WO2025197877A1 - Composition pour former un film d'apprêt, stratifié, procédé de production de stratifié, et procédé de production de substrat semi-conducteur ou substrat de dispositif électronique traité - Google Patents

Composition pour former un film d'apprêt, stratifié, procédé de production de stratifié, et procédé de production de substrat semi-conducteur ou substrat de dispositif électronique traité

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
English (en)
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/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices

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

La présente invention concerne, par exemple, un stratifié qui comprend un substrat de support, un substrat semi-conducteur ou un substrat de dispositif électronique, et une couche adhésive qui est disposée entre le substrat semi-conducteur ou le substrat de dispositif électronique et le substrat de support, et avec laquelle il est possible de commander l'interface de séparation lorsqu'une tranche semi-conductrice est séparée du substrat de support.　Ce stratifié comprend un substrat de support, un substrat semi-conducteur ou un substrat de dispositif électronique, et une couche adhésive qui est disposée entre le substrat semi-conducteur ou le substrat de dispositif électronique et le substrat de support, un film d'apprêt étant formé sur une surface de substrat de l'un du substrat semi-conducteur, du substrat de dispositif électronique et du substrat de support, et le film d'apprêt étant formé d'une composition pour former un film d'apprêt pour améliorer l'adhérence entre un substrat et une couche adhésive qui est formée d'une composition adhésive qui contient un composant adhésif qui est durci par une réaction d'hydrosilylation, la composition pour former un film d'apprêt contenant un composant qui contribue à la réaction d'hydrosilylation.
PCT/JP2025/010327 2024-03-19 2025-03-18 Composition pour former un film d'apprêt, stratifié, procédé de production de stratifié, et procédé de production de substrat semi-conducteur ou substrat de dispositif électronique traité Pending WO2025197877A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010260893A (ja) * 2009-04-30 2010-11-18 Nitto Denko Corp 積層フィルム及び半導体装置の製造方法
JP2011119427A (ja) * 2009-12-03 2011-06-16 Shin-Etsu Chemical Co Ltd 積層型半導体集積装置の製造方法
JP2012149240A (ja) * 2010-12-31 2012-08-09 Dow Corning Toray Co Ltd シリコーン粘着剤用プライマー組成物、積層体およびシリコーン粘着テープ
WO2016136244A1 (fr) * 2015-02-26 2016-09-01 東レ・ダウコーニング株式会社 Composition d'amorce, procédé de liaison, et composant électrique/électronique
WO2022226796A1 (fr) * 2021-04-27 2022-11-03 Dow Silicones Corporation Adhésif silicone sensible à la pression, composition et procédé pour sa préparation et son utilisation dans un dispositif d'affichage flexible

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010260893A (ja) * 2009-04-30 2010-11-18 Nitto Denko Corp 積層フィルム及び半導体装置の製造方法
JP2011119427A (ja) * 2009-12-03 2011-06-16 Shin-Etsu Chemical Co Ltd 積層型半導体集積装置の製造方法
JP2012149240A (ja) * 2010-12-31 2012-08-09 Dow Corning Toray Co Ltd シリコーン粘着剤用プライマー組成物、積層体およびシリコーン粘着テープ
WO2016136244A1 (fr) * 2015-02-26 2016-09-01 東レ・ダウコーニング株式会社 Composition d'amorce, procédé de liaison, et composant électrique/électronique
WO2022226796A1 (fr) * 2021-04-27 2022-11-03 Dow Silicones Corporation Adhésif silicone sensible à la pression, composition et procédé pour sa préparation et son utilisation dans un dispositif d'affichage flexible

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