Laminate and release agent composition

Abstract

A laminate comprising a semiconductor substrate, a support substrate, a release layer provided so as to be in contact with the semiconductor substrate, and an adhesive layer provided between the support substrate and the release layer, wherein the laminate is characterized in that the release layer is a film obtained from a release agent composition containing a polyorganosiloxane component formed from polydimethylsiloxane, the viscosity at 25°C of the polyorganosiloxane component is 5.50×103 Pa⋅s to 0.75×103 Pa⋅s, and the thickness of the film is 0.01-4.90 μm.

Description

[Technical Field]

[0001] The present invention relates to a laminate and a release agent composition. [Background technology]

[0002] Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of even greater integration, there is a demand for semiconductor integration technology that integrates (stacks) the plane in a three-dimensional direction. This three-dimensional stacking is a technology that integrates multiple layers while connecting them using through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are stacked.

[0003] Semiconductor wafers (herein simply referred to as wafers) before thinning are bonded to a support in preparation for polishing with a polishing device. This bond must be easily peeled off after polishing, and is therefore called a temporary bond. This temporary bond must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary bond is that it can withstand the stress during polishing and be easily removed after polishing. Under these circumstances, it is necessary to have a performance that provides high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the vertical direction during removal (for example, Patent Documents 1 and 2).

[0004] Incidentally, the semiconductor wafer is electrically connected to the semiconductor chip via bump balls made of a conductive material such as metal, and by using chips equipped with such bump balls, miniaturization of semiconductor packaging is being attempted. Bump balls are usually made of metal such as solder and are therefore vulnerable to loads such as pressure, and may be deformed by the load applied during bonding in the manufacturing process of semiconductor devices (see, for example, Patent Document 3). While these issues exist, with recent advances in the semiconductor field, there is a growing demand for technology that suppresses deformation of bump balls caused by loads such as pressure in the manufacturing process of semiconductor devices. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-64040 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-106486 [Patent Document 3] International Publication No. 2018 / 083964 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-179135 [Patent Document 5] US Publication No. 2012 / 0329249 [Patent Document 6] International Publication No. 2012 / 118700 [Patent Document 7] Japanese Patent Application Laid-Open No. 2014-146793 [Patent Document 8] International Publication No. 2015 / 190438 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminate including a release layer that has excellent heat resistance during bonding of a semiconductor substrate and a support substrate, during processing of the back surface of the semiconductor substrate, and can suppress damage to the semiconductor substrate caused by loads such as pressure during manufacturing of semiconductor devices, and a release agent composition that provides a film suitable as such a release layer. [Means for solving the problem]

[0007] As a result of intensive research by the present inventors to solve the above problems, they have found that the above problems can be solved by forming a laminate comprising a semiconductor substrate, a support substrate, a release layer provided in contact with the semiconductor substrate, and an adhesive layer provided between the support substrate and the release layer, wherein the release layer is a film obtained from a release agent composition containing a polyorganosiloxane component made of polydimethylsiloxane, and the viscosity of the polyorganosiloxane component is set to a predetermined value and the thickness of the film is set to a predetermined range, thereby completing the present invention. Patent Documents 4 to 8 disclose techniques relating to wafer processed bodies, substrate processing methods, laminates using temporary adhesives, and the like, but none of the documents specifically discloses the combination of the viscosity range and film thickness range of the present invention or the effects achieved thereby.

[0008] That is, the present invention is 1. semiconductor substrate, a supporting substrate, a release layer provided in contact with the semiconductor substrate; and A laminate including an adhesive layer provided between the support substrate and the release layer, the release layer is a film obtained from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane, The viscosity of the polyorganosiloxane component at 25°C is 5.50 x 10 3 Pa·s~0.75×10 3 Pa·s, a laminate characterized in that the thickness of the film is 0.01 μm to 4.90 μm; 2. The viscosity of the polyorganosiloxane component at 25°C is 5.00 x 10 3 Pa·s~0.80×10 3 1 laminate, which is Pa·s, 3. The viscosity of the polyorganosiloxane component at 25°C is 4.52 x 10 3 Pa·s~0.96×10 3 A laminate of 2, where Pa·s 4. The laminate of any one of 1 to 3, wherein the thickness of the film is 0.25 μm to 3.75 μm. 5. The laminate of 4, wherein the thickness of the film is 1.75 μm to 2.75 μm. 6. The laminate according to any one of 1 to 5, wherein the adhesive layer is provided so as to be in contact with the support substrate and the release layer. 7. The laminate of any one of 1 to 6, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) including at least one selected from the group consisting of polyorganosiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide-based adhesives, and phenolic resin-based adhesives. 8. The laminate of 7, wherein the adhesive component (S) contains a polysiloxane adhesive. 9. The laminate of 8, wherein the polyorganosiloxane adhesive contains a polyorganosiloxane component (A) that cures by a hydrosilylation reaction; 10. A release agent composition for forming a release layer of a laminate comprising a semiconductor substrate, a support substrate, a release layer provided in contact with the semiconductor substrate, and an adhesive layer provided between the support substrate and the release layer, wherein the release layer has a film thickness of 0.01 μm to 4.90 μm, the release agent composition comprising a polyorganosiloxane component made of polydimethylsiloxane, and a viscosity of the polyorganosiloxane component at 25°C of 5.50 × 10 3 Pa·s~0.75×10 3 a stripper composition having a Pa·s; 11. The viscosity of the polyorganosiloxane component at 25°C is 5.00 x 10 3 Pa·s~0.80×10 3 10 stripper compositions with Pa·s, 12. The viscosity of the polyorganosiloxane component at 25°C is 4.52 x 10 3 Pa·s~0.96×10 3 11 stripper compositions with Pa·s; 13. The release agent composition of any one of 10 to 12, wherein the thickness of the film is 0.25 μm to 3.75 μm. 14. The release agent composition of 13, wherein the thickness of the film is 1.75 μm to 2.75 μm. 15. The release agent composition according to any one of 10 to 14, wherein the adhesive layer is provided so as to be in contact with the support substrate and the release layer. 16. The release agent composition of any one of 10 to 15, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) including at least one adhesive selected from the group consisting of polyorganosiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide-based adhesives, and phenolic resin-based adhesives. 17. The release agent composition of 16, wherein the adhesive component (S) comprises a polyorganosiloxane adhesive. 18. The release agent composition of 17, wherein the polyorganosiloxane adhesive contains a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. to provide. [Effects of the Invention]

[0009] The laminate of the present invention is a laminate comprising a semiconductor substrate, a support substrate, a release layer provided so as to be in contact with the semiconductor substrate, and an adhesive layer provided between the support substrate and the release layer, wherein the release layer is a film obtained from a release agent composition containing a polyorganosiloxane component made of polydimethylsiloxane, a thermoplastic polymer having excellent heat resistance, and the viscosity of the polyorganosiloxane component at 25°C is adjusted to a predetermined range, and the thickness of the film is adjusted to a predetermined range, so that the laminate has excellent heat resistance and suppresses damage to the semiconductor substrate, such as deformation of the bumps on the semiconductor substrate, caused by external loads such as pressure.

[0010] By using the laminate of the present invention having such characteristics, it is expected that semiconductor elements with higher reliability can be manufactured.

[0011] The reason why the effects of the present invention are achieved by satisfying the viscosity range and film thickness range of the present invention is presumed to be as follows.

[0012] That is, if the release layer is too thin, the protective function of suppressing damage to the semiconductor substrate will be reduced, but if the release layer is too thick, the fluidity will be high, resulting in a reduction in protective function. Also, if the viscosity of the polyorganosiloxane component is too low, the fluidity will be high and the protective function will be reduced. On the other hand, if the viscosity of the polyorganosiloxane component is too high, the adhesion of the release layer between adjacent functional layers such as adhesive layers and substrates will deteriorate, and interfacial peeling will be more likely to occur. As a result, it is estimated that the protective function will be reduced. As the polyorganosiloxane component that constitutes the film, polydimethylsiloxane exhibiting good heat resistance and peelability is used, and the viscosity of the component is adjusted to a predetermined range. It is presumed that the above effect was achieved by adjusting the film thickness to a predetermined range. DETAILED DESCRIPTION OF THE INVENTION

[0013] A laminate comprising a semiconductor substrate, a support substrate, a release layer provided in contact with the semiconductor substrate, and an adhesive layer provided between the support substrate and the release layer, wherein the release layer is a film obtained from a release agent composition containing a polyorganosiloxane component made of polydimethylsiloxane, and the viscosity of the polyorganosiloxane component at 25°C is 5.50 × 10 3 Pa·s~0.75×10 3 The laminate has a viscosity of 100 Pa·s and a thickness of the film of 0.01 μm to 4.90 μm. In a preferred embodiment, the laminate of the present invention comprises a semiconductor substrate, a support substrate, a release layer provided in contact with the semiconductor substrate, and an adhesive layer in contact with the support substrate and the release layer.

[0014] The semiconductor substrate is, for example, a wafer that has a circuit surface on the front surface and is processed on the back surface. A specific example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm, but is not limited to this.

[0015] In particular, according to the present invention, even if the semiconductor substrate has functional parts on its surface, such as electrodes such as bumps or pillars, or electrical connection parts such as terminals, by providing a release layer in contact with these, damage to the functional parts due to heating or pressure can be avoided or suppressed.

[0016] Specific examples of semiconductor substrates with bumps include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, which are usually selected appropriately from the following conditions: bump height of about 1 to 200 μm, bump diameter of 1 μm to 200 μm, and bump pitch of 1 μm to 500 μm.

[0017] Specific examples of plated bumps include, but are not limited to, alloy plating mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. Examples of materials constituting the pillars of the pillar-equipped semiconductor substrate include, but are not limited to, alloys mainly containing Sn, copper and its alloys, and the like.

[0018] The support substrate is a support (carrier) that is bonded to support the semiconductor substrate, and a specific example thereof is a glass wafer with a diameter of about 300 mm and a thickness of about 700 μm, but is not limited to this.

[0019] As described above, the release layer of the laminate of the present invention is a film obtained from a release agent composition containing a polyorganosiloxane component made of polydimethylsiloxane, and the viscosity of the polyorganosiloxane component at 25°C is 5.50 × 10 3 Pa·s~0.75×10 3 Pa·s, and the thickness of the film is 0.01 μm to 4.90 μm.

[0020] From the viewpoint of reproducibly suppressing damage to the semiconductor substrate, such as deformation of bumps on the semiconductor substrate, caused by external loads such as pressure and temperature, the upper limit of the viscosity is preferably 5.00×10 3 Pa·s, more preferably 4.52×10 3The lower limit of the viscosity is preferably 0.80×10 3 Pa·s, more preferably 0.96×10 3 From the viewpoint of reproducibly obtaining a laminate from which the substrates can be easily separated even after the application of external loads such as pressure and temperature, the upper limit of the viscosity is more preferably 4.02 × 10 3 Pa·s, more preferably 3.50×10 3 The lower limit of the viscosity is more preferably 0.98×10 3 Pa·s, more preferably 1.00×10 3 Pa·s.

[0021] In the present invention, the viscosity of the polyorganosiloxane component can be measured using a rheometer such as the Viscoelasticity Measuring Apparatus MCR302 manufactured by Anton Paar Japan.

[0022] From the viewpoint of reproducibly suppressing damage to the semiconductor substrate, such as deformation of the bumps on the semiconductor substrate, caused by external loads such as pressure and temperature, the upper limit of the thickness of the film is preferably 3.75 μm, more preferably 2.75 μm, and the lower limit of the thickness of the film is preferably 0.25 μm, more preferably 1.75 μm. Furthermore, from the viewpoint of reproducibly obtaining a laminate from which the substrates can be easily separated even after application of external loads such as pressure and temperature, the upper limit of the thickness of the film is even more preferably 2.70 μm, even more preferably 2.65 μm, and the lower limit of the thickness of the film is even more preferably 1.80 μm, even more preferably 1.85 μm.

[0023] The polydimethylsiloxane used in the present invention is represented by formula (X), but it is not denied that polydimethylsiloxane may contain trace amounts of impurity structures containing groups other than -Si(CH3)3 groups and -Si(CH3)2-O- groups at the terminals or in the middle of the repeating units in the bulk of the polydimethylsiloxane.

[0024] [ka] (nm indicates the number of repeating units and is a positive integer.)

[0025] As described above, the release agent composition contains a polyorganosiloxane component made of polydimethylsiloxane. Therefore, the polyorganosiloxane component contains exclusively polydimethylsiloxane. However, it is not denied that polyorganosiloxanes other than polydimethylsiloxane may be contained in the bulk of the polydimethylsiloxane.

[0026] In this regard, the purity of the polydimethylsiloxane used in the present invention cannot be generally defined as it varies depending on the molecular weight, dispersity, purity of the raw materials used, and the synthesis method employed, but is usually 99% or higher.

[0027] The weight average molecular weight of the polydimethylsiloxane used in the present invention is usually 100,000 to 2,000,000, and the dispersity is usually 1.0 to 10.0.

[0028] The polyorganosiloxane component used in the present invention is composed of one or more polydimethylsiloxanes, and one or more polydimethylsiloxanes within the above-mentioned weight average molecular weight and dispersity ranges are appropriately selected so as to satisfy the above-mentioned viscosity conditions.

[0029] The weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxanes such as polydimethylsiloxanes can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0030] The stripping agent composition may contain a solvent. Such a solvent is not particularly limited as long as it can dissolve the polyorganosiloxane component well. Specific examples of such a good solvent include linear or branched aliphatic hydrocarbons such as linear or branched aliphatic saturated hydrocarbons, such as hexane, heptane, octane, nonane, decane, undecane, dodecane, and isododecane; cyclic aliphatic saturated hydrocarbons, such as cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, and p-menthane; and cyclic aliphatic unsaturated hydrocarbons, such as limonene. Cyclic aliphatic hydrocarbons such as hydrocarbons; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, cumene, 1,4-diisopropylbenzene, p-cymene; aliphatic saturated hydrocarbon ketones such as MIBK (methyl isobutyl ketone), ethyl methyl ketone, acetone, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, and other dialkyl ketones; cycloalkyl ketones such as cyclohexanone; and alkane such as isophorone. ketones such as aliphatic unsaturated hydrocarbon ketones such as phenyl ketone; ethers such as dialkyl ethers such as diethyl ether, di(n-propyl) ether, di(n-butyl) ether, and di(n-pentyl) ether, and cyclic alkyl ethers such as tetrahydrofuran and dioxane; sulfides such as dialkyl sulfides such as diethyl sulfide, di(n-propyl) sulfide, and di(n-butyl) sulfide; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; nitriles such as acetonitrile and 3-methoxypropionitrile; glycol monohydrocarbon ethers such as glycol monoalkyl ethers such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether, and glycol monoaryl ethers such as diethylene glycol monophenyl ether;Alkyl alcohols such as cyclic alkyl alcohols such as cyclohexanol, and monoalcohols other than alkyl alcohols such as diacetone alcohol, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; glycol monoalkyl ethers such as ethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether, 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, diethylene glycol monomethyl ether, and tripropylene glycol monobutyl ether; Glycol monoethers such as glycol monoaryl ethers such as phenoxyethanol; glycol diethers such as glycol dialkyl ethers such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether; glycol ether acetates such as glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate; cyclic carbonates such as ethylene carbonate, propylene carbonate, and vinylene carbonate;Examples of suitable solvents include esters such as butyl acetate and pentyl acetate. These solvents can be used singly or in combination of two or more.

[0031] Furthermore, the release agent composition may contain one or more poor solvents in addition to the good solvent for the purpose of adjusting viscosity or surface tension, as long as the polyorganosiloxane component does not precipitate. Specific examples of poor solvents include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; linear or branched alkyl monoalcohols such as methanol, ethanol, and propanol; and glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, triethylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.

[0032] When the release agent composition contains a solvent, the amount of the solvent can usually be 70% by mass to 99.9% by mass based on the total mass of the composition, and therefore the amount of the polyorganosiloxane component consisting of polydimethylsiloxane is 0.1% by mass to 30% by mass based on the total mass of the composition.

[0033] The release agent composition may contain other components in addition to the polyorganosiloxane component made of polydimethylsiloxane and the solvent, as long as the effects of the present invention are not impaired. However, from the viewpoint of reproducibly obtaining a film with excellent uniformity and avoiding the complication of preparing the composition, the release agent composition contains only the polyorganosiloxane component made of polydimethylsiloxane and the solvent.

[0034] The release agent composition can be produced, for example, by mixing the polyorganosiloxane component with a solvent.

[0035] The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the polyorganosiloxane components are dissolved in a solvent at once, or a method in which a part of the polyorganosiloxane components is dissolved in a solvent and the rest is separately dissolved in a solvent, and the resulting solutions are mixed. When preparing the release agent composition, heating may be performed as appropriate within a range that does not cause the components to decompose or deteriorate.

[0036] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a submicrometer-order filter during the production of the stripping composition or after all components have been mixed.

[0037] The above-described release agent composition is also a subject of the present invention, and the related conditions (preferable conditions, production conditions, etc.) are as described above. By using the release agent composition of the present invention, it is possible to reproducibly produce a film suitable as a release layer that can be used, for example, in the production of semiconductor elements.

[0038] The release layer, which is a film obtained from the release agent composition of the present invention, is composed of a polyorganosiloxane component consisting of polydimethylsiloxane, and is therefore not a cured film but a thermoplastic film. Use of such a thermoplastic film can effectively suppress damage to semiconductor substrates.

[0039] The adhesive layer provided in the laminate of the present invention can be, for example, a film obtained from an adhesive composition containing the adhesive component (S).

[0040] Such adhesive component (S) is not particularly limited as long as it is used for this type of application, and examples thereof include, but are not limited to, polyorganosiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide-based adhesives, and phenolic resin-based adhesives.

[0041] Among these, polyorganosiloxane adhesives (polyorganosiloxane components) are preferred as the adhesive component (S) because they exhibit favorable adhesive properties during processing of wafers, etc., can be easily peeled off after processing, have excellent heat resistance, and are compatible with the above-mentioned release layer.

[0042] In a preferred embodiment, the adhesive composition used in the present invention contains, as an adhesive component, a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. In a more preferred example, the polyorganosiloxane component (A) that cures by a hydrosilylation reaction contains a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 Siloxane unit (M unit) represented by R 4 R 5 SiO 2 / 2 Siloxane units (D units) represented by the formula 6 SiO 3 / 2 and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (Q' units) represented by SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane unit (M' unit) represented by R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) represented by the formula: and R 6 'SiO 3 / 2 and a polyorganosiloxane (a1) containing one or more units selected from the group consisting of siloxane units (T' units) represented by the following formula: and at least one unit selected from the group consisting of the M' units, D' units and T' units; a polyorganosiloxane (a2) containing siloxane units (Q" units) represented by the formula: 1 "R 2 "R 3 "SiO 1 / 2 Siloxane unit (M" unit) represented by R 4 "R 5 "SiO2 / 2 Siloxane units (D" units) represented by and R 6 "SiO 3 / 2 and a polyorganosiloxane (a2) containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing at least one unit selected from the group consisting of the M" units, D" units and T" units.

[0043] R 1 ~R 6 are groups or atoms bonded to the silicon atom, and each independently represents an alkyl group, an alkenyl group, or a hydrogen atom.

[0044] R 1 '~R 6 R ' is a group bonded to a silicon atom, and each independently represents an alkyl group or an alkenyl group. 1 '~R 6 At least one of the groups is an alkenyl group.

[0045] R 1 ”~R 6 " are groups or atoms bonded to the silicon atom, and each independently represents an alkyl group or a hydrogen atom, but R 1 ”~R 6 At least one of " is a hydrogen atom.

[0046] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. 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.

[0047] Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, Examples of alkyl groups include, but are not limited to, a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Of these, a methyl group is preferred.

[0048] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl cycloalkyl groups such as 1-n-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these.

[0049] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0050] Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2 -propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1 -pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4 -methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propenyl Examples of the alkyl group include, but are not limited to, ethenyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group. Of these, ethenyl group and 2-propenyl group are preferred.

[0051] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and the alkenyl group contained in the polyorganosiloxane (a1) and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2) undergo a hydrosilylation reaction in the presence of a platinum group metal catalyst (A2) to form a crosslinked structure and cure, resulting in the formation of a cured film.

[0052] The polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As the polyorganosiloxane (a1), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0053] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

[0054] Furthermore, when the polyorganosiloxane (a1) contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

[0055] The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q″ units, M″ units, D″ units, and T″ units, and also contains at least one unit selected from the group consisting of M″ units, D″ units, and T″ units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0056] Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

[0057] The polyorganosiloxane (a1) is composed of siloxane units in which alkyl and / or alkenyl groups are bonded to the silicon atoms thereof, and R1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0058] The polyorganosiloxane (a2) is composed of siloxane units in which alkyl groups and / or hydrogen atoms are bonded to the silicon atoms. 1 ”~R 6 The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R is preferably 0.1 mol % to 50.0 mol %, more preferably 10.0 mol % to 40.0 mol %, and the remaining R 1 ”~R 6 " can be an alkyl group.

[0059] The polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2). In a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0060] The weight average molecular weight of each of the polysiloxanes such as the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 500 to 1,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.

[0061] The viscosity of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 10 to 1,000,000 (mPa·s), but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 50 to 10,000 (mPa·s). The viscosity of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is a value measured at 25°C using an E-type rotational viscometer.

[0062] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film by hydrosilylation, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0063] In a preferred embodiment of the present invention, the adhesive component (S) contains a platinum group metal catalyst (A2) in addition to the above-mentioned polysiloxane (A1). Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si—H groups of the polyorganosiloxane (a2).

[0064] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate.

[0065] Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.

[0066] The amount of the platinum group metal catalyst (A2) is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0067] The polyorganosiloxane component (A) may contain a polymerization inhibitor (A3) for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol.

[0068] The amount of the polymerization inhibitor is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0069] The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition, the resulting adhesive layer can be suitably peeled off with good reproducibility.

[0070] A typical example of such a release agent component (B) is a polyorganosiloxane, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0071] Preferred examples of the polyorganosiloxane that is the release agent component (B) include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0072] The weight-average molecular weight of the polyorganosiloxane that is the release agent component (B) is usually 100,000 to 2,000,000, but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, and its dispersity is usually 1.0 to 10.0, but from the viewpoint of achieving suitable release with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured by the methods described above.

[0073] The viscosity of the polyorganosiloxane, which is the release agent component (B), is usually 1,000 to 2,000,000 mm 2The viscosity value of the polyorganosiloxane, which is the release agent component (B), is expressed as a kinematic viscosity, and is expressed as centistokes (cSt) = mm 2 / s. Viscosity (mPa s) is converted to density (g / cm 3 ) can be calculated by dividing the viscosity and density measured with an E-type rotational viscometer at 25°C. 2 / s)=viscosity (mPa s) / density (g / cm 3 ) can be calculated from the formula:

[0074] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0075] R 11 is a group bonded to a silicon atom and represents an alkyl group, and R 12 is a group bonded to a silicon atom, and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those listed above.

[0076] The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.

[0077] Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.

[0078] In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

[0079] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D10 units), but D 10 In addition to the units, the above Q units, M units and / or T units may be included.

[0080] In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D 10 Polyorganosiloxane consisting of only units, D 10 polyorganosiloxanes containing D units and Q units; 10 Polyorganosiloxanes containing D units and M units, 10 Polyorganosiloxanes containing D units and T units, 10 polyorganosiloxanes containing units, Q units and M units, D 10 Polyorganosiloxanes containing units, M units and T units, D 10 Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0081] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5, and its weight average molecular weight is usually 1,500 to 500,000, but from the viewpoint of suppressing precipitation in the adhesive, it is preferably 100,000 or less.

[0082] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0083] [ka] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0084] [ka] (m2 and n2 each represent the number of repeating units and are positive integers, and R represents an alkylene group having 1 to 10 carbon atoms.)

[0085] [ka] (m3, n3, and o3 each represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0086] Examples of the methyl group-containing polyorganosiloxane include R 210 R 220 SiO 2 / 2 The siloxane unit (D 200 units), preferably R 21 R 22 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing units.

[0087] R 210 and R 220 are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above.

[0088] R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include those listed above. 21 As the alkyl group, a methyl group is preferred.

[0089] In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0090] The methyl group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 200 Unit or D 20 units), but D 200 Units and D 20 In addition to the units, the above Q units, M units and / or T units may be included.

[0091] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D200 Polyorganosiloxane consisting of only units, D 200 polyorganosiloxanes containing D units and Q units; 200 Polyorganosiloxanes containing D units and M units, 200 Polyorganosiloxanes containing D units and T units, 200 polyorganosiloxanes containing units, Q units and M units, D 200 Polyorganosiloxanes containing units, M units and T units, D 200 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0092] In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 20 Polyorganosiloxane consisting of only units, D 20 polyorganosiloxanes containing D units and Q units; 20 Polyorganosiloxanes containing D units and M units, 20 Polyorganosiloxanes containing D units and T units, 20 polyorganosiloxanes containing units, Q units and M units, D 20 Polyorganosiloxanes containing units, M units and T units, D 20 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0093] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0094] [ka] (n4 represents the number of repeating units and is a positive integer.)

[0095] Examples of the phenyl group-containing polyorganosiloxane include R 31 R 32 SiO 2 / 2 The siloxane unit (D 30 Examples include those containing units.

[0096] R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R 32 is a group bonded to a silicon atom, and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0097] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 units), but D 30 In addition to the units, the above Q units, M units and / or T units may be included.

[0098] In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include D 30 Polyorganosiloxane consisting of only units, D 30 polyorganosiloxanes containing D units and Q units; 30 Polyorganosiloxanes containing D units and M units, 30 Polyorganosiloxanes containing D units and T units, 30 polyorganosiloxanes containing units, Q units and M units, D 30 Polyorganosiloxanes containing units, M units and T units, D 30 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0099] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0100] [ka] (m5 and n5 each represent the number of repeating units and are positive integers.)

[0101] [ka] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0102] The adhesive composition used in the present invention can contain the adhesive component (S) and the release agent component (B) in any ratio. However, in consideration of the balance between adhesion and release properties, the mass ratio of component (S) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0103] That is, when a polyorganosiloxane component (A) that cures via a hydrosilylation reaction is contained, the mass ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0104] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., and specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0105] More specific examples include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. These solvents can be used alone or in combination of two or more.

[0106] When the adhesive composition used in the present invention contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the film to be produced, etc., but is in the range of about 10 to 90 mass % of the entire composition.

[0107] The viscosity of the adhesive composition used in the present invention is typically 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s, at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratio, the concentration of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness. In the present invention, film-constituting components refer to components contained in the composition other than the solvent.

[0108] The adhesive composition used in the present invention can be prepared by mixing the adhesive component (S), the release agent component (B), if used, and a solvent.

[0109] The order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (S) and the release agent component (B) in a solvent, or a method of dissolving part of the adhesive component (S) and part of the release agent component (B) in a solvent and the rest in a solvent, and then mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause the components to decompose or deteriorate.

[0110] In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a submicrometer-order filter during the production of the adhesive composition or after all of the components have been mixed.

[0111] The thickness of the adhesive layer provided in the laminate of the present invention is usually 5 to 500 μm, but from the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more, and from the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

[0112] The laminate of the present invention can be produced, for example, by a method including: a first step of applying a release agent composition to the surface of a semiconductor substrate and, if necessary, heating the composition to form a release agent coating layer; a second step of applying an adhesive composition to the surface of a support substrate and, if necessary, heating the composition to form an adhesive coating layer; and a third step of applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring the release agent coating layer of the semiconductor substrate and the adhesive coating layer of the support substrate into close contact with each other while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate. As long as the effect of the present invention is not impaired, the coating and heating of each composition may be carried out sequentially on either one of the substrates.

[0113] The coating method is not particularly limited, but is usually a spin coating method. Alternatively, a method may be employed in which a coating film is formed separately by a spin coating method or the like, and the sheet-like coating film is attached as an adhesive coating layer or a release agent coating layer.

[0114] The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., but is usually 80°C to 150°C, and the heating time is usually 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is usually heated.

[0115] The heating temperature of the applied release agent composition cannot be generally specified because it differs depending on the type and amount of the acid generator, the boiling point of the solvent used, the desired thickness of the release layer, etc., but is 80°C or higher from the viewpoint of reproducibly realizing a suitable release layer, and is 300°C or lower from the viewpoint of suppressing decomposition of the acid generator, etc., and the heating time is determined appropriately depending on the heating temperature, usually within the range of 10 seconds to 10 minutes. When the stripper composition contains a solvent, the applied stripper composition is usually heated.

[0116] Heating can be carried out using a hot plate, an oven, or the like.

[0117] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is appropriately determined so that the final thickness of the adhesive layer falls within the above-mentioned range.

[0118] The film thickness of the release agent coating layer obtained by applying the release agent composition and heating it is appropriately determined so that the final thickness of the release layer falls within the above-mentioned range.

[0119] In the present invention, the laminate of the present invention can be obtained by placing such coated layers in contact with each other, applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment, a decompression treatment, or both, to adhere the two layers, and then performing a post-heat treatment. Note that the treatment conditions to be used, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition and the desired adhesive strength.

[0120] The heat treatment temperature is typically determined appropriately within the range of 20 to 150° C. from the viewpoint of softening the adhesive coating layer to realize suitable bonding with the release agent coating layer, and from the viewpoint of suitable curing of a type of adhesive that does not sufficiently cure by heating when forming the adhesive coating layer. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component (S), the heat treatment temperature is preferably 130° C. or lower, more preferably 90° C. or lower, and the heating time is typically 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, but typically 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0121] The reduced pressure treatment can be carried out by exposing the adhesive coated layer and the release agent coated layer, which are in contact with each other, to an air pressure of 10 Pa to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0122] From the viewpoint of reproducibly obtaining a laminate from which the substrates can be easily separated, the adhesive coating layer and the release agent coating layer that are in contact with each other are preferably bonded together by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.

[0123] 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, the support substrate, and the two layers therebetween and is a load that can firmly adhere them, but is usually in the range of 10 to 1000 N.

[0124] The post-heating temperature is preferably 120° C. or higher from the viewpoint of realizing a sufficient curing rate, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate and each layer.

[0125] The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrates and layers that constitute the laminate, and is usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating.

[0126] Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, the laminate may be heated with either the semiconductor substrate or the support substrate facing downward, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.

[0127] One purpose of the post-heat treatment is to realize an adhesive layer that is a more suitable self-standing film, and particularly, when a component that cures by a hydrosilylation reaction is included, to realize the curing in a suitable manner.

[0128] The method for producing a processed semiconductor substrate of the present invention includes a first step of processing the semiconductor substrate of the laminate of the present invention.

[0129] The processing performed on the semiconductor substrate in the first step is, for example, processing the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Then, through-silicon vias (TSVs) and other structures are formed, and the thinned wafer is then peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, before and after this, electrodes and other structures are formed on the back surface of the wafer. During the wafer thinning and TSV processes, the wafer is subjected to high temperatures of approximately 250 to 350°C while still attached to the support substrate. The laminate of the present invention, including the adhesive layer and peel layer, is heat-resistant to this load.

[0130] Furthermore, in the laminate of the present invention, the release layer is formed so as to be in contact with the semiconductor substrate, and therefore damage to the semiconductor substrate, such as deformation of bumps on the semiconductor substrate, caused by such external loads is suppressed even when high temperatures or pressure are applied. This cannot be generally defined because it differs depending on the type and film thickness of the adhesive layer, the thickness of the release layer, etc., but specifically, in the laminate of the present invention, the temperature is usually 200°C or higher, in a preferred embodiment, 250°C or higher, in a more preferred embodiment, 300°C or higher, in an even more preferred embodiment, 350°C or higher, and in an even more preferred embodiment, 350°C or higher and a pressure of 60 N / cm 2 Even under the above conditions, in an even more preferred embodiment, the temperature is 400°C or higher and the pressure is 120 N / cm 2 Even under these harsh conditions, damage to the semiconductor substrate is reduced.

[0131] The processing is not limited to the above, and also includes, for example, the implementation of a mounting process for semiconductor components when a substrate for mounting the semiconductor components is temporarily bonded to a support substrate to support the substrate.

[0132] The method for producing a processed semiconductor substrate of the present invention usually includes a second step of separating (peeling) the semiconductor substrate from the support substrate.

[0133] In the laminate of the present invention, the substrate and adhesive layer are releasably bonded via a release layer, and therefore methods for separating (peeling) the semiconductor substrate and the support substrate include, but are not limited to, immersion in a solvent, laser peeling, mechanical peeling using equipment with sharp edges, and peeling by pulling the support and wafer apart.

[0134] In particular, the laminate of the present invention has a favorably formed release layer, and therefore, by immersing the laminate in an organic solvent, the laminate can be easily peeled at the interface between the release layer and the adhesive layer. Typical examples of such organic solvents include linear or branched aliphatic hydrocarbons such as linear or branched aliphatic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, and isododecane; cyclic aliphatic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, and p-menthane; and cyclic aliphatic unsaturated hydrocarbons such as limonene; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, cumene, 1,4-diisopropylbenzene, and p-cymene; and methyl isobutyl ketone (MIBK), ethyl methyl ketone (ETK), and the like. Examples of suitable organic solvents include ketones such as dialkyl ketones (e.g., 2-octanone, 2-nonanone, 5-nonanone), saturated aliphatic hydrocarbon ketones (e.g., cycloalkyl ketones (e.g., cyclohexanone), and unsaturated aliphatic hydrocarbon ketones (e.g., alkenyl ketones (e.g., isophorone)); ethers (e.g., dialkyl ethers (e.g., diethyl ether, di(n-propyl) ether, di(n-butyl) ether, di(n-pentyl) ether), and cyclic alkyl ethers (e.g., tetrahydrofuran and dioxane); sulfides (e.g., dialkyl sulfides (e.g., diethyl sulfide, di(n-propyl) sulfide, di(n-butyl) sulfide); and esters (e.g., butyl acetate, pentyl acetate). These organic solvents can be used alone or in combination of two or more.

[0135] When the support substrate is optically transparent, the peeling layer or adhesive layer can be separated or decomposed by irradiating the peeling layer or adhesive layer with the necessary light from the support substrate side, and then, for example, one of the substrates can be pulled up to easily separate the semiconductor substrate and the support substrate. The light irradiation may be carried out using laser light or non-laser light from a light source such as a lamp.

[0136] The method for producing a processed semiconductor substrate of the present invention usually includes a third step of cleaning the separated semiconductor substrate. Cleaning can be performed by spraying a cleaning composition onto the surface of the separated semiconductor substrate or immersing the separated semiconductor substrate in a cleaning composition to remove adhesive residues and stripping agent residues. Alternatively, residues may be removed using a removal tape or the like.

[0137] The constituent elements and methodological elements relating to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways without departing from the spirit and scope of the present invention. The method for producing a processed semiconductor substrate of the present invention may include steps other than those described above.

[0138] The peeling method of the present invention involves immersing the laminate of the present invention in an organic solvent to separate the semiconductor substrate from the support substrate. [Example]

[0139] (1) Mixer: Thinky Corporation Rotating and Revolving Mixer ARE-500 (2) Rheometer: Anton Paar Japan Co., Ltd., Viscoelasticity Measuring Instrument MCR302 (3) Vacuum bonding device: SUSS MicroTec Co., Ltd., manual bonder (4) Heat-compression bonding device: SUSS MicroTec 8-inch manual bonder

[0140] [1] Preparation of adhesive composition [Preparation Example 1] A 600 mL stirring vessel designed specifically for the planetary centrifugal mixer was charged with 80 g of MQ resin (manufactured by Wacker Chemical Co.) containing a polysiloxane skeleton and vinyl groups, 2.52 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Co.) with a viscosity of 100 mPa·s, 5.89 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Co.) with a viscosity of 70 mPa·s, and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemical Co.), and the mixture was stirred for 5 minutes with a stirrer.

[0141] To the resulting mixture, 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1,000 mPa·s were stirred for 5 minutes using a stirrer, and 3.96 g of the mixture obtained separately was added and stirred for 5 minutes using a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0142] [2] Preparation of stripping agent composition [Preparation Example 2-1] 50 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were placed in a 600 mL stirring vessel designed specifically for the planetary centrifugal mixer and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0143] [Preparation Example 2-2] 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK1000000), which is a polydimethylsiloxane with a viscosity of 1,000,000 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were placed in a 600 mL stirring vessel designed for the planetary centrifugal mixer, and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0144] [Preparation Example 2-3] 50 g of polyorganosiloxane (manufactured by Wacker Chemie, product name AK1000000), which is a polydimethylsiloxane with a viscosity of 1,000,000 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were placed in a 600 mL stirring vessel designed specifically for the planetary centrifugal mixer and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0145] [Preparation Example 2-4] A 600 mL stirring vessel designed specifically for the planetary centrifugal mixer was charged with 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK10000), which is a polydimethylsiloxane with a viscosity of 10,000 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.), and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0146] [Preparation Example 2-5] A 600 mL stirring vessel designed specifically for the planetary centrifugal mixer was charged with 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK1000), which is a polydimethylsiloxane with a viscosity of 1,000 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.), and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0147] [Preparation Example 2-6] A 600 mL stirring vessel designed specifically for the planetary centrifugal mixer was charged with 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK50), which is a polydimethylsiloxane with a viscosity of 50 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.), and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0148] [Preparation Example 2-7] 25 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, 25 g of polyorganosiloxane (manufactured by Gelest, trade name PMM-1043), which is a polymethylphenylsiloxane with a viscosity of 30,000 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were placed in a 600 mL stirring vessel designed for the planetary centrifugal mixer, and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0149] [Preparation Example 2-8] A 600 mL stirring vessel designed specifically for the planetary centrifugal mixer was charged with 25 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name GENIOPLAST GUM), which is a polydimethylsiloxane with a viscosity of 5,000,000 mPa·s, 25 g of a polyorganosiloxane (manufactured by Gelest, trade name PMM-1023), which is a polymethylphenylsiloxane with a viscosity of 500 mPa·s, and 450 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.), and the mixture was stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 300 mesh nylon filter to obtain a release agent composition.

[0150] [3] Viscosity measurement of polyorganosiloxane mixture (polyorganosiloxane component) [Preparation Examples 3-1 to 3-8] First, polyorganosiloxane mixtures were prepared in the same manner as in Preparation Examples 2-1 to 2-8, except that p-menthane was not used.

[0151] Each of the resulting polyorganosiloxane mixtures was stirred overnight in a mixer rotor in a 45°C thermostatic bath. Each mixture was then allowed to cool to room temperature and stirred for an additional 5 minutes with a stirrer. This resulted in a well-mixed, highly uniform polyorganosiloxane mixture. The viscosity of each resulting mixture was then measured at 25°C using a rheometer, and the viscosity of the polyorganosiloxane component (hereinafter also referred to as the POS component) was calculated. The results are shown in Table 1.

[0152] [Table 1]

[0153] [4] Preparation of sample substrate [Manufacturing Example 1] A bumped substrate (wafer) was cut to prepare a 4cm x 4cm sample substrate for the device wafer (semiconductor substrate). Each sample substrate had 5,044 bumps, with the bump structure consisting of copper pillars, tin-silver (1.8wt% silver) caps, and nickel between the pillars and caps.

[0154] [Manufacturing Example 2] A silicon wafer was cut to prepare a 4 cm x 4 cm sample substrate as the device wafer (semiconductor substrate).

[0155] [5] Preparation of laminate for evaluation [Comparative Example 1] The adhesive composition obtained in Preparation Example 1 was spin-coated onto the bump-bearing surface of the sample substrate obtained in Production Example 1 so that the film thickness of the final laminate was 60 μm, forming an adhesive coating layer on the sample substrate, which is a semiconductor substrate. Then, using a bonding device, the sample substrate (silicon wafer) and a 100 mm glass wafer as a support substrate were bonded together with the adhesive coating layer sandwiched between them, and then the sample substrate was placed face down and post-heated on a hot plate at 200°C for 10 minutes to produce a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa.

[0156] Comparative Example 2 The release agent composition obtained in Preparation Example 2-1 was spin-coated onto the bump-bearing surface of the sample substrate obtained in Production Example 1 so that the film thickness in the final laminate would be 2.50 μm, and the resulting mixture was heated at 120° C. for 90 seconds to form a release agent coating layer on the sample substrate, which was a semiconductor substrate. On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated onto a 100 mm glass wafer (EAGLE-XG, manufactured by Corning, thickness 500 μm, same below) so that the film thickness of the final laminate was 60 μm, forming an adhesive coating layer on the glass wafer, which was the supporting substrate. Then, using a bonding device, the sample substrate (silicon wafer) and the glass wafer were bonded together so that the release agent coating layer and the adhesive coating layer were sandwiched between them, and then the sample substrate was placed face down and post-heated on a hot plate at 200°C for 10 minutes to produce a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa.

[0157] [Examples 1 to 4 and Comparative Example 3] Laminates were produced in the same manner as in Comparative Example 2, except that the release agent composition obtained in Preparation Example 2-1 was replaced with the release agent compositions obtained in Preparation Examples 2-2 to 2-6, respectively.

[0158] [Examples 5 to 8, Comparative Example 4] Laminates were prepared in the same manner as in Example 1, except that the thickness of the release layer was set to 0.50 μm, 1.00 μm, 1.50 μm, 2.00 μm, or 5.00 μm, respectively.

[0159] [Comparative Examples 5 to 6] Laminates were prepared in the same manner as in Comparative Example 2, except that the release agent composition obtained in Preparation Example 2-1 was replaced with the release agent compositions obtained in Preparation Examples 2-7 and 2-8, respectively.

[0160] [6] High-temperature and high-pressure treatment of laminated body Using a thermocompression bonding device, high-temperature, high-pressure treatment was performed on each of the laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 4. The treatment was performed according to the following procedure. The stack was placed with the support substrate facing downwards on a stage set at 70°C, and the temperature was 420°C and the pressure was 120 N / cm. 2 The semiconductor substrate and the support substrate were heated while applying pressure from the semiconductor substrate side in a direction perpendicular to the semiconductor substrate and the support substrate under the thermocompression bonding conditions of 1000 kJ / min and a treatment time of 8 seconds. The state of the semiconductor substrate of each laminate after processing was observed using an optical microscope through the glass substrate, which was the supporting substrate, and the presence or absence of bump deformation was visually confirmed. In addition, for some laminates, after observation, it was confirmed whether the substrate with bumps could be manually peeled from the laminate. The results are shown in Tables 2 and 3.

[0161] [Table 2]

[0162] [Table 3]

[0163] As shown in Tables 2 and 3, for laminates having a release layer made from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane and having a viscosity within the specified range of the present invention, and having a film having a thickness within the specified range of the present invention, bump deformation caused by high-temperature, high-pressure treatment was suppressed. Furthermore, for the laminates of Examples 1 to 3, even after high-temperature, high-pressure treatment, it was confirmed that the support substrate could be easily removed from the laminate by simply lifting it by hand, and the semiconductor substrate and support substrate could be easily separated.

[0164] On the other hand, as shown in Table 2, for laminates having a release layer made from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane, which does not have a viscosity within the specified range of the present invention, bump deformation could not be suppressed even if the film had a thickness within the specified range of the present invention.

[0165] Furthermore, as shown in Table 3, for laminates having a release layer that does not have a film thickness within the specified range of the present invention, bump deformation could not be suppressed even if the film was obtained from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane having a viscosity within the specified range of the present invention.

[0166] From the above results, it was found that in order to suppress bump deformation, a release layer having a film thickness within the specified range of the present invention and composed of a polyorganosiloxane component made of polydimethylsiloxane having a viscosity within the specified range of the present invention is required.

[0167] [7] High-temperature treatment of laminate Using a hot plate, high-temperature treatment was performed on each of the laminates obtained in Examples 1 and 5 to 8 and Comparative Examples 4 to 6. The treatment was performed according to the following procedure. The laminate was placed on a hot plate set at 280° C. with the support substrate facing downwards and heated for 5 minutes. The state of the semiconductor substrate of each laminate after processing was observed using an optical microscope through the glass substrate, which was the supporting substrate, and the presence or absence of bump deformation was visually confirmed. In addition, for some laminates, after observation, it was confirmed whether the substrate with bumps could be manually peeled from the laminate. The results are shown in Tables 4 and 5.

[0168] [Table 4]

[0169] [Table 5]

[0170] As shown in Table 4, for laminates having a release layer that does not have a film thickness within the specified range of the present invention, even if the film is obtained from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane and having a viscosity within the specified range of the present invention, bump deformation could not be suppressed when heat treated. On the other hand, for laminates having a release layer that is obtained from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane and having a viscosity within the specified range of the present invention, bump deformation caused by high-temperature treatment could be suppressed. Furthermore, for the laminates of Examples 1 and 8, even after high-temperature treatment, the support substrate could be easily removed from the laminate by simply lifting it by hand, and it was confirmed that the semiconductor substrate and the support substrate could be easily separated.

[0171] As shown in Table 5, when a laminate having a release layer made of a film obtained from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane and polymethylphenylsiloxane was subjected to heat treatment, bump deformation could not be suppressed.

[0172] From the above results, it was found that in order to suppress bump deformation, a release layer having a film thickness within the specified range of the present invention and composed of a polyorganosiloxane component made of polydimethylsiloxane having a viscosity within the specified range of the present invention is required.

[0173] [8] Checking peelability with solvents [Comparative Reference Example 1] The adhesive composition obtained in Preparation Example 1 was spin-coated onto the sample substrate obtained in Production Example 2 to a final film thickness of 60 μm to form an adhesive coating layer. The sample substrate with the adhesive coating layer formed thereon was heated with the substrate facing down on a hot plate at 200°C for 10 minutes to obtain a sample substrate with an adhesive layer. The substrate was immersed in 9 mL of p-menthane, and the time until peeling of the adhesive layer began was measured. If peeling was not confirmed within 5 minutes, it was evaluated as no peeling (the same applies below).

[0174] [Reference example 1] The release agent composition obtained in Preparation Example 2-2 was spin-coated onto the sample substrate obtained in Production Example 2 to a final film thickness of 2.50 μm to form a release agent coating layer, and the adhesive composition obtained in Preparation Example 1 was spin-coated onto the release agent coating layer to a final film thickness of 60 μm to form an adhesive coating layer. The sample substrate with these two coating layers formed was heated with the substrate facing down on a hot plate at 200°C for 10 minutes to obtain a sample substrate having an adhesive layer and a release layer. The substrate was immersed in 9 mL of p-menthane, and the time until the adhesive layer began to peel was measured.

[0175] The results are summarized in Table 6. As shown in Table 6, it was confirmed that the adhesive layer formed on the release layer obtained from the release agent composition of the present invention could be easily peeled off by immersion in an organic solvent.

[0176] [Table 6]

Claims

1. semiconductor substrate, a supporting substrate, a release layer provided in contact with the semiconductor substrate; and A laminate including an adhesive layer provided between the support substrate and the release layer, the release layer is a film obtained from a release agent composition containing a polyorganosiloxane component consisting of polydimethylsiloxane, The viscosity of the polyorganosiloxane component at 25°C is 5.50 x 10 ３ Pa・s~0.75×10 ３ Pa·s, A laminate characterized in that the thickness of the film is 0.01 μm to 4.90 μm.

2. The viscosity of the polyorganosiloxane component at 25°C is 5.00 x 10 ３ Pa・s~0.80×10 ３ The laminate according to claim 1, wherein the viscosity is Pa·s.

3. The viscosity of the polyorganosiloxane component at 25°C is 4.52 x 10 ３ Pa・s~0.96×10 ３ The laminate according to claim 2, wherein the viscosity is Pa·s.

4. 4. The laminate according to claim 1, wherein the thickness of the film is 0.25 μm to 3.75 μm.

5. 5. The laminate according to claim 4, wherein the thickness of the film is 1.75 μm to 2.75 μm.

6. 6. The laminate according to claim 1, wherein the adhesive layer is provided so as to be in contact with the support substrate and the release layer.

7. The laminate according to any one of claims 1 to 6, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) containing at least one selected from the group consisting of polyorganosiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide-based adhesives, and phenolic resin-based adhesives.

8. The laminate according to claim 7, wherein the adhesive component (S) comprises a polyorganosiloxane adhesive.

9. 9. The laminate according to claim 8, wherein the polyorganosiloxane adhesive comprises a polyorganosiloxane component (A) that cures by a hydrosilylation reaction.

10. A release agent composition for forming a release layer of a laminate comprising a semiconductor substrate, a support substrate, a release layer provided so as to be in contact with the semiconductor substrate, and an adhesive layer provided between the support substrate and the release layer, wherein the release layer has a film thickness of 0.01 μm to 4.90 μm, the release agent composition comprising a polyorganosiloxane component made of polydimethylsiloxane, wherein the viscosity of the polyorganosiloxane component at 25° C. is 5.50×10 ３ Pa・s~0.75×10 ３ A stripper composition having a Pa·s.

11. The viscosity of the polyorganosiloxane component at 25°C is 5.00 x 10 ３ Pa・s~0.80×10 ３ The stripping composition according to claim 10, wherein the viscosity is Pa·s.

12. The viscosity of the polyorganosiloxane component at 25°C is 4.52 x 10 ３ Pa・s~0.96×10 ３ The stripping composition according to claim 11, wherein the viscosity is Pa·s.

13. The stripping composition according to any one of claims 10 to 12, wherein the thickness of the film is 0.25 µm to 3.75 µm.

14. The stripping composition according to claim 13, wherein the thickness of the film is 1.75 μm to 2.75 μm.

15. The release agent composition according to any one of claims 10 to 14, wherein the adhesive layer is provided so as to be in contact with the support substrate and the release layer.

16. The release agent composition according to any one of claims 10 to 15, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) containing at least one selected from the group consisting of polyorganosiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide-based adhesives, and phenolic resin-based adhesives.

17. The release agent composition according to claim 16, wherein the adhesive component (S) comprises a polyorganosiloxane adhesive.

18. 18. The release agent composition according to claim 17, wherein the polyorganosiloxane adhesive comprises a polyorganosiloxane component (A) that cures by a hydrosilylation reaction.

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