Adhesive composition, laminate, and method for manufacturing processed semiconductor substrate

Abstract

An adhesive composition which contains an adhesive component and a methanol-modified polyorganosiloxane.

Description

TECHNICAL FIELD

[0001] The present application relates to an adhesive composition, a laminate, and a manufacturing method of a processed semiconductor substrate. BACKGROUND

[0002] As for a semiconductor wafer integrated in two-dimensional planar direction in the past, a semiconductor integration technology of further integrating the planar direction to three-dimensional direction (lamination) is pursued for the purpose of further integration. The three-dimensional lamination is a technology of integrating to multiple layers while wiring through a silicon via (TSV: through silicon via). At the time of integration to multiple layers, each wafer to be integrated is thinned by polishing the side opposite to the circuit surface (i.e., back surface) formed, and the thinned semiconductor wafers are laminated.

[0003] The semiconductor wafer before thinning (hereinafter also referred to simply as wafer) is adhered to a support for polishing by a polishing device. The adhesion at this time must be easy to peel after polishing, and is therefore called temporary adhesion. The temporary adhesion must be easy to detach from the support, and when a large force is applied to the detachment, the thinned semiconductor wafer is sometimes cut or deformed, and is easy to detach in order not to cause such a situation. However, when the back surface of the semiconductor wafer is polished, it is not preferable to be detached or deviated due to polishing stress. Therefore, the performance pursued for the temporary adhesion is to withstand the stress at the time of polishing and to be easy to detach after polishing.

[0004] As a temporary adhesive for such temporary adhesion, an adhesive containing polydimethylsiloxane (Patent Literature 1), a temporary adhesive containing an epoxy-modified polysiloxane (Patent Literature 2), and the like are proposed.

[0005] PRIOR ART DOCUMENTS PATENT LITERATURE Patent Literature 1: International Publication No. 2017 / 221772 Patent Literature 2: International Publication No. 2018 / 216732 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present application is to provide an adhesive composition capable of forming an adhesive layer excellent in peelability, a laminate using the adhesive composition, and a manufacturing method of a processed semiconductor substrate or an electronic device layer using the laminate.

[0007] SOLUTION TO PROBLEM The present inventors and others have conducted intensive studies in order to solve the technical problem described above, and as a result, have found that the technical problem described above can be solved, and have completed the present application having the following gist.

[0008] That is, the present application includes the following.

[0009] [1] An adhesive composition containing an adhesive component and a methanol-modified polyorganosiloxane.

[0010] [2] The adhesive composition according to [1], wherein the methanol-modified polyorganosiloxane is a methanol-modified polydimethylsiloxane.

[0011] [3] The adhesive composition according to [1] or [2], wherein the methanol-modified polyorganosiloxane has a hydroxyl group directly bonded to a carbon atom in a side chain.

[0012] [4] The adhesive composition according to any one of [1] to [3], wherein the methanol-modified polyorganosiloxane has a hydroxyl group directly bonded to a carbon atom at both terminals.

[0013] [5] The adhesive composition according to any one of [1] to [4], wherein the content of the methanol-modified polyorganosiloxane in a nonvolatile component of the adhesive composition is 0.01 to 30 mass%.

[0014] [6] The adhesive composition according to any one of [1] to [5], wherein the adhesive component is a component cured by a hydrosilylation reaction.

[0015] [7] The adhesive composition according to [6], wherein the component cured by a hydrosilylation reaction contains: a component (A-1) having an alkenyl group with 2 to 40 carbon atoms bonded to a silicon atom; a component (A-2) having an Si-H group; and a platinum group metal-based catalyst (A-3).

[0016] [8] The adhesive composition according to [7], wherein the component (A-1) contains a polyorganosiloxane (al) having an alkenyl group with 2 to 40 carbon atoms bonded to a silicon atom.

[0017] [9] The adhesive composition according to [7] or [8], wherein the component (A-2) contains a polyorganosiloxane having an Si-H group.

[0018]

[10] A laminate having: a semiconductor substrate or an electronic device layer; a support substrate that is transparent to light; and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, the adhesive layer being an adhesive layer formed from the adhesive composition according to any one of [1] to [9].

[0019]

[11] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: a 5A step of processing the semiconductor substrate of the laminate described in

[10] ; or a 5B step of processing the electronic device layer of the laminate described in

[10] ; and a 6A step of separating the semiconductor substrate processed by the 5A step from the support substrate; or a 6B step of separating the electronic device layer processed by the 5B step from the support substrate.

[0020] Effects of the Invention According to the present application, it is possible to provide an adhesive composition capable of forming an adhesive layer having excellent peelability, a laminate using the same, and a method for manufacturing a processed semiconductor substrate or electronic device layer using the laminate. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a schematic cross-sectional view of one example of a laminate in the first embodiment.

[0022] Figure 2 is a schematic cross-sectional view of another example of a laminate in the first embodiment.

[0023] Figure 3A is a schematic cross-sectional view for explaining a method for manufacturing a laminate representing one example in the first embodiment (one).

[0024] Figure 3B is a schematic cross-sectional view for explaining a method for manufacturing a laminate representing one example in the first embodiment (two).

[0025] Figure 4 is a schematic cross-sectional view of one example of a laminate in the second embodiment.

[0026] Figure 5 is a schematic cross-sectional view of another example of a laminate in the second embodiment.

[0027] Figure 6A is a schematic cross-sectional view for explaining a method for manufacturing a laminate representing one example in the second embodiment (one).

[0028] Figure 6B is a schematic cross-sectional view for explaining a method for manufacturing a laminate representing one example in the second embodiment (two).

[0029] Figure 6C is a schematic cross-sectional view for explaining a method for manufacturing a laminate representing one example in the second embodiment (three).

[0030] Figure 7A is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the first embodiment (one).

[0031] Figure 7B is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the first embodiment (two).

[0032] Figure 7C is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the first embodiment (three).

[0033] Figure 7D is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the first embodiment (four).

[0034] Figure 8A is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the second embodiment (one).

[0035] Figure 8B is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the second embodiment (two).

[0036] Figure 8C is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the second embodiment (three).

[0037] Figure 8D is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the second embodiment (four).

[0038] Figure 8E is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the second embodiment (five).

[0039] Figure 8F is a schematic cross-sectional view for explaining a processing method of a laminate representing one example in the second embodiment (six). DETAILED DESCRIPTION

[0040] (Adhesive composition) The adhesive composition of the present application contains an adhesive component and a methanol-modified polyorganosiloxane.

[0041] The adhesive composition can also contain other components.

[0042] As the adhesive composition, for example, a polysiloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, a phenol resin-based adhesive, and the like can be exemplified, but are not limited thereto.

[0043] Among them, the adhesive composition shows appropriate adhesive ability at the time of processing of a semiconductor substrate or the like, is appropriately peeled after processing, is also excellent in heat resistance, and is appropriately removed by the cleaning agent composition, and thus, as the adhesive composition, a polysiloxane-based adhesive is preferred.

[0044] <Adhesive Component> As the adhesive component, there is no particular limitation, and a component which is cured is preferred, and a component which is cured by a hydrosilylation reaction is more preferred.

[0045] As the component which is cured by a hydrosilylation reaction, there is no particular limitation, and a component which 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 an Si-H group (hereinafter sometimes referred to as "component (A-2)"); and a platinum group metal-based catalyst (A-3) is preferred.

[0046] < <Component (A-1) and Component (A-2)>> The adhesive composition preferably contains component (A-1).

[0047] The adhesive composition preferably contains component (A-2).

[0048] Hereinafter, the combination of component (A-1), component (A-2), and platinum group metal-based catalyst (A-3) is sometimes referred to as "component (A) which is cured" or "component (A)".

[0049] From the viewpoint of appropriately obtaining the effects of the present application, component (A-1) preferably contains: a polyorganosiloxane (al) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom.

[0050] From the viewpoint of appropriately obtaining the effects of the present application, component (A-2) preferably contains: a polyorganosiloxane (a2) having an Si-H group.

[0051] The alkenyl group having 2 to 40 carbon atoms is optionally substituted. As the substituent, for example, a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like can be exemplified.

[0052] In another preferred aspect, the adhesive composition which is cured by a hydrosilylation reaction contains a polysiloxane (Al) and a platinum group metal-based catalyst (A-3), the polysiloxane (Al) contains a siloxane unit (Q unit) represented by SiO2, R1 R 2 R 3 SiO 1 / 2 R 4 R 5 SiO 2 / 2 R 6 SiO 3 / 2 R 1 ’R 2 ’R 3 ’SiO 1 / 2 R 4 ’R 5 ’SiO 2 / 2 R 6 ’SiO 3 / 2 R 1 ”R 2 ”R 3 ”SiO 1 / 2 R 4 ”R 5 ”SiO 2 / 2 R 6 ”SiO 3 / 2 R

[0053] Note that (a1’) is an example of (a1), and (a2’) is an example of (a2).

[0054] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. As a substituent, for example, a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like can be exemplified.

[0055] R1 '~R 6 'A group bonded to a silicon atom, each independently representing an optionally substituted alkyl or optionally substituted alkenyl group, R 1 '~R 6 At least one of the groups is an alkenyl group that is optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0056] R 1 "~R 6 "R represents a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl or hydrogen atom." 1 "~R 6 At least one of the elements is a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0057] The alkyl group can be any type of straight-chain, branched, or cyclic, with straight-chain or branched alkyl groups being preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0058] Specific examples of linear or branched alkyl groups that may be optionally substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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, 4-methyl n-pentyl, 1,1 The carbon atoms are typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Methyl groups are particularly preferred.

[0059] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, and the like; dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 3 to 14, preferably from 4 to 10, and more preferably from 5 to 6.

[0060] The alkenyl group can be any of a straight chain or a branched chain, and the number of carbon atoms thereof is not particularly limited, and is usually from 2 to 40, preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less.

[0061] Specific examples of the optionally substituted straight chain or branched chain alkenyl group include ethenyl, allyl, butenyl, pentenyl, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 2 to 14, preferably from 2 to 10, and more preferably from 1 to 6. Among them, ethenyl and 2-propenyl are particularly preferred.

[0062] Specific examples of the optionally substituted cyclic alkenyl group include cyclopentenyl, cyclohexenyl, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 4 to 14, preferably from 5 to 10, and more preferably from 5 to 6.

[0063] As described above, the polysiloxane (Al) contains a polyorganosiloxane (al') and a polyorganosiloxane (a2'), and the alkenyl group contained in the polyorganosiloxane (al') and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2') are crosslinked by a hydrosilylation reaction using a platinum group metal-based catalyst (A-3) to be cured. As a result, a cured film is formed.

[0064] The polyorganosiloxane (al') contains one or two or more units selected from the group consisting of a Q' unit, an M' unit, a D' unit, and a T' unit, and contains at least one selected from the group consisting of an M' unit, a D' unit, and a T' unit. Two or more polyorganosiloxanes satisfying such conditions can also be used in combination as the polyorganosiloxane (al').

[0065] As a preferred combination of two or more selected from the group consisting of a Q' unit, an M' unit, a D' unit, and a T' unit, there can be mentioned: (a Q' unit and an M' unit), (a D' unit and an M' unit), (a T' unit and an M' unit), (a Q' unit, a T' unit, and an M' unit), but the present application is not limited thereto.

[0066] Further, in the case where the polyorganosiloxane (al') contains two or more polyorganosiloxanes, combinations of (a Q' unit and an M' unit) and (a D' unit and an M' unit), combinations of (a T' unit and an M' unit) and (a D' unit and an M' unit), combinations of (a Q' unit, a T' unit, and an M' unit) and (a T' unit and an M' unit) are preferred, but the present application is not limited thereto.

[0067] The polyorganosiloxane (a2') contains one or two or more units selected from the group consisting of a Q" unit, an M" unit, a D" unit, and a T" unit, and contains at least one selected from the group consisting of an M" unit, a D" unit, and a T" unit. Two or more polyorganosiloxanes satisfying such conditions can also be used in combination as the polyorganosiloxane (a2').

[0068] As a preferred combination of two or more selected from the group consisting of a Q" unit, an M" unit, a D" unit, and a T" unit, there can be mentioned: (an M" unit and a D" unit), (a Q" unit and an M" unit), (a Q" unit, a T" unit, and an M" unit), but the present application is not limited thereto.

[0069] The polyorganosiloxane (al') is composed of siloxane units in which silicon atoms are bonded to alkyl groups and / or alkenyl groups, R 1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be alkyl groups.

[0070] The polyorganosiloxane (a2') is composed of siloxane units in which silicon atoms are bonded to alkyl groups and / or hydrogen atoms, R 1 "~R 6The proportion of hydrogen atoms in all the substituents and substituted atoms shown in the formula is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remainder is R 1 ”~R 6 ”may be an alkyl group.

[0071] In the case where the adhesive composition contains (al) and (a2), in the preferred embodiment of the present application, the molar ratio of the alkenyl group contained in the polyorganosiloxane (al) to the hydrogen atom constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0072] The weight average molecular weight of the polyorganosiloxane (al), the polyorganosiloxane (a2), and the like is not particularly limited, and each is usually 500 to 1,000,000, and from the viewpoint of achieving the effects of the present application with good reproducibility, it is preferably 5,000 to 50,000.

[0073] Note that in the present application, the weight average molecular weight and the number average molecular weight and the dispersity of the polyorganosiloxane can be measured, for example, using a GPC device (EcoSEC, HLC-8320 GPC, manufactured by TOSOH Corporation) and a GPC column (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H, manufactured by TOSOH Corporation), setting the column temperature to 40°C, using tetrahydrofuran as the eluent (dissolution solvent), setting the flow rate (flow speed) to 0.35 mL / minute, and using polystyrene (manufactured by Showa Denko K.K., Shodex) as the standard sample.

[0074] The viscosity of the polyorganosiloxane (al) and the polyorganosiloxane (a2) is not particularly limited, and each is usually 10 to 1,000,000 (mPa-s), and from the viewpoint of achieving the effects of the present application with good reproducibility, it is preferably 50 to 10,000 (mPa-s). Note that the viscosity of the polyorganosiloxane (al) and the polyorganosiloxane (a2) is a value measured at 25°C using an E-type rotational viscometer.

[0075] The polyorganosiloxane (al) and the polyorganosiloxane (a2) react with each other through a hydrosilylation reaction. Therefore, the mechanism of its curing is different from, for example, a mechanism via a silanol group, and thus, any siloxane does not need to contain a silanol group, a functional group that forms a silanol group through hydrolysis, such as an alkoxy group.

[0076] <<Platinum Group Metal-Based Catalyst (A-3)>> The platinum group metal-based catalyst is a metal catalyst of the platinum type.

[0077] Such platinum group metal catalysts are catalysts for promoting hydrosilylation reactions of alkenyl groups with Si-H groups.

[0078] As specific examples of platinum group metal catalysts, substances known as platinum group compounds (platinum or a compound containing platinum) can be used.

[0079] As specific examples thereof, there can be mentioned platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid with a diene, a platinum-olefin complex, a platinum-carbonyl complex (bis(acetylacetone) platinum, bis(acetylacetone) platinum, etc.), a chloroplatinic acid-alkenyl siloxane complex (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), a platinum-alkenyl siloxane complex (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethyldisiloxane complex, etc.), a complex of chloroplatinic acid with an acetylenic alcohol, etc. Among these, from the viewpoint of high promotion effect of hydrosilylation reactions, a platinum-alkenyl siloxane complex is particularly preferred.

[0080] These hydrosilylation reactions can be carried out using one kind of catalyst alone or two or more kinds of catalysts in combination.

[0081] The alkenyl siloxane used for the platinum-alkenyl siloxane complex is not particularly limited, and there can be mentioned, for example, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, an alkenyl siloxane oligomer in which a part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, etc., and an alkenyl siloxane oligomer in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, etc. In particular, from the viewpoint of good stability of the resulting platinum-alkenyl siloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred.

[0082] The content of the platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, and is in the range of 0.1 to 50.0 ppm, for example, relative to the total mass of component (A-1) and component (A-2).

[0083] < Methanol-modified polyorganosiloxane > By containing a methanol-modified polyorganosiloxane in the adhesive composition, the adhesive layer formed from the adhesive composition is excellent in release properties.

[0084] The methanol-modified polyorganosiloxane is a release agent component.

[0085] The methanol-modified polyorganosiloxane contained in the adhesive composition is not particularly limited.

[0086] The carbinol-modified polyorganosiloxane is a polyorganosiloxane having a hydroxyl group directly bonded to a carbon atom. Thus, the carbinol in the "carbinol-modified polyorganosiloxane" is not limited to the narrow sense of methanol (methanol), but also includes methanol (methanol) derivatives.

[0087] The carbinol-modified polyorganosiloxane generally does not undergo a hydrosilylation reaction.

[0088] The carbinol-modified polyorganosiloxane is, for example, a carbinol-modified polydimethylsiloxane.

[0089] The number of the hydroxyl group directly bonded to a carbon atom possessed by the carbinol-modified polyorganosiloxane is not particularly limited, and can be one or more than two.

[0090] The carbinol-modified polyorganosiloxane can have a hydroxyl group directly bonded to a carbon atom in a side chain, or can have a hydroxyl group directly bonded to a carbon atom at a single terminal, or can have a hydroxyl group directly bonded to a carbon atom at both terminals.

[0091] The carbinol-modified polyorganosiloxane preferably has a hydroxyl group directly bonded to a carbon atom in a side chain. In this case, even if the content of the carbinol-modified polyorganosiloxane is small, a good peelability can be imparted to an adhesive layer formed from the adhesive composition.

[0092] The carbinol-modified polyorganosiloxane has, for example, a group represented by the following formula (Cg) as a group directly bonded to a silicon atom. (In formula (Cg), R 1 represents a group having 1 or more carbon atoms. * represents a bonding bond to a silicon atom. Among them, the hydroxyl group in formula (Cg) is directly bonded to a carbon atom.) The number of the hydroxyl group directly bonded to a carbon atom possessed by the group represented by formula (Cg) can be one or more than two. As more than two, for example, two, three, four, and the like can be exemplified.

[0093] The number of carbon atoms of R 1 is not particularly limited, and can be, for example, 1 to 30, 1 to 20, or 1 to 10.

[0094] As the group represented by formula (Cg), for example, the groups represented by the following formulas (Cg-1) to (Cg-4) can be exemplified. (In formula (Cg-1), R 11 represents an alkylene group having 1 to 6 carbon atoms optionally substituted with an alkoxy group having 1 to 3 carbon atoms.

[0095] In formula (Cg-2), R 12 represents an alkylene group having 1 to 6 carbon atoms. R 13 represents an alkylene group having 1 to 6 carbon atoms optionally substituted by an alkoxy group having 1 to 3 carbon atoms or a hydroxy group.

[0096] In formula (Cg-3), R 14 represents an alkylene group having 1 to 6 carbon atoms. R 15 represents an alkylene group having 1 to 3 carbon atoms. m represents an integer of 1 to 10.

[0097] In formula (Cg-4), R 16 ~R 18 each independently represents an alkylene group having 1 to 6 carbon atoms.

[0098] In formulae (Cg-1) to (Cg-4), * represents a bonding bond to a silicon atom. R 11 ~R 18 The alkylene group of R

[0099] As the group represented by formula (Cg), for example, the following groups can be listed. (In the formula, m1 represents an integer of 2 to 10. * represents a bonding bond to a silicon atom.) The methanol-modified polyorganosiloxane is represented by, for example, the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R 51 each independently represents a hydrocarbon group. X 1 represents the group represented by the above formula (Cg). n1 represents an integer of 0 or more. n2 represents an integer of 1 or more.

[0100] In formula (CPS-2), R 52 each independently represents a hydrocarbon group. X 2 represents the group represented by the above formula (Cg). X 3 represents a hydrocarbon group or the group represented by the above formula (Cg). n3 represents an integer of 0 or more. As the hydrocarbon group in R 51 , R 52 , and X 3 , for example, an alkyl group having 1 to 8 carbon atoms can be listed. As the alkyl group having 1 to 8 carbon atoms, a methyl group is preferred. That is, the methanol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a). (X 1 represents a group represented by the above formula (Cg). n1 represents an integer of 0 or more. n2 represents an integer of 1 or more.

[0101] (X 2 represents a group represented by the above formula (Cg). X 3 represents a methyl group or a group represented by the above formula (Cg). n3 represents an integer of 0 or more. Note that the methanol-modified polyorganosiloxane represented by formula (CPS-1) and the methanol-modified polydimethylsiloxane represented by formula (CPS-1a) have a hydroxyl group directly bonded to a carbon atom in the side chain.

[0102] The methanol-modified polyorganosiloxane represented by formula (CPS-2) and the methanol-modified polydimethylsiloxane represented by formula (CPS-2a) have a hydroxyl group directly bonded to a carbon atom at one terminal or both terminals.

[0103] Note that in the methanol-modified polyorganosiloxane represented by formula (CPS-1), in the case where n2 is 2 or more, the siloxane units represented by -Si(R 51 )(X 1 ) -O- can be arranged adjacently to form a block or can be arranged randomly.

[0104] Further, in the methanol-modified polydimethylsiloxane represented by formula (CPS-1a), in the case where n2 is 2 or more, the siloxane units represented by -Si(CH3)(X 1 ) -O- can be arranged adjacently to form a block or can be arranged randomly.

[0105] The weight average molecular weight of the methanol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of achieving the effects of the present application with good reproducibility, it is preferably 5,000 to 50,000. Further, the dispersity thereof is not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of achieving appropriate peeling with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0.

[0106] The viscosity of the methanol-modified polyorganosiloxane is not particularly limited, and is usually 100 to 200,000 mm 2 / s. Note that the value of the viscosity of polydimethylsiloxane is represented by kinematic viscosity, and is centistokes (cSt) = mm 2 / s. It can also be obtained by dividing the viscosity (mPa • s) by the density (g / cm 3). That is, its value can be calculated from the viscosity measured at 25°C using an E-type rotational viscometer and the density. It can be calculated from the kinematic viscosity (mm 2 / s) = viscosity (mPa • s) / density (g / cm 3 ) this formula.

[0107] The methanol-modified polyorganosiloxane can be a commercially available product or a synthesized substance.

[0108] As commercially available products of the methanol-modified polyorganosiloxane, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, X-22-4015 manufactured by Shin-Etsu Silicone Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, MCR-C63 manufactured by Gelest Co.; DOWSIL BY 16-201, DOWSIL SF 8427 Fluid, DOWSIL SF 8428 Fluid, and the like manufactured by Dow TORAY Co. can be listed.

[0109] As the content of the methanol-modified polyorganosiloxane in the adhesive composition, there is no particular limitation, and from the viewpoint of appropriately obtaining the effects of the present application, 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 nonvolatile components of the adhesive composition. As the upper limit value, there is no particular limitation, and it is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, relative to the nonvolatile components of the adhesive composition.

[0110] The nonvolatile components of the adhesive composition refer to components other than solvents in the adhesive composition.

[0111] The methanol-modified polyorganosiloxane having a hydroxyl group directly bonded to a carbon atom in the side chain can impart good peelability to the adhesive layer formed from the adhesive composition at a small content.

[0112] In this regard, the content of the methanol-modified polyorganosiloxane having a hydroxyl group directly bonded to a carbon atom in the side chain in the adhesive composition is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. As a lower limit value, there is no particular limitation, and 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, with respect to the nonvolatile components of the adhesive composition.

[0113] The adhesive composition used in the present application can also contain a solvent for the purpose of adjusting the viscosity and the like, and as specific examples thereof, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, and the like can be given, but are not limited thereto.

[0114] More specifically, as the solvent, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and the like can be given, but are not limited thereto. Such a solvent can be used alone or in combination with two or more kinds.

[0115] In the case where the adhesive composition used in the present application contains a solvent, the content thereof is appropriately determined in consideration of the viscosity of the desired composition, the coating method to be employed, the thickness of the film to be produced, and the like, and is in the range of about 10 to 90% by mass with respect to the entire composition.

[0116] The viscosity of the adhesive composition used in the present application is not particularly limited, and is generally 1 to 20,000 mPa-s, preferably 1 to 5,000 mPa-s, more preferably 1 to 1,000 mPa-s, and most preferably 1 to 500 mPa-s at 25°C. The viscosity of the adhesive composition used in the present application can be adjusted by changing the kind of the solvent to be used, the ratio thereof, the concentration of the film-forming component, and the like, in consideration of various factors such as the coating method to be used and the desired film thickness.

[0117] One example of the adhesive composition used in the present application can be produced by mixing the component (A), the release agent component (B), and the solvent.

[0118] The mixing order is not particularly limited, and as one example of a method capable of easily and reproducibly producing the adhesive composition, a method in which the component (A) and the release agent component (B) are dissolved in the solvent, a method in which a part of the component (A) and the release agent component (B) are dissolved in the solvent and the remaining part is dissolved in the solvent, and the resulting solutions are mixed, can be given, but is not limited thereto. Note that, when the adhesive composition is prepared, the components can also be appropriately heated within a range in which they are not decomposed or deteriorated.

[0119] In the present application, for the purpose of removing foreign matter, the solvent, solution, etc. used can be filtered using a filter, etc. at the middle of the production of the adhesive composition or after mixing all the components.

[0120] (Laminate) The laminate of the present application has a semiconductor substrate or an electronic device layer, a support substrate, and an adhesive layer.

[0121] The laminate of the present application can further have a release agent layer, in which case it is configured to have a semiconductor substrate or an electronic device layer, a support substrate, a release agent layer, and an adhesive layer.

[0122] The adhesive layer is provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0123] The laminate of the present application is used for temporary bonding when the semiconductor substrate or the electronic device layer is processed, and can be appropriately used for thinning and the like of the semiconductor substrate or the electronic device layer.

[0124] During the processing such as thinning of the semiconductor substrate, the semiconductor substrate is supported by the support substrate. On the other hand, after the processing of the semiconductor substrate, the support substrate is separated from the semiconductor substrate.

[0125] Further, during the processing such as thinning of the electronic device layer, the electronic device layer is supported by the support substrate. On the other hand, after the processing of the electronic device layer, the support substrate is then separated from the electronic device layer.

[0126] After the semiconductor substrate or the electronic device layer is separated from the support substrate, the residue of the release agent layer and the adhesive layer remaining on the semiconductor substrate, the electronic device layer, or the support substrate can be removed, for example, by a cleaning agent composition for cleaning the semiconductor substrate or the like.

[0127] The following is described in detail, separately for the case where the laminate has a semiconductor substrate and the case where the laminate has an electronic device layer.

[0128] The case where the laminate has a semiconductor substrate is described in the following <First Embodiment>, and the case where the laminate has an electronic device layer is described in the following <Second Embodiment>.

[0129] <First Embodiment> The laminate having a semiconductor substrate is used for processing of the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to the support substrate. After the processing of the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0130] <Semiconductor Substrate> As a material constituting the entire semiconductor substrate, there is no particular limitation as long as it can be used for such a purpose, and for example, silicon, silicon carbide, a compound semiconductor, a glass substrate with an organic resin, and the like can be exemplified.

[0131] The shape of the semiconductor substrate is not particularly limited, and for example, it is a disc shape. Note that the disc-shaped semiconductor substrate does not necessarily have a complete circular shape on its surface, and for example, the outer periphery of the semiconductor substrate can have a straight portion called an orientation flat, or can have a notch called a notch.

[0132] The thickness of the disc-shaped semiconductor substrate is not particularly limited as long as it is appropriately determined in accordance with the purpose of use of the semiconductor substrate or the like, and for example, it is 500 to 1000 μm.

[0133] The diameter of the disc-shaped semiconductor substrate is not particularly limited as long as it is appropriately determined in accordance with the purpose of use of the semiconductor substrate or the like, and for example, it is 100 to 1000 mm.

[0134] The semiconductor substrate can have a bump. The bump refers to a terminal in a protruding shape.

[0135] In the laminate, in the case where the semiconductor substrate has a bump, the semiconductor substrate has the bump on the side of the support substrate.

[0136] In the semiconductor substrate, the bump is generally formed on the surface on which the circuit is formed. The circuit can be a single layer or a plurality of layers. The shape of the circuit is not particularly limited.

[0137] In the semiconductor substrate, the surface (back surface) on the side opposite to the surface having the bump is a surface for processing.

[0138] The material, size, shape, structure, and density of the bump provided to the semiconductor substrate are not particularly limited.

[0139] As the bump, for example, a spherical bump, a printed bump, a stud bump, a plated bump, and the like can be exemplified.

[0140] Generally, the height, radius, and pitch of the bump are appropriately determined in accordance with the conditions of a bump height of 1 to 200 μm or so, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm.

[0141] As the material of the bump, for example, a low-melting-point solder, a high-melting-point solder, tin, indium, gold, silver, copper, and the like can be exemplified. The bump can be composed of only a single component, or can be composed of a plurality of components. More specifically, for example, a SnAg bump, a SnBi bump, a Sn bump, an AuSn bump, and the like, and an alloy plating in which Sn is the main component can be exemplified.

[0142] Further, the bump can also have a laminated structure including a metal layer composed of at least any of these components.

[0143] One example of the semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0144] <<Supporting Substrate>> As the supporting substrate, there is no particular limitation as long as it is a member capable of supporting the semiconductor substrate at the time of processing the semiconductor substrate, and for example, a glass supporting substrate, a silicon supporting substrate, and the like can be exemplified.

[0145] As the shape of the supporting substrate, there is no particular limitation, and for example, a disc shape can be exemplified. Note that the disc-shaped supporting substrate need not have a complete circular shape in the shape of its face, and for example, the outer periphery of the supporting substrate can have a straight line portion called an orientation flat, or can have a cutout called a notch.

[0146] As the thickness of the disc-shaped supporting substrate, there is no particular limitation as long as it is appropriately determined in accordance with the size of the semiconductor substrate or the like, and for example, 500 to 1000 μm.

[0147] As the diameter of the disc-shaped supporting substrate, there is no particular limitation as long as it is appropriately determined in accordance with the size of the semiconductor substrate or the like, and for example, 100 to 1000 mm.

[0148] One example of the supporting substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0149] Note that in the case where peeling in the laminate is performed by light irradiation, as the supporting substrate, for example, a substrate having light transmissivity with respect to the used light is used.

[0150] <<Adhesive Layer>> The adhesive layer is provided between the supporting substrate and the semiconductor substrate.

[0151] The adhesive layer is, for example, in contact with the semiconductor substrate. The adhesive layer can also be, for example, in contact with the supporting substrate.

[0152] The adhesive layer is an adhesive layer formed of an adhesive composition.

[0153] The thickness of the adhesive layer possessed by the laminate of the present application is not particularly limited, and is usually 5 to 500 μm. From the viewpoint of maintaining the strength of the film, it is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more. From the viewpoint of avoiding unevenness due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less, and further preferably 100 μm or less.

[0154] The method for forming the adhesive layer from the adhesive composition is described in detail in the description section of the following

[0155] <<Peeling agent layer>> The laminate can have a peeling agent layer.

[0156] In the laminate having the peeling agent layer, the separation of the semiconductor substrate from the support substrate is performed, for example, by light irradiation to the peeling agent layer.

[0157] The peeling agent layer is formed, for example, from a peeling agent composition.

[0158] <<Peeling agent composition>>> The peeling agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and further contains other components as necessary.

[0159] The organic resin is preferably a substance capable of exerting an appropriate peeling ability, and in the case where the separation of the semiconductor substrate from the support substrate is performed by light irradiation to the peeling agent layer, the organic resin absorbs light and appropriately undergoes a change such as decomposition, which is required for the increase in the peeling ability.

[0160] In the case of the laminate having the peeling agent layer formed from the peeling agent composition, peeling can be performed without applying excessive load for peeling, for example, by laser irradiation to the peeling agent layer.

[0161] The peeling agent layer possessed by the laminate is reduced in the adhesive strength by the irradiation of laser, for example. That is, in the laminate, the semiconductor substrate is appropriately supported by the support substrate transmitting laser through the adhesive layer and the peeling agent layer during the processing such as thinning of the semiconductor substrate, and after the processing is completed, the laser transmitted through the support substrate is absorbed by the peeling agent layer by the irradiation of laser from the support substrate side, and a change such as decomposition occurs in the peeling agent layer at the interface between the peeling agent layer and the adhesive layer, the interface between the peeling agent layer and the support substrate, or the inside of the peeling agent layer, as a result of which appropriate peeling (separation) can be achieved without applying excessive load for peeling.

[0162] As the organic resin, for example, a novolak resin body and the like can be mentioned. Details thereof will be described later.

[0163] As a preferred embodiment, the stripping agent composition contains at least phenolic varnish resin, and further contains other components such as crosslinking agents, acid-generating agents, acids, surfactants, and solvents as needed.

[0164] As another preferred embodiment, the stripping agent composition contains at least a polyphenol derivative and a crosslinking agent, and may further contain other components such as an acid-producing agent, an acid, a surfactant, and a solvent, as needed.

[0165] As another preferred embodiment, the stripper composition contains at least an organic resin and a branched polysilane, and further contains, as needed, other components such as a crosslinking agent, an acid-generating agent, an acid, a surfactant, and a solvent.

[0166] <<<<Phenolic Varnish Resin>>>> Phenolic varnish resins are, for example, resins obtained by condensing at least any one of phenolic compounds, carbazole compounds, and aromatic amine compounds with at least any one of aldehyde compounds, ketone compounds, and divinyl compounds under an acid catalyst.

[0167] Examples of phenolic compounds include: phenols, naphthols, anthraquinones, and hydroxypyrenes. Examples of phenols include: phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane. Examples of naphthols include: 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthol, 2,7-dihydroxynaphthol, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of anthraquinones include: 9-anthraquinone. Examples of hydroxypyrenes include: 1-hydroxypyrene and 2-hydroxypyrene.

[0168] Examples of carbazole compounds include: carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1 H-benzotriazole-1-ylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarbaldehyde, 9-benzylcarbazole-3-carbaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, carbazole potassium, carbazole-N-formyl chloride, N-ethylcarbazole-3-carbaldehyde, N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-dihydroindoleamine, etc.

[0169] As the aromatic amine compound, for example, diphenylamine, N-phenyl-1-naphthylamine, and the like can be exemplified.

[0170] They can be used singly or in combination of two or more.

[0171] They can also have a substituent. For example, they can also have a substituent on the aromatic ring.

[0172] As the aldehyde compound, for example, saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, caproaldehyde, 2-methylbutyraldehyde, hexanal, undecanal, 7-methoxy-3,7-dimethyloctanal, cyclohexanecarboxaldehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, glutaraldehyde, adipaldehyde, and the like; unsaturated aliphatic aldehydes such as acrolein, methacrolein, and the like; heterocyclic aldehydes such as furfural, pyridinecarboxaldehyde, and the like; aromatic aldehydes such as benzaldehyde, naphthaldehyde, anthracenealdehyde, phenanthrenealdehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, acetoxybenzaldehyde, and the like, and the like can be exemplified. Among them, aromatic aldehydes are preferred.

[0173] As the ketone compound, for example, diaryl ketone compounds such as diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, dimethylphenyl ketone, and the like can be exemplified.

[0174] As the divinyl compound, for example, divinylbenzene, dicyclopentadiene, tetrahydroindenyl, 4-vinylcyclohexene, 5-vinyl-2-norbornene, divinylpyrene, limonene, 5-vinyl norbornadiene, and the like can be exemplified.

[0175] They can be used singly or in combination of two or more.

[0176] The novolak resin is, for example, a novolak resin which deteriorates by absorbing light irradiated from the support substrate side. The deterioration is, for example, photodegradation.

[0177] The novolak resin, for example, contains at least any of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3). In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, C 3 represents a group derived from an aliphatic polycyclic compound, C 4a group derived from a naphthol, a group derived from a biphenyl, or a group derived from a biphenol.

[0178] That is, the novolak resin contains one or two or more of structural units including the following, for example.

[0179] • a structural unit (Formula (C1-1)) having a bond of a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain.

[0180] • a structural unit (Formula (C1-2)) having a bond of a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound.

[0181] • a structural unit (Formula (C1-3)) having a bond of a group derived from a phenol, a group derived from a bisphenol, a group derived from a naphthol, a group derived from a biphenyl, or a group derived from a biphenol and a group containing a tertiary carbon atom having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring in a side chain.

[0182] In a preferred embodiment, the novolak resin contains either or both of a structural unit (Formula (C1-1)) having a bond of a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, and a structural unit (Formula (C1-2)) having a bond of a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound.

[0183] C 1 The group derived from an aromatic compound containing a nitrogen atom of Formula (C1-1) can adopt a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, or the like, but is not limited thereto.

[0184] C 2 The group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain of Formula (C1-1) can adopt a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from acetaldehyde, or the like, but is not limited thereto.

[0185] C 3 The group derived from an aliphatic polycyclic compound of Formula (C1-2) can adopt a group derived from dicyclopentadiene, but is not limited thereto.

[0186] C 4a group derived from a phenol, a group derived from a bisphenol, a group derived from a naphthol, a group derived from a biphenyl, or a group derived from a bisphenol.

[0187] In a preferred aspect, the novolak resin contains, for example, a structural unit represented by the following formula (C1-1-1) as the structural unit represented by the formula (C1-1). In the formula (C1-1-1), R 901 and R 902 represent a substituent substituted on a ring, each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

[0188] R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

[0189] R 904 represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0190] R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0191] R 904 The group of R 905 may optionally be bonded to each other to form a divalent group.

[0192] As the substituents of the alkyl group and the alkenyl group, a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like can be exemplified.

[0193] As the substituents of the aryl group and the heteroaryl group, a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, and the like can be exemplified.

[0194] h 1 and h 2 each independently represent an integer of 0 to 3.

[0195] The number of carbon atoms of the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, and more preferably 20 or less.

[0196] The number of carbon atoms of the optionally substituted aryl group and the heteroaryl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, and more preferably 20 or less.

[0197] As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified.

[0198] Specific examples of the optionally substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, 1-methyln-butyl, 2-methyln-butyl, 3-methyln-butyl, 1,1-dimethyln-propyl, 1,2-dimethyln-propyl, 2,2-dimethyln-propyl, 1-ethyln-propyl, n-hexyl, 1-methyln-pentyl, 2-methyln-pentyl, 3-methyln-pentyl, 4-methyln-pentyl, 1,1-dimethyln-butyl, 1,2-dimethyln-butyl, 1,3-dimethyln-butyl, 2,2-dimethyln-butyl, 2,3-dimethyln-butyl, 3,3-dimethyln-butyl, 1-ethyln-butyl, 2-ethyln-butyl, 1,1,2-trimethyln-propyl, 1,2,2-trimethyln-propyl, 1-ethyl-1-methyln-propyl, 1-ethyl-2-methyln-propyl, and the like, but are not limited thereto.

[0199] Specific examples of the optionally substituted alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl- 3-Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl alkenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3 -Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylethenyl, 1-methyl-l-ethenyl-2-propenyl, 1- ethyl-2-methyl-l-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-l-propenyl, 1- isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2- methyl-l-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2- methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3- methyl-l-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3- methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1- cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, and the like, but are not limited thereto.

[0200] As specific examples of the optionally substituted aryl group, there can be mentioned phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3- chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4- methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 1-naphthyl, 2- naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, 1-anthryl, 2-anthryl, 9-anthryl, 1- phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and the like, but are not limited thereto.

[0201] As specific examples of the optionally substituted heteroaryl group, there can be mentioned 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3- isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4- isothiazolyl, 5-isothiazolyl, and the like, but are not limited thereto.

[0202] Hereinafter, specific examples of the structural unit represented by Formula (C1-1-1) will be given, but are not limited thereto. In a preferable aspect, the novolak resin contains, for example, a structural unit represented by the following Formula (C1-1-2) as the structural unit represented by Formula (C1-1). In Formula (C1-1-2), Ar 901 and Ar 902 each independently represent an aromatic ring such as a benzene ring or a naphthalene ring, R 901 ~ R 905 and h 1 and h 2 represent the same meanings as described above.

[0203] Hereinafter, specific examples of the structural unit represented by formula (C1-1-2) are listed, but are not limited thereto. In a preferred aspect, the novolak resin contains, for example, a structural unit represented by formula (C1-2-1) or (C1-2-2) below as the structural unit represented by formula (C1-2). In the above formula, R 906 ~R 909 represents a substituent bonded to a ring, each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and specific examples and preferred carbon atom numbers of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group, and the optionally substituted aryl group can be listed as the same as described above, h 3 ~h 6 each independently represents an integer of 0 to 3, R 901 ~R 903 and h 1 and h 2 represent the same meaning as described above.

[0204] Hereinafter, specific examples of the structural unit represented by formula (C1-2-1) and (C1-2-2) are listed, but are not limited thereto. Hereinafter, specific examples of the structural unit represented by formula (C1-3) are listed, but are not limited thereto. As described above, the novolak resin is, for example, a resin obtained by subjecting at least any of a phenolic compound, a carbazole compound, and an aromatic amine compound to a condensation reaction with at least any of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst.

[0205] In the condensation reaction, for example, 0.1 to 10 equivalents of the aldehyde compound or the ketone compound are used with respect to 1 equivalent of the benzene ring of the ring constituting the carbazole compound.

[0206] In the above condensation reaction, an acid catalyst is generally used.

[0207] As the acid catalyst, for example, inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid can be listed, but are not limited thereto.

[0208] The amount of the acid catalyst is appropriately determined depending on the kind of acid used, and the like, and thus cannot be generally specified, and is usually appropriately determined in the range of 0.001 to 10,000 parts by mass with respect to 100 parts by mass of the carbazole compound.

[0209] The above condensation reaction can sometimes be performed without using a solvent in the case where any of the raw material compounds and the acid catalyst used is liquid, but is usually performed using a solvent.

[0210] Such a solvent is not particularly limited as long as it does not hinder the reaction, and typical examples include cyclic ether compounds such as tetrahydrofuran and dioxane, and ether compounds.

[0211] The reaction temperature is usually appropriately determined in the range of 40°C to 200°C, and the reaction time varies depending on the reaction temperature, and thus cannot be generally specified, and is usually appropriately determined in the range of 30 minutes to 50 hours.

[0212] After the reaction is completed, purification and separation are performed as necessary according to a conventional method, and the obtained novolak resin is used for the preparation of a peeling agent composition.

[0213] The manufacturing conditions of the novolak resin can be determined without excessive burden based on the above description and technical common sense by a person skilled in the art, and thus the novolak resin can be manufactured.

[0214] The weight average molecular weight of the organic resin such as the novolak resin is usually 500 to 200,000, and is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less, further preferably 5,000 or less, and yet further preferably 3,000 or less, from the viewpoint of ensuring solubility in a solvent, the viewpoint of mixing with a branched polysilane to obtain a uniform film when a film is produced, and the like, and is preferably 600 or more, more preferably 700 or more, still more preferably 800 or more, further preferably 900 or more, and yet further preferably 1,000 or more, from the viewpoint of improving the strength of the film, and the like.

[0215] Note that, in the present application, the weight average molecular weight and the number average molecular weight and the dispersity of the organic resin such as the novolak resin as a polymer can be measured, for example, using a GPC device (EcoSEC, HLC-8320 GPC, manufactured by TOSOH Corporation) and a GPC column (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H, manufactured by TOSOH Corporation), setting the column temperature to 40°C, using tetrahydrofuran as an eluent (elution solvent), setting the flow rate (flow velocity) to 0.35 mL / minute, and using polystyrene (manufactured by Sigma Aldrich) as a standard sample.

[0216] As the organic resin contained in the above-described release agent composition, a novolak resin is preferred, and therefore the above-described release agent composition preferably contains a novolak resin alone as the organic resin, and a novolak resin and other polymers can be contained together for the purpose of adjustment of film properties and the like.

[0217] As such other polymers, for example, polyacrylate compounds, polymethacrylate compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, polyacrylonitrile compounds, and the like can be exemplified.

[0218] The content of the novolak resin in the release agent composition is not particularly limited, and is preferably 70% by mass or more relative to the total amount of the polymers contained in the release agent composition.

[0219] The content of the novolak resin in the release agent composition is not particularly limited, and is preferably 50 to 100% by mass relative to the film-constituting components. Note that, in the present application, the film-constituting components refer to the components other than the solvent contained in the composition.

[0220] <Multi-nuclear phenol derivative> The multi-nuclear phenol derivative is represented by the following formula (P), for example. In formula (P), Ar represents an arylene group, the number of carbon atoms of which is not particularly limited, and is usually 6 to 60. From the viewpoint of producing a release agent composition that is excellent in uniformity and that allows a release agent layer that is higher in flatness to be obtained with good reproducibility, the number of carbon atoms is preferably 30 or less, more preferably 20 or less, still more preferably 18 or less, and further preferably 12 or less.

[0221] As specific examples of such arylene groups, condensed ring aromatic hydrocarbon compounds from which two hydrogen atoms on aromatic rings are removed can be exemplified, such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalene diyl, 1,8-naphthalene diyl, 2,6-naphthalene diyl, 2,7-naphthalene diyl, 1,2-anthracene diyl, 1,3-anthracene diyl, 1,4-anthracene diyl, 1,5-anthracene diyl, 1,6-anthracene diyl, 1,7-anthracene diyl, 1,8-anthracene diyl, 2,3-anthracene diyl, 2,6-anthracene diyl, 2,7-anthracene diyl, 2,9-anthracene diyl, 2,10-anthracene diyl, 9,10-anthracene diyl, and the like; ring-bridged ring aromatic hydrocarbon compounds from which two hydrogen atoms on aromatic rings are removed, such as biphenyl-4,4'-diyl, p-terphenyl-4,4"-diyl, and the like, but are not limited thereto.

[0222] From the viewpoint of obtaining a support substrate-releasable layered body with good reproducibility from a peeling agent layer exhibiting good peeling properties, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and still more preferably a polynuclear phenol derivative represented by formula (P1). The content of the polynuclear phenol derivative in the peeling agent composition is not particularly limited, and is preferably 50 to 100% by mass relative to the film-forming components.

[0223] < Branched Polysilane >> The peeling agent composition described above can also contain a branched polysilane.

[0224] The branched polysilane has Si-Si bonds and has a branched structure. By including a branched polysilane in the peeling agent composition described above, the peeling agent layer formed from the resulting film cannot be appropriately removed by any of organic solvents, acids, and chemical solutions used in the production of semiconductor elements (alkaline developing solution, hydrogen peroxide water, etc.), but can be appropriately removed by a cleaning agent composition, as a result of which, by separating the semiconductor substrate from the support substrate of the layered body and then cleaning each substrate with a cleaning agent composition, the residue of the peeling agent layer on the substrate can be appropriately removed. The reason for this is not clear, but it is presumed as follows: depending on the type of the terminal group (terminal substituent (atom)) of the polysilane, the polysilane can crosslink by reacting with an organic resin, and in addition, the branched polysilane has more terminal groups (terminal substituents (atoms)) than the linear polysilane, and thus it is considered that the branched polysilane has more crosslinking points than the linear polysilane, and by moderate and appropriate solidification through such more crosslinking points in the branched polysilane, it is possible to achieve a balance between the characteristic that cannot be appropriately removed by organic solvents, acids, and chemical solutions used in the production of semiconductor elements (alkaline developing solution, hydrogen peroxide water, etc.) and the characteristic that can be appropriately removed by a cleaning agent composition.

[0225] The branched polysilane preferably contains a structural unit represented by formula (B). In formula (B), R B represents a hydrogen atom, a hydroxyl group, a silyl group, or an organic group, and as specific examples of such an organic group, there can be mentioned: hydrocarbon groups (optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, optionally substituted aralkyl groups), ether groups (optionally substituted alkoxy groups, optionally substituted aryloxy groups, optionally substituted aralkoxy groups, etc.) corresponding to these hydrocarbon groups, and the like, and the organic group is usually a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or the like. In addition, a hydrogen atom, a hydroxyl group, an alkoxy group, a silyl group, or the like is often substituted at the terminal.

[0226] The optionally substituted alkyl group can be any of linear, branched, cyclic.

[0227] As specific examples of the optionally substituted linear or branched alkyl group, there can be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, 1-methyln-butyl, 2-methyln-butyl, 3-methyln-butyl, 1,1-dimethyln-propyl, 1,2-dimethyln-propyl, 2,2-dimethyln-propyl, 1-ethyln-propyl, n-hexyl, 1-methyln-pentyl, 2-methyln-pentyl, 3-methyln-pentyl, 4-methyln-pentyl, 1,1-dimethyln-butyl, 1,2-dimethyln-butyl, 1,3-dimethyln-butyl, 2,2-dimethyln-butyl, 2,3-dimethyln-butyl, 3,3-dimethyln-butyl, 1-ethyln-butyl, 2-ethyln-butyl, 1,1,2-trimethyln-propyl, 1,2,2-trimethyln-propyl, 1-ethy l- 1-methyln-propyl, 1-ethy l-2-methyln-propyl, etc., but not limited thereto, and the number of carbon atoms thereof is usually from 1 to 14, preferably from 1 to 10, more preferably from 1 to 6.

[0228] As specific examples of the optionally substituted cyclic alkyl group, there can be mentioned cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc. cycloalkyl; dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc. bicycloalkyl, etc., but not limited thereto, and the number of carbon atoms thereof is usually from 3 to 14, preferably from 4 to 10, more preferably from 5 to 6.

[0229] The alkenyl group can be any of linear, branched, cyclic.

[0230] Specific examples of the optionally substituted straight-chain or branched-chain alkenyl group include vinyl, allyl, butenyl, pentenyl, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 2 to 14, preferably from 2 to 10, and more preferably from 1 to 6.

[0231] Specific examples of the optionally substituted cyclic alkenyl group include cyclopentenyl, cyclohexenyl, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 4 to 14, preferably from 5 to 10, and more preferably from 5 to 6.

[0232] Specific examples of the optionally substituted aryl group include phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 1-naphthyl, 2-naphthyl, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 6 to 20, preferably from 6 to 14, and more preferably from 6 to 12.

[0233] Specific examples of the optionally substituted aralkyl group include benzyl, phenethyl, phenylpropyl, and the like, but are not limited thereto. The optionally substituted aralkyl group is preferably a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0234] The alkyl moiety of the optionally substituted alkoxy group can be any of straight-chain, branched-chain, or cyclic.

[0235] Specific examples of the optionally substituted straight-chain or branched-chain alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentoxy, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 1 to 14, preferably from 1 to 10, and more preferably from 1 to 6.

[0236] Specific examples of the optionally substituted cyclic alkoxy group include cyclopentoxy, cyclohexyloxy, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 3 to 14, preferably from 4 to 10, and more preferably from 5 to 6.

[0237] Specific examples of the optionally substituted aryloxy group include phenoxy, 1-naphthoxy, 2-naphthoxy, and the like, but are not limited thereto, and the number of carbon atoms thereof is usually from 6 to 20, preferably from 6 to 14, and more preferably from 6 to 10.

[0238] Specific examples of the optionally substituted aralkyloxy group include benzyloxy, phenethyloxy, phenylpropyloxy, and the like, but are not limited thereto. The optionally substituted aralkyloxy group is preferably a group in which one hydrogen atom of an alkoxy group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0239] As specific examples of the silyl group, there can be mentioned silyl group, disilyl group, trisilyl group, and the like, but the present application is not limited thereto, and the number of silicon atoms is usually 1 to 10, and preferably 1 to 6.

[0240] In the formula, R B In the case of the above-mentioned organic group or silyl group, at least one of the hydrogen atoms thereof is optionally substituted with a substituent. As specific examples of such substituents, there can be mentioned a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and the like.

[0241] From the viewpoint of inhibiting an unintended peeling when the laminate is brought into contact with any of an organic solvent, an acid, a chemical liquid (alkali developing solution, hydrogen peroxide water, and the like) used in the production of a semiconductor element; the viewpoint of appropriately removing the residue of the peeling agent layer on the substrate in the case where the semiconductor substrate of the laminate and the support substrate are separated and each substrate is cleaned with a cleaning agent composition; and the like, R B It is preferably an alkyl group or an aryl group, more preferably an aryl group, still more preferably a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and further preferably a phenyl group.

[0242] The branched polysilane can also contain the structural unit represented by the formula (B) and the structural unit represented by the following formula (S), the structural unit represented by the following formula (N) together. From the viewpoint of inhibiting an unintended peeling when the laminate is brought into contact with any of an organic solvent, an acid, a chemical liquid (alkali developing solution, hydrogen peroxide water, and the like) used in the production of a semiconductor element; the viewpoint of appropriately removing the residue of the peeling agent layer on the substrate in the case where the semiconductor substrate of the laminate and the support substrate are separated and each substrate is cleaned with a cleaning agent composition; and the like, the content of the structural unit represented by the formula (B) in the branched polysilane is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, further preferably 90 mol% or more, and still further preferably 95 mol% or more, based on the total structural units. (R S1 and R S2 and R B have the same meanings.) The terminal group (terminal substituent (atom)) of the branched polysilane can be usually a hydrogen atom, a hydroxyl group, a halogen atom (chlorine atom, and the like), an alkyl group, an aryl group, an alkoxy group, a silyl group, and the like. Among them, a hydroxyl group, a methyl group, and a phenyl group are predominant, and a methyl group is preferred, and the terminal group can also be a trimethylsilyl group.

[0243] In one aspect, the average degree of polymerization of the branched polysilane is usually 2 to 100, preferably 3 to 80, more preferably 5 to 50, and still more preferably 10 to 30, in terms of silicon atoms (i.e., the average number of silicon atoms per molecule).

[0244] In one embodiment, the upper limit of the weight average molecular weight of the branched polysilane is usually 30,000, preferably 20,000, more preferably 10,000, still more preferably 5,000, further preferably 2,000, yet further preferably 1,500, and the lower limit thereof is usually 50, preferably 100, more preferably 150, still more preferably 200, further preferably 300, yet further preferably 500.

[0245] The average polymerization degree and the weight average molecular weight of the branched polysilane can be measured, for example, using a GPC device (EcoSEC, HLC-8220 GPC, manufactured by TOSOH Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801, manufactured by Showa Denko K.K., used in this order), setting the column temperature to 40°C, using tetrahydrofuran as an eluent (dissolution solvent), setting the flow rate (flow speed) to 1.00 mL / min, and using polystyrene (manufactured by Sigma Aldrich) as a standard sample.

[0246] If the polymerization degree and the weight average molecular weight of the branched polysilane used are too small, the branched polysilane can be vaporized due to heating when forming a film as a release agent layer, when processing a laminate provided with the obtained release agent layer, or the like, or an adverse condition can occur due to poor strength of the film. If the polymerization degree and the molecular weight of the branched polysilane used are too large, depending on the type of solvent used for preparation of the release agent composition, sufficient solubility can not be ensured and precipitation can occur in the composition, or mixing with the resin can not be sufficient, and a film with high uniformity can not be obtained with good reproducibility.

[0247] Therefore, from the viewpoint of further obtaining a laminate provided with a release agent layer that contributes to appropriate manufacturing of a semiconductor element with good reproducibility, it is desirable that the polymerization degree and the weight average molecular weight of the branched polysilane satisfy the above range.

[0248] From the viewpoint of obtaining a release agent layer with excellent heat resistance with good reproducibility, the 5% weight reduction temperature of the branched polysilane is usually 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, still more preferably 380°C or higher, further preferably 395°C or higher, yet further preferably 400°C or higher.

[0249] The 5% weight reduction temperature of the branched polysilane can be measured, for example, by using a 2010SR manufactured by NETZSCH, and raising the temperature from room temperature (25°C) to 400°C at 10°C / min under air.

[0250] From the viewpoint of properly removing residues of the release agent layer on the substrate after separating the semiconductor substrate from the support substrate of the laminate and cleaning each substrate with a cleaning agent composition; and from the viewpoint of preparing a release agent composition with good reproducibility and excellent uniformity, branched polysilanes are preferably soluble in any of the following: ether compounds such as tetrahydrofuran; aromatic compounds such as toluene; glycol ether ester compounds such as propylene glycol monomethyl ether acetate; ketone compounds such as cyclohexanone and methyl ethyl ketone; and glycol ether compounds such as propylene glycol monomethyl ether. It should be noted that, in this case, dissolution refers to the situation where, when attempting to dissolve a 10% by mass solution at room temperature (25°C) using a shaker, it can be visually confirmed that the solution dissolves within 1 hour.

[0251] Branched polysilanes can be in any form, either solid or liquid, at room temperature.

[0252] Branched polysilanes can be manufactured using methods known in publications such as Japanese Patent Application Publication No. 2011-208054, Japanese Patent Application Publication No. 2007-106894, Japanese Patent Application Publication No. 2007-145879, and WO2005 / 113648, and are also available as commercially available products. Specific examples of commercially available products include, but are not limited to, OGSOL SI-20-10 and SI-20-14, polysilanes for silicon materials manufactured by OSAKA GASCHEMICALS Co., Ltd.

[0253] As a preferred example of a branched polysilane, the following substances can be listed, but are not limited thereto. (Ph represents phenyl, R) E Each independently represents a terminal substituent, representing an atom or group, n b (Indicates the number of repeating units.) The content of branched polysilane in the above-mentioned stripping agent composition is generally 10 to 90% by mass relative to the film composition. From the viewpoint of achieving good reproducibility of a film that cannot be properly removed by organic solvents, acids or chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.), but can be properly removed by the cleaning agent composition, it is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and even more preferably 30 to 50% by mass.

[0254] <<<<Cross-linking agent>>>> The stripper composition may also contain a crosslinking agent.

[0255] The crosslinking agent sometimes also causes a crosslinking reaction based on self-condensation, and in the case where crosslinkable substituents are present in the novolak resin, can cause a crosslinking reaction with these crosslinkable substituents.

[0256] Specific examples of the crosslinking agent are not particularly limited, and typical examples that can be cited include: phenol-based crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, thiourea-based crosslinking agents, and the like, which have a crosslink-forming group such as a hydroxymethyl group, a methoxymethyl group, a butoxymethyl group, or the like within the molecule, and which can be either low-molecular-weight compounds or high-molecular-weight compounds.

[0257] The crosslinking agent contained in the release agent composition generally has two or more crosslink-forming groups, and from the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslink-forming groups contained in the compound serving as the crosslinking agent is preferably from 2 to 10, and more preferably from 2 to 6.

[0258] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (e.g., a benzene ring, a naphthalene ring) within the molecule, and typical examples of such a crosslinking agent, without being limited thereto, include phenol-based crosslinking agents.

[0259] The phenol-based crosslinking agent having a crosslink-forming group refers to a compound having a crosslink-forming group bonded to an aromatic ring, and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group, and as such an alkoxy group derived from the phenolic hydroxyl group, a methoxy group, a butoxy group, and the like can be cited, but are not limited thereto.

[0260] The aromatic ring to which the crosslink-forming group is bonded, and the aromatic ring to which the phenolic hydroxyl group and / or the alkoxy group derived from the phenolic hydroxyl group is bonded are not limited to non-condensed ring-type aromatic rings such as benzene rings, and can also be condensed ring-type aromatic rings such as naphthalene rings, anthracene, and the like.

[0261] In the case where a plurality of aromatic rings are present within the molecule of the phenol-based crosslinking agent, the crosslink-forming group, and the phenolic hydroxyl group and the alkoxy group derived from the phenolic hydroxyl group can be bonded to the same aromatic ring within the molecule, or can be bonded to different aromatic rings.

[0262] The aromatic ring to which the crosslink-forming group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group is bonded can also be further substituted with a hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, a butyl group, or the like, an aryl group such as a phenyl group, or the like; a halogen atom such as a fluorine atom, or the like.

[0263] For example, as specific examples of the phenol-based crosslinking agent having a crosslink-forming group, compounds represented by any of the formulas of Formulas (L1) to (L4) can be cited. Among them, each R' independently represents a fluorine atom, an aryl group or an alkyl group, each R" independently represents a hydrogen atom or an alkyl group, L 1 and L 2 each independently represents a single bond, a methylene group or a propane-2, 2-diyl group, L 3 is determined in accordance with q1, represents a single bond, a methylene group, a propane-2, 2-diyl group, a methane triyl group or an ethane-1, 1, 1-triyl group, t11, t12 and t13 are integers satisfying 2≤t11≤5, 1≤t12≤4, 0≤t13≤3 and t11+t12+t13≤6, t21, t22 and t23 are integers satisfying 2≤t21≤4, 1≤t22≤3, 0≤t23≤2 and t21+t22+t23≤5, t24, t25 and t26 are integers satisfying 2≤t24≤4, 1≤t25≤3, 0≤t26≤2 and t24+t25+t26≤5, t27, t28 and t29 are integers satisfying 0≤t27≤4, 0≤t28≤4, 0≤t29≤4 and t27+t28+t29≤4, t31, t32 and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2 and t31+t32+t33≤5, t41, t42 and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1 and t41+t42+t43≤4, q1 is 2 or 3, q2 represents the number of repetitions and is an integer of 0 or more, as specific examples of the aryl group and the alkyl group, the same groups as the specific examples described below can be cited, as the aryl group, a phenyl group is preferred, and as the alkyl group, a methyl group or a tert-butyl group is preferred.

[0264] Hereinafter, specific examples of the compounds represented by the formulae (L1) to (L4) will be cited, but the present application is not limited thereto. Note that these compounds can be synthesized by publicly known methods, or can be obtained as products of, for example, Asahi Organic Chemicals Industry Co., Ltd., or Hokuriku Chemical Industry Co., Ltd. The melamine-based crosslinking agent having a crosslinking-forming group means a melamine derivative, a 2, 4-diamino-l, 3, 5-triazine derivative or a 2-amino-l, 3, 5-triazine derivative in which at least one of the hydrogen atoms of the amino group bonded to the triazine ring is substituted with a crosslinking-forming group, and the triazine ring can further have an aryl group such as a phenyl group as a substituent.

[0265] Specific examples of melamine-based crosslinking agents with crosslinking-forming groups include: mono-, bis-, tri-, tetra-, penta-, or hexaalkoxymethyl melamines such as N,N,N',N',N",N"-hexa(methoxymethyl)melamine and N,N,N',N',N",N"-hexa(butoxymethyl)melamine; mono-, bis-, tri-, or tetraalkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N'-tetra(butoxymethyl)benzoguanamine, but not limited to these.

[0266] A urea-based crosslinking agent with a crosslinking-forming group refers to a derivative of a compound containing a urea bond, having at least one hydrogen atom of the NH group constituting the urea bond replaced by a crosslinking-forming group.

[0267] Specific examples of urea-based crosslinking agents having crosslinking-forming groups include: mono-, di-, tri-, or tetraalkoxymethyl ureas such as 1,3,4,6-tetra(methoxymethyl) urea and 1,3,4,6-tetra(butoxymethyl) urea; mono-, di-, tri-, or tetraalkoxymethyl ureas such as 1,3-bis(methoxymethyl) urea and 1,1,3,3-tetramethoxymethyl urea, but are not limited to these.

[0268] Thiourea-based crosslinking agents with crosslinking-forming groups refer to derivatives of compounds containing thiourea bonds, having a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is replaced by a crosslinking-forming group.

[0269] Specific examples of thiourea-based crosslinking agents with crosslinking-forming groups include mono-, di-, tri-, or tetra-alkoxymethyl thioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetramethoxymethylthiourea, but are not limited to these.

[0270] The amount of crosslinking agent contained in the release agent composition varies depending on the coating method used, the desired film thickness, etc., and therefore cannot be specified in general terms. It is usually 0.01 to 50% by mass relative to the organic resin or polyphenol derivative. From the viewpoint of achieving proper curing and obtaining a laminate in which the semiconductor substrate and the support substrate can be well separated with good reproducibility, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0271] <<<<Acid-producing agents and acids>>>> For purposes such as promoting cross-linking reactions, the stripping agent composition may also contain an acid-producing agent or an acid.

[0272] Examples of acid-producing agents include thermal acid-producing agents and photoacid-producing agents.

[0273] The thermal acid generator is not particularly limited as long as it generates an acid by heat, and as specific examples thereof, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG 2689, K-PURE TAG 2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Shinnakamura Chemical Co., Ltd.), other alkyl esters of organic sulfonic acids, and the like can be given, but are not limited thereto.

[0274] As the photoacid generator, for example, onium salt compounds, sulfimide compounds, and disulfonyl diazomethane compounds, and the like can be given.

[0275] As specific examples of the onium salt compounds, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl) iodonium camphorsulfonate, bis(4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and the like can be given, but are not limited thereto.

[0276] As specific examples of the sulfimide compounds, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalene dicarboxylic acid imide, and the like can be given, but are not limited thereto.

[0277] As specific examples of the disulfonyl diazomethane compounds, bis(trifluoromethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane, bis(phenylsulfonyl) diazomethane, bis(p-toluenesulfonyl) diazomethane, bis(2,4-dimethylphenylsulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyl diazomethane, and the like can be given, but are not limited thereto.

[0278] As specific examples of the acid, there can be mentioned p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium trifluoromethanesulfonic acid salt, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, arylsulfonic acids such as 1-naphthalenesulfonic acid, pyridinium salts and the like, salts thereof; arylcarboxylic acids such as salicylic acid, benzoic acid, hydroxybenzoic acid, naphthoic acid and the like, salts thereof; chain or cyclic alkylsulfonic acids such as trifluoromethanesulfonic acid, camphorsulfonic acid and the like, salts thereof; chain or cyclic alkylcarboxylic acids such as citric acid and the like, salts thereof and the like, but are not limited thereto.

[0279] The amounts of the acid generator and the acid contained in the release agent composition vary depending on the kind of the crosslinking agent used, the heating temperature at the time of forming the film and the like, and thus cannot be generally specified, and are usually 0.01 to 5% by mass with respect to the film-constituting components.

[0280] < Surface active agent > > The release agent composition can also contain a surface active agent, with the aim of adjusting the liquid properties of the composition itself, the film properties of the obtained film; and producing a release agent composition having high uniformity with good reproducibility and the like.

[0281] As the surface active agent, there can be mentioned, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like; polyoxyethylene alkylaryl ether such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and the like; polyoxyethylene-polyoxypropylene block copolymer; sorbitan fatty acid ester such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and the like; polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and the like; nonionic surface active agent such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene-polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like; fluorine-based surface active agent such as EFTOP EF301, EF303, EF352 (Tohkem Products, trade name), MEGAFACE F171, F173, R-30, R-30N (DIC, trade name), Fluorad FC430, FC431 (Sumitomo 3M, trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass, trade name) and the like; silicone polymer KP341 (Shin-Etsu Chemical, trade name) and the like.

[0282] The surfactant can be used singly or in combination of two or more.

[0283] The amount of the surfactant is usually 2% by mass or less relative to the film-forming components of the release agent composition.

[0284] <<<<Solvent>>>> The release agent composition preferably contains a solvent.

[0285] As such a solvent, for example, a high-polar solvent capable of dissolving the above-mentioned film-forming components, such as the organic resin, the polynuclear phenol derivative, the branched polysilane, the crosslinking agent, etc., well can be used, and, as necessary, a low-polar solvent can also be used for the purpose of adjustment of viscosity, surface tension, etc. Note that, in the present application, the low-polar solvent refers to a solvent defined as having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and the high-polar solvent refers to a solvent defined as having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvent can be used singly or in combination of two or more.

[0286] Further, as the high-polar solvent, for example, amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.; ketone-based solvents such as ethyl methyl ketone, isophorone, cyclohexanone, etc.; cyano-based solvents such as acetonitrile, 3-methoxypropionitrile, etc.; polyhydric alcohol-based solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol, etc.; monohydric alcohol-based solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, tetrahydrofurfuryl alcohol, etc.; sulfoxide-based solvents such as dimethyl sulfoxide, etc. can be listed.

[0287] As the low-polar solvent, for example, chlorine-based solvents such as chloroform, chlorobenzene, etc.; aromatic hydrocarbon-based solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene, etc.; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol, 1-decanol, etc.; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, etc.; ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. can be listed.

[0288] The content of the solvent is appropriately determined in consideration of the viscosity of the desired composition, the coating method to be employed, the thickness of the film to be produced, and the like, and is 99% by mass or less of the entire composition, preferably 70 to 99% by mass with respect to the entire composition, i.e., the amount of the film-forming component in this case is 1 to 30% by mass with respect to the entire composition.

[0289] The viscosity and surface tension of the release agent composition are appropriately adjusted by changing the kinds of solvents used, their ratios, the concentration of the film-forming component, and the like in consideration of the coating method to be employed, the desired film thickness, and the like.

[0290] In one aspect of the present application, the release agent composition contains a glycol-based solvent in consideration of the fact that a composition with high uniformity is obtained with good reproducibility, a composition with high storage stability is obtained with good reproducibility, a composition that provides a film with high uniformity is obtained with good reproducibility, and the like. Note that the "glycol-based solvent" as used herein refers to glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0291] One example of the preferred glycol-based solvent is represented by formula (G). In formula (G), R G1 each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, R G2 and R G3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms, n g is an integer of 1 to 6.

[0292] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-l,3-diyl, pentamethylene, hexamethylene, and the like, but are not limited thereto.

[0293] Among these, a linear or branched alkylene group having 2 to 3 carbon atoms is preferred, and a linear or branched alkylene group having 3 carbon atoms is more preferred in consideration of the fact that a composition with high uniformity is obtained with good reproducibility, a composition with high storage stability is obtained with good reproducibility, a composition that provides a film with high uniformity is obtained with good reproducibility, and the like.

[0294] As specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms, there can be mentioned methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 1-methyln-butyl group, 2-methyln-butyl group, 3-methyln-butyl group, 1,1-dimethyln-propyl group, 1,2-dimethyln-propyl group, 2,2-dimethyln-propyl group, 1-ethyln-propyl group, n-hexyl group, 1-methyln-pentyl group, 2-methyln-pentyl group, 3-methyln-pentyl group, 4-methyln-pentyl group, 1,1-dimethyln-butyl group, 1,2-dimethyln-butyl group, 1,3-dimethyln-butyl group, 2,2-dimethyln-butyl group, 2,3-dimethyln-butyl group, 3,3-dimethyln-butyl group, 1-ethyln-butyl group, 2-ethyln-butyl group, 1,1,2-trimethyln-propyl group, 1,2,2-trimethyln-propyl group, 1-ethyl-1-methyln-propyl group, 1-ethyl-2-methyln-propyl group, and the like, but are not limited thereto.

[0295] Among them, from the viewpoint of obtaining a composition having high uniformity with good reproducibility, the viewpoint of obtaining a composition having high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, and the like, a methyl group, an ethyl group are preferred, and a methyl group is more preferred.

[0296] As specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the linear or branched alkyl group having 1 to 8 carbon atoms in the alkylcarbonyl group, there can be mentioned the same groups as the above-mentioned specific examples.

[0297] Among them, from the viewpoint of obtaining a composition having high uniformity with good reproducibility, the viewpoint of obtaining a composition having high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, and the like, a methylcarbonyl group, an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0298] From the viewpoint of obtaining a composition having high uniformity with good reproducibility, the viewpoint of obtaining a composition having high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, and the like, n g It is preferably 4 or less, more preferably 3 or less, further more preferably 2 or less, and most preferably 1.

[0299] From the viewpoint of obtaining a composition having high uniformity with good reproducibility, the viewpoint of obtaining a composition having high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, and the like, in the formula (G), R G2 and R G3 is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R G2 and R G3one of which is a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, and the other of which is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0300] From the viewpoint of obtaining a composition having high uniformity with good reproducibility, the viewpoint of obtaining a composition having high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, and the like, the content of the glycol-based solvent with respect to the solvent contained in the release agent composition is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, further preferably 90% by mass or more, and yet further preferably 95% by mass or more.

[0301] From the viewpoint of obtaining a composition having high uniformity with good reproducibility, the viewpoint of obtaining a composition having high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, and the like, in the release agent composition, the film-constituting components are preferably uniformly dispersed or dissolved in the solvent.

[0302] The release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative, a solvent, and a crosslinking agent as necessary.

[0303] The mixing order is not particularly limited, and as one example of a method that enables easy and good reproducibility in the production of the release agent composition, a method in which the organic resin or the polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent at one time, a method in which a part of the organic resin or the polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent and the remaining part is separately dissolved in the solvent, and the obtained solutions are mixed, or the like can be exemplified, but the present application is not limited thereto. Furthermore, when the release agent composition is prepared, the components can be appropriately heated within a range in which the components are not decomposed or deteriorated.

[0304] In the present application, for the purpose of removing foreign matter, the solvent, the solution, or the like used can be filtered using a filter or the like at the middle of the production of the release agent composition or after all the components are mixed.

[0305] The thickness of the release agent layer is not particularly limited, and is usually 5 nm to 100 μm, in one aspect, 10 nm to 10 μm, in another aspect, 50 nm to 1 μm, and in still another aspect, 100 nm to 700 nm.

[0306] The method of forming the release agent layer from the release agent composition is not particularly limited, and a method in which coating of the release agent composition is performed to form the release agent layer can be exemplified, for example.

[0307] The coating method of the release agent composition is not particularly limited, and is usually a spin coating method.

[0308] The heating temperature of the coated release agent composition varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., and therefore cannot be specified in general. From the viewpoint of achieving a suitable release agent layer with good reproducibility, it is preferably 80°C or higher and 300°C or lower. The heating time is usually appropriately determined within the range of 10 seconds to 10 minutes, depending on the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds or higher and 8 minutes or lower, more preferably 1 minute or higher and 5 minutes or lower.

[0309] Heating can be done using heating plates, ovens, etc.

[0310] The following description uses the accompanying drawings to illustrate an example of the structure of the laminate of the first embodiment.

[0311] Figure 1 A schematic cross-sectional view showing an example of a stacked body according to the first embodiment.

[0312] Figure 1 The laminate sequentially comprises: a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4. That is, the adhesive layer 2 is disposed between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with both the semiconductor substrate 1 and the support substrate 4.

[0313] The following description uses the accompanying drawings to illustrate another example of the structure of the laminate of the first embodiment.

[0314] Figure 2 A schematic cross-sectional view showing another example of a laminated body according to the first embodiment.

[0315] Figure 2 The laminate sequentially comprises: a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4.

[0316] Adhesive layer 2 and release agent layer 3 are disposed between semiconductor substrate 1 and support substrate 4. Adhesive layer 2 is in contact with semiconductor substrate 1. Release agent layer 3 is in contact with adhesive layer 2 and support substrate 4.

[0317] <<Method for manufacturing an example of a laminate in the first embodiment>> In the laminate of the first embodiment Figure 1 The laminate shown is an example. The manufacturing method of the laminate is described below.

[0318] An example of the laminate of the present invention can be manufactured by a method including the following first step to second step.

[0319] First step: a step of applying the adhesive composition to the semiconductor substrate to form an adhesive coating layer.

[0320] Second step: a step of heating the adhesive coating layer to form an adhesive layer.

[0321] The method of applying the adhesive composition is not particularly limited, and is typically spin coating. Note that a method in which a coating film is formed separately by spin coating or the like, and the coating film is formed into a sheet shape and the sheet-shaped coating film is attached as the adhesive coating layer can be employed.

[0322] The heating temperature of the adhesive composition after application is different depending on the type and amount of the adhesive component 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, and thus cannot be specified generally, and is typically 80 to 150°C, and the heating time thereof is typically 30 seconds to 5 minutes.

[0323] In the case where the adhesive composition contains a solvent, the adhesive composition after application is typically heated.

[0324] The film thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating the same is typically about 5 to 500 μm, and is appropriately determined in a range such that the thickness of the adhesive layer described above is ultimately obtained.

[0325] In the present application, the thickness direction load of the semiconductor substrate and the support substrate can be applied while the heating treatment or the reduced pressure treatment or both are performed, and then, the post-heating treatment is performed, whereby the laminate of the present application is obtained. Note that any of the treatment conditions of the heating treatment, the reduced pressure treatment, and the combination thereof is appropriately determined on the basis of consideration of the type of the adhesive composition, the film thickness, the required adhesive strength, and the like.

[0326] The heating treatment is typically appropriately determined in a range of 20 to 160°C from the viewpoint of removing the solvent from the composition and the like. In particular, from the viewpoint of inhibiting or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), it is preferred to be 150°C or lower, and more preferred to be 130°C or lower, and the heating time thereof is appropriately determined depending on the heating temperature and the type of the adhesive, and is typically 30 seconds or more, and preferably 1 minute or more from the viewpoint of reliably achieving appropriate adhesion, and is typically 10 minutes or less, and preferably 5 minutes or less from the viewpoint of inhibiting the deterioration of the adhesive layer and other members.

[0327] The reduced pressure treatment is performed by exposing the adhesive coating layers in contact with each other to a gas pressure of 10 to 10,000 Pa. The time of the reduced pressure treatment is typically 1 to 30 minutes.

[0328] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the layers between them, and can make them firmly and tightly bonded. It is usually in the range of 10 to 50,000 N.

[0329] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260°C or lower.

[0330] From the viewpoint of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or more, preferably 5 minutes or more. From the viewpoint of suppressing or avoiding adverse effects on each layer caused by excessive heating, the post-heating time is usually 180 minutes or less, preferably 120 minutes or less.

[0331] Heating can be performed using a heating plate, oven, or similar equipment. When using a heating plate for post-heating, either the semiconductor substrate or the support substrate of the laminate can be heated with the substrate facing downwards. However, from the viewpoint of achieving proper peeling with good reproducibility, it is preferable to heat the substrate with the semiconductor substrate facing downwards.

[0332] It should be noted that one of the purposes of the post-heat treatment is to achieve an adhesive layer that functions as a more suitable self-supporting film, particularly to achieve proper curing based on the hydrosilanization reaction.

[0333] Figure 3A Figure 3C is a diagram illustrating one method for manufacturing a laminated body.

[0334] First, a laminate with an adhesive coating layer 2a is prepared on a semiconductor substrate 1. Figure 3A This laminate can be obtained, for example, by applying an adhesive composition onto a semiconductor substrate 1 and then heating it.

[0335] Next, Figure 3A The laminate and support substrate 4 shown are bonded together with the adhesive coating layer 2a in contact with the support substrate 4. 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 (not shown; heating plate) is placed on the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive coating layer 2a. The adhesive coating layer 2a is heated by the heating device to cure it, transforming it into adhesive layer 2 ( Figure 3B ).

[0336] pass Figures 3A-3B The process shown can yield Figure 1 The layered structure shown.

[0337] <Second Implementation Plan> The layer stack with the electronic device layer is used for processing of the electronic device layer. During the processing of the electronic device layer, the electronic device layer is bonded to the support substrate. After the processing of the electronic device layer, the electronic device layer is separated from the support substrate.

[0338] <<Electronic device layer>> The electronic device layer refers to a layer with electronic devices, and in the present application, refers to a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, refers to a layer including a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.

[0339] Here, the "electronic device" refers to a member constituting at least a part of an electronic component. The electronic device is not particularly limited, and can be an electronic device in which various mechanical structures, circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a member composed of a metal or a semiconductor and a resin sealing or insulating the member. The electronic device can be an electronic device sealed or insulated by a sealing material or an insulating material for a rewiring layer and / or a semiconductor element or other elements described later, and has a single layer or a multilayer structure.

[0340] <<Support substrate>> As the support substrate, the same support substrate as that described in the column of <<Support substrate>> of the above-described <First Embodiment> of the present application can be exemplified.

[0341] <<Peeling agent layer>> The peeling agent layer is formed using the peeling agent composition for light irradiation peeling of the present application described above.

[0342] The peeling agent layer is described in detail in the column of <<Peeling agent layer>> of the above-described <First Embodiment>.

[0343] <<Adhesive layer>> The adhesive layer is formed using the adhesive composition described above.

[0344] The adhesive layer is described in detail in the column of <<Adhesive layer>> of the above-described <First Embodiment>.

[0345] One example of the configuration of the layer stack of the second embodiment will be described below using the drawings.

[0346] Figure 4 The layer stack of the second embodiment has, in order, a support substrate 24, an adhesive layer 22, and an electronic device layer 26.

[0347] The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21.

[0348] The adhesive layer 22 is provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26 and the support substrate 24.

[0349] Figure 5 A schematic cross-sectional view showing another example of the laminate of the second embodiment.

[0350] Figure 5 The laminate of the second embodiment has, in order, the support substrate 24, the release agent layer 23, the adhesive layer 22, and the electronic device layer 26.

[0351] The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material provided between the semiconductor chip substrates 21.

[0352] The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0353] <<Manufacturing method of one example of the laminate in the second embodiment>> The laminate in the second embodiment is described above. Figure 4 The laminate described above will be described below as an example of the manufacturing method of the laminate.

[0354] The laminate of the present application can be manufactured, for example, by a method including the following first to fourth processes.

[0355] First process: a process of applying an adhesive composition to the surface of the above-described support substrate to form an adhesive application layer (further heated as necessary to form an adhesive layer).

[0356] Second process: a process of placing a semiconductor chip substrate on the adhesive application layer or the adhesive layer, and adhering the semiconductor chip substrate to the adhesive application layer or the adhesive layer while at least either one of a heating treatment and a reduced pressure treatment is performed.

[0357] Third process: a process of forming an adhesive layer by performing a post-heating treatment on the adhesive application layer to cure it.

[0358] Fourth process: a process of sealing the semiconductor chip substrate fixed to the adhesive layer with a sealing resin.

[0359] The second process will be described in more detail, for example, by the following (i).

[0360] (i) placing the semiconductor chip substrate on the adhesive-coated layer or the adhesive layer, while at least one of a heat treatment and a reduced pressure treatment is performed, applying a load in the thickness direction of the semiconductor chip substrate and the support substrate to adhere them, and adhering the semiconductor chip substrate to the adhesive-coated layer or the adhesive layer.

[0361] Note that the third process can be performed after the semiconductor chip substrate is adhered to the adhesive-coated layer in the second process, or can be performed together with the second process. For example, the semiconductor chip substrate can be placed on the adhesive-coated layer, while a load in the thickness direction of the semiconductor chip substrate and the support substrate is applied, the adhesive-coated layer is heated to cure it, thereby adhering the semiconductor chip substrate to the adhesive-coated layer and curing the adhesive-coated layer to the adhesive layer at the same time, and adhering the adhesive layer to the semiconductor chip substrate.

[0362] Further, the third process can be performed before the second process, or the semiconductor chip substrate can be placed on the adhesive layer, while a load in the thickness direction of the semiconductor chip substrate and the support substrate is applied, and the adhesive layer is adhered to the semiconductor chip substrate.

[0363] The coating method, the heating temperature of the coated adhesive composition, the heating method, and the like are as described above in the above-mentioned

[0364] The manufacturing method of the laminate of the second embodiment will be further described in detail below with reference to the drawings. In this manufacturing method, a laminate as shown in FIG. 2 is manufactured. Figure 4

[0365] As shown in FIG. 2, an adhesive-coated layer 22' formed of an adhesive composition is formed on a support substrate 24. At this time, the adhesive-coated layer 22' can be heated to form an adhesive layer 22. Figure 6A

[0366] Next, as shown in FIG. 2, a semiconductor chip substrate 21 is placed on the adhesive layer 22 or the adhesive-coated layer 22', while at least one of a heat treatment and a reduced pressure treatment is performed, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to adhere them, and the semiconductor chip substrate 21 is adhered to the adhesive layer 22 or the adhesive-coated layer 22'. In the case where the semiconductor chip substrate 21 is adhered to the adhesive-coated layer 22', the adhesive-coated layer 22' is cured by a post-heating treatment to form the adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22. Figure 6B

[0367] Next, as shown in FIG. 2, a semiconductor chip substrate 21 is placed on the adhesive layer 22 or the adhesive-coated layer 22', while at least one of a heat treatment and a reduced pressure treatment is performed, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to adhere them, and the semiconductor chip substrate 21 is adhered to the adhesive layer 22 or the adhesive-coated layer 22'. In the case where the semiconductor chip substrate 21 is adhered to the adhesive-coated layer 22', the adhesive-coated layer 22' is cured by a post-heating treatment to form the adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22. Figure 6C ​​​As shown, the semiconductor chip substrates 21 fixed on the adhesive layer 22 are sealed using a sealing resin 25. In Figure 6C In this case, the plurality of semiconductor chip substrates 21 temporarily adhered to the support substrate 24 via the adhesive layer 22 are sealed with the sealing resin 25. An electronic device layer 26 having the semiconductor chip substrates 21 and the sealing resin 25 arranged between the semiconductor chip substrates 21 is formed on the adhesive layer 22, and thus the electronic device layer 26 becomes a base material layer in which the plurality of semiconductor chip substrates are embedded in the sealing resin.

[0368] <<Sealing Process>> The semiconductor chip substrates 21 are sealed using a sealing material.

[0369] As the sealing material for sealing the semiconductor chip substrates 21, a member capable of insulating or sealing a member composed of a metal or a semiconductor is used.

[0370] In the present application, as the sealing material, for example, a resin composition (sealing resin) is used. As the kind of the sealing resin, there is no particular limitation as long as it can seal and / or insulate a metal or a semiconductor, and for example, an epoxy-based resin or a silicone-based resin or the like is preferably used.

[0371] The sealing material can contain other components such as a filler in addition to the resin component. As the filler, for example, spherical silica particles or the like can be listed.

[0372] In the sealing process, for example, the sealing resin is heated to 130 to 170°C to maintain a state of high viscosity and is supplied to the adhesive layer 22 in a manner of covering the semiconductor chip substrates 21, compression molding is performed, and thus a layer formed of the sealing resin 25 is formed on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170°C. In addition, the pressure applied to the semiconductor chip substrates 21 is, for example, 50 to 500 N / cm 2 .

[0373] (Method for manufacturing processed semiconductor substrate or electronic device layer) If the laminate of the present application is used, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided.

[0374] The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the column of the above-described <first embodiment> of the above-described (laminate). In addition, the "method for manufacturing a processed electronic device layer" uses the laminate described in the column of the above-described <second embodiment> of the above-described (laminate).

[0375] A method for manufacturing a processed semiconductor substrate will be described in the following <Third Embodiment>, and a method for manufacturing a processed electronic device layer will be described in the following <Fourth Embodiment>.

[0376] <Third Embodiment> The method for manufacturing a processed semiconductor substrate of the present application includes the following 5A step and the following 6A step. The method for manufacturing a processed semiconductor substrate can further include the following 7A step.

[0377] Here, the 5A step is a step of processing the semiconductor substrate in the laminate described in the column of the above <First Embodiment>.

[0378] Further, the 6A step is a step of separating the semiconductor substrate processed by the 5A step from the support substrate.

[0379] Further, the 7A step is a step of cleaning the processed semiconductor substrate after the 6A step.

[0380] The processing of the semiconductor substrate in the 5A step refers to, for example, processing of the side opposite to the circuit surface of the wafer, and the thinning of the wafer by polishing of the back surface of the wafer can be cited. Then, formation of a silicon through electrode (TSV) or the like is performed, and then the thinned wafer is peeled from the support substrate, the laminate of the wafer is formed, and three-dimensional mounting is performed. Further, formation of the wafer back surface electrode or the like is performed before and after the three-dimensional mounting. In the thinning of the wafer and the TSV process, heat of about 250 to 350°C is applied in a state of being adhered to the support substrate. The laminate of the present application generally includes an adhesive layer, and has heat resistance against the application thereof.

[0381] Note that the processing is not limited to the above processing, and for example, mounting processes of semiconductor components in the case where temporary adhesion to the support substrate is performed for the purpose of supporting a substrate for mounting the semiconductor components, or the like can be included.

[0382] In the 6A step, the method of separating (peeling) the semiconductor substrate from the support substrate is not particularly limited.

[0383] For example, a method of performing mechanical peeling using a tool having a sharp portion (so-called peeler) can be cited. Specifically, for example, after inserting the sharp portion between the semiconductor substrate and the support substrate, the semiconductor substrate and the support substrate are separated.

[0384] Further, in the case where the laminate has a release agent layer, in the 6A step, the method of separating (peeling) the semiconductor substrate from the support substrate can be peeling or the like by tearing between the semiconductor substrate and the support substrate after irradiating light to the release agent layer.

[0385] By irradiating light to the peeling agent layer from the supporting substrate side, the deterioration of the peeling agent layer (for example, separation or decomposition of the peeling agent layer) occurs as described above, and then, for example, by pulling up either of the substrates, the semiconductor substrate can be easily separated from the supporting substrate.

[0386] The irradiation of light to the peeling agent layer does not necessarily need to be performed to the entire area of the peeling agent layer. Even if the area irradiated with light and the area not irradiated with light are mixed, as long as the peeling ability of the peeling agent layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the supporting substrate by a slight external force such as pulling up the supporting substrate. The ratio and positional relationship of the area irradiated with light to the area not irradiated with light vary depending on the kind of the adhesive used, the specific composition thereof; the thickness of the adhesive layer; the thickness of the peeling agent layer; the intensity of the light irradiated; and the like, but if it is a person skilled in the art, appropriate conditions can be set without excessive experiments. Due to such a situation, the manufacturing method of the processed semiconductor substrate according to the present application, for example, in the case where the supporting substrate of the laminate used has light transmittance, the light irradiation time can be shortened when peeling is performed by light irradiation from the supporting substrate side, as a result, not only improvement in production amount can be expected, but also physical stress and the like for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the supporting substrate only by the irradiation of light.

[0387] Generally, the amount of light irradiated for peeling is 50 to 3000 mJ / cm 2 The irradiation time is appropriately determined depending on the wavelength and the amount of irradiation.

[0388] The wavelength of the light used for peeling is, for example, preferably a wavelength of 250 to 600 nm, and more preferably a wavelength of 250 to 370 nm. A more appropriate wavelength is 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light irradiated for peeling is the amount of irradiation that causes appropriate deterioration of a specific compound and a polymer, for example, decomposition.

[0389] The light used for peeling can be laser light, or non-laser light emitted from a light source such as an ultraviolet lamp.

[0390] The surface of at least either of the separated semiconductor substrate and the supporting substrate can be cleaned by spraying a cleaning agent composition thereon, or by immersing the separated semiconductor substrate or the supporting substrate in a cleaning agent composition.

[0391] In addition, the surface of the processed semiconductor substrate and the like can be cleaned using a tape and the like.

[0392] As one example of cleaning the substrate, a 7A process of cleaning the processed semiconductor substrate can be performed after the 6A process.

[0393] The cleaning agent composition used for cleaning can be exemplified by the following substances.

[0394] The cleaning agent composition generally contains a solvent.

[0395] As the solvent, for example, lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, aromatic organic solvents, and the like can be exemplified.

[0396] As the lactones, for example, γ-butyrolactone and the like can be exemplified.

[0397] As the ketones, for example, acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone, and the like can be exemplified.

[0398] As the polyhydric alcohols, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and the like can be exemplified.

[0399] As the compounds having an ester bond, for example, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, and the like can be exemplified.

[0400] As the derivatives of polyhydric alcohols, for example, monoalkyl ethers such as mono methyl ether, mono ethyl ether, mono propyl ether, mono butyl ether, or mono phenyl ether of the above polyhydric alcohols or the above compounds having an ester bond, or compounds having an ether bond can be exemplified. Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferred.

[0401] As the cyclic ethers, for example, dioxane and the like can be exemplified.

[0402] As the esters, for example, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and the like can be exemplified.

[0403] As the aromatic organic solvents, for example, anisole, benzyl ethyl ether, methyl anisole, diphenyl ether, dibenzyl ether, phenyl ethyl ether, phenyl butyl ether, ethyl benzene, diethyl benzene, amyl benzene, isopropyl benzene, toluene, xylene, isopropyl toluene, mesitylene, and the like can be exemplified.

[0404] They can be used singly or in combination of two or more.

[0405] Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate (EL) are preferred.

[0406] Further, a mixed solvent in which PGMEA is mixed with a polar solvent is also preferred. The mixing ratio (mass ratio) of PGMEA and the polar solvent is appropriately determined taking into account the compatibility of PGMEA and the polar solvent, and is preferably in the range of 1:9 to 9:1, more preferably in the range of 2:8 to 8:2.

[0407] For example, in the case where EL is used as the polar solvent, the mass ratio of PGMEA:EL is preferably in the range of 1:9 to 9:1, more preferably in the range of 2:8 to 8:2. Further, in the case where PGME is used as the polar solvent, the mass ratio of PGMEA:PGME is preferably in the range of 1:9 to 9:1, more preferably in the range of 2:8 to 8:2, further preferably in the range of 3:7 to 7:3. Further, in the case where PGME and cyclohexanone are used as the polar solvent, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably in the range of 1:9 to 9:1, more preferably in the range of 2:8 to 8:2, further preferably in the range of 3:7 to 7:3.

[0408] The cleaning agent composition can or can not contain a salt, and it is preferred that the cleaning agent composition does not contain a salt from the viewpoint of improving the versatility in the processing of a semiconductor substrate using the layered body and the viewpoint of suppressing the cost.

[0409] As one example of the case where the cleaning agent composition contains a salt, a cleaning agent composition containing a quaternary ammonium salt and a solvent can be given.

[0410] 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 such a purpose.

[0411] As such a quaternary ammonium cation, a tetra(hydrocarbon)ammonium cation can be typically given. On the other hand, as an anion paired with the same, a hydroxide ion (OH － ), a fluoride ion (F － ), a chloride ion (Cl － ), a bromide ion (Br － ), an iodide ion (I － ), halogen ions, a tetrafluoroborate ion (BF4 － ), a hexafluorophosphate ion (PF6 － ), and the like can be given, but are not limited thereto.

[0412] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0413] In the quaternary ammonium salt, the halogen atom can be contained in the cation or the anion, and is preferably contained in the anion.

[0414] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.

[0415] As specific examples of the hydrocarbon group in the tetra(hydrocarbon)ammonium fluoride, there can be mentioned an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like.

[0416] In a more preferable aspect, the tetra(hydrocarbon)ammonium fluoride contains a tetraalkylammonium fluoride.

[0417] As specific examples of the tetraalkylammonium fluoride, there can be mentioned tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride), and the like, but the present application is not limited thereto. Among them, tetrabutylammonium fluoride is preferable.

[0418] The quaternary ammonium salt such as the tetra(hydrocarbon)ammonium fluoride can also be a hydrate. Furthermore, the quaternary ammonium salt such as the tetra(hydrocarbon)ammonium fluoride can be used alone or in combination of two or more.

[0419] The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the cleaning agent composition, and is usually 0.1 to 30 mass% relative to the cleaning agent composition.

[0420] In the case where the cleaning agent composition contains a salt, as the solvent to be used in combination, there is no particular limitation as long as it is used for such a purpose and dissolves the salt such as the quaternary ammonium salt, and the cleaning agent composition preferably contains one or two or more amide-based solvents from the viewpoint of obtaining a cleaning agent composition having excellent cleaning properties with good reproducibility, the viewpoint of obtaining a cleaning agent composition having excellent uniformity by dissolving the salt such as the quaternary ammonium salt well, and the like.

[0421] As a preferable example of the amide-based solvent, there can be mentioned an amide derivative represented by formula (Z). In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms can be any of a linear shape, a branched shape, and a cyclic shape, and specifically there can be mentioned a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a cyclobutyl group, and the like. Among them, as R A and R B , a methyl group or an ethyl group is preferable, and more preferably both are a methyl group or an ethyl group, and still more preferably both are a methyl group.

[0422] As the amide derivative represented by formula (Z), N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, N-ethyl-N-methylisobutyramide, and the like can be exemplified. Among them, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are particularly preferable, and N,N-dimethylpropionamide is more preferable.

[0423] The amide derivative represented by formula (Z) can be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, and commercially available products can also be used.

[0424] As another example of the preferred amide-based solvent, a lactam compound represented by formula (Y) can be exemplified. In 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. As specific examples of the alkyl group having 1 to 6 carbon atoms, methyl group, ethyl group, n-propyl group, n-butyl group, and the like can be exemplified, and as specific examples of the alkylene group having 1 to 6 carbon atoms, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and the like can be exemplified, but are not limited thereto.

[0425] As specific examples of the lactam compound represented by formula (Y), α-lactam compound, β-lactam compound, γ-lactam compound, δ-lactam compound, and the like can be exemplified, and one kind alone or two or more kinds in combination can be used.

[0426] In a preferred embodiment, the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), and in a more preferred embodiment, N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP) is contained, and in a still more preferred embodiment, N-methylpyrrolidone (NMP) is contained.

[0427] Note that the cleaning agent composition used in the present application can also contain water as a solvent, but generally, it is intended to use only an organic solvent as a solvent from the viewpoint of avoiding corrosion of the substrate and the like. Note that in this case, water of hydration of a salt, and a trace amount of water contained in the organic solvent can be contained in the cleaning agent composition, and this is not denied. The water content of the cleaning agent composition used in the present application is generally 5 mass% or less.

[0428] Regarding the constituent elements and method elements related to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention, various modifications may be made as long as they do not depart from the spirit of the present invention.

[0429] The manufacturing method of the processed semiconductor substrate of the present invention may also include steps other than those described above.

[0430] In one example of the peeling method of the present invention, when the semiconductor substrate or support substrate of the laminate of the present invention is transparent, the semiconductor substrate of the laminate is separated from the support substrate by irradiating the peeling agent layer with light from the semiconductor substrate side or the support substrate side.

[0431] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are appropriately and peelably temporarily bonded by an adhesive layer and a release agent layer. Therefore, for example, if the support substrate is light-transmitting, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer from the support substrate side of the laminate. Typically, the peeling is performed after the semiconductor substrate of the laminate has been processed.

[0432] use Figures 7A-7D An example of the third embodiment will be described. This example is an example of manufacturing a thinned semiconductor substrate.

[0433] First, prepare the stacked body ( Figure 7A This laminate is with Figure 1 and Figure 3B The stack shown is the same as the stack shown.

[0434] Next, a polishing apparatus (not shown) is used to polish the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1. Figure 7B It should be noted that through-electrodes can also be formed on the thinned semiconductor substrate 1.

[0435] Next, using a peeling device (not shown), the thinned semiconductor substrate 1 is separated from the support substrate 4. Figure 7C ).

[0436] Thus, a thinned semiconductor substrate 1 is obtained. Figure 7D ).

[0437] Here, adhesive layer 2 residues sometimes remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 with a cleaning agent composition to remove the adhesive layer 2 residues from the semiconductor substrate 1.

[0438] <Fourth Implementation Plan> The method for manufacturing the processed electronic device layer of the present invention includes steps 5B and 6B as described below. The method for manufacturing the processed electronic device layer may further include step 7B as described below.

[0439] Here, step 5B is the process of processing the electronic device layer in the laminate described in the column of the above-mentioned <Second Implementation Scheme>.

[0440] In addition, step 6B is a process that separates the electronic device layer processed in step 5B from the support substrate.

[0441] In addition, step 7B is the process of cleaning the processed electronic device layer after step 6B.

[0442] The following uses Figures 8A-8F Specific examples of the fourth implementation method will be described.

[0443] The processing performed on the electronic device layer in process 5B can include, for example, grinding and wiring layer formation.

[0444] <<Grinding Process>> The grinding process is a process of grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 with a portion of the semiconductor chip substrate 21 exposed.

[0445] Grinding of the sealing resin portion, for example, Figure 8B As shown, by Figure 8A The sealing resin 25 of the laminate shown is ground to approximately the same thickness as the semiconductor chip substrate 21. It should be noted that... Figure 8A The stacked body shown is with Figure 4 and Figure 6C The stack shown is the same as the stack shown.

[0446] <<Wireline Layer Formation Process>> The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding process.

[0447] exist Figure 8C In this process, a wiring layer 28 is formed on an electronic device layer 26 that includes a semiconductor chip substrate 21 and a sealing resin 25.

[0448] The wiring layer 28, also known as the RDL (Redistribution Layer), is a thin film of wiring that forms the wiring connected to the substrate. It can have a single-layer or multi-layer structure. The wiring layer can utilize a conductor (such as metals like aluminum, copper, titanium, nickel, gold, and silver, as well as alloys like silver-tin alloys) on a dielectric (silicon oxide (SiO2)). xThe wiring layer 28 is formed by forming a wiring between the layers of the sealing resin 25, the oxide layer 26, the dielectric layer 27 (a photosensitive resin layer, a photosensitive epoxy resin layer, or the like), and the like, but is not limited thereto.

[0449] As a method of forming the wiring layer 28, for example, the following methods can be listed.

[0450] First, the oxide layer 26 (SiO2 layer) is formed on the layer of the sealing resin 25. x The dielectric layer formed of the photosensitive resin is formed, for example, by applying the photosensitive resin to the layer of the sealing resin 25 using a method such as spin coating, dipping, a roller blade, spray coating, slit coating, or the like.

[0451] Next, a wiring is formed on the dielectric layer using a conductive body such as a metal. As a method of forming the wiring, for example, a known semiconductor process method such as a photolithography process (resist photolithography), an etching process, or the like can be used. As such a photolithography process, for example, a photolithography process using a positive resist material, a photolithography process using a negative resist material can be listed.

[0452] In the manufacturing method of the laminate of the fourth embodiment, the formation of a bump or the mounting of a component on the wiring layer 28 can be further performed. The mounting of a component on the wiring layer 28 can be performed, for example, using a chip mounter or the like.

[0453] The laminate of the fourth embodiment can be a laminate manufactured in a process based on a fan-out technology in which a terminal provided on a semiconductor chip substrate is mounted on a wiring layer extended outside a chip region.

[0454] In the sixth B process, a method of separating (peeling) the electronic device layer from the support substrate can be listed as follows: mechanical peeling using a tool having a sharp portion, peeling by tearing between the support body and the electronic device layer, or the like, but is not limited thereto.

[0455] In a case where the laminate has a release agent layer, for example, by irradiating light to the release agent layer from the support substrate side, the deterioration (for example, separation or decomposition of the release agent layer) of the release agent layer occurs as described above, and then, for example, by pulling up either of the substrates, the electronic device layer can be easily separated from the support substrate.

[0456] Figures 8D-8E is a schematic cross-sectional view for explaining a separation method of a laminate, Figure 8F is a schematic cross-sectional view for explaining a cleaning method after the separation of a laminate. By Figures 8D-8F , one embodiment of a manufacturing method of a semiconductor package (electronic component) can be explained.

[0457] like Figure 8D and Figure 8E As shown, the process of separating the laminate is a process of separating the electronic device layer 26 from the support substrate 24 using a peeling device (not shown).

[0458] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least any of the separated electronic device layer and the support substrate, or by immersing the separated electronic device layer or the support substrate in the cleaning agent composition.

[0459] In addition, it can also be used to clean the surface of processed electronic device layers, etc., by removing adhesive tape.

[0460] For example, in Figure 8E In the process, after the separation step, an adhesive layer 22 is attached to the electronic device layer 26. This adhesive layer 22 can be removed by using a cleaning agent composition such as an acid or alkali to decompose it. By removing the adhesive layer, a suitable product can be obtained... Figure 8F The processed electronic device layer (electronic component) is shown.

[0461] Regarding the constituent elements and methodological elements related to the above-described steps of the method for manufacturing the processed electronic device layer of the present invention, various modifications may be made as long as they do not depart from the spirit of the present invention.

[0462] The manufacturing method of the processed electronic device layer of the present invention may also include processes other than those described above.

[0463] Example The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that the apparatus used is as described below.

[0464] [Apparatus] (1) Mixer: ARE-500 self-rotating and revolution-rotating mixer manufactured by THINKY Corporation.

[0465] (2) Vacuum bonding device: SUSS MicroTec Co., Ltd., XBS-300.

[0466] (3) Debonding device: SUSS MicroTec Co., Ltd., automatic debonder.

[0467] [1] Preparation of adhesive composition [Example 1-1] To a 300 mL stirring container for a blender, 70.1 g of MQ resin containing polysiloxane and vinyl (manufactured by Wacker Chemie) and 37.5 g of linear polydimethylsiloxane containing vinyl having a viscosity of 200 mPa-s (manufactured by Wacker Chemie) as polyorganosiloxane (al), 9.3 g of linear polydimethylsiloxane containing SiH group having a viscosity of 100 mPa-s (manufactured by Wacker Chemie) as polyorganosiloxane (a2), 0.15 g of 1,1-diphenyl-l,2- propargyl-l-alcohol (manufactured by Tokyo Chemical Industry) as polymerization inhibitor, 0.18 g of platinum catalyst (manufactured by Wacker Chemie) as platinum group metal-based catalyst (A-3), and 1.1 g of methanol-modified silicone oil (X-22-4015, side chain type, manufactured by Shin-Etsu Chemical) as release agent component were added, and stirred for 5 minutes with a blender. To the resulting mixture, 0.15 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as polymerization inhibitor and 14.5 g of p-menthane (manufactured by Tokyo Chemical Industry) as solvent were added, and stirred for 5 minutes with a blender, to obtain an adhesive composition. Note that the proportion of the components other than the solvent in the resulting adhesive composition (nonvolatile components) was 88.0 mass%. The content of the methanol-modified silicone oil with respect to the nonvolatile components was 1 mass%.

[0468] [Example 1-2] To a 300 mL stirring container for a blender, 84.1 g of MQ resin containing polysiloxane and vinyl (manufactured by Wacker Chemie) and 23.6 g of linear polydimethylsiloxane containing vinyl having a viscosity of 200 mPa-s (manufactured by Wacker Chemie) as polyorganosiloxane (al), 10.9 g of linear polydimethylsiloxane containing SiH group having a viscosity of 100 mPa-s (manufactured by Wacker Chemie) as polyorganosiloxane (a2), 0.2 g of 1,1-diphenyl-l,2- propargyl-l-alcohol (manufactured by Tokyo Chemical Industry) as polymerization inhibitor, 0.2 g of platinum catalyst (manufactured by Wacker Chemie) as platinum group metal-based catalyst (A-3), and 0.3 g of methanol-modified silicone oil (X-22-4015, side chain type, manufactured by Shin-Etsu Chemical) as release agent component were added, and stirred for 5 minutes with a blender. To the resulting mixture, 0.2 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as polymerization inhibitor and 16.8 g of p-menthane (manufactured by Tokyo Chemical Industry) as solvent were added, and stirred for 5 minutes with a blender, to obtain an adhesive composition. Note that the proportion of the components in the resulting adhesive composition other than the solvent (nonvolatile components) was 86.3 mass%. The content of the methanol-modified silicone oil with respect to the nonvolatile components was 0.25 mass%.

[0469] [Examples 1-3] To a 300 mL stirring container for a blender, 94.8 g of MQ resin containing polysiloxane and vinyl (manufactured by Wacker Chemie) and 0.2 g of linear vinyl group-containing polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 200 mPa-s as polyorganosiloxane (al), 12.0 g of linear SiH group-containing polydimethylsiloxane (Wacker Chemie) having a viscosity of 100 mPa-s as polyorganosiloxane (a2), 0.2 g of 1,1-diphenyl-1,2- propargyl-1-alcohol (manufactured by Tokyo Chemical Industry) as a polymerization inhibitor, 0.3 g of platinum catalyst (manufactured by Wacker Chemie) as a platinum group metal-based catalyst (A-3), and 15.9 g of methanol-modified silicone oil (KF-6003, both end type, manufactured by Shin-Etsu Chemical) as a release agent component were added, and stirred for 5 minutes with a blender. To the resulting mixture, 0.2 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as a polymerization inhibitor and 15.4 g of p-menthane (manufactured by Tokyo Chemical Industry) as a solvent were added, and stirred for 5 minutes with a blender, to obtain an adhesive composition. Note that the proportion of the components other than the solvent in the resulting adhesive composition (nonvolatile components) was 88.0% by mass. The content of the methanol-modified silicone oil with respect to the nonvolatile components was 15% by mass.

[0470] [Comparative Example 1-1] To a 300 mL stirring container for a blender, 94.8 g of MQ resin containing polysiloxane and vinyl (manufactured by Wacker Chemie) and 0.2 g of linear vinyl group-containing polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 200 mPa-s as polyorganosiloxane (al), 12.0 g of linear SiH group-containing polydimethylsiloxane (Wacker Chemie) having a viscosity of 100 mPa-s as polyorganosiloxane (a2), 0.2 g of 1,1-diphenyl-1,2- propargyl-1-alcohol (manufactured by Tokyo Chemical Industry) as a polymerization inhibitor, 0.3 g of platinum catalyst (manufactured by Wacker Chemie) as a platinum group metal-based catalyst (A-3), and 15.9 g of methanol-modified silicone oil (KF-6003, both end type, manufactured by Shin-Etsu Chemical) as a release agent component were added, and stirred for 5 minutes with a blender. To the resulting mixture, 0.2 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as a polymerization inhibitor and 15.4 g of p-menthane (manufactured by Tokyo Chemical Industry) as a solvent were added, and stirred for 5 minutes with a blender, to obtain an adhesive composition. Note that the proportion of the components other than the solvent in the resulting adhesive composition (nonvolatile components) was 88.0% by mass. The content of the methanol-modified silicone oil with respect to the nonvolatile components was 15% by mass.

[0471] [2] Manufacture of laminates and confirmation of release properties [Example 2-1] The adhesive composition obtained in Examples 1-1 was spin-coated onto a 300 mm thick silicon wafer (thickness: 775 μm) serving as the device side. The wafer was then heated at 90°C for 1.5 minutes (pre-heat treatment) to remove residual solvent, forming an adhesive coating layer approximately 60 μm thick. Next, in a vacuum bonding apparatus, the silicon wafer with the adhesive coating layer was bonded to a 300 mm thick silicon wafer (thickness: 775 μm) serving as the carrier side (support) by clamping the adhesive coating layer. The wafer was heated on a hot plate with the device side facing down at 130°C for 5 minutes, followed by a further heating at 200°C for 5 minutes (post-heat treatment), thereby producing a laminate. It should be noted that the bonding was performed under a load of 500 N for 3 minutes at a temperature of 50°C and a pressure reduction of 1000 Pa.

[0472] [Example 2-2], [Example 2-3] and [Comparative Example 2-1] The adhesive compositions obtained in Examples 1-2, 1-3 and Comparative Example 1-1 were used instead of the adhesive composition obtained in Example 1-1, and otherwise, the laminates were obtained by the same method as in Example 2-1.

[0473] The obtained laminates were examined using a peeling device to confirm their debonding properties. In the evaluation of debonding properties, cases where debonding was achieved using the peeling device were classified as good, and cases where debonding was not achieved were classified as poor. The results are shown in Table 1. As a result, the de-adhesion properties of the laminates of Examples 2-1, 2-2, and 2-3 were good, while the de-adhesion properties of the laminate of Comparative Example 2-1, which did not contain the release agent component, were poor. Thus, it can be confirmed that de-adhesion properties can be obtained by introducing methanol-modified polyorganosiloxane in the adhesive composition of the present invention.

[0474] Furthermore, compared to methanol-terminated polyorganosiloxanes, side-chain-modified polyorganosiloxanes can impart good de-adhesion properties with a smaller addition amount.

[0475] Explanation of reference numerals in the attached figures 1: Semiconductor substrate; 2: Adhesive layer; 2a: Adhesive coating layer; 3: Release agent layer; 4: Support substrate; 21: Semiconductor chip substrate; 22: Adhesive layer; 22': Adhesive coating layer; 23: Release agent layer; 24: Support substrate; 25: Sealing resin; 26: Electronic device layer; 28: Wiring layer.

Claims

1. An adhesive composition comprising an adhesive component and a methanol-modified polyorganosiloxane.

2. The adhesive composition according to claim 1, wherein, The methanol-modified polyorganosiloxane is methanol-modified polydimethylsiloxane.

3. The adhesive composition according to claim 1, wherein, The methanol-modified polyorganosiloxane has hydroxyl groups on its side chains that are directly bonded to carbon atoms.

4. The adhesive composition according to claim 1, wherein, The methanol-modified polyorganosiloxane has hydroxyl groups at both ends that are directly bonded to carbon atoms.

5. The adhesive composition according to claim 1, wherein, The content of the methanol-modified polyorganosiloxane in the non-volatile component of the adhesive composition is 0.01% to 30% by mass.

6. The adhesive composition according to claim 1, wherein, The adhesive component is a component that is cured through a hydrogenation silanization reaction.

7. The adhesive composition according to claim 6, wherein, The component cured by the hydrogenation silanization reaction contains: Composition A-1 has an alkenyl group with 2 to 40 carbon atoms bonded to silicon atoms; Component A-2 containing Si-H groups; and Platinum group metal catalyst A-3.

8. The adhesive composition according to claim 7, wherein, The component A-1 contains a polyorganosiloxane a1 having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.

9. The adhesive composition according to claim 7, wherein, The component A-2 contains a polyorganosiloxane with Si-H groups.

10. A laminated body having: Semiconductor substrate or electronic device layer; Transparent support substrate; and An adhesive layer disposed between the semiconductor substrate or the electronic device layer and the support substrate. The adhesive layer is an adhesive layer formed from the adhesive composition as described in any one of claims 1 to 9.

11. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: Step 5A involves processing the semiconductor substrate of the laminate as described in claim 10; Alternatively, in step 5B, the electronic device layer of the laminate as described in claim 10 is processed; as well as In step 6A, the semiconductor substrate processed in step 5A is separated from the support substrate; or in step 6B, the electronic device layer processed in step 5B is separated from the support substrate.

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