Release agent composition for light irradiation stripping, laminate, and method for manufacturing processed semiconductor substrate

Abstract

The invention relates to a stripping agent composition, which is used for light irradiation stripping and comprises novolac resin, a (methyl) acrylic acid ester polymer and a solvent.

Description

Technical Field

[0001] The present invention relates to a stripping agent composition for photoirradiation stripping, a laminate, and a method for producing a processed semiconductor substrate. Background Art

[0002] With respect to semiconductor wafers that were previously integrated in a two-dimensional plane direction, a semiconductor integration technology that further integrates (stacks) the plane in a three-dimensional direction is pursued for the purpose of further integration. This three-dimensional stacking is a technology that connects through silicon via electrodes (TSV: through silicon vias) and integrates into multiple layers. When integrating into multiple layers, the side opposite to the circuit surface formed on each wafer to be integrated (i.e., the back side) is thinned by grinding, and the thinned semiconductor wafers are stacked.

[0003] The semiconductor wafer (also referred to herein as wafer) before thinning is bonded to a support body in order to be ground using a grinding device. The bonding at this time must be easy to peel off after grinding, so it is called temporary bonding. The temporary bonding must be easy to disassemble from the support body. When a large force is applied to the disassembly, the thinned semiconductor wafer is sometimes cut or deformed, so it is easy to disassemble in a way that avoids such a situation. However, when the back side of the semiconductor wafer is ground, it is not preferred that it is detached or offset due to the grinding stress. Therefore, the performance sought for temporary bonding is: to withstand the stress during grinding and to be easy to disassemble after grinding.

[0004] For example, the following properties are sought: high stress (strong adhesive force) with respect to the planar direction during grinding, and low stress (weak adhesive force) with respect to the longitudinal direction during removal.

[0005] For such bonding and separation processes, methods using laser irradiation have been disclosed (see, for example, Patent Documents 1 and 2). However, with recent progress in the semiconductor field, new technologies related to peeling by irradiation with light such as laser light have been increasingly required.

[0006] The applicant has proposed a laminate, which is a laminate for processing a workpiece and has an intermediate layer bonded in a removable manner between a support and the workpiece, wherein the intermediate layer at least includes a peeling layer connected to the support side, and the peeling layer includes a phenolic varnish resin that absorbs light with a wavelength of 190nm to 600nm irradiated through the support and deteriorates (see patent document 3).

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2004-64040

[0010] Patent Document 2: Japanese Patent Application Publication No. 2012-106486

[0011] Patent Document 3: International Publication No. 2019 / 088103 Pamphlet Summary of the invention

[0012] Problems to be solved by the invention

[0013] The surface of a semiconductor substrate such as a semiconductor wafer may have irregularities due to bumps, etc. Generally, a release agent layer is formed with a thin thickness of about 200 nm, but a thin release agent layer may have difficulty covering the irregularities of a semiconductor substrate.

[0014] The present invention is completed in view of the above situation, and its purpose is to provide a stripping agent composition for light irradiation stripping, and a method for manufacturing a laminate and a processed semiconductor substrate using the stripping agent composition, wherein the stripping agent composition for light irradiation stripping can form a thick stripping agent layer in a state with good appearance, strippability, and cleaning properties.

[0015] Solutions for solving problems

[0016] The present inventors have conducted intensive studies to solve the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved, thereby completing the present invention having the following gist.

[0017] That is, the present invention includes the following contents.

[0018] [1] A stripping agent composition for stripping by light irradiation, comprising a novolac resin, a (meth)acrylate polymer, and a solvent.

[0019] [2] The release agent composition according to [1], wherein the (meth)acrylate polymer contains a repeating unit derived from an alkyl (meth)acrylate having 4 to 20 carbon atoms.

[0020] [3] The release agent composition according to [1] or [2], wherein the (meth)acrylate polymer contains a repeating unit derived from methyl methacrylate.

[0021] [4] The release agent composition according to any one of [1] to [3], wherein the (meth)acrylate polymer contains polymethyl methacrylate.

[0022] [5] The stripping agent composition according to any one of [1] to [4], wherein the novolac resin contains at least any of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3).

[0023]

[0024] (In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom or a quaternary carbon atom, wherein the side chain has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom and an aromatic ring, or represents a methylene group, C 3 represents a group derived from an aliphatic polycyclic compound, C 4 represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl or a group derived from biphenol. )

[0025] [6] The stripping agent composition according to [5], wherein the novolac resin contains at least any one of a structural unit represented by the following formula (C1-1-1) and a structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1).

[0026]

[0027]

[0028] (In formula (C1-1-1) and formula (C1-1-2), R 901 and R 902 The substituents substituted on the ring each independently represent a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0029] R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0030] R 904 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0031] R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0032] R 904 The group and R 905 The groups are optionally bonded to each other to form a divalent group.

[0033] Ar 901 and Ar 902 Each independently represents an aromatic ring.

[0034] h 1 and h2 Each independently represents an integer from 0 to 3. )

[0035] [7] The release agent composition according to any one of [1] to [6], wherein the content of the (meth)acrylate polymer is 35% by mass or more relative to the total of the novolac resin and the (meth)acrylate polymer.

[0036] [8] A laminated body, wherein the laminated body comprises:

[0037] Semiconductor substrate or electronic device layer;

[0038] a light-transmitting supporting substrate; and

[0039] a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate,

[0040] The release agent layer is a release agent layer formed from the release agent composition described in any one of [1] to [7].

[0041] [9] The laminate according to [8], wherein the release agent layer has a thickness of 0.5 μm to 10 μm.

[0042]

[10] The laminate according to [8] or [9], wherein the laminate has an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0043]

[11] The laminate according to [8] or

[10] , wherein the release agent layer is in contact with the semiconductor substrate.

[0044]

[12] The stacked body according to any one of [8] to

[11] , wherein the surface of the semiconductor substrate on the support substrate side has a bump.

[0045]

[13] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising:

[0046] A fifth step A of processing the semiconductor substrate of the stacked body as described in any one of [8] to

[12] ; or a fifth step B of processing the electronic device layer of the stacked body as described in any one of [8] to

[12] ; and

[0047] The sixth A step is to separate the semiconductor substrate processed in the fifth A step from the support substrate; or the sixth B step is to separate the electronic device layer processed in the fifth B step from the support substrate.

[0048]

[14] The method for manufacturing a processed semiconductor substrate or electronic device layer according to

[13] , wherein the sixth step A or the sixth step B includes a step of irradiating the stacked body with laser light from the supporting substrate side.

[0049] Effects of the Invention

[0050] According to the present invention, there can be provided a stripping agent composition for photo-irradiation stripping, which can form a thick stripping agent layer with good appearance, stripping properties, and cleaning properties, and a method for producing a laminate and a processed semiconductor substrate using the stripping agent composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is a schematic cross-sectional view of an example of the laminated body in the first embodiment.

[0052] Figure 2A This is a schematic cross-sectional view (part 1) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0053] Figure 2B This is a schematic cross-sectional view (part 2) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0054] Figure 2C This is a schematic cross-sectional view (part 3) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0055] Figure 2D This is a schematic cross-sectional view (part 4) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0056] Figure 2E This is a schematic cross-sectional view (part 5) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0057] Figure 3 This is a schematic cross-sectional view of an example of a laminated body in the second embodiment.

[0058] Figure 4 It is a schematic cross-sectional view of another example of the laminated body in the second embodiment.

[0059] Figure 5A This is a schematic cross-sectional view (part 1) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0060] Figure 5B This is a schematic cross-sectional view (part 2) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0061] Figure 5C This is a schematic cross-sectional view (part 3) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0062] Figure 5D This is a schematic cross-sectional view (part 4) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0063] Fig. 6A This is a schematic cross-sectional view (part 1) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0064] Figure 6B This is a schematic cross-sectional view (part 2) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0065] Figure 6C This is a schematic cross-sectional view (part 3) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0066] Fig. 7A This is a schematic cross-sectional view (part 1) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0067] Figure 7B This is a schematic cross-sectional view (part 2) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0068] Figure 7C This is a schematic cross-sectional view (part 3) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0069] Fig.7D This is a schematic cross-sectional view (part 4) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0070] Fig. 7E This is a schematic cross-sectional view (part 5) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0071] Figure 7F This is a schematic cross-sectional view (part six) for explaining a method for processing a laminated body showing an example of the second embodiment. DETAILED DESCRIPTION

[0072] (Removal agent composition for light irradiation removal)

[0073] The stripping agent composition for light irradiation stripping of the present invention contains a novolac resin, a (meth)acrylate polymer, and a solvent.

[0074] The present inventors attempted to form a release agent layer having a thickness of about 1500 nm using a release agent composition containing a novolac resin and a solvent. However, the release agent layer had poor coating properties, cracks were generated in the formed release agent layer, and liquid shrinkage cavities were observed, resulting in a poor appearance.

[0075] Therefore, the present inventors have studied the use of other resins (polymers) in combination with a stripping agent composition containing a novolac resin and a solvent. As other resins, for example, (meth)acrylate polymers, polystyrene, polyhydroxystyrene, hydrogenated styrene thermoplastic elastomers, etc. have been studied.

[0076] As a result, when a resin (polymer) other than a (meth)acrylate polymer is used in combination, a thick release agent layer having good appearance, peelability and washability is not obtained. However, when a (meth)acrylate polymer is used in combination, it was found that a release agent layer having no problems in appearance, peelability and washability can be obtained, thereby completing the present invention.

[0077] <Novolac resin>

[0078] The novolac resin is a resin obtained by, for example, subjecting at least any one of a phenolic compound, a carbazole compound, and an aromatic amine compound to a condensation reaction with at least any one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst.

[0079] Examples of phenolic compounds include phenols, naphthols, anthranols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of anthranols include 9-anthrol. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene.

[0080] Examples of the carbazole compound include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1 H-benzotriazol-1-ylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarbaldehyde, 9-benzylcarbazole-3-carbaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, carbazole potassium, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carbaldehyde, N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-dihydroindoleamine, etc.

[0081] Examples of the aromatic amine compound include diphenylamine and N-phenyl-1-naphthylamine.

[0082] These can be used alone or in combination of two or more.

[0083] They may have a substituent. For example, they may have a substituent on the aromatic ring.

[0084] As aldehyde compounds, for example, saturated aliphatic aldehydes, unsaturated aliphatic aldehydes, heterocyclic aldehydes, aromatic aldehydes, etc. can be cited. As saturated aliphatic aldehydes, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexanal, 2-methylbutyraldehyde, hexanal, undecanal, 7-methoxy-3,7-dimethyloctanal, cyclohexanecarboxaldehyde, 3-methyl-2-butyraldehyde, 2-ethylhexanal, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, etc. can be cited. As unsaturated aliphatic aldehydes, for example, acrolein, methacrolein, etc. can be cited. As heterocyclic aldehydes, for example, furfural, pyridinecarboxaldehyde, etc. can be cited. Examples of the aromatic aldehydes include benzaldehyde, naphthaldehyde, anthracenealdehyde, phenanthraldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolualdehyde, (N,N-dimethylamino)benzaldehyde, acetoxybenzaldehyde, etc. Among them, saturated aliphatic aldehydes and aromatic aldehydes are preferred.

[0085] Examples of the ketone compound include diaryl ketone compounds, such as diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, and xylyl ketone.

[0086] Examples of the divinyl compound include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene, divinylpyrene, limonene, and 5-vinylnorbornadiene.

[0087] These can be used alone or in combination of two or more.

[0088] The novolac resin is, for example, a novolac resin that is degraded by absorbing light, and the degraded state is, for example, photodecomposition.

[0089] The novolac resin includes, for example, at least any of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3).

[0090]

[0091] In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom or a quaternary carbon atom, wherein the side chain has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom and an aromatic ring, or represents a methylene group, C 3 represents a group derived from an aliphatic polycyclic compound, C 4 It represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl or a group derived from biphenol.

[0092] That is, the novolac resin contains, for example, one or two or more of the following structural units.

[0093] A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group or a methylene group having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom and an aromatic ring as a side chain (Formula (C1-1)).

[0094] A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (Formula (C1-2)).

[0095] A structural unit having a bond between a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl or a group derived from biphenol and a side chain having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring, a group containing a tertiary carbon atom or a quaternary carbon atom or a methylene group (Formula (C1-3)).

[0096] In a preferred embodiment, the novolac resin comprises either or both of a structural unit (Formula (C1-1)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group or a methylene group having a side chain having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom and an aromatic ring, and a structural unit (Formula (C1-2)), wherein the structural unit (Formula (C1-1)) has a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound.

[0097] C 1 That is, the group derived from an aromatic compound containing a nitrogen atom may be, for example, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, etc., but is not limited thereto.

[0098] C 2 That is, the side chain has a group or methylene group containing a tertiary carbon atom or a quaternary carbon atom, which is selected from at least one of the group consisting of a secondary carbon atom, a quaternary carbon atom and an aromatic ring. For example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from 2-ethylhexanal, a group derived from acetaldehyde, etc. can be used, but it is not limited to these.

[0099] C 3 That is, the group derived from the aliphatic polycyclic compound can be a group derived from dicyclopentadiene, but is not limited thereto.

[0100] C 4 It is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl or a group derived from biphenol.

[0101] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-1) as the structural unit represented by the formula (C1-1).

[0102]

[0103] In formula (C1-1-1), R 901 and R 902 The substituents substituted on the ring each independently represent a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0104] R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0105] R 904represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0106] R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0107] R 904 The group and R 905 The groups are optionally bonded to each other to form a divalent group.

[0108] Examples of the substituent of the alkyl group and the alkenyl group include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0109] Examples of the substituent for the aryl group and the heteroaryl group include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an alkyl group, and an alkenyl group.

[0110] h 1 and h 2 Each independently represents an integer from 0 to 3.

[0111] In the present invention, the "aryl group" refers to an aromatic group (aromatic hydrocarbon group) having no hetero atom.

[0112] The carbon number of the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, preferably 30 or less, more preferably 20 or less from the viewpoint of solubility.

[0113] The number of carbon atoms of the optionally substituted aryl group and heteroaryl group is usually 40 or less, preferably 30 or less, more preferably 20 or less from the viewpoint of solubility.

[0114] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0115] Specific examples of the optionally substituted alkyl group 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 The present invention includes, but is not limited to, 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, and 2-ethylhexyl.

[0116] Specific examples of the optionally substituted alkenyl group 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 1,2-dimethyl-2-butenyl, 1,2-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- 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutyl vinyl, 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 1-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, etc., but are not limited to these. ,

[0117] Specific examples of the optionally substituted aryl group include, but are not limited to, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 1-naphthyl, 2-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, and 9-phenanthrenyl.

[0118] Specific examples of the optionally substituted heteroaryl group include, but are not limited to, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl.

[0119] Specific examples of the structural unit represented by formula (C1-1-1) are listed below, but the present invention is not limited to these.

[0120]

[0121] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1).

[0122]

[0123] In formula (C1-1-2), Ar 901 and Ar 902 Each independently represents an aromatic ring, R 901 ~R 905 and h1 and h 2 Means the same as above.

[0124] Examples of the aromatic ring include a benzene ring and a naphthalene ring.

[0125] Specific examples of the structural unit represented by formula (C1-1-2) are listed below, but the present invention is not limited to these.

[0126]

[0127] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2) as the structural unit represented by the formula (C1-2).

[0128]

[0129] In the above formula, R 906 ~R 909 is a substituent bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, and specific examples of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group and the optionally substituted aryl group and preferred carbon number thereof are the same as those mentioned above, 3 ~h 6 Each independently represents an integer from 0 to 3, R 901 ~R 903 and h 1 and h 2 Means the same as above.

[0130] Specific examples of the structural units represented by formulae (C1-2-1) and (C1-2-2) are listed below, but the present invention is not limited to these.

[0131]

[0132] Specific examples of the structural unit represented by formula (C1-3) are listed below, but the present invention is not limited to these.

[0133]

[0134] As described above, the novolac resin is a resin obtained by condensing at least any one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least any one of an aldehyde compound, a ketone compound, and a divinyl compound under an acid catalyst.

[0135] In the condensation reaction, for example, the aldehyde compound or the ketone compound is usually used in a ratio of 0.1 to 10 equivalents based on 1 equivalent of the benzene ring constituting the ring of the carbazole compound.

[0136] In the above condensation reaction, an acid catalyst is usually used.

[0137] Examples of the acid catalyst include, but are not limited to, inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid.

[0138] The amount of the acid catalyst is appropriately determined depending on the type of acid used, etc., and therefore cannot be generally specified, but is usually appropriately determined within the range of 0.001 to 10,000 parts by mass based on 100 parts by mass of the carbazole compound.

[0139] The above-mentioned condensation reaction may be carried out without using a solvent when any of the raw material compound and the acid catalyst used is a liquid, but is usually carried out using a solvent.

[0140] Such a solvent is not particularly limited as long as it does not inhibit the reaction, and typical examples thereof include ether compounds and ether ester compounds.

[0141] Examples of the ether compound include cyclic ether compounds such as tetrahydrofuran and dioxane.

[0142] Examples of the ether ester compound include methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and propylene glycol monopropyl ether propionate.

[0143] The reaction temperature is usually appropriately determined within the range of 40° C. to 200° C. The reaction time varies depending on the reaction temperature and therefore cannot be generally determined, but is usually appropriately determined within the range of 30 minutes to 50 hours.

[0144] After the reaction is completed, the novolac resin is purified and separated according to a conventional method as necessary, and the obtained novolac resin is used for the preparation of a stripping agent composition.

[0145] A person skilled in the art can determine the production conditions of the novolac resin without undue burden based on the above description and common technical knowledge, and thus can produce the novolac resin.

[0146] The weight average molecular weight of the novolac resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in a solvent, it is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, further preferably 5,000 or less, and further preferably 3,000 or less. From the viewpoint of improving the strength of the film, it is preferably 600 or more, more preferably 700 or more, further preferably 800 or more, further preferably 900 or more, and further preferably 1,000 or more.

[0147] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight and dispersion degree of the novolac resin can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH (Co., Ltd.)) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by TOSOH (Co., Ltd.), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich Co., Ltd.) used as a standard sample.

[0148] The lower limit of the content of the novolac resin in the stripper composition is not particularly limited. The content of the novolac resin in the stripper composition is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more relative to the total of the novolac resin and the (meth)acrylate polymer.

[0149] The upper limit of the content of the novolac resin in the stripper composition is not particularly limited. The content of the novolac resin in the stripper composition is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less, relative to the total of the novolac resin and the (meth)acrylate polymer.

[0150] <(Meth)acrylate polymer>

[0151] The (meth)acrylate polymer is a polymer containing a repeating unit derived from an alkyl (meth)acrylate.

[0152] Alkyl (meth)acrylate is a general term for alkyl acrylate and alkyl methacrylate.

[0153] The number of carbon atoms in the alkyl (meth)acrylate is not particularly limited, but is preferably 4 to 20, more preferably 4 to 10.

[0154] Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and decyl acrylate.

[0155] Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and decyl methacrylate.

[0156] These can be used alone or in combination of two or more.

[0157] Among them, methyl methacrylate is preferred.

[0158] The (meth)acrylate polymer may have repeating units other than the repeating units derived from the (meth)acrylate alkyl ester. Examples of monomers constituting such repeating units include monomers containing polymerizable unsaturated groups other than the (meth)acrylate polymer. Examples of such monomers include carboxyl-containing monomers, hydroxyl-containing monomers, (meth)acrylamide-based monomers, and styrene-based monomers.

[0159] The (meth)acrylate polymer may be a homopolymer or a copolymer.

[0160] As the (meth)acrylate polymer, polymethylmethacrylate is preferably contained.

[0161] The molar ratio of the repeating unit derived from the alkyl (meth)acrylate in all repeating units of the (meth)acrylate polymer is not particularly limited, but is preferably 50 to 100 mol %, more preferably 75 to 100 mol %, and particularly preferably 90 to 100 mol %.

[0162] Although Tg of the (meth)acrylate polymer is not particularly limited, it is preferably 30°C to 150°C, and more preferably 40°C to 120°C.

[0163] The Tg of the (meth)acrylate polymer can be determined by, for example, differential scanning calorimetry.

[0164] The molecular weight of the (meth)acrylate polymer is not particularly limited, but the weight average molecular weight of the (meth)acrylate polymer is preferably 10,000 to 200,000, more preferably 30,000 to 100,000.

[0165] The molecular weight of the (meth)acrylate polymer can be determined by, for example, gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0166] The lower limit of the content of the (meth)acrylate polymer in the stripper composition is not particularly limited. The content of the (meth)acrylate polymer in the stripper composition is preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more, relative to the total of the novolac resin and the (meth)acrylate polymer.

[0167] There is no particular restriction on the upper limit of the content of the (meth)acrylate polymer in the stripper composition. The content of the (meth)acrylate polymer in the stripper composition is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 75% by mass or less, relative to the total of the novolac resin and the (meth)acrylate polymer.

[0168] The total content of the novolac resin and the (meth)acrylate polymer in the stripper composition is not particularly limited, but is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and particularly preferably 90% to 100% by mass relative to the film constituent components. It should be noted that in the present invention, the film constituent components refer to the components contained in the composition except the solvent.

[0169] <Cross-linking agent>

[0170] The release agent composition may also contain a crosslinking agent.

[0171] The crosslinking agent may also cause a crosslinking reaction by self-condensation, and when a crosslinkable substituent is present in the novolac resin, the crosslinking agent may cause a crosslinking reaction with the crosslinkable substituent.

[0172] Specific examples of crosslinking agents are not particularly limited, and typically include: phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, thiourea crosslinking agents, etc., which have crosslinking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl and other alkoxymethyl groups in the molecule. They can be low molecular weight compounds or high molecular weight compounds.

[0173] The crosslinking agent contained in the release agent composition generally has two or more crosslinking groups. From the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking groups contained in the compound as the crosslinking agent is preferably 2 to 10, more preferably 2 to 6.

[0174] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (eg, a benzene ring or a naphthalene ring) in the molecule. Typical examples of such a crosslinking agent include, but are not limited to, phenolic crosslinking agents.

[0175] The phenolic crosslinking agent having a crosslinking group refers to a compound having a crosslinking 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 an alkoxy group derived from a phenolic hydroxyl group include, but are not limited to, a methoxy group and a butoxy group.

[0176] The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxyl group and / or the alkoxy group derived from the phenolic hydroxyl group is bonded are not limited to non-condensed aromatic rings such as benzene rings, but may be condensed aromatic rings such as naphthalene ring and anthracene ring.

[0177] When a plurality of aromatic rings are present in the molecule of the phenolic crosslinking agent, the crosslinking group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group may be bonded to the same aromatic ring in the molecule or to different aromatic rings.

[0178] The crosslinking group, the phenolic hydroxyl group, and the aromatic ring bonded to the alkoxy group derived from the phenolic hydroxyl group may be further substituted with a hydrocarbon group such as an alkyl group such as methyl, ethyl, or butyl; an aryl group such as phenyl; or a halogen atom such as a fluorine atom.

[0179] For example, specific examples of the phenolic crosslinking agent having a crosslinking-forming group include compounds represented by any of the formulae (L1) to (L4).

[0180]

[0181] In each formula, each R' independently represents a fluorine atom, an aryl group or an alkyl group, each R" independently represents a hydrogen atom or an alkyl group, and L 1 and L 2 Each independently represents a single bond, a methylene group or a propane-2,2-diyl group, L 3It is determined based on q1, represents a single bond, methylene, propane-2,2-diyl, methanetriyl or ethane-1,1,1-triyl, 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≤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 0. Specific examples of aryl and alkyl groups include the same groups as described below. As the aryl group, phenyl is preferred, and as the alkyl group, methyl and tert-butyl are preferred.

[0182] Specific examples of the compounds represented by formulae (L1) to (L4) are listed below, but are not limited thereto. It should be noted that these compounds can be synthesized by known methods, or can be obtained as products of, for example, Asahi Organic Materials Industries, Ltd. or Honshu Chemical Industries, Ltd.

[0183]

[0184]

[0185] The melamine-based crosslinking agent having a crosslinking group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative or a 2-amino-1,3,5-triazine derivative in which at least one of the hydrogen atoms of the amino group bonded to the triazine ring is substituted with a crosslinking group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group.

[0186] Specific examples of melamine-based crosslinking agents having a crosslinking-forming group include, but are not limited to, mono-, di-, tri-, tetra-, penta- or hexa-alkoxymethyl melamines such as N,N,N',N',N",N"-hexa(methoxymethyl)melamine and N,N,N',N',N",N"-hexa(butoxymethyl)melamine; and mono-, di-, tri- or tetra-alkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N'-tetra(butoxymethyl)benzoguanamine.

[0187] The urea-based crosslinking agent having a crosslinking group refers to a derivative of a urea bond-containing compound having a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is substituted with a crosslinking group.

[0188] Specific examples of the urea crosslinking agent having a crosslinking group include, but are not limited to, mono-, di-, tri- or tetra-alkoxymethyl glycolurils such as 1,3,4,6-tetra(methoxymethyl) glycoluril and 1,3,4,6-tetra(butoxymethyl) glycoluril; and mono-, di-, tri- or tetra-alkoxymethyl ureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetramethoxymethylurea.

[0189] The thiourea-based crosslinking agent having a crosslinking group refers to a derivative of a thiourea bond-containing compound having a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is substituted with a crosslinking group.

[0190] Specific examples of the thiourea crosslinking agent having a crosslinking group include mono-, di-, tri- or tetra-alkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetramethoxymethylthiourea, but are not limited thereto.

[0191] The amount of the crosslinking agent contained in the stripping agent composition varies depending on the coating method adopted, the desired film thickness, etc., and therefore cannot be generally specified. It is usually 0.01 to 50% by mass relative to the total of the novolac resin and the (meth)acrylate polymer. From the viewpoint of achieving appropriate curing and obtaining a laminate in which the semiconductor substrate or the electronic device layer and the supporting substrate can be well separated with good reproducibility, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, further preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and further preferably 30% by mass or less.

[0192] <Acid generator and acid>

[0193] The release agent composition may contain an acid generator or an acid for the purpose of promoting a crosslinking reaction or the like.

[0194] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0195] The thermal acid generator is not particularly limited as long as it generates an acid by heat. Specific examples thereof include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG-2689, K-PURE TAG-2700 (manufactured by King Industries), SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters, but the present invention is not limited to these.

[0196] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0197] Specific examples of the onium salt compound include: iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, but are not limited to these.

[0198] Specific examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited thereto.

[0199] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0200] Specific examples of the acid include: p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid and other arylsulfonic acids, pyridinium salts, and their salts; salicylic acid, benzoic acid, hydroxybenzoic acid, naphthoic acid and other arylcarboxylic acids, and their salts; trifluoromethanesulfonic acid, camphorsulfonic acid and other chain or cyclic alkylsulfonic acids, and their salts; citric acid and other chain or cyclic alkylcarboxylic acids, and their salts, but are not limited to these.

[0201] The amounts of the acid generator and acid contained in the release agent composition vary depending on the type of crosslinking agent used, the heating temperature during film formation, etc., and therefore cannot be generally specified, but are usually 0.01 to 5% by mass based on the film constituent components.

[0202] <Surfactant>

[0203] The stripping agent composition may contain a surfactant for the purpose of adjusting the liquid properties of the composition itself, the film properties of the obtained film, or preparing a stripping agent composition with high uniformity with good reproducibility.

[0204] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and EFTOP. Fluorine-based surfactants such as EF301, EF303, EF352 (trade names, manufactured by Tohkem Products Co., Ltd.), MEGAFACE F171, F173, R-30, R-30N (trade names, manufactured by DIC Corporation), Fluorad FC430, FC431 (trade names, manufactured by Sumitomo 3M Co., Ltd.), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade names, manufactured by AGC Corporation); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0205] The surfactant may be used alone or in combination of two or more.

[0206] The amount of the surfactant is usually 2% by mass or less based on the film-constituting components of the release agent composition.

[0207] <Solvent>

[0208] The stripper composition contains a solvent.

[0209] As the solvent, for example, a high polar solvent that can dissolve the above-mentioned novolac resin, (meth) acrylate polymer, crosslinking agent and other film constituents well can be used. As required, for the purpose of adjusting viscosity, surface tension, etc., a low polar solvent can also be used. It should be noted that in the present invention, a low polar solvent refers to a solvent whose relative dielectric constant is less than 7 under a frequency of 100kHz, and a high polar solvent refers to a solvent whose relative dielectric constant is more than 7 under a frequency of 100kHz. The solvent can be used alone or in combination of two or more.

[0210] In addition, examples of high polarity solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; 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; sulfoxide solvents such as dimethyl sulfoxide, etc.

[0211] Examples of the low polarity solvent include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isopentyl 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.

[0212] The content of the solvent is appropriately determined in consideration of the desired viscosity of the composition, the coating method to be adopted, the thickness of the film to be produced, etc., and is less than 99% by mass of the entire composition, preferably 70 to 99% by mass relative to the entire composition, and more preferably 75 to 90% by mass relative to the entire composition. That is, the amount of the film constituent components in this case is preferably 1 to 30% by mass relative to the entire composition, and more preferably 10 to 25% by mass relative to the entire composition.

[0213] The viscosity and surface tension of the release agent composition can be appropriately adjusted by changing the type of solvent used, their ratio, concentration of film constituent components, etc., in consideration of various factors such as the coating method used and the desired film thickness.

[0214] In one embodiment of the present invention, the release agent composition contains a glycol solvent from the viewpoint of obtaining a composition with high uniformity with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition providing a film with high uniformity with good reproducibility, etc. It should be noted that the "glycol solvent" referred to herein is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0215] An example of a preferred diol solvent is represented by formula (G).

[0216]

[0217] In formula (G), R G1 Each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, and R G2 and R G3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms, n g An integer from 1 to 6.

[0218] Specific examples of the linear or branched alkylene group 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.

[0219] Among them, from the viewpoint of obtaining a composition with high uniformity with good reproducibility, the viewpoint of obtaining a composition with high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film with high uniformity with good reproducibility, etc., a straight-chain or branched alkylene group having 2 to 3 carbon atoms is preferred, and a straight-chain or branched alkylene group having 3 carbon atoms is more preferred.

[0220] Specific examples of the linear or branched alkyl group 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-butyl, The present invention includes, but is not limited to, 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, and 1-ethyl-2-methyl-n-propyl.

[0221] Among them, from the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, etc., a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0222] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same groups as mentioned above.

[0223] Among them, from the viewpoint of obtaining a composition having high uniformity with good reproducibility, from the viewpoint of obtaining a composition having high storage stability with good reproducibility, from the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, etc., a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0224] From the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a highly stable composition with good reproducibility, obtaining a composition providing a highly uniform film with good reproducibility, etc., n g It is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and most preferably 1 or less.

[0225] From the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a highly stable composition with good reproducibility, obtaining a composition providing a highly uniform film with good reproducibility, etc., in formula (G), R is preferably 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 R G2 and R G3One of them 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 moiety is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0226] From the viewpoint of obtaining a highly uniform composition with good reproducibility, the viewpoint of obtaining a composition with high storage stability with good reproducibility, the viewpoint of obtaining a composition that provides a highly uniform film with good reproducibility, etc., the content of the diol solvent is preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, further preferably 90 mass % or more, and further preferably 95 mass % or more, relative to the solvent contained in the stripping agent composition.

[0227] From the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition providing a highly uniform film with good reproducibility, etc., in the release agent composition, the film constituent components are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0228] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the release agent composition or after all components are mixed.

[0229] (Laminated body)

[0230] The laminated body of the present invention comprises a semiconductor substrate or an electronic device layer, a supporting substrate, and a release agent layer for release by light irradiation.

[0231] Preferably, the laminate of the present invention further has an adhesive layer, and has a structure including a semiconductor substrate or an electronic device layer, a supporting substrate, a release agent layer for release by light irradiation, and an adhesive layer.

[0232] It should be noted that, when the release agent layer of the present invention is formed to have not only a release function of peeling off the semiconductor substrate or electronic device layer from the supporting substrate by light irradiation, but also a bonding function of bonding the semiconductor substrate or electronic device layer to the supporting substrate (that is, when the release agent layer is formed using a release agent composition containing components that exert two functions), the laminate can be formed by a single layer of the release agent layer having bonding properties, rather than a double layer of the release agent layer and the adhesive layer.

[0233] The supporting substrate has light-transmitting properties.

[0234] The release agent layer for light irradiation release is provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0235] The laminate is used to peel off the semiconductor substrate or the electronic device layer from the support substrate after the release agent layer absorbs light irradiated from the support substrate side.

[0236] The release agent layer for light irradiation removal is a layer formed of the above-mentioned release agent composition for light irradiation removal of the present invention.

[0237] The laminate of the present invention is used for temporary bonding in order to process a semiconductor substrate or an electronic device layer, and can be suitably used for processing such as thinning of a semiconductor substrate or an electronic device layer.

[0238] During the thinning process of the semiconductor substrate, the semiconductor substrate is supported by the supporting substrate. On the other hand, after the processing of the semiconductor substrate, the stripping agent layer is irradiated with light, and then the supporting substrate is separated from the semiconductor substrate. The novolac resin contained in the stripping agent composition absorbs light (such as laser) in the stripping agent layer formed by the stripping agent composition, and the stripping agent layer is deteriorated (such as separated or decomposed). As a result, after the stripping agent layer is irradiated with light, it is easy to peel off the semiconductor substrate and the supporting substrate.

[0239] Furthermore, the electronic device layer is supported by the support substrate while the electronic device layer is being processed such as being thinned. On the other hand, after the processing of the electronic device layer, the release agent layer is irradiated with light, and then the support substrate and the electronic device layer are separated.

[0240] The stripping agent layer of the present invention makes it easy to strip the semiconductor substrate or the electronic device layer from the support substrate after irradiation with light. Furthermore, after the semiconductor substrate or the electronic device layer and the support substrate are stripped, the residue of the stripping agent layer and the adhesive layer remaining on the semiconductor substrate, the electronic device layer, or the support substrate can be removed, for example, by a cleaning agent composition for cleaning the semiconductor substrate.

[0241] The wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm, and more preferably 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the novolac resin, such as decomposition.

[0242] The light used for stripping can be laser or non-laser emitted from a light source such as ultraviolet lamp.

[0243] The case where the laminated body has a semiconductor substrate and the case where the laminated body has an electronic device layer are described in detail below according to each case.

[0244] In the following <First Embodiment>, a case where the laminated body has a semiconductor substrate will be described, and in the following <Second Embodiment>, a case where the laminated body has an electronic device layer will be described.

[0245] <First embodiment>

[0246] The laminated body having the semiconductor substrate is used for processing the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to the support substrate. After the processing of the semiconductor substrate, the release agent layer is irradiated with light, and the semiconductor substrate is separated from the support substrate.

[0247] <<Semiconductor substrate>>

[0248] The main material constituting the entire semiconductor substrate is not particularly limited as long as it is a material used for such applications, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0249] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc. It should be noted that the surface of the disc-shaped semiconductor substrate does not need to be a perfect circle, and for example, the periphery of the semiconductor substrate may have a straight portion called an orientation flat, or may have a cutout called a notch.

[0250] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1000 μm.

[0251] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 100 to 1000 mm.

[0252] The semiconductor substrate may have a bump. A bump is a protruding terminal.

[0253] In the laminated body, when the semiconductor substrate has the bump, the semiconductor substrate has the bump on the supporting substrate side.

[0254] In a semiconductor substrate, bumps are usually formed on the surface where a circuit is formed. The circuit may be a single layer or a multilayer. There is no particular limitation on the shape of the circuit.

[0255] In the semiconductor substrate, the surface (back surface) opposite to the surface having the bumps is a surface to be processed.

[0256] The material, size, shape, structure, and density of the bumps included in the semiconductor substrate are not particularly limited.

[0257] Examples of the bump include a ball bump, a printed bump, a stud bump, and a plated bump.

[0258] Normally, the height, radius, and pitch of the bumps are appropriately determined from conditions such as a bump height of about 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm.

[0259] Examples of materials for the bumps include low melting point solder, high melting point solder, tin, indium, gold, silver, copper, etc. The bumps may be made of a single component or a plurality of components. More specifically, SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy platings based on Sn may be included.

[0260] Furthermore, the bump may have a stacked structure including a metal layer made of at least any one of these components.

[0261] An example of a semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0262] <<Support substrate>>

[0263] The supporting substrate is not particularly limited as long as it is a member that is light-transmissive to the light irradiated to the release agent layer and can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include glass supporting substrates.

[0264] The shape of the support substrate is not particularly limited, and an example thereof may be a disk shape.

[0265] The thickness of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 500 to 1000 μm.

[0266] The diameter of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 100 to 1000 mm.

[0267] An example of the supporting substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0268] <<Release agent layer>>

[0269] The release agent layer is a layer formed of a release agent composition.

[0270] The release agent layer is provided between the semiconductor substrate and the support substrate.

[0271] The release agent layer may be in contact with the supporting substrate or may be in contact with the semiconductor substrate.

[0272] The release agent layer is formed using the above-mentioned release agent composition for light irradiation release of the present invention.

[0273] The stripping agent composition of the present invention can be suitably used to form a stripping agent layer of a laminate having a semiconductor substrate, a supporting substrate, and a stripping agent layer disposed between the semiconductor substrate and the supporting substrate. The laminate is used to strip the semiconductor substrate from the supporting substrate after the stripping agent layer absorbs light irradiated from the supporting substrate side.

[0274] One of the characteristics of the release agent layer obtained from the release agent composition of the present invention is that the semiconductor substrate and the supporting substrate can be easily peeled off after light irradiation.

[0275] When forming a release agent layer from the release agent composition, the novolac resin may crosslink itself or react with other components to form a crosslinked structure, or may not crosslink or react and maintain its structure, as long as the effects of the present invention can be obtained.

[0276] In other words, in the release agent layer, the novolac resin may cross-link itself or react with other components to form a cross-linked structure, or may exist while maintaining its structure.

[0277] The thickness of the release agent layer is not particularly limited, but is usually 0.01 to 15 μm, preferably 0.05 to 10 μm, more preferably 0.1 to 8 μm, and further preferably 0.2 to 5 μm from the viewpoint of maintaining film strength.

[0278] Furthermore, when a release agent layer is formed on a semiconductor substrate having bumps, the thickness of the release agent layer is preferably 0.5 μm to 10 μm.

[0279] The method of forming the release agent layer from the release agent composition is described in detail in the explanation section of "Method for producing an example of a laminated body in the first embodiment" described below.

[0280] <<Adhesive layer>>

[0281] The adhesive layer is provided between the support substrate and the semiconductor substrate.

[0282] The adhesive layer is in contact with, for example, a semiconductor substrate. The adhesive layer may be in contact with, for example, a support substrate.

[0283] The adhesive layer is not particularly limited, but is preferably a layer formed of an adhesive composition.

[0284] <<Adhesive composition>>

[0285] Examples of the adhesive composition include silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives, but are not limited thereto.

[0286] Among them, polysiloxane-based adhesives are preferred as adhesive compositions because they exhibit appropriate adhesion during processing of semiconductor substrates and the like, can be appropriately peeled off after processing, have excellent heat resistance, and can be appropriately removed by a cleaning composition.

[0287] In a preferred embodiment, the adhesive composition contains polyorganosiloxane.

[0288] Furthermore, in another preferred embodiment, the adhesive composition contains a component that cures by a hydrosilylation reaction.

[0289] For example, the adhesive composition used in the present invention contains a cured component (A) that becomes an adhesive component. The adhesive composition used in the present invention may also contain a cured component (A) that becomes an adhesive component and a component (B) that does not undergo a curing reaction. Here, as a component (B) that does not undergo a curing reaction, for example, polyorganosiloxane can be cited. It should be noted that in the present invention, "no curing reaction occurs" does not mean that no curing reaction occurs, but refers to a curing reaction that does not occur in the cured component (A).

[0290] In a preferred embodiment, the component (A) may be a component that is cured by a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0291] In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2). The alkenyl group having 2 to 40 carbon atoms may be optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0292] In another preferred embodiment, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises a siloxane unit (Q unit) selected from the group consisting of SiO2, R 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit), R 4 R 5 SiO 2 / 2 The siloxane units (D units) and R 6 SiO 3 / 2The polysiloxane (A1) comprises a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises a siloxane unit (Q' unit) represented by SiO2, a R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane units (M' units), R 4 'R 5 'SiO 2 / 2 The 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 SiO2, and at least one unit selected from the group consisting of M' units, D' units and T' units, wherein the polyorganosiloxane (a2') comprises a siloxane unit (Q" unit) represented by SiO2, R 1 ”R 2 ”R 3 "SiO 1 / 2 The siloxane units (M" units), R 4 ”R 5 "SiO 2 / 2 The siloxane units (D" units) and R 6 "SiO 3 / 2 The siloxane units (T" units) shown in the figure contain one or more units selected from the group consisting of M" units, D" units and T" units.

[0293] It should be noted that (a1′) is an example of (a1), and (a2′) is an example of (a2).

[0294] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0295] R 1 '~R 6 ' is a group bonded to a silicon atom, each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0296] R 1 ”~R 6 " is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group or a hydrogen atom, R 1 ”~R 6 " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like.

[0297] The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched. 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 further preferably 10 or less.

[0298] Specific examples of the optionally substituted linear or branched alkyl group 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- The present invention is not limited to 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., and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among them, methyl is particularly preferred.

[0299] Specific examples of the optionally substituted cyclic alkyl group 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, and 2,4-dimethylcyclobutyl. Cycloalkyl groups such as cyclobutyl, 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, and 2-ethyl-3-methylcyclopropyl; bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, bicyclononyl, and dicyclodecyl, but are not limited to these, and the number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0300] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0301] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, pentenyl, etc., and the number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0302] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0303] As described above, the polysiloxane (A1) includes the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl groups contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction using a platinum group metal catalyst (A2) and cure. As a result, a cured film is formed.

[0304] 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 selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0305] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include: (Q' units and M' units), (D' units and M' units), (T' units and M' units), (Q' units, T' units and M' units), but are not limited to these.

[0306] In addition, when the polyorganosiloxane (a1') includes two or more 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 to these.

[0307] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units and T" units, and contains at least one selected from the group consisting of M" units, D" units and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0308] Preferred combinations of two or more selected from the group consisting of "Q" units, "M" units, "D" units and "T" units include, but are not limited to, (M" units and "D" units), (Q" units and "M" units), and (Q" units, "T" units and "M" units).

[0309] The polyorganosiloxane (a1′) is composed of siloxane units having alkyl and / or alkenyl groups bonded to silicon atoms. 1 '~R 6 The ratio of alkenyl groups in all substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be set to an alkyl group.

[0310] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. 1 ”~R 6The ratio of all substituents and hydrogen atoms in the substituent atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 ”~R 6 " can be set to an alkyl group.

[0311] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si—H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0312] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0313] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxane (excluding the above-mentioned organosiloxane polymer) can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH (Co., Ltd.)) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgelSuperMultiporeHZ-H manufactured by TOSOH (Co., Ltd.), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko (Co., Ltd.)) used as a standard sample.

[0314] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and is usually 10 to 1,000,000 (mPa·s) each, and is 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 of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured at 25° C. using an E-type rotational viscometer.

[0315] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other by a hydrosilylation reaction to form a film. Therefore, the curing mechanism is different from the mechanism by a silanol group, and therefore, all siloxanes do not need to contain a functional group that forms a silanol group by hydrolysis, such as a silanol group or an alkoxy group.

[0316] In a preferred embodiment of the present invention, the adhesive composition contains a polyorganosiloxane component (A') and a platinum group metal catalyst (A2).

[0317] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si—H group of the polyorganosiloxane (a2).

[0318] Specific examples of the platinum-based metal catalyst include platinum-based catalysts such as platinum black, platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and bisacetoacetate platinum, but are not limited thereto.

[0319] Examples of the complex of platinum and olefins include a complex of divinyltetramethyldisiloxane and platinum, but the complex is not limited thereto.

[0320] The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually within a range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0321] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.

[0322] The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0323] The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect thereof, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0324] In one example of the adhesive composition used in the present invention, a component (B) that does not undergo a curing reaction and serves as a release agent component may be included together with the cured component (A). By including such a component (B) in the adhesive composition, the obtained adhesive layer can be appropriately peeled off with good reproducibility.

[0325] As such a component (B), a non-curable polyorganosiloxane is typically mentioned, and specific examples thereof include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, etc., but it is not limited to these.

[0326] In addition, as component (B), polydimethylsiloxane can be listed. The polydimethylsiloxane is optionally modified. As the optionally modified polydimethylsiloxane, for example, epoxy-containing polydimethylsiloxane, unmodified polydimethylsiloxane, phenyl-containing polydimethylsiloxane, etc. can be listed, but it is not limited to these.

[0327] Preferred examples of the polyorganosiloxane as the component (B) include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, and the like, but are not limited thereto.

[0328] The weight average molecular weight of the polyorganosiloxane as component (B) is not particularly limited, but is usually 100,000 to 2,000,000. From the viewpoint of achieving the effect of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. In addition, the dispersity thereof is not particularly limited, but is usually 1.0 to 10.0. From the viewpoint of achieving appropriate peeling with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight average molecular weight and dispersity can be measured by the above-mentioned method related to polyorganosiloxane.

[0329] The viscosity of the polyorganosiloxane as component (B) is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 / s. It should be noted that the viscosity of the polyorganosiloxane as the component (B) is represented by the kinematic viscosity, which is centistoke (cSt) = mm 2 / s. You can also divide the viscosity (mPa·s) by the density (g / cm 3 That is, it can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer, or it can be obtained from the kinematic viscosity (mm 2 / s) = viscosity (mPa·s) / density (g / cm 3 ) is calculated using this formula.

[0330] Examples of the epoxy-containing polyorganosiloxane include: 11 R 12 SiO 2 / 2 The siloxane units (D 10 Unit) polyorganosiloxane.

[0331] R 11 is a group bonded to a silicon atom, represents an alkyl group, and R 12 It is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include those described above.

[0332] The epoxy group in the organic group including an epoxy group may be an independent epoxy group without being condensed with other rings, or may be an epoxy group forming a condensed ring with other rings such as 1,2-epoxycyclohexyl group.

[0333] Specific examples of the organic group containing an epoxy group include a 3-glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group, but are not limited to these.

[0334] In the present invention, a preferred example of the epoxy-containing polyorganosiloxane is an epoxy-containing polydimethylsiloxane, but the present invention is not limited thereto.

[0335] The epoxy-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 10 Unit), but except D 10 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0336] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: 10 Polyorganosiloxane composed of units; containing D 10 Units and Q units of polyorganosiloxane; containing D 10 Polyorganosiloxane containing D 10 Units and T units of polyorganosiloxane; containing D 10 Unit, Q unit and M unit of polyorganosiloxane; containing D 10 Unit, M unit and T unit of polyorganosiloxane; containing D 10 Unit, Q unit, M unit and T unit of polyorganosiloxane, etc.

[0337] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight is not particularly limited but is usually 1,500 to 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0338] Specific examples of the epoxy-containing polyorganosiloxane include polyorganosiloxanes represented by formulae (E1) to (E3), but are not limited to these.

[0339]

[0340] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0341]

[0342] (m2 and n2 represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0343]

[0344] (m3, n3 and o3 represent the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0345] Examples of the methyl group-containing polyorganosiloxane include: 210 R 220 SiO 2 / 2 The siloxane units (D 200 Units), preferably comprising R 21 R 21 SiO 2 / 2 The siloxane units (D 20 Unit) polyorganosiloxane.

[0346] R 210 and R 220 is a group bonded to a silicon atom, each independently represents an alkyl group, but at least one of them is a methyl group. Specific examples of the alkyl group include those described above.

[0347] R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include the above examples. 21 , preferably methyl.

[0348] In the present invention, polydimethylsiloxane is mentioned as a preferred example of the methyl group-containing polyorganosiloxane, but the present invention is not limited to this.

[0349] The methyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 200 Unit or D 20 Unit), but except D 200 Unit and D 20 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0350] In one embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 200 Polyorganosiloxane composed of units; containing D 200 Units and Q units of polyorganosiloxane; containing D 200 Polyorganosiloxane containing D 200 Units and T units of polyorganosiloxane; containing D 200 Unit, Q unit and M unit of polyorganosiloxane; containing D 200Unit, M unit and T unit of polyorganosiloxane; containing D 200 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0351] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 20 Polyorganosiloxane composed of units; containing D 20 Units and Q units of polyorganosiloxane; containing D 20 Polyorganosiloxane containing D 20 Units and T units of polyorganosiloxane; containing D 20 Unit, Q unit and M unit of polyorganosiloxane; containing D 20 Unit, M unit and T unit of polyorganosiloxane; containing D 20 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0352] Specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane represented by formula (M1), but the present invention is not limited thereto.

[0353]

[0354] (n4 represents the number of repeating units, which is a positive integer.)

[0355] Examples of the phenyl group-containing polyorganosiloxane include: 31 R 32 SiO 2 / 2 The siloxane units (D 30 Unit) polyorganosiloxane.

[0356] R 31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group, R 32 It is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those described above, and a methyl group is preferred.

[0357] The phenyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 30 Unit), but except D 30 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0358] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include: 30 Polyorganosiloxane composed of units; containing D 30 Units and Q units of polyorganosiloxane; containing D 30 Polyorganosiloxane containing D30 Units and T units of polyorganosiloxane; containing D 30 Unit, Q unit and M unit of polyorganosiloxane; containing D 30 Unit, M unit and T unit of polyorganosiloxane; containing D 30 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0359] Specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes represented by the formula (P1) or (P2), but are not limited to these.

[0360]

[0361] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0362]

[0363] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0364] The polyorganosiloxane as the release agent component (B) may be a commercially available product or a synthesized polyorganosiloxane.

[0365] Examples of commercially available polyorganosiloxanes include Wacker Chemie products such as the Wackersilicon Fluid AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000), GENIOPLAST GUM, Shin-Etsu Chemical Co., Ltd. dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995); Gelest Co., Ltd. epoxy-containing polyorganosiloxanes (trade names: CMS-227, ECMS-327); Shin-Etsu Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343); and Dow Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-102, KF-103, KF-104, KF-1056, X-22-347). Epoxy-containing polyorganosiloxane manufactured by Corning (BY16-839); phenyl-containing polyorganosiloxane manufactured by Gelest (PMM-1043, PMM-1025, PDM-0421, PDM-0821), phenyl-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (KF50-3000CS), phenyl-containing polyorganosiloxane manufactured by Momentive (TSF431, TSF433), etc., but not limited to these.

[0366] In one embodiment, the adhesive composition used in the present invention contains a curable component (A) and a non-curing component (B). In another embodiment, the adhesive composition contains a polyorganosiloxane as the component (B).

[0367] An example of the adhesive composition used in the present invention may contain component (A) and component (B) in an arbitrary ratio. If the balance between adhesion and releasability is taken into consideration, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A):(B)].

[0368] That is, when the polyorganosiloxane component (A') that cures by hydrosilylation reaction is included, the ratio of component (A') to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A'):(B)].

[0369] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s at 25° C., and preferably 1,000 to 10,000 mPa·s.

[0370] One example of the adhesive composition used in the present invention can be produced by mixing the component (A), the component (B) when used, and a solvent.

[0371] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing an adhesive composition, for example, there can be cited: a method of dissolving component (A) and component (B) in a solvent; a method of dissolving a part of component (A) and component (B) in a solvent, dissolving the rest in a solvent, and mixing the resulting solutions, but the method is not limited to these. It should be noted that when preparing the adhesive composition, it can also be heated appropriately within a range in which the components are not decomposed or deteriorated.

[0372] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the preparation of the adhesive composition or after all the components are mixed.

[0373] From the viewpoint of unevenness due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and further preferably 70 μm or less.

[0374] The method of forming the adhesive layer from the adhesive composition is described in detail in the explanation section of "Method for producing an example of a laminated body in the first embodiment" described below.

[0375] Hereinafter, an example of the structure of the laminated body according to the first embodiment will be described using drawings.

[0376] Figure 1 A schematic cross-sectional view showing an example of the laminated body according to the first embodiment.

[0377] Figure 1 The laminated body includes a semiconductor substrate 1 having bumps 1 a , a release agent layer 2 , an adhesive layer 3 , and a support substrate 4 in this order.

[0378] The bumps 1 a included in the semiconductor substrate 1 are arranged on the support substrate 4 side.

[0379] The release agent layer 2 is interposed between the semiconductor substrate 1 and the support substrate 4. The release agent layer 2 is in contact with the semiconductor substrate 1. Furthermore, the release agent layer 2 covers the bumps 1a.

[0380] The adhesive layer 3 is interposed between the release agent layer 2 and the support substrate 4. The adhesive layer 3 is in contact with the release agent layer 2 and the support substrate 4.

[0381] The thickness of the release agent layer 2 is, for example, 0.5 μm to 10 μm. If the thickness is within this range, a semiconductor substrate having bumps with a height of about 30 μm to 40 μm can be covered.

[0382] <<Method for producing an example of a laminate in the first embodiment>>

[0383] In the laminated body of the first embodiment, Figure 1 The following method for producing the laminate will be described using the laminate shown in FIG. 1 as an example.

[0384] An example of the laminate of the present invention can be produced by, for example, a method including the following first to third steps.

[0385] First step: a step of applying a release agent composition to the surface of the semiconductor substrate where the bumps are present to form a release agent layer.

[0386] Second step: a step of applying an adhesive composition on the surface of the release agent layer to form an adhesive coating layer.

[0387] The third step is a step of heating the adhesive coating layer to form an adhesive layer in a state where the support substrate is in contact with the adhesive coating layer and the adhesive coating layer is in contact with the release agent layer.

[0388] The coating method of the release agent composition is not particularly limited, but is usually a spin coating method.

[0389] The heating temperature of the stripper composition after coating varies according to the type and amount of the stripper component contained in the stripper composition, the thickness of the desired stripper layer, etc., and therefore cannot be generally specified. From the perspective of achieving an appropriate stripper layer with good reproducibility, it is 80°C or more and 300°C or less, and the heating time is appropriately determined in the range of 10 seconds to 10 minutes according to the heating temperature. The heating temperature is preferably 100°C or more and 280°C or less, more preferably 150°C or more and 250°C or less. The heating time is preferably 30 seconds or more and 8 minutes or less, more preferably 1 minute or more and 5 minutes or less.

[0390] Heating can be performed using a hot plate, an oven, or the like.

[0391] The film thickness of the release agent layer obtained by applying the release agent composition and heating it as needed is usually about 5 nm to 100 μm.

[0392] The method for applying the adhesive composition is not particularly limited, but is usually spin coating. It is also possible to form a coating film separately by spin coating or the like to form a sheet-like coating film, and to attach the sheet-like coating film as the adhesive coating layer.

[0393] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive components contained in the adhesive composition, whether a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., and therefore cannot be generally specified, but is usually 80 to 150° C., and the heating time is usually 30 seconds to 5 minutes.

[0394] When the adhesive composition contains a solvent, the adhesive composition after application is usually heated.

[0395] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it as needed is usually about 5 to 500 μm, and is appropriately determined so that the thickness of the adhesive layer finally falls within the above-mentioned range.

[0396] In the present invention, such coating layers can be put together in a mutually contacting manner, and a load in the thickness direction of the semiconductor substrate and the supporting substrate is applied to make the two layers close to each other while performing a heating treatment or a decompression treatment or both, and then a post-heating treatment is performed, thereby obtaining the laminate of the present invention. It should be noted that the treatment conditions of any of the heating treatment, the decompression treatment, and the combination of the two are appropriately determined based on various situations such as the type of the adhesive composition, the specific composition of the stripper composition, the phase of the film obtained from the two compositions, the film thickness, and the bonding strength obtained.

[0397] The heating treatment temperature is usually appropriately determined within the range of 20 to 150° C. from the viewpoint of removing the solvent from the composition, softening the adhesive coating layer and achieving appropriate bonding with the release agent layer, etc. In particular, from the viewpoint of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), it is preferably 130° C. or less, more preferably 90° C. or less. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, and is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably achieving appropriate bonding, and is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other members.

[0398] The reduced pressure treatment may be performed by exposing the adhesive coating layer and the release agent layer in contact with each other to a gas pressure of 10 to 10000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

[0399] From the viewpoint of obtaining a laminated body in which the substrates can be well separated with good reproducibility, the two layers in contact with each other are preferably bonded together by a reduced pressure treatment, more preferably a combined heating treatment and a reduced pressure treatment.

[0400] 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 and the support substrate and the two layers therebetween and allows them to be firmly adhered to each other, but is usually in the range of 10 to 1000N.

[0401] From the viewpoint of achieving a sufficient curing speed, the post-heating temperature is preferably 120° C. or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260° C. or lower.

[0402] From the perspective of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually more than 1 minute, preferably more than 5 minutes. From the perspective of suppressing or avoiding the adverse effects of excessive heating on the layers, the post-heating time is usually less than 180 minutes, preferably less than 120 minutes.

[0403] Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, the semiconductor substrate and the support substrate of the stack can be heated with either side facing downward. From the perspective of achieving appropriate peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.

[0404] It should be noted that one of the purposes of the post-heat treatment is to achieve a more appropriate adhesive layer and release agent layer as a self-supporting film, and in particular, to appropriately achieve curing by a hydrosilylation reaction.

[0405] Below, use Figure 2A to Figure 2E About Manufacturing Figure 1An example of a method for forming a laminated body will be described.

[0406] Figure 2A to Figure 2E This is a diagram for explaining one method of manufacturing a laminated body.

[0407] First, a semiconductor substrate 1 having bumps 1a is prepared. Figure 2A ).

[0408] Next, a release agent composition is applied to the surface of the semiconductor substrate 1 where the bumps 1a are present to form a release agent layer 2 ( Figure 2B ).

[0409] Next, an adhesive composition is applied on the release agent layer 2 to form an adhesive coating layer 3a ( Figure 2C ).

[0410] Next, a supporting substrate 4 ( Figure 2D ).

[0411] Next, after a load is applied in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; heating plate) is arranged on the surface opposite to the surface of the semiconductor substrate 1 where the bump 1a exists, and the adhesive coating layer 3a is heated and cured by the heating device to be converted into an adhesive layer 3( Figure 2E ).

[0412] pass Figure 2A to Figure 2E The steps shown in can obtain a laminated body.

[0413] It should be noted that in Figure 1 In the embodiment, the laminated body is sequentially laminated with a semiconductor substrate 1, a release agent layer 2, an adhesive layer 3, and a supporting substrate 4, so the above-mentioned manufacturing method is cited as an example, but for example, in the case of manufacturing a laminated body in which a semiconductor substrate 1, an adhesive layer 3, a release agent layer 2, and a supporting substrate 4 are sequentially laminated, it can be manufactured by a method including the following steps: a first step, applying an adhesive composition on the surface of the semiconductor substrate, heating it as needed to form an adhesive coating layer; a second step, applying a release agent composition on the surface of the supporting substrate, heating it as needed to form a release agent layer; and a third step, applying a load in the thickness direction of the semiconductor substrate and the supporting substrate to make them fit together while subjecting the adhesive coating layer of the semiconductor substrate and the release agent layer of the supporting substrate to at least one of a heating treatment and a decompression treatment, and then subjecting the semiconductor substrate and the supporting substrate to a post-heating treatment, thereby forming a laminated body.

[0414] It should be noted that, as long as the effects of the present invention are not impaired, the coating and heating of the respective compositions may be performed sequentially on either substrate.

[0415] <Second Implementation Method>

[0416] The laminate having the electronic device layer is used for processing the electronic device layer. During the processing of the electronic device layer, the electronic device layer is adhered to the support substrate. After the processing of the electronic device layer, the release agent layer is irradiated with light, and the electronic device layer is separated from the support substrate.

[0417] <<Electronic device layer>>

[0418] The electronic device layer refers to a layer having electronic devices, and in the present invention, refers to a layer in which a plurality of semiconductor chip substrates are buried in a sealing resin, that is, a layer including a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.

[0419] Here, "electronic device" refers to a member that constitutes at least a part of an electronic component. There are no particular restrictions on the electronic device, and it can be an electronic device in which various mechanical structures and circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a member composed of a metal or semiconductor and a resin that seals or insulates the member. The electronic device can be an electronic device in which a redistribution layer and / or a semiconductor element or other element described later is sealed or insulated with a sealing material or an insulating material, and has a single-layer or multi-layer structure.

[0420] <<Support substrate>>

[0421] As the supporting substrate, the same supporting substrate as that described in the column of <<Supporting substrate>> in the <First embodiment> is exemplified.

[0422] <<Release agent layer>>

[0423] The release agent layer is formed using the above-mentioned release agent composition for light irradiation release of the present invention.

[0424] The details of the release agent layer are as described in the above-mentioned <<Release agent layer>> section of the <First embodiment>.

[0425] <<Adhesive layer>>

[0426] The adhesive layer is formed using the above-mentioned adhesive composition.

[0427] The details of the adhesive layer are as described in the section of <<Adhesive layer>> in the <First embodiment>.

[0428] Hereinafter, an example of the structure of the laminated body according to the second embodiment will be described using drawings.

[0429] Figure 3 A schematic cross-sectional view showing an example of a laminate according to the second embodiment.

[0430] Figure 3 The laminated body includes a supporting substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26 in this order.

[0431] The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .

[0432] The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0433] In addition, another example of the structure of the laminated body of the second embodiment is shown in Figure 4 .

[0434] When the release agent layer of the present invention is a release agent layer having adhesive properties having both release and adhesive functions, the laminate may be formed of a single layer of a release agent layer having adhesive properties instead of a double layer of a release agent layer and an adhesive layer.

[0435] Figure 4 A schematic cross-sectional view showing another example of the laminated body.

[0436] Figure 4 The laminated body has a supporting substrate 24, a release agent layer 27 having adhesive properties, and an electronic device layer 26 in this order.

[0437] The release agent layer 27 having adhesive properties is provided between the support substrate 24 and the electronic device layer 26. The release agent layer 27 having adhesive properties can be produced by mixing components of a release agent composition forming a release agent with components of an adhesive composition forming an adhesive layer.

[0438] <<Method for producing an example of a laminate in the second embodiment>>

[0439] In the laminated body of the second embodiment, Figure 3 Taking the laminate shown in the figure as an example, a method for producing the laminate will be described below.

[0440] The laminate of the present invention can be produced, for example, by a method including the following first to fifth steps.

[0441] First step: a step of applying a release agent composition on the surface of the support substrate to form a release agent coating layer (if necessary, further heating to form a release agent layer).

[0442] Second step: a step of applying an adhesive composition to the release agent coating layer or the surface of the release agent layer to form an adhesive coating layer (if necessary, further heating to form an adhesive layer).

[0443] The third step is a step of placing a semiconductor chip substrate on the adhesive coating layer or the adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer while performing at least one of a heating treatment and a reduced pressure treatment.

[0444] Fourth step: a step of forming an adhesive layer by subjecting the adhesive coating layer to post-heat treatment to cure the adhesive coating layer.

[0445] Fifth step: a step of sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin.

[0446] When the third step is described in more detail, for example, the step of the following embodiment (i) can be cited.

[0447] (i) placing a semiconductor chip substrate on an adhesive coating layer or an adhesive layer, applying a load in the thickness direction of the semiconductor chip substrate and the supporting substrate to make them closely fit together while performing at least one of a heating treatment and a decompression treatment, thereby bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer.

[0448] It should be noted that the fourth step can be performed after the semiconductor chip substrate is bonded to the adhesive coating layer in the third step, or can be performed together with the third step. For example, the semiconductor chip substrate is placed on the adhesive coating layer, and a load in the thickness direction of the semiconductor chip substrate and the supporting substrate is applied while the adhesive coating layer is heated to cure it, thereby performing the bonding of the semiconductor chip substrate and the adhesive coating layer and the curing of the adhesive coating layer to the adhesive layer at the same time, and the adhesive layer can be bonded to the semiconductor chip substrate.

[0449] The fourth step may be performed before the third step, or the semiconductor chip substrate may be placed on the adhesive layer and the adhesive layer and the semiconductor chip substrate may be bonded together while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0450] The coating method, the release agent composition to be coated, the heating temperature and heating method of the adhesive composition are the same as those described in the above-mentioned <<Method for producing an example of a laminated body in the first embodiment>> of the above-mentioned <First embodiment>.

[0451] The manufacturing method of the laminated body of the second embodiment is described in more detail below using the drawings. Figure 3 The stack shown.

[0452] like Figure 5A As shown, a release agent coating layer 23' made of a release agent composition is formed on a support substrate 24. At this time, the release agent coating layer 23' may be heated to form the release agent layer 23.

[0453] Then, if Figure 5B As shown, an adhesive coating layer 22' made of an adhesive composition is formed on the release coating layer 23' or the release layer 23. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22.

[0454] Then, if Figure 5C As shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22', and a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to make them close while performing at least one of a heating treatment and a decompression treatment, so that the semiconductor chip substrate 21 is attached to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is attached to the adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heating to form an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0455] It should be noted that when the adhesive coating layer 22 ′ is subjected to post-heat treatment, the release agent coating layer 23 ′ may be subjected to post-heat treatment at the same time to form the release agent layer 23 .

[0456] Then, if Figure 5D As shown, the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed with a sealing resin 25 . Figure 5D In the embodiment, a plurality of semiconductor chip substrates 21 temporarily bonded to a support substrate 24 via an adhesive layer 22 are sealed by a sealing resin 25. An electronic device layer 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22, so that the electronic device layer 26 becomes a base material layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0457] <<<Sealing process>>>

[0458] The semiconductor chip substrate 21 is sealed using a sealing material.

[0459] As a sealing material for sealing the semiconductor chip substrate 21, a member capable of insulating or sealing a member made of metal or semiconductor is used.

[0460] In the present invention, as the sealing material, for example, a resin composition (sealing resin) is used. The type of the sealing resin is not particularly limited as long as it can seal and / or insulate a metal or a semiconductor, and for example, epoxy resins or silicone resins are preferably used.

[0461] The sealing material may contain other components such as fillers in addition to the resin component. Examples of the filler include spherical silica particles.

[0462] In the sealing process, the sealing resin heated to, for example, 130 to 170° C. is supplied to the adhesive layer 22 in a manner that covers the semiconductor chip substrate 21 while maintaining a high viscosity, and compression molding is performed, thereby forming a layer composed of the sealing resin 25 on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170° C. In addition, the pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm 2 .

[0463] (Method for manufacturing processed semiconductor substrate or electronic device layer)

[0464] By using the laminated body of the present invention, a method for producing a processed semiconductor substrate or a method for producing a processed electronic device layer can be provided.

[0465] The "processed semiconductor substrate manufacturing method" uses the laminate described in the column of the above <First Embodiment> of the above (laminated body). In addition, the "processed electronic device layer manufacturing method" uses the laminate described in the column of the above <Second Embodiment> of the above (laminated body).

[0466] The “method for producing a processed semiconductor substrate” will be described in the following <Third Embodiment>, and the “method for producing a processed electronic device layer” will be described in the following <Fourth Embodiment>.

[0467] <Third Implementation Plan>

[0468] The method for producing a processed semiconductor substrate of the present invention includes the following fifth step A and the following sixth step A. The method for producing a processed electronic device layer may further include the following seventh step A.

[0469] Here, the fifth step A is a step of processing the semiconductor substrate in the laminated body described in the column of the above-mentioned <First Embodiment>.

[0470] In addition, the sixth A step is a step of separating the semiconductor substrate processed in the fifth A step from the support substrate.

[0471] In addition, the seventh A step is a step of cleaning the processed semiconductor substrate after the sixth A step.

[0472] In the fifth A step, the processing performed on the semiconductor substrate refers to, for example, the processing on the opposite side of the circuit surface of the wafer, and the thinning of the wafer by grinding the back side of the wafer can be cited. Then, for example, through silicon vias (TSV) are formed, and then the thinned wafer is peeled off from the supporting substrate to form a stack of wafers for three-dimensional mounting. In addition, for example, the formation of electrodes on the back side of the wafer is also performed before and after three-dimensional mounting. In the thinning and TSV processes of the wafer, heat of about 250 to 350°C is applied in a state bonded to the supporting substrate. The stack of the present invention generally includes an adhesive layer and has heat resistance to the load.

[0473] It should be noted that the processing is not limited to the above processing, and includes, for example, a semiconductor component mounting process when temporary bonding with a support substrate is performed in order to support a base material for mounting a semiconductor component.

[0474] In the sixth step A, the method of separating (peeling off) the semiconductor substrate from the supporting substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the peeling agent layer with light, peeling by tearing between the supporting body and the semiconductor chip, etc.

[0475] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the semiconductor substrate from the support substrate.

[0476] It is not necessary to irradiate the release agent layer with light to the entire area of ​​the release agent layer. Even if the area irradiated with light and the area not irradiated with light are mixed, as long as the peeling ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the supporting substrate by a slight external force such as pulling up the supporting substrate. The ratio and positional relationship of the area irradiated with light and the area not irradiated with light vary depending on the type of adhesive used, its specific composition; the thickness of the adhesive layer; the thickness of the adhesive layer; the thickness of the release agent layer; the intensity of the irradiated light, etc., but if a person skilled in the art is skilled in the art, appropriate conditions can be set without excessive experiments. Due to such a situation, according to the method for manufacturing a processed semiconductor substrate of the present invention, for example, when the supporting substrate of the stacked body used is light-transmissive, the light irradiation time can be shortened when peeling is performed by irradiating light from the supporting substrate side. As a result, not only can an improvement in throughput be expected, but also physical stress used for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the supporting substrate only by irradiation with light.

[0477] Generally, the irradiation dose of light used for peeling is 50 to 3000 mJ / cm 2The irradiation time is appropriately determined according to the wavelength and the irradiation amount.

[0478] As described above, the wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the novolac resin, such as decomposition.

[0479] The light used for stripping can be laser or non-laser emitted from a light source such as ultraviolet lamp.

[0480] The cleaning composition may be sprayed on the surface of at least any one of the separated semiconductor substrate and the supporting substrate, or the separated semiconductor substrate or the supporting substrate may be immersed in the cleaning composition to clean the substrate.

[0481] In addition, the surface of a processed semiconductor substrate or the like can also be cleaned using a removal tape or the like.

[0482] As an example of cleaning the substrate, a seventh A step of cleaning the processed semiconductor substrate may be performed after the sixth A step.

[0483] Examples of the cleaning agent composition used for cleaning include the following.

[0484] Cleaner compositions typically comprise a salt and a solvent.

[0485] A preferred example of the cleaning composition is a cleaning composition containing a quaternary ammonium salt and a solvent.

[0486] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for such a purpose.

[0487] As such quaternary ammonium cations, tetra(alkyl)ammonium cations are typically mentioned. On the other hand, as anions forming pairs with them, hydroxide ions (OH － );Fluoride ion (F － ), chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ion (BF4 － );PF6 － ), etc., but are not limited to these.

[0488] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0489] In the quaternary ammonium salt, the halogen atom may be contained in the cation or in the anion, but is preferably contained in the anion.

[0490] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0491] Specific examples of the hydrocarbon group in tetrahydrocarbyl ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

[0492] In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.

[0493] Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Among them, tetrabutylammonium fluoride is preferred.

[0494] A quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used in the form of a hydrate. In addition, a quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used alone or in combination of two or more.

[0495] The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the cleaning composition, but is generally 0.1 to 30% by mass based on the cleaning composition.

[0496] The solvent contained in the cleaning composition is not particularly limited as long as it can be used for such purposes and dissolves salts such as quaternary ammonium salts. From the viewpoint of obtaining a cleaning composition with excellent cleaning properties with good reproducibility and from the viewpoint of dissolving salts such as quaternary ammonium salts well and obtaining a cleaning composition with excellent uniformity, the cleaning composition preferably contains one or more amide solvents.

[0497] As a preferred example of the amide solvent, an amide derivative represented by formula (Z) can be mentioned.

[0498]

[0499] In the formula, R 0 R represents ethyl, propyl or isopropyl, preferably ethyl or isopropyl, more preferably ethyl. A and R B Each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be any of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl. A and R B, preferably methyl or ethyl, more preferably both are methyl or ethyl, further preferably both are methyl.

[0500] Examples of the amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutanamide, N,N-diethylbutanamide, N-ethyl-N-methylbutanamide, N,N-dimethylisobutanamide, N,N-diethylisobutanamide, and N-ethyl-N-methylisobutanamide. Among them, N,N-dimethylpropanamide and N,N-dimethylisobutanamide are particularly preferred, and N,N-dimethylpropanamide is more preferred.

[0501] The amide derivative represented by the formula (Z) can be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product can be used.

[0502] Another example of a preferred amide solvent includes a lactam compound represented by formula (Y).

[0503]

[0504] In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 It represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and n-butyl, and specific examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, but are not limited thereto.

[0505] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, and the like, and these may be used alone or in combination of two or more.

[0506] In a preferred embodiment, the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, contains N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment, contains N-methylpyrrolidone (NMP).

[0507] The cleaning composition may contain one or two or more other organic solvents other than the above-mentioned amide compound.

[0508] Such other organic solvent is not particularly limited as long as it is an organic solvent used for such an application and is compatible with the above-mentioned amide compound.

[0509] Preferred other solvents include alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing a cyclic structure, but are not limited thereto.

[0510] The amount of the organic solvent other than the above-mentioned amide compound is appropriately determined so as to be 95% by mass or less in the solvent contained in the cleaning composition, as long as the quaternary ammonium salt contained in the cleaning composition does not precipitate or separate and is uniformly mixed with the above-mentioned amide compound.

[0511] It should be noted that the cleaning agent composition may also contain water as a solvent, but from the perspective of avoiding corrosion of the substrate, etc., it is generally intended to use only organic solvents as solvents. It should be noted that in this case, the cleaning agent composition may contain hydration water of salts and trace amounts of water contained in the organic solvent, but this is not to deny them all. The water content of the cleaning agent composition is generally 5% by mass or less.

[0512] The constituent elements and method elements related to the above-mentioned steps of the method for manufacturing a processed semiconductor substrate of the present invention may be variously modified without departing from the gist of the present invention.

[0513] The method for producing a processed semiconductor substrate of the present invention may include steps other than the above-mentioned steps.

[0514] In the peeling method of the present invention, when the semiconductor substrate or the supporting substrate of the laminated body of the present invention is light-transmissive, the semiconductor substrate and the supporting substrate of the laminated body are separated by irradiating the peeling agent layer with light from the semiconductor substrate side or the supporting substrate side.

[0515] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and releasably by the adhesive layer and the release agent layer, so that, for example, when the support substrate is light-transmissive, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Usually, the peeling is performed after the semiconductor substrate of the laminate is processed.

[0516] use Figure 6A to Figure 6C An example of the third embodiment will be described. This example is an example of manufacturing a thinned semiconductor substrate.

[0517] First, prepare a laminate ( Fig. 6A ). The laminate is Figure 1 and Figure 2E The stack shown is the same stack.

[0518] Next, a grinding device (not shown) is used to grind the surface of the semiconductor substrate 1 opposite to the surface on which the bumps 1a are present, so that the semiconductor substrate 1 is thinned ( Figure 6B ) It should be noted that the thinned semiconductor substrate 1 may be subjected to formation of through electrodes and the like.

[0519] Next, after the release agent layer 2 is irradiated with light from the support substrate 4 side, a peeling device (not shown) is used to peel the thinned semiconductor substrate 1 and the support substrate 4. In this way, the thinned semiconductor substrate 1 ( Figure 6C ).

[0520] Here, residues of the release agent layer 2 and the adhesive layer 3 may remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 with a cleaning composition to remove the residues of the release agent layer 2 and the adhesive layer 3 from the semiconductor substrate 1.

[0521] <Fourth Implementation Plan>

[0522] The method for producing a processed electronic device layer of the present invention includes the following fifth step B and the following sixth step B. The method for producing a processed electronic device layer may further include the following seventh step B.

[0523] Here, the fifth step B is a step of processing the electronic device layer in the laminate described in the above-mentioned <Second embodiment> section.

[0524] In addition, the sixth B step is a step of separating the electronic device layer processed in the fifth B step from the support substrate.

[0525] In addition, the seventh B step is a step of cleaning the processed electronic device layer after the sixth B step.

[0526] Below, use Figure 7A to Figure 7F A specific example of the fourth embodiment will be described.

[0527] Examples of the processing performed on the electronic device layer in the fifth B step include a grinding step and a wiring layer forming step.

[0528] <<Grinding process>>

[0529] The grinding step is a step of grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 so that a portion of the semiconductor chip substrate 21 is exposed.

[0530] Grinding of sealing resin parts, for example Figure 7B As shown, by Fig. 7A The sealing resin 25 layer of the laminated body shown is ground to a thickness substantially the same as that of the semiconductor chip substrate 21. Fig. 7A The stack shown is with Figure 3 and Figure 5D The stack shown is the same stack.

[0531] <<Wiring layer formation process>>

[0532] The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding step.

[0533] Figure 7C In the embodiment, a wiring layer 28 is formed on an electronic device layer 26 including a semiconductor chip substrate 21 and a sealing resin 25 .

[0534] The wiring layer 28 is also called RDL (Redistribution Layer), which is a thin-film wiring body that constitutes wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer can be made of a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) on a dielectric (silicon oxide (SiO X ), photosensitive resin such as photosensitive epoxy, etc.) to form a wiring layer, but is not limited to this.

[0535] As a method of forming the wiring layer 28 , for example, the following method can be cited.

[0536] First, silicon oxide (SiO X ), photosensitive resin and other dielectric layers. The dielectric layer composed of silicon oxide can be formed by, for example, sputtering, vacuum evaporation, etc. The dielectric layer composed of photosensitive resin can be formed by, for example, applying photosensitive resin on the layer of sealing resin 25 by spin coating, dipping, roller blade, spray coating, slit coating, etc.

[0537] Next, wiring is formed on the dielectric layer using a conductor such as a metal. As a method for forming wiring, for example, a known semiconductor process method such as a lithography process such as photolithography (resist lithography) and an etching process can be used. As such a lithography process, for example, a lithography process using a positive resist material and a lithography process using a negative resist material can be listed.

[0538] In the method for manufacturing the laminated body of the fourth embodiment, bumps may be further formed or components may be mounted on the wiring layer 28. The components may be mounted on the wiring layer 28 using, for example, a chip mounter or the like.

[0539] The laminated body of the fourth embodiment may be a laminated body produced by a process based on a fan-out technology in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer extending outside a chip region.

[0540] In the sixth step B, the method of separating (peeling off) the electronic device layer from the supporting substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the peeling agent layer with light, peeling by tearing between the supporting body and the electronic device layer, etc.

[0541] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the electronic device layer from the support substrate.

[0542] Figure 7D to Figure 7E is a schematic cross-sectional view for explaining a method for separating a laminated body. Figure 7F This is a schematic cross-sectional view for explaining a method for cleaning a laminated body after separation. Figure 7D to Figure 7F , which can illustrate an embodiment of a method for manufacturing a semiconductor package (electronic component).

[0543] like Fig.7D As shown in FIG. 1 , the step of separating the laminated body is a step of irradiating the release agent layer 23 with light (arrow) via the support substrate 24 to modify the release agent layer 23 , thereby separating the electronic device layer 26 from the support substrate 24 .

[0544] After the release agent layer 23 is irradiated with light (arrow) to deteriorate the release agent layer 23, Fig. 7E As shown, the support substrate 24 is separated from the electronic device layer 26 .

[0545] The conditions and method of irradiating the adhesive layer with light are the same as those described in the above-mentioned section of <Third Embodiment>.

[0546] The substrate may be cleaned by spraying the cleaning composition on the surface of at least any one of the separated electronic device layer and the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition.

[0547] In addition, the surface of the processed electronic device layer or the like can also be cleaned using a removal tape or the like.

[0548] For example, in Fig. 7E In the embodiment, after the separation step, the adhesive layer 22 and the release agent layer 23 are attached to the electronic device layer 26, but by using a cleaning agent composition such as an acid or an alkali to decompose the adhesive layer 22 and the release agent layer 23, the adhesive layer 22 and the release agent layer 23 can be removed. By removing the release agent layer and the adhesive layer, the following can be appropriately obtained: Figure 7F The processed electronic device layer (electronic component) is shown.

[0549] The constituent elements and method elements related to the above-mentioned steps of the method for producing a processed electronic device layer of the present invention may be variously modified without departing from the gist of the present invention.

[0550] The method for producing a processed electronic device layer of the present invention may include steps other than the above-mentioned steps.

[0551] In the laminate of the present invention, the electronic device layer and the supporting substrate are temporarily bonded appropriately and releasably by the adhesive layer, so that, for example, when the supporting substrate is light-transmissive, the electronic device layer and the supporting substrate can be easily separated by irradiating light to the release agent layer from the supporting substrate side of the laminate. Usually, the peeling is performed after the electronic device layer of the laminate is processed.

[0552] Example

[0553] 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.

[0554] [Device]

[0555] (1) Mixer A: ARE-500, a rotary and revolving mixer manufactured by THINKY Co., Ltd.

[0556] (2) Mixer H: AS ONE heated swing mixer HRM-1.

[0557] (3) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.

[0558] (4) Optical film thickness meter (film thickness measurement): F-50 manufactured by Filmetrics Co., Ltd.

[0559] (5) Vacuum bonding device: manufactured by SUSS MicroTec Co., Ltd., manual bonding machine.

[0560] (6) Determination of weight average molecular weight and dispersity:

[0561] GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by TOSOH Corporation).

[0562] Column temperature: 40°C.

[0563] · Eluent (elution solvent): tetrahydrofuran.

[0564] · Flow rate: 0.35 mL / min.

[0565] Standard sample: polystyrene (manufactured by Sigma Aldrich).

[0566] (7) Laser irradiation device: Lambda SX manufactured by Coherent Corporation.

[0567] [1] Synthesis of polymer contained in release agent layer

[0568] [Synthesis Example 1-1]

[0569] Under nitrogen, 15.0 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.88 g of 2-ethylhexanal (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.90 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 200 mL four-necked flask, and 64.33 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd., hereinafter referred to as PGMEA) was further added, stirred, and heated to 150°C to dissolve it to initiate polymerization. After 24 hours, it was cooled to room temperature and reprecipitated into 300 g of methanol: water (7:3 (mass ratio)). The obtained precipitate was separated by decantation and dried at 60°C for 24 hours using a reduced pressure dryer to obtain the target polymer (hereinafter referred to as PCzEHA).

[0570] The weight average molecular weight Mw of PCzEHA measured by GPC in terms of polystyrene was 1800. The obtained polymer was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target polymer solution.

[0571] PCzEHA has the following repeating units.

[0572]

[0573] [Synthesis Example 1-2]

[0574] Under nitrogen, 15.03 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.51 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.44 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 200 mL four-necked flask, and 58.24 g of PGMEA (manufactured by Kanto Chemical Co., Ltd.) was further added, stirred, and heated to 120°C to dissolve it to initiate polymerization. After 3 hours, it was cooled to room temperature and reprecipitated into 300 g of methanol: water (7:3 (mass ratio)). The precipitate obtained was filtered and dried at 60°C for 24 hours using a reduced pressure dryer to obtain the target polymer (hereinafter referred to as PCzBA).

[0575] The weight average molecular weight Mw of PCzBA measured by GPC in terms of polystyrene was 3200. The obtained polymer was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target polymer solution.

[0576] PCzBA has the following repeating units.

[0577]

[0578] [Synthesis Example 1-3]

[0579] Under nitrogen, 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.55 g of 1-naphthaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.95 g of p-toluenesulfonic acid monohydrate (manufactured by Kanto Chemical Co., Ltd.) were added to a 100 mL four-necked flask, and 8 g of 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.) was further added, stirred, and heated to 100°C to dissolve it to initiate polymerization. After cooling to 60°C after 4 hours, 40 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) was added to dilute it and reprecipitate it in 200 g of methanol. The precipitate obtained by filtration was dried at 60°C for 10 hours using a reduced pressure dryer, and further dried at 120°C for 24 hours to obtain the target polymer (hereinafter referred to as PCzNA).

[0580] The weight average molecular weight Mw of PCzNA measured by GPC in terms of polystyrene was 2600. The obtained polymer was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target polymer solution.

[0581] PCzNA has the following repeating units.

[0582]

[0583] [Synthesis Example 1-4]

[0584] Under nitrogen, 8.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.63 g of 9-fluorenone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2.3 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 200 mL four-necked flask, and 18.93 g of PGMEA (manufactured by Kanto Chemical Co., Ltd.) was further added, stirred, and heated to 150°C to dissolve it to initiate polymerization. After 1.5 hours, it was cooled to room temperature and reprecipitated into 300 g of methanol: water (7:3 (mass ratio)). The precipitate obtained was filtered and dried at 60°C for 24 hours using a reduced pressure dryer to obtain the target polymer (hereinafter referred to as PCzFL).

[0585] The weight average molecular weight Mw of PCzFL measured by GPC in terms of polystyrene was 2600. The obtained polymer was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target polymer solution.

[0586] PCzFL has the following repeating units.

[0587]

[0588] [Synthesis Example 1-5]

[0589] Under nitrogen, 9.99 g of diphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.52 g of 2-ethylhexanal (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.86 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 200 mL four-necked flask, and 42.88 g of PGMEA (manufactured by Kanto Chemical Co., Ltd.) was further added, stirred, and heated to 150°C to dissolve it to initiate polymerization. After 24 hours, it was cooled to room temperature and reprecipitated into 300 g of methanol: water (7:3 (mass ratio)). The obtained precipitate was separated by decantation and dried at 60°C for 24 hours using a reduced pressure dryer to obtain the target polymer (hereinafter referred to as DPAEHA).

[0590] The weight average molecular weight Mw of DPAEHA measured by GPC in terms of polystyrene was 1200. The obtained polymer was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target polymer solution.

[0591] DPAEHA has the following repeating units.

[0592]

[0593] [Synthesis Example 1-6]

[0594] 1,4-dioxane 86.36g and toluene 86.36g were added to 56.02g of 1-phenylnaphthylamine, 50.00g of 1-pyrene carboxaldehyde (made by Maruzen Chemical Industry Co., Ltd.), 6.67g of 4-(trifluoromethyl)benzaldehyde, and 2.46g of methanesulfonic acid, and refluxed and stirred for 18 hours under a nitrogen atmosphere. After the reaction was completed, it was diluted with 96g of tetrahydrofuran, and the dilution was added dropwise to methanol to obtain a precipitate. The precipitate obtained was filtered, washed with methanol, and dried at 60°C for 24 hours to obtain the target polymer (hereinafter referred to as PPNAPCA-F).

[0595] The weight average molecular weight of PPNAPCA-F measured by GPC in terms of standard polystyrene was 1100. The obtained polymer was dissolved in PGMEA, and ion exchange was performed for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target polymer solution.

[0596] PPNAPCA-F has the following structural units in the following ratios.

[0597]

[0598] [2] Preparation of stripping agent composition

[0599] [Preparation Example 2-1]

[0600] Into a 50 mL screw-cap bottle, 0.92 g of the polymer solution obtained in Synthesis Example 1-1 (30% by mass solution of PCzEHA in PGMEA) and 2.76 g of a 10% by mass solution of polymethyl methacrylate (Tg: 48° C., weight average molecular weight: 54,000, manufactured by FUJIFILM Wako Chemicals Co., Ltd.) dissolved in PGMEA were added, and 1.33 g of PGMEA as a solvent was further added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0601] [Preparation Example 2-2]

[0602] In a 50 mL screw-cap bottle, 3.01 g of the polymer solution obtained in Synthesis Example 1-2 (30% by mass solution of PCzBA in PGMEA) and 4.50 g of a 20% by mass solution of polymethyl methacrylate (Tg: 48°C, weight average molecular weight: 54,000, manufactured by FUJIFILM Wako Chemicals Co., Ltd.) dissolved in PGMEA were added, and 2.50 g of PGMEA as a solvent was further added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0603] [Preparation Example 2-3]

[0604] In a 50 mL screw-cap bottle, 6.74 g of the polymer solution obtained in Synthesis Example 1-3 (30 wt % PGMEA solution of PCzNA) and 11.26 g of a 20 wt % solution of polymethyl methacrylate (Tg: 48°C, weight average molecular weight: 54,000, manufactured by FUJIFILM Wako Chemicals Co., Ltd.) dissolved in PGMEA were added, and 7.01 g of PGMEA as a solvent was further added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0605] [Preparation Example 2-4]

[0606] In a 50 mL screw-cap bottle, 3.03 g of the polymer solution obtained in Synthesis Example 1-4 (30% by mass PGMEA solution of PCzFL) and 4.50 g of a 20% by mass solution of polymethyl methacrylate (Tg: 48°C, weight average molecular weight: 54,000, manufactured by FUJIFILM Wako Chemicals Co., Ltd.) dissolved in PGMEA were added, and 2.51 g of PGMEA as a solvent was further added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0607] [Preparation Example 2-5]

[0608] In a 50 mL screw-cap bottle, 3.01 g of the polymer solution obtained in Synthesis Example 1-5 (a 30% by mass solution of DPAEHA in PGMEA) and 4.50 g of a 20% by mass solution of polymethyl methacrylate (Tg: 48°C, weight average molecular weight: 54,000, manufactured by FUJIFILM Wako Chemicals Co., Ltd.) dissolved in PGMEA were added, and 2.51 g of PGMEA as a solvent was further added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0609] [Preparation Example 2-6]

[0610] Into a 50 mL screw-cap bottle, 3.34 g of the polymer solution obtained in Synthesis Example 1-6 (a 30% by mass solution of PPNAPCA-F in PGMEA) and 4.51 g of a 20% by mass solution of polymethyl methacrylate (Tg: 48°C, weight average molecular weight: 54,000, manufactured by FUJIFILM Wako Chemicals Co., Ltd.) dissolved in PGMEA were added, and 2.16 g of PGMEA as a solvent was further added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0611] [Comparative Preparation Example 2-1]

[0612] 4.08 g of the polymer solution obtained in Synthesis Example 1-1 (30 mass % PGMEA solution of PCzEHA) and 1.02 g of PGMEA as a solvent were added to a 50 mL screw bottle, and stirred for 5 minutes using a stirrer A to obtain a release agent composition.

[0613] [Comparative Preparation Example 2-2]

[0614] 10.00 g of the polymer solution obtained in Synthesis Example 1-3 (30 mass % PGMEA solution of PCzNA) and 6.70 g of PGMEA as a solvent were added to a 50 mL screw bottle, and stirred for 5 minutes using a stirrer A to obtain a release agent composition.

[0615] [Comparative Preparation Examples 2-3]

[0616] 10.01 g of the polymer solution obtained in Synthesis Example 1-6 (30 mass % PPMEA solution of PPNAPCA-F) and 2.50 g of PGMEA as a solvent were added to a 50 mL screw bottle, and stirred for 5 minutes using a stirrer A to obtain a release agent composition.

[0617] [Comparative Preparation Examples 2-4]

[0618] 6.60 g of the polymer solution obtained in Synthesis Example 1-1 (30 mass % PGMEA solution of PCzEHA) and 2.01 g of polystyrene (manufactured by Sigma Aldrich) were added to a 50 mL screw bottle, and 20.00 g of PGMEA was further added as a solvent. The mixture was stirred for 5 minutes using a stirrer A to obtain a release agent composition.

[0619] [Comparative Preparation Examples 2-5]

[0620] 6.68 g of the polymer solution obtained in Synthesis Example 1-1 (30% PGMEA solution of PCzEHA) and 2.00 g of polyhydroxystyrene were added to a 50 mL screw bottle, and 20.01 g of PGMEA as a solvent was further added, and stirred for 5 minutes using a stirrer A to obtain a release agent composition.

[0621] [Comparative Preparation Examples 2-6]

[0622] Into a 50 mL screw-cap bottle, 1.25 g of a solution obtained by dissolving the dried polymer obtained in Synthesis Example 1-1 in mesitylene (30% by mass solution of PCzEHA in mesitylene) and 3.75 g of a solution obtained by dissolving SEPTON 4033 (manufactured by Kuraray Co., Ltd.) in mesitylene (10% by mass solution of SEPTON 4033) were added, and the mixture was stirred for 5 minutes using a stirrer A to obtain a stripping agent composition.

[0623] It should be noted that SEPTON 4033 is a hydrogenated styrene-based thermoplastic elastomer and does not have a (meth)acrylate unit.

[0624] [3] Preparation of adhesive composition

[0625] [Preparation Example 3]

[0626] Into a 600 mL stirring container dedicated to the autorotating and revolving stirrer, 104.14 g of a p-menthane solution (concentration 80.6 mass %) of an MQ resin (manufactured by Wacker Chemie) having a polysiloxane skeleton and a vinyl group as component (a1), 104.14 g of a polyorganosiloxane (manufactured by Wacker Chemie, trade name AK1000000, viscosity 1000000 mm) as component (B) were added. 2 / s) 58.11 g, p-menthane (manufactured by Nippon Terpene Chemicals Co., Ltd.) 34.94 g and n-decane (manufactured by Sankyo Chemical Co., Ltd.) 6.20 g as a solvent were stirred for 5 minutes using a stirrer A to obtain a mixture (I).

[0627] To the obtained mixture (I), 16.79 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa·s as component (a2) and 24.54 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 200 mPa·s as component (a1) were added to obtain a mixture (II).

[0628] 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 the component (A3) and 3.23 g of p-menthane (manufactured by Nippon Terpene Chemicals Co., Ltd.) as the solvent were stirred for 60 minutes by the stirrer to obtain a mixture (III).

[0629] 1.29 g of the obtained mixture (III) was added to the mixture (II), and the mixture was stirred for 5 minutes using the stirrer to obtain a mixture (IV).

[0630] 0.65 g of a platinum catalyst (manufactured by Wacker Chemie) as component (A2) and 19.37 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa·s as component (a1) were stirred for 5 minutes using a stirrer A to obtain a mixture (V).

[0631] 4.00 g of the obtained mixture (V) was added to the mixture (IV), and stirred for 5 minutes using a stirrer A to obtain a mixture (VI).

[0632] Finally, the obtained mixture (VI) was filtered through a 300-mesh nylon filter to obtain an adhesive composition. The viscosity of the obtained adhesive composition was 3000 mPa·s.

[0633] [4] Preparation of cleaning agent composition

[0634] [Preparation Example 4]

[0635] 95 g of N,N-dimethylpropionamide was added to 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.), and the mixture was stirred to obtain a cleaning agent composition.

[0636] [5] Coating test

[0637] [Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-6]

[0638] The release compositions obtained in Preparation Examples 2-1 to 2-6 and Comparative Preparation Examples 2-1 to 2-6 were applied to a 100 mm silicon wafer (thickness: 770 μm) as a wafer (semiconductor substrate) on the device side by spin coating, and heated at 200° C. for 5 minutes to form a release agent layer on the silicon wafer so that the final thickness of the release agent layer was about 1500 nm.

[0639] The coating property was evaluated by indicating that no cracks or liquid shrinkage cavities were observed in the release agent layer applied to the silicon wafer, and was rated as “×” if cracks or liquid shrinkage cavities were observed. The coating property evaluation results are shown in Table 1 below.

[0640] It should be noted that even when a device wafer having bumps with a height of 30 to 40 μm was used as the wafer on the device side, similar coating properties were obtained.

[0641] [Table 1]

[0642]

[0643] In Table 1, PMMA represents polymethyl methacrylate, PSt represents polystyrene, and PHSt represents polyhydroxystyrene.

[0644] [5] Peelability test

[0645] [5-1] Preparation of laminated body

[0646] [Example 2-1]

[0647] The stripper composition obtained in Preparation Example 2-1 was applied to a 100 mm silicon wafer (thickness: 770 μm) as a wafer (semiconductor substrate) on the device side by spin coating, and heated at 200° C. for 5 minutes, thereby forming a stripper layer on the silicon wafer in a manner that the final thickness of the stripper layer in the laminate is about 1500 nm. Then, the adhesive composition obtained in Preparation Example 3 was applied to the silicon wafer on which the stripper layer was formed by spin coating, and heated at 120° C. for 1.5 minutes (preheating treatment), thereby forming an adhesive coating layer in a manner that the final thickness of the adhesive layer in the laminate is about 60 μm. Then, in a vacuum bonding device, the semiconductor substrate and a 100 mm glass wafer (thickness: 500 μm) as a supporting substrate were bonded in a manner that the adhesive coating layer and the stripper layer were sandwiched, and heated at 200° C. for 10 minutes on a hot plate with the semiconductor substrate side facing downward (post-heating treatment), thereby producing a laminate. In addition, the bonding was performed at a temperature of 23° C. and a reduced pressure of 1000 Pa.

[0648] [Examples 2-2 to 2-6 and Comparative Examples 2-1 and 2-2]

[0649] A laminate was produced by the same method as in Example 2-1, except that the release agent compositions obtained in Preparation Examples 2-2 to 2-6 and Comparative Preparation Examples 2-5 and 2-6 were used instead of the release agent composition obtained in Preparation Example 2-1.

[0650] [5-2] Evaluation of laser peeling properties

[0651] A laser irradiation device was used to irradiate the release agent layer from the glass wafer side of the fixed laminate at 120 mJ / cm 2 Irradiate with a laser of 308 nm wavelength. Then, manually lift the support substrate to check whether it can be peeled off. For the evaluation of peelability, the case where the support substrate can be peeled off without load by pulling up is marked as "○", and the case where a load is applied to the peeling is marked as "×". The results are shown in Table 2.

[0652] It should be noted that even when a device wafer having bumps with a height of 30 to 40 μm was used as the wafer on the device side, similar peeling properties were obtained.

[0653] [Table 2]

[0654] Composition for release agent layer Peelability Example 2-1 Preparation Example 2-1 ○ Example 2-2 Preparation Example 2-2 ○ Example 2-3 Preparation Example 2-3 ○ Embodiment 2-4 Preparation Example 2-4 ○ Embodiment 2-5 Preparation Example 2-5 ○ Embodiment 2-6 Preparation Example 2-6 ○ Comparative Example 2-1 Comparative Preparation Examples 2-5 ○ Comparative Example 2-2 Comparative Preparation Examples 2-6 ×

[0655] [6] Cleaning test

[0656] [Examples 3-1 to 3-6 and Comparative Example 3-1]

[0657] The wafer (semiconductor substrate) on the device side after laser peeling obtained in Examples 2-1 to 2-6 and Comparative Example 2-1 was cut into 4 cm square chips, placed in a stainless steel culture dish with a diameter of 9 cm, 7 mL of the cleaning agent composition obtained in Preparation Example 4 was added, the lid was closed, and the dish was placed in a mixer H for stirring and cleaning at 23°C for 5 minutes.

[0658] After cleaning, the chip was taken out, cleaned with isopropyl alcohol and pure water, and dried at 120° C. for 1 minute. Then, the case where no residue of the adhesive composition or the stripping agent composition was confirmed on the device wafer was marked as “○”, and the case where the residue of the adhesive composition or the stripping agent composition was confirmed on the device wafer was marked as “×”. The results are shown in Table 3.

[0659] It should be noted that even when a device wafer having bumps with a height of 30 to 40 μm was used as the wafer on the device side, the same cleaning performance was obtained.

[0660] [Table 3]

[0661] Composition for release agent layer Cleanability Example 3-1 Preparation Example 2-1 ○ Example 3-2 Preparation Example 2-2 ○ Example 3-3 Preparation Example 2-3 ○ Embodiment 3-4 Preparation Example 2-4 ○ Embodiment 3-5 Preparation Example 2-5 ○ Embodiment 3-6 Preparation Example 2-6 ○ Comparative Example 3-1 Comparative Preparation Examples 2-5 ×

[0662] Description of Reference Numerals

[0663] 1: semiconductor substrate; 1a: bump; 2: release agent layer; 3: adhesive layer; 3a: adhesive coating layer; 4: supporting substrate; 21: semiconductor chip substrate; 22: adhesive layer; 23: release agent layer; 24: supporting substrate; 25: sealing resin; 26: electronic device layer; 27: release agent layer with adhesive properties; 28: wiring layer.

Claims

1. A stripping agent composition for stripping by light irradiation, comprising: a novolac resin, a (meth)acrylate polymer, and a solvent.

2. The stripping agent composition according to claim 1, wherein The (meth)acrylate polymer includes a repeating unit derived from an alkyl (meth)acrylate having 4 to 20 carbon atoms.

3. The stripping agent composition according to claim 1, wherein The (meth)acrylate polymer includes a repeating unit derived from methyl methacrylate.

4. The stripping agent composition according to claim 1, wherein The (meth)acrylate polymer includes polymethyl methacrylate.

5. The stripping agent composition according to claim 1, wherein The novolac resin includes at least any of the structural units represented by the following formula (C1-1), the structural units represented by the following formula (C1-2), and the structural units represented by the following formula (C1-3), In formulas (C1-1) to (C1-3), C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom or a quaternary carbon atom, wherein the side chain has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom and an aromatic ring, or represents a methylene group, C 3 represents a group derived from an aliphatic polycyclic compound, C 4 It represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl or a group derived from biphenol.

6. The stripping agent composition according to claim 5, wherein The novolac resin includes at least any one of a structural unit represented by the following formula (C1-1-1) and a structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1), In formula (C1-1-1) and formula (C1-1-2), R 901 and R 902 represents a substituent substituted on the ring, each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, R 904 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group, R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, R 904 The group and R 905 The groups are optionally bonded to each other to form a divalent group, Ar 901 and Ar 902 Each independently represents an aromatic ring, h 1 and h 2 Each independently represents an integer from 0 to 3.

7. The stripping agent composition according to claim 1, wherein The content of the (meth)acrylate polymer is 35% by mass or more based on the total of the novolac resin and the (meth)acrylate polymer.

8. A laminate, wherein: The laminated body has: Semiconductor substrate or electronic device layer; A light-transmitting supporting substrate; as well as a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate, The release agent layer is a release agent layer formed from the release agent composition according to any one of claims 1 to 7.

9. The laminate according to claim 8, wherein The release agent layer has a thickness of 0.5 μm to 10 μm.

10. The laminate according to claim 8, wherein The laminated body has an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

11. The laminate according to claim 8, wherein The release agent layer is in contact with the semiconductor substrate.

12. The laminate according to claim 8, wherein The surface of the semiconductor substrate on the support substrate side has bumps.

13. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: A fifth step A of processing the semiconductor substrate of the stacked body according to claim 8; or a fifth step B of processing the electronic device layer of the laminate according to claim 8; and The sixth A step is to separate the semiconductor substrate processed in the fifth A step from the support substrate; or the sixth B step is to separate the electronic device layer processed in the fifth B step from the support substrate.

14. The method for manufacturing a processed semiconductor substrate or an electronic device layer according to claim 13, wherein: The sixth step A or the sixth step B includes the step of irradiating the laminated body with a laser beam from the support substrate side.

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