されるシロキサン単位（Ｑ単位）、Ｒ１Ｒ２Ｒ３ＳｉＯ１／２で表されるシロキサン単位（Ｍ単位）、Ｒ４Ｒ５ＳｉＯ２／２で表されるシロキサン単位（Ｄ単位）及びＲ６ＳｉＯ３／２で表されるシロキサン単位（Ｔ単位）からなる群より選ばれる１種又は２種以上の単位を含むポリシロキサン（Ａ１）と、白金族金属系触媒（Ａ－３）とを含み、ポリシロキサン（Ａ１）は、ＳｉＯ２で表されるシロキサン単位（Ｑ’単位）、Ｒ１’Ｒ２’Ｒ３’ＳｉＯ１／２で表されるシロキサン単位（Ｍ’単位）、Ｒ４’Ｒ５’ＳｉＯ２／２で表されるシロキサン単位（Ｄ’単位）及びＲ６’ＳｉＯ３／２で表されるシロキサン単位（Ｔ’単位）からなる群より選ばれる１種又は２種以上の単位を含むとともに、Ｍ’単位、Ｄ’単位及びＴ’単位からなる群より選ばれる少なくとも１種を含むポリオルガノシロキサン（ａ１’）と、ＳｉＯ２で表されるシロキサン単位（Ｑ”単位）、Ｒ１”Ｒ２”Ｒ３”ＳｉＯ１／２で表されるシロキサン単位（Ｍ”単位）、Ｒ４”Ｒ５”ＳｉＯ２／２で表されるシロキサン単位（Ｄ”単位）及びＲ６”ＳｉＯ３／２で表されるシロキサン単位（Ｔ”単位）からなる群より選ばれる１種又は２種以上の単位を含むとともに、Ｍ”単位、Ｄ”単位及びＴ”単位からなる群より選ばれる少なくとも１種を含むポリオルガノシロキサン（ａ２’）とを含む。
　なお、（ａ１’）は、（ａ１）の一例であり、（ａ２’）は、（ａ２）の一例である。 In another preferred embodiment, the adhesive composition that cures via a hydrosilylation reaction comprises a polysiloxane (A1) containing one or more units selected from the group consisting of siloxane units represented by SiO 2 (Q units), siloxane units represented by R 1 R 2 R 3 SiO 1/2 (M units), siloxane units represented by R 4 R 5 SiO 2/2 (D units), and siloxane units represented by R 6 SiO 3/2 (T units), and a platinum group metal catalyst (A-3). The polysiloxane (A1) contains siloxane units represented by SiO 2 (Q' units), siloxane units represented by R 1 'R 2 'R 3 'SiO 1/2 (M' units), siloxane units represented by R 4 'R 5 'SiO 2/2 (D' units), and siloxane units represented by R 6 'SiO and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T' units) represented by SiO 2 (Q" units), siloxane units (M " units) represented by R 4 "R 5 "SiO 2/2 (D" units) and siloxane units (T" units) represented by R 6 "SiO 3/2 , and containing at least one unit selected from the group consisting of M" units, D " units and T" units.
Note that (a1') is an example of (a1), and (a2') is an example of (a2).

　Ｒ１～Ｒ６は、ケイ素原子に結合する基又は原子であり、それぞれ独立して、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は水素原子を表す。置換基としては、例えば、ハロゲン原子、ニトロ基、シアノ基、アミノ基、ヒドロキシ基、カルボキシル基、アリール基、ヘテロアリール基等が挙げられる。 R 1 to R 6 are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

　Ｒ１’～Ｒ６’は、ケイ素原子に結合する基であり、それぞれ独立して、置換されていてもよいアルキル基又は置換されていてもよいアルケニル基を表すが、Ｒ１’～Ｒ６’の少なくとも１つは、置換されていてもよいアルケニル基である。置換基としては、例えば、ハロゲン原子、ニトロ基、シアノ基、アミノ基、ヒドロキシ基、カルボキシル基、アリール基、ヘテロアリール基等が挙げられる。 R 1 ' to R 6 ' are groups bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, provided that at least one of R 1 ' to R 6 ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

　Ｒ１”～Ｒ６”は、ケイ素原子に結合する基又は原子であり、それぞれ独立して、置換されていてもよいアルキル基又は水素原子を表すが、Ｒ１”～Ｒ６”の少なくとも１つは、水素原子である。置換基としては、例えば、ハロゲン原子、ニトロ基、シアノ基、アミノ基、ヒドロキシ基、カルボキシル基、アリール基、ヘテロアリール基等が挙げられる。 R 1 ″ to R 6 ″ are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, provided that at least one of R 1 ″ to R 6 ″ is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

　アルキル基は、直鎖状、分岐鎖状、環状のいずれでもよいが、直鎖状又は分岐鎖状アルキル基が好ましく、その炭素原子数は、特に限定されるものではないが、通常１～４０であり、好ましくは３０以下、より好ましくは２０以下、より一層好ましくは１０以下である。 The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. There are no particular restrictions on the number of carbon atoms, but it is typically 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

　置換されていてもよい直鎖状又は分岐鎖状アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ターシャリーブチル基、ｎ－ペンチル基、１－メチル－ｎ－ブチル基、２－メチル－ｎ－ブチル基、３－メチル－ｎ－ブチル基、１，１－ジメチル－ｎ－プロピル基、１，２－ジメチル－ｎ－プロピル基、２，２－ジメチル－ｎ－プロピル基、１－エチル－ｎ－プロピル基、ｎ－ヘキシル基、１－メチル－ｎ－ペンチル基、２－メチル－ｎ－ペンチル基、３－メチル－ｎ－ペンチル基、４－メチル－ｎ－ペンチル基、１，１－ジメチル－ｎ－ブチル基、１，２－ジメチル－ｎ－ブチル基、１，３－ジメチル－ｎ－ブチル基、２，２－ジメチル－ｎ－ブチル基、２，３－ジメチル－ｎ－ブチル基、３，３－ジメチル－ｎ－ブチル基、１－エチル－ｎ－ブチル基、２－エチル－ｎ－ブチル基、１，１，２－トリメチル－ｎ－プロピル基、１，２，２－トリメチル－ｎ－プロピル基、１－エチル－１－メチル－ｎ－プロピル基、１－エチル－２－メチル－ｎ－プロピル基等が挙げられるが、これらに限定されず、その炭素原子数は、通常１～１４であり、好ましくは１～１０、より好ましくは１～６である。中でもメチル基が特に好ましい。 Specific examples of optionally substituted straight-chain or branched-chain alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, and 4-methyl-n-pentyl. Examples of such groups include, but are not limited to, methyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups. The number of carbon atoms is typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

　置換されていてもよい環状アルキル基の具体例としては、シクロプロピル基、シクロブチル基、１－メチル－シクロプロピル基、２－メチル－シクロプロピル基、シクロペンチル基、１－メチル－シクロブチル基、２－メチル－シクロブチル基、３－メチル－シクロブチル基、１，２－ジメチル－シクロプロピル基、２，３－ジメチル－シクロプロピル基、１－エチル－シクロプロピル基、２－エチル－シクロプロピル基、シクロヘキシル基、１－メチル－シクロペンチル基、２－メチル－シクロペンチル基、３－メチル－シクロペンチル基、１－エチル－シクロブチル基、２－エチル－シクロブチル基、３－エチル－シクロブチル基、１，２－ジメチル－シクロブチル基、１，３－ジメチル－シクロブチル基、２，２－ジメチル－シクロブチル基、２，３－ジメチル－シクロブチル基、２，４－ジメチル－シクロブチル基、３，３－ジメチル－シクロブチル基、１－ｎ－プロピル－シクロプロピル基、２－ｎ－プロピル－シクロプロピル基、１－ｉ－プロピル－シクロプロピル基、２－ｉ－プロピル－シクロプロピル基、１，２，２－トリメチル－シクロプロピル基、１，２，３－トリメチル－シクロプロピル基、２，２，３－トリメチル－シクロプロピル基、１－エチル－２－メチル－シクロプロピル基、２－エチル－１－メチル－シクロプロピル基、２－エチル－２－メチル－シクロプロピル基、２－エチル－３－メチル－シクロプロピル基等のシクロアルキル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等のビシクロアルキル基等が挙げられるが、これらに限定されず、その炭素原子数は、通常３～１４であり、好ましくは４～１０、より好ましくは５～６である。 Specific examples of optionally substituted cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 4,4-dimethylcyclobutyl, 5,5-dimethylcyclobutyl, 6,5-dimethylcyclobutyl, 7,5-dimethylcyclobutyl, 8,5-dimethylcyclobutyl, 9,5-dimethylcyclobutyl, 10,5-dimethylcyclobutyl, 11,5-dimethylcyclobutyl, 12,5-dimethylcyclobutyl, 13,5-dimethylcyclobutyl, 14,5-dimethylcyclobutyl, 15,5-dimethylcyclobutyl, 16,5-dimethylcyclobutyl, 17,5-dimethylcyclobutyl, 18,5-dimethylcyclobutyl, 19,5-dimethylcyclobutyl, 20,5-dimethylcyclobutyl, 21,5-dimethylcyclobutyl, 22,5-dimethylcyclobutyl, 23,5-dimethylcyclobutyl, 24,5-dimethylcyclobutyl, 25,5-dimethylcyclobutyl, 26,5-dimethylcyclobutyl, 27,5-dimethylcyclobutyl, 28,5-dimethylcyclobutyl, 29,5-dimethylcyclobutyl, 30,5-dimethylcyclobutyl, 31,5-dimethylcyclobutyl, 32,5-dimethylcyclobutyl, 33,5-dimethylcyclobutyl, 34,5-dimethylcyclobutyl, 35,5-dimethylcyclobutyl, Examples of cycloalkyl groups include 1-ethyl-2-methylcyclopropyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-i-propylcyclopropyl, 2-i-propylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl; and bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl. These groups typically contain 3 to 14 carbon atoms, preferably 4 to 10, and more preferably 5 to 6.

　アルケニル基は、直鎖状、分岐鎖状のいずれでもよく、その炭素原子数は、特に限定されるものではないが、通常２～４０であり、好ましくは３０以下、より好ましくは２０以下、より一層好ましくは１０以下である。 The alkenyl group may be either linear or branched, and although there are no particular limitations on the number of carbon atoms, it is typically 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

　置換されていてもよい直鎖状又は分岐鎖状アルケニル基の具体例としては、ビニル基、アリル基、ブテニル基、ペンテニル基等が挙げられるが、これらに限定されず、その炭素原子数は、通常２～１４であり、好ましくは２～１０、より好ましくは１～６である。中でも、エテニル基、２－プロペニル基が特に好ましい。
　置換されていてもよい環状アルケニル基の具体例としては、シクロペンテニル、シクロヘキセニル等が挙げられるが、これらに限定されず、その炭素原子数は、通常４～１４であり、好ましくは５～１０、より好ましくは５～６である。 Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a pentenyl group, and the number of carbon atoms therein is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, an ethenyl group and a 2-propenyl group are particularly preferred.
Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

　上述の通り、ポリシロキサン（Ａ１）は、ポリオルガノシロキサン（ａ１’）とポリオルガノシロキサン（ａ２’）を含むが、ポリオルガノシロキサン（ａ１’）に含まれるアルケニル基と、ポリオルガノシロキサン（ａ２’）に含まれる水素原子（Ｓｉ－Ｈ基）とが白金族金属系触媒（Ａ－３）によるヒドロシリル化反応によって架橋構造を形成し硬化する。その結果、硬化膜が形成される。 As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl groups contained in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2') undergo a hydrosilylation reaction in the presence of a platinum group metal catalyst (A-3) to form a crosslinked structure and cure. As a result, a cured film is formed.

　ポリオルガノシロキサン（ａ１’）は、Ｑ’単位、Ｍ’単位、Ｄ’単位及びＴ’単位からなる群から選ばれる１種又は２種以上の単位を含むとともに、Ｍ’単位、Ｄ’単位及びＴ’単位からなる群より選ばれる少なくとも１種を含むものである。ポリオルガノシロキサン（ａ１’）としては、このような条件を満たすポリオルガノシロキサンを２種以上組み合わせて用いてもよい。 Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying these conditions may be used in combination as polyorganosiloxane (a1').

　Ｑ’単位、Ｍ’単位、Ｄ’単位及びＴ’単位からなる群から選ばれる２種以上の好ましい組み合わせとしては、（Ｑ’単位とＭ’単位）、（Ｄ’単位とＭ’単位）、（Ｔ’単位とＭ’単位）、（Ｑ’単位とＴ’単位とＭ’単位）、が挙げられるが、これらに限定されない。 Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

　また、ポリオルガノシロキサン（ａ１’）に包含されるポリオルガノシロキサンが２種以上含まれる場合、（Ｑ’単位とＭ’単位）と（Ｄ’単位とＭ’単位）との組み合わせ、（Ｔ’単位とＭ’単位）と（Ｄ’単位とＭ’単位）との組み合わせ、（Ｑ’単位とＴ’単位とＭ’単位）と（Ｔ’単位とＭ’単位）との組み合わせが好ましいが、これらに限定されない。 Furthermore, when polyorganosiloxane (a1') contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

　ポリオルガノシロキサン（ａ２’）は、Ｑ”単位、Ｍ”単位、Ｄ”単位及びＴ”単位からなる群から選ばれる１種又は２種以上の単位を含むとともに、Ｍ”単位、Ｄ”単位及びＴ”単位からなる群より選ばれる少なくとも１種を含むものである。ポリオルガノシロキサン（ａ２’）としては、このような条件を満たすポリオルガノシロキサンを２種以上組み合わせて用いてもよい。 Polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. Two or more polyorganosiloxanes satisfying these conditions may be used in combination as polyorganosiloxane (a2').

　Ｑ”単位、Ｍ”単位、Ｄ”単位及びＴ”単位からなる群から選ばれる２種以上の好ましい組み合わせとしては、（Ｍ”単位とＤ”単位）、（Ｑ”単位とＭ”単位）、（Ｑ”単位とＴ”単位とＭ”単位）が挙げられるが、これらに限定されない。 Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

　ポリオルガノシロキサン（ａ１’）は、そのケイ素原子にアルキル基及び／又はアルケニル基が結合したシロキサン単位で構成されるものであるが、Ｒ１’～Ｒ６’で表される全置換基中におけるアルケニル基の割合は、好ましくは０．１～５０．０モル％、より好ましくは０．５～３０．０モル％であり、残りのＲ１’～Ｒ６’はアルキル基とすることができる。 The polyorganosiloxane (a1') is composed of siloxane units in which alkyl and/or alkenyl groups are bonded to the silicon atoms thereof, and the proportion of alkenyl groups in all the substituents represented by R 1 ' to R 6 ' is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R 1 ' to R 6 ' can be alkyl groups.

　ポリオルガノシロキサン（ａ２’）は、そのケイ素原子にアルキル基及び／又は水素原子が結合したシロキサン単位で構成されるものであるが、Ｒ１”～Ｒ６”で表される全ての置換基及び置換原子中における水素原子の割合は、好ましくは０．１～５０．０モル％、より好ましくは１０．０～４０．０モル％であり、残りのＲ１”～Ｒ６”はアルキル基とすることができる。 The polyorganosiloxane (a2') is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to the silicon atoms, and the proportion of hydrogen atoms in all the substituents and substituted atoms represented by R 1 '' to R 6 '' is preferably 0.1 to 50.0 mol %, more preferably 10.0 to 40.0 mol %, and the remaining R 1 '' to R 6 '' can be alkyl groups.

　接着剤組成物が（ａ１）と（ａ２）とを含む場合、本発明の好ましい態様においては、ポリオルガノシロキサン（ａ１）に含まれるアルケニル基とポリオルガノシロキサン（ａ２）に含まれるＳｉ－Ｈ結合を構成する水素原子とのモル比は、１．０：０．５～１．０：０．６６の範囲である。 When the adhesive composition contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in the polyorganosiloxane (a1) to hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

　ポリオルガノシロキサン（ａ１）、ポリオルガノシロキサン（ａ２）等のポリシロキサンの重量平均分子量は、特に限定されないが、それぞれ、通常５００～１，０００，０００であり、本発明の効果を再現性よく実現する観点から、好ましくは５，０００～５０，０００である。
　なお、本発明において、ポリオルガノシロキサンの重量平均分子量及び数平均分子量並びに分散度は、例えば、ＧＰＣ装置（東ソー（株）製ＥｃｏＳＥＣ，ＨＬＣ－８３２０ＧＰＣ）及びＧＰＣカラム（東ソー（株）ＴＳＫｇｅｌ　ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ－Ｎ，　ＴＳＫｇｅｌ　ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ－Ｈ）を用い、カラム温度を４０℃とし、溶離液（溶出溶媒）としてテトラヒドロフランを用い、流量（流速）を０．３５ｍＬ／分とし、標準試料としてポリスチレン（昭和電工（株）製、Ｓｈｏｄｅｘ）を用いて、測定することができる。 The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.
In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

　ポリオルガノシロキサン（ａ１）及びポリオルガノシロキサン（ａ２）の粘度は、特に限定されないが、それぞれ、通常１０～１００００００（ｍＰａ・ｓ）であり、本発明の効果を再現性よく実現する観点から、好ましくは５０～１００００（ｍＰａ・ｓ）である。なお、ポリオルガノシロキサン（ａ１）及びポリオルガノシロキサン（ａ２）の粘度は、２５℃においてＥ型回転粘度計で測定した値である。 The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, but are typically 10 to 1,000,000 (mPa·s), and from the perspective of achieving the effects of the present invention with good reproducibility, are preferably 50 to 10,000 (mPa·s). The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured at 25°C using an E-type rotational viscometer.

　ポリオルガノシロキサン（ａ１）とポリオルガノシロキサン（ａ２）は、ヒドロシリル化反応によって、互いに反応する。従って、その硬化のメカニズムは、例えばシラノール基を介したそれとは異なり、それ故、いずれのシロキサンも、シラノール基や、アルキルオキシ基のような加水分解によってシラノール基を形成する官能基を含む必要は無い。 Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction. Therefore, the curing mechanism is different from, for example, that via silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

＜＜＜＜白金族金属系触媒（Ａ－３）＞＞＞＞
　白金族金属系触媒は、白金系の金属触媒である。
　このような白金系の金属触媒は、アルケニル基とＳｉ－Ｈ基とのヒドロシリル化反応を促進するための触媒である。 <<<<Platinum group metal catalyst (A-3)>>>>
The platinum group metal catalyst is a platinum group metal catalyst.
Such platinum-based metal catalysts are catalysts for promoting the hydrosilylation reaction between alkenyl groups and Si—H groups.

　白金系の金属触媒の具体例としては、白金系化合物（白金または白金を含む化合物）として公知のものを使用することができる。
　その具体例としては、白金微粉末、白金黒、塩化白金酸、塩化白金酸のアルコール変性物、塩化白金酸とジオレフィンとの錯体、白金－オレフィン錯体、白金－カルボニル錯体〔白金ビス（アセトアセテート）、白金ビス（アセチルアセトネート）等〕、塩化白金酸－アルケニルシロキサン錯体（塩化白金酸－ジビニルテトラメチルジシロキサン錯体、塩化白金酸－テトラビニルテトラメチルシクロテトラシロキサン錯体等）、白金－アルケニルシロキサン錯体（白金－ジビニルテトラメチルジシロキサン錯体、白金－テトラビニルテトラメチルシクロテトラシロキサン錯体等）、塩化白金酸とアセチレンアルコール類との錯体等が挙げられる。これらの中でも、ヒドロシリル化反応の促進効果が高いことから、白金－アルケニルシロキサン錯体が特に好ましい。
　これらのヒドロシリル化反応用触媒は、一種単独で用いてもよいし、二種以上を併用してもよい。 As specific examples of platinum-based metal catalysts, known platinum-based compounds (platinum or compounds containing platinum) can be used.
Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), complexes of chloroplatinic acid and acetylene alcohols, etc. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high hydrosilylation reaction-accelerating effect.
These hydrosilylation reaction catalysts may be used either individually or in combination of two or more.

　白金－アルケニルシロキサン錯体に用いられるアルケニルシロキサンは、特に限定されないが、例えば、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサン、１,３,５,７－テトラメチル－１,３,５,７－テトラビニルシクロテトラシロキサン、これらのアルケニルシロキサンのメチル基の一部をエチル基、フェニル基等で置換したアルケニルシロキサンオリゴマー、およびこれらのアルケニルシロキサンのビニル基をアリル基、ヘキセニル基等で置換したアルケニルシロキサンオリゴマー等が挙げられる。特に、生成する白金－アルケニルシロキサン錯体の安定性が良好であることから、１,３－ジビニル－１,１,３,３－テトラメチルジシロキサンが好ましい。 The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, but examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred due to the good stability of the resulting platinum-alkenylsiloxane complex.

　接着剤組成物における白金族金属系触媒（Ａ－３）の含有量は、特に限定されないが、例えば、成分（Ａ－１）と成分（Ａ－２）との合計質量に対して、０．１～５０．０ｐｐｍの範囲である。 The content of platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).

＜＜＜＜重合抑制剤＞＞＞＞
　接着剤成分は、ヒドロシリル化反応の進行を抑制する目的で、重合抑制剤を含んでもよい。
　重合抑制剤は、ヒドロシリル化反応の進行を抑制できる限り特に限定されるものではなく、その具体例としては、１－エチニル－１－シクロヘキサノール、１，１－ジフェニル－２－プロピン－１－オール等のアルキニルアルコール等が挙げられる。
　重合抑制剤の量は、特に限定されないが、例えば、ポリオルガノシロキサン（ａ１）及びポリオルガノシロキサン（ａ２）の合計量に対して、通常、その効果を得る観点から１０００．０ｐｐｍ以上であり、ヒドロシリル化反応の過度な抑制を防止する観点から１００００．０ｐｐｍ以下である。 <<<<<Polymerization inhibitors>>>>
The adhesive component may contain a polymerization inhibitor for the purpose of inhibiting the progress of the hydrosilylation reaction.
The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.
The amount of the polymerization inhibitor is not particularly limited, but is, for example, usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

＜＜＜剥離剤成分＞＞＞
　剥離剤成分としては、特に限定されないが、本発明の効果をより好適に得る観点から、ポリオルガノシロキサンが好ましい。
　剥離剤成分としてのポリオルガノシロキサンは、通常、接着剤成分とは反応しない。
　例えば、剥離剤成分としてのポリオルガノシロキサンは、ヒドロシリル化反応を起こさない成分である。 <<<Removal agent ingredients>>>
The release agent component is not particularly limited, but from the viewpoint of more suitably achieving the effects of the present invention, polyorganosiloxane is preferred.
The polyorganosiloxane used as the release agent component generally does not react with the adhesive component.
For example, polyorganosiloxane as a release agent component is a component that does not undergo hydrosilylation reaction.

　ポリオルガノシロキサンとしては、特に限定されず、例えば、ポリジメチルシロキサン、エポキシ基含有ポリオルガノシロキサン、フェニル基含有ポリオルガノシロキサン、カルビノール変性ポリオルガノシロキサンなどが挙げられる。 The polyorganosiloxane is not particularly limited, but examples include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.

　本発明の効果をより好適に得る観点から、２種類以上の剥離剤成分は、２種以上のポリオルガノシロキサンを含むことが好ましい。
　２種以上のポリオルガノシロキサンにおける２種とは、例えば、ポリジメチルシロキサンとエポキシ基含有ポリオルガノシロキサンとの組み合わせ、ポリジメチルシロキサンとフェニル基含有ポリオルガノシロキサンとの組み合わせ、フェニル基含有ポリオルガノシロキサンとエポキシ基含有ポリオルガノシロキサンとの組み合わせなどを意味し、例えば、分子量、粘度、エポキシ基の種類などが異なる２つのエポキシ基含有ポリオルガノシロキサンの組み合わせを指すものではない。 From the viewpoint of more suitably achieving the effects of the present invention, the two or more types of release agent components preferably include two or more types of polyorganosiloxanes.
The term "two" in the two or more polyorganosiloxanes refers to, for example, a combination of polydimethylsiloxane and an epoxy group-containing polyorganosiloxane, a combination of polydimethylsiloxane and a phenyl group-containing polyorganosiloxane, or a combination of a phenyl group-containing polyorganosiloxane and an epoxy group-containing polyorganosiloxane. It does not refer to a combination of two epoxy group-containing polyorganosiloxanes that differ in molecular weight, viscosity, type of epoxy group, etc.

　２種類以上の剥離剤成分における２種としては、例えば、以下の組み合わせが挙げられる。
　・ポリジメチルシロキサンとエポキシ基含有ポリオルガノシロキサンとの組み合わせ
　・ポリジメチルシロキサンとフェニル基含有ポリオルガノシロキサンとの組み合わせ
　・ポリジメチルシロキサンとカルビノール変性ポリオルガノシロキサンとの組み合わせ
　・エポキシ基含有ポリオルガノシロキサンとフェニル基含有ポリオルガノシロキサンとの組み合わせ
　・エポキシ基含有ポリオルガノシロキサンとカルビノール変性ポリオルガノシロキサンとの組み合わせ
　・フェニル基含有ポリオルガノシロキサンとカルビノール変性ポリオルガノシロキサンとの組み合わせ
　これらの組み合わせの中でも本発明の効果がもっとも得られやすい組み合わせとしてはポリジメチルシロキサンとエポキシ基含有ポリオルガノシロキサンとの組み合わせが好ましい。 Examples of the two or more types of release agent components include the following combinations.
Combination of polydimethylsiloxane and epoxy group-containing polyorganosiloxane Combination of polydimethylsiloxane and phenyl group-containing polyorganosiloxane Combination of polydimethylsiloxane and carbinol-modified polyorganosiloxane Combination of epoxy group-containing polyorganosiloxane and phenyl group-containing polyorganosiloxane Combination of epoxy group-containing polyorganosiloxane and carbinol-modified polyorganosiloxane Combination of phenyl group-containing polyorganosiloxane and carbinol-modified polyorganosiloxane Among these combinations, the combination of polydimethylsiloxane and epoxy group-containing polyorganosiloxane is preferred as the combination that is most likely to achieve the effects of the present invention.

＜＜＜＜ポリジメチルシロキサン＞＞＞＞
　接着剤組成物に含有されるポリジメチルシロキサンとしては、特に制限されない。
　ポリジメチルシロキサンは、ヒドロシリル化反応を起こさない成分である。
　本発明における「ポリジメチルシロキサン」は、エポキシ基含有ポリジメチルシロキサン、フェニル基含有ポリジメチルシロキサン等と異なり、無変性のポリオルガノシロキサンであって、ケイ素原子に結合する有機基としてメチル基を有するポリオルガノシロキサンである。 <<<<<Polydimethylsiloxane>>>>
The polydimethylsiloxane contained in the adhesive composition is not particularly limited.
Polydimethylsiloxane is a component that does not undergo hydrosilylation reactions.
The "polydimethylsiloxane" in the present invention is an unmodified polyorganosiloxane, unlike epoxy group-containing polydimethylsiloxane, phenyl group-containing polydimethylsiloxane, etc., and is a polyorganosiloxane having a methyl group as an organic group bonded to a silicon atom.

　ポリジメチルシロキサンの具体例としては、式（Ｍ１）で表されるものが挙げられるが、これに限定されない。 Specific examples of polydimethylsiloxane include, but are not limited to, those represented by formula (M1):

（ｎ４は、繰り返し単位の数を示し、正の整数である。） ( n4 represents the number of repeating units and is a positive integer.)

　ポリジメチルシロキサンの重量平均分子量は、特に限定されないものの、通常１００，０００～２，０００，０００であり、本発明の効果を再現性よく実現する観点から、好ましくは２００，０００～１，２００，０００、より好ましくは３００，０００～９００，０００である。また、その分散度は、特に限定されないものの、通常１．０～１０．０であり、好適な剥離を再現性よく実現する観点等から、好ましくは１．５～５．０、より好ましくは２．０～３．０である。なお、重量平均分子量及び分散度は、接着剤成分としてのポリオルガノシロキサンに関する上述の方法で測定することができる。
　ポリジメチルシロキサンの粘度は、特に限定されないが、通常１，０００～２，０００，０００ｍｍ２／ｓである。なお、ポリジメチルシロキサンの粘度の値は、動粘度で示され、センチストークス（ｃＳｔ）＝ｍｍ２／ｓである。粘度（ｍＰａ・ｓ）を密度（ｇ／ｃｍ３）で割って求めることもできる。すなわち、その値は、２５℃で測定したＥ型回転粘度計で測定した粘度と密度から求めることができ、動粘度（ｍｍ２／ｓ）＝粘度（ｍＰａ・ｓ）／密度（ｇ／ｃｍ３）という式から算出することができる。 The weight average molecular weight of the polydimethylsiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. The dispersity is also not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane as an adhesive component.
The viscosity of polydimethylsiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm 2 /s. The viscosity value of polydimethylsiloxane is expressed as kinematic viscosity, where centistokes (cSt) = mm 2 /s. It can also be determined by dividing viscosity (mPa·s) by density (g/cm 3 ). That is, this value can be determined from the viscosity and density measured using an E-type rotational viscometer at 25°C, and can be calculated using the formula kinematic viscosity (mm 2 /s) = viscosity (mPa·s) / density (g/cm 3 ).

＜＜＜＜エポキシ基含有ポリオルガノシロキサン＞＞＞＞
　接着剤組成物に含有されるエポキシ基含有ポリオルガノシロキサンとしては、特に制限されない。
　エポキシ基含有ポリオルガノシロキサンは、ヒドロシリル化反応を起こさない成分である。 <<<<<Epoxy group-containing polyorganosiloxane>>>>
The epoxy group-containing polyorganosiloxane contained in the adhesive composition is not particularly limited.
The epoxy group-containing polyorganosiloxane is a component that does not undergo a hydrosilylation reaction.

　エポキシ基含有ポリオルガノシロキサンとしては、例えば、Ｒ１１Ｒ１２ＳｉＯ２／２で表されるシロキサン単位（Ｄ１０単位）を含むものが挙げられる。 Examples of epoxy group-containing polyorganosiloxanes include those containing siloxane units ( D10 units) represented by R 11 R 12 SiO 2/2 .

　Ｒ１１は、ケイ素原子に結合する基であり、アルキル基を表し、Ｒ１２は、ケイ素原子に結合する基であり、エポキシ基又はエポキシ基を含む有機基を表し、アルキル基の具体例としては、上述の例示を挙げることができる。
　エポキシ基を含む有機基におけるエポキシ基は、その他の環と縮合せずに、独立したエポキシ基であってもよく、１，２－エポキシシクロヘキシル基のように、その他の環と縮合環を形成しているエポキシ基であってもよい。
　エポキシ基を含む有機基の具体例としては、３－グリシドキシプロピル、２－（３，４－エポキシシクロヘキシル）エチルが挙げられるが、これらに限定されない。
　本発明において、エポキシ基含有ポリオルガノシロキサンの好ましい一例としては、エポキシ基含有ポリジメチルシロキサンを挙げることができるが、これに限定されない。 R11 is a group bonded to a silicon atom and represents an alkyl group, R12 is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those listed above.
The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.
Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

　エポキシ基含有ポリオルガノシロキサンは、上述のシロキサン単位（Ｄ１０単位）を含むものであるが、Ｄ１０単位以外に、Ｑ単位、Ｍ単位及び／又はＴ単位を含んでもよい。
　本発明の好ましい態様においては、エポキシ基含有ポリオルガノシロキサンの具体例としては、Ｄ１０単位のみからなるポリオルガノシロキサン、Ｄ１０単位とＱ単位とを含むポリオルガノシロキサン、Ｄ１０単位とＭ単位とを含むポリオルガノシロキサン、Ｄ１０単位とＴ単位とを含むポリオルガノシロキサン、Ｄ１０単位とＱ単位とＭ単位とを含むポリオルガノシロキサン、Ｄ１０単位とＭ単位とＴ単位とを含むポリオルガノシロキサン、Ｄ１０単位とＱ単位とＭ単位とＴ単位とを含むポリオルガノシロキサン等が挙げられる。 The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( D10 units), but may also contain Q units, M units and/or T units in addition to the D10 units.
In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include a polyorganosiloxane consisting only of D 10 units, a polyorganosiloxane containing D 10 units and Q units, a polyorganosiloxane containing D 10 units and M units, a polyorganosiloxane containing D 10 units and T units, a polyorganosiloxane containing D 10 units, Q units, and M units, a polyorganosiloxane containing D 10 units, M units, and T units, and a polyorganosiloxane containing D 10 units, Q units, M units, and T units.

　エポキシ基含有ポリオルガノシロキサンは、エポキシ価が０．１～５であるエポキシ基含有ポリジメチルシロキサンが好ましい。また、その重量平均分子量は、特に限定されないものの、通常１，５００～５００，０００であり、組成物中での析出抑制の観点から、好ましくは１００，０００以下である。 The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane with an epoxy value of 0.1 to 5. Its weight average molecular weight is not particularly limited, but is typically 1,500 to 500,000, and is preferably 100,000 or less from the standpoint of suppressing precipitation in the composition.

　エポキシ基含有ポリオルガノシロキサンの具体例としては、式（Ｅ１）～（Ｅ３）で表されるものが挙げられるが、これらに限定されない。 Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

（ｍ１及びｎ１は、各繰り返し単位の数を示し、正の整数である。） ( m1 and n1 represent the number of each repeating unit and are positive integers.)

（ｍ２及びｎ２は、各繰り返し単位の数を示し、正の整数であり、Ｒは、酸素原子及び不飽和結合（例えば、炭素－炭素二重結合、炭素－炭素三重結合、－Ｎ＝Ｎ－）の少なくともいずれかで中断されていてもよい炭素原子数１～１０のアルキレン基である。） ( m2 and n2 each represent the number of repeating units and are positive integers, and R represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).)

（ｍ３、ｎ３及びｏ３は、各繰り返し単位の数を示し、正の整数であり、Ｒは、酸素原子及び不飽和結合（例えば、炭素－炭素二重結合、炭素－炭素三重結合、－Ｎ＝Ｎ－）の少なくともいずれかで中断されていてもよい炭素原子数１～１０のアルキレン基である。） ( m3 , n3 , and o3 each represent the number of repeating units and are positive integers, and R represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).)

　上記一般式において、ｍ１、ｍ２、ｍ３、及びｏ３が２以上の場合、それらの繰り返し単位は、隣接して並んでブロックを形成していてもよいし、ランダムに並んでいてもよい。 In the above general formula, when m 1 , m 2 , m 3 and o 3 are 2 or more, the repeating units thereof may be arranged adjacent to each other to form a block, or may be arranged randomly.

　なお、式（Ｅ３）で表されるポリオルガノシロキサンは、エポキシ基とフェニル基とを有することから、エポキシ基含有ポリオルガノシロキサンであり、かつフェニル基含有ポリオルガノシロキサンでもある。なお、エポキシ基含有ポリオルガノシロキサンは、フェニル基を有していてもよいし、フェニル基を有していなくてもよい。 Note that the polyorganosiloxane represented by formula (E3) contains both epoxy groups and phenyl groups, and is therefore both an epoxy group-containing polyorganosiloxane and a phenyl group-containing polyorganosiloxane. Note that the epoxy group-containing polyorganosiloxane may or may not contain phenyl groups.

　エポキシ基含有ポリオルガノシロキサンの重量平均分子量は、特に限定されないものの、通常１００，０００～２，０００，０００であり、本発明の効果を再現性よく実現する観点から、好ましくは２００，０００～１，２００，０００、より好ましくは３００，０００～９００，０００である。また、その分散度は、特に限定されないものの、通常１．０～１０．０であり、好適な剥離を再現性よく実現する観点等から、好ましくは１．５～５．０、より好ましくは２．０～３．０である。なお、重量平均分子量及び分散度は、接着剤成分としてのポリオルガノシロキサンに関する上述の方法で測定することができる。
　エポキシ基含有ポリオルガノシロキサンの粘度は、特に限定されないが、通常１，０００～２，０００，０００ｍｍ２／ｓである。なお、エポキシ基含有ポリオルガノシロキサンの粘度の値は、動粘度で示され、センチストークス（ｃＳｔ）＝ｍｍ２／ｓである。粘度（ｍＰａ・ｓ）を密度（ｇ／ｃｍ３）で割って求めることもできる。すなわち、その値は、２５℃で測定したＥ型回転粘度計で測定した粘度と密度から求めることができ、動粘度（ｍｍ２／ｓ）＝粘度（ｍＰａ・ｓ）／密度（ｇ／ｃｍ３）という式から算出することができる。 The weight average molecular weight of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable peeling, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane as an adhesive component.
The viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 /s. The viscosity value of the epoxy group-containing polyorganosiloxane is expressed as kinematic viscosity, where centistokes (cSt) = mm 2 /s. It can also be determined by dividing the viscosity (mPa·s) by the density (g/cm 3 ). That is, this value can be determined from the viscosity and density measured using an E-type rotational viscometer at 25°C, and can be calculated from the formula kinematic viscosity (mm 2 /s) = viscosity (mPa·s) / density (g/cm 3 ).

＜＜＜＜フェニル基含有ポリオルガノシロキサン＞＞＞＞
　フェニル基含有ポリオルガノシロキサンとしては、例えば、Ｒ３１Ｒ３２ＳｉＯ２／２で表されるシロキサン単位（Ｄ３０単位）を含むものが挙げられる。 <<<<<Phenyl group-containing polyorganosiloxane>>>>
Examples of the phenyl group-containing polyorganosiloxane include those containing siloxane units ( D30 units) represented by R 31 R 32 SiO 2/2 .

　Ｒ３１は、ケイ素原子に結合する基であり、フェニル基又はアルキル基を表し、Ｒ３２は、ケイ素原子に結合する基であり、フェニル基を表し、アルキル基の具体例としては、上述の例示を挙げることができるが、メチル基が好ましい。 R31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group, R32 is a group bonded to a silicon atom and represents a phenyl group, and specific examples of the alkyl group include those listed above, with a methyl group being preferred.

　フェニル基含有ポリオルガノシロキサンは、上述のシロキサン単位（Ｄ３０単位）を含むものであるが、Ｄ３０単位以外に、Ｑ単位、Ｍ単位及び／又はＴ単位を含んでもよい。 The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane units ( D30 units), but may also contain Q units, M units and/or T units in addition to the D30 units.

　好ましい態様においては、フェニル基含有ポリオルガノシロキサンの具体例としては、Ｄ３０単位のみからなるポリオルガノシロキサン、Ｄ３０単位とＱ単位とを含むポリオルガノシロキサン、Ｄ３０単位とＭ単位とを含むポリオルガノシロキサン、Ｄ３０単位とＴ単位とを含むポリオルガノシロキサン、Ｄ３０単位とＱ単位とＭ単位とを含むポリオルガノシロキサン、Ｄ３０単位とＭ単位とＴ単位とを含むポリオルガノシロキサン、Ｄ３０単位とＱ単位とＭ単位とＴ単位とを含むポリオルガノシロキサンが挙げられる。 In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include a polyorganosiloxane consisting only of D30 units, a polyorganosiloxane containing D30 units and Q units, a polyorganosiloxane containing D30 units and M units, a polyorganosiloxane containing D30 units and T units, a polyorganosiloxane containing D30 units, Q units, and M units, a polyorganosiloxane containing D30 units, M units, and T units, and a polyorganosiloxane containing D30 units, Q units, M units , and T units.

　フェニル基含有ポリオルガノシロキサンの具体例としては、式（Ｐ１）又は（Ｐ２）で表されるものが挙げられるが、これらに限定されない。 Specific examples of phenyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

（ｍ５及びｎ５は、各繰り返し単位の数を示し、正の整数である。） (m5 and n5 represent the number of each repeating unit and are positive integers.)

（ｍ６及びｎ６は、各繰り返し単位の数を示し、正の整数である。） (m6 and n6 represent the number of each repeating unit and are positive integers.)

　上記一般式において、ｍ５、及びｍ６が２以上の場合、それらの繰り返し単位は、隣接して並んでブロックを形成していてもよいし、ランダムに並んでいてもよい。 In the above general formula, when m 5 and m 6 are 2 or more, the repeating units thereof may be arranged adjacent to each other to form a block, or may be arranged randomly.

＜＜＜＜カルビノール変性ポリオルガノシロキサン＞＞＞＞
　カルビノール変性ポリオルガノシロキサンとしては、特に制限されない。
　カルビノール変性ポリオルガノシロキサンは、炭素原子に直接結合したヒドロキシ基を有するポリオルガノシロキサンである。このように、「カルビノール変性ポリオルガノシロキサン」におけるカルビノールとは、狭義の意味でのメタノールに限定されず、メタノール誘導体を含む。 <<<<<Carbinol-modified polyorganosiloxane>>>>
The carbinol-modified polyorganosiloxane is not particularly limited.
Carbinol-modified polyorganosiloxanes are polyorganosiloxanes having hydroxy groups directly bonded to carbon atoms. Thus, the carbinol in "carbinol-modified polyorganosiloxanes" is not limited to methanol in the narrow sense, but also includes methanol derivatives.

　カルビノール変性ポリオルガノシロキサンは、例えば、カルビノール変性ポリジメチルシロキサンである。 An example of the carbinol-modified polyorganosiloxane is carbinol-modified polydimethylsiloxane.

　カルビノール変性ポリオルガノシロキサンが有する、炭素原子に直接結合したヒドロキシ基の数としては、特に限定されず、１つであってもよいし、２つ以上であってもよい。 The number of hydroxy groups directly bonded to carbon atoms in the carbinol-modified polyorganosiloxane is not particularly limited, and may be one or two or more.

　カルビノール変性ポリオルガノシロキサンは、側鎖に、炭素原子に直接結合したヒドロキシ基を有していてもよいし、片末端に、炭素原子に直接結合したヒドロキシ基を有していてもよいし、両末端に、炭素原子に直接結合したヒドロキシ基を有していてもよい。
　カルビノール変性ポリオルガノシロキサンは、側鎖に、炭素原子に直接結合したヒドロキシ基を有することが好ましい。この場合、カルビノール変性ポリオルガノシロキサンの含有量が少量でも、接着剤組成物から形成される接着剤層に良好な剥離性を付与させることができる。 The carbinol-modified polyorganosiloxane may have a hydroxy group bonded directly to a carbon atom in a side chain, may have a hydroxy group bonded directly to a carbon atom at one end, or may have hydroxy groups bonded directly to carbon atoms at both ends.
The carbinol-modified polyorganosiloxane preferably has a hydroxy group directly bonded to a carbon atom in the side chain. In this case, even if the content of the carbinol-modified polyorganosiloxane is small, the adhesive layer formed from the adhesive composition can be imparted with good releasability.

　カルビノール変性ポリオルガノシロキサンは、例えば、ケイ素原子に直接結合した基として、下記式（Ｃｇ）で表される基を有する。 Carbinol-modified polyorganosiloxanes have, for example, groups represented by the following formula (Cg) as groups directly bonded to silicon atoms.

 
（式（Ｃｇ）中、Ｒ１は、炭素原子数１以上の基を表す。＊は、ケイ素原子に結合する結合手を表す。ただし、式（Ｃｇ）中のヒドロキシ基は、炭素原子に直接結合している。）
(In formula (Cg), R1 represents a group having one or more carbon atoms. * represents a bond bonded to a silicon atom. However, the hydroxy group in formula (Cg) is directly bonded to a carbon atom.)

　式（Ｃｇ）で表される基が有する、炭素原子に直接結合したヒドロキシ基の数としては、１つであってもよいし、２つ以上であってもよい。２つ以上としては、例えば、２つ、３つ、４つなどが挙げられる。 The group represented by formula (Cg) may have one hydroxy group directly bonded to a carbon atom, or two or more hydroxy groups. Examples of two or more hydroxy groups include two, three, and four.

　Ｒ１の炭素原子数としては、特に限定されず、例えば、１～３０であってもよいし、１～２０であってもよいし、１～１０であってもよい。 The number of carbon atoms in R 1 is not particularly limited, and may be, for example, 1 to 30, 1 to 20, or 1 to 10.

　式（Ｃｇ）で表される基としては、例えば、下記式（Ｃｇ－１）～式（Ｃｇ－４））で表される基が挙げられる。
 
（式（Ｃｇ－１）中、Ｒ１１は、炭素原子数１～３のアルコキシ基で置換されていてもよい炭素原子数１～６のアルキレン基を表す。
　式（Ｃｇ－２）中、Ｒ１２は、炭素原子数１～６のアルキレン基を表す。Ｒ１３は、炭素原子数１～３のアルコキシ基又はヒドロキシ基で置換されていてもよい炭素原子数１～６のアルキレン基を表す。
　式（Ｃｇ－３）中、Ｒ１４は、炭素原子数１～６のアルキレン基を表す。Ｒ１５は、炭素原子数１～３のアルキレン基を表す。ｍは、１～１０の整数を表す。
　式（Ｃｇ－４）中、Ｒ１６～Ｒ１８は、それぞれ独立して、炭素原子数１～６のアルキレン基を表す。
　式（Ｃｇ－１）～式（Ｃｇ－４）中、＊は、ケイ素原子に結合する結合手を表す。） Examples of the group represented by formula (Cg) include groups represented by the following formulae (Cg-1) to (Cg-4).

(In formula (Cg-1), R 11 represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms.
In formula (Cg-2), R 12 represents an alkylene group having 1 to 6 carbon atoms, and R 13 represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a hydroxy group.
In formula (Cg-3), R 14 represents an alkylene group having 1 to 6 carbon atoms, R 15 represents an alkylene group having 1 to 3 carbon atoms, and m represents an integer of 1 to 10.
In formula (Cg-4), R 16 to R 18 each independently represent an alkylene group having 1 to 6 carbon atoms.
In formulas (Cg-1) to (Cg-4), * represents a bond bonded to a silicon atom.

　Ｒ１１～Ｒ１８のアルキレン基は、直鎖状であってもよいし、分岐状であってもよいし、環状であってもよい。 The alkylene groups of R 11 to R 18 may be linear, branched, or cyclic.

　式（Ｃｇ）で表される基としては、例えば、以下の基が挙げられる。
 
（式中、ｍ１は、２～１０の整数を表す。＊は、ケイ素原子に結合する結合手を表す。） Examples of the group represented by formula (Cg) include the following groups.

(In the formula, m1 represents an integer of 2 to 10. * represents a bond bonded to a silicon atom.)

　カルビノール変性ポリオルガノシロキサンは、例えば、下記式（ＣＰＳ－１）又は式（ＣＰＳ－２）で表される。
 
（式（ＣＰＳ－１）中、Ｒ５１は、それぞれ独立して、炭化水素基を表す。Ｘ１は、上記式（Ｃｇ）で表される基を表す。ｎ１は、０以上の整数を表す。ｎ２は、１以上の整数を表す。
　式（ＣＰＳ－２）中、Ｒ５２は、それぞれ独立して、炭化水素基を表す。Ｘ２は、上記式（Ｃｇ）で表される基を表す。Ｘ３は、炭化水素基、又は上記式（Ｃｇ）で表される基を表す。ｎ３は、０以上の整数を表す。） The carbinol-modified polyorganosiloxane is represented, for example, by the following formula (CPS-1) or formula (CPS-2).

(In formula (CPS-1), R 51 each independently represents a hydrocarbon group. X 1 represents a group represented by formula (Cg) above. n1 represents an integer of 0 or more. n2 represents an integer of 1 or more.
In formula (CPS-2), R 52 each independently represents a hydrocarbon group. X 2 represents a group represented by formula (Cg) above. X 3 represents a hydrocarbon group or a group represented by formula (Cg) above. n3 represents an integer of 0 or greater.

　Ｒ５１、Ｒ５２、及びＸ３における炭化水素基としては、例えば、炭素原子数１～８のアルキル基が挙げられる。炭素原子数１～８のアルキル基としては、メチル基が好ましい。即ち、カルビノール変性ポリオルガノシロキサンは、下記式（ＣＰＳ－１ａ）又は式（ＣＰＳ－２ａ）で表されるポリジメチルシロキサンが好ましい。
 
（式（ＣＰＳ－１ａ）中、Ｘ１は、上記式（Ｃｇ）で表される基を表す。ｎ１は、０以上の整数を表す。ｎ２は、１以上の整数を表す。
　式（ＣＰＳ－２ａ）中、Ｘ２は、上記式（Ｃｇ）で表される基を表す。Ｘ３は、メチル基、又は上記式（Ｃｇ）で表される基を表す。ｎ３は、０以上の整数を表す。） Examples of the hydrocarbon group for R 51 , R 52 , and X 3 include an alkyl group having 1 to 8 carbon atoms. A methyl group is preferred as the alkyl group having 1 to 8 carbon atoms. That is, the carbinol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a):

(In formula (CPS-1a), X1 represents a group represented by formula (Cg) above. n1 represents an integer of 0 or more. n2 represents an integer of 1 or more.
In formula (CPS-2a), X2 represents a group represented by formula (Cg) above. X3 represents a methyl group or a group represented by formula (Cg) above. n3 represents an integer of 0 or greater.

　なお、式（ＣＰＳ－１）で表されるカルビノール変性ポリオルガノシロキサン、及び式（ＣＰＳ－１ａ）で表されるカルビノール変性ポリジメチルシロキサンは、炭素原子に直接結合したヒドロキシ基を、側鎖に有する。
　式（ＣＰＳ－２）で表されるカルビノール変性ポリオルガノシロキサン、及び式（ＣＰＳ－２ａ）で表されるカルビノール変性ポリジメチルシロキサンは、炭素原子に直接結合したヒドロキシ基を、片末端又は両末端に有する。 The carbinol-modified polyorganosiloxane represented by formula (CPS-1) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a) have a hydroxy group directly bonded to a carbon atom in the side chain.
The carbinol-modified polyorganosiloxane represented by formula (CPS-2) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-2a) have hydroxy groups directly bonded to carbon atoms at one end or both ends.

　なお、式（ＣＰＳ－１）で表されるカルビノール変性ポリオルガノシロキサンにおいて、ｎ２が２以上の場合、－Ｓｉ（Ｒ５１）（Ｘ１）－Ｏ－で表されるシロキサンユニットは、隣接して並んでブロックを形成していてもよいし、ランダムに並んでいてもよい。
　また、式（ＣＰＳ－１ａ）で表されるカルビノール変性ポリジメチルシロキサンにおいて、ｎ２が２以上の場合、－Ｓｉ（ＣＨ３）（Ｘ１）－Ｏ－で表されるシロキサンユニットは、隣接して並んでブロックを形成していてもよいし、ランダムに並んでいてもよい。 In the carbinol-modified polyorganosiloxane represented by formula (CPS-1), when n2 is 2 or greater, the siloxane units represented by —Si(R 51 )(X 1 )—O— may be arranged adjacent to each other to form a block, or may be arranged randomly.
In the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a), when n2 is 2 or greater, the siloxane units represented by —Si(CH 3 )(X 1 )—O— may be arranged adjacent to each other to form a block, or may be arranged randomly.

　カルビノール変性ポリオルガノシロキサンの重量平均分子量は、特に限定されないものの、通常５００～１，０００，０００であり、本発明の効果を再現性よく実現する観点から、好ましくは５，０００～５０，０００である。また、その分散度は、特に限定されないものの、通常１．０～１０．０であり、好適な剥離を再現性よく実現する観点等から、好ましくは１．５～５．０、より好ましくは２．０～３．０である。
　カルビノール変性ポリオルガノシロキサンの粘度は、特に限定されないが、通常１００～２００，０００ｍｍ２／ｓである。なお、ポリジメチルシロキサンの粘度の値は、動粘度で示され、センチストークス（ｃＳｔ）＝ｍｍ２／ｓである。粘度（ｍＰａ・ｓ）を密度（ｇ／ｃｍ３）で割って求めることもできる。すなわち、その値は、２５℃で測定したＥ型回転粘度計で測定した粘度と密度から求めることができ、動粘度（ｍｍ２／ｓ）＝粘度（ｍＰａ・ｓ）／密度（ｇ／ｃｍ３）という式から算出することができる。 The weight average molecular weight of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of reproducibly realizing the effects of the present invention, it is preferably 5,000 to 50,000. Furthermore, the dispersity is not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of reproducibly realizing suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0.
The viscosity of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 100 to 200,000 mm 2 /s. The viscosity value of polydimethylsiloxane is expressed as kinematic viscosity, where centistokes (cSt) = mm 2 /s. It can also be determined by dividing the viscosity (mPa·s) by the density (g/cm 3 ). That is, this value can be determined from the viscosity and density measured using an E-type rotational viscometer at 25°C, and can be calculated using the formula kinematic viscosity (mm 2 /s) = viscosity (mPa·s) / density (g/cm 3 ).

　剥離剤成分（Ｂ）であるポリオルガノシロキサンは、市販品であってもよいし、合成したものであってもよい。
　ポリオルガノシロキサンの市販品としては、例えば、ワッカーケミ社製の製品であるＷＡＣＫＥＲＳＩＬＩＣＯＮＥ　ＦＬＵＩＤ　ＡＫ　シリーズ（ＡＫ５０、ＡＫ　３５０、ＡＫ　１０００、ＡＫ　１００００、ＡＫ　１００００００）やＧＥＮＩＯＰＬＡＳＴ　ＧＵＭ、信越化学工業（株）製　ジメチルシリコーンオイル（ＫＦ－９６Ｌ、ＫＦ－９６Ａ、ＫＦ－９６、ＫＦ－９６Ｈ、ＫＦ－６９、ＫＦ－９６５、ＫＦ－９６８）、環状ジメチルシリコーンオイル（ＫＦ－９９５）；ゲレスト社製　エポキシ基含有ポリオルガノシロキサン（商品名ＣＭＳ－２２７、ＥＣＭＳ－３２７、ＥＭＳ－６２２）、信越化学工業（株）製　エポキシ基含有ポリオルガノシロキサン（ＫＦ－１０１、ＫＦ－１００１、ＫＦ－１００５、Ｘ－２２－３４３）、ダウ・東レ社製　エポキシ基含有ポリオルガノシロキサン（ＤＯＷＳＩＬ　ＢＹ１６－８３９、ＤＯＷＳＩＬ８４１３、ＤＯＷＳＩＬ８４１１）；ゲレスト社製　フェニル基含有ポリオルガノシロキサン（ＰＭＭ－１０４３、ＰＭＭ－１０２５、ＰＤＭ－０４２１、ＰＤＭ－０８２１）、信越化学工業（株）製　フェニル基含有ポリオルガノシロキサン（ＫＦ５０－３０００ＣＳ）、ＭＯＭＥＮＴＩＶＥ社製　フェニル基含有ポリオルガノシロキサン（ＴＳＦ４３１、ＴＳＦ４３３）等が挙げられるが、これらに限定されない。 The polyorganosiloxane that is the release agent component (B) may be a commercially available product or may be synthesized.
Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, manufactured by Wacker Chemie, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (trade names CMS-227, ECMS-327, EMS-622) manufactured by Gelest, and Shin-Etsu Chemical Co., Ltd. Epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), epoxy group-containing polyorganosiloxanes (DOWSIL BY16-839, DOWSIL8413, DOWSIL8411) manufactured by Dow-Toray Industries, Inc.; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, but are not limited to these.

　また、カルビノール変性ポリオルガノシロキサンの市販品としては、例えば、信越シリコーン社製のＫＦ６０００、ＫＦ６００１、ＫＦ６００２、ＫＦ６００３、Ｘ－２２－４０３９、Ｘ－２２－４０１５；Ｇｅｌｅｓｔ社製のＤＭＳ－Ｃ１５、ＤＭＳ－Ｃ１６、ＤＭＳ－Ｃ２１、ＤＭＳ－Ｃ２３、ＤＢＥ－Ｃ２５、ＤＢＥ－Ｃ２２、ＤＭＳ－ＣＡ２１、ＤＭＳ－ＣＳ２６、ＣＭＳ－２２１、ＣＭＳ－２２２、ＣＭＳ－８３２、ＣＭＳ－６２６、ＭＣＲ－Ｃ１２、ＭＣＲ－Ｃ１８、ＭＣＲ－Ｃ２２、ＭＣＳ－Ｃ１１、ＭＣＳ－Ｃ１３、ＭＣＲ－Ｃ６１、ＭＣＲ－Ｃ６２、ＭＣＲ－Ｃ６３；ダウ・東レ社製のＤＯＷＳＩＬ　ＢＹ　１６－２０１、ＤＯＷＳＩＬ　ＳＦ　８４２７　Ｆｌｕｉｄ、ＤＯＷＳＩＬ　ＳＦ　８４２８　Ｆｌｕｉｄなどが挙げられる。 Commercially available carbinol-modified polyorganosiloxanes include, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, and X-22-4015 manufactured by Shin-Etsu Silicone Co., Ltd.; and DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, and DMS-C27 manufactured by Gelest. Examples include MS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, and MCR-C63; and Dow-Toray Industries, Inc.'s DOWSIL BY 16-201, DOWSIL SF 8427 Fluid, and DOWSIL SF 8428 Fluid.

　接着剤組成物における剥離剤成分の含有量としては、特に制限されないが、本発明の効果を好適に得る観点から、接着剤組成物の不揮発分に対して、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１０質量％以上が特に好ましい。上限値としては、特に限定されないが、例えば、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が特に好ましい。
　接着剤組成物の不揮発分とは、接着剤組成物における溶媒以外の成分を指す。 The content of the release agent component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
The non-volatile content of the adhesive composition refers to the components other than the solvent in the adhesive composition.

　接着剤組成物がポリジメチルシロキサンを含有する場合、接着剤組成物におけるポリジメチルシロキサンの含有量としては、特に制限されないが、本発明の効果を好適に得る観点から、接着剤成分に対して、０．５質量％～３０質量％が好ましく、１質量％～１０質量％がより好ましく、２質量％～８質量％が特に好ましい。
　なお、ここでの接着剤成分には溶媒は含まれない。 When the adhesive composition contains polydimethylsiloxane, the content of polydimethylsiloxane in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the content is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 10% by mass, and particularly preferably 2% by mass to 8% by mass, relative to the adhesive components.
The adhesive component here does not include a solvent.

　接着剤組成物がエポキシ基含有ポリオルガノシロキサンを含有する場合、接着剤組成物におけるエポキシ基含有ポリオルガノシロキサンの含有量としては、特に制限されないが、本発明の効果を好適に得る観点から、接着剤成分に対して、０．０５質量％～３０質量％が好ましく、０．１質量％～５質量％がより好ましく、０．２質量％～３質量％が特に好ましい。
　なお、ここでの接着剤成分には溶媒は含まれない。 When the adhesive composition contains an epoxy group-containing polyorganosiloxane, the content of the epoxy group-containing polyorganosiloxane in the adhesive composition is not particularly limited, but from the viewpoint of preferably obtaining the effects of the present invention, it is preferably 0.05% by mass to 30% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.2% by mass to 3% by mass, based on the adhesive component.
The adhesive component here does not include a solvent.

　接着剤組成物がポリジメチルシロキサン及びエポキシ基含有ポリオルガノシロキサンを含有する場合、接着剤組成物におけるポリジメチルシロキサン（Ｂ－１）と、エポキシ基含有ポリオルガノシロキサン（Ｂ－２）との質量比率（Ｂ－１：Ｂ－２）としては、特に制限されないが、本発明の効果を好適に得る観点から、２０：１～１：１０が好ましく、１５：１～１：７．５がより好ましく、１５：１～５：１が特に好ましい。 When the adhesive composition contains polydimethylsiloxane and epoxy group-containing polyorganosiloxane, the mass ratio (B-1:B-2) of the polydimethylsiloxane (B-1) to the epoxy group-containing polyorganosiloxane (B-2) in the adhesive composition is not particularly limited, but from the viewpoint of optimally achieving the effects of the present invention, it is preferably 20:1 to 1:10, more preferably 15:1 to 1:7.5, and particularly preferably 15:1 to 5:1.

　接着剤組成物における、接着剤成分に対する、ポリジメチルシロキサンとエポキシ基含有ポリオルガノシロキサンとの合計の割合としては、特に制限されないが、本発明の効果を好適に得る観点から、１質量％～３０質量％が好ましく、２質量％～１０質量％が好ましく、３質量％～８質量％が特に好ましい。
　なお、ここでの接着剤成分には溶媒は含まれない。 The total ratio of polydimethylsiloxane and epoxy group-containing polyorganosiloxane to the adhesive component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 10% by mass, and particularly preferably 3% by mass to 8% by mass.
The adhesive component here does not include a solvent.

＜＜＜溶媒＞＞＞
　接着剤組成物は、粘度の調整等を目的に、溶媒を含んでもよく、その具体例としては、脂肪族炭化水素、芳香族炭化水素、ケトン等が挙げられるが、これらに限定されない。
　より具体的には、ヘキサン、へプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、イソドデカン、メンタン、リモネン、トルエン、キシレン、メチシレン、クメン、ＭＩＢＫ（メチルイソブチルケトン）、酢酸ブチル、ジイソブチルケトン、２－オクタノン、２－ノナノン、５－ノナノン等が挙げられるが、これらに限定されない。このような溶媒は、１種単独で又は２種以上組み合わせて用いることができる。 <<<Solvent>>>
The adhesive composition may contain a solvent for the purpose of adjusting viscosity, etc., and specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.
More specific examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, methylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. These solvents can be used alone or in combination of two or more.

　接着剤組成物が溶媒を含む場合、その含有量は、所望の組成物の粘度、採用する塗布方法、作製する薄膜の厚み等を勘案して適宜設定されるものではあるが、組成物全体に対して、例えば、１０～９０質量％程度の範囲である。 If the adhesive composition contains a solvent, the content of the solvent is set appropriately taking into consideration the desired viscosity of the composition, the application method to be used, the thickness of the thin film to be produced, etc., but is typically in the range of approximately 10 to 90% by mass of the entire composition.

　本発明で用いる接着剤組成物の粘度は、特に限定されないが、２５℃で、通常５００～２０，０００ｍＰａ・ｓであり、好ましくは１，０００～１，００００ｍＰａ・ｓである。 The viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s at 25°C, and preferably 1,000 to 1,0000 mPa·s.

　本発明で用いる接着剤組成物の一例は、接着剤成分（Ａ）、剥離剤成分（Ｂ）及び溶媒を混合することによって製造できる。
　その混合順序は特に限定されるものではないが、容易にかつ再現性よく接着剤組成物を製造できる方法の一例としては、例えば、接着剤成分（Ａ）と剥離剤成分（Ｂ）を溶媒に溶解させる方法や、接着剤成分（Ａ）と剥離剤成分（Ｂ）の一部を溶媒に溶解させ、残りを溶媒に溶解させ、得られた溶液を混合する方法が挙げられるが、これらに限定されない。なお、接着剤組成物を調製する際、成分が分解したり変質したりしない範囲で、適宜加熱してもよい。
　本発明においては、異物を除去する目的で、接着剤組成物を製造する途中で又は全ての成分を混合した後に、用いる溶媒や溶液等をフィルター等を用いてろ過してもよい。 An example of the adhesive composition used in the present invention can be produced by mixing the adhesive component (A), the release agent component (B), and a solvent.
The order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (A) and the release agent component (B) in a solvent, or a method of dissolving a portion of the adhesive component (A) and the remainder of the release agent component (B) in a solvent and then mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components.
In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter during the production of the adhesive composition or after all of the components have been mixed.

＜プライマー皮膜＞
　プライマー皮膜は、接着剤層に対し、剥離界面を生じさせたい側でない側にある基板の表面上に形成される。
　ここで、プライマー皮膜が形成される基板としては、支持基板も、半導体基板又は電子デバイス基板（半導体基板等）も対象となる。
　界面剥離を、半導体基板又は電子デバイス基板（半導体基板等）と接着剤層との界面で生じさせたい場合（デバイス剥離の場合）には、プライマー皮膜は、支持基板の表面に形成される。
　一方、界面剥離を、支持基板と接着剤層との界面で生じさせたい場合（キャリア剥離の場合）には、プライマー皮膜は、半導体基板又は電子デバイス基板（半導体基板等）の表面に形成される。 <Primer coating>
The primer coating is formed on the surface of the substrate on the side opposite to the side where a peel interface is desired to form relative to the adhesive layer.
The substrate on which the primer film is formed may be a support substrate, a semiconductor substrate, or an electronic device substrate (semiconductor substrate, etc.).
When interfacial delamination is desired to occur at the interface between the semiconductor substrate or electronic device substrate (such as a semiconductor substrate) and the adhesive layer (in the case of device delamination), the primer coating is formed on the surface of the supporting substrate.
On the other hand, when interfacial peeling is desired to occur at the interface between the support substrate and the adhesive layer (in the case of carrier peeling), the primer coating is formed on the surface of a semiconductor substrate or electronic device substrate (semiconductor substrate, etc.).

　プライマー皮膜は、ヒドロシリル化反応によって硬化する接着剤成分を含有する接着剤組成物から形成される接着剤層と基板との接着力を高めるために設けられる。 The primer coating is applied to enhance the adhesive strength between the substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction.

　プライマー皮膜は、プライマー皮膜形成用組成物により形成される。 The primer film is formed using a primer film-forming composition.

＜＜プライマー皮膜形成用組成物＞＞
　本発明に係るプライマー皮膜形成用組成物は、接着剤層を形成する際に利用されるヒドロシリル化反応をより促進させるような成分、つまりヒドロシリル化反応に寄与する成分を含有する。
　プライマー皮膜形成用組成物は、プライマー皮膜を表面に有する基板と、接着剤層との接着力を上げる機能を有することから、本明細書では、プライマー皮膜形成用組成物のことを接着補助剤組成物ともいう。 <<Primer film-forming composition>>
The primer coating composition according to the present invention contains a component that further accelerates the hydrosilylation reaction used in forming the adhesive layer, that is, a component that contributes to the hydrosilylation reaction.
The composition for forming a primer film has the function of increasing the adhesive strength between a substrate having a primer film on its surface and an adhesive layer, and therefore, in this specification, the composition for forming a primer film is also referred to as an adhesion auxiliary composition.

　ヒドロシリル化反応に寄与する成分としては、例えば、白金を含む化合物、Ｓｉ－Ｈ基を含む化合物、及びビニル基を含む化合物のいずれかから選ばれる成分が挙げられる。 Components that contribute to the hydrosilylation reaction include, for example, compounds selected from the group consisting of platinum-containing compounds, Si-H group-containing compounds, and vinyl group-containing compounds.

　白金を含む化合物としては、例えば、白金族金属又は白金族金属を含有する化合物が挙げられる。
　白金を含む化合物としては、例えば、その表面に白金族金属を有する固体担体を含む担持ヒドロシリル化触媒であってもよい。担持触媒の例としては、白金担持炭素、パラジウム担持炭素、ルテニウム担持炭素、ロジウム担持炭素、白金担持シリカ、パラジウム担持シリカ、白金担持アルミナ、パラジウム担持アルミナ、及びルテニウム担持アルミナが挙げられるが、これらに限定されない。 Examples of the platinum-containing compound include platinum group metals and compounds containing platinum group metals.
The platinum-containing compound may be, for example, a supported hydrosilylation catalyst comprising a solid support having a platinum group metal on its surface. Examples of supported catalysts include, but are not limited to, platinum on carbon, palladium on carbon, ruthenium on carbon, rhodium on carbon, platinum on silica, palladium on silica, platinum on alumina, palladium on alumina, and ruthenium on alumina.

　白金を含む化合物としては、例えば、照射及び／又は加熱によって硬化を開始することができる光活性化可能なヒドロシリル化触媒であってもよい。光活性化可能なヒドロシリル化触媒としては、例えば、特に、１５０～８００ナノメートル（ｎｍ）の波長を有する放射線への曝露によりヒドロシリル化反応を触媒することができる任意のヒドロシリル化触媒をいう。本発明の組成物にて使用するための、特定の光活性可能なヒドロシリル化触媒の適合性は、ルーチン実験により速やかに測定することができる。 The platinum-containing compound may be, for example, a photoactivatable hydrosilylation catalyst capable of initiating curing upon irradiation and/or heating. A photoactivatable hydrosilylation catalyst refers to, for example, any hydrosilylation catalyst capable of catalyzing a hydrosilylation reaction upon exposure to radiation, particularly those having wavelengths between 150 and 800 nanometers (nm). The suitability of a particular photoactivatable hydrosilylation catalyst for use in the compositions of the present invention can be readily determined through routine experimentation.

　上記光活性化可能なヒドロシリル化触媒の具体例としては、白金（ＩＩ）ビス（２，４－ペンタンジオエート）、白金（ＩＩ）ビス（２，４－ヘキサンジオエート）、白金（ＩＩ）ビス（２，４－ヘプタンジオエート）、白金（ＩＩ）ビス（１－フェニル－１，３－ブタンジオエート）、白金（ＩＩ）ビス（１，３－ジフェニル－１，３－プロパンジオエート）、白金（ＩＩ）ビス（１，１，１，５，５，５－ヘキサフルオロ－２，４－ペンタンジオエート）などの白金（ＩＩ）β－ジケトネート錯体；（Ｃｐ）トリメチル白金、（Ｃｐ）エチルジメチル白金、（Ｃｐ）トリエチル白金、（クロロ－Ｃｐ）トリメチル白金、及び（トリメチルシリル－Ｃｐ）トリメチル白金等であって、Ｃｐがシクロペンタジエニルを表す、（h－シクロペンタジエニル）トリアルキル白金錯体；［Ｐｔ［Ｃ６Ｈ５ＮＮＮＯＣＨ３］４、Ｐｔ［ｐ－ＣＮ－Ｃ６Ｈ４ＮＮＮＯＣ６Ｈ１１］４、Ｐｔ［ｐ－Ｈ３ＣＯＣ６Ｈ４ＮＮＮＯＣ６Ｈ１１］４、Ｐｔ［ｐ－ＣＨ３（ＣＨ２）ｘ－Ｃ６Ｈ４ＮＮＮＯＣＨ３］４、１，５－シクロオクタジエンＰｔ［ｐ－ＣＮ－Ｃ６Ｈ４ＮＮＮＯＣ６Ｈ１１］２、１，５－シクロオクタジエンＰｔ［ｐ－ＣＨ３Ｏ－Ｃ６Ｈ４ＮＮＮＯＣＨ３］２、［（Ｃ６Ｈ５）３Ｐ］３Ｒｈ［ｐ－ＣＮ－Ｃ６Ｈ４ＮＮＮＯＣ６Ｈ１１］、及びＰｄ［ｐ－ＣＨ３（ＣＨ２）ｘ－Ｃ６Ｈ４ＮＮＮＯＣＨ３］２［式中、ｘは１、３、５、１１、又は１７である］等のトリアゼンオキシド－遷移金属錯体；（ｈ４－１，５－シクロオクタジエニル）ジフェニル白金、（ｈ４－１，３，５，７－シクロオクタテトラエニル）ジフェニル白金、（ｈ４－２，５－ノルボラジエニル）ジフェニル白金、（ｈ４－１，５－シクロオクタジエニル）ビス－（４－ジメチルアミノフェニル）白金、（ｈ４－１，５－シクロオクタジエニル）ビス－（４－アセチルフェニル）白金、及び（ｈ４－１，５－シクロオクタジエニル）ビス－（４－トリフルオロメチルフェニル）白金等の、（ｈ－ジオレフィン）（σ－アリール）白金錯体が挙げられるが、これらに限定されない。一般的に、光活性化可能なヒドロシリル化触媒は、Ｐｔ（ＩＩ）β－ジケトネート錯体であり、より一般的には、触媒は白金（ＩＩ）ビス（２，４－ペンタンジオエート）である。 Specific examples of the photoactivatable hydrosilylation catalyst include platinum(II) β-diketonate complexes such as platinum(II) bis(2,4-pentanedioate), platinum(II) bis(2,4-hexanedioate), platinum(II) bis(2,4-heptanedioate), platinum(II) bis(1-phenyl-1,3-butanedioate), platinum(II) bis(1,3-diphenyl-1,3-propanedioate), and platinum(II) bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedioate); (h-cyclopentadienyl)trialkylplatinum complexes such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl-Cp)trimethylplatinum, where Cp represents cyclopentadienyl; [Pt[C 6 H 5 NNNOCH 3 ] 4 , Pt[p-CN-C 6 H 4 NNNOC 6 H 11 ] 4 , Pt[p-H 3 COC 6 H 4 NNNOC 6 H 11 ] 4 , Pt[p-CH 3 (CH 2 ) x -C 6 H 4 NNNOCH 3 ] 4 , 1,5-cyclooctadiene Pt[p-CN-C 6 H 4 NNNOC 6 H 11 ] 2 , 1,5-cyclooctadiene Pt[p-CH 3 O-C 6 H 4 NNNOCH 3 ] 2 , [(C 6 H 5 ) 3 P] 3 Rh[p-CN-C 6 H 4 NNNOC 6 H 11 ], and triazene oxide-transition metal complexes such as Pd[p-CH 3 (CH 2 ) x —C 6 H 4 NNNOCH 3 ] 2 [where x is 1, 3, 5, 11, or 17]; (h 4 -1,5-cyclooctadienyl)diphenylplatinum, (h 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (h 4 -2,5-norborazienyl)diphenylplatinum, (h 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (h 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum, and (h 4 Photoactivatable hydrosilylation catalysts include, but are not limited to, (h-diolefin)(σ-aryl)platinum complexes such as (h-diolefin)(σ-aryl)platinum complexes, such as (h-diolefin)(σ-aryl)platinum (1,5-cyclooctadienyl)bis-(4-trifluoromethylphenyl)platinum. Typically, the photoactivatable hydrosilylation catalyst is a Pt(II) β-diketonate complex, and more typically, the catalyst is platinum(II) bis(2,4-pentanedioate).

　Ｓｉ－Ｈ基を含む化合物としては、Ｓｉ－Ｈ基を含んでいれば特に制限はないが、例えば、重量平均分子量（Ｍｗ）が１００以上４０万以下の化合物が挙げられる。また、１分子中に２個以上Ｓｉ－Ｈ基が含まれている化合物であると好ましい。
　Ｓｉ－Ｈ基を含む化合物としては、直鎖タイプの化合物であっても、環状タイプの化合物であってもよく、例えば、溶媒との溶解性を考慮すると、環状タイプの化合物であることが好ましい。 The compound containing an Si—H group is not particularly limited as long as it contains an Si—H group, and examples thereof include compounds having a weight average molecular weight (Mw) of 100 or more and 400,000 or less. In addition, compounds containing two or more Si—H groups per molecule are preferred.
The compound containing a Si—H group may be a linear compound or a cyclic compound, and is preferably a cyclic compound in terms of solubility in a solvent, for example.

　ビニル基を含む化合物としては、ビニル基を含んでいれば特に制限はないが、例えば、重量平均分子量（Ｍｗ）が１００以上４０万以下の化合物が挙げられる。また、１分子中に２個以上ビニル基が含まれている化合物であると好ましい。 There are no particular restrictions on the vinyl group-containing compound as long as it contains a vinyl group, but examples include compounds with a weight average molecular weight (Mw) of 100 or more and 400,000 or less. Furthermore, compounds containing two or more vinyl groups per molecule are preferred.

　白金を含む化合物、Ｓｉ－Ｈ基を含む化合物、及びビニル基を含む化合物としては、例えば、上記＜＜接着剤組成物＞＞の＜＜＜接着剤成分＞＞＞の欄で説明した接着剤成分であってもよい。 The platinum-containing compound, the Si-H group-containing compound, and the vinyl group-containing compound may be, for example, the adhesive components described in the "Adhesive Components" section of the "Adhesive Composition" above.

　ヒドロシリル化反応に寄与する成分の好ましい実施態様として、以下の実施例でも用いている、例えば、下記式（Ｘ－１）～下記式（Ｘ－４）で表される、白金を含む化合物やＳｉ－Ｈ基を含む化合物が挙げられる。ただし、これらに限定されない。
 Preferred embodiments of the component that contributes to the hydrosilylation reaction include, but are not limited to, platinum-containing compounds and Si—H group-containing compounds represented by the following formulae (X-1) to (X-4), which are also used in the following examples.

　プライマー皮膜形成用組成物は、例えば、ヒドロシリル化反応に寄与する成分と、溶媒とを混合することによって製造できる。
　溶媒としては、例えば、プロピレングリコールモノメチルエーテルやプロピレングリコールモノメチルエーテルアセテートなどが用いられる。 The primer coating composition can be produced, for example, by mixing components that contribute to the hydrosilylation reaction with a solvent.
As the solvent, for example, propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate is used.

　プライマー皮膜形成用組成物からプライマー皮膜を形成する方法としては、特に限定されないが、例えば、プライマー皮膜形成用組成物を塗布してプライマー皮膜を形成する方法が挙げられる。
　プライマー皮膜形成用組成物の塗布方法は、特に限定されるものではないが、通常、スピンコート法である。 The method for forming a primer film from the primer film-forming composition is not particularly limited, but examples thereof include a method in which the primer film is formed by applying the primer film-forming composition.
The method for applying the primer film-forming composition is not particularly limited, but is usually a spin coating method.

＜支持基板＞
　支持基板としては、半導体基板が加工される際に、半導体基板を支持できる部材であれば、特に限定されないが、例えば、ガラス製支持基板、シリコン製支持基板などが挙げられる。 <Support substrate>
The support substrate is not particularly limited as long as it is a member that can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.

　支持基板の形状としては、特に限定されないが、例えば、円盤状が挙げられる。なお、円盤状の支持基板は、その面の形状が完全な円形である必要はなく、例えば、支持基板の外周は、オリエンテーション・フラットと呼ばれる直線部を有していてもよいし、ノッチと呼ばれる切込みを有していてもよい。
　円盤状の支持基板の厚さとしては、半導体基板の大きさなどに応じて適宜定めればよく、特に限定されないが、例えば、５００～１，０００μｍである。
　円盤状の支持基板の直径としては、半導体基板の大きさなどに応じて適宜定めればよく、特に限定されないが、例えば、１００～１，０００ｍｍである。 The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped support substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat or a notch.
The thickness of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm.
The diameter of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

　支持基板の一例は、直径３００ｍｍ、厚さ７００μｍ程度のガラスウエハーである。 An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

　なお、積層体における剥離が光照射によって行われる場合、支持基板としては、例えば、使用される光に対して光透過性がある基板が使用される。 If peeling of the laminate is performed by light irradiation, the support substrate used is, for example, a substrate that is optically transparent to the light used.

＜半導体基板又は電子デバイス基板＞
＜＜半導体基板＞＞
　半導体基板全体を構成する主な材質としては、この種の用途に用いられるものであれば特に限定されないが、例えば、シリコン、シリコンカーバイド、化合物半導体、有機樹脂付のガラス基板などが挙げられる。
　半導体基板の形状は、特に限定されないが、例えば、円盤状である。なお、円盤状の半導体基板は、その面の形状が完全な円形である必要はなく、例えば、半導体基板の外周は、オリエンテーション・フラットと呼ばれる直線部を有していてもよいし、ノッチと呼ばれる切込みを有していてもよい。
　円盤状の半導体基板の厚さとしては、半導体基板の使用目的などに応じて適宜定めればよく、特に限定されないが、例えば、５００～１，０００μｍである。
　円盤状の半導体基板の直径としては、半導体基板の使用目的などに応じて適宜定めればよく、特に限定されないが、例えば、１００～１，０００ｍｍである。 <Semiconductor substrate or electronic device substrate>
<<Semiconductor substrate>>
The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins.
The shape of the semiconductor substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped semiconductor substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch.
The thickness of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm.
The diameter of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

　半導体基板は、バンプを有していてもよい。バンプとは、突起状の端子である。
　積層体において、半導体基板がバンプを有する場合、半導体基板は、支持基板側にバンプを有する。
　半導体基板において、バンプは、通常、回路が形成された面上に形成されている。回路は、単層であってもよし、多層であってもよい。回路の形状としては特に制限されない。
　半導体基板において、バンプを有する面と反対側の面（裏面）は、加工に供される面である。
　半導体基板が有するバンプの材質、大きさ、形状、構造、密度としては、特に限定されない。
　バンプとしては、例えば、ボールバンプ、印刷バンプ、スタッドバンプ、めっきバンプなどが挙げられる。
　通常、バンプ高さ１～２００μｍ程度、バンプ半径１～２００μｍ、バンプピッチ１～５００μｍという条件からバンプの高さ、半径及びピッチは適宜決定される。
　バンプの材質としては、例えば、低融点はんだ、高融点はんだ、スズ、インジウム、金、銀、銅などが挙げられる。バンプは、単一の成分のみで構成されていてもよいし、複数の成分から構成されていてもよい。より具体的には、ＳｎＡｇバンプ、ＳｎＢｉバンプ、Ｓｎバンプ、ＡｕＳｎバンプ等のＳｎを主体とした合金めっき等が挙げられる。
　また、バンプは、これらの成分の少なくともいずれかからなる金属層を含む積層構造を有してもよい。 The semiconductor substrate may have bumps, which are protruding terminals.
In the laminate, when the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side.
In a semiconductor substrate, bumps are usually formed on the surface on which a circuit is formed. The circuit may be a single layer or a multilayer. There are no particular limitations on the shape of the circuit.
In the semiconductor substrate, the surface opposite to the surface having the bumps (back surface) is the surface to be processed.
The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited.
Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps.
Normally, the height, radius and pitch of the bumps are appropriately determined based on the conditions of a bump height of about 1 to 200 μm, a bump radius of 1 to 200 μm and a bump pitch of 1 to 500 μm.
Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, may be used.
The bump may also have a laminated structure including a metal layer made of at least one of these components.

　半導体基板の一例は、直径３００ｍｍ、厚さ７７０μｍ程度のシリコンウエハーである。 An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

＜＜電子デバイス基板＞＞
　電子デバイス基板とは、電子デバイスを有する基板をいい、本発明においては、例えば、封止樹脂に複数の半導体チップ基板が埋め込まれた層からなる基板、つまり複数の半導体チップ基板と該半導体チップ基板間に配された封止樹脂とからなる基板をいう。
　ここで、「電子デバイス」とは、電子部品の少なくとも一部を構成する部材を意味する。電子デバイスは、特に制限されず、半導体基板の表面に、各種機械構造や回路が形成されたものであることができる。電子デバイスは、好ましくは、金属又は半導体により構成される部材と、該部材を封止又は絶縁する樹脂と、の複合体である。電子デバイスは、後述する再配線層、及び／又は半導体素子若しくはその他素子が、封止材又は絶縁材で封止又は絶縁されたものであってもよく、単層又は複数層の構造を有してなる。 <<Electronic device substrate>>
An electronic device substrate refers to a substrate having an electronic device, and in the present invention, for example, refers to a substrate consisting of a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a substrate consisting of a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.
Here, "electronic device" refers to a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited and can be one in which various mechanical structures or circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. The electronic device may have a rewiring layer (described later) and/or a semiconductor element or other element sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

＜積層体の層構成＞
　以下、積層体の構成の一例を、図を用いて説明する。
　図１は、積層体の一例の概略断面図を示す。
　図１の積層体は、半導体基板１と、接着剤層２と、支持基板４とをこの順で有する。即ち、接着剤層２は、半導体基板１と支持基板４との間に設けられている。支持基板４の表面には、プライマー皮膜３が形成されている。
　図１の積層体は、デバイス剥離タイプの積層体となっている。 <Layer structure of laminate>
An example of the structure of the laminate will be described below with reference to the drawings.
FIG. 1 shows a schematic cross-sectional view of an example of a laminate.
1 includes, in this order, a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. A primer coating 3 is formed on the surface of the support substrate 4.
The laminate in FIG. 1 is a device peelable type laminate.

　図２は、積層体の他の一例の概略断面図を示す。
　図２の積層体は、支持基板２４と、接着剤層２２と、電子デバイス基板２６とをこの順で有する。
　電子デバイス基板２６は、複数の半導体チップ基板２１と、該半導体チップ基板２１間に配された封止材である封止樹脂２５とを有してなる。
　接着剤層２２は、電子デバイス基板２６と支持基板２４との間に設けられている。支持基板２４の表面には、プライマー皮膜２３が形成されている。
　図２の積層体は、デバイス剥離タイプの積層体となっている。 FIG. 2 shows a schematic cross-sectional view of another example of the laminate.
The laminate of FIG. 2 includes, in order, a support substrate 24, an adhesive layer 22, and an electronic device substrate 26.
The electronic device substrate 26 includes a plurality of semiconductor chip substrates 21 and sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .
The adhesive layer 22 is provided between the electronic device substrate 26 and the support substrate 24. A primer film 23 is formed on the surface of the support substrate 24.
The laminate in FIG. 2 is a device peelable type laminate.

（積層体の製造方法）
　本発明の積層体の製造方法は、
　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層と、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面に形成されたプライマー皮膜と、を有する積層体の製造方法であって、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面に、上述したプライマー皮膜形成用組成物を塗布することによりプライマー皮膜を形成する工程、を含むことを特徴とする。
　また、本発明の積層体の製造方法は、
　さらに、前記プライマー皮膜が形成されていない、前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板に対し、前記接着剤層を形成するための接着剤組成物を塗布する工程、
　前記プライマー皮膜が形成された基板と、前記接着剤組成物が塗布されている基板とを貼り合わせ、その後加熱処理を行うことにより、前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に接着剤層を形成する工程、
を含む製造方法であってもよい。 (Method for manufacturing laminate)
The method for producing the laminate of the present invention comprises:
A support substrate;
a semiconductor substrate or an electronic device substrate;
an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate;
a primer coating formed on a surface of either the semiconductor substrate or the electronic device substrate, or the support substrate, the method comprising:
The method is characterized by including a step of forming a primer film by applying the above-mentioned composition for forming a primer film to the surface of any one of the semiconductor substrate or the electronic device substrate and the support substrate.
Further, the method for producing the laminate of the present invention comprises the steps of:
Furthermore, a step of applying an adhesive composition for forming the adhesive layer to any one of the semiconductor substrate or the electronic device substrate and the support substrate on which the primer film is not formed;
a step of bonding a substrate on which the primer film has been formed and a substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate;
The manufacturing method may include the steps of:

　また、本発明の積層体の製造方法は、
　積層体が、特にデバイス剥離タイプの積層体であることを考慮し、
　支持基板の表面に、上述したプライマー皮膜形成用組成物を塗布することによりプライマー皮膜を形成する工程、
　半導体基板又は電子デバイス基板に対し、接着剤層を形成するための接着剤組成物を塗布する工程、
　前記プライマー皮膜が形成された前記支持基板と、前記接着剤組成物が塗布されている前記半導体基板又は前記電子デバイス基板とを貼り合わせ、その後加熱処理を行うことにより、前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に接着剤層を形成する工程、を含む製造方法であることが好ましい。 Further, the method for producing the laminate of the present invention comprises the steps of:
Considering that the laminate is particularly a device peel-off type laminate,
A step of forming a primer film by applying the above-mentioned composition for forming a primer film to the surface of a support substrate;
applying an adhesive composition to a semiconductor substrate or an electronic device substrate to form an adhesive layer;
Preferably, the manufacturing method includes a step of bonding the support substrate on which the primer coating has been formed and the semiconductor substrate or the electronic device substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate.

　図１で示される積層体を例に、以下積層体の製造方法について説明する。
　本発明の積層体の一例は、例えば、以下の第１工程～第４工程を含む方法で製造することができる。
　第１工程：支持基板上にプライマー皮膜形成用組成物を塗布し支持基板の表面にプライマー皮膜を形成する工程
　第２工程：半導体基板上に接着剤組成物を塗布し接着剤塗布層を形成する（必要に応じ、さらに加熱して接着剤層を形成する）工程
　第３工程：表面にプライマー皮膜が配された支持基板を接着剤塗布層又は接着剤層上に載置して、加熱処理及び減圧処理の少なくともいずれかを実施しながら、表面にプライマー皮膜が配された支持基板と半導体基板とを、接着剤塗布層又は接着剤層を介して貼り合わせる工程
　第４工程：接着剤塗布層を後加熱処理することにより硬化させ接着剤層を形成する工程 A method for manufacturing a laminate will be described below using the laminate shown in FIG. 1 as an example.
An example of the laminate of the present invention can be produced by a method including the following first to fourth steps.
First step: A step of applying a primer film-forming composition onto a support substrate to form a primer film on the surface of the support substrate. Second step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer (if necessary, further heating to form an adhesive layer). Third step: A step of placing a support substrate having a primer film disposed on its surface on the adhesive coating layer or adhesive layer, and bonding the support substrate having a primer film disposed on its surface and the semiconductor substrate via the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment. Fourth step: A step of curing the adhesive coating layer by post-heat treatment to form an adhesive layer.

　プライマー皮膜形成用組成物の塗布方法は、特に限定されるものではないが、通常、スピンコート法である。
　スピンコートの条件としては、例えば、１０００ｒｐｍで６０秒間である。 The method for applying the primer film-forming composition is not particularly limited, but is usually a spin coating method.
The spin coating conditions are, for example, 1000 rpm for 60 seconds.

　接着剤組成物の塗布方法は、特に限定されるものではないが、通常、スピンコート法である。なお、別途スピンコート法等で塗布膜を形成し、シート状の塗布膜を形成し、シート状の塗布膜を、接着剤塗布層として貼付する方法を採用し得る。
　塗布した接着剤組成物の加熱温度は、接着剤組成物が含む接着剤成分の種類や量、溶媒が含まれるか否か、用いる溶媒の沸点、所望の接着剤層の厚さ等に応じて異なるため一概に規定できないが、通常８０～１５０℃、その加熱時間は、通常３０秒～５分である。
　接着剤組成物が溶媒を含む場合、通常、塗布した接着剤組成物を加熱する。
　接着剤組成物を塗布し、必要があればそれを加熱して得られる接着剤塗布層の膜厚は、通常５～５００μｍ程度であり、最終的に、上述の接着剤層の厚さの範囲となるように適宜定められる。 The method for applying the adhesive composition is not particularly limited, but is usually a spin coating method. Alternatively, a method may be employed in which a coating film is separately formed by a spin coating method or the like to form a sheet-like coating film, and the sheet-like coating film is then attached as an adhesive coating layer.
The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and the like, but is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes.
When the adhesive composition contains a solvent, the applied adhesive composition is usually heated.
The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is usually about 5 to 500 μm, and is appropriately determined so that the final thickness of the adhesive layer falls within the above-mentioned range.

　本発明においては、加熱処理若しくは減圧処理又はこれら両方を実施しながら、半導体基板及び支持基板の厚さ方向の荷重をかけて、その後、後加熱処理を実施することによって、本発明の積層体を得ることができる。なお、加熱処理、減圧処理、両者の併用のいずれの処理条件を採用するかは、接着剤組成物の種類、膜厚、求める接着強度等の各種事情を勘案した上で適宜決定される。 In the present invention, the laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment. The treatment conditions to be used, whether heat treatment, decompression treatment, or a combination of both, are determined appropriately taking into consideration various factors such as the type of adhesive composition, film thickness, and desired adhesive strength.

　加熱処理は、組成物から溶媒を除去する観点等から、通常２０～１６０℃の範囲から適宜決定される。特に、接着剤成分（Ａ）の過度の硬化や不要な変質を抑制又は回避する観点から、好ましくは１５０℃以下、より好ましくは１３０℃以下であり、その加熱時間は、加熱温度や接着剤の種類に応じて適宜決定されるものではあるが、好適な接着を確実に発現させる観点から、通常３０秒以上であり、好ましくは１分以上であるが、接着剤層やその他の部材の変質を抑制する観点から、通常１０分以下、好ましくは５分以下である。 The heating temperature is typically determined appropriately from the range of 20 to 160°C, taking into account factors such as removing the solvent from the composition. In particular, to prevent or avoid excessive curing or unnecessary deterioration of adhesive component (A), the temperature is preferably 150°C or lower, more preferably 130°C or lower. The heating time is determined appropriately depending on the heating temperature and type of adhesive, but is typically 30 seconds or longer, preferably 1 minute or longer, to ensure optimal adhesion. However, to prevent deterioration of the adhesive layer and other components, the heating time is typically 10 minutes or shorter, preferably 5 minutes or shorter.

　減圧処理は、互いに接する接着剤塗布層を１０～１０，０００Ｐａの気圧下にさらせばよい。減圧処理の時間は、通常１～３０分である。 The vacuum treatment can be carried out by exposing the adhesive coating layers that come into contact with each other to an air pressure of 10 to 10,000 Pa. The vacuum treatment time is usually 1 to 30 minutes.

　半導体基板及び支持基板の厚さ方向の荷重は、半導体基板及び支持基板とそれらの間の層に悪影響を及ぼさず、かつこれらをしっかりと密着させることができる荷重である限り特に限定されないが、通常１０～５００００Ｎの範囲内である。 The load applied in the thickness direction of the semiconductor substrate and support substrate is not particularly limited, as long as it does not adversely affect the semiconductor substrate, support substrate, or layers between them and is a load that can firmly adhere them together, but is usually in the range of 10 to 50,000 N.

　後加熱の温度は、十分な硬化速度を実現する観点等から、好ましくは１２０℃以上であり、基板や各層の変質を防ぐ観点等から、好ましくは２６０℃以下である。
　後加熱の時間は、積層体を構成する基板及び層の好適な接合を実現する観点から、通常１分以上、好ましくは５分以上であり、過度の加熱による各層への悪影響等を抑制又は回避する観点から、通常１８０分以下、好ましくは１２０分以下である。
　加熱は、ホットプレート、オーブン等を用いて行うことができる。ホットプレートを用いて後加熱をする場合、積層体の半導体基板と支持基板のいずれを下にして加熱してもよいが、好適な剥離を再現性よく実現する観点から、半導体基板を下にして後加熱することが好ましい。
　なお、後加熱処理の一つの目的は、より好適な自立膜である接着剤層を実現することであり、特にヒドロシリル化反応による硬化を好適に実現することである。 The post-heating temperature is preferably 120° C. or higher from the viewpoint of realizing a sufficient curing rate, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate and each layer.
The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrates and layers constituting the laminate, and is usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating.
Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, the laminate may be heated with either the semiconductor substrate or the support substrate facing downward, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.
One purpose of the post-heat treatment is to realize an adhesive layer that is a more suitable self-supporting film, and in particular to realize suitable curing by the hydrosilylation reaction.

　図３Ａ～図３Ｃは、図１に示す積層体の製造を行う一態様を説明するための図である。
　まず、支持基板４上にプライマー皮膜３が形成された積層体を用意する（図３Ａ）。この積層体は、例えば、支持基板４上にプライマー皮膜形成用組成物をスピンコートにより塗布することで得ることができる。
　次に、半導体基板１上に接着剤塗布層２ａが形成された積層体を用意する（図３Ｂ）。この積層体は、例えば、半導体基板１上に接着剤組成物を塗布し、加熱することで得ることができる。
　次に、図３Ａに示す表面にプライマー皮膜３が形成された支持基板４からなる積層体と、図３Ｂに示す接着剤塗布層２ａを有する半導体基板１からなる積層体とを、接着剤塗布層２ａがプライマー皮膜３を介して支持基板４と接するように貼り合せる。そして、減圧下で半導体基板１と支持基板４との厚さ方向に荷重を掛けた後、半導体基板１の接着剤塗布層２ａが接する面と反対側の面に、加熱装置（不図示；ホットプレート）を配し、加熱装置によって接着剤塗布層２ａを加熱して硬化させ接着剤層２に転化する（図３Ｃ）。
　図３Ａ～図３Ｃで示した工程によって、図１に示す積層体が得られる。 3A to 3C are diagrams for explaining one embodiment of the manufacturing method of the laminate shown in FIG.
First, a laminate is prepared in which a primer film 3 is formed on a support substrate 4 (FIG. 3A). This laminate can be obtained, for example, by applying a primer film-forming composition onto the support substrate 4 by spin coating.
Next, a laminate is prepared in which an adhesive coating layer 2a is formed on the semiconductor substrate 1 (FIG. 3B). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating it.
Next, a laminate made of a support substrate 4 having a primer coating 3 formed on its surface as shown in Fig. 3A and a laminate made of a semiconductor substrate 1 having an adhesive coating layer 2a as shown in Fig. 3B are bonded together so that the adhesive coating layer 2a contacts the support substrate 4 via the primer coating 3. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (hot plate, not shown) is placed on the surface of the semiconductor substrate 1 opposite to the surface where the adhesive coating layer 2a contacts, and the adhesive coating layer 2a is heated and hardened by the heating device, converting it into the adhesive layer 2 (Fig. 3C).
The laminate shown in FIG. 1 is obtained by the steps shown in FIGS. 3A to 3C.

　また、図２で示される積層体を例に、以下積層体の製造方法について説明する。
　本発明の積層体の一例は、例えば、以下の第１（Ｄ）工程～第５（Ｄ）工程を含む方法で製造することができる。
　第１（Ｄ）工程：支持基板上にプライマー皮膜形成用組成物を塗布し支持基板の表面にプライマー皮膜を形成する工程
　第２（Ｄ）工程：半導体チップ基板上に接着剤組成物を塗布し接着剤塗布層を形成する（必要に応じ、さらに加熱して接着剤層を形成する）工程
　第３（Ｄ）工程：表面にプライマー皮膜が配された支持基板を接着剤塗布層又は接着剤層上に載置して、加熱処理及び減圧処理の少なくともいずれかを実施しながら、表面にプライマー皮膜が配された支持基板と半導体チップ基板とを、接着剤塗布層又は接着剤層を介して貼り合わせる工程
　第４（Ｄ）工程：接着剤塗布層を後加熱処理することにより硬化させ接着剤層を形成する工程
　第５（Ｄ）工程：接着剤層上に固定された半導体チップ基板に対して封止樹脂を用いて封止する工程 A method for manufacturing a laminate will be described below using the laminate shown in FIG. 2 as an example.
An example of the laminate of the present invention can be produced by a method including the following steps 1 (D) to 5 (D).
Step 1 (D): A step of applying a primer film-forming composition onto a support substrate to form a primer film on the surface of the support substrate. Step 2 (D): A step of applying an adhesive composition onto a semiconductor chip substrate to form an adhesive coating layer (if necessary, further heating to form an adhesive layer). Step 3 (D): A step of placing a support substrate having a primer film disposed on its surface on the adhesive coating layer or adhesive layer, and bonding the support substrate having a primer film disposed on its surface and the semiconductor chip substrate via the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment. Step 4 (D): A step of curing the adhesive coating layer by post-heat treatment to form an adhesive layer. Step 5 (D): A step of sealing the semiconductor chip substrate fixed on the adhesive layer using a sealing resin.

　図４Ａ～図４Ｄは、図２に示す積層体の製造を行う一態様を説明するための図である。
　まず、支持基板２４上にプライマー皮膜２３が形成された積層体を用意する（図４Ａ）。この積層体は、例えば、支持基板２４上にプライマー皮膜形成用組成物をスピンコートにより塗布することで得ることができる。
　次に、半導体チップ基板２１上に接着剤塗布層２２ａが形成された積層体を用意する（図４Ｂ）。この積層体は、例えば、半導体チップ基板２１上に接着剤組成物を塗布し、加熱することで得ることができる。その際、接着剤塗布層２２ａを加熱し、接着剤層２２を形成してもよい。
　次に、図４Ａに示す表面にプライマー皮膜２３が形成された支持基板２４からなる積層体と、図４Ｂに示す接着剤塗布層２２ａを有する半導体チップ基板２１からなる積層体とを、接着剤塗布層２２ａがプライマー皮膜２３を介して支持基板２４と接するように貼り合せる。そして、減圧下で半導体チップ基板２１と支持基板２４との厚さ方向に荷重を掛けた後、半導体チップ基板２１の接着剤塗布層２２ａが接する面と反対側の面に、加熱装置（不図示；ホットプレート）を配し、加熱装置によって接着剤塗布層２２ａを加熱して硬化させ接着剤層２２に転化する（図４Ｃ）。
　次に、図４Ｄで示すように、接着剤層２２上に固定された半導体チップ基板２１を、封止樹脂２５を用いて封止する。図４Ｄでは、接着剤層２２を介して、支持基板２４上に仮接着された複数の半導体チップ基板２１が、封止樹脂２５により封止されている。接着剤層２２上に、半導体チップ基板２１と半導体チップ基板２１間に配された封止樹脂２５とを有する電子デバイス基板２６が形成されており、このように、電子デバイス基板２６は、封止樹脂に複数の半導体チップ基板が埋め込まれた基材層となっている。
　図４Ａ～図４Ｄで示した工程によって、図２に示す積層体が得られる。 4A to 4D are diagrams for explaining one mode of manufacturing the laminate shown in FIG.
First, a laminate is prepared in which a primer film 23 is formed on a support substrate 24 (FIG. 4A). This laminate can be obtained, for example, by applying a primer film-forming composition onto the support substrate 24 by spin coating.
Next, a laminate is prepared in which adhesive coating layer 22a is formed on semiconductor chip substrate 21 (FIG. 4B). This laminate can be obtained, for example, by applying an adhesive composition to semiconductor chip substrate 21 and heating it. At this time, adhesive coating layer 22a may be heated to form adhesive layer 22.
Next, a laminate made of a support substrate 24 having a primer coating 23 formed on its surface as shown in Fig. 4A and a laminate made of a semiconductor chip substrate 21 having an adhesive coating layer 22a as shown in Fig. 4B are bonded together so that the adhesive coating layer 22a contacts the support substrate 24 via the primer coating 23. Then, after applying a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 under reduced pressure, a heating device (hot plate, not shown) is placed on the surface of the semiconductor chip substrate 21 opposite to the surface where the adhesive coating layer 22a contacts, and the adhesive coating layer 22a is heated and hardened by the heating device to convert it into the adhesive layer 22 (Fig. 4C).
Next, as shown in Fig. 4D, the semiconductor chip substrates 21 fixed on the adhesive layer 22 are sealed with sealing resin 25. In Fig. 4D, the plurality of semiconductor chip substrates 21 temporarily adhered to the support substrate 24 via the adhesive layer 22 are sealed with sealing resin 25. An electronic device substrate 26 having the semiconductor chip substrates 21 and the sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22. In this way, the electronic device substrate 26 is a base layer in which the plurality of semiconductor chip substrates are embedded in the sealing resin.
The process shown in FIGS. 4A to 4D results in the laminate shown in FIG.

＜封止工程＞
　封止材を用いて、半導体チップ基板２１を封止する。
　半導体チップ基板２１を封止するための封止材としては、金属または半導体により構成される部材を絶縁または封止可能な部材が用いられる。
　本発明では、封止材として、例えば、樹脂組成物（封止樹脂）が用いられる。封止樹脂の種類としては、金属または半導体を封止および／または絶縁可能なものであれば、特に限定されないが、例えば、エポキシ系樹脂又はシリコーン系樹脂等を用いることが好ましい。
　封止材は、樹脂成分のほか、フィラー等の他の成分を含んでいてもよい。フィラーとしては、例えば、球状シリカ粒子等が挙げられる。
　封止工程においては、例えば１３０～１７０℃に加熱された封止樹脂が、高粘度の状態を維持しつつ、半導体チップ基板２１を覆うように、接着剤層２２上に供給され、圧縮成形されることによって、接着剤層２２上に封止樹脂２５からなる層が形成される。その際、温度条件は、例えば１３０～１７０℃である。また、半導体チップ基板２１に加えられる圧力は、例えば５０～５００Ｎ／ｃｍ２である。 <Sealing process>
The semiconductor chip substrate 21 is sealed using a sealing material.
As a sealing material for sealing the semiconductor chip substrate 21, a material capable of insulating or sealing a member made of metal or semiconductor is used.
In the present invention, for example, a resin composition (encapsulating resin) is used as the encapsulating material. The type of encapsulating resin is not particularly limited as long as it can encapsulate and/or insulate metals or semiconductors, but it is preferable to use, for example, an epoxy-based resin or a silicone-based resin.
The sealing material may contain other components such as a filler in addition to the resin component. Examples of the filler include spherical silica particles.
In the sealing process, sealing resin heated to, for example, 130 to 170°C is supplied onto adhesive layer 22 while maintaining a high viscosity, so as to cover semiconductor chip substrate 21, and is compression molded to form a layer made of sealing resin 25 on adhesive layer 22. The temperature condition at this time is, for example, 130 to 170°C. The pressure applied to semiconductor chip substrate 21 is, for example, 50 to 500 N/ cm2 .

（加工された半導体基板又は電子デバイス基板の製造方法）
　本発明に係る積層体を用いると、加工された半導体基板の製造方法、あるいは加工された電子デバイス基板の製造方法を提供することができる。
　本発明の加工された半導体基板又は電子デバイス基板の製造方法は、
　上記本発明の積層体における半導体基板又は電子デバイス基板（半導体基板等）が加工される第５工程と、
　前記第５工程によって加工された前記半導体基板又は前記電子デバイス基板（半導体基板等）と、積層体における支持基板とが分離される第６工程と、
を含むことを特徴とする。
　このように、本発明の加工された半導体基板の製造方法は、下記第５工程と、下記第６工程とを含む。加工された電子デバイス基板の製造方法は、更に、下記第７工程を含んでいてもよい。
　第５工程：本発明の積層体における半導体基板又は電子デバイス基板（半導体基板等）を加工する工程
　第６工程：第５工程によって加工された半導体基板又は電子デバイス基板（半導体基板等）と、支持基板とを分離する工程
　第７工程：第６工程の後に、加工された半導体基板又は電子デバイス基板を洗浄する工程 (Method for manufacturing processed semiconductor substrates or electronic device substrates)
The use of the laminate according to the present invention makes it possible to provide a method for producing a processed semiconductor substrate or a processed electronic device substrate.
The method for producing a processed semiconductor substrate or electronic device substrate of the present invention includes:
a fifth step in which the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the laminate of the present invention is processed;
a sixth step of separating the semiconductor substrate or the electronic device substrate (semiconductor substrate or the like) processed in the fifth step from a support substrate in a laminate;
The present invention is characterized by comprising:
Thus, the method for producing a processed semiconductor substrate of the present invention includes the following fifth step and the following sixth step. The method for producing a processed electronic device substrate may further include the following seventh step.
Fifth step: A step of processing the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the laminate of the present invention. Sixth step: A step of separating the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) processed in the fifth step from the support substrate. Seventh step: A step of cleaning the processed semiconductor substrate or electronic device substrate after the sixth step.

　第５工程において半導体基板又は電子デバイス基板（半導体基板等）に施される加工とは、例えば、ウエハーの回路面の反対側の加工であり、ウエハー裏面の研磨によるウエハーの薄化が挙げられる。その後、例えば、シリコン貫通電極（ＴＳＶ）等の形成を行い、その後に支持基板から薄化ウエハーを剥離してウエハーの積層体を形成し、３次元実装化される。また、例えば、それに前後してウエハー裏面電極等の形成も行われる。ウエハーの薄化とＴＳＶプロセスには支持基板に接着された状態で２５０～３５０℃程度の熱が負荷される。本発明の積層体は、通常、接着剤層を含め、その負荷に対する耐熱性を備えるものである。
　なお、加工は、上述したものに限定されず、例えば、半導体部品を実装するための基材をサポートするために支持基板と仮接着した場合の半導体部品の実装プロセスの実施等も含まれる。 The processing performed on the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) in the fifth step is, for example, processing of the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Thereafter, for example, through-silicon vias (TSVs) are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, for example, before or after this, wafer backside electrodes are formed. During the wafer thinning and TSV process, the wafer is subjected to a heat load of approximately 250 to 350°C while adhered to the support substrate. The laminate of the present invention, including the adhesive layer, typically has heat resistance to this load.
The processing is not limited to the above, and also includes, for example, the implementation of a semiconductor component mounting process when a substrate for mounting a semiconductor component is temporarily bonded to a support substrate to support the substrate.

　特に、積層体として、電子デバイス基板を有する積層体である場合には、第５工程において電子デバイス基板に施される加工とは、例えば、以下に記載の研削工程や配線層形成工程等が挙げられる。 In particular, when the laminate includes an electronic device substrate, the processing performed on the electronic device substrate in step 5 includes, for example, the grinding step and wiring layer formation step described below.

＜研削工程＞
　研削工程は、電子デバイス基板２６における封止樹脂２５の層の樹脂部分を、半導体チップ基板２１の一部が露出するように研削する工程である。 <Grinding process>
The grinding step is a step of grinding away the resin portion of the sealing resin 25 layer on the electronic device substrate 26 so that a part of the semiconductor chip substrate 21 is exposed.

＜配線層形成工程＞
　配線層形成工程は、上記研削工程の後、露出した半導体チップ基板２１上に配線層を形成する工程である。
　配線層は、ＲＤＬ（Ｒｅｄｉｓｔｒｉｂｕｔｉｏｎ　Ｌａｙｅｒ：再配線層）とも呼ばれ、基板に接続する配線を構成する薄膜の配線体であり、単層又は複数層の構造を有し得る。配線層は、誘電体（酸化シリコン（ＳｉＯｘ）、感光性エポキシ等の感光性樹脂など）の間に導電体（例えば、アルミニウム、銅、チタン、ニッケル、金及び銀等の金属並びに銀一錫合金等の合金）によって配線が形成されたものであり得るが、これに限定されない。
　配線層を形成する方法としては、例えば、以下の方法が挙げられる。
　まず、封止樹脂２５の層上に、酸化シリコン（ＳｉＯｘ）、感光性樹脂等の誘電体層を形成する。酸化シリコンからなる誘電体層は、例えばスパッタ法、真空蒸着法等により形成することができる。感光性樹脂からなる誘電体層は、例えばスピンコート、ディッピング、ローラーブレード、スプレー塗布、スリット塗布等の方法により、封止樹脂２５の層上に、感光性樹脂を塗布することで形成することができる。
　続いて、誘電体層に、金属等の導電体によって配線を形成する。配線を形成する方法としては、例えば、フォトリソグラフィー（レジストリソグラフィー）等のリソグラフィー処理、エッチング処理等の公知の半導体プロセス手法を用いることができる。このような、リソグラフィー処理としては、例えば、ポジ型レジスト材料を用いたリソグラフィー処理、ネガ型レジスト材料を用いたリソグラフィー処理が挙げられる。 <Wiring layer formation process>
The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor chip substrate 21 after the grinding step.
The wiring layer, also called an RDL (Redistribution Layer), is a thin-film wiring body that constitutes wiring connected to a substrate, and may have a single-layer or multi-layer structure. The wiring layer may be, but is not limited to, wiring formed by a conductor (e.g., metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) between dielectrics ( e.g. , silicon oxide (SiO x ), photosensitive resins such as photosensitive epoxy, etc.).
The wiring layer may be formed, for example, by the following method.
First, a dielectric layer made of silicon oxide (SiO x ), photosensitive resin, or the like is formed on the layer of sealing resin 25. The dielectric layer made of silicon oxide can be formed by, for example, sputtering, vacuum deposition, or the like. The dielectric layer made of photosensitive resin can be formed by applying the photosensitive resin onto the layer of sealing resin 25 by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like.
Subsequently, wiring is formed on the dielectric layer using a conductor such as a metal. Examples of methods for forming the wiring include known semiconductor processing techniques such as lithography (e.g., photolithography) and etching. Examples of such lithography include lithography using a positive resist material and lithography using a negative resist material.

　第６工程において、半導体基板又は電子デバイス基板と支持基板（半導体基板等）とを分離（剥離）する方法は、特に限定されない。
　例えば、鋭部を有する機材（いわゆるディボンダー）で機械的に剥離する方法が挙げられる。具体的には、例えば、半導体基板又は電子デバイス基板（半導体基板等）と支持基板との間に鋭部を挿入した後、半導体基板又は電子デバイス基板（半導体基板等）と支持基板とを分離する。 In the sixth step, the method for separating (peeling) the semiconductor substrate or electronic device substrate from the support substrate (semiconductor substrate or the like) is not particularly limited.
For example, mechanical peeling may be performed using equipment with a sharp part (a so-called debonder). Specifically, for example, the sharp part is inserted between the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the support substrate, and then the semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) is separated from the support substrate.

　分離した半導体基板又は電子デバイス基板（半導体基板等）及び支持基板の少なくともいずれかの表面に、洗浄剤組成物を吹き付けたり、分離した半導体基板又は電子デバイス基板（半導体基板等）又は支持基板を洗浄剤組成物に浸漬したりして基板を洗浄することができる。
　また、除去テープ等を用いて、加工された半導体基板等の表面を洗浄してもよい。
　基板の洗浄の一例として、第６工程の後に、加工された半導体基板等を洗浄する第７工程を行ってもよい。
　洗浄に用いる洗浄剤組成物は、以下のものが挙げられる。 The substrates can be cleaned by spraying the cleaning composition onto the surface of at least one of the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) and the supporting substrate, or by immersing the separated semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) or the supporting substrate in the cleaning composition.
Furthermore, the surface of the processed semiconductor substrate or the like may be cleaned using a removal tape or the like.
As an example of cleaning the substrate, a seventh step of cleaning the processed semiconductor substrate or the like may be performed after the sixth step.
Examples of detergent compositions used for cleaning include the following.

　洗浄剤組成物は、通常、溶媒を含む。
　溶媒としては、例えば、ラクトン類、ケトン類、多価アルコール類、エステル結合を有する化合物、多価アルコール類の誘導体、環式エーテル類、エステル類、芳香族系有機溶剤などが挙げられる。
　ラクトン類としては、例えば、γ－ブチロラクトンなどが挙げられる。
　ケトン類としては、例えば、アセトン、メチルエチルケトン、シクロヘキサノン、メチル－ｎ－ペンチルケトン、メチルイソペンチルケトン、２－ヘプタノンなどが挙げられる。
　多価アルコール類としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコールなどが挙げられる。
　エステル結合を有する化合物としては、例えば、エチレングリコールモノアセテート、ジエチレングリコールモノアセテート、プロピレングリコールモノアセテート、ジプロピレングリコールモノアセテートなどが挙げられる
　多価アルコール類の誘導体としては、例えば、上記多価アルコール類または上記エステル結合を有する化合物のモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテル等のモノアルキルエーテルまたはモノフェニルエーテル等のエーテル結合を有する化合物が挙げられる。これらの中では、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）が好ましい。
　環式エーテル類としては、例えば、ジオキサンなどが挙げられる。
　エステル類としては、例えば、乳酸メチル、乳酸エチル（ＥＬ）、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチルなどが挙げられる。
　芳香族系有機溶剤としては、例えば、アニソール、エチルベンジルエーテル、クレジルメチルエーテル、ジフェニルエーテル、ジベンジルエーテル、フェネトール、ブチルフェニルエーテル、エチルベンゼン、ジエチルベンゼン、ペンチルベンゼン、イソプロピルベンゼン、トルエン、キシレン、シメン、メシチレンなどが挙げられる。
　これらは、１種を単独で又は２種以上を組み合わせて使用することができる。
　これらの中でも、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）、シクロヘキサノン、乳酸エチル（ＥＬ）が好ましい。 The cleaning composition typically contains a solvent.
Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents.
Examples of lactones include γ-butyrolactone.
Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone.
Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.
Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers (e.g., monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether) or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.
Examples of cyclic ethers include dioxane.
Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.
Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, and mesitylene.
These may be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

　また、ＰＧＭＥＡと極性溶剤とを混合した混合溶媒も好ましい。その配合比（質量比）は、ＰＧＭＥＡと極性溶剤との相溶性等を考慮して適宜決定すればよいが、好ましくは１：９～９：１、より好ましくは２：８～８：２の範囲内とすることが好ましい。
　たとえば極性溶剤としてＥＬを配合する場合は、ＰＧＭＥＡ：ＥＬの質量比は、好ましくは１：９～９：１、より好ましくは２：８～８：２である。また、極性溶剤としてＰＧＭＥを配合する場合は、ＰＧＭＥＡ：ＰＧＭＥの質量比は、好ましくは１：９～９：１、より好ましくは２：８～８：２、さらに好ましくは３：７～７：３である。また、極性溶剤としてＰＧＭＥおよびシクロヘキサノンを配合する場合は、ＰＧＭＥＡ：（ＰＧＭＥ＋シクロヘキサノン）の質量比は、好ましくは１：９～９：１、より好ましくは２：８～８：２、さらに好ましくは３：７～７：３である。 A mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility of PGMEA with the polar solvent, and is preferably within a range of 1:9 to 9:1, and more preferably 2:8 to 8:2.
For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are blended as the polar solvents, the mass ratio of PGMEA:(PGME+cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

　洗浄剤組成物は、塩を含んでいてもよいし、塩を含んでいなくてもよいが、塩を含んでいないことが、積層体を用いた半導体基板の加工の際の汎用性が高くなる点、及びコストが抑えられる点で好ましい。 The cleaning composition may or may not contain salt, but a salt-free composition is preferred in that it will be more versatile when processing semiconductor substrates using the laminate and will help reduce costs.

　洗浄剤組成物が塩を含む場合の一例としては、第四級アンモニウム塩と、溶媒とを含む洗浄剤組成物が挙げられる。
　第四級アンモニウム塩は、第四級アンモニウムカチオンと、アニオンとから構成されるものであって、この種の用途に用いられるものであれば特に限定されるものではない。
　このような第四級アンモニウムカチオンとしては、典型的には、テトラ（炭化水素）アンモニウムカチオンが挙げられる。一方、それと対を成すアニオンとしては、水酸化物イオン（ＯＨ－）；フッ素イオン（Ｆ－）、塩素イオン（Ｃｌ－）、臭素イオン（Ｂｒ－）、ヨウ素イオン（Ｉ－）等のハロゲンイオン；テトラフルオロホウ酸イオン（ＢＦ４ －）；ヘキサフルオロリン酸イオン（ＰＦ６ －）等が挙げられるが、これらに限定されない。 An example of a cleaning composition containing a salt is a cleaning composition containing a quaternary ammonium salt and a solvent.
The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application.
Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations, while their counter anions include, but are not limited to, hydroxide ion (OH − ), halogen ions such as fluoride ion (F − ), chloride ion (Cl − ), bromide ion (Br − ), and iodide ion (I − ), tetrafluoroborate ion (BF 4 − ), and hexafluorophosphate ion (PF 6 − ).

　第四級アンモニウム塩は、好ましくは含ハロゲン第四級アンモニウム塩であり、より好ましくは含フッ素第四級アンモニウム塩である。
　第四級アンモニウム塩中、ハロゲン原子は、カチオンに含まれていても、アニオンに含まれていてもよいが、好ましくはアニオンに含まれる。 The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.
In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

　好ましい一態様においては、含フッ素第四級アンモニウム塩は、フッ化テトラ（炭化水素）アンモニウムである。
　フッ化テトラ（炭化水素）アンモニウムにおける炭化水素基の具体例としては、炭素原子数１～２０のアルキル基、炭素原子数２～２０のアルケニル基、炭素原子数２～２０のアルキニル基、炭素原子数６～２０のアリール基等が挙げられる。
　より好ましい一態様においては、フッ化テトラ（炭化水素）アンモニウムは、フッ化テトラアルキルアンモニウムを含む。
　フッ化テトラアルキルアンモニウムの具体例としては、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化テトラプロピルアンモニウム、フッ化テトラブチルアンモニウム（テトラブチルアンモニウムフルオリドともいう）等が挙げられるが、これらに限定されない。中でも、フッ化テトラブチルアンモニウムが好ましい。 In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.
Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.
In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.
Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.

　フッ化テトラ（炭化水素）アンモニウム等の第四級アンモニウム塩は、水和物を用いてもよい。また、フッ化テトラ（炭化水素）アンモニウム等の第四級アンモニウム塩は、１種単独で又は２種以上組み合わせて用いてもよい。
　第四級アンモニウム塩の量は、洗浄剤組成物に含まれる溶媒に溶解する限り特に制限されるものではないが、洗浄剤組成物に対して、通常０．１～３０質量％である。 The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more.
The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass based on the detergent composition.

　洗浄剤組成物が塩を含む場合、併用される溶媒としては、この種の用途に用いられ、かつ第四級アンモニウム塩等の塩を溶解するものであれば特に限定されるものではないが、優れた洗浄性を有する洗浄剤組成物を再現性よく得る観点、第四級アンモニウム塩等の塩を良好に溶解させて、均一性に優れる洗浄剤組成物を得る観点等から、好ましくは、洗浄剤組成物は、１種又は２種以上のアミド系溶媒を含む。 When a cleaning composition contains a salt, the solvent used in combination is not particularly limited, as long as it is suitable for this type of application and dissolves salts such as quaternary ammonium salts. However, from the perspective of reproducibly obtaining a cleaning composition with excellent cleaning properties, and from the perspective of successfully dissolving salts such as quaternary ammonium salts to obtain a cleaning composition with excellent uniformity, the cleaning composition preferably contains one or more amide solvents.

　アミド系溶媒の好適な一例としては、式（Ｚ）で表される酸アミド誘導体が挙げられる。
 A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

　式中、Ｒ０は、エチル基、プロピル基又はイソプロピル基を表し、エチル基、イソプロピル基が好ましく、エチル基がより好ましい。ＲＡ及びＲＢは、それぞれ独立して、炭素原子数１～４のアルキル基を表す。炭素原子数１～４のアルキル基は直鎖状、分岐鎖状、環状のいずれでもよく、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基等が挙げられる。これらのうち、ＲＡ及びＲＢとしては、メチル基又はエチル基が好ましく、ともにメチル基又はエチル基がより好ましく、ともにメチル基がより一層好ましい。 In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R A and R B are preferably a methyl group or an ethyl group, more preferably both are a methyl group or an ethyl group, and even more preferably both are a methyl group.

　式（Ｚ）で表される酸アミド誘導体としては、Ｎ，Ｎ－ジメチルプロピオンアミド、Ｎ，Ｎ－ジエチルプロピオンアミド、Ｎ－エチル－Ｎ－メチルプロピオンアミド、Ｎ，Ｎ－ジメチル酪酸アミド、Ｎ，Ｎ－ジエチル酪酸アミド、Ｎ－エチル－Ｎ－メチル酪酸アミド、Ｎ，Ｎ－ジメチルイソ酪酸アミド、Ｎ，Ｎ－ジエチルイソ酪酸アミド、Ｎ－エチル－Ｎ－メチルイソ酪酸アミド等が挙げられる。これらのうち、特に、Ｎ，Ｎ－ジメチルプロピオンアミド、Ｎ，Ｎ－ジメチルイソブチルアミドが好ましく、Ｎ，Ｎ－ジメチルプロピオンアミドがより好ましい。 Examples of acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, and N-ethyl-N-methylisobutyric acid amide. Of these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, with N,N-dimethylpropionamide being more preferred.

　式（Ｚ）で表される酸アミド誘導体は、対応するカルボン酸エステルとアミンの置換反応によって合成してもよいし、市販品を使用してもよい。 The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

　好ましいアミド系溶媒の他の一例としては、式（Ｙ）で表されるラクタム化合物が挙げられる。
 Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

　式（Ｙ）において、Ｒ１０１は水素原子又は炭素原子数１～６のアルキル基を表し、Ｒ１０２は炭素原子数１～６のアルキレン基を表す。炭素原子数１～６のアルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基等が挙げられ、炭素原子数１～６のアルキレン基の具体例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が挙げられるが、これらに限定されない。 In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include, but are not limited to, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

　式（Ｙ）で表されるラクタム化合物の具体例としては、α－ラクタム化合物、β－ラクタム化合物、γ－ラクタム化合物、δ－ラクタム化合物等を挙げることができ、これらは１種単独で又は２種以上を組み合わせて用いることができる。 Specific examples of lactam compounds represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, which can be used alone or in combination of two or more.

　好ましい一態様においては、式（Ｙ）で表されるラクタム化合物は、１－アルキル－２－ピロリドン（Ｎ－アルキル－γ－ブチロラクタム）を含み、より好ましい一態様においては、Ｎ－メチルピロリドン（ＮＭＰ）又はＮ－エチルピロリドン（ＮＥＰ）を含み、より一層好ましい一態様においては、Ｎ－メチルピロリドン（ＮＭＰ）を含む。 In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), and in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

　なお、本発明で用いる洗浄剤組成物は、溶媒として、水を含んでもよいが、基板の腐食等を回避する観点等から、通常、有機溶媒のみが、溶媒として意図して用いられる。なお、この場合において、塩の水和水や、有機溶媒に含まれる微量含まれる水が、洗浄剤組成物に含まれてしまうことまでもが、否定される訳ではない。本発明で用いる洗浄剤組成物の含水量は、通常５質量％以下である。 The cleaning composition used in the present invention may contain water as a solvent, but from the perspective of avoiding corrosion of the substrate, etc., typically only an organic solvent is intended to be used as the solvent. In this case, however, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is typically 5% by mass or less.

　本発明の加工された半導体基板又は電子デバイス基板（半導体基板等）の製造方法の上述の工程に関する構成要素及び方法的要素については、本発明の要旨を逸脱しない範囲であれば種々変更しても差し支えない。
　本発明の加工された半導体基板又は電子デバイス基板（半導体基板等）の製造方法は、上述の工程以外の工程を含んでもよい。 The constituent elements and methodological elements of the above-described steps of the method for manufacturing a processed semiconductor substrate or electronic device substrate (semiconductor substrate, etc.) of the present invention may be modified in various ways without departing from the spirit and scope of the present invention.
The method of manufacturing a processed semiconductor substrate or an electronic device substrate (such as a semiconductor substrate) of the present invention may include steps other than those described above.

（プライマー皮膜形成用組成物）
　本発明のプライマー皮膜形成用組成物は、ヒドロシリル化反応によって硬化する接着剤成分を含有する接着剤組成物から形成される接着剤層と基板との接着力を高めるためのプライマー皮膜形成用組成物であって、前記ヒドロシリル化反応に寄与する成分を含有する組成物であり、詳しくは、上記（積層体）中の＜プライマー皮膜＞の＜＜プライマー皮膜形成用組成物＞＞の欄で記載したとおりである。
　プライマー皮膜形成用組成物が、該プライマー皮膜形成用組成物を介して、基板との接着性を高める対象である、接着剤層とは、上記（積層体）中の＜接着剤層＞の欄で記載したとおりである。 (Primer film-forming composition)
The primer coating composition of the present invention is a primer coating composition for increasing the adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction, and is a composition containing a component that contributes to the hydrosilylation reaction, as described in detail above in the section <<Primer coating composition>> of <<Primer coating>> in (Laminate)>.
The adhesive layer, which is the target of the primer coating-forming composition for increasing the adhesion to the substrate via the primer coating-forming composition, is as described in the <Adhesive Layer> section in the above (Laminate).

　以下、実施例を挙げて本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、使用した装置は以下のとおりである。 The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples. The equipment used is as follows:

［装置］
（１）撹拌機Ａ：（株）シンキー製、自転公転ミキサー　ＡＲＥ―５００
（２）撹拌機Ｂ：アズワン（株）　ミックスローター　ＶＭＲ－５Ｒ
（３）撹拌機Ｃ：新東科学（株）スリーワンモーター　ＢＬＷ－６００
（４）スピン塗布装置：ＡＰＯＧＥＥ（株）製　コーター
（５）複素粘度の測定：アントンパール（株）製　レオメータＭＣＲ－３０２
（６）真空貼り合わせ装置：ズースマイクロテック（株）製　オートボンダー
（７）剥離装置Ｙ：ズースマイクロテック（株）製　オートデボンダー [Device]
(1) Mixer A: ARE-500 planetary centrifugal mixer, manufactured by Thinky Corporation
(2) Agitator B: AS ONE Corporation Mix Rotor VMR-5R
(3) Mixer C: Shinto Scientific Co., Ltd. Three-One Motor BLW-600
(4) Spin coating device: Coater manufactured by APOGEE Co., Ltd. (5) Measurement of complex viscosity: Rheometer MCR-302 manufactured by Anton Paar Co., Ltd.
(6) Vacuum bonding device: Autobonder manufactured by SUSS MicroTec Co., Ltd. (7) Peeling device Y: Autodebonder manufactured by SUSS MicroTec Co., Ltd.

［１］プライマー皮膜形成用組成物（接着補助剤組成物）の調製
［調製例１－１］
　１００ｍＬの蓋付きガラス容器に、下記式（Ｘ－１）で示されるＴｅｔｒａｋｉｓ（ｔｒｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｅ）ｐｌａｔｉｎｕｍ（東京化成工業（株）製）０．０１ｇ及びプロピレングリコールモノメチルエーテル４９．９９５ｇ、プロピレングリコールモノメチルエーテルアセテート４９．９９５ｇを加え、撹拌機Ａで５分間撹拌し、プライマー皮膜形成用組成物（以下、接着補助剤組成物ともいう）を得た。 [1] Preparation of primer film-forming composition (adhesion aid composition) [Preparation Example 1-1]
To a 100 mL glass container with a lid, 0.01 g of Tetrakis(triphenylphosphine) platinum (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (X-1), 49.995 g of propylene glycol monomethyl ether, and 49.995 g of propylene glycol monomethyl ether acetate were added, and the mixture was stirred for 5 minutes with Stirrer A to obtain a composition for forming a primer film (hereinafter also referred to as an adhesion aid composition).

［調製例１－２］
　１００ｍＬの蓋付きガラス容器に、下記式（Ｘ－２）で示されるＯｃｔａｋｉｓ（ｄｉｍｅｔｈｙｌｓｉｌｙｌｏｘｙ）ｏｃｔａｓｉｌｓｅｓｑｕｉｏｘａｎｅ（東京化成工業（株）製）０．０１ｇ及びプロピレングリコールモノメチルエーテルアセテート９９．９９ｇを加え、撹拌機Ａで５分間撹拌し、接着補助剤組成物を得た。 [Preparation Example 1-2]
To a 100 mL glass container with a lid, 0.01 g of Octakis(dimethylsilyloxy)octasilsesquioxane (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (X-2) and 99.99 g of propylene glycol monomethyl ether acetate were added, and the mixture was stirred with Stirrer A for 5 minutes to obtain an adhesive auxiliary composition.

［調製例１－３］
　１００ｍＬの蓋付きガラス容器に、下記式（Ｘ－３）で示されるＢｉｓ（２，４－ｐｅｎｔａｎｅｄｉｏｎａｔｏ）ｐｌａｔｉｎｕｍ（東京化成工業（株）製）０．０１ｇ及びｐ－メンタン４９．９９５ｇ、プロピレングリコールモノメチルエーテルアセテート４９．９９５ｇを加え、撹拌機Ａで５分間撹拌し、接着補助剤組成物を得た。 [Preparation Example 1-3]
To a 100 mL glass container with a lid, 0.01 g of Bis(2,4-pentanedionato)platinum (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (X-3), 49.995 g of p-menthane, and 49.995 g of propylene glycol monomethyl ether acetate were added, and the mixture was stirred with Stirrer A for 5 minutes to obtain an adhesion auxiliary composition.

［調製例１－４］
　１００ｍＬの蓋付きガラス容器に、下記式（Ｘ－４）で示される白金（０）－１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体溶液（Ｓｉｇｍａ－Ａｌｄｒｉｃｈ製）０．０１ｇ及びｐ－メンタン９９．９９ｇを加え、撹拌機Ａで５分間撹拌し、接着補助剤組成物を得た。 [Preparation Example 1-4]
To a 100 mL glass container with a lid, 0.01 g of a platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution represented by the following formula (X-4) (manufactured by Sigma-Aldrich) and 99.99 g of p-menthane were added, and the mixture was stirred for 5 minutes with Stirrer A to obtain an adhesion promoter composition.

［調製例１－５］
　１００ｍＬの蓋付きガラス容器に、下記式（ＸＲ－１）で示される［Ｂｉｃｙｃｌｏ［２．２．１］ｈｅｐｔ－５－ｅｎ－２－ｙｌ］ｔｒｉｅｔｈｏｘｙｓｉｌａｎｅ（Ｇｅｌｅｓｔ　Ｉｎｃ．）０．０１ｇ及びプロピレングリコールモノメチルエーテルアセテート９９．９９ｇを加え、撹拌機Ａで５分間撹拌し、接着補助剤組成物を得た。 [Preparation Example 1-5]
To a 100 mL glass container with a lid, 0.01 g of [Bicyclo[2.2.1]hept-5-en-2-yl]triethoxysilane (Gelest Inc.) represented by the following formula (XR-1) and 99.99 g of propylene glycol monomethyl ether acetate were added, and the mixture was stirred with Stirrer A for 5 minutes to obtain an adhesive auxiliary composition.

［調製例１－６］
　１００ｍＬの蓋付きガラス容器に、［Ｂｉｃｙｃｌｏ［２．２．１］ｈｅｐｔ－５－ｅｎ－２－ｙｌ］ｔｒｉｅｔｈｏｘｙｓｉｌａｎｅ（Ｇｅｌｅｓｔ　Ｉｎｃ．）０．１ｇ及びプロピレングリコールモノメチルエーテルアセテート９９．９ｇを加え、撹拌機Ａで５分間撹拌し、接着補助剤組成物を得た。 [Preparation Example 1-6]
To a 100 mL glass container with a lid, 0.1 g of [Bicyclo[2.2.1]hept-5-en-2-yl]triethoxysilane (Gelest Inc.) and 99.9 g of propylene glycol monomethyl ether acetate were added and stirred with Stirrer A for 5 minutes to obtain an adhesive auxiliary composition.

   

［２］接着剤組成物の調製
［調製例２－１］
　５０ｍＬの蓋付きガラス容器に、１，１－ジフェニル－２－プロピン－１－オール（東京化成工業（株）製）１．６７ｇ及び１－エチニル－１－シクロヘキサノール（ワッカーケミ社製）１．６７ｇを加え、撹拌機Ａで５分間撹拌することで、混合物（Ｉ）を得た。
　次に２００ｍＬの蓋付きガラス容器に、ポリオルガノシロキサン（複素粘度６０００Ｐａ・ｓ、重量平均分子量６４２，０００（分散度２．６）、ワッカーケミ社製　商品名ＧＥＮＩＯＰＬＡＳＴ　ＧＵＭ）４７．８４ｇ、粘度１００ｍＰａ・ｓのＳｉＨ基含有直鎖状ポリジメチルシロキサン（ワッカーケミ社製）１００．１８ｇ及びｐ‐メンタン（日本テルペン化学（株）製）９．７７ｇを加え、撹拌機Ａで混合物が均一になるまで撹拌することで混合物（ＩＩ）を得た。
　続いて、１Ｌの蓋付きプラスチック容器に、ビニル基含有ＭＱ樹脂（ワッカーケミ社製）のｐ－メンタン溶液（濃度８１．２質量％）９２１．１４ｇ、白金触媒（ワッカーケミ社製）０．２ｇを加え、撹拌機Ｂを用いて混合物が均一になるまで撹拌することで混合物（ＩＩＩ）を得た。
　次に、１Ｌの蓋付きプラスチック容器に、混合物（Ｉ）を１．６７ｇ、別途ビニル基含有ＭＱ樹脂（ワッカーケミ社製）、粘度２００ｍＰａ・ｓのビニル基含有直鎖状ポリジメチルシロキサン（ワッカーケミ社製）、粘度１００ｍＰａ・ｓのＳｉＨ基含有直鎖状ポリジメチルシロキサン（ワッカーケミ社製）を５１．６：３８．９：９．５の比率で混合した溶液１５７．６７ｇ、混合液（ＩＩ）１３１．４９ｇを加え、撹拌機Ｂを用いて混合物が均一になるまで撹拌した。
　そこに、混合液（ＩＩＩ）６１４．２３ｇ、エポキシ変性シリコーンオイル（信越化学工業（株）製　商品名Ｘ－２２－３４３）７．９７ｇ及びｐ‐メンタン（日本テルペン化学（株）製）２１．７２ｇを加え、撹拌機Ｂを用いて混合物が均一になるまで撹拌した。
　最後に、得られた混合物をナイロンフィルター３００メッシュでろ過し、接着剤組成物を得た。 [2] Preparation of adhesive composition [Preparation Example 2-1]
To a 50 mL glass container with a lid, 1.67 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.67 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added, and the mixture was stirred for 5 minutes with Stirrer A to obtain a mixture (I).
Next, to a 200 mL glass container with a lid, 47.84 g of polyorganosiloxane (complex viscosity 6000 Pa s, weight average molecular weight 642,000 (dispersity 2.6), trade name GENIOPLAST GUM manufactured by Wacker Chemie) and 100.18 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa s and 9.77 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were added, and the mixture was stirred with a stirrer A until the mixture became uniform to obtain a mixture (II).
Subsequently, 921.14 g of a p-menthane solution (concentration: 81.2% by mass) of a vinyl group-containing MQ resin (manufactured by Wacker Chemical Co.) and 0.2 g of a platinum catalyst (manufactured by Wacker Chemical Co.) were added to a 1 L plastic container with a lid, and the mixture was stirred using a stirrer B until it became uniform, thereby obtaining a mixture (III).
Next, 1.67 g of mixture (I), 157.67 g of a solution prepared by mixing a vinyl group-containing MQ resin (manufactured by Wacker Chemical Co.), a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa·s (manufactured by Wacker Chemical Co.), and a SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa·s (manufactured by Wacker Chemical Co.) in a ratio of 51.6:38.9:9.5, and 131.49 g of mixed liquid (II) were added to a 1 L plastic container with a lid, and the mixture was stirred using stirrer B until it became uniform.
To this mixture, 614.23 g of the mixed solution (III), 7.97 g of epoxy-modified silicone oil (trade name X-22-343, manufactured by Shin-Etsu Chemical Co., Ltd.), and 21.72 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were added, and the mixture was stirred using stirrer B until it became uniform.
Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

［３］積層体の作製
［実施例１－１］
　調製例１－１で得られた接着補助剤組成物を、キャリア側の基板として３００ｍｍのシリコンウエハー（厚さ７７５μｍ）に回転数１５００ｒｐｍで６０秒間スピンコートし、支持基板であるシリコンウエハー上にプライマー皮膜（接着補助剤塗布膜ともいう）を形成した。
　一方、調製例２－１で得られた接着剤組成物をデバイス側の基板として３００ｍｍのシリコンウエハー（厚さ７７５μｍ）に、最終的に得られる積層体中の膜厚が５０μｍとなるようにスピンコートし、半導体基板であるシリコンウエハー上に接着剤塗布層を形成した。
　そして、貼り合せ装置を用いて、接着補助剤塗布膜を形成した支持基板と接着剤塗布層を形成した半導体基板を、接着補助剤塗布膜及び接着剤塗布層を挟み込むように貼り合わせた後、１３０℃５分間及び２００℃５分間の加熱処理をすることにより積層体を作製した。なお、貼り合せは、温度２３℃、減圧度１，０００Ｐａで、３０Ｎの荷重をかけて行った。 [3] Preparation of laminate [Example 1-1]
The adhesive auxiliary composition obtained in Preparation Example 1-1 was spin-coated onto a 300 mm silicon wafer (thickness: 775 μm) as a carrier-side substrate at a rotation speed of 1500 rpm for 60 seconds to form a primer film (also referred to as an adhesive auxiliary coating film) on the silicon wafer as a supporting substrate.
On the other hand, the adhesive composition obtained in Preparation Example 2-1 was spin-coated onto a 300 mm silicon wafer (thickness 775 μm) as the device-side substrate so that the film thickness in the final laminate was 50 μm, forming an adhesive coating layer on the silicon wafer, which was the semiconductor substrate.
Then, using a bonding device, the support substrate on which the adhesion auxiliary agent coating film was formed and the semiconductor substrate on which the adhesive coating layer was formed were bonded together so as to sandwich the adhesion auxiliary agent coating film and the adhesive coating layer, and then a laminate was produced by heat treatment at 130° C. for 5 minutes and at 200° C. for 5 minutes. The bonding was performed at a temperature of 23° C., a reduced pressure of 1,000 Pa, and a load of 30 N.

［実施例１－２］
　調製例１－１で得られた接着補助剤組成物の代わりに、調製例１－２で得られた接着補助組成物を用いた以外は、実施例１－１と同様の方法で積層体を得た。 [Example 1-2]
A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-2 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.

［実施例１－３］
　調製例１－１で得られた接着補助剤組成物の代わりに、調製例１－３で得られた接着補助組成物を用いた以外は、実施例１－１と同様の方法で積層体を得た。 [Examples 1-3]
A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-3 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.

［実施例１－４］
　調製例１－１で得られた接着補助剤組成物の代わりに、調製例１－４で得られた接着補助組成物を用いた以外は、実施例１－１と同様の方法で積層体を得た。 [Examples 1-4]
A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-4 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.

［比較例１－１］
　調製例１－１で得られた接着補助剤組成物の代わりに、調製例１－５で得られた接着補助組成物を用いた以外は、実施例１－１と同様の方法で積層体を得た。 [Comparative Example 1-1]
A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-5 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.

［比較例１－２］
　調製例１－１で得られた接着補助剤組成物の代わりに、調製例１－６で得られた接着補助組成物を用いた以外は、実施例１－１と同様の方法で積層体を得た。 [Comparative Example 1-2]
A laminate was obtained in the same manner as in Example 1-1, except that the adhesion auxiliary composition obtained in Preparation Example 1-6 was used instead of the adhesion auxiliary agent composition obtained in Preparation Example 1-1.

［比較例１－３］
　調製例１－１で得られた接着補助剤組成物を使用せず、キャリア側の基板に接着補助剤塗布層を形成しない支持基板を用いた以外は、実施例１－１と同様の方法で積層体を得た。 [Comparative Examples 1-3]
A laminate was obtained in the same manner as in Example 1-1, except that the adhesive auxiliary agent composition obtained in Preparation Example 1-1 was not used and a support substrate on which no adhesive auxiliary agent coating layer was formed was used as the substrate on the carrier side.

［４］接着性の評価
　得られた積層体を用いて剥離後の残渣の様子を確認した。具体的には、剥離装置Ｙを用いて支持基板と半導体基板を剥離した後のキャリア側（支持基板側）のウエハー上、及びデバイス側（半導体基板側）のウエハー上の膜の有無を確認した。その結果、実施例１－１、１－２、１－３、１－４の積層体に関しては、デバイス側のウエハー上に膜が確認されず、キャリア側のウエハー上に接着層の膜が残ったのに対し、比較例１－１、１－２、１－３の積層体に関しては、デバイス側のウエハー上に接着層の膜が確認された。
　このように、本発明のプライマー皮膜形成用組成物（接着補助剤組成物）を用いた場合は、接着剤組成物の接着力が向上し、プライマー皮膜形成用組成物（接着補助剤組成物）を表面に塗布した支持基板とは反対側のデバイス側（半導体基板側）で界面剥離を生じさせ、積層体の剥離後に接着剤組成物の膜がプライマー皮膜形成用組成物（接着補助剤組成物）を塗布した支持基板側に残ることが確認できた。 [4] Evaluation of Adhesion The state of residue after peeling was confirmed using the obtained laminate. Specifically, the presence or absence of a film on the wafer on the carrier side (support substrate side) and on the wafer on the device side (semiconductor substrate side) after peeling the support substrate and semiconductor substrate using peeling device Y was confirmed. As a result, for the laminates of Examples 1-1, 1-2, 1-3, and 1-4, no film was observed on the wafer on the device side, and a film of the adhesive layer remained on the wafer on the carrier side, whereas for the laminates of Comparative Examples 1-1, 1-2, and 1-3, a film of the adhesive layer was observed on the wafer on the device side.
In this way, it was confirmed that when the primer film-forming composition (adhesion auxiliary composition) of the present invention is used, the adhesive strength of the adhesive composition is improved, interfacial peeling occurs on the device side (semiconductor substrate side) opposite to the support substrate on whose surface the primer film-forming composition (adhesion auxiliary composition) has been applied, and after peeling of the laminate, a film of the adhesive composition remains on the support substrate side on which the primer film-forming composition (adhesion auxiliary composition) has been applied.

　上記の結果から、プライマー皮膜を支持基板側、あるいは半導体基板又は電子デバイス基板側のいずれに配するか選択することで、支持基板を半導体基板又は電子デバイス基板から剥がす際、剥離する場所（剥離界面）をコントロールすることができる。 The above results show that by choosing whether to place the primer film on the support substrate side or on the semiconductor substrate or electronic device substrate side, it is possible to control the location of peeling (peeling interface) when peeling the support substrate from the semiconductor substrate or electronic device substrate.

　１　　　半導体基板
　２　　　接着剤層
　２ａ　　接着剤塗布層
　３　　　プライマー皮膜
　４　　　支持基板
　２１　　半導体チップ基板
　２２　　接着剤層
　２２ａ　接着剤塗布層
　２３　　プライマー皮膜
　２４　　支持基板
　２５　　封止樹脂
　２６　　電子デバイス基板 REFERENCE SIGNS LIST 1 Semiconductor substrate 2 Adhesive layer 2a Adhesive coating layer 3 Primer film 4 Support substrate 21 Semiconductor chip substrate 22 Adhesive layer 22a Adhesive coating layer 23 Primer film 24 Support substrate 25 Sealing resin 26 Electronic device substrate

Claims (11)

　ヒドロシリル化反応によって硬化する接着剤成分を含有する接着剤組成物から形成される接着剤層と基板との接着力を高めるためのプライマー皮膜形成用組成物であって、
　前記ヒドロシリル化反応に寄与する成分を含有するプライマー皮膜形成用組成物。 A primer coating-forming composition for enhancing adhesive strength between a substrate and an adhesive layer formed from an adhesive composition containing an adhesive component that cures by a hydrosilylation reaction, comprising:
A primer film-forming composition containing a component that contributes to the hydrosilylation reaction. 　前記プライマー皮膜形成用組成物は、前記ヒドロシリル化反応に寄与する成分として、白金を含む化合物、Ｓｉ－Ｈ基を含む化合物、及びビニル基を含む化合物のいずれかから選ばれる成分を含有する、請求項１に記載のプライマー皮膜形成用組成物。 The primer film-forming composition according to claim 1, wherein the primer film-forming composition contains, as a component that contributes to the hydrosilylation reaction, a component selected from the group consisting of a platinum-containing compound, a Si-H group-containing compound, and a vinyl group-containing compound. 　前記接着剤層を形成する接着剤組成物は、前記接着剤成分と、剥離剤成分とを含有する、請求項１に記載のプライマー皮膜形成用組成物。 The primer coating composition according to claim 1, wherein the adhesive composition forming the adhesive layer contains the adhesive component and a release agent component. 　前記剥離剤成分が、ポリオルガノシロキサンを含む、請求項３に記載のプライマー皮膜形成用組成物。 The primer film-forming composition according to claim 3, wherein the release agent component includes polyorganosiloxane. 　前記ヒドロシリル化反応によって硬化する接着剤成分が、
　　ケイ素原子に結合した炭素原子数２～４０のアルケニル基を有する成分（Ａ－１）と、
　　Ｓｉ－Ｈ基を有する成分（Ａ－２）と、
　　白金族金属系触媒（Ａ－３）と
を含有する、請求項１に記載のプライマー皮膜形成用組成物。 The adhesive component that cures by a hydrosilylation reaction is
Component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom;
a component (A-2) having an Si—H group;
The primer coating composition according to claim 1, further comprising a platinum group metal catalyst (A-3). 　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層とを有し、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面にプライマー皮膜が形成されており、
　前記プライマー皮膜は、請求項１から５のいずれかに記載のプライマー皮膜形成用組成物から形成されたプライマー皮膜である、積層体。 A support substrate;
a semiconductor substrate or an electronic device substrate;
an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate,
a primer coating is formed on a surface of any one of the semiconductor substrate or the electronic device substrate and the support substrate;
A laminate, wherein the primer film is a primer film formed from the composition for forming a primer film according to claim 1 . 　前記プライマー皮膜は、前記支持基板の表面に形成されている、請求項６に記載の積層体。 The laminate described in claim 6, wherein the primer coating is formed on the surface of the support substrate. 　支持基板と、
　半導体基板又は電子デバイス基板と、
　前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に設けられた、接着剤層と、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面に形成されたプライマー皮膜と、を有する積層体の製造方法であって、
　前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板表面に、請求項１から５のいずれかに記載のプライマー皮膜形成用組成物を塗布することによりプライマー皮膜を形成する工程、
を含む積層体の製造方法。 A support substrate;
a semiconductor substrate or an electronic device substrate;
an adhesive layer provided between the semiconductor substrate or the electronic device substrate and the support substrate;
a primer coating formed on a surface of either the semiconductor substrate or the electronic device substrate, or the support substrate, the method comprising:
a step of forming a primer film by applying the primer film-forming composition according to any one of claims 1 to 5 to a surface of the semiconductor substrate or the electronic device substrate and the support substrate;
A method for producing a laminate comprising the steps of: 　さらに、前記プライマー皮膜が形成されていない、前記半導体基板又は前記電子デバイス基板、及び前記支持基板のいずれかの基板に対し、前記接着剤層を形成するための接着剤組成物を塗布する工程、
　前記プライマー皮膜が形成された基板と、前記接着剤組成物が塗布されている基板とを貼り合わせ、その後加熱処理を行うことにより、前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に接着剤層を形成する工程、
を含む、請求項８に記載の積層体の製造方法。 Furthermore, a step of applying an adhesive composition for forming the adhesive layer to any one of the semiconductor substrate or the electronic device substrate and the support substrate on which the primer film is not formed;
a step of bonding a substrate on which the primer film has been formed and a substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate;
The method for producing the laminate according to claim 8, comprising: 　支持基板の表面に、請求項１から５のいずれかに記載のプライマー皮膜形成用組成物を塗布することによりプライマー皮膜を形成する工程、
　半導体基板又は電子デバイス基板に対し、接着剤層を形成するための接着剤組成物を塗布する工程、
　前記プライマー皮膜が形成された前記支持基板と、前記接着剤組成物が塗布されている前記半導体基板又は前記電子デバイス基板とを貼り合わせ、その後加熱処理を行うことにより、前記半導体基板又は前記電子デバイス基板と、前記支持基板との間に接着剤層を形成する工程、
を含む、請求項９に記載の積層体の製造方法。 A step of forming a primer film by applying the primer film-forming composition according to any one of claims 1 to 5 to the surface of a supporting substrate;
applying an adhesive composition to a semiconductor substrate or an electronic device substrate to form an adhesive layer;
a step of bonding the support substrate on which the primer film has been formed and the semiconductor substrate or the electronic device substrate on which the adhesive composition has been applied, and then performing a heat treatment to form an adhesive layer between the semiconductor substrate or the electronic device substrate and the support substrate;
The method for producing the laminate according to claim 9, comprising: 　加工された半導体基板又は電子デバイス基板の製造方法であって、
　請求項６に記載の積層体の前記半導体基板又は前記電子デバイス基板が加工される第５工程と、
　前記第５工程によって加工された前記半導体基板又は前記電子デバイス基板と、前記支持基板とが分離される第６工程と、
を含む、加工された半導体基板又は電子デバイス基板の製造方法。

  1. A method for manufacturing a processed semiconductor substrate or electronic device substrate, comprising:
a fifth step of processing the semiconductor substrate or the electronic device substrate of the laminate according to claim 6;
a sixth step of separating the semiconductor substrate or the electronic device substrate processed in the fifth step from the support substrate;
1. A method for producing a processed semiconductor substrate or electronic device substrate, comprising:
PCT/JP2025/010327 2024-03-19 2025-03-18 Composition for forming primer film, laminate, method for producing laminate, and method for producing processed semiconductor substrate or electronic device substrate Pending WO2025197877A1 (en)

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JP2011119427A (en) * 2009-12-03 2011-06-16 Shin-Etsu Chemical Co Ltd Method of manufacturing stacked semiconductor integrated device
JP2012149240A (en) * 2010-12-31 2012-08-09 Dow Corning Toray Co Ltd Primer composition for silicone adhesive, laminate, and silicone adhesive tape
WO2016136244A1 (en) * 2015-02-26 2016-09-01 東レ・ダウコーニング株式会社 Primer composition, bonding method, and electric/electronic component
WO2022226796A1 (en) * 2021-04-27 2022-11-03 Dow Silicones Corporation Silicone pressure sensitive adhesive, composition and method for its preparation, and use in a flexible display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010260893A (en) * 2009-04-30 2010-11-18 Nitto Denko Corp LAMINATED FILM AND METHOD FOR MANUFACTURING SEMICONDUCTOR DEVICE
JP2011119427A (en) * 2009-12-03 2011-06-16 Shin-Etsu Chemical Co Ltd Method of manufacturing stacked semiconductor integrated device
JP2012149240A (en) * 2010-12-31 2012-08-09 Dow Corning Toray Co Ltd Primer composition for silicone adhesive, laminate, and silicone adhesive tape
WO2016136244A1 (en) * 2015-02-26 2016-09-01 東レ・ダウコーニング株式会社 Primer composition, bonding method, and electric/electronic component
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