Stripping composition, laminate, method for manufacturing laminate, and method for manufacturing semiconductor substrate

Abstract

To provide a release agent composition, a laminate, a manufacturing method of the laminate, and a manufacturing method of a semiconductor substrate, in which the semiconductor substrate and a support substrate are not separated from each other at the time of temporary adhesion even when the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate, and the semiconductor substrate and the support substrate can be separated easily from each other when attempting to separate the semiconductor substrate and the support substrate.SOLUTION: A laminate includes a support substrate 5, a semiconductor substrate 1, a release layer 2 interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer 4 interposed between the support substrate and the release layer. The release layer is a layer formed of a release agent composition containing polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a stripping composition, a laminate, a method for producing a laminate, and a method for producing a semiconductor substrate. [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. An unthinned semiconductor wafer (also referred to herein simply as a wafer) is bonded to a support for polishing in a polishing apparatus. The adhesive used in this process must be easily peeled off after polishing, and is therefore called a temporary adhesive. This temporary adhesive 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 adhesive 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 adhesive is that it can withstand the stress during polishing and be easily removed after polishing. For example, the required performance is high stress (strong adhesive strength) in the planar direction during polishing, and low stress (weak adhesive strength) in the vertical direction during removal.

[0003] As an example of such an adhesion process, a wafer support structure has been proposed, which has, from the wafer (1) side, a silicone oil layer, a separation layer (4) which is a plasma polymer layer, and a layer (5) of a partially cured or curable elastomer material between a semiconductor wafer (1) and a support layer (6) which is a support, and in which the adhesive bond between the support layer system and the separation layer (4) after the elastomer material has completely cured is greater than the adhesive bond between the wafer (1) and the separation layer (4) (see, for example, the examples in Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5335443 Summary of the Invention [Problem to be solved by the invention]

[0005] The thinned wafer may be heated to temperatures exceeding 200°C before being separated from the support. The heating temperature depends on the processing to be performed on the wafer, and in some cases can be as high as 280°C or higher. However, the inventors have found that when a semiconductor substrate wafer is heated to a high temperature, even if an attempt is made to subsequently separate the semiconductor substrate and the support substrate using a peeling layer interposed therebetween, a force stronger than when the heating temperature is low is required for separation, and in some cases, such a force is required that the semiconductor substrate after thinning cracks.

[0006] Therefore, an object of the present invention is to provide a laminate that does not peel off when the semiconductor substrate and the support substrate are temporarily bonded together, even after the semiconductor substrate has been exposed to high temperatures, and that allows the semiconductor substrate and the support substrate to be easily peeled off when an attempt is made to peel them off; a method for manufacturing a semiconductor substrate using the laminate; a method for manufacturing the laminate; and a release agent composition for use with the laminate. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0008] That is, the present invention includes the following. [1] A support substrate; a semiconductor substrate; a release layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; an adhesive layer interposed between the support substrate and the release layer; A laminate having A laminate, wherein the release layer is a layer formed from a release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000. [2] The laminate according to [1], wherein the polyorganosiloxane is polydimethylsiloxane. [3] The laminate according to [1] or [2], wherein the adhesive layer is a layer formed from an adhesive composition. [4] The laminate according to [3], wherein the adhesive composition contains a curable component (A). [5] The laminate according to [4], wherein the component (A) is a component that cures via a hydrosilylation reaction. [6] The component (A) a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; a polyorganosiloxane (a2) having Si-H groups; a platinum group metal catalyst (A2); The laminate according to [4] or [5], [7] The laminate according to any one of [1] to [6], which has an inorganic material layer interposed between the release layer and the adhesive layer. [8] The laminate according to [7], wherein the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound. [9] The laminate according to any one of [1] to [8], wherein the semiconductor substrate is used in a treatment in which the semiconductor substrate is heated to 280°C or higher.

[10] A step of processing the semiconductor substrate in the laminate according to any one of [1] to [8]; separating the support substrate from the processed semiconductor substrate; A method for manufacturing a semiconductor substrate, comprising:

[11] The method for manufacturing a semiconductor substrate according to

[10] , wherein the processing step includes a process of polishing a surface of the semiconductor substrate opposite to the surface in contact with the release layer, thereby thinning the semiconductor substrate.

[12] The method for manufacturing a semiconductor substrate according to

[10] or

[11] , wherein the processing step includes a treatment in which the semiconductor substrate is heated to 280°C or higher.

[13] A method for producing a laminate according to any one of [1] to [9], forming an adhesive coating layer that provides the adhesive layer; a step of heating the adhesive coating layer to form the adhesive layer while the support substrate and the semiconductor substrate are in contact with each other with the release layer and the adhesive coating layer interposed therebetween; A method for producing a laminate, comprising:

[14] A release agent composition used to form a release layer in contact with a semiconductor substrate heated to 280°C or higher, A release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.

[15] The release agent composition according to

[14] , wherein the polyorganosiloxane is polydimethylsiloxane.

[16] The release agent composition according to

[14] or

[15] , which is used to form the release layer of a laminate having a support substrate, the semiconductor substrate, the release layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the support substrate and the release layer, and which is in contact with the semiconductor substrate that is heated to 280°C or higher when the semiconductor substrate of the laminate is processed. [Effects of the Invention]

[0009] According to the present invention, there are provided a laminate that does not peel off when the semiconductor substrate and the support substrate are temporarily bonded together, even after the semiconductor substrate has been exposed to high temperatures, and that allows the semiconductor substrate and the support substrate to be easily peeled off when an attempt is made to peel them off; a method for manufacturing a semiconductor substrate using the laminate; a method for manufacturing the laminate; and a release agent composition for use in the laminate. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of an example of a laminate. DETAILED DESCRIPTION OF THE INVENTION

[0011] (Laminate) The laminate of the present invention comprises a support substrate, a semiconductor substrate, a release layer, an adhesive layer, and, if necessary, an inorganic material layer. The release layer is interposed between the support substrate and the semiconductor substrate and is in contact with the semiconductor substrate. The adhesive layer is interposed between the support substrate and the release layer.

[0012] <Support substrate> The support substrate is not particularly limited as long as it is a member that can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.

[0013] The shape of the support substrate is not particularly limited, but may be, for example, a disk. Note that the surface of a disk-shaped support substrate does not necessarily have to be a perfect circle, and for example, the outer periphery of the support substrate may have a straight portion called an orientation flat or a notch. The thickness of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be appropriately determined depending on the size of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0014] An example of the support substrate is a glass wafer or a silicon wafer with a diameter of about 300 mm and a thickness of about 700 μmm.

[0015] <Semiconductor substrate> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples thereof include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, but may be, for example, a disk shape. Note that the disk-shaped semiconductor substrate does not need to have a perfectly circular surface, and for example, the outer periphery of the semiconductor substrate may have a straight portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be appropriately determined depending on the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0016] The semiconductor substrate may have bumps, which are protruding terminals. In the laminate, when the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side. In a semiconductor substrate, bumps are usually formed on the surface on which a circuit is formed. The circuit may be a single layer or a multilayer. There are no particular limitations on the shape of the circuit. In the semiconductor substrate, the surface opposite to the surface having the bumps (back surface) is the surface to be processed. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps. Generally, the height, diameter and pitch of the bumps are determined appropriately based on the conditions of a bump height of about 1 to 200 μm, a bump diameter of 1 to 200 μm and a bump pitch of 1 to 500 μm. Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, may be used. The bump may also have a laminated structure including a metal layer made of at least one of these components.

[0017] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0018] <Release layer> The release layer is interposed between the support substrate and the semiconductor substrate and is in contact with the semiconductor substrate. The release layer is a layer formed from a release agent composition.

[0019] <<Removal agent composition>> The release agent composition contains a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000, and may further contain other components as required. That is, the weight average molecular weight of the polyorganosiloxane contained in the release agent composition is 22,000 to 68,000. The release layer may be composed only of polyorganosiloxane, or may contain other components. For example, when the release agent composition is composed only of polyorganosiloxane and a volatile component, the volatile component usually volatilizes due to heating when forming the release layer, and therefore the release layer formed from the release agent composition contains only polyorganosiloxane.

[0020] When the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is 22,000 or more, even after the semiconductor substrate is exposed to high temperatures (e.g., 280°C or higher) during processing of the semiconductor substrate of the laminate, the semiconductor substrate and the support substrate can be easily peeled off when an attempt is made to peel them off using a peeling device, etc. On the other hand, when the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is 68,000 or less, the semiconductor substrate and the support substrate can be maintained in a temporary adhesive state even after the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate of the laminate, and the semiconductor substrate and the support substrate can be maintained in a state where they are difficult to peel off until an attempt is made to peel them off using a peeling device, etc. If the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is less than 22,000, after the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate of the laminate, the semiconductor substrate and the support substrate of the laminate cannot be easily peeled off when an attempt is made to peel them off using a peeling device, etc., and in some cases the semiconductor substrate may crack when trying to peel it off from the support substrate. If the weight-average molecular weight of the polyorganosiloxane contained in the release agent composition is more than 68,000, the adhesive strength of the release layer is weak after the semiconductor substrate is exposed to high temperatures during processing of the semiconductor substrate of the laminate, etc., and peeling occurs even when temporary adhesion between the semiconductor substrate and the support substrate is required.

[0021] From the viewpoint of achieving the effects of the present invention with good reproducibility, the weight average molecular weight of the polyorganosiloxane is preferably 25,000 to 65,000, and more preferably 30,000 to 60,000.

[0022] The weight average molecular weight and number average molecular weight of polyorganosiloxane can be measured, for example, using a GPC apparatus (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 Shodex Corporation) as a standard sample.

[0023] The dispersity of the polyorganosiloxane (weight average molecular weight (Mw) / number average molecular weight (Mn)) is not particularly limited, but is preferably from 1.50 to 20.0, more preferably from 2.00 to 15.0.

[0024] In the present invention, the volatile silicone oil described below is not included in the polyorganosiloxane.

[0025] Examples of polyorganosiloxanes include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0026] In addition, the polyorganosiloxane may be polydimethylsiloxane. The polydimethylsiloxane may be modified. Therefore, examples of the polydimethylsiloxane include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

[0027] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0028] R 11 is a group bonded to a silicon atom and represents an alkyl group; R 12 is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. 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. The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

[0029] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 10 units), but D 10 In addition to units, Q units, M units and / or T units may be included. 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.

[0030] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5.

[0031] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0032] [ka] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0033] [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.)

[0034] [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.)

[0035] 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 21 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing units.

[0036] 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. 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. In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0037] 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 units, Q units, M units and / or T units may be included.

[0038] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 200 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.

[0039] 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.

[0040] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0041] [ka] (n4 represents the number of repeating units and is a positive integer of 4 or more.)

[0042] The methyl group-containing polyorganosiloxane represented by formula (M1) is a polydimethylsiloxane, but it cannot be denied that there exists polydimethylsiloxane in the bulk that contains trace amounts of other groups other than -Si(CH3)3 groups and -Si(CH3)2-O- groups as impurity structures at the ends or in the middle of the repeating units.

[0043] 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.

[0044] 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.

[0045] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 units), but D 30 In addition to units, Q units, M units and / or T units may be included.

[0046] 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 30Polyorganosiloxanes containing units, M units and T units, D 30 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0047] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0048] [ka] (m5 and n5 each represent the number of repeating units and are positive integers.)

[0049] [ka] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0050] The polyorganosiloxane may be a commercially available product or may be synthesized. Commercially available polyorganosiloxanes include, for example, products manufactured by Wacker Chemie under the trade names AK 50, AK 350, AK 1000, AK 10000, and AK 1000000.

[0051] A commercially available polyorganosiloxane may be used alone if its weight-average molecular weight is the desired value, or two or more polyorganosiloxanes with different weight-average molecular weights may be used in combination so that the weight-average molecular weight of the polyorganosiloxane in the release layer is the desired value. Furthermore, when the synthesized polyorganosiloxane has a desired weight-average molecular weight, it may be used alone. Alternatively, for example, two or more polyorganosiloxanes having different weight-average molecular weights, each synthesized separately, may be used in combination so that the weight-average molecular weight of the polyorganosiloxane in the release layer has a desired value. Furthermore, a combination of a commercially available product and a synthesized product may be used.

[0052] The stripper composition may contain a solvent. Such a solvent is not particularly limited as long as it can dissolve polyorganosiloxane well. Specific examples of such a good solvent include linear or branched aliphatic 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 hydrogen chloride; 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 alkoxycarbonyl ketones such as isophorone. ketones such as aliphatic unsaturated hydrocarbon ketones, such as methyl ketones; 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; and 2-phenoxyethanol. Examples of the glycol monoether include glycol monoaryl ether; 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; and esters such as butyl acetate and pentyl acetate. Volatile silicone oil may also be used as the solvent. In the present invention, the volatile silicone oil refers to the following compounds having 2 to 5 silicon atoms. Hexamethyldisiloxane, heptamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethylcyclotetrasiloxane, and pentamethylcyclopentasiloxane These solvents can be used alone or in combination of two or more.

[0053] 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 does not precipitate. Specific examples of such 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.

[0054] 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 entire composition, and therefore the amount of the polyorganosiloxane will be 0.1% by mass to 30% by mass based on the entire composition.

[0055] The release agent composition may contain components other than the polyorganosiloxane 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 from the viewpoint of avoiding the complication of the preparation of the composition, it is preferable that the release agent composition contains only the polyorganosiloxane and the solvent.

[0056] The release agent composition can be produced, for example, by mixing a polyorganosiloxane with a solvent. The order of mixing is not particularly limited, but examples of a method that can easily and reproducibly produce a release agent composition include, but are not limited to, a method of dissolving the polyorganosiloxane in a solvent at once, or a method of dissolving a part of the polyorganosiloxane in a solvent and the rest in a separate solvent, and then mixing the resulting solutions. 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.

[0057] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter during the production of the stripping composition or after all of the components have been mixed.

[0058] 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.

[0059] The release agent composition is used, for example, to form a release layer that comes into contact with a semiconductor substrate that is heated to 280° C. or higher. The release agent composition is used to form a release layer in a laminate having, for example, a support substrate, a semiconductor substrate, a release layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the support substrate and the release layer, the release layer being in contact with the semiconductor substrate that is heated to 280°C or higher when the semiconductor substrate of the laminate is processed.

[0060] The content of polyorganosiloxane in release layer is not particularly limited, but is preferably 95% by mass or more, more preferably 99% by mass or more, and most preferably 100% by mass.In addition, the content of polyorganosiloxane in release layer is 100% by mass, which means that release layer is composed only of the components that are intentionally included as polyorganosiloxane, but in this case, it does not deny the existence of the solvent used to dissolve polyorganosiloxane or the impurities contained in bulk polyorganosiloxane.

[0061] The thickness of the release layer provided in the laminate of the present invention is not particularly limited, but is usually 10 to 500 nm. From the viewpoint of maintaining film strength, it is preferably 50 nm or more, more preferably 80 nm or more, and even more preferably 100 nm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, and even more preferably 250 nm or less.

[0062] <Adhesive layer> The adhesive layer is interposed between the support substrate and the release layer. The adhesive layer is typically in contact with the supporting substrate.

[0063] The adhesive layer is not particularly limited, but is preferably a layer formed from an adhesive composition.

[0064] <<Adhesive composition>> Examples of adhesive compositions include, but are not limited to, polysiloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. Among these, polysiloxane adhesives are preferred as adhesive compositions because they exhibit suitable adhesive properties when processing semiconductor substrates and the like, can be easily peeled off after processing, and also have excellent heat resistance. The adhesive composition may be a thermosetting adhesive or a thermoplastic adhesive.

[0065] In a preferred embodiment, the adhesive composition contains a polyorganosiloxane. In another preferred embodiment, the thermosetting adhesive composition includes a component that cures via a hydrosilylation reaction. More specific embodiments of the thermosetting adhesive composition used in the present invention include, for example, the following <<First embodiment>> to <<Third embodiment>>. Furthermore, a more specific embodiment of the thermoplastic adhesive composition used in the present invention is, for example, the <<fourth embodiment>>.

[0066] <<First embodiment>> In a preferred embodiment, the adhesive composition used in the present invention contains a polyorganosiloxane. For example, the adhesive composition used in the present invention contains a curable component (A) that becomes an adhesive component. The adhesive composition used in the present invention may contain a curable component (A) that becomes an adhesive component and a component (B) that does not undergo a curing reaction. Here, an example of the component (B) that does not undergo a curing reaction is polyorganosiloxane. Note that in the present invention, "does not undergo a curing reaction" does not mean that any curing reaction does not occur, but rather that the curing reaction that occurs in the curable component (A) does not occur. In another preferred embodiment, component (A) may be a component that cures via a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that cures via a hydrosilylation reaction. In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (as an example of component (A')), a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group. In another preferred embodiment, the polyorganosiloxane component (A') that cures via a hydrosilylation reaction contains siloxane units (Q units) represented by SiO, 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 M' units, D' units and T' units; a polyorganosiloxane (a1') containing siloxane units (Q" units) represented by the following formula: 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 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 M" units, D" units, and T" units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0067] R 1 ~R 6 are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0068] R 1 '~R 6 R ' is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group. 1 '~R 6 At least one of the groups ' is an alkenyl group which may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0069] R 1 ”~R 6 " are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but R 1 ”~R 6 At least one of " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0070] 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.

[0071] Specific examples of the optionally substituted straight-chain or branched-chain 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, a 4-methyl-n-pentyl group, a 5-methyl-n-pentyl group, a 6-methyl-n-pentyl group, a 7-methyl-n-pentyl group, a 8-methyl-n-pentyl group, a 9-methyl-n-pentyl group, a 10-methyl-n-pentyl group, a 11-methyl-n-pentyl group, a 12-methyl-n-pentyl group, a 13-methyl-n-pentyl group, a 14-methyl-n-pentyl group, a 15-methyl-n-pentyl group, a 16-methyl-n-pentyl group, a 17-methyl-n-pentyl group, a 18-methyl-n-pentyl group, a 19-methyl-n-pentyl group, a 20-methyl-n-pentyl group, a 21-methyl-n-pentyl group, a 22-methyl-n-pentyl group, a 23-methyl-n-pentyl group, a 24-methyl-n-pentyl group, a 25-methyl-n-pentyl group, a 26-methyl-n-pentyl group, a 27-methyl-n-pentyl group, a 2 Examples of such alkyl groups include, but are not limited to, a methyl 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, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

[0072] Specific examples of the optionally substituted 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-cyclobutyl group, a 3,3-dimethyl-cyclobutyl group, a cyclohexyl ... Examples of cycloalkyl groups include cycloalkyl groups such as 1-n-ethyl-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. The number of carbon atoms in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0073] 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.

[0074] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a pentenyl group, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, an ethenyl group and a 2-propenyl group are particularly preferred. Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0075] 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 with the platinum group metal catalyst (A2) to form a crosslinked structure and cure, resulting in the formation of a cured film.

[0076] 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.

[0077] 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).

[0078] 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.

[0079] 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.

[0080] 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).

[0081] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof, and R 1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0082] 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 1 ”~R6 " can be an alkyl group.

[0083] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si-H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0084] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Shodex Co., Ltd.) as a standard sample.

[0085] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are typically 10 to 1,000,000 (mPa·s), and from the viewpoint of achieving the effects of the present invention with good reproducibility, are preferably 50 to 10,000 (mPa·s). The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are values ​​measured at 25°C using an E-type rotational viscometer.

[0086] 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.

[0087] In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal catalyst (A2) together with the polyorganosiloxane component (A'). 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).

[0088] 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. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum. The amount of the platinum group metal catalyst (A2) is not particularly limited, but 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).

[0089] 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. The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of the polyorganosiloxane (a1) and the 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.

[0090] An example of the adhesive composition used in the present invention may contain a component (B) that does not undergo a curing reaction to become a release agent component in addition to the curable component (A). By including such component (B) in the adhesive composition, the resulting adhesive layer can be suitably peeled with good reproducibility. Such component (B) typically includes polyorganosiloxanes, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes. Component (B) may also include polydimethylsiloxane. The polydimethylsiloxane may be modified. Examples of the optionally modified polydimethylsiloxane include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

[0091] Preferred examples of the polyorganosiloxane of component (B) include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0092] The weight-average molecular weight of the polyorganosiloxane of component (B) is not particularly limited, but is usually 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is usually 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured by the methods described above for the polyorganosiloxane contained in the release agent composition. The viscosity of the polyorganosiloxane, component (B), is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 The viscosity value of the polyorganosiloxane, which is component (B), is expressed as a kinematic viscosity, and is expressed in 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:

[0093] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0094] R 11 is a group bonded to a silicon atom and represents an alkyl group; 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. The epoxy group in the epoxy group-containing organic group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

[0095] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 10 units), but D 10 In addition to units, Q units, M units and / or T units may be included. 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.

[0096] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight thereof is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the composition, it is preferably 100,000 or less.

[0097] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0098] [ka] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0099] [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.)

[0100] [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.)

[0101] 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 21 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing units.

[0102] 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. 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. In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0103] 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 units, Q units, M units and / or T units may be included.

[0104] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 200 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.

[0105] 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.

[0106] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0107] [ka] (n4 represents the number of repeating units and is a positive integer.)

[0108] 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.

[0109] 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.

[0110] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 units), but D 30 In addition to units, Q units, M units and / or T units may be included.

[0111] 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.

[0112] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0113] [ka] (m5 and n5 each represent the number of repeating units and are positive integers.)

[0114] [ka] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0115] In one embodiment, the adhesive composition used in the present invention contains a component (A) that cures and a component (B) that does not undergo a curing reaction, and in a more preferred embodiment, component (B) contains a polyorganosiloxane.

[0116] An example of the adhesive composition used in the present invention can contain component (A) and component (B) in any ratio. However, taking into consideration the balance between adhesion and releasability, the ratio of component (A) to component (B) in mass ratio [(A):(B)] is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25. That is, when a polyorganosiloxane component (A') that cures by a hydrosilylation reaction is included, the mass ratio of component (A') to component (B) [(A'):(B)] is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.

[0117] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 1,0000 mPa·s at 25°C.

[0118] <<Second embodiment>> In a preferred embodiment, the adhesive composition used in the present invention contains, for example, the curable adhesive material described below, or the curable adhesive material and a release additive. The curable adhesive material may be selected from, for example, polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof. The release additive may, for example, be a polyether compound. Preferably, the polyether compound comprises end groups selected from the group consisting of hydroxy, alkoxy, aryloxy, and mixtures thereof. Preferably, the polyether compound is selected from polyethylene glycol, polypropylene glycol, poly(1,3-propanediol), polybutylene glycol, poly(tetrahydrofuran), ethylene glycol-propylene glycol copolymer, and mixtures thereof. Preferably, the release additive is selected from the group consisting of polyalkylene oxide homopolymers and polyalkylene oxide copolymers. As the adhesive composition of the second embodiment, for example, the temporary bonding composition described in JP 2014-150239 A can be used. The adhesive composition of the second embodiment will be described in more detail below.

[0119] The adhesive composition used in the present invention comprises a curable adhesive material, a release additive, and optionally an organic solvent. Typically, the curable adhesive material has a modulus of >1 GPa when cured. Exemplary curable adhesive materials include, but are not limited to, polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof. The curable adhesive material may be substituted with any suitable moiety, such as a fluorine-containing group, to provide additional hydrophobicity, provided that such moiety does not adversely affect the mechanical properties of the cured adhesive material. Preferably, the curable adhesive material is selected from polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof, more preferably one or more of arylcyclobutene oligomers, vinyl aromatic oligomers, or mixtures thereof. When a mixture of different curable adhesive materials is used in the present invention, these materials are selected to cure together during the curing process. If a mixture of different curable materials is used, these curable materials are used in a weight ratio of 99:1 to 1:99, preferably 95:5 to 5:95, more preferably 90:10 to 10:90, even more preferably 75:25 to 25:75.

[0120] A wide variety of polyarylene oligomers can be used in the present invention. As used herein, the term "polyarylene" includes polyarylene ethers. Suitable polyarylene oligomers may be synthesized from precursors, such as ethynyl aromatic compounds of the following formula:

[0121] [ka] wherein each Ar is an aromatic group or an inertly substituted aromatic group; each R is independently hydrogen, alkyl, aryl, or an inertly substituted alkyl or aryl group; L is a covalent bond or a group linking one Ar to at least one other Ar; n and m are integers of at least 2; and q is an integer of at least 1. As such, ethynyl aromatic compounds typically have four or more ethynyl groups (e.g., tetraethynyl aromatic compounds).

[0122] Suitable polyarylene oligomers for use in the temporary bonding composition as the adhesive composition of the second embodiment may include polymers that include, as polymerized units:

[0123] [ka] where Ar' is the residue of the (C≡C)n-Ar or Ar-(C≡C)m portion of the reaction product, and R, L, n, and m are as defined above. Polyarylene copolymers useful in the present invention include, as polymerized units, monomers having the following formula:

[0124] [ka] wherein Ar′ and R are as defined above.

[0125] Exemplary polyarylenes include those where Ar-L-Ar is: biphenyl; 2,2-diphenylpropane; 9,9'-diphenylfluorene; 2,2-diphenylhexafluoropropane; diphenyl sulfide; oxydiphenylene; diphenyl ether; bis(phenylene)diphenylsilane; bis(phenylene)phosphine oxide; bis(phenylene)benzene; bis(phenylene)naphthalene; bis(phenylene)anthracene; thiodiphenylene; 1,1,1-triphenyleneethane; 1,3,5-triphenylenebenzene; 1,3,5-(2-phenylene-2-propyl)benzene; 1,1,1-triphenylenemethane; 1,1 , 2,2-tetraphenylene-1,2-diphenylethane; bis(1,1-diphenyleneethyl)benzene; 2,2'-diphenylene-1,1,1,3,3,3-hexafluoropropane; 1,1-diphenylene-1-phenylethane; naphthalene; anthracene; or bis(phenylene)naphthacene; more preferably biphenylene; naphthylene; p,p'-(2,2-diphenylenepropane) (or CH-C(CH)-CH-); p,p'-(2,2-diphenylene-1,1,1,3,3,3-hexafluoropropene) and (-CH-C(CF)-CH-). Useful bisphenyl derivatives include 2,2-diphenylpropane; 9,9'-diphenylfluorene; 2,2-diphenylhexafluoropropane; diphenyl sulfide; diphenyl ether; bis(phenylene)diphenylsilane; bis(phenylene)phosphine oxide; bis(phenylene)benzene; bis(phenylene)naphthalene; bis(phenylene)anthracene; or bis(phenylene)naphthacene.

[0126] Polyarylene precursor monomers can be prepared by a variety of methods known in the art, such as (a) selectively halogenating, preferably brominating, a polyphenol (preferably a bisphenol) in a solvent, where each phenolic ring is halogenated with one halogen at one of the two positions ortho to the phenolic hydroxyl group, (b) selectively brominating the phenolic hydroxyls on the resulting poly(ortho-halophenol) with a leaving group (e.g., a sulfonate ester) that is reactive with and displaced by a terminal ethynyl compound, preferably in a solvent. (e.g., trifluoromethanesulfonate ester prepared from trifluoromethanesulfonyl halide or trifluoromethanesulfonic anhydride), and (c) reacting the reaction product of step (b) with an ethynyl-containing compound or ethynyl synthon in the presence of an aryl ethynylation catalyst, preferably a palladium catalyst, and an acid acceptor to simultaneously replace the halogen and trifluoromethylsulfonate with an ethynyl-containing group (e.g., acetylene, phenylacetylene, substituted phenylacetylene, or substituted acetylene). Further description of this synthesis is provided in International Publication No. WO 97 / 10193 (Babb).

[0127] The ethynyl aromatic monomers of formula (I) are useful for preparing polymers of either formula (II) or (III). Polymerization of ethynyl aromatic monomers is well within the capabilities of those skilled in the art. While the specific conditions for polymerization depend on various factors, including the specific ethynyl aromatic monomer(s) being polymerized and the desired properties of the resulting polymer, general polymerization conditions are detailed in International Publication WO 97 / 10193 (Babb).

[0128] Particularly suitable polyarylenes for use in the present invention include those sold as SiLK™ semiconductor dielectrics (available from Dow Electronic Materials, Marlborough, Massachusetts). Other particularly suitable polyarylenes include those disclosed in WO 00 / 31183, WO 98 / 11149, WO 97 / 10193, WO 91 / 09081, EP 755957, and U.S. Pat. Nos. 5,115,082; 5,155,175; 5,179,188; 5,874,516; and 6,093,636.

[0129] A suitable cyclic olefin material is a poly(cyclic olefin), which may be thermoplastic and have a weight average molecular weight (Mw) of preferably 2000 to 200,000 daltons, more preferably 5000 to 100,000 daltons, and even more preferably 2000 to 50,000 daltons. Preferred poly(cyclic olefins) have a softening temperature (melt viscosity at 3,000 PaS) of at least 100°C, more preferably at least 140°C. Suitable poly(cyclic olefins) also preferably have a glass transition temperature (Tg) of at least 60°C, more preferably 60 to 200°C, and most preferably 75 to 160°C.

[0130] Preferred poly(cyclic olefins) comprise repeating monomers of cyclic olefins and acyclic olefins, or ring-opened polymers based on cyclic olefins. Cyclic olefins suitable for use in the present invention are selected from norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, Diels-Alder polymers such as those derived from furans and maleimides, and derivatives thereof. Derivatives include alkyl (preferably C1-C6) olefins. 20 Alkyl, more preferably C1-C 10 alkyl), alkylidene (preferably C-C 20 Alkylidene, more preferably C1-C 10 alkylidene), aralkyl (preferably C6-C 30Aralkyl, more preferably C6-C 18 aralkyl), cycloalkyl (preferably C3-C 30 Cycloalkyl, more preferably C3-C 18 cycloalkyl), ether, acetyl, aromatic, ester, hydroxy, alkoxy, cyano, amide, imide, and silyl-substituted derivatives. Particularly preferred cyclic olefins for use in the present invention include those selected from the following and combinations thereof:

[0131] [ka]

[0132] [ka] In the formula, each R 1 and R 2 are independently H and alkyl groups (preferably C-C 20 Alkyl, more preferably C1-C 10 alkyl), and each R 3 are independently H, substituted and unsubstituted aryl groups (preferably C-C 18 aryl), alkyl groups (preferably C1-C 20 Alkyl, more preferably C1-C 10 alkyl), cycloalkyl groups (preferably C3-C 30 Cycloalkyl groups, more preferably C3-C 18 cycloalkyl groups), aralkyl groups (preferably C6-C 30 Aralkyl, more preferably C6-C 18 Aralkyl groups, such as benzyl, phenethyl, and phenylpropyl, ester groups, ether groups, acetyl groups, alcohols (preferably C1-C 10 alcohols), aldehyde groups, ketones, nitriles, and combinations thereof.

[0133] Preferred acyclic olefins are branched and unbranched C2-C 20Alkenes (preferably C2-C 10 More preferably, the acyclic olefin is selected from the group consisting of the structure (R 4 )2C=C(R 4 )2, where each R 4 are independently H and alkyl groups (preferably C-C 20 Alkyl, more preferably C1-C 10 Particularly preferred acyclic olefins for use in the present invention include those selected from ethene, propene and butene, with ethene being most preferred.

[0134] Methods for producing cyclic olefin copolymers are known in the art. For example, cyclic olefin copolymers can be produced by chain polymerization of cyclic and acyclic monomers. When norbornene is reacted with ethene under these conditions, an ethene-norbornene copolymer containing alternating norbornanediyl and ethylene units is obtained. Examples of copolymers produced by this method include those available under the TOPAS™ (manufactured by Topas Advanced Polymers) and APEL™ (manufactured by Mitsui Chemicals, Inc.) brands. A suitable method for producing these copolymers is disclosed in U.S. Pat. No. 6,008,298. Cycloolefin copolymers can also be produced by ring-opening metathesis polymerization of various cyclic monomers followed by hydrogenation. The polymer resulting from this type of polymerization can be conceptualized as a copolymer of ethene and a cyclic olefin monomer (e.g., alternating units of ethylene and cyclopentane-1,3-diyl). Examples of copolymers made by this ring-opening method include those offered under the ZEONOR™ (from Zeon Chemicals) and ARTON™ (manufactured by JSR Corporation) brands. A suitable method for making these copolymers by this ring-opening method is disclosed in U.S. Patent No. 5,191,026.

[0135] Arylcyclobutene oligomers useful as curable adhesive materials of the present invention are well known in the art. Suitable arylcyclobutene oligomers include, but are not limited to, those having the following formula:

[0136] [ka] wherein B is an n-valent linking group; Ar is a polyvalent aryl group, and carbon atoms of the cyclobutene ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar; m is an integer of 1 or greater; n is an integer of 1 or greater; and R 5 is a monovalent group. Preferably, the polyvalent aryl group Ar may be composed of 1 to 3 aromatic carbocyclic or heteroaromatic rings. The aryl group preferably contains a single aromatic ring, more preferably a phenyl ring. The aryl group is optionally substituted with 1 to 3 groups selected from (C1-C6) alkyl, tri(C1-C6) alkylsilyl, (C1-C6) alkoxy, and halo, preferably one or more of (C1-C6) alkyl, tri(C1-C3) alkylsilyl, (C1-C3) alkoxy, and chloro, more preferably one or more of (C1-C3) alkyl, tri(C1-C3) alkylsilyl, and (C1-C3) alkoxy. Preferably, the aryl group is unsubstituted. Preferably, n=1 or 2, more preferably n=1. Preferably, m=1 to 4, more preferably m=2 to 4, and even more preferably m=2. Preferably, R 5 is selected from H and (C1-C6) alkyl, more preferably H and (C1-C3) alkyl. Preferably B contains one or more carbon-carbon double bonds (ethylenically unsaturated). Suitable monovalent B groups are preferably of the formula -[C(R 10 )=CR 11 ]xZ, where R 10 and R 11 is independently selected from hydrogen, (C-C) alkyl, and aryl; Z is hydrogen, (C-C) alkyl, aryl, siloxanyl, -COR 12 Each R is selected from 12are independently selected from H, (C1-C6) alkyl, aryl, aralkyl, and alkaryl; and x=1 or 2. Preferably, R 10 and R 11 are independently selected from H, (C1-C3) alkyl, and aryl, more preferably H and (C1-C3) alkyl. 12 is preferably (C1-C3) alkyl, aryl, and aralkyl. Z is preferably siloxyl. Preferred siloxyl groups are of the formula -[Si(R 13 )2-O]p-Si(R 13 )2-, where each R 13 is independently selected from H, (C1-C6) alkyl, aryl, aralkyl, and alkaryl; and p is an integer greater than or equal to 1. 13 is selected from (C1-C3) alkyl, aryl and aralkyl. Suitable aralkyl groups include benzyl, phenethyl and phenylpropyl.

[0137] Preferably, the arylcyclobutene oligomer comprises one or more oligomers of the following formula:

[0138] [ka] In the formula, each R 6 are independently selected from H and (C1-C6) alkyl, preferably H and (C1-C3) alkyl; each R 7 is independently selected from (C-C)alkyl, tri(C-C)alkylsilyl, (C-C)alkoxy, and halo; each R 8 are independently a divalent ethylenically unsaturated organic group; each R 9 is independently selected from H, (C1-C6) alkyl, aralkyl, and phenyl; p is an integer greater than or equal to 1; and q is an integer from 0 to 3. 6 are preferably independently selected from H and (C-C) alkyl, more preferably each R 6is H. Preferably, each R is independently selected from (C1-C6) alkyl, tri(C1-C3) alkylsilyl, (C1-C3) alkoxy and chloro, more preferably (C1-C3) alkyl, tri(C1-C3) alkylsilyl and (C1-C3) alkoxy. Preferably, each R 8 are independently selected from (C-C)alkenyl, more preferably each R 8 is -CH=CH-. Each R 9 is preferably selected from (C1-C3) alkyl, more preferably each R 9 is methyl. Preferably, p=1 to 5, more preferably p=1 to 3, and even more preferably p=1. Preferably, q=0. A particularly preferred arylcyclobutene oligomer, 1,3-bis(2-bicyclo[4.2.0]octa-1,3,5-trien-3-ylethenyl)-1,1,3,3-tetramethyldisiloxane ("DVS-bisBCB"), has the formula:

[0139] [ka]

[0140] Arylcyclobutene oligomers may be prepared by any suitable means, such as those described in U.S. Pat. Nos. 4,812,588; 5,136,069; 5,138,081 and International Publication WO 94 / 25903. Suitable arylcyclobutene oligomers are also commercially available under the CYCLOTENE™ brand, available from Dow Electronic Materials. The arylcyclobutene oligomers may be used as is or may be further purified by any suitable means.

[0141] Curable vinyl aromatic oligomers can be used as curable adhesive materials in the present invention. Such vinyl aromatic oligomers are typically oligomers of one or more reactive ethylenically unsaturated comonomers and vinyl aromatic monomers. Preferably, the vinyl aromatic monomer contains one vinyl group. Suitable vinyl aromatic monomers include unsubstituted vinyl aromatic monomers and substituted vinyl aromatic monomers in which one or more hydrogens are replaced with a substituent selected from the group consisting of (C-C) alkyl, (C-C) alkoxy, halo, and amino. Exemplary vinyl aromatic monomers include, but are not limited to, styrene, vinyl toluene, vinyl xylene, vinyl anisole, vinyl dimethoxy benzene, vinyl aniline, halostyrenes such as fluorostyrene, α-methyl styrene, β-methoxy styrene, ethyl vinyl benzene, vinyl pyridine, vinyl imidazole, vinyl pyrrole, and mixtures thereof. Preferred vinyl aromatic monomers are styrene, vinyl toluene, vinyl xylene, vinyl anisole, ethyl vinyl benzene, and mixtures thereof. Preferred reactive comonomers are those that contain a reactive moiety, i.e., a moiety capable of further polymerization (or crosslinking) after the formation of the vinyl aromatic oligomer, in addition to the olefin (or ethylenically unsaturated) moiety used to form the vinyl aromatic oligomer, such as an allyl moiety or a vinyl group.Such reactive comonomers may suitably be any asymmetric diene or triene that can be further polymerized by Diels-Alder reaction after oligomerization with the vinyl aromatic monomer.More preferably, the reactive comonomer contains an allyl moiety in addition to the ethylenically unsaturated moiety used to form the vinyl aromatic oligomer, and even more preferably contains an allyl ester moiety in addition to this ethylenically unsaturated moiety.Exemplary reactive comonomers useful for forming vinyl aromatic oligomers include, but are not limited to, vinylcyclohexene, vinyl ethers, asymmetric dienes or trienes, such as terpene monomers, dicyclopentadiene, diallyl maleate, allyl acrylate, allyl methacrylate, allyl cinnamate, diallyl fumarate, allyl tiglate, divinylbenzene, and mixtures thereof. Preferred reactive comonomers are diallyl maleate, allyl acrylate, allyl methacrylate, allyl cinnamate, diallyl fumarate, and mixtures thereof, more preferably diallyl maleate, allyl methacrylate, and mixtures thereof. Exemplary terpene monomers include, but are not limited to, limonene, dipentene, myrcene, and the like. It will be understood by those skilled in the art that one or more second comonomers may also be used to form vinyl aromatic oligomers. Such second comonomers are ethylenically unsaturated but do not contain reactive moieties. Exemplary second comonomers include, but are not limited to, (meth)acrylic acid, (meth)acrylamide, (C1-C10) alkyl (meth)acrylates, aromatic (meth)acrylates, substituted ethylene monomers, and poly(alkylene oxide) monomers.

[0142] The molar ratio of vinyl aromatic monomer to comonomer in such vinyl aromatic oligomers is preferably 99:1 to 1:99, more preferably 95:5 to 5:95, and even more preferably 90:10 to 10:90. Such vinyl aromatic oligomers may be prepared by any suitable method, for example, by any method known in the art. Typically, vinyl aromatic oligomers are prepared by free radical polymerization of vinyl aromatic monomers and comonomers. Preferred vinyl aromatic oligomers contain unreacted allyl moieties that can further cure such oligomers.

[0143] A wide variety of materials may be used as release additives in temporary bonding compositions, provided that such materials do not react with the adhesive material under storage and use conditions and are non-curable under the conditions used to cure the adhesive material. Additionally, the release additive should be compatible with the temporary bonding composition; i.e., the release additive must be dispersible, miscible, or otherwise substantially compatible with the adhesive material and any other components used in the temporary bonding composition, such as organic solvents. If an organic solvent (or mixed solvent system) is used in the temporary bonding composition, the release additive and the curable adhesive material must be soluble in such solvent. In the present invention, the release additives are sufficiently nonvolatile so that they do not substantially evaporate under use conditions; i.e., they do not substantially evaporate during the deposition process, e.g., spin coating, or any subsequent heating step used to remove the organic solvent or cure the adhesive material. When a film or layer of the temporary bonding composition is cast, e.g., by spin coating, much (or all) of the solvent evaporates. Preferably, the release additive is soluble in any organic solvent used, but not completely soluble in the curable adhesive material. The release additive is predominantly hydrophilic compared to the cured adhesive material. Without being bound by theory, it is believed that upon curing of the adhesive material, the release additive phase separates and preferentially migrates toward the active surface of the wafer (a surface that is more hydrophilic than the carrier surface). The use of an appropriate hydrophilic moiety in the release additive allows for complete dispersion, or preferably dissolution, of the release additive in the temporary bonding composition and allows for phase separation of the release additive during curing of the adhesive material, with migration of the release additive toward the more hydrophilic surface. Any material that does not phase separate from the adhesive material during curing will not function as a release additive in accordance with the present invention.

[0144] Generally, the release additive will contain one or more relatively hydrophilic moieties, such as one or more oxygen-, nitrogen-, phosphorus-, and sulfur-containing moieties. Suitable release additives include, but are not limited to: ethers, esters, carboxylates, alcohols, thioethers, thiols, amines, imines, amides, phosphate esters, sulfonate esters, and mixtures thereof. Preferably, the release additive contains one or more polar end groups, which contain one or more of oxygen, nitrogen, and sulfur, preferably oxygen. Exemplary polar end groups include alkoxy, aryloxy, hydroxy, carboxylate, alkoxycarbonyl, mercapto, alkylthio, primary amine, secondary amine, and tertiary amine, with preferred end groups being (C1-C6)alkoxy, (C6-C 10 )aryloxy, hydroxy, carboxylate, (C1-C6)alkoxycarbonyl, mercapto, (C1-C6)alkylthio, amino, (C1-C6)alkylamino, and di(C1-C6)alkylamino, more preferably (C1-C6)alkoxy, (C6-C 10 )aryloxy, hydroxy, carboxylate, and (C1-C6)alkoxycarbonyl, and even more preferably selected from (C1-C6)alkoxy, hydroxy, carboxylate, and (C1-C6)alkoxycarbonyl. Particularly preferred polar end groups are selected from hydroxy, methoxy, ethoxy, propoxy, butoxy, carboxyl, and acetoxy. Preferably, the release additive is silicone-free.

[0145] Suitable release additives have a number average molecular weight (Mn) of ≦10,000 Daltons, preferably ≦7500 Daltons, and more preferably ≦7000 Daltons. The release additive has a minimum molecular weight (Mn) sufficient to render the release additive substantially nonvolatile under use conditions (i.e., <5%, preferably <3%, more preferably ≦1% of the release additive volatilizes during use). Preferably, the release additive has an Mn of ≧500 Daltons. A preferred range of Mn is 500-10,000 Daltons, more preferably 500-7500 Daltons, and even more preferably 500-7000 Daltons. The release additive may be a linear polymer; a branched polymer, such as a dendritic polymer, a star polymer, or the like; or a polymer particle; however, the release additive is preferably a linear polymer or polymer particle, and more preferably a linear polymer. Without being bound by theory, it is believed that linear polymers are better able to migrate through the cured adhesive material phase toward the hydrophilic wafer surface than branched polymers.

[0146] Polyethers are preferred release additives. Polyether compounds include alkylene oxide homopolymers and alkylene oxide copolymers, and these copolymers may be random or block. The polyalkylene oxide release additives may have various polar end groups, preferably hydroxy, (C1-C6) alkoxy, and (C1-C6) alkoxycarbonyl, more preferably hydroxy, (C1-C3) alkoxy, and acetoxy. Preferred polyether compounds are polyglycols (or polyalkylene oxides), such as poly(C1-C4) alkylene oxide compounds, which may contain a single type of alkylene oxide repeat unit or two or more different types of alkylene oxide repeat units. Preferred polyether compounds include polyethylene glycol, polypropylene glycol, poly(1,3-propanediol), poly(tetrahydrofuran), ethylene oxide-propylene oxide copolymer, ethylene oxide-butylene oxide copolymer, and mixtures thereof. Preferably, when the release additive contains butylene oxide as a repeating unit, it is a copolymer with one or more different alkylene oxide repeating units. Those skilled in the art will understand that mixtures of release additives may be used in the temporary bonding composition of the present invention. Suitable release additives include polyethers sold under the product names PLURONIC®, TETRONIC, and POLYTHF (available from BASF, Ludwigshafen, Germany), FORTEGRA (The Dow Chemical Company, Midland, Michigan), and TERATHANE (available from Invista, Wichita, Kansas), all of which may be used without further purification.

[0147] It is preferred that one or more organic solvents are used in the temporary bonding composition. Any solvent or mixture of solvents that dissolves or disperses, preferably dissolves, the curable adhesive material and the release additive can be suitably used in the temporary bonding composition. Exemplary organic solvents include, but are not limited to: aromatic hydrocarbons such as toluene, xylene, and mesitylene; alcohols such as 2-methyl-1-butanol, 4-methyl-2-pentanol, and methyl isobutyl carbinol; esters such as ethyl lactate, propylene glycol methyl ether acetate, and methyl 2-hydroxyisobutyrate; lactones such as gamma-butyrolactone; lactams such as N-methylpyrrolidinone; ethers such as propylene glycol methyl ether and dipropylene glycol dimethyl ether isomers (commercially available from The Dow Chemical Company as PROGLYDE™ DMM); ketones such as cyclohexanone and methylcyclohexanone; and mixtures thereof.

[0148] <<Third Embodiment>> As a preferred embodiment, the adhesive composition used in the present invention contains, for example, a thermosetting polymer described below. As the adhesive composition of the third embodiment, for example, the thermosetting polymer described in Japanese Patent No. 6528747 can be used. The thermosetting polymer is not particularly limited, but preferred examples include a siloxane bond-containing polymer (hereinafter also referred to as silicone A) having a weight average molecular weight of 3,000 to 500,000, which consists of a repeating unit represented by the following formula (3) and, if necessary, a repeating unit represented by the following formula (4).

[0149] [Chemical formula] [In the formula, R 6 ~R 9 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms. Also, m represents an integer of 1 to 100. A and B are positive numbers satisfying 0 < A < 1, 0 < B < 1, and A + B = 1. T 1 and T2 is a divalent organic group represented by the following formula (5).

[0150] [Chemical formula] (In the formula, A 1 is a single bond or a divalent organic group selected from the groups represented by the following formula

[0151] [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​is a divalent organic group represented by the following formula (8).

[0155] [ka] (In the formula, A 2 is a single bond or the following formula

[0156] [ka] R is a divalent organic group selected from groups represented by the following formula: 16 and R 17 are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms, and each k is independently 0, 1, or 2.)

[0157] In this case, R 11 ~R 14 The monovalent hydrocarbon group represented by R 5 ~R 8 Examples include the same as those exemplified as those represented by the formula: where p is preferably an integer of 3 to 60, more preferably an integer of 8 to 40. Furthermore, C is preferably 0.3 to 1, D is preferably 0 to 0.7, and C+D=1.

[0158] The adhesive layer formed using the thermosetting polymer as the adhesive composition of the third embodiment is preferably a layer of a cured product of a thermosetting resin composition containing silicone A or silicone B as a main component. Silicone A and silicone B can be used in combination. In this case, the ratio (polymerization ratio) of silicone A:silicone B is preferably 0.1:99.9 to 99.9:0.1, more preferably silicone A:silicone B = 20:80 to 80:20.

[0159] The thermosetting resin composition containing silicone A as a main component contains, for thermal curing, one or more crosslinking agents selected from an amino condensate modified with formalin or formalin-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups per molecule, and an epoxy compound having an average of two or more epoxy groups per molecule.

[0160] On the other hand, the thermosetting resin composition containing Silicone B as the main component contains, for thermal curing, one or more crosslinking agents selected from phenol compounds having an average of two or more phenol groups per molecule and epoxy compounds having an average of two or more epoxy groups per molecule.

[0161] Furthermore, the thermosetting resin composition containing silicone A and silicone B contains, for thermal curing, one or more crosslinking agents selected from epoxy compounds having an average of two or more epoxy groups per molecule.

[0162] Examples of the amino condensates include melamine resins, urea resins, etc. Examples of melamine resins modified with formalin or formalin-alcohol include those obtained by addition-condensation polymerization of modified melamine monomers (e.g., trimethoxymethyl monomethylol melamine) or their multimers (e.g., oligomers such as dimers and trimers) with formaldehyde according to known methods until a desired molecular weight is reached. These may be used alone or in combination of two or more.

[0163] Examples of urea resins modified with formalin or formalin-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates. These can be used alone or in combination of two or more. Urea resins modified with formalin or formalin-alcohol can be prepared, for example, by modifying a urea condensate of a desired molecular weight with formalin according to a known method, or by further modifying the urea condensate by alkoxylation with an alcohol.

[0164] Examples of phenol compounds having two or more methylol groups or alkoxymethylol groups per molecule on average include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A. These compounds may be used alone or in combination of two or more.

[0165] The epoxy compound having two or more epoxy groups per molecule on average is not particularly limited, but examples thereof include bifunctional, trifunctional, tetrafunctional or higher functional epoxy resins, such as EOCN-1020 (see the formula below), EOCN-102S, XD-1000, NC-2000-L, EPPN-201, GAN, and NC6000 manufactured by Nippon Kayaku Co., Ltd., and compounds represented by the formula below.

[0166] [ka]

[0167] Examples of phenol compounds having two or more phenol groups per molecule on average include m- or p-cresol novolak resins (e.g., EP-6030G manufactured by Asahi Organic Chemicals Co., Ltd.), trifunctional phenol compounds (e.g., Tris-P-PA manufactured by Honshu Chemical Industry Co., Ltd.), and tetrafunctional phenol compounds (e.g., TEP-TPA manufactured by Asahi Organic Chemicals Co., Ltd.).

[0168] The amount of the crosslinking agent in the thermosetting resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the thermosetting polymer. The crosslinking agent may be used alone or in combination of two or more.

[0169] The thermosetting resin composition may contain a curing catalyst such as an acid anhydride in an amount of 10 parts by mass or less per 100 parts by mass of the thermosetting polymer.

[0170] <<Fourth embodiment>> In a preferred embodiment, the adhesive composition used in the present invention is a thermoplastic composition, for example, as described below. As the adhesive composition of the fourth embodiment, for example, a thermoplastic composition for forming a bonding composition layer described in Japanese Patent No. 5788173 (hereinafter referred to as "bonding composition") can be used. The bonding composition is not particularly limited, but a preferred example is one that is dispersed or dissolved in a solvent system and contains a compound selected from the group consisting of imide, amide-imide, and amide-imide-siloxane polymers and oligomers. The compound is selected from the group consisting of polymers and oligomers having repeating units of at least one of the following formula (I) and formula (II): Formula (I): [ka] [Wherein R is [ka] wherein R1 is alkyl-substituted phenyl, JPEG0007730456000030.jpg23152.)

[0171] Formula (II): [ka] wherein Z is selected from the group consisting of siloxanes and moieties having ether bridges.

[0172] Preferred alkyl-substituted phenyls are C1-C6 alkyl-substituted phenyls. Particularly preferred examples of alkyl-substituted phenyls include: [ka] Examples include those selected from the group consisting of:

[0173] In formula (I), X is phenylsulfone, (preferably C6-C 60 , more preferably C6-C 30 , more preferably C6-C 24 aromatic compounds (preferably C2-C 15 , more preferably C2-C 10 , more preferably C2-C6) aliphatic compounds, and (preferably C4-C 60 , more preferably C4-C 20 , more preferably C4-C 12 cycloaliphatic compounds)

[0174] In one embodiment, X may be an aromatic, aliphatic, or cycloaliphatic group as described above, while in other embodiments, X may include an aromatic group having an ether bridge (as discussed with respect to Z) or an aromatic group having a linking group and / or —NH group in the meta position.

[0175] Particularly preferred X groups are selected from the group consisting of alkyl-substituted phenyl (as described above), isopropylidenediphenyl, and hexafluoroisopropylidene.

[0176] In the embodiment where Z in formula (II) is a siloxane, preferred siloxanes are of the formula: [ka] [In the formula, each R 3 are each independently hydrogen, (preferably C-C 10 is selected from the group consisting of alkyl, more preferably C1-C2, and phenyl; m is 1 to 6; and p is 1 to 50, preferably 1 to 20, and more preferably 1 to 10.

[0177] In formula (II), preferred moieties having an ether bridge for Z are: [ka] is selected from the group consisting of:

[0178] In the embodiment of Formula (I) or the embodiment of Formula (II), it is preferred that the polymer or oligomer further comprises an end-capping group. Preferred end-capping groups are derived from compounds selected from the group consisting of aromatic monoamines, aliphatic monoamines, cycloaliphatic monoamines, and phthalic anhydride. Particularly preferred end-capping groups are (preferably C1-C 15 , more preferably C1-C 10 (more preferably C1-C6) alkyl, [ka] wherein R4 is (preferably C1-C 15 , more preferably C1-C 10 , more preferably C1-C6) alkyl, and R5 is (preferably C3-C 12 and more preferably a C5-C6) alicyclic group, and k is an integer of 0 to 20, preferably 0 to 10, and more preferably 0 to 5.].

[0179] The bonding composition is, for example, a compound dispersed or dissolved in a solvent system. This compound may be a polymer or oligomer, and is present in the composition at a level of preferably about 1% to about 70% by mass, more preferably about 5% to about 50% by mass, and even more preferably about 15% to about 40% by mass, based on 100% by mass of the total mass of the film-constituting components in the composition.

[0180] The polymeric or oligomeric compounds are thermoplastic and preferably have a weight average molecular weight of about 3,000 to about 300,000 daltons, more preferably about 6,000 to about 50,000 daltons. Preferred compounds have a softening temperature (at a melt viscosity of 3,000 Pa·s) of at least about 150°C, more preferably at least about 200°C, and even more preferably about 200°C to about 250°C.

[0181] A preferred compound dissolves at least about 95% by mass, preferably at least about 98% by mass, and more preferably about 100% by mass, when left at room temperature for about 1 to 24 hours in a medium such as N-methyl-2-pyrrolidone, xylene, dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, or a mixture thereof.

[0182] The bonding composition contains at least about 30% by weight of the solvent system, preferably about 50% to about 90% by weight, more preferably about 60% to about 90% by weight, and even more preferably about 70% to about 90% by weight of the solvent system, based on 100% by weight of the total weight of the bonding composition. The solvent system should have a boiling point of about 100 to 250°C, preferably 120 to 220°C.

[0183] Suitable solvents include those selected from the group consisting of N-methyl-2-pyrrolidone, xylene, dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and mixtures thereof.

[0184] The amount of the film constituent components in the bonding composition should be at least about 10% by mass, preferably about 10% by mass to about 40% by mass, and more preferably about 10% by mass to about 30% by mass, with the total mass of the composition being 100% by mass.

[0185] 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.

[0186] More specifically, examples of the solvent 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. Such solvents may be used alone or in combination of two or more.

[0187] 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.

[0188] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s, and preferably 1,000 to 10,000 mPa·s, at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the type and ratio of solvents used, the concentration of 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 other than the solvent contained in the composition.

[0189] An example of an adhesive composition for use in the present invention can be prepared by mixing component (A) with component (B), if used, and a solvent. The order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving component (A) and component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of component (B) in a solvent and the remaining portion 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. In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter during the production of the adhesive composition or after all of the components have been mixed.

[0190] The thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, but is usually 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

[0191] <Inorganic material layer> The laminate may include an inorganic material layer. The inorganic material layer is usually interposed between the release layer and the adhesive layer, and the inorganic material layer prevents the release layer and the adhesive layer from intermixing.

[0192] The inorganic material layer is not particularly limited as long as it is a layer made of an inorganic material, and examples thereof include layers formed from compounds such as oxides, nitrides, and carbides of at least one element selected from the group consisting of silicon, boron, titanium, zirconium, and aluminum, and mixtures thereof. Preferably, the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound.

[0193] The inorganic material layer is formed, for example, by chemical vapor deposition (CVD), which involves, for example, plasma polymerization coating. Examples of materials used in plasma polymerization coating include organosilicon compounds. For example, by performing plasma polymerization coating of an organosilicon compound on a release layer or an adhesive layer, a source gas containing the organosilicon compound is decomposed, and an inorganic material layer, which is a thin film containing Si-O bonds, can be formed on the release layer or the adhesive layer. It is preferable to blend an oxygen-containing gas such as O2 or N2O into the source gas containing the organosilicon compound. Alternatively, a rare gas such as argon or helium may be blended into the source gas as a carrier gas. In a preferred example of a method for decomposing the source gas, a plasma generator is used to generate plasma under appropriate pressure conditions, and the source gas is decomposed by the plasma. The technique of using plasma to decompose the source gas and form a film (layer) is generally referred to as plasma polymerization.

[0194] Examples of the organosilicon compound include a siloxane compound, a disilazane compound, and a silane compound. Examples of siloxane compounds include 1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, 1,1,3,3-tetraphenyl-1,3-dimethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, octamethyltrisiloxane, and 1,1,1,3,5,7,7,7-octamethyl Examples of the siloxane include linear siloxanes such as tetrasiloxane, decamethyltetrasiloxane, and 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane; and cyclic siloxanes such as hexamethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. Examples of disilazane compounds include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, heptamethyldisilazane, hexamethylcyclotrisilazane, and 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane. Examples of silane compounds include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, trimethoxysilane, triethylsilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetramethoxysilane, trimethoxymethylsilane, ethyltrimethoxysilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, triethoxyethylsilane, diethoxydimethylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethoxydimethylsilane, acetoxytrimethylsilane, allyloxytrimethylsilane, allyltrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, diacetoxydimethylsilane, dimethoxydiphenylsilane, and diethoxytrimethylsilane. Examples of the silane include diphenylsilane, dimethoxymethylphenylsilane, ethoxydimethylvinylsilane, diphenylsilanediol, triacetoxymethylsilane, triacetoxyethylsilane, 3-glycidyloxypropyltrimethoxysilane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, octadecyltriethoxysilane, triethoxyoctylsilane, triethoxyphenylsilane, trimethylphenylsilane, propoxytrimethylsilane, triethoxypropylsilane, tetraacetoxysilane, tetrabutoxysilane, tetrapropoxysilane, triacetoxyvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, triphenylsilanol, trimethylvinylsilane, and tris(2-methoxyethoxy)vinylsilane.

[0195] The thickness of the inorganic material layer is not particularly limited, but is usually 1 to 1,000 nm, and preferably 100 to 500 nm.

[0196] An example of the laminate will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view of an example of a laminate. The laminate in FIG. 1 includes a semiconductor substrate 1, a release layer 2, an inorganic material layer 3, an adhesive layer 4, and a support substrate 5 in this order. The separation layer 2 is in contact with the semiconductor substrate 1 . The adhesive layer 4 is interposed between the support substrate 5 and the release layer 2. The adhesive layer 4 is in contact with the support substrate 5 and the inorganic material layer 3. The inorganic material layer 3 is interposed between the release layer 2 and the adhesive layer 4. The inorganic material layer 3 is in contact with the release layer 2 and the adhesive layer 4. 1 has an inorganic material layer 3 in contact with the release layer 2 and the adhesive layer 4, but in the laminate of the present invention, the inorganic material layer 3 does not have to be used, and the inorganic material layer 3 may be in contact with only one of the release layer 2 and the adhesive layer 4, or may be in contact with neither. Furthermore, the laminate of Fig. 1 has an adhesive layer 4 in contact with the support substrate 5 and the inorganic material layer 3, but in the laminate of the present invention, the adhesive layer 4 may be in contact with only one of the support substrate 5 and the inorganic material layer 3, or may be in contact with neither.

[0197] The laminate of the present invention is preferably produced, for example, by the following method for producing the laminate of the present invention.

[0198] (Method of manufacturing laminate) The method for producing the laminate of the present invention includes, for example, a release layer forming step, an adhesive coating layer forming step, and an adhesive layer forming step, and may further include other steps such as an inorganic material layer forming step and a laminating step, as necessary.

[0199] <Release layer formation process> The release layer forming step is a step in which a release layer is formed. When the release agent composition used does not contain a solvent, a release layer is formed, for example, by applying the release agent composition to a semiconductor substrate. If necessary, the layer may be heated during the layer formation process in order to soften the layer and improve its adhesion to the substrate, for example. When the release agent composition used contains a solvent, the release layer is formed, for example, by applying the release agent composition to a semiconductor substrate to form a release agent coating layer, and then heating the release agent coating layer to remove the solvent. However, if not necessary, heating may not be performed in the process of forming the layer, for example, because the solvent is also removed during film formation by spinning. The coating method is not particularly limited, but is usually a spin coating method. The heating temperature is determined appropriately depending on the boiling point of the solvent and the purpose of heating, but is usually 50 to 250°C, and the heating time is determined appropriately depending on the heating temperature, but is usually 30 seconds to 1 hour. Heating can be carried out using, for example, an oven or a hot plate.

[0200] <Inorganic material layer formation process> The inorganic material layer forming step is not particularly limited as long as it is a step in which an inorganic material layer is formed, and examples thereof include a step including the inorganic material layer forming method described above in the description of the inorganic material layer.

[0201] <Adhesive Coating Layer Forming Process> The adhesive coating layer forming step is not particularly limited as long as it is a step in which an adhesive coating layer is formed, and examples thereof include a step in which an adhesive composition is applied onto a release layer, an inorganic material layer, or a support substrate, and then heated (preheating treatment) to form an adhesive coating layer that is an uncured or incompletely cured adhesive layer. In this way, the adhesive coating layer is formed, for example, on the release layer, the inorganic material layer, or the support substrate.

[0202] 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. The thickness of the adhesive coating layer is determined appropriately taking into consideration the thickness of the adhesive layer in the laminate, etc. When the adhesive composition contains a solvent, the applied adhesive composition is usually heated. 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 to 150°C, and the heating time is usually 30 seconds to 5 minutes. Heating can be carried out using a hot plate, an oven, or the like.

[0203] <Adhesive layer formation process> The adhesive layer forming step is not particularly limited as long as it is a step in which the adhesive coating layer is heated to form an adhesive layer (post-heat treatment). For example, a semiconductor substrate having a release layer and an adhesive coating layer formed thereon and a support substrate may be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the two layers (release layer and adhesive coating layer) so that the support substrate and the adhesive coating layer come into contact with each other, and then a heat treatment may be performed. Alternatively, a semiconductor substrate having a release layer formed thereon and a support substrate having an adhesive coating layer formed thereon may be used to arrange the two substrates (semiconductor substrate and support substrate) so as to sandwich the two layers (release layer and adhesive coating layer) so that the release layer and the adhesive coating layer come into contact with each other, and then a heat treatment may be performed. For example, a semiconductor substrate having a release layer, an inorganic material layer, and an adhesive coating layer formed thereon and a support substrate are disposed so as to sandwich the three layers (the release layer, the inorganic material layer, and the adhesive coating layer) between the two substrates (the semiconductor substrate and the support substrate), so that the support substrate and the adhesive coating layer come into contact with each other, and then a heat treatment is performed. Alternatively, a semiconductor substrate having a release layer and an inorganic material layer formed thereon and a support substrate are disposed so as to sandwich the three layers (the release layer, the inorganic material layer, and the adhesive coating layer) between the two substrates (the semiconductor substrate and the support substrate), so that the inorganic material layer and the adhesive coating layer come into contact with each other, and then a heat treatment is performed. The heating temperature and time are not particularly limited as long as the temperature and time are such that the adhesive coating layer is converted into an adhesive layer. The heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and is preferably 260°C or lower from the viewpoint of preventing deterioration of each layer (including the support substrate and semiconductor substrate) that constitutes the laminate. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of each layer (including the support substrate and semiconductor substrate) constituting the laminate, and is preferably 180 minutes or less, more preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be carried out using a hot plate, an oven, or the like. Heating may be carried out in stages.

[0204] <Lamination process> Between the adhesive coating layer forming step and the adhesive layer forming step, a bonding step is preferably carried out to ensure sufficient bonding between the semiconductor substrate and the support substrate. The bonding step is not particularly limited as long as it allows the substrate and the layer to be bonded together and does not damage the substrate or the layer, but is typically a step in which a load is applied in the thickness direction of the support substrate and the semiconductor substrate, and more preferably a step in which a load is applied in the thickness direction of the support substrate and the semiconductor substrate under reduced pressure. The load is not particularly limited as long as it allows the substrate and layer to be bonded together and does not damage the substrate or layer, but is, for example, 10 to 1,000 N. The degree of reduced pressure is not particularly limited as long as it allows bonding of the substrate and the layer and does not damage the substrate or the layer, but is, for example, 10 to 10,000 Pa.

[0205] (Method of manufacturing semiconductor substrate) The method for manufacturing a semiconductor substrate of the present invention includes at least a processing step, a peeling step, and a removing step, and may further include other steps as necessary.

[0206] <Processing process> The processing step is not particularly limited as long as it is a step in which the semiconductor substrate in the laminate of the present invention is processed, and includes, for example, a polishing process, a through electrode formation process, and the like.

[0207] <<Polishing process>> The polishing process is not particularly limited as long as it is a process for polishing the surface of the semiconductor substrate opposite to the surface on which the bumps are present, thereby thinning the semiconductor substrate. For example, physical polishing using an abrasive or a grinding stone may be used. The polishing process can be carried out using a general polishing device used for polishing semiconductor substrates. The polishing process reduces the thickness of the semiconductor substrate, resulting in a semiconductor substrate thinned to a desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, but may be, for example, 30 to 300 μm or 30 to 100 μm.

[0208] <<Through electrode formation process>> In some cases, through electrodes are formed in the polished semiconductor substrate to realize electrical continuity between the thinned semiconductor substrates when a plurality of thinned semiconductor substrates are stacked. Therefore, the method for manufacturing a semiconductor substrate may include a through electrode forming process for forming a through electrode in the polished semiconductor substrate after the polishing process and before the peeling step. The method for forming a through electrode in a semiconductor substrate is not particularly limited, but may include, for example, forming a through hole and filling the formed through hole with a conductive material. The through holes are formed by, for example, photolithography. The through holes are filled with a conductive material by, for example, plating techniques.

[0209] <Peeling process> The peeling step is not particularly limited as long as it is a step in which the support substrate and the processed semiconductor substrate are separated after the processing step. For example, mechanical peeling can be performed using a device with a sharp part (a so-called debonder). Specifically, for example, a sharp part is inserted between the semiconductor substrate and the support substrate, and then the semiconductor substrate and the support substrate are separated. Usually, peeling occurs at the interface between the release layer and the semiconductor substrate or the inorganic material layer.

[0210] <Removal process> The removal step is not particularly limited as long as it is a step in which the release layer is removed after the peeling step, and examples thereof include dissolution removal. Removal may also be performed using a removal tape or the like. Note that, if there is a residue of the adhesive layer on the semiconductor substrate via the release layer after the peeling step, the residue is also removed in the removal step. When using the cleaning composition, for example, the semiconductor substrate with the release layer can be immersed in the cleaning composition or sprayed with the cleaning composition.

[0211] A suitable example of the cleaning composition used in the present invention is a cleaning composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, an anion paired with the quaternary ammonium cation is a hydroxide ion (OH - ); fluorine ion (F - ), chloride ions (Cl - ), bromide ion (Br - ), iodine ion (I - ) and other halogen ions; tetrafluoroborate ion (BF4 - ); Hexafluorophosphate ion (PF6 - ) and the like, but are not limited to these.

[0212] In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0213] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.

[0214] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of hydrates. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass relative to the detergent composition.

[0215] The solvent contained in the cleaning composition used in the present invention is not particularly limited as long as it is used for this type of application and can dissolve salts such as the quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving salts such as the quaternary ammonium salt to obtain a cleaning composition with excellent uniformity, the cleaning composition used in the present invention preferably contains one or more amide solvents.

[0216] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z). [ka]

[0217] In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, and an ethyl group is preferred. A and R Beach independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R A and R B As the alkyl group, a methyl group or an ethyl group is preferred.

[0218] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Of these, N,N-dimethylpropionamide is particularly preferred.

[0219] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0220] Another example of a preferred amide solvent is a lactam compound represented by formula (Y). [ka]

[0221] In the formula (Y), specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, but are not limited to these.

[0222] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, which can be used alone or in combination of two or more.

[0223] In a preferred embodiment of the present invention, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0224] The cleaning composition used in the present invention may contain one or more other organic solvents different from the above-mentioned amide compound. Such other organic solvents are not particularly limited as long as they are used for this type of application and are compatible with the above-mentioned amide compounds. Other preferred solvents include, but are not limited to, alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing a ring structure. The amount of the organic solvent other than the above-mentioned amide compound is usually determined appropriately so as to be 95 mass % or less of the solvent contained in the cleaning composition, as long as the quaternary ammonium salt contained in the cleaning composition does not precipitate or separate and is uniformly mixed with the above-mentioned amide compound. The cleaning composition used in the present invention may contain water as a solvent, but typically only an organic solvent is used as the solvent to avoid corrosion of the substrate, etc. In this case, however, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is typically 5% by mass or less. [Example]

[0225] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0226] (1) Mixer: Thinky Corporation, Planetary Planetary Mixer ARE-500 (2) Vacuum bonding device: XBS300 manufactured by SUSS MicroTec Co., Ltd. (3) Manual peeling device: SUSS MicroTec Manual Debonder (4) Vacuum heating device: Ayumi Industries Co., Ltd., VJ-300-S

[0227] [Molecular weight measurement] The weight-average molecular weight and number-average molecular weight of polydimethylsiloxane were measured using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation) at a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow velocity) of 0.35 mL / min, and polystyrene (manufactured by Shodex Corporation) as the standard sample.

[0228] [1] Preparation of adhesive composition [Preparation Example 1] A 600 mL stirring vessel designed specifically for a 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 to obtain mixture (I). 0.147 g of platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1,000 mPa·s were stirred with a stirrer for 5 minutes to obtain mixture (II). 3.96 g of mixture (II) was added to the total amount of mixture (I), and the mixture was stirred for 5 minutes with a stirrer to obtain mixture (III). Finally, the obtained mixture (III) was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[0229] [2] Preparation of stripping agent composition [Preparation Example 2-1] In a 250 mL stirring vessel, 1.81 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 50), which is a polydimethylsiloxane having a weight average molecular weight of 7120 and a dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.41, and 98.19 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[0230] [Preparation Example 2-2] In a 250 mL stirring vessel, 1.80 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350), which is a polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72, and 98.2 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[0231] [Preparation Example 2-3] In a 250 mL stirring vessel, 1.81 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, and 98.19 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[0232] [Preparation Example 2-4] In a 250 mL stirring vessel, 1.70 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is a polydimethylsiloxane having a weight average molecular weight of 69980 and a dispersity of 3.66, and 98.3 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[0233] [Preparation Example 2-5] In a 250 mL stirring vessel, 1.34 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000000), which is a polydimethylsiloxane having a weight average molecular weight of 171,860 and a dispersity of 2.18, and 98.66 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes with a stirrer. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition.

[0234] [Preparation Example 2-6] In a 250 mL stirring vessel, 1.17 g of a polydimethylsiloxane (manufactured by Wacker Chem, trade name AK 350) having a weight average molecular weight of 21110 and a dispersity of 1.72, 0.52 g of a polydimethylsiloxane (manufactured by Wacker Chem, trade name AK 1000) having a weight average molecular weight of 34550 and a dispersity of 2.24, and 98.33 g of hexamethyldisiloxane (manufactured by Wacker Chem, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition. In a mixture of 1.17 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 350), which is a polydimethylsiloxane having a weight-average molecular weight of 21110 and a dispersity of 1.72, and 0.52 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 1000), which is a polydimethylsiloxane having a weight-average molecular weight of 34550 and a dispersity of 2.24, the weight-average molecular weight of the polydimethylsiloxane was 25100. The dispersity was 4.04.

[0235] [Preparation Example 2-7] In a 250 mL stirring vessel, 0.50 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 350), which is a polydimethylsiloxane having a weight average molecular weight of 21110 and a dispersity of 1.72, 1.38 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, and 98.32 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition. In a mixture of 0.50 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 350), which is a polydimethylsiloxane having a weight-average molecular weight of 21110 and a dispersity of 1.72, and 1.38 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 1000), which is a polydimethylsiloxane having a weight-average molecular weight of 34550 and a dispersity of 2.24, the weight-average molecular weight of the polydimethylsiloxane was 29270. The dispersity was 4.94.

[0236] [Preparation Example 2-8] In a 250 mL stirring vessel, 1.33 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, 0.57 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is a polydimethylsiloxane having a weight average molecular weight of 69980 and a dispersity of 3.66, and 98.10 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition. In a mixture of 1.33 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 1000), which is a polydimethylsiloxane having a weight-average molecular weight of 34550 and a dispersity of 2.24, and 0.57 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 10000), which is a polydimethylsiloxane having a weight-average molecular weight of 69980 and a dispersity of 3.66, the weight-average molecular weight of the polydimethylsiloxane was 49350. The dispersity was 8.37.

[0237] [Preparation Example 2-9] In a 250 mL stirring vessel, 0.55 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 1000), which is a polydimethylsiloxane having a weight average molecular weight of 34550 and a dispersity of 2.24, 1.28 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK 10000), which is a polydimethylsiloxane having a weight average molecular weight of 69980 and a dispersity of 3.66, and 98.17 g of hexamethyldisiloxane (manufactured by Wacker Chemie, trade name AK 0.65) were placed and stirred for 5 minutes. Finally, the resulting mixture was filtered through a 0.2 μm PTFE filter to obtain a release agent composition. In a mixture of 0.55 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 1000), which is a polydimethylsiloxane having a weight-average molecular weight of 34,550 and a dispersity of 2.24, and 1.28 g of a polyorganosiloxane (manufactured by Wacker Chemie, product name AK 10000), which is a polydimethylsiloxane having a weight-average molecular weight of 69,980 and a dispersity of 3.66, the weight-average molecular weight of the polydimethylsiloxane was 68,740. The dispersity was 12.5.

[0238] [3] Preparation of laminate for evaluation (Comparative Example 1) The release agent composition obtained in Preparation Example 2-1 was spin-coated onto a 12-inch silicon wafer, which was a semiconductor substrate, so that the film thickness in the final laminate was 170 nm, thereby forming a release layer. Next, a plasma polymer layer, an inorganic material layer, was formed on the release layer so that the final laminate had a thickness of 160 nm. The plasma polymer layer was formed by chemical vapor deposition (CVD). Specifically, CVD was performed under the following conditions: 40 W, 65 mTorr, and a hexamethyldisiloxane flow rate of 15 sccm. Next, the adhesive composition obtained in Preparation Example 1 was spin coated so that the film thickness in the final laminate was 60 μm, forming an adhesive coating layer on the plasma polymer layer. Then, using a bonding device, a silicon wafer serving as the semiconductor substrate and a 12-inch glass wafer serving as the support substrate were bonded together so that the release layer, plasma polymer layer, and adhesive coating layer were sandwiched between them, and then the semiconductor substrate was placed face down on a hot plate, where the layers were sequentially heated at 170°C for 7 minutes and then at 190°C for 7 minutes to produce a laminate. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,000 Pa.

[0239] Examples 1 to 4 Laminates were prepared in the same manner as in Comparative Example 1, except that the release agent composition obtained in Preparation Example 2-1 was replaced with the release agent compositions obtained in Preparation Examples 2-3 and 2-6 to 2-8, respectively.

[0240] (Comparative Examples 2 to 5) Laminates were prepared in the same manner as in Comparative Example 1, 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, 2-4, 2-5, and 2-9, respectively.

[0241] [High-temperature treatment of laminate] The laminate was subjected to a heat treatment using a vacuum heating device according to the following procedure. The stack was placed with the semiconductor substrate facing downwards on a heating stage set at 300° C. and heated for 10 minutes in a nitrogen atmosphere. The state of the semiconductor substrate of each laminate after processing was observed using an optical microscope through the glass wafer support substrate, and the presence or absence of voids and delamination was visually confirmed. After the observation, a manual peeling device was used to insert a sharp object between the semiconductor substrate and support substrate of the laminate to confirm whether the semiconductor substrate and support substrate could be easily separated manually. The peelability evaluation results were rated as "possible" if the semiconductor substrate and support substrate could be manually separated at the interface between the release layer and the inorganic material layer without applying a force that felt like a heavy load was being applied to the substrate, and "failed" otherwise. Note that a "failed" evaluation result indicated that even when further force was applied to peel the substrates, they still could not be separated at all, or the substrates could be forcibly separated but cracked. Here, "voids" refers to the presence of air bubbles between the substrate and a layer of the laminate, between two layers, or within a layer, and in such a state where undesirable air bubbles exist, sufficient protection of the semiconductor substrate cannot be expected. "Delamination" refers to the state where the release layer is partially peeled off from the semiconductor substrate, and in this state, sufficient protection of the semiconductor substrate cannot be expected. The results are shown in Table 1 below.

[0242] [Table 1]

[0243] As shown in the table, even in laminates having a release layer made from a release agent composition containing polyorganosiloxane (polydimethylsiloxane), when the weight average molecular weight was outside the specified range of the present invention (Comparative Examples 1 to 5), delamination could not be suppressed during heat treatment at high temperatures (300°C), or even if delamination did not occur during heat treatment, peeling was impossible after heat treatment. However, when the weight average molecular weight was within the specified range of the present invention (Examples 1 to 4), delamination could be suppressed during heat treatment at high temperatures (300°C), and in addition, peeling was possible after heat treatment. In terms of whether peeling is possible, Comparative Example 2 is better than Comparative Example 1, and it is thought that peeling would be possible if a polyorganosiloxane with a weight average molecular weight slightly higher than that of the polyorganosiloxane of Comparative Example 2 (for example, a polyorganosiloxane with a weight average molecular weight of 22,000) were used. In terms of the degree of delamination, Comparative Examples 3 and 5 are better than Comparative Example 4, and it is believed that delamination would not occur if a polyorganosiloxane with a weight average molecular weight slightly smaller than that of the polyorganosiloxane of Comparative Example 5 (for example, a polyorganosiloxane with a weight average molecular weight of 68,000) were used. [Industrial Applicability]

[0244] According to the present invention, the laminate of the present invention is useful for producing processed semiconductor substrates, since it does not peel off when the semiconductor substrate and the support substrate are temporarily bonded together, even after the semiconductor substrate has been exposed to high temperatures, and can be easily peeled off when an attempt is made to peel the semiconductor substrate and the support substrate. [Explanation of symbols]

[0245] 1. Semiconductor substrate 2. Peel layer 3 Inorganic material layer 4 Adhesive layer 5 Support substrate

Claims

1. A support substrate; a semiconductor substrate; a release layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate; an adhesive layer interposed between the support substrate and the release layer; A laminate having A laminate, wherein the release layer is a layer formed from a release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.

2. The laminate of claim 1 , wherein the polyorganosiloxane is polydimethylsiloxane.

3. The laminate according to claim 1 or 2, wherein the adhesive layer is a layer formed from an adhesive composition.

4. The laminate of claim 3 , wherein the adhesive composition contains a curable component (A).

5. 5. The laminate according to claim 4, wherein the component (A) is a component that cures via a hydrosilylation reaction.

6. The component (A) is A polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having Si—H groups; a platinum group metal catalyst (A2); The laminate according to claim 4 or 5, comprising:

7. 7. The laminate according to claim 1, further comprising an inorganic material layer interposed between the release layer and the adhesive layer.

8. The laminate according to claim 7 , wherein the inorganic material layer is a layer obtained by plasma polymerization of an organosilicon compound.

9. 9. The laminate according to claim 1, which is used in a treatment in which the semiconductor substrate is heated to 280° C. or higher.

10. A step of processing the semiconductor substrate in the stack according to any one of claims 1 to 8; separating the support substrate from the processed semiconductor substrate; A method for manufacturing a semiconductor substrate, comprising:

11. The method for manufacturing a semiconductor substrate according to claim 10 , wherein the processing step includes a process of polishing a surface of the semiconductor substrate opposite to a surface in contact with the release layer, thereby thinning the semiconductor substrate.

12. The method for manufacturing a semiconductor substrate according to claim 10 or 11, wherein the processing step includes a treatment in which the semiconductor substrate is heated to 280° C. or higher.

13. A method for producing a laminate according to any one of claims 1 to 9, comprising: forming an adhesive coating layer that provides the adhesive layer; a step of heating the adhesive coating layer to form the adhesive layer while the support substrate and the semiconductor substrate are in contact with each other with the release layer and the adhesive coating layer interposed therebetween; A method for producing a laminate, comprising:

14. A release agent composition used in forming the release layer of a laminate having a support substrate, a semiconductor substrate, a release layer interposed between the support substrate and the semiconductor substrate and in contact with the semiconductor substrate, and an adhesive layer interposed between the support substrate and the release layer, the release layer being in contact with the semiconductor substrate that is heated to 280°C or higher when the semiconductor substrate of the laminate is processed, A release agent composition containing a polyorganosiloxane having a weight average molecular weight of 22,000 to 68,000.

15. 15. The stripper composition of claim 14, wherein the polyorganosiloxane is polydimethylsiloxane.

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