Method for manufacturing machined semiconductor substrate

Abstract

A method for manufacturing a machined semiconductor substrate (1) comprises: a step for preparing a laminate having a semiconductor substrate (1), a support substrate (4), an adhesive agent layer (2) provided between the semiconductor substrate (1) and the support substrate (4), and a release agent layer (3) provided between the semiconductor substrate (1) and the support substrate (4); a machining step for machining the semiconductor substrate (1) in the laminate; an irradiation step for, after the machining step, irradiating the release agent layer (3) with an ultraviolet laser; and a separation step for, after the irradiation step, separating the machined semiconductor substrate (1) and the support substrate (4). The adhesive agent layer (2) is formed from an adhesive composition which contains an adhesive component, and the area of irradiation in the irradiation step is smaller than the area of the adhesive agent layer (2).

Description

Method for manufacturing a processed semiconductor substrate

[0001] The present invention relates to a method for manufacturing a processed semiconductor substrate.

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

[0003] Semiconductor wafers (herein simply referred to as wafers) before thinning are bonded to a support in preparation for polishing with a polishing device. This bond must be easily peeled off after polishing, and is therefore called a temporary bond. This temporary bond must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary bond is to withstand the stress during polishing and be easily removed after polishing.

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] On the other hand, methods using laser irradiation for the bonding and separation process have been disclosed (see, for example, Patent Documents 3 and 4).

[0006] With regard to a technology that utilizes light irradiation when separating a semiconductor substrate from a support substrate, a laminate has been proposed that includes a semiconductor substrate, a support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, wherein the release layer is a film obtained from a release agent composition that includes an organic resin, a branched-chain polysilane, and a solvent (see Patent Document 5).

[0007] International Publication No. 2017 / 221772 Pamphlet International Publication No. 2018 / 216732 Pamphlet Japanese Patent Application Laid-Open No. 2004-64040 Japanese Patent Application Laid-Open No. 2012-106486 Pamphlet International Publication No. 2022 / 019211 Pamphlet

[0008] With the recent advances in the semiconductor field, new technologies related to delamination by irradiation with light such as laser are constantly being sought.

[0009] An object of the present invention is to provide a method for manufacturing a processed semiconductor substrate that can shorten the time required for peeling using ultraviolet laser irradiation.

[0010] 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.

[0011] That is, the present invention includes the following: [1] A method for producing a processed semiconductor substrate, comprising the steps of: preparing a laminate having a semiconductor substrate, a support substrate, an adhesive layer provided between the semiconductor substrate and the support substrate, and a release agent layer provided between the semiconductor substrate and the support substrate; a processing step in which the semiconductor substrate in the laminate is processed; an irradiation step in which, after the processing step, the release agent layer is irradiated with an ultraviolet laser; and a separation step in which, after the irradiation step, the processed semiconductor substrate and the support substrate are separated, wherein the adhesive layer is formed from an adhesive composition containing an adhesive component, and the irradiated area in the irradiation step is smaller than the area of ​​the adhesive layer. [2] A method for producing a processed semiconductor substrate according to [1], wherein the ratio (S1 / S3) of the irradiated area (S1) to the area (S3) of the release agent layer is 0.01 or more and 0.5 or less. [3] A method for producing a processed semiconductor substrate according to [1] or [2], wherein the irradiating of the release agent layer with an ultraviolet laser in the irradiating step is irradiating only a portion of the release agent layer. [4] The method for producing a processed semiconductor substrate according to any one of [1] to [3], wherein the area of ​​the release agent layer in the laminate is smaller than the area of ​​the adhesive layer. [5] The method for producing a processed semiconductor substrate according to any one of [1] to [4], wherein the area of ​​the release agent layer is 1% to 90% of the area of ​​the adhesive layer. [6] The method for producing a processed semiconductor substrate according to [4] or [5], wherein the release agent layer is arranged in the laminate so as to contact the adhesive layer in at least a part of the outer periphery of the adhesive layer. [7] The method for producing a processed semiconductor substrate according to any one of [1] to [6], wherein the semiconductor substrate has an electrode on its surface, and the irradiation of the release agent layer with an ultraviolet laser in the irradiation step is not performed at a position in the thickness direction where the electrode of the semiconductor substrate is located. [8] The method for producing a processed semiconductor substrate according to any one of [1] to [7], wherein the adhesive composition contains a release agent component.

[0012] According to the present invention, it is possible to provide a method for manufacturing a processed semiconductor substrate that can shorten the time required for peeling using ultraviolet laser irradiation.

[0013] FIG. 1 is a schematic cross-sectional view of an example of a laminate. FIG. 2A is a schematic cross-sectional view (part 1) for explaining an example of a method for manufacturing a laminate. FIG. 2B is a schematic cross-sectional view (part 2) for explaining an example of a method for manufacturing a laminate. FIG. 2C is a schematic cross-sectional view (part 3) for explaining an example of a method for manufacturing a laminate. FIG. 3 is a perspective view of an example of a laminate structure of a release agent layer and a support substrate. FIG. 4 is a perspective view of another example of a laminate structure of a release agent layer and a support substrate. FIG. 5 is a perspective view of another example of a laminate structure of a release agent layer and a support substrate. FIG. 6A is a schematic top view of an example showing the relationship between an ultraviolet laser irradiation region and a release agent layer. FIG. 6B is a schematic top view of another example showing the relationship between an ultraviolet laser irradiation region and a release agent layer. FIG. 6C is a schematic top view of another example showing the relationship between an ultraviolet laser irradiation region and a release agent layer. FIG. 6D is a schematic top view of another example showing the relationship between an ultraviolet laser irradiation region and a release agent layer. FIG. 7A is a schematic cross-sectional view (part 1) for explaining an example of a method for manufacturing a processed semiconductor substrate. Fig. 7B is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 2). Fig. 7C is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 3). Fig. 7D is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 4). Fig. 7E is a schematic cross-sectional view for explaining an example of a method for manufacturing a processed semiconductor substrate (part 5).

[0014] (Method for manufacturing a processed semiconductor substrate) The method for manufacturing a processed semiconductor substrate of the present invention includes a step of preparing a stack, a processing step, an irradiation step, and a separation step. The method for manufacturing a processed semiconductor substrate may further include other steps such as a cleaning step.

[0015] The laminate includes a semiconductor substrate, a support substrate, an adhesive layer, and a release agent layer. The adhesive layer is provided between the semiconductor substrate and the support substrate. The release agent layer is provided between the semiconductor substrate and the support substrate.

[0016] The processing step is a step in which the semiconductor substrate in the laminate is processed. The irradiation step is a step in which the release agent layer is irradiated with an ultraviolet laser after the processing step. The separation step is a step in which the processed semiconductor substrate and the support substrate are separated after the irradiation step.

[0017] The adhesive layer in the laminate is formed from an adhesive composition containing adhesive components, and the irradiated area in the irradiation step is smaller than the area of ​​the adhesive layer.

[0018] After processing a semiconductor substrate of a laminate having a semiconductor substrate, an adhesive layer, a release agent layer, and a support substrate, light is irradiated onto the release agent layer to reduce the adhesive strength of the release agent layer when separating the semiconductor substrate from the support substrate. In this case, the light is usually irradiated onto the entire surface of the release agent layer. On the other hand, irradiating the entire surface of the release agent layer with light poses the problem of a long irradiation time. Furthermore, when the irradiated light hits an electrode on the semiconductor substrate, the electrode may be damaged. Therefore, the present inventors conducted extensive research. The present inventors found that peeling is possible even when the irradiation area of ​​the ultraviolet laser irradiated onto the release agent layer is smaller than the area of ​​the adhesive layer. By reducing the irradiation area of ​​the ultraviolet laser irradiated onto the release agent layer, the time required for peeling using ultraviolet laser irradiation can be shortened. Furthermore, irradiation of the ultraviolet laser onto the electrode on the surface of the semiconductor substrate can be avoided, thereby preventing damage to the electrode.

[0019] The adhesive strength of the release agent layer at the location irradiated with the ultraviolet laser is lower than that before irradiation.On the other hand, even if the adhesive strength of the entire surface of the release agent layer is not reduced by irradiating the entire surface of the release agent layer with the ultraviolet laser, the semiconductor substrate and the support substrate can be separated from each other without applying excessive load, starting from the location irradiated with the ultraviolet laser.That is, in the laminate, for example, while the semiconductor substrate is being processed, such as thinned, the semiconductor substrate is suitably supported on the support substrate via the adhesive layer and the release agent layer, and after the processing is completed, by irradiating the release agent layer with an ultraviolet laser, the ultraviolet laser is absorbed by the release agent layer, and the release agent layer is altered (for example, separated) at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or inside the release agent layer, and as a result, suitable peeling (separation) can be achieved without applying excessive load, starting from the location irradiated with the ultraviolet laser.

[0020] <Step of Preparing a Laminate> The laminate prepared in this step includes a semiconductor substrate, a support substrate, an adhesive layer, and a release agent layer. The adhesive layer is provided between the semiconductor substrate and the support substrate. The release agent layer is provided between the semiconductor substrate and the support substrate.

[0021] In one example of the laminate, the release agent layer is in contact with, for example, the adhesive layer and the support substrate, but not with the semiconductor substrate. In another example of the laminate, the release agent layer is in contact with, for example, the adhesive layer and the semiconductor substrate, but not with the support substrate.

[0022] <<Semiconductor Substrate>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is suitable for this type of application, and examples thereof include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0023] The semiconductor substrate may have an electrode. The electrode is, for example, a bump or a pad. In a laminate, when the semiconductor substrate has an electrode, the semiconductor substrate has the electrode on the support substrate side. In a semiconductor substrate, the electrode is usually formed on the surface on which a circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface having the electrode (back surface) is the surface used for processing. The material, size, shape, structure, and density of the electrode of the semiconductor substrate are not particularly limited. Examples of materials for the pad include gold, silver, and copper. The size of the pad is not particularly limited. Examples of shapes of the pad include a circle and a square. Examples of bumps (protruding terminals) include ball bumps, printed bumps, stud bumps, and plated bumps. Typically, the height, radius, and pitch of the bumps are determined appropriately based on the following conditions: bump height is approximately 1 to 200 μm, bump radius is 1 to 200 μm, and bump pitch is 1 to 500 μm. Examples of bump materials 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, examples include alloy platings primarily containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bumps may also have a layered structure including a metal layer composed of at least one of these components.

[0024] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0025] Although the arrangement of the electrodes on the semiconductor substrate is not particularly limited, it is preferable that the electrodes are not arranged on the periphery of the semiconductor substrate, so that even if the release agent layer located on the periphery of the semiconductor substrate when viewed in the thickness direction is irradiated with an ultraviolet laser, the ultraviolet laser does not hit the electrodes, and damage to the electrodes can be prevented.

[0026] <<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, a silicon support substrate, etc. The support substrate is preferably transparent to the ultraviolet laser irradiated in the irradiation step.

[0027] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The disk-shaped support substrate does not need to have a perfectly circular surface; for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat, or a notch. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0028] An example of the support substrate is a glass wafer having a diameter of about 300 mm and a thickness of about 700 μm.

[0029] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate and is formed from an adhesive composition.

[0030] In one example of the laminate, the adhesive layer is in contact with, for example, the semiconductor substrate and the release agent layer. In another example of the laminate, the adhesive layer is in contact with, for example, the support substrate and the release agent layer. Furthermore, when the area of ​​the release agent layer is smaller than the area of ​​the adhesive layer, in one example of the laminate, one side of the adhesive layer is in contact with the semiconductor substrate, and the other side of the adhesive layer has a portion that is in contact with the release agent layer and a portion that is in contact with the support substrate. Alternatively, in another example of the laminate, one side of the adhesive layer is in contact with the support substrate, and the other side of the adhesive layer has a portion that is in contact with the release agent layer and a portion that is in contact with the semiconductor substrate. Furthermore, it is preferable that the adhesive layer itself can be easily peeled from both the semiconductor substrate and / or the support substrate without applying an excessive load. When the adhesive layer is in contact with the release agent layer, it is preferable that the adhesive layer can be easily peeled from the release agent layer without applying an excessive load.

[0031] <<<Adhesive Composition>>> The adhesive composition contains an adhesive component. The adhesive composition may also contain a release agent component.

[0032] -Adhesive Component- The adhesive component is not particularly limited, but is preferably a component that cures, and more preferably a component that cures by a hydrosilylation reaction. The component that cures by a hydrosilylation reaction is not particularly limited, but preferably contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter sometimes referred to as "component (A-1)"), a component having a Si-H group (hereinafter sometimes referred to as "component (A-2)"), and a catalyst (A-3).

[0033] --Component (A-1) and Component (A-2)-- The adhesive component preferably contains component (A-1). The adhesive component preferably contains component (A-2). Hereinafter, the combination of component (A-1), component (A-2), and catalyst (A-3) may be referred to as "curable component (A)" or "component (A)."

[0034] From the viewpoint of optimally achieving the effects of the present invention, component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. From the viewpoint of optimally achieving the effects of the present invention, component (A-2) preferably contains a polyorganosiloxane (a2) having a Si—H group. 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.

[0035] In another preferred embodiment, the adhesive composition that cures by a hydrosilylation reaction is ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５SiO ２／２ Siloxane units (D units) represented by the formula: and R ６ SiO ３／２ and a catalyst (A-3), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (T units) represented by the following formula: ２ Siloxane units (Q′ units) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ Siloxane units (D′ units) represented by the formula: ６ 'SiO ３／２ and a polyorganosiloxane (a1') containing at least one unit selected from the group consisting of M' units, D' units, and T' units, and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by the formula: 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).

[0036] R １ ~R ６are 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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, and a 4-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, 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.

[0041] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a cyclopropyl ... Examples of such cycloalkyl groups include cycloalkyl groups such as 1-n-propyl-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.

[0042] 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.

[0043] Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of optionally substituted cyclic alkenyl groups 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.

[0044] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), and the alkenyl group contained in polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in polyorganosiloxane (a2') form a crosslinked structure through a hydrosilylation reaction with catalyst (A-3), and then the crosslinked structure is cured. As a result, a cured film is formed.

[0045] 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.

[0046] 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).

[0047] In addition, when two or more types of polyorganosiloxanes are included in the polyorganosiloxane (a1'), a combination of (Q' units and M' units) and (D' units and M' units), a combination of (T' units and M' units) and (D' units and M' units), a combination of (Q' units, T' units and M' units) and (T' units and M' units) is preferred, but is not limited to these.

[0048] 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.

[0049] 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).

[0050] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof. １ '~R ６ The proportion of alkenyl groups in all the substituents represented by R ′ is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R １ '~R ６ ' can be an alkyl group.

[0051] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. １ "~R ６ The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R １ "~R ６ " can be an alkyl group.

[0052] When the adhesive composition contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0053] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0054] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa s), and from the viewpoint of realizing 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.

[0055] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0056] --Catalyst (A-3)-- The catalyst (A-3) is not particularly limited as long as it is a catalyst that promotes the hydrosilylation reaction between an alkenyl group and a Si—H group. Examples of the catalyst (A-3) include platinum group metal catalysts. Platinum group metal catalysts are platinum-based metal catalysts.

[0057] Specific examples of platinum-based metal catalysts that can be used include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), and complexes of chloroplatinic acid and acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high hydrosilylation reaction-accelerating effect. These hydrosilylation reaction catalysts may be used either individually or in combination of two or more.

[0058] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, and examples thereof include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0059] The content of catalyst (A-3) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).

[0060] --Polymerization Inhibitor-- The adhesive component may contain a polymerization inhibitor for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it inhibits the progress of the hydrosilylation reaction. Specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol. The amount of the polymerization inhibitor is not particularly limited, but is typically 1,000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of achieving the effect, and 10,000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0061] The content of the adhesive component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but may be, for example, 95% by mass or less, 90% by mass or less, or 85% by mass or less. The non-volatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0062] -Release Agent Component- The release agent component is not particularly limited, but from the viewpoint of more suitably obtaining the effects of the present invention, polyorganosiloxane is preferred. The polyorganosiloxane used as the release agent component usually does not react with the adhesive component. For example, the polyorganosiloxane used as the release agent component is a component that does not undergo a hydrosilylation reaction.

[0063] Polyorganosiloxane usually contains siloxane units (D units), but may also contain Q units, M units, and T units. For example, when consisting of only D units, when a combination of D units and Q units, when a combination of D units and M units, when a combination of D units and T units, when a combination of D units, Q units, and M units, when a combination of D units, M units, and T units, when a combination of D units, Q units, M units, and T units, and when a combination of D units, Q units, M units, and T units, etc. can be mentioned.

[0064] The polyorganosiloxane is not particularly limited, and examples thereof include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.

[0065] --Polydimethylsiloxane-- The "polydimethylsiloxane" in the present invention is an unmodified polyorganosiloxane that differs from epoxy group-containing polydimethylsiloxanes, phenyl group-containing polydimethylsiloxanes, carbinol-modified polyorganosiloxanes, etc., and has methyl groups as organic groups bonded to silicon atoms.

[0066] Specific examples of polydimethylsiloxane include, but are not limited to, those represented by formula (M1).

[0067] (n ４ indicates the number of repeating units and is a positive integer.)

[0068] The weight-average molecular weight of the polydimethylsiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. The dispersity is also not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane. The viscosity of the polydimethylsiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm. ２ The viscosity value of polydimethylsiloxane is expressed as kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0069] --Epoxy group-containing polyorganosiloxane-- Examples of the epoxy group-containing polyorganosiloxane include R １１ R １２ SiO ２／２ The siloxane unit (D １０ Examples include those containing units.

[0070] 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 organic group containing an epoxy group may be an independent epoxy group that is not condensed with another ring, or may be an epoxy group that forms a condensed ring with another ring, 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, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0071] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D １０ units), but D １０ In addition to the units, the epoxy group-containing polyorganosiloxane may contain Q units, M units and / or T units. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D １０ Polyorganosiloxane consisting only of 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, １０Polyorganosiloxanes containing units, M units and T units, D １０ Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0072] The epoxy group-containing polyorganosiloxane may have an epoxy group on a side chain, may have an epoxy group at one end, or may have epoxy groups at both ends.

[0073] 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.

[0074] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0075] (m １ and n １ indicates the number of each repeating unit and is a positive integer.)

[0076] (m ２ and n ２ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0077] (m ３ , n ３ and ３ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0078] In the above general formula, m １ , m ２ , m ３ , and O３ When the number of repeating units is two or more, the repeating units may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0079] Since the polyorganosiloxane represented by formula (E3) has an epoxy group and a phenyl group, it is an epoxy group-containing polyorganosiloxane and also a phenyl group-containing polyorganosiloxane. The epoxy group-containing polyorganosiloxane may or may not have a phenyl group.

[0080] The weight-average molecular weight of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the method described above for polyorganosiloxane. The viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is typically 1,000 to 2,000,000 mm. ２ The viscosity value of the epoxy group-containing polyorganosiloxane is expressed as a kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0081] --Phenyl group-containing polyorganosiloxane-- Examples of the phenyl group-containing polyorganosiloxane include R ３１ R ３２ SiO ２／２ The siloxane unit (D ３０Examples include those containing units.

[0082] 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.

[0083] 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.

[0084] In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include D ３０ Polyorganosiloxane consisting only of 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, ３０ Polyorganosiloxanes containing units, M units and T units, D ３０ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0085] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0086] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0087] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0088] In the above general formula, m ５ , and m ６ When the number of repeating units is two or more, the repeating units may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0089] --Carbinol-modified polyorganosiloxane-- The carbinol-modified polyorganosiloxane is not particularly limited. The carbinol-modified polyorganosiloxane is a polyorganosiloxane having a hydroxy group directly bonded to a carbon atom. Thus, the carbinol in "carbinol-modified polyorganosiloxane" is not limited to methanol in the narrow sense, but also includes methanol derivatives.

[0090] The carbinol-modified polyorganosiloxane is, for example, a carbinol-modified polydimethylsiloxane.

[0091] The number of hydroxy groups directly bonded to carbon atoms in the carbinol-modified polyorganosiloxane is not particularly limited, and may be one or two or more.

[0092] The carbinol-modified polyorganosiloxane may have a hydroxy group bonded directly to a carbon atom in the side chain, or may have a hydroxy group bonded directly to a carbon atom at one end, or may have hydroxy groups bonded directly to a carbon atom at both ends. The carbinol-modified polyorganosiloxane preferably has a hydroxy group bonded directly to a carbon atom in the side chain. In this case, even if the content of the carbinol-modified polyorganosiloxane is small, the adhesive layer formed from the adhesive composition can be imparted with good releasability.

[0093] The carbinol-modified polyorganosiloxane has, for example, a group represented by the following formula (Cg) as a group directly bonded to a silicon atom.

[0094] (In formula (Cg), R １ represents a group having one or more carbon atoms. * represents a bond bonded to a silicon atom. However, the hydroxy group in formula (Cg) is directly bonded to a carbon atom.

[0095] The number of hydroxy groups directly bonded to a carbon atom in the group represented by formula (Cg) may be 1 or 2 or more. Examples of 2 or more include 2, 3, and 4.

[0096] R １ The number of carbon atoms is not particularly limited, and may be, for example, 1 to 30, 1 to 20, or 1 to 10.

[0097] Examples of the group represented by formula (Cg) include groups represented by the following formulae (Cg-1) to (Cg-4). (In formula (Cg-1), R １１ represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms. １２ represents an alkylene group having 1 to 6 carbon atoms. １３ represents an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a hydroxy group. １４ represents an alkylene group having 1 to 6 carbon atoms. １５ represents an alkylene group having 1 to 3 carbon atoms, and m represents an integer of 1 to 10. In formula (Cg-4), R １６ ~R １８ each independently represents an alkylene group having 1 to 6 carbon atoms. In formulas (Cg-1) to (Cg-4), * represents a bond bonded to a silicon atom.

[0098] R １１ ~R １８ The alkylene group may be linear, branched, or cyclic.

[0099] Examples of the group represented by formula (Cg) include the following groups. (In the formula, m1 represents an integer of 2 to 10. * represents a bond bonded to a silicon atom.)

[0100] The carbinol-modified polyorganosiloxane is represented, for example, by the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R５１ Each of X independently represents a hydrocarbon group. １ represents a group represented by the above formula (Cg). n1 represents an integer of 0 or more. n2 represents an integer of 1 or more. In formula (CPS-2), R ５２ Each of X independently represents a hydrocarbon group. ２ represents a group represented by the above formula (Cg). ３ represents a hydrocarbon group or a group represented by the above formula (Cg); and n3 represents an integer of 0 or more.

[0101] R ５１ , R ５２ , and X ３ Examples of the hydrocarbon group in the formula (CPS-1a) include alkyl groups having 1 to 8 carbon atoms. As the alkyl group having 1 to 8 carbon atoms, a methyl group is preferred. That is, the carbinol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a). (In formula (CPS-1a), X １ represents a group represented by the above formula (Cg). n1 represents an integer of 0 or more. n2 represents an integer of 1 or more. In formula (CPS-2a), X ２ represents a group represented by the above formula (Cg). ３ represents a methyl group or a group represented by the above formula (Cg); and n3 represents an integer of 0 or more.

[0102] The carbinol-modified polyorganosiloxane represented by formula (CPS-1) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a) have hydroxy groups directly bonded to carbon atoms in their side chains. The carbinol-modified polyorganosiloxane represented by formula (CPS-2) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-2a) have hydroxy groups directly bonded to carbon atoms at one or both ends.

[0103] In the carbinol-modified polyorganosiloxane represented by formula (CPS-1), when n2 is 2 or more, -Si(R ５１ ) (X １The siloxane units represented by —Si(CH )—O— may be arranged adjacent to each other to form a block, or may be arranged randomly. In the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a), when n2 is 2 or more, ３ ) (X １ The siloxane units represented by —O— may be arranged adjacent to each other to form a block, or may be arranged randomly.

[0104] The weight average molecular weight of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of reproducibly realizing the effects of the present invention, it is preferably 5,000 to 50,000. The degree of dispersion is also not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of reproducibly realizing suitable release, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The viscosity of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 100 to 200,000 mm ２ The viscosity value of polydimethylsiloxane is expressed as kinematic viscosity, and is expressed as centistokes (cSt) = mm ２ Viscosity (mPa s) is converted to density (g / cm ３ That is, the value can be calculated from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm ２ / s)=viscosity (mPa・s) / density (g / cm ３ ) can be calculated using the formula:

[0105] The polyorganosiloxane as a release agent component can be used alone or in combination of two or more. Here, the two or more polyorganosiloxanes referred to as "two" refer to, for example, a combination of polydimethylsiloxane and epoxy group-containing polyorganosiloxane, or a combination of polydimethylsiloxane and phenyl group-containing polyorganosiloxane, but do not refer to a combination of two epoxy group-containing polyorganosiloxanes that differ in molecular weight, viscosity, type of epoxy group, etc.

[0106] The polyorganosiloxane that is the release agent component (B) may be a commercially available product or may be synthesized. Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, manufactured by Wacker Chemie, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (trade names CMS-227, ECMS-327, EMS-622) manufactured by Gelest, and Shin-Etsu Chemical Co., Ltd. Epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), epoxy group-containing polyorganosiloxanes (DOWSIL BY16-839, DOWSIL8413, DOWSIL8411) manufactured by Dow-Toray Industries, Inc.; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, but are not limited to these.

[0107] Commercially available carbinol-modified polyorganosiloxanes include, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, and X-22-4015 manufactured by Shin-Etsu Silicone Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, and MCR-C63 manufactured by Gelest; and DOWSIL BY 16-201, DOWSIL SF 8427 Fluid, DOWSIL SF 8428 Fluid, etc.

[0108] The content of the release agent component in the adhesive composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0109] -Solvent- The adhesive composition may contain a solvent for purposes such as adjusting viscosity. Specific examples include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specific examples include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, methylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Such solvents may be used alone or in combination of two or more.

[0110] When the adhesive composition 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 thin film to be produced, etc., but is, for example, in the range of about 10 to 90 mass % with respect to the entire composition.

[0111] 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.

[0112] An example of the adhesive composition used in the present invention can be produced by mixing component (A), release agent component (B), and a solvent. The order of mixing is not particularly limited, and 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 release agent component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of release agent 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 decomposition or deterioration of the components. In the present invention, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all components have been mixed, in order to remove foreign matter.

[0113] Examples of adhesive compositions that can be used include the adhesives described in WO2017 / 221772, the temporary adhesives described in WO2018 / 216732, the temporary adhesives described in WO2019 / 009365, the adhesive compositions described in WO2020 / 111069, and the adhesive compositions described in WO2021 / 131925. The contents of these publications are incorporated herein by reference to the same extent as if expressly set forth herein.

[0114] The thickness of the adhesive layer 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 100 μm or less.

[0115] <<Release Agent Layer>> The laminate has a release agent layer. The release agent layer is formed from, for example, a release agent composition.

[0116] The area of ​​the release agent layer may be approximately the same as or smaller than the area of ​​the adhesive layer. When the area of ​​the release agent layer is smaller than the area of ​​the adhesive layer, the adhesive composition preferably contains a release agent component. Because the adhesive layer is formed from an adhesive composition containing a release agent component, even if the area of ​​the release agent layer is smaller than the area of ​​the adhesive layer and there are areas where the release agent layer is absent when viewed in the thickness direction, the semiconductor substrate and the support substrate can be separated. Here, "approximately the same" means that the area of ​​the release agent layer is 90% to 110% of the area of ​​the adhesive layer. When the area of ​​the release agent layer is smaller than the area of ​​the adhesive layer, the area of ​​the release agent layer may be, for example, 1% to 90%, 1% to 50%, or 1% to 10% of the area of ​​the adhesive layer. The release agent layer may be disposed only in areas located on the periphery of the semiconductor substrate when viewed in the thickness direction. In this case, the release agent layer may be disposed in areas located on the entire periphery of the semiconductor substrate, or in areas located on a portion of the periphery.

[0117] <<<Release Agent Composition>>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and further contains other components as necessary. The organic resin is preferably one that can exhibit suitable release ability, and when the semiconductor substrate and the support substrate are separated by ultraviolet light applied to the release agent layer, the organic resin absorbs the ultraviolet light and suitably undergoes a change in quality, such as decomposition, required to improve the release ability.

[0118] Examples of organic resins include novolac resins, etc. Details of these will be described later.

[0119] In a preferred embodiment, the release agent composition contains at least a novolac resin, and further contains other components such as a crosslinker, an acid generator, an acid, a surfactant, a solvent, etc., as needed. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinker, and further contains other components such as an acid generator, an acid, a surfactant, a solvent, etc. In another preferred embodiment, the release agent composition contains at least an organic resin and a branched-chain polysilane, and further contains other components such as a crosslinker, an acid generator, an acid, a surfactant, a solvent, etc., as needed.

[0120] Novolac Resin Novolac resin is a resin obtained by, for example, subjecting at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound to a condensation reaction with at least one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst.

[0121] Examples of phenolic compounds include phenols, naphthols, anthrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of anthrols include 9-anthrole. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of the carbazole compound include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazol-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1H-benzotriazol-1-yl)methylcarbazole, 4 ... Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These compounds may be used alone or in combination of two or more. These compounds may have a substituent.For example, they may have a substituent on the aromatic ring.

[0122] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, capronaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanoic aldehyde, 7-methoxy-3,7-dimethyloctyl aldehyde, cyclohexane aldehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and adipic acid. Examples of the ketone compound include saturated aliphatic aldehydes such as benzoic acid aldehyde, unsaturated aliphatic aldehydes such as acrolein and methacrolein, heterocyclic aldehydes such as furfural and pyridine aldehyde, and aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred. Examples of the ketone compound include diaryl ketone compounds such as diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, 5-vinylnorbornadiene, etc. These can be used alone or in combination of two or more.

[0123] The novolac resin is, for example, a novolac resin that absorbs light irradiated from the support substrate side and changes in quality, for example, by photolysis.

[0124] The novolac resin contains, for example, at least one of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3).

[0125]

[0126] In the formula, C １ represents a group derived from an aromatic compound containing a nitrogen atom, C ２ represents a group containing a tertiary carbon atom having at least one member selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, and C ３ represents a group derived from an aliphatic polycyclic compound, C ４ represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0127] That is, the novolac resin contains, for example, one or more of the following structural units: A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one carbon atom selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain (formula (C1-1)); A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)); A structural unit having a bond between a group derived from a phenol, a group derived from a bisphenol, a group derived from a naphthol, a group derived from a biphenyl, or a group derived from a biphenol and a group containing a tertiary carbon atom having at least one carbon atom selected from the group consisting of a quaternary carbon atom and an aromatic ring in its side chain (formula (C1-3)).

[0128] In a preferred embodiment, the novolak resin contains either or both of a structural unit (formula (C1-1)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one kind selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain, and a structural unit (formula (C1-2)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound.

[0129] C １ Examples of the group derived from an aromatic compound containing a nitrogen atom include, but are not limited to, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, and a group derived from N-phenyl-2-naphthylamine.２ Examples of the group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain include, but are not limited to, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, and a group derived from acetaldehyde. ３ The group derived from an aliphatic polycyclic compound of can be, but is not limited to, a group derived from dicyclopentadiene. ４ is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0130] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, a structural unit represented by formula (C1-1-1) below.

[0131]

[0132] In formula (C1-1-1), R ９０１ and R ９０２ represents a substituent substituted on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０３ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０４ represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０５ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０４ and R ９０５The groups may be bonded to each other to form a divalent group. Examples of substituents on the alkyl and alkenyl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxy groups, aryl groups, and heteroaryl groups. Examples of substituents on the aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxy groups, alkyl groups, and alkenyl groups. １ and h ２ each independently represents an integer of 0 to 3.

[0133] The number of carbon atoms in the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less. The number of carbon atoms in the optionally substituted aryl group and heteroaryl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less.

[0134] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0135] Specific examples of the optionally substituted 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 t-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, and a 3-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.

[0136] Specific examples of the optionally substituted alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, and 1-methyl-3-butenyl. nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group , 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, and the like.

[0137] Specific examples of the optionally substituted aryl group include, but are not limited to, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-nitrophenyl group, a 4-cyanophenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl-4-yl group, a biphenyl-3-yl group, a biphenyl-2-yl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0138] Specific examples of the optionally substituted heteroaryl group include, but are not limited to, a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, a 4-isoxazolyl group, a 5-isoxazolyl group, a 2-thiazolyl group, a 4-thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, a 5-isothiazolyl group, and the like.

[0139] Specific examples of the structural unit represented by formula (C1-1-1) are listed below, but the present invention is not limited to these.

[0140]

[0141] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, a structural unit represented by the following formula (C1-1-2).

[0142]

[0143] In formula (C1-1-2), Ar ９０１ and Ar ９０２ each independently represents an aromatic ring such as a benzene ring or a naphthalene ring, and R ９０１ ~R ９０５ and h １ and h ２ has the same meaning as above.

[0144] Specific examples of the structural unit represented by formula (C1-1-2) are listed below, but the present invention is not limited to these.

[0145]

[0146] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-2), for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2).

[0147]

[0148] In the above formula, R ９０６ ~R ９０９ are substituents bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and specific examples and suitable numbers of carbon atoms of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group, and the optionally substituted aryl group are the same as those described above, and h ３ ~h ６ each independently represents an integer of 0 to 3; R ９０１ ~R ９０３ and h １ and h ２ has the same meaning as above.

[0149] Specific examples of the structural units represented by formulae (C1-2-1) and (C1-2-2) are listed below, but are not limited to these.

[0150]

[0151] Specific examples of the structural unit represented by formula (C1-3) are listed below, but the present invention is not limited to these.

[0152]

[0153] As described above, novolac resins are resins obtained by, for example, condensation reaction of at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst. In this condensation reaction, for example, 0.1 to 10 equivalents of the aldehyde compound or ketone compound are typically used per equivalent of the benzene ring constituting the ring of the carbazole compound.

[0154] In the condensation reaction, an acid catalyst is usually used. Examples of the acid catalyst include, but are not limited to, mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of the acid catalyst cannot be generally specified because it is determined appropriately depending on the type of acid used, etc., but is usually determined appropriately in the range of 0.001 to 10,000 parts by mass per 100 parts by mass of the carbazole compound.

[0155] The condensation reaction can be carried out without a solvent if either the starting compounds or the acid catalyst used are liquid, but is usually carried out using a solvent. Such a solvent is not particularly limited as long as it does not inhibit the reaction, and typical examples include ether compounds such as cyclic ether compounds such as tetrahydrofuran and dioxane.

[0156] The reaction temperature is usually appropriately set within the range of 40° C. to 200° C. The reaction time cannot be generally defined as it varies depending on the reaction temperature, but is usually appropriately set within the range of 30 minutes to 50 hours.

[0157] After the reaction is completed, if necessary, purification and isolation are carried out according to a standard method, and the obtained novolak resin is used for preparing a release agent composition. A person skilled in the art can determine the production conditions of the novolak resin without undue burden based on the above explanation and technical common sense, and therefore can produce the novolak resin.

[0158] The weight-average molecular weight of the organic resin such as a novolac resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in a solvent, mixing well with the branched-chain polysilane when formed into a film, and obtaining a uniform film, the weight-average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 5,000 or less, and still more preferably 3,000 or less. From the viewpoint of improving the strength of the film, the weight-average molecular weight is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, still more preferably 900 or more, and still more preferably 1,000 or more. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of an organic resin such as a polymer novolac resin can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0159] The organic resin contained in the release agent composition is preferably a novolac resin, and therefore, the release agent composition preferably contains only a novolac resin as the organic resin, but may contain other polymers together with the novolac resin for the purpose of adjusting the film properties, etc. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydrides, polyacrylonitrile compounds, etc.

[0160] The content of the novolac resin in the release agent composition is not particularly limited, but is preferably 70% by mass or more based on the total amount of polymers contained in the release agent composition. The content of the novolac resin in the release agent composition is not particularly limited, but is preferably 50 to 100% by mass based on the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0161] -Polynuclear Phenol Derivative- The polynuclear phenol derivative is represented, for example, by the following formula (P).

[0162] In formula (P), Ar represents an arylene group, and the number of carbon atoms therein is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition having excellent uniformity and reproducibly obtaining a release agent layer having higher flatness, the number of carbon atoms therein is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0163] Specific examples of such an arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples of the anthracene-4,4′-diyl group include, but are not limited to, groups derived by removing two hydrogen atoms on the aromatic ring of a fused-ring aromatic hydrocarbon compound, such as anthracene-4,6-diyl, 2,7-anthracene-4,9-diyl, 2,10-anthracene-4,10-diyl, and 9,10-anthracene-4,4′-diyl group, and groups derived by removing two hydrogen atoms on the aromatic ring of a biphenyl-4,4′-diyl group and para-terphenyl-4,4″-diyl group.

[0164] From the viewpoint of providing a release agent layer exhibiting good releasability and reproducibly obtaining a laminate from which the support substrate can be easily separated, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0165]

[0166] The content of the polynuclear phenol derivative in the stripping composition is not particularly limited, but is preferably 50 to 100% by mass based on the film-constituting components.

[0167] -Branched Polysilane- The release agent composition may contain a branched polysilane. The branched polysilane has a Si-Si bond and a branched structure. By including a branched polysilane in the release agent composition, the release agent layer formed from the obtained film cannot be suitably removed by any of organic solvents, acids, and chemical solutions used in the production of semiconductor devices (such as alkaline developers and hydrogen peroxide solutions), but can be suitably removed by the cleaning composition. As a result, by separating the semiconductor substrate and support substrate of the laminate and then cleaning each substrate with the cleaning composition, the residue of the release agent layer on the substrate can be suitably removed. Although the reason for this is not clear, depending on the type of polysilane terminal group (terminal substituent (atom)), the polysilane can react with an organic resin to form crosslinks. Furthermore, since branched-chain polysilanes have more terminal groups (terminal substituent (atom)) than linear polysilanes, branched-chain polysilanes are thought to have more crosslinking points than linear polysilanes. It is speculated that moderate and suitable curing via such more crosslinking points in the branched-chain polysilanes can achieve both the property of being resistant to removal by organic solvents, acids, and chemical solutions used in the production of semiconductor devices (such as alkaline developers and hydrogen peroxide solutions), and the property of being easily removed by cleaning compositions.

[0168] The branched polysilane preferably contains a structural unit represented by formula (B).

[0169]

[0170] In formula (B), R Ｂ represents a hydrogen atom, a hydroxy group, a silyl group, or an organic group, and specific examples of such organic groups include hydrocarbon groups (optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, and optionally substituted aralkyl groups), and ether groups corresponding to these hydrocarbon groups (optionally substituted alkoxy groups, optionally substituted aryloxy groups, and optionally substituted aralkyloxy groups), and the organic group is usually often a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group. Furthermore, a hydrogen atom, a hydroxy group, an alkoxy group, a silyl group, or the like is often substituted at the terminal.

[0171] The optionally substituted alkyl group may be linear, branched, or cyclic. Specific examples of the optionally substituted linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, 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 2 Examples of alkyl groups include, but are not limited to, ethyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3- Examples of cycloalkyl groups include dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0172] The alkenyl group may be linear, branched, or cyclic. Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Specific examples of optionally substituted cyclic alkenyl groups 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.

[0173] Specific examples of the optionally substituted aryl group include, but are not limited to, a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 3,5-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group, and the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0174] Specific examples of the optionally substituted aralkyl group include, but are not limited to, a benzyl group, a phenethyl group, a phenylpropyl group, etc. The optionally substituted aralkyl group is preferably a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0175] The alkyl moiety of the optionally substituted alkoxy group may be linear, branched, or cyclic. Specific examples of the optionally substituted linear or branched alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, and a pentyloxy group, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Specific examples of the optionally substituted cyclic alkoxy group include, but are not limited to, cyclopentyloxy and cyclohexyloxy, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0176] Specific examples of the optionally substituted aryloxy group include, but are not limited to, phenoxy, 1-naphthyloxy, and 2-naphthyloxy, and the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0177] Specific examples of the optionally substituted aralkyloxy group include, but are not limited to, benzyloxy, phenethyloxy, phenylpropyloxy, etc. The optionally substituted aralkyloxy group is preferably a group in which one hydrogen atom of an alkyloxy group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0178] Specific examples of the silyl group include, but are not limited to, a silyl group, a disilanyl group, a trisilanyl group, and the like. The number of silicon atoms is usually 1 to 10, preferably 1 to 6.

[0179] R Ｂ When is the organic group or silyl group, at least one of the hydrogen atoms may be substituted with a substituent, specific examples of which include a hydroxy group, an alkyl group, an aryl group, and an alkoxy group.

[0180] From the viewpoint of preventing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor elements (such as an alkaline developer or hydrogen peroxide solution), and from the viewpoint of suitably removing residues of the release agent layer on the substrate when the semiconductor substrate and the support substrate of the laminate are separated and then washed with the cleaning agent composition, R Ｂ is preferably an alkyl group or an aryl group, more preferably an aryl group, even more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and even more preferably a phenyl group.

[0181] The branched-chain polysilane may contain, in addition to the structural unit represented by formula (B), a structural unit represented by formula (S) below or a structural unit represented by formula (N) below. However, from the viewpoint of suppressing unintended peeling when the laminate is brought into contact with any of an organic solvent, an acid, or a chemical solution used in the production of semiconductor devices (such as an alkaline developer or hydrogen peroxide solution), and from the viewpoint of suitably removing residue of the release agent layer on the substrate when the semiconductor substrate and the support substrate of the laminate are separated and then each substrate is washed with a cleaning composition, the content of the structural unit represented by formula (B) in the branched-chain polysilane is usually 50 mol % or more, preferably 60 mol % or more, more preferably 70 mol % or more, still more preferably 80 mol % or more, even more preferably 90 mol % or more, and still more preferably 95 mol % or more, of all structural units.

[0182] (R Ｓ１ and Ｓ２ is R Ｂ It has the same meaning as

[0183] The terminal group (terminal substituent (atom)) of the branched chain polysilane may usually be a hydrogen atom, a hydroxy group, a halogen atom (such as a chlorine atom), an alkyl group, an aryl group, an alkoxy group, a silyl group, etc. Among these, a hydroxy group, a methyl group, or a phenyl group is often used, and a methyl group is particularly preferred, and the terminal group may also be a trimethylsilyl group.

[0184] In one embodiment, the average degree of polymerization of the branched-chain polysilane, in terms of silicon atoms (i.e., the average number of silicon atoms per molecule), is usually 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30. In one embodiment, the upper limit of the weight-average molecular weight of the branched-chain polysilane is usually 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, even more preferably 2,000, and even more preferably 1,500, and the lower limit is usually 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500. The average degree of polymerization and weight-average molecular weight of the branched polysilane can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K., used in this order), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 1.00 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample. If the degree of polymerization and weight-average molecular weight of the branched-chain polysilane used are too small, the branched-chain polysilane may be vaporized by heating when forming a film that serves as a release agent layer or when processing the resulting laminate comprising the release agent layer, or problems may occur due to poor film strength. On the other hand, if the degree of polymerization and molecular weight of the branched-chain polysilane used are too large, sufficient solubility may not be ensured depending on the type of solvent used in preparing the release agent composition, causing precipitation in the composition, or mixing with the resin may be insufficient, making it difficult to reproducibly obtain a highly uniform film. Therefore, from the viewpoint of more reproducibly obtaining a laminate comprising a release agent layer that contributes to the favorable production of semiconductor elements, it is desirable that the degree of polymerization and weight-average molecular weight of the branched-chain polysilane satisfy the above-mentioned ranges.

[0185] From the viewpoint of reproducibly obtaining a release agent layer having excellent heat resistance, the 5% weight loss temperature of the branched chain polysilane is usually 300° C. or higher, preferably 350° C. or higher, more preferably 365° C. or higher, even more preferably 380° C. or higher, even more preferably 395° C. or higher, and even more preferably 400° C. or higher. The 5% weight loss temperature of the branched chain polysilane can be measured, for example, by using a NETZSCH 2010SR thermometer in air, by increasing the temperature from room temperature (25° C.) to 400° C. at a rate of 10° C. / min.

[0186] When the semiconductor substrate and the support substrate of the laminate are separated and then each substrate is washed with a cleaning composition, from the viewpoint of suitably removing the residue of the release agent layer on the substrate and from the viewpoint of reproducibly preparing a release agent composition with excellent uniformity, the branched-chain polysilane is preferably soluble in any one of ether compounds such as tetrahydrofuran, aromatic compounds such as toluene, glycol ether ester compounds such as propylene glycol monomethyl ether acetate, ketone compounds such as cyclohexanone and methyl ethyl ketone, and glycol ether compounds such as propylene glycol monomethyl ether. In this case, "dissolution" means that when dissolution is attempted using a shaker at room temperature (25°C) to give a 10% by mass solution, dissolution can be visually confirmed within 1 hour.

[0187] The branched chain polysilane may be in either a solid or liquid state at room temperature.

[0188] Branched chain polysilanes can be produced by reference to known methods described in, for example, JP 2011-208054 A, JP 2007-106894 A, JP 2007-145879 A, ​​WO 2005 / 113648 A, etc., or can be obtained as commercially available products. Specific examples of commercially available products include, but are not limited to, silicon materials polysilanes OGSOL SI-20-10 and SI-20-14 manufactured by Osaka Gas Chemicals Co., Ltd.

[0189] Suitable examples of branched polysilanes include, but are not limited to, the following: (Ph represents a phenyl group, R Ｅeach independently represents a terminal substituent, represents an atom or a group, n ｂ indicates the number of repeating units.)

[0190] The content of the branched-chain polysilane in the stripper composition is usually 10 to 90% by mass relative to the film-constituting components. From the viewpoint of reproducibly realizing a film that cannot be suitably removed by organic solvents, acids, or chemical solutions used in the production of semiconductor elements (such as alkaline developers and hydrogen peroxide solutions) but can be suitably removed by the cleaning composition, the content is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.

[0191] Crosslinking Agent The release agent composition may contain a crosslinking agent. The crosslinking agent may undergo a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the novolak resin, the crosslinking agent can undergo a crosslinking reaction with the crosslinkable substituents.

[0192] Specific examples of crosslinking agents are not particularly limited, but typically include phenol-based crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, and thiourea-based crosslinking agents, each of which has a crosslinking group, such as an alkoxymethyl group (e.g., hydroxymethyl group, methoxymethyl group, or butoxymethyl group), in the molecule; these may be low-molecular-weight compounds or high-molecular-weight compounds. The crosslinking agent contained in the release agent composition usually has two or more crosslinking groups, but from the viewpoint of achieving more suitable curing with good reproducibility, the number of crosslinking groups contained in the crosslinking agent compound is preferably 2 to 10, and more preferably 2 to 6. From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule; a typical example of such a crosslinking agent includes, but is not limited to, a phenol-based crosslinking agent.

[0193] A phenolic crosslinking agent having a crosslinking group is a compound having a crosslinking group bonded to an aromatic ring and at least one of a phenolic hydroxy group and an alkoxy group derived from the phenolic hydroxy group. Examples of the alkoxy group derived from the phenolic hydroxy group include, but are not limited to, a methoxy group and a butoxy group. The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxy group and / or the alkoxy group derived from the phenolic hydroxy group are bonded are not limited to non-fused aromatic rings such as a benzene ring, but may also be a fused aromatic ring such as a naphthalene ring or anthracene ring. When multiple aromatic rings are present in the molecule of the phenolic crosslinking agent, the crosslinking group, the phenolic hydroxy group, and the alkoxy group derived from the phenolic hydroxy group may be bonded to the same aromatic ring or to different aromatic rings in the molecule. The aromatic ring to which the crosslinking group, the phenolic hydroxy group, and the alkoxy group derived from the phenolic hydroxy group are bonded may be further substituted with a hydrocarbon group such as an alkyl group (e.g., methyl, ethyl, or butyl), an aryl group (e.g., phenyl), or a halogen atom (e.g., fluorine).

[0194] For example, specific examples of phenol-based crosslinking agents having a crosslinking group include compounds represented by any of formulas (L1) to (L4).

[0195]

[0196] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, each R'' independently represents a hydrogen atom or an alkyl group, and L １ and L ２ each independently represents a single bond, a methylene group, or a propane-2,2-diyl group; L ３is determined depending on q1 and represents a single bond, a methylene group, a propane-2,2-diyl group, a methanetriyl group, or an ethane-1,1,1-triyl group; t11, t12, and t13 are integers that satisfy 2≦t11≦5, 1≦t12≦4, 0≦t13≦3, and t11+t12+t13≦6; t21, t22, and t23 are integers that satisfy 2≦t21≦4, 1≦t22≦3, 0≦t23≦2, and t21+t22+t23≦5; t24, t25, and t26 are integers that satisfy 2≦t24≦4, 1≦t25≦3, 0≦t26≦2, and t24+t25+t26≦5; and t27, t28, and t29 are integers that satisfy 0≦t27≦4, 0≦t28≦ t31, t32, and t33 are integers that satisfy 2≦t31≦4, 1≦t32≦3, 0≦t33≦2, and t31+t32+t33≦5; t41, t42, and t43 are integers that satisfy 2≦t41≦3, 1≦t42≦2, 0≦t43≦1, and t41+t42+t43≦4; q1 is 2 or 3, and q2 represents the number of repetitions and is an integer of 0 or more. Specific examples of the aryl group and alkyl group include the same as those described below, although a phenyl group is preferred as the aryl group, and a methyl group or a t-butyl group is preferred as the alkyl group.

[0197] Specific examples of compounds represented by formulas (L1) to (L4) are listed below, but are not limited to these. These compounds may be synthesized by known methods or are available as products from, for example, Asahi Organic Chemicals Co., Ltd. or Honshu Chemical Industry Co., Ltd.

[0198]

[0199]

[0200]

[0201]

[0202] The melamine-based crosslinking agent having a crosslink-forming group is a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative in which at least one hydrogen atom of an amino group bonded to the triazine ring is substituted with a crosslink-forming group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group. Specific examples of melamine-based crosslinking agents having a crosslinking group include mono-, bis-, tris-, tetrakis-, pentakis- or hexakisalkoxymethylmelamines such as N,N,N',N',N",N"-hexakis(methoxymethyl)melamine and N,N,N',N',N",N"-hexakis(butoxymethyl)melamine; and mono-, bis-, tris- or tetrakisalkoxymethylbenzoguanamines such as N,N,N',N'-tetrakis(methoxymethyl)benzoguanamine and N,N,N',N'-tetrakis(butoxymethyl)benzoguanamine, but are not limited to these.

[0203] A urea-based crosslinking agent having a crosslink-forming group is a derivative of a urea bond-containing compound and has a structure in which at least one hydrogen atom of an NH group constituting a urea bond is substituted with a crosslink-forming group. Specific examples of the urea-based crosslinking agent having a crosslink-forming group include mono-, bis-, tris-, or tetrakisalkoxymethylglycolurils such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril and 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and mono-, bis-, tris-, or tetrakisalkoxymethylureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetrakismethoxymethylurea, but are not limited to these.

[0204] A thiourea-based crosslinking agent having a crosslink-forming group is a derivative of a thiourea bond-containing compound, and has a structure in which at least one hydrogen atom of an NH group constituting a thiourea bond is substituted with a crosslink-forming group. Specific examples of thiourea-based crosslinking agents having a crosslink-forming group include, but are not limited to, mono-, bis-, tris-, or tetrakis-alkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetrakismethoxymethylthiourea.

[0205] The amount of crosslinking agent contained in the release agent composition cannot be generally defined because it differs depending on the coating method used, the desired film thickness, etc., but is usually 0.01 to 50% by mass relative to the organic resin or polynuclear phenol derivative. From the viewpoint of achieving suitable curing and reproducibly obtaining a laminate from which the semiconductor substrate and the support substrate can be easily separated, the amount is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, and is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and still more preferably 30% by mass or less.

[0206] - Acid Generator and Acid - For the purpose of accelerating the crosslinking reaction, the stripping composition may contain an acid generator or an acid.

[0207] Examples of the acid generator include thermal acid generators and photoacid generators. The thermal acid generator is not particularly limited as long as it generates an acid by heat, and specific examples include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0208] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0209] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, but are not limited to these.

[0210] Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited to these.

[0211] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0212] Specific examples of acids include arylsulfonic acids and pyridinium salts such as p-toluenesulfonic acid, pyridinium p-toluenesulfonate (pyridinium paratoluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid, and salts thereof; arylcarboxylic acids and salts thereof such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; linear or cyclic alkylsulfonic acids and salts thereof such as trifluoromethanesulfonic acid and camphorsulfonic acid; and linear or cyclic alkylcarboxylic acids and salts thereof such as citric acid, but are not limited to these.

[0213] The amounts of the acid generator and acid contained in the stripping composition cannot be generally defined because they vary depending on the type of crosslinking agent used, the heating temperature during film formation, and the like, but are usually 0.01 to 5 mass % based on the film-constituting components.

[0214] -Surfactant- The stripping composition may contain a surfactant for the purposes of adjusting the liquid properties of the composition itself and the film properties of the resulting film, preparing a highly uniform stripping composition with good reproducibility, etc. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-30N (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactant may be used alone or in combination of two or more. The amount of the surfactant is usually 2% by mass or less based on the film-constituting components of the stripping composition.

[0215] -Solvent- The stripper composition preferably contains a solvent. Examples of such solvents include highly polar solvents capable of dissolving the aforementioned film-constituting components, such as the organic resin, polynuclear phenol derivative, branched polysilane, and crosslinking agent. If necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, and the like. In the present invention, a low-polarity solvent is defined as one having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as one having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvents may be used singly or in combination of two or more.

[0216] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0217] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

[0218] The content of the solvent is determined appropriately taking into consideration the viscosity of the desired composition, the coating method to be used, the thickness of the film to be produced, and the like, but is 99% by mass or less of the entire composition, and preferably 70 to 99% by mass of the entire composition, i.e., the amount of the film-constituting components in this case is 1 to 30% by mass of the entire composition.

[0219] The viscosity and surface tension of the stripping composition are appropriately adjusted by changing the types of solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0220] In one embodiment of the present invention, the stripper composition contains a glycol-based solvent from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a highly uniform film, etc. Note that the term "glycol-based solvent" used here is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0221] An example of a preferred glycol-based solvent is represented by formula (G).

[0222]

[0223] In formula (G), R Ｇ１ each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms; R Ｇ２ and R Ｇ３ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms; n ｇ is an integer from 1 to 6.

[0224] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 2-methylpropane-1,3-diyl group, a pentamethylene group, a hexamethylene group, etc. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, linear or branched alkylene groups having 2 to 3 carbon atoms are preferred, and linear or branched alkylene groups having 3 carbon atoms are more preferred.

[0225] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms 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 Examples of the alkyl group include, but are not limited to, a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0226] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same as the specific examples described above. Among these, from the viewpoints of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition having high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0227] n ｇ is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1, from the viewpoint of reproducibly obtaining a highly uniform composition, from the viewpoint of reproducibly obtaining a composition with high storage stability, from the viewpoint of reproducibly obtaining a composition that gives a highly uniform film, etc.

[0228] From the viewpoint of reproducibly obtaining a composition having high uniformity, a composition having high storage stability, and a composition that gives a film having high uniformity, it is preferable that R Ｇ２ and R Ｇ３ At least one of R is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R Ｇ２ and R Ｇ３ One of the groups is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkylacyl group in which the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0229] From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more, relative to the solvent contained in the stripper composition. From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the film constituent components in the stripper composition are uniformly dispersed or dissolved, preferably dissolved, in the solvent.

[0230] The release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative, a solvent, and, if necessary, a crosslinker. The order of mixing is not particularly limited, and examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinker are dissolved in a solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinker are dissolved in a solvent and the remainder is separately dissolved in a solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the release agent composition or after mixing all the components.

[0231] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, in one embodiment 10 nm to 10 μm, in another embodiment 50 nm to 1 μm, and in still another embodiment 100 nm to 700 nm.

[0232] An example of the configuration of a laminate will be described below with reference to the drawings. FIG. 1 shows a schematic cross-sectional view of an example of a laminate. The laminate of FIG. 1 has a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4, in this order. The adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The release agent layer 3 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0233] <<Method of Manufacturing Laminate>> A method of manufacturing a laminate will be described below using the laminate shown in Figure 1 as an example. An example of the laminate of the present invention can be manufactured by a method including the following first to third steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. Second step: A step of applying a release agent composition onto a support substrate to form a release agent layer. Third step: A step of heating the adhesive coating layer while the adhesive coating layer and the release agent layer are in contact with each other to form an adhesive layer.

[0234] The method for applying the adhesive composition is not particularly limited, but is typically spin coating. Alternatively, a method can be employed in which a coating film is formed separately by spin coating or the like, a sheet-like coating film is formed, and the sheet-like coating film is then applied as an adhesive coating layer. The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and other factors. However, it is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is typically heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is typically about 5 to 500 μm, and is appropriately determined so as to ultimately achieve the above-mentioned range of adhesive layer thickness.

[0235] The method for applying the release agent composition is not particularly limited, but is usually spin coating. The heating temperature of the applied release agent composition cannot be generally specified because it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., but from the viewpoint of achieving a suitable release agent layer with good reproducibility, it is 80°C or higher and 300°C or lower, and the heating time is usually appropriately determined within the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds or higher and 8 minutes or lower, more preferably 1 minute or higher and 5 minutes or lower. Heating can be performed using a hot plate, oven, etc.

[0236] In the present invention, the laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment. The treatment conditions to be adopted, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition, the film thickness, and the desired adhesive strength.

[0237] The heat treatment temperature is determined appropriately from the viewpoint of removing the solvent from the composition, etc., usually within the range of 20 to 160° C. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive components, the heat treatment temperature is preferably 150° C. or lower, more preferably 130° C. or lower, and the heating time is determined appropriately depending on the heating temperature and the type of adhesive, but is usually 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, and is usually 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0238] The reduced pressure treatment can be carried out by exposing the adhesive coated layers in contact with each other to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0239] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 50,000 N.

[0240] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or longer, preferably 5 minutes or longer, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, or the like. When post-heating is performed using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be heated facing down, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating with the semiconductor substrate facing down is preferred. Note that one purpose of the post-heating treatment is to achieve an adhesive layer that is a more suitable free-standing film, and in particular to achieve suitable curing by a hydrosilylation reaction.

[0241] An example of a method for producing the laminate of FIG. 1 will be described below with reference to FIGS. 2A to 2C. FIGS. 2A to 2C are diagrams illustrating one embodiment of producing a laminate. First, a laminate structure is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 ( FIG. 2A ). This laminate structure can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating the resulting laminate. Separately, a laminate structure is prepared in which a release agent layer 3 is formed on a support substrate 4 ( FIG. 2B ). This laminate structure can be obtained, for example, by applying a release agent composition to the support substrate 4 and heating the resulting laminate. Next, the laminate structure shown in FIG. 2A and the laminate structure shown in FIG. 2B are bonded together so that the adhesive coating layer 2a and the release agent layer 3 are in contact with each other. Then, a load is applied to the semiconductor substrate 1 and the support substrate 4 in the thickness direction under reduced pressure. After that, a heating device (not shown; hot plate) is placed on the surface of the semiconductor substrate 1 opposite the surface where the adhesive coating layer 2a is in contact. The adhesive coating layer 2a is heated and cured by the heating device, converting it into the adhesive layer 2 ( FIG. 2C ). A laminate is obtained by the steps shown in FIGS. 2A to 2C.

[0242] Here, we introduce modifications of the laminate prepared in FIG. 2B , in which a release agent layer 3 is formed on a support substrate 4. FIGS. 3 to 5 are perspective views of examples of laminate structures of a release agent layer and a support substrate. In the laminate structure shown in FIG. 3 , the release agent layer 3 is formed over almost the entire surface of the support substrate 4. When a laminate is formed using this laminate structure, the area of ​​the release agent layer 3 is approximately the same as the area of ​​the adhesive layer 2, and almost the entire surface of the release agent layer 3 contacts almost the entire surface of the adhesive layer 2. In the laminate structure shown in FIG. 4 , the release agent layer 3 is formed only on the periphery of the support substrate 4. When a laminate is formed using this laminate structure, the area of ​​the release agent layer 3 is smaller than the area of ​​the adhesive layer 2. In the laminate structure shown in FIG. 5 , the release agent layer 3 is formed on a portion of the periphery (edge) of the support substrate 4. When a laminate is formed using this laminate structure, the area of ​​the release agent layer 3 is much smaller than the area of ​​the adhesive layer 2. Even with the release agent layer 3 as shown in FIGS. 4 and 5 , the adhesive strength of the release agent layer at the point irradiated with the ultraviolet laser is reduced compared to before irradiation. Therefore, even without irradiating the entire surface of the release agent layer with an ultraviolet laser to reduce the adhesive strength of the entire surface of the release agent layer, the semiconductor substrate and the support substrate can be separated from each other starting from the point irradiated with the ultraviolet laser without applying an excessive load.

[0243] <Processing Step> The processing performed on the semiconductor substrate in the processing step is, for example, processing of the side opposite the circuit surface of the semiconductor substrate, such as thinning the semiconductor substrate by polishing the back surface of the semiconductor substrate. Thereafter, for example, through-silicon vias (TSVs) are formed, and then the thinned semiconductor substrate is peeled off from the support substrate to form a semiconductor substrate stack, which is then three-dimensionally mounted. Also, for example, before or after this, the formation of a semiconductor substrate backside electrode, etc., is also performed. During the thinning and TSV process of the semiconductor substrate, a heat load of approximately 250 to 350°C is applied while the substrate is adhered to the support substrate. The laminate of the present invention, including the adhesive layer, typically has heat resistance to this load. Note that the processing is not limited to the above-described processing, and also includes, for example, the implementation of a semiconductor component mounting process when the substrate is temporarily adhered to a support substrate to support the substrate for mounting the semiconductor component.

[0244] <Irradiation Step> The irradiation step is a step in which the release agent layer is irradiated with an ultraviolet laser after the processing step.

[0245] The wavelength of the ultraviolet laser is preferably, for example, 250 to 370 nm, and more preferably 308 nm, 343 nm, 355 nm, or 365 nm.

[0246] The irradiation dose of the ultraviolet laser is not particularly limited as long as it is the irradiation dose necessary for peeling, and may be, for example, 50 to 3,000 mJ / cm ２ The irradiation time is appropriately determined depending on the wavelength and the irradiation amount.

[0247] The irradiation area in the irradiation step is smaller than the area of ​​the adhesive layer. Here, the irradiation area and the area of ​​the adhesive layer are areas when viewed from the thickness direction of the laminate. The ratio (S1 / S2) of the irradiation area (S1) to the area of ​​the adhesive layer (S2) is not particularly limited as long as it is less than 1, but is preferably 0.5 or less, more preferably 0.1 or less. The lower limit of the ratio (S1 / S2) is not particularly limited, and for example, the ratio (S1 / S2) may be 0.01 or more, or may be 0.05 or more.

[0248] In the irradiation step, the release agent layer may be irradiated with the ultraviolet laser light only partially or entirely, but it is preferable to irradiate only partially in terms of shortening the time required for the irradiation step.

[0249] In the irradiation step, the release agent layer is irradiated with an ultraviolet laser, basically at the portion of the release agent layer that is in contact with the adhesive layer.

[0250] The irradiation of the release agent layer with an ultraviolet laser in the irradiation step may be performed on the surface (main surface) of the release agent layer, or on the side surface of the release agent layer, or a combination thereof. The irradiation of the release agent layer with an ultraviolet laser in the irradiation step may be performed from the surface (main surface) side of the release agent layer to the surface, or from the side surface side of the release agent layer to the side surface, or a combination thereof.

[0251] In the irradiation step, the release agent layer is preferably irradiated with an ultraviolet laser on the periphery of the semiconductor substrate when viewed from the thickness direction. In this case, the ultraviolet laser irradiation on the periphery of the semiconductor substrate may be performed on the entire periphery (whole circumference) or on a part of the periphery. By irradiating the release agent layer with an ultraviolet laser on the periphery of the semiconductor substrate instead of the entire surface of the semiconductor substrate when viewed from the thickness direction, the time required for the irradiation step can be further shortened. The irradiation location may be one location or two or more locations, but one location is preferred.

[0252] The irradiated area in the irradiation step is preferably smaller than the area of ​​the release agent layer. Here, the area of ​​the release agent layer refers to the area when viewed from the thickness direction (top) of the laminate. The ratio (S1 / S3) of the irradiated area (S1) to the area (S3) of the release agent layer is not particularly limited, but is preferably 0.5 or less, more preferably 0.1 or less. The lower limit of the ratio (S1 / S3) is not particularly limited, and for example, the ratio (S1 / S3) may be 0.01 or more, or 0.05 or more. The range of the above (S1 / S3) is, for example, 0.01 to 0.5, 0.01 to 0.2, 0.01 to 0.1, 0.02 to 0.1, 0.03 to 0.2, or 0.05 to 0.2.

[0253] When the ultraviolet laser irradiation of the release agent layer in the irradiation step is performed on the outer periphery of the release agent layer, the ratio (L1 / L3) of the irradiation length (L1) to the outer periphery length (L3) of the release agent layer is not particularly limited, but is preferably 0.5 or less, more preferably 0.1 or less. The lower limit of the ratio (L1 / L3) is not particularly limited, and for example, the ratio (L1 / L3) may be 0.01 or more, or 0.05 or more. The range of the above (L1 / L3) is, for example, 0.01 to 0.5, 0.01 to 0.2, 0.01 to 0.1, 0.02 to 0.1, 0.03 to 0.2, or 0.05 to 0.2.

[0254] In the irradiation step, when the ultraviolet laser is irradiated onto the release agent layer from the side of the release agent layer, for example, if (L1 / L3) is 0.5, half of the entire outer periphery of the release agent layer is irradiated (if the release agent layer is a perfect circle, the length is diameter × π (pi) / 2). If (L1 / L3) is 0.1, 10% of the entire outer periphery of the release agent layer is irradiated (if the release agent layer is a perfect circle, the length is diameter × π (pi) / 10).

[0255] When the semiconductor substrate has electrodes on its surface, it is preferable that the release agent layer is not irradiated with the ultraviolet laser in the irradiation step at locations where the electrodes of the semiconductor substrate are located in the thickness direction, thereby preventing damage to the electrodes by the ultraviolet laser.

[0256] The irradiation location may be the center or edge of the release agent layer in the surface direction. The number of irradiation locations may be one or more. When irradiating the release agent layer with an ultraviolet laser from above, the shape of the ultraviolet laser irradiation area may be approximately circular, approximately semicircular, approximately circular outer periphery (approximately annular), approximately rectangular, approximately square, approximately triangular, circle, semicircle, circular outer periphery (annular), rectangular, square, or triangular, and may be the entire shape or a portion thereof. In the case of an approximately circular outer periphery or a circular outer periphery, it is preferable to irradiate the edge of the release agent layer from the side or from above. In this case, the width of the laser irradiation area is preferably in the range of 1 to 5 mm, or a constant width within the above range. The shape of the ultraviolet laser irradiation area may be a combination of these shapes. When the semiconductor substrate has a circular or approximately circular shape, the shape of the ultraviolet laser irradiation area may be one of the parts separated by a chord. In this case, the irradiation area may be the one with the longer arc or the one with the shorter arc of the two parts separated by the chord. The arc may also be an arc that bisects a circle or a substantially circle.

[0257] An example of an ultraviolet laser irradiation region will be described using the drawings. FIGS. 6A to 6D are schematic top views showing an example of the relationship between the ultraviolet laser irradiation region R and the release agent layer 3. In FIGS. 6A to 6D, the outline of the release agent layer 3 that overlaps with the ultraviolet laser irradiation region R is indicated by a dashed line. In FIG. 6A, the ultraviolet laser irradiation region R is rectangular, and this rectangular irradiation region R overlaps with a portion of the circular release agent layer 3. In FIG. 6B, the ultraviolet laser irradiation region R is annular, and this annular irradiation region R overlaps with the entire outer periphery of the circular release agent layer 3. In FIG. 6C, the ultraviolet laser irradiation region R is arc-shaped, and this arc-shaped irradiation region R overlaps with a portion of the outer periphery of the circular release agent layer 3. In FIG. 6D, the ultraviolet laser irradiation region R is polygonal, formed by two rectangles overlapping at their ends, and this polygonal irradiation region R overlaps with approximately half of the outer periphery of the circular release agent layer 3.

[0258] <Separation Process> In the separation process, the method for separating (peeling) the semiconductor substrate and the support substrate is not particularly limited. In the separation process, the location irradiated with the ultraviolet laser serves as the starting point for separation, and the semiconductor substrate and the support substrate are separated. Examples of methods for separating the semiconductor substrate and the support substrate in the separation process include a method in which the semiconductor substrate and the support substrate are each held by a holder, and one or both of the holders are moved in a direction that separates the semiconductor substrate and the support substrate. In this case, since the adhesive strength at the location irradiated with the ultraviolet laser is reduced, for example, separation of the semiconductor substrate and the support substrate begins from the location irradiated with the ultraviolet laser. Examples of the holder include an adsorption plate.

[0259] <Cleaning Step> In the cleaning step, the substrate can be cleaned by spraying a cleaning composition onto the surface of at least one of the separated semiconductor substrate and the support substrate, or by immersing the separated semiconductor substrate or the support substrate in the cleaning composition. Alternatively, the surface of the processed semiconductor substrate or the like may be cleaned using a removal tape or the like. Examples of cleaning compositions used for cleaning include the following.

[0260] The cleaning agent composition usually contains a solvent. Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of the lactones include γ-butyrolactone. Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond, such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. These can be used alone or in combination of two or more.Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0261] Also preferred are mixed solvents containing PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into account the compatibility of the PGMEA and the polar solvent, but is preferably within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2. For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are blended as the polar solvents, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0262] The cleaning composition may or may not contain a salt; however, the absence of a salt is preferred in terms of increasing versatility in processing semiconductor substrates using the laminate and reducing costs.

[0263] An example of a detergent composition containing a salt is a detergent 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, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF４ － ) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0264] 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.

[0265] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is 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 includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0266] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition, but is usually 0.1 to 30 mass% based on the cleaning composition.

[0267] When the cleaning composition contains a salt, the solvent to be used in combination with the salt is not particularly limited as long as it is used for this type of application and dissolves the salt such as a quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving the salt such as a quaternary ammonium salt to obtain a cleaning composition having excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0268] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

[0269] In the formula, R ０ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. Ａ and R Ｂ each 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, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0270] 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. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0271] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0272] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0273] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １０２ represents an alkylene group having 1 to 6 carbon atoms. 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.

[0274] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0275] In a preferred embodiment, 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).

[0276] The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, 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 usually 5 mass% or less.

[0277] The constituent elements and methodological elements of the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways without departing from the spirit and scope of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may include steps other than those described above.

[0278] In one example of the peeling method of the present invention, when the semiconductor substrate or support substrate of the laminate of the present invention is optically transparent, the semiconductor substrate and support substrate of the laminate are separated by irradiating the release agent layer with light from the semiconductor substrate side or the support substrate side. In one example of the laminate of the present invention, the semiconductor substrate and support substrate are suitably and releasably temporarily bonded by the adhesive layer and the release agent layer. Therefore, for example, when the support substrate is optically transparent, the semiconductor substrate and support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Usually, peeling is performed after processing the semiconductor substrate of the laminate.

[0279] An example of a method for manufacturing a processed semiconductor substrate is described with reference to FIGS. 7A to 7E. This example is an example of manufacturing a thinned semiconductor substrate. First, a laminate is prepared ( FIG. 7A ). This laminate is the same as the laminate shown in FIGS. 1 and 2C . Next, a polishing device (not shown) is used to polish the surface of the semiconductor substrate 1 opposite the surface in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1 ( FIG. 7B ). The thinned semiconductor substrate 1 may also be subjected to the formation of through-hole electrodes. Next, an ultraviolet laser L is irradiated onto the release agent layer 3 from the support substrate 4 side ( FIG. 7C ). The irradiation area of ​​the ultraviolet laser L is smaller than the area of ​​the adhesive layer, and the ultraviolet laser L is irradiated only onto the release agent layer 3 located on the outer periphery (edge) of the semiconductor substrate 1. Next, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4, starting from the portion of the release agent layer 3 irradiated with the ultraviolet laser L ( FIG. 7D ). This results in a thinned semiconductor substrate 1. Here, residues of the adhesive layer 2 and the release agent layer 3 may remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 with a cleaning agent composition to remove the residues of the adhesive layer 2 and the release agent layer 3 from the semiconductor substrate 1 ( FIG. 7E ).

[0280] 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.

[0281] [Apparatus] (1) Mixer: ARE-500, a planetary centrifugal mixer manufactured by Thinky Corporation (2) Viscometer: TVE-22H, a rotational viscometer manufactured by Toki Sangyo Co., Ltd. (3) Vacuum bonding device: Autobonder manufactured by SUSS Microtec Co., Ltd. (4) Film thickness measurement: DEKTAK XT-A manufactured by BRUKER (5) Laser irradiation device: IPEX-848 manufactured by Light Machinery Co., Ltd.

[0282] [Conditions for Measuring Molecular Weight] The weight average molecular weight of the resin was measured using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel Super-Multipore HZ-N (two columns)), with a column temperature of 40°C, THF (tetrahydrofuran) as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0283] [1] Preparation of adhesive composition [Preparation Example 1] In a 600 mL stirring vessel dedicated to Stirrer A, 104.14 g of a p-menthane solution (concentration 80.6% by mass) of MQ resin (manufactured by Wacker Chemie) having a polysiloxane skeleton and a vinyl group, 58.11 g of a polyorganosiloxane represented by the following formula (M1) (complex viscosity 800 Pa s, weight average molecular weight 171,899 (dispersity 2.18), manufactured by Wacker Chemie), 34.94 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent, and 6.20 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added, and the mixture was stirred for 5 minutes with Stirrer A to obtain a mixture (I). To the resulting mixture (I), 16.79 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Co.) having a viscosity of 100 mPa·s and 24.54 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Co.) having a viscosity of 200 mPa·s and represented by the following formula (V) were added to obtain mixture (II). 1.61 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.61 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemical Co.), and 3.23 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent were stirred with Stirrer A for 60 minutes to obtain mixture (III). 1.29 g of the resulting mixture (III) was added to mixture (II), and the mixture was stirred with Stirrer A for 5 minutes to obtain mixture (IV). 0.65 g of a platinum catalyst (manufactured by Wacker Chemie) and 19.37 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa·s and represented by the following formula (W) were stirred for 5 minutes with Stirrer A to obtain Mixture (V). 4.00 g of the obtained Mixture (V) was added to Mixture (IV), and the mixture was stirred for 5 minutes with Stirrer A to obtain Mixture (VI). Finally, the obtained Mixture (VI) was filtered through a 300-mesh nylon filter to obtain Adhesive Composition 1. The viscosity of the obtained Adhesive Composition 1 was 3000 mPa·s.

[0284] The structural formulas of the above components are shown below. n ４ indicates the number of repeating units and is a positive integer. n represents the number of repeating units and is a positive integer. n and m each represent the number of repeating units and are positive integers.

[0285] [2] Preparation of Stripping Agent Composition [Preparation Example 2] 56.02 g of N-phenyl-1-naphthylamine, 50.00 g of 1-pyrenecarboxaldehyde, 6.67 g of 4-(trifluoromethyl)benzaldehyde, and 2.46 g of methanesulfonic acid were placed in a flask, and 86.36 g of 1,4-dioxane and 86.36 g of toluene were added thereto, followed by reflux and stirring under a nitrogen atmosphere for 18 hours. The resulting reaction mixture was allowed to cool, and then diluted with 96 g of tetrahydrofuran. The resulting diluted solution was added dropwise to methanol to obtain a precipitate. The resulting precipitate was collected by filtration, washed with methanol, and dried at 60°C under reduced pressure to obtain 72.12 g of a reaction product. The resulting reaction product corresponded to the following formula, and as measured by the method described above, its weight average molecular weight was 1,100.

[0286] 60 g of the resulting reaction product was dissolved in 849 g of propylene glycol monomethyl ether acetate, and the solution was filtered through a polyethylene microfilter having a pore size of 0.2 μm to prepare a release agent composition.

[0287] [3] Production of Laminate [Preparation Example 3] The release agent composition obtained in Preparation Example 2 was spin-coated onto a 300 mm glass wafer (EAGLE-SG, manufactured by Corning Incorporated, thickness 700 μm) as the carrier-side substrate so that the film thickness in the final laminate would be 200 nm, and the resulting laminate was baked at 230°C for 5 minutes to form a release agent coating layer on the glass wafer. Meanwhile, the adhesive composition 1 obtained in Preparation Example 1 was spin-coated onto a 300 mm silicon wafer (thickness 775 μm) as the device-side substrate so that the film thickness in the final laminate would be 65 μm. Next, 7 mm of the adhesive from the edge was removed using p-menthane, forming an adhesive coating layer on the silicon wafer, which was the semiconductor substrate. Then, using a bonding device, the glass wafer and the silicon wafer were bonded together so that the release agent coating layer and the adhesive coating layer were sandwiched between them, and then post-heat treatment was performed at 200°C for 10 minutes to produce a laminate. The lamination was carried out at a temperature of 23° C., a reduced pressure of 1,000 Pa, and a load of 30 N.

[0288] [4] Confirmation of Peelability [Example 1] Using a laser irradiation device, a laser having a wavelength of 308 nm was irradiated from the glass wafer side of the fixed laminate (the laminate produced in Preparation Example 3) at an intensity of 200 mJ / cm. ２ The release agent layer was irradiated with an irradiation dose of 144 mm. The support substrate was then manually lifted to check whether peeling was possible. A mark "Good" was given if peeling was possible without damaging the silicon wafer, and a mark "Poor" was given if peeling was not possible. The peeling results are shown in Table 1. The irradiation was performed on an area surrounded by an arc of the glass wafer (part of the circumference, 144 mm long) and a straight line connecting one end of the arc to the other end. The distance from the midpoint of the 144 mm long arc to the straight line (distance from the edge) was 17 mm.

[0289] Comparative Example 1 Except for not irradiating with an ultraviolet laser, the peelability was confirmed in the same manner as in Example 1. The results are shown in Table 1.

[0290]

[0291] REFERENCE SIGNS LIST 1 semiconductor substrate 2 adhesive layer 2a adhesive coating layer 3 release agent layer 4 support substrate L ultraviolet laser

Claims

1. A method for producing a processed semiconductor substrate, comprising: a step of preparing a laminate having a semiconductor substrate, a support substrate, an adhesive layer provided between the semiconductor substrate and the support substrate, and a release agent layer provided between the semiconductor substrate and the support substrate; a processing step in which the semiconductor substrate in the laminate is processed; an irradiation step in which, after the processing step, an ultraviolet laser is irradiated onto the release agent layer; and a separation step in which, after the irradiation step, the processed semiconductor substrate and the support substrate are separated; wherein the adhesive layer is formed from an adhesive composition containing an adhesive component, and the irradiated area in the irradiation step is smaller than the area of ​​the adhesive layer.

2. The method for producing a processed semiconductor substrate according to claim 1, wherein the ratio (S1 / S3) of the irradiated area (S1) to the area (S3) of the release agent layer is 0.01 or more and 0.5 or less.

3. The method for producing a processed semiconductor substrate according to claim 1, wherein the ultraviolet laser irradiation onto the release agent layer in the irradiation step is irradiation onto a part of the release agent layer.

4. The method for producing a processed semiconductor substrate according to claim 1, wherein the area of ​​the release agent layer in the laminate is smaller than the area of ​​the adhesive layer.

5. The method for producing a processed semiconductor substrate according to claim 1, wherein the area of ​​the release agent layer is 1% to 90% of the area of ​​the adhesive layer.

6. The method for producing a processed semiconductor substrate according to claim 4, wherein the release agent layer is disposed in the laminate so as to contact the adhesive layer in at least a portion of the outer peripheral region of the adhesive layer.

7. The method for producing a processed semiconductor substrate according to claim 1, wherein the semiconductor substrate has an electrode on its surface, and the ultraviolet laser irradiation to the release agent layer in the irradiation step is not performed at a location of the semiconductor substrate where the electrode is located in the thickness direction.

8. The method of producing a processed semiconductor substrate according to claim 1, wherein the adhesive composition contains a release agent component.

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