Laminate and release agent composition

Abstract

The present application relates to a kind of laminates, it is characterized in that, with: by the first substrate of semiconductor substrate, by the second substrate of light-transmitting support substrate, and in the adhesive layer and release layer between the first substrate and the second substrate, the release layer is the film obtained from the following release agent composition, the release agent composition includes at least any one of acid generator and acid, the polynuclear phenol derivative shown in formula (P) and crosslinking agent.(In formula, Ar indicates arylene.)

Description

Technical Field

[0001] This invention relates to a laminate and a release agent composition. Background Technology

[0002] In contrast to semiconductor wafers traditionally integrated in a two-dimensional planar direction, the pursuit of further integration involves stacking (decorranging) the planar surface in a three-dimensional direction. This three-dimensional stacking is achieved through interconnects via through-silicon vias (TSVs) and the resulting multi-layered integration. During multi-layer integration, the back side (opposite to the circuit plane) of each wafer is thinned using a grinding process, and the thinned semiconductor wafers are then stacked.

[0003] For semiconductor wafers before thinning (hereinafter referred to as wafers), they are bonded to a support for polishing using a polishing apparatus. This bonding must be easily peeled off after polishing; therefore, it is called a temporary bond. This temporary bond must be easily detached from the support because when a large force is applied during removal, the thinned semiconductor wafer may sometimes be cut or deformed. To prevent this, easy removal is necessary. However, during polishing of the back side of the semiconductor wafer, detachment or displacement due to polishing stress is undesirable. Therefore, the desired performance for temporary bonds is: resistance to polishing stress and easy removal after polishing.

[0004] For example, the following properties are desired: high stress (strong adhesion) relative to the planar direction during grinding, and low stress (weak adhesion) relative to the longitudinal direction during disassembly.

[0005] To perform such bonding and separation processes, methods using laser irradiation have been disclosed (see, for example, Patent Document 1 and Patent Document 2), but with recent advancements in the semiconductor field, new technologies related to peeling using laser irradiation are constantly being sought.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2004-64040

[0009] Patent Document 2: Japanese Patent Application Publication No. 2012-106486 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The present invention was made in view of the above circumstances, and its object is to provide a laminate having a release layer and a release agent composition having a film as a preferred release layer, wherein the release layer has excellent heat resistance when bonding a support substrate and a semiconductor substrate, when processing the back side of the semiconductor substrate, when mounting parts, etc., and can be easily peeled off by light irradiation when peeling off the support substrate and the semiconductor substrate.

[0012] Solution for solving the problem

[0013] In order to solve the above-mentioned problems, the inventors conducted various studies and found that the above-mentioned problems could be solved by using a film obtained from a release agent composition as the release layer of a laminate, thereby completing the present invention. The laminate comprises: a first substrate made of a semiconductor substrate, a second substrate made of a light-transmitting support substrate, and an adhesive layer and a release layer between the first substrate and the second substrate. The release agent composition comprises at least one of an acid-generating agent and an acid, a specified polyphenol derivative, and a crosslinking agent.

[0014] That is, the present invention provides the following content.

[0015] 1. A laminate comprising: a first substrate made of a semiconductor substrate, a second substrate made of a light-transmitting support substrate, and an adhesive layer and a release layer between the first substrate and the second substrate, wherein the release layer is a film obtained from a release agent composition comprising at least one of an acid-generating agent and an acid, a polyphenol derivative of formula (P), and a crosslinking agent.

[0016]

[0017] (In the formula, Ar represents aryl.)

[0018] 2. The laminate according to 1, wherein the above-mentioned polynucleophenol derivative is represented by formula (P-1).

[0019]

[0020] 3. The laminate according to 2, wherein the above-mentioned polynucleophenol derivative is represented by formula (P-1-1).

[0021]

[0022] 4. The laminate according to 3, wherein the above-mentioned polynucleophenol derivative is represented by formula (P1).

[0023]

[0024] 5. The laminate according to any one of 1 to 4, wherein the crosslinking agent comprises at least one selected from phenolic crosslinking agents having crosslinking forming groups, melamine crosslinking agents having crosslinking forming groups, urea crosslinking agents having crosslinking forming groups, and thiourea crosslinking agents having crosslinking forming groups.

[0025] 6. The laminate according to 5, wherein the crosslinking agent comprises a phenolic crosslinking agent having crosslinking forming groups.

[0026] 7. The laminate according to any one of 1 to 6, wherein the stripping agent composition comprises an acid.

[0027] 8. The laminate according to 7, wherein the acid comprises at least one selected from arylsulfonic acid, salts of arylsulfonic acid, aryl carboxylic acid, aryl carboxylate, chain or cyclic alkylsulfonic acid, salts of chain or cyclic alkylsulfonic acid, chain or cyclic alkyl carboxylic acid, and chain or cyclic alkyl carboxylate.

[0028] 9. The laminate according to any one of 1 to 8, characterized in that the adhesive layer is a film obtained using an adhesive composition comprising an adhesive component (S), wherein the adhesive component (S) comprises at least one selected from silicone adhesives, acrylic adhesives, epoxy adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

[0029] 10. The laminate according to 9, wherein the adhesive component (S) comprises an organosilicon adhesive.

[0030] 11. The laminate according to 10, wherein the aforementioned silicone adhesive comprises a polyorganosiloxane component (A) cured by a hydrosilylation reaction.

[0031] 12. A stripping agent composition comprising at least one of an acid-producing agent and an acid, a polyphenol derivative of formula (P), and a crosslinking agent.

[0032]

[0033] (In the formula, Ar represents aryl.)

[0034] 13. The stripping agent composition according to 12, wherein the above-mentioned polyphenolic derivative is represented by formula (P-1).

[0035]

[0036] 14. The stripping agent composition according to 13, wherein the above-mentioned polynucleophenol derivative is represented by formula (P-1-1).

[0037]

[0038] 15. The stripping agent composition according to 14, wherein the above-mentioned polyphenolic derivative is represented by formula (P1).

[0039]

[0040] 16. The stripping agent composition according to any one of 12 to 15, wherein the crosslinking agent comprises at least one selected from phenolic crosslinking agents having crosslinking forming groups, melamine crosslinking agents having crosslinking forming groups, urea crosslinking agents having crosslinking forming groups, and thiourea crosslinking agents having crosslinking forming groups.

[0041] 17. The stripping agent composition according to any one of 12 to 16, wherein the crosslinking agent comprises a phenolic crosslinking agent having a crosslinking forming group.

[0042] 18. The stripping agent composition according to any one of 12 to 17, wherein the stripping agent composition comprises an acid.

[0043] 19. The stripping agent composition according to 18, wherein the acid comprises at least one selected from arylsulfonic acids, salts of arylsulfonic acids, aryl carboxylic acids, aryl carboxylic acid salts, chain or cyclic alkylsulfonic acids, salts of chain or cyclic alkylsulfonic acids, chain or cyclic alkyl carboxylic acids, and chain or cyclic alkyl carboxylic acid salts.

[0044] 20. A release agent composition according to any one of 12 to 19, wherein the release agent composition is used to form a release layer of a laminate comprising: a first substrate made of a semiconductor substrate, a second substrate made of a light-transmitting support substrate, and an adhesive layer and a release layer between the first substrate and the second substrate.

[0045] Invention Effects

[0046] The laminate of the present invention comprises: a first substrate made of a semiconductor substrate, a second substrate made of a light-transmitting support substrate, and an adhesive layer and a release layer between the first substrate and the second substrate. The release layer is a film obtained from a release agent composition comprising at least one of an acid-generating agent and an acid, a specified polyphenol derivative, and a crosslinking agent. When light is irradiated from the second substrate side, the release layer receiving the light exerts its release capability, resulting in easy separation of the second substrate from the first substrate and the adhesive layer. The reason for such easy separation is presumably that the release layer absorbs light irradiated through the second substrate and decomposes or deteriorates. It can be considered that through such decomposition or deterioration, separation 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 within the release layer itself.

[0047] By using the laminate of the present invention with these characteristics, for example, when separating the processed wafer from the support substrate serving as the second substrate after processing the back side of the wafer, the processed wafer can be easily separated by irradiating it with a laser from the second substrate side. This avoids mechanical stress on the wafer, and consequently, prevents damage such as warping and deformation. Furthermore, the release layer of the laminate of the present invention does not generate significant gases or excessive heat that could cause adverse effects when it exerts its release capability, thus reducing the impact on the first substrate composed of a semiconductor substrate. Therefore, by using the laminate of the present invention, it is expected that semiconductor devices with higher reliability can be manufactured.

[0048] The release agent composition of the present invention comprises at least one of an acid-producing agent and an acid, and a crosslinking agent, and includes a specified polyphenol derivative exhibiting excellent solubility in an organic solvent. The film obtained from said composition absorbs light well. Therefore, by providing the film obtained from the release agent composition of the present invention as a release layer, together with an adhesive layer, between a first substrate made of a semiconductor substrate and a second substrate made of a light-transmitting support substrate, a laminate can be obtained in which the semiconductor substrate and other workpieces are peeled from the support substrate without applying excessive load for peeling, and by light irradiation such as laser irradiation.

[0049] Furthermore, the discoloration or staining of the release agent composition of the present invention over time is suppressed, exhibiting excellent storage stability. Therefore, for example, the amount of release agent composition that has been prepared to date can be prepared in advance, resulting in efficient use of manufacturing equipment, and thus it is expected to reduce the manufacturing cost of the release agent composition itself and the cost of semiconductor devices manufactured using the release agent composition. Detailed Implementation

[0050] The laminate of the present invention comprises: a first substrate made of a semiconductor substrate, a second substrate made of a light-transmitting support substrate, and an adhesive layer and a release layer between the first substrate and the second substrate, wherein the release layer is a film obtained by a release agent composition comprising at least one of an acid-generating agent and an acid, a polyphenol derivative of formula (P), and a crosslinking agent.

[0051]

[0052] (In the formula, Ar represents an aryl group with 6 to 60 carbon atoms.)

[0053] The first substrate, which is composed of a semiconductor substrate, is, for example, a wafer. Specific examples include glass wafers with a diameter of about 300 mm and a thickness of about 770 μm and silicon wafers, but it is not limited to these.

[0054] The second substrate, which is composed of a support substrate, is a support (carrier) joined to support the first substrate. It is not particularly limited as long as it is transparent. As a specific example, a glass wafer with a diameter of about 300 mm and a thickness of about 700 μm can be listed, but it is not limited to this.

[0055] The transmittance of the light-transmitting support substrate is typically 50% or more, preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and even more preferably 90% or more.

[0056] Typically, the transparent support substrate is a substrate that transmits laser light, with the wavelength of such laser typically ranging from 190 nm to 600 nm. The lower limit of this laser is 250 nm in one embodiment and 300 nm in another, while the upper limit is 580 nm in one embodiment and 560 nm in another. The laminate of this invention can be appropriately peeled off using lasers with wavelengths of 308 nm, 343 nm, 355 nm, or 532 nm.

[0057] In a preferred embodiment, the laminate of the present invention comprises: a first substrate made of a semiconductor substrate, a second substrate made of a light-transmitting support substrate, and an adhesive layer disposed between the first substrate and the second substrate and disposed in contact with the first substrate and a release layer disposed in contact with the second substrate and the adhesive layer.

[0058] In the case of the laminate of the present invention, by irradiating the release layer with a laser from the light-transmitting second substrate side, for example, it is possible to peel without applying excessive load for peeling. Here, "able to peel" means that the adhesive strength is lower than that of other parts, that is, the peelability is excellent and it is easy to peel. The release layer of the laminate of the present invention has a reduced adhesive strength than before irradiation, for example, by laser irradiation. That is, in the laminate of the present invention, for example, during the thinning or other processing of the wafer on the first substrate made of a wafer and the second substrate made of a laser-transmitting support substrate, the wafer is properly supported by the adhesive layer and the release layer. After the processing is completed, by irradiating the second substrate side with a laser, the laser transmitted through the second substrate is absorbed by the release layer, and separation of the release layer occurs at the interface between the release layer and the adhesive layer, the interface between the release layer and the support, or inside the release layer. As a result, proper peeling can be achieved without applying excessive load for peeling.

[0059] As described above, the release layer of the laminate of the present invention is a film obtained from a release agent composition comprising at least one of an acid-producing agent and an acid, a polyphenol derivative of formula (P), and a crosslinking agent.

[0060]

[0061] In the formula, Ar represents arylene, and its number of carbon atoms is not particularly limited, usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release layer with better reproducibility and higher flatness, its number of carbon atoms is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and even more preferably 12 or less.

[0062] Specific examples of such aryl groups include: 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthylene, 1,8-naphthylene, 2,6-naphthylene, 2,7-naphthylene, 1,2-anthraylene, 1,3-anthraylene, 1,4-anthraylene, 1,5-anthraylene, 1,6-anthraylene, 1,7-anthraylene, 1,8-anthraylene, 2,3-anthraylene, 2,6-anthraylene, 2,7-anthraylene, 2,9-anthraylene, 2,10-anthraylene, 9,10-anthraylene, etc., derived by removing hydrogen atoms from the aromatic rings of two condensed-ring aromatic hydrocarbon compounds; biphenyl-4,4'-diyl, p-terphenyl-4,4”-diyl, etc., derived by removing hydrogen atoms from the aromatic rings of two ring-linked aromatic hydrocarbon compounds, etc., but are not limited to these.

[0063] From the viewpoint of producing a release layer with good peelability and a laminate with good reproducibility that can be well separated from the support substrate, the polynucleophenol derivative shown in formula (P) is preferably the polynucleophenol derivative shown in formula (P-1), more preferably the polynucleophenol derivative shown in formula (P-1-1), and even more preferably the polynucleophenol derivative shown in formula (P1).

[0064]

[0065] The above-mentioned stripping agent composition contains a crosslinking agent.

[0066] As specific examples of such crosslinking agents, there are no particular limitations as long as they can crosslink with the aforementioned polycyclic phenol derivatives. Typical examples include phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, and thiourea crosslinking agents that have crosslinking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl, etc. in the molecule. These can be low molecular weight compounds or high molecular weight compounds.

[0067] The crosslinking agent containing the above-mentioned stripping agent composition usually has two or more crosslinking forming groups, but from the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking forming groups contained in the compound as a crosslinking agent is preferably 2 to 10, more preferably 2 to 6.

[0068] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the above-mentioned stripping agent composition preferably has an aromatic ring (e.g., benzene ring, naphthalene ring) in the molecule. Phenolic crosslinking agents are typical examples of such crosslinking agents, but are not limited thereto.

[0069] A phenolic crosslinking agent having a crosslinking forming group refers to a compound having a crosslinking forming group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of such alkoxy groups derived from the phenolic hydroxyl group include methoxy and butoxy, but it is not limited to these.

[0070] The aromatic rings bonded by the cross-linking groups and the aromatic rings bonded by the phenolic hydroxyl groups and / or the alkoxy groups derived from the phenolic hydroxyl groups are not limited to non-condensed aromatic rings such as benzene rings, but can also be condensed aromatic rings such as naphthalene rings and anthracene rings.

[0071] In the case of multiple aromatic rings within the molecule of a phenolic crosslinking agent, the crosslinking forming group, as well as the phenolic hydroxyl group and the alkoxy group derived from the phenolic hydroxyl group, can be bonded to the same aromatic ring within the molecule, or they can be bonded to different aromatic rings.

[0072] The cross-linking group, the phenolic hydroxyl group, and the aromatic ring bonded by the phenolic hydroxyl group are optionally further replaced by alkyl groups such as methyl, ethyl, and butyl, hydrocarbon groups such as aryl groups such as phenyl, halogen atoms, etc.

[0073] For example, as specific examples of phenolic crosslinking agents having crosslinking forming groups, compounds represented by any of the formulas (L1) to (L4) can be listed.

[0074]

[0075] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, and each R” independently represents a hydrogen atom or an alkyl group, L 1 and L 2 Each independently represents a single bond, methylene or propane-2,2-diyl, L 3Based on q1, t11, t12, and t13 are integers satisfying 2≤t11≤5, 1≤t12≤4, 0≤t13≤3, and t11+t12+t13≤6. t21, t22, and t23 are integers satisfying 2≤t21≤4, 1≤t22≤3, 0≤t23≤2, and t21+t22+t23≤5. t24, t25, and t26 are integers satisfying 2≤t24≤4, 1≤t25≤3, 0≤t26≤2, and t24+t25+t26≤5. t27, t28, and t29 are integers satisfying 0≤t27. The integers ≤4, 0≤t28≤4, 0≤t29≤4, and t27+t28+t29≤4, t31, t32, and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2, and t31+t32+t33≤5, t41, t42, and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1, and t41+t42+t43≤4, q1 is 2 or 3, q2 represents the number of repetitions and is an integer greater than or equal to 0. As specific examples of the above aryl and alkyl groups, the same aryl and alkyl groups as the specific examples below can be listed. As an aryl group, phenyl is preferred, and as an alkyl group, methyl and tert-butyl are preferred.

[0076] The following are specific examples of compounds represented by formulas (L1) to (L4), but are not limited to these examples. It should be noted that these compounds can be synthesized by known methods, and can also be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd.

[0077]

[0078]

[0079] A melamine-based crosslinking agent having a crosslinking-forming group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative formed by replacing at least one hydrogen atom of the amino group bonded to its triazine ring with a crosslinking-forming group, wherein the triazine ring optionally also has substituents such as phenyl or aryl groups.

[0080] Specific examples of melamine-based crosslinking agents with crosslinking-forming groups include: N,N,N',N',N",N"-hexa(methoxymethyl)melamine; N,N,N',N',N",N"-hexa(butoxymethyl)melamine and other mono-, bis-, tri-, tetra-, penta-, or hexaalkoxymethylmelamines; N,N,N',N'-tetra(methoxymethyl)benzoguanamine; N,N,N',N'-tetra(butoxymethyl)benzoguanamine and other mono-, bis-, tri-, or tetraalkoxymethylbenzoguanamines, but are not limited to these.

[0081] Urea-based crosslinking agents with crosslinking-forming groups are derivatives of compounds containing urea bonds, which have a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is replaced by a crosslinking-forming group.

[0082] Specific examples of urea-based crosslinking agents having crosslinking-forming groups include: 1,3,4,6-tetra(methoxymethyl)glycourea; 1,3,4,6-tetra(butoxymethyl)glycourea, etc. (mono, di, tri, or tetraalkoxymethylglycoureas); 1,3-bis(methoxymethyl)urea; 1,1,3,3-tetramethoxymethylurea, etc. (mono, di, tri, or tetraalkoxymethylureas), etc., but are not limited to these.

[0083] Thiourea-based crosslinking agents with crosslinking-forming groups refer to derivatives of compounds containing thiourea bonds, which have a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is replaced by a crosslinking-forming group.

[0084] Specific examples of thiourea-based crosslinking agents having crosslinking-forming groups include: 1,3-bis(methoxymethyl)thiourea; 1,1,3,3-tetramethoxymethylthiourea, etc., as well as mono-, bis-, tri-, or tetra-alkoxymethylthioureas, but are not limited to these.

[0085] The amount of crosslinking agent contained in the above-mentioned release agent composition varies depending on the coating method used, the desired film thickness, etc., and therefore cannot be specified in general terms. It is usually 0.001 to 80% by mass relative to the film composition. From the viewpoint of achieving proper curing and obtaining a laminate with good reproducibility that can be well separated from the support substrate, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0086] It should be noted that, in this invention, the membrane constituents refer to components other than the solvent contained in the composition.

[0087] The crosslinking agent contained in the above-mentioned stripping agent composition can undergo a crosslinking reaction based on self-condensation between crosslinking agents, but it can also undergo a crosslinking reaction with the polycyclic phenol derivative contained in the composition to ultimately form a cured film.

[0088] The above-described stripping agent composition contains at least one of an acid-generating agent and an acid. The acid-generating agent and the acid promote the crosslinking reaction, which helps to obtain a properly cured film with good reproducibility.

[0089] Examples of acid-producing agents include, for example, thermal acid-producing agents and photo-producing acid-producing agents.

[0090] There are no particular limitations on thermally generated acid-producing agents, as long as they can produce acid through heat. Specific examples include: 2,4,4,6-tetrabromocyclohexadienone; benzoin tosylate; 2-nitrobenzyl tosylate; K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries); and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.) and other organic alkyl sulfonic acid esters, but they are not limited to these.

[0091] Examples of photoacid-generating agents include, for example, onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0092] Specific examples of onionium salt compounds include: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, and other iodonium salt compounds; triphenylthionium hexafluoroantimonate, triphenylthionium nonafluoron-butane sulfonate, triphenylthionium camphor sulfonate, triphenylthionium trifluoromethane sulfonate, and other thionium salt compounds, but are not limited to these.

[0093] Specific examples of sulfonylimide compounds include: N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenediformimide, etc., but are not limited to these.

[0094] Specific examples of disulfonyl diazonium methane compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyl diazonium methane, etc., but are not limited to these.

[0095] Specific examples of acids include: p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzene disulfonic acid, 1-naphthalenesulfonic acid, and other aryl sulfonic acids, pyridinium salts, and their salts; salicylic acid, benzoic acid, hydroxybenzoic acid, naphtholic acid, and other aryl carboxylic acids, and their salts; trifluoromethanesulfonic acid, camphorsulfonic acid, and other chain or cyclic alkyl sulfonic acids and their salts; citric acid and other chain or cyclic alkyl carboxylic acids and their salts, but are not limited to these.

[0096] The amounts of acid-generating agent and acid contained in the above-mentioned release agent composition vary depending on the type of crosslinking agent used, heating temperature, etc., and therefore cannot be specified in general terms. The amounts of acid-generating agent and acid contained in the above-mentioned release agent composition are generally 0.01% to 5% by mass relative to the film composition. From the viewpoint of achieving proper curing and obtaining a laminate with good reproducibility that can be well separated from the support substrate, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0097] The above-described stripping agent composition may also include a solvent for purposes such as viscosity adjustment. For example, a highly soluble solvent capable of readily dissolving components such as polyphenol derivatives can be used, or a low-polarity solvent may be used as needed for purposes such as viscosity and surface tension adjustment. It should be noted that, in this invention, a low-polarity solvent is defined as a solvent with a relative permittivity of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as a solvent with a relative permittivity of 7 or higher at a frequency of 100 kHz. Solvents may be used alone or in combination of two or more.

[0098] In addition, examples of highly polar solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyanide solvents such as acetonitrile and 3-methoxypropionitrile; polyol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0099] Examples of low-polarity solvents include: chlorinated solvents such as chloroform and chlorobenzene; aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester 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.

[0100] When the above-mentioned stripping agent composition contains a solvent, its content is appropriately set taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is less than 99% by mass of the total composition.

[0101] The viscosity and surface tension of the above-mentioned stripping agent composition are appropriately adjusted by changing the type and ratio of the organic solvent used, the concentration of the film components, etc., taking into account various factors such as the coating method used and the desired film thickness.

[0102] In a preferred embodiment, the stripping agent composition comprises a solvent. Its amount is 80-99% by mass relative to the total composition, that is, in this case, the amount of the film-forming component is 1-20% by mass relative to the total composition.

[0103] In one aspect of the present invention, from the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the above-mentioned stripping agent composition comprises a glycol-based solvent. It should be noted that "glycol-based solvent" here refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0104] An example of a preferred diol solvent is represented by formula (G).

[0105]

[0106] In formula (G), R G1 Each independently represents a straight-chain or branched alkylene group having 2 to 4 carbon atoms, R G2 and R G3 Each group independently represents a hydrogen atom, an alkyl group consisting of 1 to 8 straight-chain or branched carbon atoms, or an alkyl group whose alkyl portion is a straight-chain or branched alkyl group consisting of 1 to 8 carbon atoms, n g It is an integer from 1 to 6.

[0107] Specific examples of straight-chain or branched alkylene groups with 2 to 4 carbon atoms include: ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, etc., but are not limited to these.

[0108] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, straight-chain or branched alkylene groups with 2 to 3 carbon atoms are preferred, and straight-chain or branched alkylene groups with 3 carbon atoms are more preferred.

[0109] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-propyl. n-Amyl, 4-methyln-amyl, 1,1-dimethyln-butyl, 1,2-dimethyln-butyl, 1,3-dimethyln-butyl, 2,2-dimethyln-butyl, 2,3-dimethyln-butyl, 3,3-dimethyln-butyl, 1-ethyln-butyl, 2-ethyln-butyl, 1,1,2-trimethyln-propyl, 1,2,2-trimethyln-propyl, 1-ethyl-1-methyln-propyl, 1-ethyl-2-methyln-propyl, etc., but not limited to these.

[0110] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl and ethyl are preferred, and methyl is more preferred.

[0111] Among the alkyl acyl groups of a straight-chain or branched alkyl group having 1 to 8 carbon atoms, specific examples of such straight-chain or branched alkyl groups having 1 to 8 carbon atoms can be listed as the same groups as the specific examples mentioned above.

[0112] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl carbonyl and ethyl carbonyl are preferred, and methyl carbonyl is more preferred.

[0113] From the perspectives of obtaining compositions with good reproducibility and high uniformity, obtaining compositions with good reproducibility and high storage stability, and obtaining compositions with good reproducibility that provide highly uniform films, n g Preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0114] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, R is preferred in formula (G). G2 and R G3 At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably R G2 and R G3One of them is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, and the other is an alkyl acyl group with hydrogen atoms or an alkyl part having 1 to 8 carbon atoms in a straight-chain or branched alkyl group.

[0115] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the content of the glycol 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 stripping agent composition.

[0116] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility and providing a film with high uniformity, the film components in the above-mentioned stripping agent composition are uniformly dispersed or dissolved in a solvent, preferably dissolved in a solvent.

[0117] The above-mentioned stripping agent composition can be manufactured by mixing the polyphenol derivative of formula (P), a crosslinking agent, an acid-producing agent and / or an acid, and a solvent as used.

[0118] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing a stripping agent composition, the following methods can be listed: dissolving the polyphenol derivative, crosslinking agent, and acid-producing agent and / or acid shown in formula (P) in a solvent in one step; dissolving a portion of the polyphenol derivative, crosslinking agent, and acid-producing agent and / or acid shown in formula (P) in a solvent, dissolving the remaining portion separately in a solvent, and mixing the resulting solutions. However, this method is not limited to these methods. It should be noted that when preparing the stripping agent composition, appropriate heating may be applied within a range that does not cause the components to decompose or deteriorate.

[0119] In this invention, for the purpose of removing foreign matter, filtration can also be performed using a submicron-sized filter or the like during the manufacturing of the stripping agent composition or after all the components have been mixed.

[0120] The thickness of the release layer in the laminate of the present invention is typically 10 nm to 10 μm.

[0121] The release agent composition described above is also the subject of this invention, and the relevant conditions (appropriate conditions, manufacturing conditions, etc.) are as described above. By using the release agent composition of this invention, films suitable for use in the manufacture of semiconductor devices, for example, can be manufactured with good reproducibility.

[0122] The adhesive layer of the laminate of the present invention may, for example, be a film obtained from an adhesive composition containing adhesive component (S).

[0123] Such adhesive component (S) is not particularly limited as long as it is an adhesive component used for this purpose. Examples include: silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, phenolic resin adhesives, etc., but it is not limited to these.

[0124] Among these considerations, silicone-based adhesives are preferred as adhesive components (S) because they exhibit appropriate adhesion during the processing of wafers, can be properly peeled off after processing, and have excellent heat resistance.

[0125] In a preferred embodiment, the adhesive composition used in this invention comprises a polyorganosiloxane component (A) cured by a hydrosilylation reaction as an adhesive component. In a more preferred example, the polyorganosiloxane component (A) cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises siloxane units (Q units) selected from SiO2 and R... 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit) and R shown are shown. 4 R 5 SiO 2 / 2 The siloxane unit (D unit) and R shown are shown. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units from the group consisting of the shown siloxane units (T units), wherein the polysiloxane (A1) includes polyorganosiloxane (a1) and polyorganosiloxane (a2), and the polyorganosiloxane (a1) includes siloxane units (Q' units) selected from SiO2 and R... 1 'R 2 'R 3 'SiO 1 / 2 The siloxane unit (M' unit) and R shown are shown. 4 'R 5 'SiO 2 / 2 The siloxane unit (D' unit) and R shown are shown. 6 'SiO 3 / 2 The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of the siloxane units (T' units) shown, and includes at least one unit selected from the group consisting of the M' units, D' units, and T' units described above.1 R 2 R 3 "SiO" 1 / 2 The siloxane unit (M” unit) and R shown 4 R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R shown are shown. 6 "SiO" 3 / 2 The siloxane unit (T” unit) shown is one or more units from the group consisting of the siloxane unit (T” unit) shown, and includes at least one unit selected from the group consisting of the M” unit, D” unit and T” unit.

[0126] R 1 ~R 6 The groups or atoms bonded to silicon atoms are represented independently as alkyl, alkenyl, or hydrogen atoms, respectively.

[0127] R 1 '~R 6 'A group bonded to a silicon atom, independently representing either an alkyl or alkenyl group, R 1 '~R 6 At least one of them is an alkenyl group.

[0128] R 1 "~R 6 "R represents a group or atom bonded to a silicon atom, and is independently represented by an alkyl group or a hydrogen atom." 1 "~R 6 At least one of them is a hydrogen atom.

[0129] The alkyl group can be any of straight-chain, branched, or cyclic, preferably straight-chain or branched alkyl groups. The number of carbon atoms is not particularly limited, usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0130] Specific examples of straight-chain or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4 -Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these.

[0131] Among them, methyl is preferred.

[0132] Specific examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl Cycloalkyl groups such as 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, as well as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc., but not limited to these.

[0133] The alkenyl group can be any of straight-chain or branched, and its number of carbon atoms is not particularly limited, usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0134] Specific examples of alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl 3-Methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-di Methyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2 The range includes, but is not limited to, methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl.

[0135] Among them, vinyl and 2-propylene groups are preferred.

[0136] As described above, polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). The alkenyl group contained in polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2) form a cross-linked structure and are cured through a hydrosilylation reaction based on a platinum group metal catalyst (A2).

[0137] The polyorganosiloxane (a1) comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and comprises at least one unit selected from the group consisting of the aforementioned M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying this condition may also be used in combination as the polyorganosiloxane (a1).

[0138] As for two or more preferred combinations selected from the group consisting of Q' unit, M' unit, D' unit and T' unit, examples include: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.

[0139] Furthermore, when the polyorganosiloxane contained in the polyorganosiloxane (a1) contains two or more types of polyorganosiloxanes, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited thereto.

[0140] The polyorganosiloxane (a2) comprises one or more units selected from the group consisting of Q” units, M” units, D” units and T” units, and comprises at least one unit selected from the group consisting of the aforementioned M” units, D” units and T” units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0141] As a preferred combination of two or more selected from the group consisting of Q” unit, M” unit, D” unit and T” unit, examples include: (M” unit and D” unit), (Q” unit and M” unit), (Q” unit, T” unit and M” unit), but it is not limited to these.

[0142] Polyorganosiloxanes (a1) are composed of siloxane units formed by the bonding of alkyl and / or alkenyl groups to their silicon atoms, R 1 '~R 6 The proportion of alkenyl groups in all the substituents shown is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, with the remaining R... 1 '~R 6 'It can be set as an alkyl group.'

[0143] Polyorganosiloxanes (a2) are composed of siloxane units formed by the bonding of alkyl and / or hydrogen atoms with their silicon atoms, R 1 "~R 6 The proportion of all substituents and hydrogen atoms in the substituted atoms shown is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, with the remaining R... 1 "~R 6 "It can be set as an alkyl group."

[0144] Polysiloxane (A1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2). In a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in polyorganosiloxane (a1) to the hydrogen atoms constituting Si-H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0145] The weight-average molecular weights of polyorganosiloxane (a1) and polyorganosiloxane (a2) are typically 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0146] It should be noted that the weight-average molecular weight, number-average molecular weight, and dispersity in this invention can be determined using, for example, a GPC apparatus (Tosoh Corporation EcoSEC, HLC-8320GPC) and a GPC column (Tosoh Corporation TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Sigma-Aldrich) used as the standard sample.

[0147] The viscosities of the polyorganosiloxanes (a1) and (a2) are typically 10 to 1,000,000 mPa·s, and preferably 50 to 10,000 mPa·s from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the viscosity in the present invention is a value measured using an E-type rotational viscometer at 25°C.

[0148] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other through a hydrosilylation reaction to form a film. Therefore, their curing mechanism is different from that via silanol groups, and thus, no siloxane needs to contain functional groups such as silanol groups or alkyloxy groups that form silanol groups through hydrolysis.

[0149] In a preferred embodiment of the invention, the adhesive component (S) also includes the polysiloxane (A1) and platinum group metal catalyst (A2) described above.

[0150] Such platinum-based metal catalysts are used to promote the hydrosilylation reaction of the alkenyl group of polyorganosiloxane (a1) with the Si-H group of polyorganosiloxane (a2).

[0151] Specific examples of platinum-based metal catalysts include: platinum black, platinum dichloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, the complex of chloroplatinic acid and an olefin, and platinum diacetate, but are not limited to these.

[0152] As a platinum-olefin complex, for example, a platinum-divinyltetramethyldisiloxane complex can be listed, but is not limited to this.

[0153] The amount of platinum group metal catalyst (A2) is typically in the range of 1.0 to 50.0 ppm relative to the combined amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0154] The polyorganosiloxane component (A) may also contain a polymerization inhibitor (A3) for the purpose of inhibiting the hydrosilylation reaction.

[0155] There are no particular limitations on polymerization inhibitors as long as they can inhibit the hydrosilylation reaction. Specific examples include 1-ethynyl-1-cyclohexanol, 1,1-diphenyl-2-propynyl-1-ol, and other alkynyl alcohols.

[0156] From the viewpoint of achieving its effect, the amount of polymerization inhibitor relative to the combined amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) is usually above 1000.0 ppm, while from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction, the amount of polymerization inhibitor relative to the combined amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) is usually below 10000.0 ppm.

[0157] The adhesive composition used in this invention may also contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in this invention, the adhesive layer can be reproducibly and appropriately peeled off.

[0158] As such a stripping agent component (B), typically, polyorganosiloxanes can be listed, and specific examples include: epoxy-modified polyorganosiloxanes, methyl-containing polyorganosiloxanes, phenyl-containing polyorganosiloxanes, etc., but are not limited to these.

[0159] The complex viscosity of the polyorganosiloxane used as the release agent component (B) is not particularly limited, but from the viewpoint of obtaining an adhesive layer with good reproducibility and excellent peelability and adhesion, it is generally 100 to 10,000 Pa·s. In this invention, the complex viscosity of the polyorganosiloxane used as the release agent component (B) refers to the value measured using a rheometer at 25°C. Such a complex viscosity can be measured, for example, using an Anton Paar MCR-302 rheometer.

[0160] Preferred examples of polyorganosiloxanes as stripping agent component (B) include, but are not limited to, epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, and phenyl-containing polyorganosiloxanes.

[0161] The weight-average molecular weight of the polyorganosiloxane used as the stripping agent component (B) is typically 100,000 to 2,000,000, and preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, from the viewpoint of achieving the effects of the present invention with good reproducibility. Its dispersibility is typically 1.0 to 10.0, and preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the weight-average molecular weight and dispersibility can be determined by the methods described above.

[0162] As epoxy-containing polyorganosiloxanes, examples include those containing R 11 R 12 SiO 2 / 2 The siloxane unit shown (D) 10 Polyorganosiloxane (unit).

[0163] R 11 The group that bonds to silicon atoms represents an alkyl group, R. 12 The group that bonds to silicon atoms represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be listed above.

[0164] Furthermore, the epoxy group in an organic group containing an epoxy group can be an independent epoxy group that does not condense with other rings, or it can be an epoxy group that forms a condensation ring with other rings, such as 1,2-epoxycyclohexyl.

[0165] Specific examples of organic groups containing epoxy groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these.

[0166] In this invention, epoxy-modified polydimethylsiloxane is a preferred example of an epoxy-containing polyorganosiloxane, but it is not limited thereto.

[0167] Epoxy-containing polyorganosiloxanes comprise the aforementioned siloxane units (D 10 Unit), except D 10 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0168] In a preferred embodiment of the invention, specific examples of epoxy-containing polyorganosiloxanes include: those consisting only of D 10 Polyorganosiloxanes composed of units; containing D 10 Polyorganosiloxanes containing D and Q units; 10 Polyorganosiloxanes containing D and M units; 10 Polyorganosiloxanes containing D and T units; 10 Polyorganosiloxanes containing D, Q, and M units; 10 Polyorganosiloxanes containing D, M, and T units; 10 Polyorganosiloxanes with units such as Q-unit, M-unit, and T-unit.

[0169] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane with an epoxy value of 0.1 to 5, and its weight-average molecular weight is usually 1,500 to 500,000. From the viewpoint of inhibiting precipitation in the adhesive, it is preferably 100,000 or less.

[0170] Specific examples of epoxy-containing polyorganosiloxanes include those represented by formulas (E1) to (E3), but are not limited to these.

[0171]

[0172] (m1 and n1 represent the number of each repeating unit, which are positive integers.)

[0173]

[0174] (m2 and n2 represent the number of each repeating unit, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms.)

[0175]

[0176] (m3, n3, and o3 represent the number of each repeating unit, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms.)

[0177] As methyl-containing polyorganosiloxanes, for example, those containing R 210 R 220 SiO 2 / 2 The siloxane unit shown (D) 200 Polyorganosiloxanes (units), preferably containing R 21 R 21 SiO 2 / 2 The siloxane unit shown (D) 20 Polyorganosiloxane (unit).

[0178] R 210 and R 220 The groups bonded to silicon atoms are each independently represented as alkyl groups, with at least one being methyl. The examples above can be cited as specific examples of alkyl groups.

[0179] R 21 The group that bonds to a silicon atom is represented by an alkyl group, and the examples above can be cited as specific examples of alkyl groups. Wherein, as R 21 Methyl group is preferred.

[0180] In this invention, polydimethylsiloxane is cited as a preferred example of a methyl-containing polyorganosiloxane, but it is not limited thereto.

[0181] Methyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D... 200 Unit or D 20 Unit), except D 200 Unit and D 20 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0182] In one aspect of the present invention, as a specific example of a methyl-containing polyorganosiloxane, the following can be listed: consisting only of D 200 Polyorganosiloxanes composed of units; containing D 200 Polyorganosiloxanes containing D and Q units; 200 Polyorganosiloxanes containing D and M units; 200 Polyorganosiloxanes containing D and T units; 200 Polyorganosiloxanes containing D, Q, and M units; 200 Polyorganosiloxanes containing D, M, and T units; 200 Polyorganosiloxanes with units of Q, M, and T.

[0183] In a preferred embodiment of the invention, specific examples of methyl-containing polyorganosiloxanes include: those consisting only of D 20 Polyorganosiloxanes composed of units; containing D 20 Polyorganosiloxanes containing D and Q units; 20 Polyorganosiloxanes containing D and M units; 20 Polyorganosiloxanes containing D and T units; 20 Polyorganosiloxanes containing D, Q, and M units; 20 Polyorganosiloxanes containing D, M, and T units; 20 Polyorganosiloxanes with units of Q, M, and T.

[0184] As specific examples of methyl-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes of formula (M1) can be listed, but are not limited thereto.

[0185]

[0186] (n4 represents the number of repeating units, which is a positive integer.)

[0187] As phenyl-containing polyorganosiloxanes, examples include those containing R 31 R 32 SiO 2 / 2 The siloxane unit shown (D) 30 (unit) phenyl-containing polyorganosiloxanes.

[0188] R 31 The group that bonds to silicon atoms represents a phenyl or alkyl group, R. 32 The group that bonds to silicon atoms is represented by phenyl. Specific examples of alkyl groups can be listed above, with methyl being preferred.

[0189] Phenyl-containing polyorganosiloxanes comprise the aforementioned siloxane units (D 30 Unit), except D 30 In addition to the unit, it may also include the above-mentioned Q unit, M unit and / or T unit.

[0190] In a preferred embodiment of the invention, specific examples of phenyl-containing polyorganosiloxanes include: those consisting only of D 30 Polyorganosiloxanes composed of units; containing D 30 Polyorganosiloxanes containing D and Q units; 30 Polyorganosiloxanes containing D and M units; 30 Polyorganosiloxanes containing D and T units; 30 Polyorganosiloxanes containing D, Q, and M units; 30 Polyorganosiloxanes containing D, M, and T units; 30 Polyorganosiloxanes with units of Q, M, and T.

[0191] Specific examples of methyl-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

[0192]

[0193] (m5 and n5 represent the number of each repeating unit, which are positive integers.)

[0194]

[0195] (m6 and n6 represent the number of each repeating unit, which are positive integers.)

[0196] In a preferred embodiment, the adhesive composition used in this invention comprises a polyorganosiloxane component (A) cured by a hydrosilanization reaction and a release agent component (B). In a preferred embodiment, the polyorganosiloxane is included as the release agent component (B).

[0197] The adhesive composition used in this invention may contain adhesive component (S) and release agent component (B) in any ratio. Considering the balance between adhesion and release properties, the ratio of component (S) to component (B) by mass is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0198] That is, when the polyorganosiloxane component (A) is included and cured by the hydrosilanization reaction, the ratio of component (A) to component (B) by mass is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0199] The adhesive composition used in this invention may also contain solvents for purposes such as viscosity adjustment. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but it is not limited thereto.

[0200] More specifically, examples include: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.

[0201] When the adhesive composition used in this invention contains a solvent, its content is appropriately set taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is in the range of about 10 to 90% by mass relative to the total composition.

[0202] The viscosity of the adhesive composition used in this invention is typically 500–20000 mPa·s at 25°C, preferably 1000–5000 mPa·s. The viscosity of the adhesive composition of this invention can be adjusted by changing the type and ratio of the organic solvent used, the concentration of film components, etc., taking into account various factors such as the coating method used and the desired film thickness.

[0203] The adhesive composition used in this invention can be manufactured by mixing the adhesive component (S) with the release agent component (B) and solvent as used in the case of application.

[0204] The mixing order is not particularly limited. As an example of a method for easily and reproducibly preparing an adhesive composition, examples include: dissolving the adhesive component (S) and the release agent component (B) in a solvent; dissolving a portion of the adhesive component (S) and the release agent component (B) in a solvent, dissolving the remaining portion in the solvent, and mixing the resulting solutions. However, this method is not limited to these methods. It should be noted that when preparing the adhesive composition, appropriate heating may be applied within a range that does not cause the components to decompose or deteriorate.

[0205] In this invention, for the purpose of removing foreign matter, the adhesive composition may be filtered using a submicron-sized filter or the like during the manufacturing process of the adhesive composition or after all the components have been mixed.

[0206] The thickness of the adhesive layer in the laminate of the present invention is typically 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick film, the thickness of the adhesive layer in the laminate of the present invention is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

[0207] The laminate of the present invention can be manufactured, for example, by a method comprising the following steps: a first step, applying an adhesive composition to the surface of a first substrate and heating it to form an adhesive coating layer; a second step, applying a release agent composition to the surface of a second substrate and heating it to form a release agent coating layer; and a third step, while subjecting the adhesive coating layer of the first substrate and the release agent coating layer of the second substrate to at least one of heat treatment and decompression treatment, applying a load in the thickness direction of the first substrate and the second substrate to make them adhere, and then performing a post-heat treatment, thereby producing the laminate.

[0208] Here, the adhesive composition can be applied to the first substrate and the release agent composition can be applied to the second substrate separately, and then heated. However, as long as the effect of the present invention is not impaired, the adhesive composition and the release agent composition can be applied to either substrate in sequence and then heated. The order of application is also arbitrary. In the present invention, from the viewpoint of obtaining a laminate that can be well separated from the second substrate with good reproducibility, it is preferable to apply the adhesive composition to the surface of the first substrate to form an adhesive coating layer and apply the release agent composition to the surface of the second substrate to form a release agent coating layer.

[0209] More specifically, an adhesive composition or a release agent composition can be applied to the circuit surface of a wafer serving as a first substrate or the surface of a support serving as a second substrate, and then heated to form an adhesive coating layer or a release agent coating layer, respectively. The circuit surface of the wafer and the surface of the support are then joined together in a manner that the two coating layers are in contact. While performing heat treatment or depressurization treatment, or both, a load in the thickness direction of the first substrate and the second substrate is applied to make the two layers adhere tightly. Then, a post-heat treatment is performed to manufacture a laminate.

[0210] There are no particular limitations on the coating method; spin coating is the most common. It should be noted that a separate coating film can be formed using spin coating or other methods, and then a sheet-like coating film can be attached. This is also called coating or coating film.

[0211] The heating temperature of the coated adhesive composition varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the desired thickness of the adhesive layer, etc., so it cannot be specified in general terms. The heating temperature of the coated adhesive composition is usually 80℃ to 150℃, and the heating time is usually 30 seconds to 5 minutes.

[0212] The heating temperature of the applied release agent composition varies depending on the type and amount of crosslinking agent, acid-generating agent or acid, whether it contains solvent, and the desired thickness of the release layer. Therefore, it cannot be specified in general terms. From the viewpoint of achieving proper curing with good reproducibility, the heating temperature of the applied release agent composition is above 120°C. From the viewpoint of preventing over-curing, the heating temperature of the applied release agent composition is below 400°C, and the heating time is usually 1 to 10 minutes.

[0213] Heating can be done using heating plates, ovens, etc.

[0214] The thickness of the adhesive coating layer obtained by coating the adhesive composition and heating it is typically around 5 to 500 μm, and is appropriately determined in a way that ultimately results in the thickness range of the adhesive layer described above.

[0215] The thickness of the release agent coating layer obtained by coating the release agent composition and heating it is typically around 10 nm to 10 μm, and is appropriately determined in a way that ultimately becomes the thickness range of the release layer described above.

[0216] In this invention, such coating layers can be joined together in an adjoint manner, and while performing heat treatment or depressurization treatment, or both, a load in the thickness direction of the first and second substrates is applied to bring the two layers into close contact. Then, a post-heat treatment is performed, thereby obtaining the laminate of this invention. It should be noted that the choice of heat treatment, depressurization treatment, or a combination of both is determined based on various factors such as the type of adhesive composition, the specific composition of the release agent composition, the phase properties of the films obtained from the two compositions, the film thickness, and the calculated adhesive strength.

[0217] From the viewpoints of softening the adhesive coating layer to achieve proper adhesion with the release agent coating layer and achieving proper curing of the release agent coating layer, the heat treatment is generally appropriately determined within the range of 20 to 150°C. In particular, from the viewpoint of suppressing / avoiding excessive curing and unwanted deterioration of the adhesive component (S), the heat treatment is preferably below 130°C, more preferably below 90°C. From the viewpoint of reliably demonstrating adhesive ability, the heating time is generally 30 seconds or more, preferably 1 minute or more. From the viewpoint of suppressing deterioration of the adhesive layer and other components, the heating time is generally 10 minutes or less, preferably 5 minutes or less.

[0218] The decompression treatment simply involves exposing the adhesive coating layers and release agent coating layers that are in contact with each other to a pressure of 10 Pa to 10,000 Pa. The decompression treatment time is usually 1 to 30 minutes.

[0219] From the viewpoint of obtaining a laminate with good reproducibility that allows for good separation of the support substrate, the adhesive coating layer and the release agent coating layer that are in contact with each other are preferably bonded by decompression treatment, and more preferably by a combination of heat treatment and decompression treatment.

[0220] The loads in the thickness direction of the first substrate and the second substrate are not particularly limited as long as they do not adversely affect the first substrate and the second substrate and the two layers between them, and can firmly seal them together. They are usually in the range of 10 to 1000 N.

[0221] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher; from the viewpoint of preventing deterioration of the substrate and adhesive, the post-heating temperature is preferably 260°C or lower. From the viewpoint of achieving proper bonding between the substrate and layers constituting the laminate, the heating time is typically 1 minute or more, preferably 5 minutes or more; from the viewpoint of avoiding adverse effects on the adhesive layer and release layer caused by excessive heating, the heating time is typically 180 minutes or less, preferably 120 minutes or less. Heating is performed using a heating plate, oven, or the like.

[0222] It should be noted that one of the purposes of post-heat treatment is to allow the adhesive component (S) to cure more properly.

[0223] The peeling method of the present invention is as follows: Light is irradiated onto the release layer from the second substrate side of the laminate of the present invention, separating the second substrate from the first substrate and the adhesive layer. In the laminate of the present invention, the first substrate and the light-transmitting second substrate are temporarily bonded in a manner that allows for proper peeling through the adhesive layer and the light-absorbing release layer. Therefore, when a laser is irradiated from the second substrate side, for example, the release layer is irradiated by the laser, and its peeling ability is exercised as described above, easily separating the second substrate from the first substrate and the adhesive layer. Typically, peeling is performed after the laminate of the present invention has been manufactured and subjected to prescribed processing, etc.

[0224] Here, processing refers to, for example, processing on the opposite side of the circuit surface of a wafer, such as wafer thinning through grinding of the wafer's back side. Then, through-silicon via (TSV) electrodes are formed, and the thinned wafer is peeled off from the support to form a wafer stack, which is then three-dimensionally mounted. Furthermore, back-side electrodes are formed before and after three-dimensional mounting. During the wafer thinning and TSV processes, the wafer is bonded to the support and subjected to heat of 250–350°C, but the stack of the present invention includes an adhesive layer, thus exhibiting heat resistance to this load.

[0225] Furthermore, the processing is not limited to the processing described above. For example, the processing may also include a semiconductor component mounting process in which the substrate for mounting semiconductor components is temporarily bonded to a support.

[0226] For example, for a wafer with a diameter of 300 mm and a thickness of about 770 μm, the back side opposite to the circuit surface can be ground to thin it to a thickness of about 10 μm to 100 μm.

[0227] It should be noted that laser irradiation does not necessarily need to cover the entire adhesive layer. Even if irradiated and unirradiated areas are mixed, as long as the overall adhesive strength of the adhesive layer is sufficiently reduced, the second substrate can be removed from the laminate by applying a small external force, such as lifting the second substrate. The ratio and positional relationship between irradiated and unirradiated areas vary depending on the type and composition of the adhesive used, the thickness of the adhesive layer, and the intensity of the laser irradiation, but those skilled in the art can set appropriate conditions without excessive experimentation. For example, the unirradiated area can be placed next to the irradiated area with a width equal to the width of the laser-drawn line.

[0228] Thus, even when only a portion of the adhesive layer is irradiated with laser, the second substrate can be separated, thereby shortening the laser irradiation time for each laminate, which in turn shortens the total time required for peeling.

[0229] The method for manufacturing the processed semiconductor substrate of the present invention is a method for manufacturing a semiconductor substrate that has undergone thinning and other processing. The manufacturing method includes: a first step of manufacturing the laminate of the present invention; a second step of processing the semiconductor substrate, which serves as a first substrate, of the obtained laminate; a third step of separating a support substrate, which serves as a second substrate, from the processed semiconductor substrate, which serves as a first substrate, and an adhesive layer; and a fourth step of removing the adhesive layer from the processed semiconductor substrate, which serves as a first substrate, and cleaning the processed semiconductor substrate, which serves as a first substrate.

[0230] Here, the conditions (appropriate conditions, etc.) related to the method of manufacturing the laminate of the present invention in the first step, the method of processing the semiconductor substrate in the second step, and the method of separating the support substrate from the processed semiconductor substrate and the adhesive layer in the third step are the same as described above.

[0231] In the fourth step, which involves removing the adhesive layer from the processed semiconductor substrate (which serves as the first substrate) and cleaning the processed semiconductor substrate, the adhesive layer on the semiconductor substrate that has undergone thinning or other processing is removed. At this time, if a release layer remains on the adhesive layer, it is also removed. Removal can be performed, for example, using a salt-containing cleaning agent composition.

[0232] The method for manufacturing the processed semiconductor substrate of the present invention includes the first to fourth steps described above, and may also include steps other than these steps. Furthermore, various modifications can be made to the constituent elements and method elements related to the first to fourth steps, as long as they do not depart from the spirit of the present invention.

[0233] Example

[0234] The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that the apparatus used is as described below.

[0235] (1) Mixer A: (Company) THINKY manufactures Awatori Rentaro.

[0236] (2) Mixer B: AS ONE (Co., Ltd.) mixing rotor VMR-5R.

[0237] (3) Bonding device: manual bonder manufactured by SUSS MicroTec.

[0238] (4) Laser irradiation device (stripping device): Lotus-TII, LT-2137.

[0239] [1] Preparation of adhesive composition

[0240] [Preparation Example 1]

[0241] Add 104.14 g of a solution of p-menthane (concentration 80.6% by mass) of vinyl-containing MQ resin (manufactured by Wacker Chemie Co., Ltd.) as (a1), 58.11 g of polyorganosiloxane (complex viscosity 800 Pa·s) of formula (A) as (B), 34.94 g of p-menthane (manufactured by TERPENE Chemical Co., Ltd., Japan) and 6.20 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) as solvent to a 600 mL mixing container dedicated to mixer A, and stir for 5 minutes using mixer A.

[0242] To the obtained mixture, add 16.79 g of a SiH-based linear polydimethylsiloxane (manufactured by Wacker Chemie Co., Ltd.) with a viscosity of 100 mPa·s as (a2) and 24.54 g of a vinyl-based linear polydimethylsiloxane (manufactured by Wacker Chemie Co., Ltd.) with a viscosity of 200 mPa·s as (a1). Further add 1.29 g of a mixture obtained separately by stirring with stirrer B for 60 minutes with 1.61 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.61 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie Co., Ltd.) as (A3) and 3.23 g of p-menthane (manufactured by TERPENE Chemical Co., Ltd., Japan) as a solvent. Stir with stirrer A for 5 minutes.

[0243] Add 0.65 g of platinum catalyst (manufactured by Wacker Chemie) as (A2) and 19.37 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as (a1) to the mixture obtained by stirring for 5 minutes using mixer A, and stir for 5 minutes using mixer A.

[0244] Finally, the mixture obtained by filtration through a 300-mesh nylon filter yielded the adhesive composition.

[0245] It should be noted that the viscosity of the obtained adhesive composition is 3000 mPa·s.

[0246]

[0247] (a represents the number of repeating units, which is a positive integer.)

[0248] [2] Preparation of the stripping agent composition

[0249] [Example 1-1]

[0250] 1.11 g of the polyphenol derivative shown in formula (P1) (manufactured by Asahi Organics Co., Ltd., trade name TEP-TPA) was mixed with 0.22 g of the compound shown in formula (L17M) (manufactured by Honshu Chemical Industry Co., Ltd., trade name TMOM-BP) as a crosslinking agent and 2.23 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium p-toluenesulfonate as an acid, and stirred. Then, 10.84 g of propylene glycol monomethyl ether and 5.59 g of propylene glycol monomethyl ether acetate were added and stirred to obtain a solution.

[0251] The solution obtained by filtering with a polyethylene microfilter with a pore size of 0.2 μm yielded a stripping agent composition.

[0252]

[0253] [3] Fabrication of laminates

[0254] [Example 2-1]

[0255] The release agent composition obtained in Examples 1-1 was spin-coated onto a 100 mm glass wafer with a final laminate thickness of about 200 nm. The wafer was heated at 250 °C for 5 minutes to form a release agent coating layer on the glass wafer, which served as the second substrate.

[0256] On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated onto a 100 mm silicon wafer with a film thickness of about 60 μm in the final laminate, and heated at 120°C for 1.5 minutes to form an adhesive coating layer on the silicon wafer, which serves as the first substrate.

[0257] Then, using a bonding apparatus, the glass wafer and the silicon wafer are bonded together with a release agent coating layer and an adhesive coating layer sandwiched between them, followed by a post-heat treatment at 200°C for 10 minutes, thereby producing a laminate. It should be noted that the bonding is performed at a temperature of 23°C and a pressure reduction of 1500 Pa.

[0258] [4] Confirmation of the optimal irradiation dose using 355nm laser

[0259] The resulting laminate was irradiated with a laser from the glass wafer side using a laser irradiation device, with an output of 40–160 mJ / cm². 2 The lowest laser output that produces ablation within a certain range was identified and taken as the optimal irradiation dose. The result was that the optimal irradiation dose was 100 mJ / cm². 2 .

[0260] [5] Confirmation of peelability using 355nm laser (confirmation of peelability by full-surface irradiation)

[0261] The laminate obtained using the same method as in Example 2-1 was subjected to laser irradiation from the glass wafer side onto the entire surface of the wafer using a laser irradiation device. After irradiation, it was confirmed whether the glass wafer could be peeled off. In this case, the laser irradiation was performed without overlap in the front, back, left, or right directions. Furthermore, the laser output was set to 100 mJ / cm² as the optimal irradiation dose. 2 .

[0262] As a result, after irradiation, it was confirmed that the glass wafer (carrier side) could be easily peeled off manually with almost no force applied.

[0263] [6] Storage stability test of the stripping agent composition

[0264] [Example 3-1]

[0265] The stripping agent composition obtained in Example 1-1 was stored at 23°C for one month. It should be noted that the transmittance of the composition at a wavelength of 560 nm before storage was 89%. As a result, the transmittance of the composition at a wavelength of 560 nm after storage was 88%, and no substantial change in transmittance could be confirmed, nor was any significant change confirmed by visual inspection.

[0266] Thus, the stripping agent composition of the present invention exhibits excellent storage stability.

Claims

1. A laminate characterized by comprising: Possessing: a first base body composed of a semiconductor substrate, a second base body composed of a light-transmissive support substrate, and a bonding layer and a release layer between the first base body and the second base body, the release layer is a film obtained from a release agent composition containing at least either one of an acid generator and an acid, a polynuclear phenol derivative represented by formula (P), and a crosslinking agent, in the formula, Ar represents an arylene group.

2. The laminate according to claim 1, wherein the polynuclear phenol derivative is represented by formula (P-1), 3. The laminate according to claim 2, wherein the polynuclear phenol derivative is represented by formula (P-1-1), 4. The laminate according to claim 3, wherein the polynuclear phenol derivative is represented by formula (P1), 5. The laminate according to any one of claims 1 to 4, wherein the crosslinking agent contains at least one selected from a phenol-based crosslinking agent having a crosslink-forming group, a melamine-based crosslinking agent having a crosslink-forming group, a urea-based crosslinking agent having a crosslink-forming group, and a thiourea-based crosslinking agent having a crosslink-forming group.

6. The laminate according to claim 5, wherein the crosslinking agent contains a phenol-based crosslinking agent having a crosslink-forming group.

7. The laminate according to any one of claims 1 to 4, wherein the release agent composition contains an acid.

8. The laminate according to claim 7, wherein the acid contains at least one selected from an arylsulfonic acid, a salt of an arylsulfonic acid, an arylcarboxylic acid, a salt of an arylcarboxylic acid, a chain or cyclic alkylsulfonic acid, a salt of a chain or cyclic alkylsulfonic acid, a chain or cyclic alkylcarboxylic acid, and a salt of a chain or cyclic alkylcarboxylic acid.

9. The laminate according to any one of claims 1 to 4, characterized in that the bonding layer is a film obtained using a bonding agent composition containing a bonding agent component (S) containing at least one selected from a silicone-based bonding agent, an acrylic resin-based bonding agent, an epoxy resin-based bonding agent, a polyamide-based bonding agent, a polystyrene-based bonding agent, a polyimide bonding agent, and a phenol resin-based bonding agent.

10. The laminate according to claim 9, wherein the bonding agent component (S) contains a silicone-based bonding agent.

11. The laminate according to claim 10, wherein the silicone-based bonding agent contains a polyorganosiloxane component (A) cured by hydrosilylation reaction.

12. Use of a composition for forming a release layer of a laminate possessing: a first base body composed of a semiconductor substrate, a second base body composed of a light-transmissive support substrate, and a bonding layer and a release layer between the first base body and the second base body, the composition containing at least either one of an acid generator and an acid, a polynuclear phenol derivative represented by formula (P), and a crosslinking agent, in the formula, Ar represents an arylene group.

13. The use according to claim 12, wherein the polynuclear phenol derivative is represented by formula (P-1), 14. The use according to claim 13, wherein the polynuclear phenol derivative is represented by formula (P-1-1), 15. The use according to claim 14, wherein The polynuclear phenol derivative is represented by formula (P1), 16. The use according to any one of claims 12 to 15, wherein The crosslinking agent comprises at least one selected from a phenol-based crosslinking agent having a crosslink-forming group, a melamine-based crosslinking agent having a crosslink-forming group, a urea-based crosslinking agent having a crosslink-forming group, and a thiourea-based crosslinking agent having a crosslink-forming group.

17. The use according to any one of claims 12 to 15, wherein The crosslinking agent comprises a phenol-based crosslinking agent having a crosslink-forming group.

18. The use according to any one of claims 12 to 15, wherein The composition comprises an acid.

19. The use according to claim 18, wherein The acid comprises at least one selected from an arylsulfonic acid, a salt of arylsulfonic acid, an arylcarboxylic acid, a salt of arylcarboxylic acid, a chain or cyclic alkylsulfonic acid, a salt of chain or cyclic alkylsulfonic acid, a chain or cyclic alkylcarboxylic acid, and a salt of chain or cyclic alkylcarboxylic acid.

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