Laminate, release agent composition, and method for manufacturing a processed semiconductor substrate

Abstract

Provided is a laminate characterized by comprising a semiconductor substrate, a support substrate that transmits ultraviolet rays, and an adhesive layer and a release layer that are provided between the semiconductor substrate and the support substrate, the laminate moreover being characterized in that the release layer is a film obtained from a release agent composition containing a photoacid generator, a solvent, and a polymer of ethylenic unsaturated monomers including tertiary butoxycarbonyl groups.

Description

[Technical Field]

[0001] The present invention relates to a laminate, a release agent composition, and a method for manufacturing a processed semiconductor substrate. [Background technology]

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional planar direction. To achieve even greater integration, there is a need for semiconductor integration technology that integrates (stacks) in a three-dimensional direction as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting them with through silicon vias (TSVs). When integrating multiple layers, the side opposite to the circuit surface (i.e., the back surface) of each wafer to be integrated is thinned by polishing, and the thinned semiconductor wafers are stacked.

[0003] Before thinning, the semiconductor wafer (also simply called a wafer here) is bonded to a support in order to be polished using a polishing device. This bonding is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying too much force during removal can cause the thinned semiconductor wafer to cut or deform. To prevent this, it must be easily removed. However, it is undesirable for the temporary bonding to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the performance required of temporary bonding is to withstand the stress during polishing and to be easily removed after polishing. Under these circumstances, the material needs to exhibit high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the longitudinal direction during removal. In this regard, various technologies using light irradiation for adhesion and separation processes have been reported (see, for example, Patent Documents 1 and 2), but with the recent advancements in the semiconductor field, new technologies related to delamination by light irradiation such as ultraviolet irradiation are always in demand. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2004-64040 [Patent Document 2] Japanese Patent Publication No. 2012-106486 [Patent Document 3] Japanese Patent Publication No. 2004-43732 [Patent Document 4] International Gazette No. 2016 / 121855 [Non-patent literature]

[0005] [Non-Patent Document 1] Proceedings of the 56th Annual Meeting of the College of Science and Technology, Nihon University, FY2012 (N-28) Photopolymerization Reaction of t-butyl Acrylate [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention has been made in view of the above circumstances, and aims to provide a laminate that has excellent heat resistance during bonding of a semiconductor substrate and a support substrate, processing of the back surface of a semiconductor substrate, and component mounting, and that has a release layer that can be easily peeled off by irradiation with ultraviolet light followed by heating; a release agent composition that provides a film suitable as such a release layer; and a method for manufacturing a processed semiconductor substrate using such a laminate. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by using a film obtained from a release agent composition containing a polymer of an ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent as the release layer of a laminate comprising a semiconductor substrate, a support substrate that transmits ultraviolet light, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, and have completed the present invention. While Patent Document 3 discloses a predetermined composition containing a foaming component having a t-butyloxycarbonyl structure, Patent Document 4 discloses a predetermined composition containing a polymer of an ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group and a urethane (meth)acrylate compound, and Non-Patent Document 1 discloses a resin containing a tert-leaved toxiccarbonyl group that decomposes under acidic conditions to generate gas, none of these documents specifically disclose the laminate of the present invention, the release agent composition used for a predetermined application of the present invention, or the method for manufacturing the processed semiconductor substrate of the present invention.

[0008] In other words, the present invention is 1. Semiconductor substrate and, A support substrate that transmits ultraviolet light, The semiconductor substrate and the support substrate are provided with an adhesive layer and a release layer, The laminate is characterized in that the above-mentioned release layer is a film obtained from a release agent composition comprising a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent. 2. A laminate comprising at least one ethylenically unsaturated monomer containing the above tert-leaf toxic carbonyl group, selected from the group consisting of formulas (T1) to (T3), [ka] (Each R1 independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.) Each R2 and each R3 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group with 1 to 12 carbon atoms, an arylene group with 6 to 16 carbon atoms, or a heteroarylene group with 3 to 12 carbon atoms. Each X independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. n represents the number of substituents X on the benzene ring, and is an integer between 0 and 4. 3. The above ethylenically unsaturated monomer containing a tert-butyl carbonyl group is a laminate containing tert-butyl (meth)acrylate. 4. The laminate is one of 1 to 3, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) which includes at least one selected from polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives. 5. The above adhesive component (S) is a laminate of 4 containing a polysiloxane-based adhesive. 6. The above polysiloxane-based adhesive is a laminate of 5 containing a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction. 7. A release agent composition for forming the release layer of a laminate comprising a semiconductor substrate, an ultraviolet-transmitting support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, A stripping agent composition comprising a polymer of an ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent. 8. Seven stripping agent compositions comprising at least one ethylenically unsaturated monomer containing the above-mentioned tert-leaf-toxic-carbonyl group, selected from the group consisting of formulas (T1) to (T3). [ka] (Each R1 independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.) Each R2 and each R3 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group with 1 to 12 carbon atoms, an arylene group with 6 to 16 carbon atoms, or a heteroarylene group with 3 to 12 carbon atoms. Each X independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. n represents the number of substituents X on the benzene ring, and is an integer between 0 and 4. 9. The above ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group is part of the stripping agent composition 7 containing tert-leaved butyl (meth)acrylate. 10. The above adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) which includes at least one selected from polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives, one of the release agent compositions from 7 to 9. 11. The above adhesive component (S) comprises 10 release agent compositions including a polysiloxane-based adhesive. 12. Eleven release agent compositions comprising a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction, the above polysiloxane-based adhesive 13. A method for manufacturing a processed semiconductor substrate, A first step of processing a semiconductor substrate in a laminate comprising a semiconductor substrate, an ultraviolet-transmitting 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 containing a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent, Following the first step described above, a second step is performed in which ultraviolet light is irradiated onto the release layer from the support substrate side. After the second step described above, a third step is taken to heat the peeling layer. A method for manufacturing a processed semiconductor substrate, including 14. Thirteen methods for manufacturing a processed semiconductor substrate, wherein the ethylenically unsaturated monomer containing the above-mentioned tert-leaf toxic carbonyl group is selected from the group consisting of formulas (T1) to (T3). [ka] (Each R1 independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.) Each R2 and each R3 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group with 1 to 12 carbon atoms, an arylene group with 6 to 16 carbon atoms, or a heteroarylene group with 3 to 12 carbon atoms. Each X independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. n represents the number of substituents X on the benzene ring, and is an integer between 0 and 4. 15. A method for manufacturing a processed semiconductor substrate containing the above-mentioned ethylenically unsaturated monomer containing a tert-butyl(meth)acrylate, 16. A method for manufacturing a processed semiconductor substrate according to any of 13 to 15, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) which includes at least one selected from polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives. 17. The above adhesive component (S) comprises a polysiloxane-based adhesive, 16 methods for manufacturing a processed semiconductor substrate. 18. A method for manufacturing a processed semiconductor substrate comprising the above polysiloxane-based adhesive containing a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction. To provide. [Effects of the Invention]

[0009] The laminate of the present invention comprises a semiconductor substrate, a support substrate that transmits ultraviolet light, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate. The release layer is a film obtained from a release agent composition comprising a polymer of an ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent. By irradiating the release layer with ultraviolet light from the support substrate side and heating the irradiated release layer, a suitable elimination reaction from the tert-leaved toxiccarbonyl group occurs in the release layer, thereby exhibiting good release ability. The reason why such good release ability can be achieved is thought to be that the heat treatment after irradiation with ultraviolet light appropriately separates or decomposes the release layer at the interface between the release layer and other layers such as the adhesive layer in contact with it, at the interface between the release layer and the support substrate or semiconductor substrate, or within the release layer itself. By using the laminate of the present invention having these characteristics, for example, when separating a silicon wafer, which is a semiconductor substrate, from a glass substrate, which is a support substrate, after processing the back surface of the silicon wafer, which is a semiconductor substrate, ultraviolet light can be irradiated from the support substrate side and then heat treatment can be performed to easily separate the processed silicon wafer, thereby avoiding mechanical stress on the silicon wafer and, as a result, avoiding damage such as warping and deformation of the silicon wafer. Furthermore, the release layer of the laminate of the present invention does not generate significant gases or generate large amounts of heat that would adversely affect the release ability when the release layer is exerted, and therefore the impact on the semiconductor substrate is greatly reduced. Accordingly, by using the laminate of the present invention, it is possible to expect the manufacture of more reliable semiconductor devices.

[0010] The release agent composition of the present invention contains a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, along with a photoacid generator. When a film obtained from this composition is irradiated with ultraviolet light and then subjected to heat treatment, the elimination reaction from the tert-leaved toxiccarbonyl group proceeds appropriately in the film, resulting in improved release properties. Therefore, by providing a film obtained from the release agent composition of the present invention as a release layer, together with an adhesive layer, between a semiconductor substrate and a support substrate, a laminate that can be easily separated by irradiation of the release layer with ultraviolet light and subsequent heat treatment can be obtained without applying excessive load for release to the workpiece, such as the support substrate or semiconductor substrate. [Modes for carrying out the invention]

[0011] The laminate of the present invention comprises a semiconductor substrate, a support substrate that transmits ultraviolet light, 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 comprising a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent.

[0012] A semiconductor substrate is, for example, a wafer, and a specific example of such a wafer is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm, but it is not limited to this.

[0013] The support substrate is a support (carrier) bonded to a semiconductor substrate, and is not particularly limited as long as it transmits ultraviolet light.

[0014] In this invention, ultraviolet light refers to light with a wavelength in the range of 100 nm to 400 nm, and for example, preferred wavelengths are 308 nm, 343 nm, 355 nm, or 365 nm. The light used for stripping may include light other than ultraviolet light, such as visible light.

[0015] The transmittance of the support substrate that transmits ultraviolet light is usually 50% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and still more preferably 90% or more.

[0016] A specific example of a support substrate that transmits ultraviolet light is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm, but it is not limited to this.

[0017] In a preferred embodiment, the laminate of the present invention comprises a semiconductor substrate, an ultraviolet light-transmitting support substrate, an adhesive layer provided between the semiconductor substrate and the support substrate in contact with the semiconductor substrate, and a release layer provided in contact with the support substrate and the adhesive layer, or a release layer provided in contact with the semiconductor substrate and an adhesive layer provided in contact with the support substrate and the release layer. That is, a laminate comprising a semiconductor substrate and a support substrate, and two layers between these substrates, wherein one of the two layers is an adhesive layer and the other is a release layer, is preferred.

[0018] The laminate of the present invention can be separated from the semiconductor substrate and the support substrate by irradiating the release layer with ultraviolet light from the support substrate side which transmits ultraviolet light, and then applying a heat treatment, without applying an excessive load for release. As a result, the semiconductor substrate and the support substrate can be separated. In other words, the release layer of the laminate of the present invention has improved release ability upon irradiation with ultraviolet light and subsequent heat treatment compared to before irradiation and heating. In the laminate of the present invention, for example, a silicon wafer, which is a semiconductor substrate, is suitably supported by an adhesive layer and a release layer on a glass wafer, which is a support substrate that transmits ultraviolet light, while the silicon wafer is being processed such as thinning. After processing is completed, by irradiating the support substrate with ultraviolet light, the ultraviolet light that has passed through the support substrate is absorbed by the release layer. Furthermore, when the release layer is subjected to heat treatment, separation or decomposition of the release layer occurs at the interface between the release layer and the adhesive layer, at the interface between the release layer and the support substrate or semiconductor substrate, or within the release layer. As a result, suitable release can be achieved without applying excessive load for release.

[0019] As described above, the release layer of the laminate of the present invention is a film obtained from a release agent composition comprising a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent. Ethylene-unsaturated monomers containing a tert-leaved toxiccarbonyl group are ethylenically unsaturated monomers that contain a group represented by formula (1) in their molecule. An elimination reaction (gas generation reaction) occurs from the tert-leaved toxiccarbonyl group due to the acid generated by the acid generator produced by ultraviolet irradiation. As a result, the film, which is the release layer, is dismantled, and the release properties are improved. Ethylene-unsaturated monomers containing a tert-leaved toxiccarbonyl group can be used alone or in combination of two or more types.

[0020] [ka] (In the formula, * indicates a bond.)

[0021] The group represented by formula (1) may be directly bonded to the carbon atom constituting the ethylenically unsaturated bond of the monomer containing it, or it may be indirectly bonded via other atoms or other groups. For example, in the present invention, preferred examples of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group include ethylenically unsaturated monomers represented by formulas (T1) to (T3).

[0022] [ka]

[0023] Each R1 independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Of these, a hydrogen atom or a methyl group is preferred from the viewpoint of the availability of the compound or its raw material compound.

[0024] Each R2 and each R3 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. C1-C10 alkyl groups can be linear, branched, or cyclic. Examples include linear or branched C1-C10 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclic alkyl groups with C3-C10 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl groups.

[0025] In particular, from the viewpoint of the availability of the compound or its raw material compound, R2 and R3 are preferably a hydrogen atom and a linear alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, and an ethyl group, even more preferably a hydrogen atom and a methyl group, and still most preferably a hydrogen atom.

[0026] Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group with 1 to 12 carbon atoms, an arylene group with 6 to 16 carbon atoms, or a heteroarylene group with 3 to 12 carbon atoms. Examples of alkylene groups having 1 to 12 carbon atoms include groups derived by removing another hydrogen atom from an alkyl group having 1 to 12 carbon atoms, and specific examples of such alkyl groups are those mentioned above. Specific examples include, but are not limited to, methylene groups, ethylene groups, trimethylene groups, 2,2-propanediyl groups, tetramethylene groups, pentamethylene groups, hexamethylene groups, heptamethylene groups, octamethylene groups, nonamethylene groups, decamethylene groups, etc.

[0027] Arylene groups with 6 to 16 carbon atoms include those derived by removing two hydrogen atoms from an aryl group with 6 to 16 carbon atoms. Examples of such aryl groups include benzene, naphthalene, and anthracene. Specific examples include, but are not limited to, o-phenylene groups, m-phenylene groups, p-phenylene groups, naphthalene-1,2-diyl groups, naphthalene-1,3-diyl groups, naphthalene-1,4-diyl groups, naphthalene-1,5-diyl groups, naphthalene-1,6-diyl groups, naphthalene-1,7-diyl groups, naphthalene-1,8-diyl groups, naphthalene-2,3-diyl groups, naphthalene-2,6-diyl groups, and naphthalene-2,7-diyl groups.

[0028] Examples of heteroarylene groups having 3 to 12 carbon atoms include those derived by removing two hydrogen atoms from a heteroaryl group. Such heteroaryl groups include oxygen-containing heteroaryls such as furan, sulfur-containing heteroaryls such as thiophene, and nitrogen-containing heteroaryls such as pyridine, triazine, and imidazole. Specific examples include, but are not limited to, furan-2,3-diyl group, furan-2,4-diyl group, furan-2,5-diyl group, furan-3,4-diyl group, thiophene-2,3-diyl group, thiophene-2,4-diyl group, thiophene-2,5-diyl group, thiophene-3,4-diyl group, imidazole-2,4-diyl group, imidazole-4,5-diyl group, pyridine-2,3-diyl group, pyridine-2,4-diyl group, pyridine-2,5-diyl group, pyridine-2,6-diyl group, pyridine-3,4-diyl group, pyridine-3,5-diyl group, triazine-2,4-diyl group, etc.

[0029] In particular, from the viewpoint of the availability of the compound or its raw material compound, A is preferably a single bond, ether group, carbonyl group, amide group, C1-C8 alkylene group, or C6-C12 arylene group; more preferably a single bond, ether group, carbonyl group, amide group, C1-C4 alkylene group, o-phenylene group, m-phenylene group, or p-phenylene group; and even more preferably a single bond, ether group, carbonyl group, amide group, methylene group, ethylene group, trimethylene group, 2,2-propanediyl group, m-phenylene group, or p-phenylene group. Furthermore, from the viewpoint of the gas generation ability of the compound, A is preferably a single bond, ether group, or carbonyl group. Furthermore, in formula (T2), the substitution position of the tert-leaf toxic carbonyl group is preferably the para position relative to A.

[0030] Each X represents a substituent on a benzene ring and independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. Examples of halogen atoms include fluorine, chlorine, and bromine atoms.

[0031] Examples of C1-C10 haloalkyl groups include trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, and 1,1,2,2,3,3,4,4,4-nonafluorobutyl. Specific examples of alkyl groups having 1 to 10 carbon atoms are the same as those mentioned above.

[0032] n represents the number of substituents on the benzene ring and is an integer between 0 and 4.

[0033] In particular, from the viewpoint of the availability of the compound or its raw material compound, X is preferably a halogen atom, cyano group, nitro group, methyl group, ethyl group, propyl group, isopropyl group, halomethyl group, haloethyl group, halopropyl group, or haloisopropyl group, and more preferably a halogen atom, cyano group, nitro group, methyl group, ethyl group, halomethyl group, or haloethyl group. Furthermore, n is preferably 0 to 2, more preferably 0 or 1, and optimally 0.

[0034] Specific examples of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group include, but are not limited to, tert-leaved butyl (meth)acrylate, N-(tert-leaved toxiccarbonyl)(meth)acrylamide, 4-tert-leaved toxicstyrene, tert-leaved butyl 4-vinylphenyl carbonate, tert-leaved butyl (4-vinylphenyl)carbamate, tert-leaved butyloxycarbonyl (meth)acrylate, N-(tert-leaved toxiccarbonyl)maleimide, and 2-(tert-leaved toxiccarbonylamino)ethyl acrylate.

[0035] In this invention, the term "(meth)acrylate" encompasses both acrylate and methacrylate. Therefore, for example, tert-butyl methacrylate includes both tert-butyl acrylate (tert-butyl acrylate) and tert-butyl methacrylate.

[0036] In the present invention, the polymer of an ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group included in the above-mentioned stripping agent composition may also contain monomer units of ethylenically unsaturated monomers other than the ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group, for the purpose of adjusting the strength of the resulting film, adjusting the reactivity of the polymer, etc. Ethylene-unsaturated monomers other than those containing a tert-leaved toxiccarbonyl group are ethylenically unsaturated monomers that do not contain the group represented by formula (1) above. Specifically, examples include monofunctional (meth)acrylates that do not contain the group represented by formula (1) above, and bifunctional or more (meth)acrylates that do not contain the group represented by formula (1) above. Ethylene-unsaturated monomers other than those containing a tert-leaved toxiccarbonyl group can be used individually or in combination of two or more.

[0037] As the monofunctional (meth)acrylate, alkyl monofunctional (meth)acrylates are preferred, and alkyl monofunctional (meth)acrylates with 6 or more carbon atoms in the alkyl group are more preferred. The alkyl group can be linear, branched, or cyclic. Examples include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; and cyclic alkyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and bicyclodecyl groups.

[0038] Specific examples of monofunctional alkyl (meth)acrylates with six or more carbon atoms in the alkyl group include hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, isoamyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and others.

[0039] Furthermore, specific examples of (meth)acrylates other than monofunctional alkyl (meth)acrylates with 6 or more carbon atoms in the alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, glycerin mono(meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, benzyl (meth)acrylate, ethylene oxide-modified (n=2) phenol (meth)acrylate, propylene oxide-modified (n=2.5) nonylphenol (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, and furfuryl Examples include (meth)acrylate, carbitol (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, etc., among which those that do not contain hydroxyl groups are preferred, and a molecular weight of about 100 to 300 is preferred. Monofunctional (meth)acrylates can be used individually or in combination of two or more types.

[0040] Among these, isodecyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, isostearyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred.

[0041] Examples of (meth)acrylates with two or more functionalities include difunctional (meth)acrylates and (meth)acrylates with three or more functionalities. Examples of difunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and ethylene oxide-modified bisphenol. Examples include bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, and the like.

[0042] Examples of (meth)acrylates with three or more functionalities include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, and glycerin polyglycidyl ether poly(meth)acrylate.

[0043] In the present invention, from the viewpoint of reproducibly achieving suitable peeling, the content of ethylenically unsaturated monomer units other than ethylenically unsaturated monomers containing tert-leaved toxiccarbonyl groups is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 5 mol% or less, of the total units of the polymer. In a preferred embodiment of the present invention, from the viewpoint of reproducibly achieving suitable peeling, the polymer is composed only of ethylenically unsaturated monomer units containing a tert-leaved toxiccarbonyl group.

[0044] In other words, in the present invention, the content of monomer units represented by any of formulas (M1) to (M3), for example, is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more, of the total units of the polymer. In a preferred embodiment of the present invention, from the viewpoint of reproducibly achieving suitable peeling, the polymer is composed of, for example, only monomer units represented by any of formulas (M1) to (M3), preferably only monomer units represented by formula (M1). In this invention, "being composed solely of a certain monomer unit" means that it is derived solely from that monomer and is substantially composed solely of that monomer unit. This does not negate the possibility that trace amounts of units resulting from impurities in the bulk monomer, or from unintended structural changes or decomposition during or after polymerization, may be present in the polymer. [ka] (In the formula, R1 to R3, A, X, and n have the same meanings as above.)

[0045] The polymer used in this invention can be obtained by polymerizing the above monomer using a radical polymerization initiator. Radical polymerization initiators can be any substance capable of releasing a substance that initiates radical polymerization upon light irradiation and / or heating, and include, but are not limited to, benzophenone compounds, acetophenone compounds, benzoin ether compounds, thioxanthone compounds, azo compounds, peroxides, sulfonium salts, iodonium salts, and persulfates. Specifically, benzophenone, 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, bis(2,4,5-triphenyl)imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, ditert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, tert-butyl Peroxyacetate, tertiary butyl peroxypivalate, tertiary butyl peroxy-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), (1-phenylethyl)azodiphenylmethane, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, 2,2'-azobi Examples of suitable materials include, but are not limited to, 2-methylbutyronitrile, 1,1'-azobis(1-cyclohexanecarbonitride), 2-(carbamoylazo)isobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), ammonium persulfate, sodium persulfate, potassium persulfate, etc.

[0046] The amount of the above-mentioned radical polymerization initiator used is typically 1 to 3% by mass relative to the above-mentioned monomer.

[0047] The polymerization reaction of the above monomers may be carried out in a solvent for the purpose of efficiently obtaining the desired polymer. Such a solvent is not particularly limited as long as it does not have adverse effects such as inhibiting the reaction, but glycol-based solvents described below are preferred because, by using a glycol-based solvent as the solvent for the polymerization reaction, the reaction solution of the obtained polymer can be used directly in the preparation of the above-mentioned release agent composition without isolating the polymer.

[0048] The reaction temperature and reaction time for the polymerization reaction of the above monomers are usually determined appropriately from the range of 50 to 150°C and 5 minutes to 72 hours, taking into consideration the desired molecular weight of the polymer, the reactivity and amount of the initiator used, the boiling point of the solvent used, etc.

[0049] If necessary, the polymer may be isolated and purified according to standard procedures before being used in the preparation of the release agent composition.

[0050] The weight-average molecular weight (Mw) of the above polymer is usually 1,000 to 200,000 from the viewpoint of reproducibly achieving suitable peeling, preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 75,000 or less from the viewpoint of suppressing polymer precipitation and reproducibly achieving a peeling agent composition with excellent storage stability, and preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more from the viewpoint of increasing the strength of the resulting film and reproducibly achieving a peeling layer with excellent uniformity. The dispersion degree (Mw / Mn) of the above polymer is usually in the range of 2 to 6.

[0051] The weight-average molecular weight, number-average molecular weight, and degree of dispersion of the above polymer can be measured, for example, by using a Tosoh Corporation HLC-8320GPC along with a Tosoh Corporation TSKgel Super-MultiporeHZ-N column (column temperature: 40°C, flow rate: 0.35 mL / min, eluent: tetrahydrofuran, standard sample: polystyrene (Showa Denko K.K.)).

[0052] The above-mentioned stripping agent composition contains a photoacid generator. Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0053] Specific examples of onium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0054] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0055] Specific examples of disulfonyl diazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0056] Commercially available photoacid generators include sulfonium salt compounds such as "TPS105" (CAS No. 66003789), "TPS109" (CAS No. 144317442), "MDS105" (CAS No. 116808674), "MDS205" (CAS No. 81416377), "DTS105" (CAS No. 111281120), "NDS105" (CAS No. 195057831), "NDS165" (CAS No. 316821984), "DPI105" (CAS No. 66003767), "DPI106" (CAS No. 214534448), "DPI109" (CAS No. 194999821), "DPI201" (CAS No. 6293669), and "BI105" (CAS No. 6 iodonium salt compounds such as No. 154557161), "MPI105" (CAS No. 115298630), "MPI106" (CAS No. 260061469), "MPI109" (CAS No. 260061470), "BBI105" (CAS No. 84563542), "BBI106" (CAS No. 185195306), "BBI109" (CAS No. 194999854), "BBI110" (CAS No. 213740808), "BBI201" (CAS No. 142342334), "NAI106" (naphthalimide camphasulfonate, CAS No. 83697567), "NAI100" (CAS No. 83697534), "NAI1002" (CAS No.76656489), "NAI1004" (CAS No.83697603), "NAI101" (CAS No.5551724), "NAI105" (CAS No.85342627), "NAI109" (CAS No.171417917), "NI101" (CAS No.131526993), "NI105" (CAS No.85342638), "NDI101" (CAS No.141714821), "NDI105" (CAS No.133710620), "NDI106" (CAS No.210218578), "NDI109" (CAS No.307531766), "PAI01" (CAS No.17512888), "PAI101" (CAS No.Examples include, but are not limited to, compounds that use BF4 as a counterion, such as "82424531", "PAI106" (CAS No. 202419883), "PAI1001" (CAS No. 193222025), "SI101" (CAS No. 55048390), "SI105" (CAS No. 34684407), "SI106" (CAS No. 179419320), "SI109" (CAS No. 252937669), "PI105" (CAS No. 41580589), "PI106" (CAS No. 83697512), and "DTS200" (CAS No. 203573062). The photoacid generator can be used individually or in combination of two or more types.

[0057] The amount of photoacid generator contained in the above release agent composition cannot be specified in general terms as it varies depending on the heating temperature during film formation, the desired degree of release properties, etc. However, it is usually 0.1 to 30% by mass relative to the polymer, and from the viewpoint of achieving suitable curing and obtaining a laminate in which the semiconductor substrate and the support substrate can be separated well with good reproducibility, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0058] The above-mentioned stripping agent composition contains a solvent. Such solvents can include, for example, highly polar solvents that can dissolve the polymer and other components well, and, if necessary, low-polarity solvents may be used to adjust viscosity, surface tension, etc. In this invention, a low-polarity solvent is defined as one with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polar solvent is defined as one with a relative permittivity of 7 or more at a frequency of 100 kHz. The solvents can be used individually or in combination of two or more.

[0059] Furthermore, examples of highly polar solvents include, Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, 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; Sulfoxide solvents such as dimethyl sulfoxide These are some examples.

[0060] Examples of low-polarity solvents include, Chlorinated solvents such as chloroform and chlorobenzene; Aromatic hydrocarbon solvents such as toluene, xylene, tetralin, cyclohexylbenzene, decylbenzene, and other alkylbenzenes; Aliphatic alcohol 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; Ester 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. These are some examples.

[0061] The solvent content is set appropriately considering the viscosity of the desired composition, the coating method used, the thickness of the film to be produced, etc., but is 99% by mass or less of the total composition, preferably 70 to 99% by mass of the total composition, that is, the amount of film components in that case is 1 to 30% by mass of the total composition. In this invention, film components refer to components other than the solvent contained in the composition.

[0062] The viscosity and surface tension of the above-mentioned release agent composition can be appropriately adjusted by changing the type of solvent used, their ratios, and the concentration of film components, taking into consideration various factors such as the application method used and the desired film thickness.

[0063] In one aspect of the present invention, the stripping agent composition contains a glycol-based solvent, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility. The term "glycol-based solvent" as used herein refers to glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0064] An example of a preferred glycol-based solvent is represented by formula (G). [ka]

[0065] In formula (G), R G1 Each of these independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, and RG2 and R G3 Each of these 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 portion is a linear or branched alkyl group having 1 to 8 carbon atoms, n g This is an integer between 1 and 6.

[0066] Specific examples of linear or branched alkylene groups having 2 to 4 carbon atoms include, but are not limited to, ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, and hexamethylene groups. In particular, 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, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility.

[0067] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, and 3-methyl-n Examples of dimethyl-n-butyl groups include, but are not limited to, pentyl groups, 4-methyl-n-pentyl groups, 1,1-dimethyl-n-butyl groups, 1,2-dimethyl-n-butyl groups, 1,3-dimethyl-n-butyl groups, 2,2-dimethyl-n-butyl groups, 2,3-dimethyl-n-butyl groups, 3,3-dimethyl-n-butyl groups, 1-ethyl-n-butyl groups, 2-ethyl-n-butyl groups, 1,1,2-trimethyl-n-propyl groups, 1,2,2-trimethyl-n-propyl groups, 1-ethyl-1-methyl-n-propyl groups, and 1-ethyl-2-methyl-n-propyl groups. Among them, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a film with high uniformity, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

[0068] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkylacyl group in which the alkyl part is a linear or branched alkyl group having 1 to 8 carbon atoms include the same ones as the above specific examples. Among them, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a film with high uniformity, a methylcarbonyl group and an ethylcarbonyl group are preferable, and a methylcarbonyl group is more preferable.

[0069] n g From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a film with high uniformity, etc., it is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0070] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a film with high uniformity, etc., in formula (G), preferably, R G2 and R G3 at least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably, one of R G2 and R G3 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 part is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0071] From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility, 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, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the solvent contained in the above-mentioned release agent composition.

[0072] From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility, in the above-mentioned release agent composition, the film components are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0073] The above-mentioned stripping agent composition can be manufactured by mixing a polymer, a photoacid generator, and a solvent. The mixing order is not particularly limited, but examples of methods for easily and reproducibly producing a release agent composition include, but are not limited to, a method in which the polymer and the photoacid generator are dissolved in the solvent at the same time, or a method in which a portion of the polymer and photoacid generator are dissolved in the solvent, the remainder is dissolved separately in the solvent, and the resulting solutions are mixed. In this case, the polymer solution can be used as is, or concentrated or diluted, the reaction solution obtained from the synthesis of the polymer. Furthermore, when preparing the release agent composition, heating may be used as appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a sub-micrometer-order filter or the like during the manufacturing process of the release agent composition or after all components have been mixed.

[0074] The thickness of the release layer in the laminate of the present invention is typically 10 nm to 10 μm.

[0075] The release agent composition described above is also a subject of the present invention, and the relevant conditions (preferred conditions, manufacturing conditions, etc.) are as described above. By using the release agent composition of the present invention, it is possible to reproducibly manufacture a film suitable as a release layer that can be used, for example, in the manufacture of semiconductor devices. In particular, the release agent composition of the present invention can be suitably used to form the release layer of a laminate comprising a semiconductor substrate, an ultraviolet-transmitting support substrate, and two layers between these substrates, where one of the two layers is an adhesive layer and the other is a release layer. In such a laminate, by irradiating the release layer with ultraviolet light from the support substrate side and then subjecting it to heat treatment, the separation or decomposition of the release layer proceeds suitably as described above, and as a result, the semiconductor substrate can be separated from the support substrate without applying excessive load for release.

[0076] The adhesive layer of the laminate of the present invention can be, for example, a film obtained from an adhesive composition containing an adhesive component (S). Such adhesive components (S) are not particularly limited as long as they are used in this type of application, and include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenol resin-based adhesives, etc. Among these, polysiloxane-based adhesives are preferred as the adhesive component (S) because they exhibit suitable adhesive properties during wafer processing, can be readily peeled off after processing, and also have excellent heat resistance.

[0077] In a preferred embodiment, the adhesive composition used in the present invention includes a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction as an adhesive component, and in a more preferred example, the polyorganosiloxane component (A) that hardens by a hydrosilylation reaction is represented by siloxane units (Q units) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 Siloxane units (M units) are expressed as R 4 R 5 SiO2 / 2 Siloxane units (D units) and R are represented by these units. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units selected from the group consisting of siloxane units (T units) represented by SiO2, and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises siloxane units (Q' units) represented by SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane units (M' units) are represented as R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) and R are represented by these units. 6 'SiO 3 / 2 A polyorganosiloxane (a1) containing one or more units selected from the group consisting of siloxane units (T' units) represented by the above, and at least one unit selected from the group consisting of M' units, D' units and T' units, and a siloxane unit (Q'' unit) represented by SiO2, R 1 "R 2 "R 3 SiO 1 / 2 Siloxane units (M'' units) are expressed as R 4 "R 5 SiO 2 / 2 Siloxane units (D'' units) and R 6 SiO 3 / 2 The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of siloxane units (T'' units) represented by the above, and at least one unit selected from the group consisting of M'' units, D'' units and T'' units.

[0078] R 1 ~R 6 These are groups or atoms bonded to a silicon atom, and each independently represents an alkyl group, an alkenyl group, or a hydrogen atom.

[0079] R 1 '~R 6 ' is a group that bonds to a silicon atom, and each independently represents an alkyl group or an alkenyl group, R1 '~R 6 At least one of the groups is an alkenyl group.

[0080] R 1 "~R 6 " is a group or atom bonded to a silicon atom, and each independently represents an alkyl group or a hydrogen atom, but R 1 "~R 6 At least one of them is a hydrogen atom.

[0081] The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0082] Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, and 3-methyl-n-pentyl group. Examples include, but are not limited to, ethyl-n-butyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. Among these, the methyl group is preferred.

[0083] Specific examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, and 2,4-dimethyl Examples of cycloalkyl groups include, but are not limited to, cycloalkyl groups such as -cyclobutyl group, 3,3-dimethylcyclobutyl 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; bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0084] The alkenyl group may be linear, branched, or cyclic, and its carbon number 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.

[0085] Specific examples of alkenyl groups include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl 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, 1-methyl-1- Pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4 -methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-prop Examples include, but are not limited to, the ethanol-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group. Among these, the ethenyl group and the 2-propenyl group are preferred.

[0086] As described above, polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2). The alkenyl groups in polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) in polyorganosiloxane (a2) form a cross-linked structure through a hydrosilylation reaction by a platinum group metal catalyst (A2), resulting in hardening. As a result, a hardened film is formed.

[0087] 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 polyorganosiloxane (a1), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0088] Two or more preferred combinations 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).

[0089] Furthermore, when polyorganosiloxane (a1) contains two or more polyorganosiloxanes, the combinations of (Q' units and M' units) and (D' units and M' units), (T' units and M' units) and (D' units and M' units), and (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

[0090] 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 polyorganosiloxane (a2), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0091] Two or more preferred combinations 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).

[0092] Polyorganosiloxane (a1) is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, R1 '~R 6 The proportion of alkenyl groups in the total substituents represented by ' is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, and the remaining R 1 '~R 6 ' can be an alkyl group.

[0093] Polyorganosiloxane (a2) is composed of siloxane units in which an alkyl group and / or a hydrogen atom are bonded to the silicon atom, R 1 "~R 6 The proportion of hydrogen atoms in all substituents and substituted atoms represented by " is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, and the remaining R 1 "~R 6 " can be an alkyl group.

[0094] Polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). In a preferred embodiment of the present invention, the molar ratio of alkenyl groups in polyorganosiloxane (a1) to hydrogen atoms constituting the Si-H bond in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0095] The weight-average molecular weights of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 500 to 1,000,000, but are preferably 5,000 to 50,000 from the viewpoint of reproducibly achieving the effects of the present invention. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of polysiloxane can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0096] The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 10 to 1,000,000 (mPa·s), but are preferably 50 to 10,000 (mPa·s) from the viewpoint of reproducibly achieving the effects of the present invention. The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) were measured using an E-type rotational viscometer at 25°C.

[0097] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via hydrosilylation to form a film. Therefore, the mechanism of curing is different from that mediated by silanol groups, for example, and consequently, neither siloxane needs to contain silanol groups or functional groups that form silanol groups through hydrolysis, such as alkyloxy groups.

[0098] In a preferred embodiment of the present invention, the adhesive component (S) includes a platinum group metal catalyst (A2) together with the polysiloxane (A1) described above. Such platinum-based metal catalysts are catalysts for promoting the hydrosilylation reaction between the alkenyl group of polyorganosiloxane (a1) and the Si-H group of polyorganosiloxane (a2).

[0099] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum-based catalysts such as platinum black, platinum-dic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetate. Examples of complexes between platinum and olefins include, but are not limited to, complexes between divinyltetramethyldisiloxane and platinum. The amount of platinum group metal catalyst (A2) is typically in the range of 1.0 to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0100] The polyorganosiloxane component (A) may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction. Polymerization inhibitors are not particularly limited as long as they can suppress the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of polymerization inhibitor is typically 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), from the viewpoint of obtaining its effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0101] The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition, the resulting adhesive layer can be peeled off reproducibly and effectively. Typical examples of such release agent components (B) include polyorganosiloxanes, and specific examples include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0102] Preferred examples of the polyorganosiloxane, which is the release agent component (B), include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, and phenyl group-containing polyorganosiloxane.

[0103] The weight-average molecular weight of the polyorganosiloxane, which is the release agent component (B), is usually 100,000 to 2,000,000, but 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, and its dispersion degree is usually 1.0 to 10.0, but 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 dispersion degree can be measured by the method described above for polysiloxanes. The viscosity of polyorganosiloxane, which is the release agent component (B), is typically 1,000 to 2,000,000 mm². 2 The viscosity of polyorganosiloxane, which is the release agent component (B), is expressed as kinematic viscosity, and centistokes (cSt) = mm². 2 It is / s. Viscosity (mPa·s) is compared to density (g / cm³). 3 It can also be calculated by dividing by ). In other words, the value can be determined from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) 2 / s)=viscosity (mPa s) / density (g / cm 3 It can be calculated using the formula ).

[0104] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 Siloxane units (D) are represented by these units. 10 Examples include those containing units.

[0105] R 11 R is a group that bonds to a silicon atom and represents an alkyl group. 12This refers to a group that bonds to a silicon atom, representing an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be given above. In an organic group containing an epoxy group, the epoxy group may be an independent epoxy group that does not condense with other rings, or it may be an epoxy group that forms a fused ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing epoxy groups include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of an epoxy group-containing polyorganosiloxane is, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0106] Epoxy group-containing polyorganosiloxanes are the siloxane units (D) described above. 10 It includes units, but D 10 In addition to the units mentioned above, the Q unit, M unit, and / or T unit may also be included. In preferred embodiments of the present invention, specific examples of epoxy group-containing polyorganosiloxanes include D 10 Polyorganosiloxanes consisting only of units, D 10 Polyorganosiloxane containing units and Q units, D 10 Polyorganosiloxane containing units and M units, D 10 Polyorganosiloxanes containing units and T units, D 10 Polyorganosiloxane containing units, Q units, and M units, D 10 Polyorganosiloxane containing units, M units, and T units, D 10 Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0107] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane with an epoxy value of 0.1 to 5, and its weight-average molecular weight is usually 1,500 to 500,000, but is preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive.

[0108] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0109] [ka] (m1 and n1 are positive integers, representing the number of each repeating unit.)

[0110] [ka] (m2 and n2 are positive integers indicating the number of repeating units, and R is an alkylene group with 1 to 10 carbon atoms.)

[0111] [ka] (m3, n3, and o3 represent the number of repeating units and are positive integers; R is an alkylene group with 1 to 10 carbon atoms.)

[0112] Examples of methyl group-containing polyorganosiloxanes include R 210 R 220 SiO 2 / 2 Siloxane units (D) are represented by these units. 200 Units), preferably R 21 R 21 SiO 2 / 2 Siloxane units (D) are represented by these units. 20 Examples include those containing units.

[0113] R 210 and R 220 These are groups that bond to a silicon atom, and each independently represents an alkyl group, but at least one of them is a methyl group, and the examples given above can be given as specific examples of alkyl groups. R 21 R is a group that bonds to a silicon atom and represents an alkyl group. Specific examples of alkyl groups include those mentioned above. Among them, R 21As for this, a methyl group is preferable. In the present invention, as a preferable example of the methyl group-containing polyorganosiloxane, polydimethylsiloxane can be mentioned, but it is not limited thereto.

[0114] The methyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 200 unit or D 20 unit), but in addition to the D 200 unit and D 20 unit, it may also contain the above Q unit, M unit and / or T unit.

[0115] In a certain aspect of the present invention, specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane consisting only of D 200 unit, polyorganosiloxane containing D 200 unit and Q unit, polyorganosiloxane containing D 200 unit and M unit, polyorganosiloxane containing D 200 unit and T unit, polyorganosiloxane containing D 200 unit, Q unit and M unit, polyorganosiloxane containing D 200 unit, M unit and T unit, and polyorganosiloxane containing D 200 unit, Q unit, M unit and T unit.

[0116] In a preferable aspect of the present invention, specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane consisting only of D 20 unit, polyorganosiloxane containing D 20 unit and Q unit, polyorganosiloxane containing D 20 unit and M unit, polyorganosiloxane containing D 20 unit and T unit, polyorganosiloxane containing D 20 unit, Q unit and M unit, polyorganosiloxane containing D 20 unit, M unit and T unit, and polyorganosiloxane containing D 20 unit, Q unit, M unit and T unit.

[0117] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0118] [ka] (n4 represents the number of repeating units and is a positive integer.)

[0119] Examples of phenyl group-containing polyorganosiloxanes include R 31 R 32 SiO 2 / 2 Siloxane units (D) are represented by these units. 30 Examples include those containing units.

[0120] R 31 R is a group that bonds to a silicon atom and represents a phenyl group or an alkyl group. 32 This is a group that bonds to a silicon atom, representing a phenyl group. Specific examples of alkyl groups include those mentioned above, but a methyl group is preferred.

[0121] Phenyl group-containing polyorganosiloxanes are the siloxane units (D) mentioned above. 30 It includes units, but D 30 In addition to the units mentioned above, the Q unit, M unit, and / or T unit may also be included.

[0122] In preferred embodiments of the present invention, a specific example of a phenyl group-containing polyorganosiloxane is D 30 Polyorganosiloxanes consisting only of units, D 30 Polyorganosiloxane containing units and Q units, D 30 Polyorganosiloxane containing units and M units, D 30 Polyorganosiloxanes containing units and T units, D 30 Polyorganosiloxane containing units, Q units, and M units, D 30 Polyorganosiloxane containing units, M units, and T units, D 30Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0123] Specific examples of phenyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

[0124] [ka] (m5 and n5 are positive integers indicating the number of each repeating unit.)

[0125] [ka] (m6 and n6 are positive integers that indicate the number of each repeating unit.)

[0126] In a preferred embodiment, the adhesive composition used in the present invention comprises a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction, along with a release agent component (B), wherein in a preferred embodiment, the release agent component (B) is a polyorganosiloxane.

[0127] The adhesive composition used in the present invention may contain an adhesive component (S) and a release agent component (B) in any ratio. However, considering the balance between adhesion and release properties, the ratio of component (S) to component (B) is preferably 99.995:0.005 to 30:70 by mass, and more preferably 99.9:0.1 to 75:25. In other words, when a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction is included, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70 by mass ratio, and more preferably 99.9:0.1 to 75:25.

[0128] The adhesive composition used in the present invention may contain a solvent for purposes such as adjusting viscosity. Specific examples of such solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0129] More specifically, examples include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Such solvents can be used individually or in combination of two or more.

[0130] When the adhesive composition used in the present invention contains a solvent, its content is appropriately set considering the viscosity of the desired composition, the application method used, the thickness of the film to be produced, etc., but is in the range of approximately 10 to 90% by mass of the total composition.

[0131] The viscosity of the adhesive composition used in the present invention is typically 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s, at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratios, the concentration of film components, etc., taking into consideration various factors such as the application method used and the desired film thickness.

[0132] The adhesive composition used in the present invention can be manufactured by mixing an adhesive component (S) with a release agent component (B) and a solvent, if applicable. The mixing order is not particularly limited, but examples of methods for easily and reproducibly producing an adhesive composition include, for example, dissolving the adhesive component (S) and the release agent component (B) in a solvent, or dissolving a portion of the adhesive component (S) and the release agent component (B) in a solvent, dissolving the remainder in a solvent, and then mixing the resulting solutions. However, the method is not limited to these. When preparing the adhesive composition, heating may be used as appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a sub-micrometer-order filter or the like during the manufacturing of the adhesive composition or after all components have been mixed.

[0133] The thickness of the adhesive layer in the laminate of the present invention is usually 5 to 500 μm, but from the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick films, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and still more preferably 70 μm or less.

[0134] The laminate of the present invention can be manufactured by a method comprising, for example, a first step of applying an adhesive composition to the surface of a semiconductor substrate and heating it to form an adhesive coating layer; a second step of applying a release agent composition to the surface of a support substrate and, if necessary, heating it to form a release agent coating layer; and a third step of applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact while performing at least one of a heat treatment and a vacuum treatment, and then performing a post-heat treatment to form a laminate.

[0135] Furthermore, the laminate of the present invention can be manufactured by a method comprising, for example, a first step of applying a release agent composition to the surface of a semiconductor substrate and heating it to form a release agent coating layer; a second step of applying an adhesive composition to the surface of a support substrate and, if necessary, heating it to form an adhesive coating layer; and a third step of applying a load in the thickness direction to the semiconductor substrate and the support substrate to bring them into close contact while performing at least one of a heat treatment and a vacuum treatment, and then performing a post-heat treatment to form a laminate. Furthermore, as long as the effects of the present invention are not impaired, the coating and heating of each composition may be performed sequentially on either substrate.

[0136] The coating method is not particularly limited, but it is usually the spin coating method. Alternatively, a method may be used in which a coating film is formed separately by the spin coating method or the like, and then a sheet-like coating film is attached; this is also referred to as coating or coating film.

[0137] The heating temperature of the applied adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc. However, it is usually between 80°C and 150°C, and the heating time is usually between 30 seconds and 5 minutes. If the adhesive composition contains a solvent, the applied adhesive composition is usually heated.

[0138] The heating temperature of the applied release agent composition cannot be specified in general terms, as it varies depending on the type and amount of acid generator, the boiling point of the solvent used, and the desired thickness of the release layer. However, from the viewpoint of reproducibly achieving a suitable release layer, it is 80°C or higher, and from the viewpoint of suppressing the decomposition of the acid generator, it is 300°C or lower. The heating time is usually appropriately determined in the range of 10 seconds to 10 minutes, depending on the heating temperature.

[0139] Heating can be done using a hot plate, oven, etc.

[0140] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually around 5 to 500 μm, and is ultimately determined as appropriate so that it falls within the aforementioned range of adhesive layer thickness.

[0141] The thickness of the release agent coating layer obtained by applying the release agent composition and heating it is usually about 10 nm to 10 μm, and is ultimately determined as appropriate so that it falls within the aforementioned range of release layer thickness.

[0142] In the present invention, such coated layers are brought into contact with each other, and while performing heat treatment, vacuum treatment, or both, a load is applied in the thickness direction of the semiconductor substrate and the support substrate to bring the two layers into close contact, and then a post-heat treatment is performed to obtain the laminate of the present invention. The choice of which treatment conditions to adopt—heat treatment, vacuum treatment, or a combination of both—is determined appropriately after considering various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from both compositions, the film thickness, and the desired adhesive strength.

[0143] The heat treatment is usually appropriately determined from a range of 20 to 150°C, from the viewpoint of softening the adhesive coating layer to achieve suitable bonding with the release agent coating layer, and from the viewpoint of suppressing the decomposition of the photoacid generator and reproducibly achieving a suitable release agent coating layer. In particular, from the viewpoint of suppressing or avoiding excessive hardening or unwanted deterioration of the adhesive component (S), the temperature is preferably 130°C or lower, more preferably 90°C or lower. The heating time is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably developing adhesive properties, but usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0144] The vacuum treatment involves exposing the adhesive coating layer and the release agent coating layer, which are in contact with each other, to a pressure of 10 Pa to 10,000 Pa. The vacuum treatment time is usually 1 to 30 minutes.

[0145] From the viewpoint of obtaining a laminate in which the substrate can be easily separated with good reproducibility, the two layers that are in contact with each other are preferably bonded together by a reduced pressure treatment, more preferably by a combination of heat treatment and reduced pressure treatment.

[0146] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate and the two layers between them, and can firmly adhere them together, but is usually in the range of 10 to 1000 N.

[0147] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing speed, 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 more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrates and layers constituting the laminate, and is usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, etc. When post-heating using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be placed facing downwards during heating, but from the viewpoint of achieving suitable delamination with good reproducibility, it is preferable to post-heat with the semiconductor substrate facing downwards. One of the purposes of the post-heat treatment is to make the adhesive component (S) more suitable as a self-supporting film, and in particular to suitably achieve curing by hydrosilylation reaction.

[0148] The present invention provides a method for manufacturing a processed semiconductor substrate, comprising: a first step of processing a laminated semiconductor substrate comprising a semiconductor substrate, a support substrate that transmits ultraviolet light, 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 comprising a polymer of an ethylenically unsaturated monomer containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent; a second step of irradiating the release layer with ultraviolet light from the support substrate side after the first step; and a third step of heating the release layer after the second step.

[0149] The processing performed on the semiconductor substrate in the first step is, for example, processing on the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface. Subsequently, through-silicon viable (TSV) electrodes are formed, and then the thinned wafer is peeled off the support substrate to form a wafer laminate for 3D mounting. Before or after this, wafer back-side electrodes are also formed. During the wafer thinning and TSV processes, heat of 250-350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention, including the adhesive layer and the release layer, has heat resistance to this load. Furthermore, the processing is not limited to those described above, and also includes, for example, the implementation of the semiconductor component mounting process when a substrate is temporarily bonded to a support substrate to support the substrate for mounting semiconductor components.

[0150] In the second step, the irradiation of the release layer with ultraviolet light does not necessarily have to be applied to the entire area of ​​the release layer. Even if there is a mixture of areas irradiated with ultraviolet light and areas that are not irradiated with ultraviolet light, if the release ability of the entire release layer is sufficiently improved after the subsequent heat treatment, the semiconductor substrate and the support substrate can be separated by a small external force, such as lifting the support substrate. The ratio and positional relationship between the areas irradiated with ultraviolet light and those that are not irradiated will vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release layer, the intensity of the ultraviolet light used, etc. However, a person skilled in the art can set the conditions appropriately without requiring excessive testing. Typically, the amount of ultraviolet radiation is 100-1,500 mJ / cm². 2 The irradiation time is determined appropriately according to the wavelength and irradiation dose. Ultraviolet irradiation may be performed using a laser or a light source such as an ultraviolet lamp.

[0151] The heating conditions applied to the release layer in the third step cannot be specified in general, as they are determined appropriately depending on the thickness of the release layer, the type and amount of photoacid generated, the amount of ultraviolet light irradiated, etc., but are usually 50 to 200°C for 1 second to 30 minutes. The reason why suitable release can be achieved by heating the release layer irradiated with ultraviolet light is thought to be that the diffusion of the acid generated from the photoacid generator is promoted, which in turn promotes the generation of gas from the polymer, and as a result, the decomposition of the release layer is promoted, or the gas generated from the polymer expands, which in turn promotes the decomposition of the release layer. Heating can be done using an oven or a hot plate. As long as the release layer is properly heated, heating may be done from only one substrate side of the laminate, for example, by heating the laminate on a hot plate with the semiconductor substrate facing downwards.

[0152] In the present invention, by using ultraviolet irradiation in combination with subsequent heat treatment, it is possible to achieve suitable peeling that cannot be achieved by ultraviolet irradiation alone, heat treatment alone, or by a combination of heat treatment and subsequent ultraviolet irradiation. Furthermore, in this invention, since ultraviolet light is used for peeling, non-laser light using a general-purpose lamp as the light source can be used. As a result, damage to semiconductor substrates such as silicon wafers, which is a concern with peeling using high-energy lasers, can be avoided. Moreover, because non-laser light is used, the light irradiation time per laminate can be shortened compared to when laser light is used, and as a result, an improvement in throughput can be expected.

[0153] The method for manufacturing a processed semiconductor substrate according to the present invention typically includes a fourth step of cleaning the separated processed semiconductor substrate after the third step. Because the delamination interface differs depending on the layer structure of the laminated substrate, after the third step, the materials to be removed from the processed semiconductor substrate vary depending on whether both the adhesive layer and the delamination layer are present on the processed semiconductor substrate, or only the delamination layer is present. Unwanted materials are removed using removal tape, organic solvents, cleaners containing ammonium fluoride, etc., and the surface of the processed semiconductor substrate is cleaned.

[0154] The components and method elements relating to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention may be modified in various ways as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed semiconductor substrate according to the present invention may include steps other than those described above.

[0155] The delamination method of the present invention involves irradiating the delamination layer of the laminate with light from the support substrate side, and then heating the delamination layer to separate the semiconductor substrate and the support substrate of the laminate. In the laminate of the present invention, the semiconductor substrate and the ultraviolet-transmitting support substrate are temporarily bonded together in a suitably peelable manner by an adhesive layer and a release layer. Therefore, by irradiating the release layer with ultraviolet light from the support substrate side of the laminate and then performing a heat treatment, the semiconductor substrate and the support substrate can be easily separated. Typically, peeling is performed after processing has been carried out on the semiconductor substrate. [Examples]

[0156] 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. [Device] (1) Bonding device: Manual bonder manufactured by Suss Microtec (2) UV irradiation device: Omiya Kogyo Co., Ltd. UVI-MA [Molecular weight measurement of polymers] (1) The molecular weight of the tertiary butyl acrylate polymer was measured under the following conditions. Equipment: HLC-8320GPC manufactured by Tosoh Corporation GPC column: TSKgel Super-MultiporeHZ-N (2 tubes) manufactured by Tosoh Corporation Column temperature: 40℃ Flow rate: 0.35mL / min Eluent: Tetrahydrofuran Standard sample: Polystyrene (manufactured by Showa Denko Corporation)

[0157] [1] Preparation of adhesive composition [Preparation Example 1] In a 600 mL stirring container specifically designed for stirrers, 80 g of MQ resin (manufactured by Wacker Chem Ltd.) containing a polysiloxane structure and vinyl groups, 2.52 g of linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chem Ltd.), 5.89 g of linear polydimethylsiloxane containing SiH groups with a viscosity of 70 mPa·s (manufactured by Wacker Chem Ltd.), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Ltd.) were placed, and the mixture was stirred with a stirrer for 5 minutes. To the obtained mixture, 0.147 g of platinum catalyst (manufactured by Wacker Chem Ltd.) and 5.81 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) with a viscosity of 1,000 mPa·s were stirred with a stirrer for 5 minutes, and 3.96 g of the mixture obtained separately was added and stirred with a stirrer for 5 minutes. Finally, the resulting mixture was filtered through a 300-mesh nylon filter to obtain the adhesive composition.

[0158] [2] Preparation of compositions containing acrylate polymers (polymers) [Preparation Example 2] In a flask, 30.0 g of tert-butyl acrylate as a monomer, 0.75 g of 2,2'-azobisisobutyronitrile as a radical polymerization initiator, and 71.75 g of propylene glycol monomethyl ether acetate as a solvent were added and stirred. The resulting mixture was then heated overnight at 60°C to allow the polymerization reaction to proceed. After cooling the reaction mixture to room temperature, the cooled reaction mixture was obtained as a composition containing the target tert-butyl acrylate polymer (Mw=45,565, Mw / Mn=5.83).

[0159] [3] Preparation of the release agent composition [Preparation Example 3-1] A solution was prepared by mixing the composition obtained in Preparation Example 2 with propylene glycol monomethyl ether acetate so that the final concentration of the tertiary butyl acrylate polymer was 32% by mass. To 5.042 g of the obtained solution, 0.164 g of DTS-105 (manufactured by Midori Chemical Co., Ltd.) as a photoacid generator and 3.429 g of propylene glycol monomethyl ether acetate were added and stirred to obtain a stripping agent composition.

[0160] [Preparation Examples 3-2 to 3-4] A stripping agent composition was obtained in the same manner as in Preparation Example 3-1, except that the amounts used for the solution, photoacid generator, and propylene glycol monomethyl ether acetate were 5.116 g, 0.108 g, and 3.476 g (Preparation Example 3-2), 5.124 g, 0.176 g, and 6.959 g (Preparation Example 3-3), and 5.131 g, 0.210 g, and 7.050 g (Preparation Example 3-4), respectively.

[0161] [4] Manufacturing of laminates [Manufacturing Example 1-1] The release agent composition obtained in Preparation Example 3-1 was spin-coated onto a 100 mm glass wafer so that the final film thickness in the resulting laminate was approximately 2.0 μm. The wafer was then heated at 200°C for 1 minute to form a release agent coating layer on the glass wafer, which served as the support substrate. On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated onto a 100 mm silicon wafer so that the final film thickness in the resulting laminate was approximately 60 μm, thereby forming an adhesive coating layer on the silicon wafer, which is a semiconductor substrate. Then, using a bonding apparatus, the glass wafer and the silicon wafer were bonded together, sandwiching the release agent coating layer and the adhesive coating layer between them. After this, a laminate was fabricated by post-heat treatment at 200°C for 10 minutes. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The required number of laminates were manufactured.

[0162] [Manufacturing Examples 1-2 to 1-4] The laminate was prepared in the same manner as in Production Example 1-1, except that the release agent compositions obtained in Production Examples 3-2 to 3-4 were used instead of the release agent composition obtained in Production Example 3-1.

[0163] [Manufacturing Example 2-1] The adhesive composition obtained in Preparation Example 1 was spin-coated onto a 100 mm glass wafer so that the final film thickness in the resulting laminate was approximately 60 μm, thereby forming an adhesive coating layer on the glass wafer, which served as the support substrate. On the other hand, the release agent composition obtained in Preparation Example 3-1 was spin-coated onto a 100 mm silicon wafer so that the final film thickness in the resulting laminate was approximately 2.0 μm, and the wafer was heated at 200°C for 1 minute to form a release agent coating layer on the silicon wafer, which is a semiconductor substrate. Then, using a bonding apparatus, a glass wafer and a silicon wafer were bonded together, sandwiching the adhesive coating layer and the release agent coating layer between them. After this, a laminate was fabricated by post-heat treatment at 200°C for 10 minutes. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. The required number of laminates were manufactured.

[0164] [Comparative Manufacturing Example 1-1] The release agent composition obtained in Preparation Example 3-1 was spin-coated onto a 100 mm glass wafer so that the final film thickness in the resulting laminate was approximately 2.0 μm, thereby forming a release agent coating layer on the glass wafer, which served as the support substrate. Then, using a bonding apparatus, a glass wafer and a 100 mm silicon wafer were bonded together, sandwiching a release agent coating layer between them. After this, a laminate was fabricated by post-heat treatment at 200°C for 1 minute. The bonding was performed at a temperature of 23°C and a reduced pressure of 1,500 Pa. Visual inspection of the resulting laminate revealed numerous voids, indicating that the bonding process was not performed correctly.

[0165] [5] Confirmation of the optimal irradiation dose of 365nm UV light In the laminate obtained in Manufacturing Example 1-1, UV light was irradiated onto the entire surface of the delamination layer from the glass wafer side using a UV irradiation device, at an output of 100-1000 mJ / cm². 2 The lowest UV irradiation output that caused delamination within the specified range was identified and defined as the optimal irradiation dose. As a result, the optimal irradiation dose was found to be 500 mJ / cm². 2 That was the case.

[0166] [6] Confirmation of peelability using 365nm UV light (confirmation of peeling by full surface irradiation) [Example 1-1] In the laminate obtained in Manufacturing Example 1-1, UV light was irradiated onto the entire surface of the release layer from the glass wafer side using a UV irradiation device. Then, the laminate was heated on a hot plate set to 200°C for approximately 5 seconds with the silicon wafer facing downwards. The feasibility of peeling the glass wafer was then confirmed. The UV output was 500 mJ / cm². 2 That's what I decided. As a result, the glass wafer (carrier side) could be easily peeled off manually with almost no force required.

[0167] [Comparative Example 1-1] The laminate obtained in Manufacturing Example 1-1 was heated on a hot plate set to 200°C with the silicon wafer facing down for about 1 minute. Then, UV light was irradiated onto the entire surface of the release layer of the laminate from the glass wafer side using a UV irradiation device. The feasibility of peeling the glass wafer was then confirmed. The UV output was 500 mJ / cm². 2 That's what I decided. As a result, even with force applied, it was difficult to manually detach the glass wafer (carrier side).

[0168] [Comparative Example 1-2] The laminate obtained in Manufacturing Example 1-1 was heated on a hot plate set to 200°C with the silicon wafer facing down for about 30 minutes. Then, it was checked whether the glass wafer could be peeled off. As a result, even with force applied, it was difficult to manually detach the glass wafer (carrier side).

[0169] [Example 2-1] In the laminate obtained in Manufacturing Example 2-1, UV light was irradiated onto the entire surface of the release layer from the glass wafer side using a UV irradiation device. Then, the laminate was heated on a hot plate set to 200°C for approximately 10 seconds with the silicon wafer facing downwards. The feasibility of peeling the glass wafer was then confirmed. The UV output was 330 mJ / cm². 2 That's what I decided. As a result, the glass wafer (carrier side) could be easily peeled off manually with almost no force required.

[0170] [Comparative Example 2-1] The entire delamination layer of the laminate obtained in Manufacturing Example 2-1 was irradiated with UV light from the glass wafer side using a UV irradiation device. The feasibility of delamination of the glass wafer was then confirmed. The UV output was 500 mJ / cm². 2 The following was chosen: As a result, even with force applied, it was difficult to manually detach the glass wafer (carrier side).

Claims

1. Semiconductor substrate and A support substrate that transmits ultraviolet light, The semiconductor substrate and the support substrate are provided with an adhesive layer and a release layer, The above-mentioned release layer is a film obtained from a release agent composition comprising a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent. A laminate characterized in that the total content of ethylenically unsaturated monomer units containing a tert-leaved toxiccarbonyl group in all units of the above polymer is 50 mol% or more, and the content of ethylenically unsaturated monomer units other than the above-mentioned tert-leaved toxiccarbonyl group is 20 mol% or less.

2. The laminate according to claim 1, wherein the ethylenically unsaturated monomer containing the above-mentioned tert-leaved toxiccarbonyl group is selected from the group consisting of formulas (T1) to (T3). 【Chemistry 1】 (Each R 1 Each of these independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Each R ２ and each R ３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 16 carbon atoms, or a heteroarylene group having 3 to 12 carbon atoms. Each X independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. n represents the number of substituents X on the benzene ring, and is an integer between 0 and 4.

3. The laminate according to claim 1, wherein the ethylenically unsaturated monomer containing the tert-leaved toxiccarbonyl group comprises tert-butyl (meth)acrylate.

4. The laminate according to any one of claims 1 to 3, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) which includes at least one selected from polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.

5. The laminate according to claim 4, wherein the adhesive component (S) includes a polysiloxane-based adhesive.

6. The laminate according to claim 5, wherein the polysiloxane-based adhesive contains a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction.

7. A release agent composition for forming the release layer of a laminate comprising a semiconductor substrate, an ultraviolet-transmitting support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, The product comprises a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent. A stripping agent composition wherein the total content of ethylenically unsaturated monomer units containing a tert-leaved toxiccarbonyl group in all units of the above polymer is 50 mol% or more, and the content of ethylenically unsaturated monomer units other than the above-mentioned tert-leaved toxiccarbonyl group is 20 mol% or less.

8. The stripping agent composition according to claim 7, wherein the ethylenically unsaturated monomer containing the tert-leaved toxiccarbonyl group is selected from the group consisting of formulas (T1) to (T3). 【Chemistry 2】 (Each R 1 Each of these independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Each R ２ and each R ３ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 16 carbon atoms, or a heteroarylene group having 3 to 12 carbon atoms. Each X independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. n represents the number of substituents X on the benzene ring, and is an integer between 0 and 4.

9. The stripping agent composition according to claim 7, wherein the ethylenically unsaturated monomer containing the tert-leaved toxiccarbonyl group comprises tert-leaved butyl (meth)acrylate.

10. The release agent composition according to any one of claims 7 to 9, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) which includes at least one selected from polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.

11. The release agent composition according to claim 10, wherein the adhesive component (S) includes a polysiloxane-based adhesive.

12. The release agent composition according to claim 11, wherein the polysiloxane-based adhesive contains a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction.

13. A method for manufacturing a processed semiconductor substrate, A first step in processing a laminated semiconductor substrate which is a film obtained from a release agent composition comprising a semiconductor substrate, an ultraviolet light-transmitting support substrate, and an adhesive layer and a release layer provided between the semiconductor substrate and the support substrate, wherein the release layer comprises a polymer of ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group, a photoacid generator, and a solvent, wherein the content of ethylenically unsaturated monomer units containing a tert-leaved toxiccarbonyl group in all units of the polymer is 50 mol% or more, and the content of ethylenically unsaturated monomer units other than the ethylenically unsaturated monomers containing a tert-leaved toxiccarbonyl group is 20 mol% or less, Following the first step described above, a second step is performed in which ultraviolet light is irradiated onto the release layer from the support substrate side. After the second step described above, a third step is taken to heat the peeling layer. A method for manufacturing a processed semiconductor substrate that includes [the specified component].

14. A method for manufacturing a processed semiconductor substrate according to claim 13, wherein the ethylenically unsaturated monomer containing the above-mentioned tert-leaved toxiccarbonyl group is selected from the group consisting of formulas (T1) to (T3). 【Transformation 3】 (Each R 1 Each of these independently represents a hydrogen atom, a cyano group, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. Each R ２ and each R ３ independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Each A independently represents a single bond, an ether group (-O-), a carbonyl group (-CO-), an amide group (-CONH-), an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 16 carbon atoms, or a heteroarylene group having 3 to 12 carbon atoms. Each X independently represents a halogen atom, a cyano group, a nitro group, a C1-C10 alkyl group, or a C1-C10 haloalkyl group. n represents the number of substituents X on the benzene ring, and is an integer between 0 and 4.

15. A method for producing a processed semiconductor substrate according to claim 13, wherein the ethylenically unsaturated monomer containing the above-mentioned tert-leaved toxiccarbonyl group contains tert-leaved butyl (meth)acrylate.

16. A method for manufacturing a processed semiconductor substrate according to any one of claims 13 to 15, wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S) which includes at least one selected from polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenol resin-based adhesives.

17. A method for manufacturing a processed semiconductor substrate according to claim 16, wherein the adhesive component (S) above comprises a polysiloxane-based adhesive.

18. The method for producing a processed semiconductor substrate according to claim 17, wherein the polysiloxane-based adhesive contains a polyorganosiloxane component (A) that hardens by a hydrosilylation reaction.

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