Manufacturing method of laminate, release agent composition and processed semiconductor substrate

Abstract

This invention provides a laminate, which has: Semiconductor substrate, Transparent support substrate, and An adhesive layer and a release layer are disposed between the aforementioned semiconductor substrate and the aforementioned support substrate; The aforementioned release layer is used to peel the semiconductor substrate from the aforementioned support substrate after absorbing light irradiated from the aforementioned support substrate side; its characteristic is that... The aforementioned release layer is a layer formed by the composition of the release agent; and The aforementioned stripping agent composition contains a compound having: a first structure that absorbs the aforementioned light, thereby facilitating the easy separation of the aforementioned semiconductor substrate from the aforementioned support substrate by absorbing the aforementioned light, and having two or more aromatic rings constituting a π-electron conjugation system; and a siloxane structure as the second structure.

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a laminate, a release agent composition, and a processed semiconductor substrate. [Previous Technology]

[0002] In the past, semiconductor wafers were stacked in a two-dimensional planar direction. To achieve further stacking, a semiconductor stacking technology was pursued that further stacks (layers) the planar surface in a three-dimensional direction. This three-dimensional stacking is a technology that uses through silicon vias (TSVs) for wiring and stacking into multiple layers. When stacking into multiple layers, each wafer is thinned by grinding the side opposite to the circuit surface (i.e., the back side), and then the thinned semiconductor wafers are stacked.

[0003] To polish a thinned semiconductor wafer (hereinafter simply referred to as a wafer) using a polishing apparatus, the wafer is attached to a support. This attachment must be easily peeled off after polishing, hence it is called a temporary attachment. This temporary attachment must be easily removed from the support; if a large force is applied for removal, the thinned semiconductor wafer may be cut or deformed. To avoid this, it must be easily removable. However, when polishing the back side of the semiconductor wafer, it is undesirable for it to detach or deviate due to polishing stress. Therefore, the temporary attachment must withstand the stress during polishing and be easily removed after polishing.

[0004] Currently, there is a pursuit for a method that, for example, maintains high stress (strong adhesion) in the planar direction during grinding and low stress (weak adhesion) in the longitudinal direction during removal. While a laser irradiation method for such bonding and separation processes has been disclosed (see, for example, Patent Documents 1 and 2), with the further development of the semiconductor field, there is a continuous pursuit of new technologies related to peeling by irradiation with light such as lasers. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2004-64040 [Patent Document 2] Japanese Patent Application Publication No. 2012-106486 [Summary of the Invention]

[0006] [The technical problem that the invention is intended to solve]

[0007] Furthermore, in the technology described in Patent Document 2, it is not easy to dissolve the separation layer after light irradiation by means of the cleaning agent composition when cleaning the semiconductor substrate.

[0008] This invention is made in view of the foregoing circumstances, and its object is to provide: a laminate that allows for easy separation of a support substrate and a semiconductor substrate during separation, and allows the release layer after light irradiation to be dissolved by a cleaning agent composition during cleaning of the semiconductor substrate; a release agent composition that can impart an ideal film as such a release layer; and a method for manufacturing a processed semiconductor substrate using such a laminate. [Technical Means]

[0009] After conducting in-depth research in order to solve the aforementioned problems, the inventors discovered that the aforementioned problems could be solved, thereby completing the present invention having the following essential points.

[0010] That is, the present invention includes the following invention. [1] A laminate comprising: a semiconductor substrate, a light-transmitting support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate; the release layer is used to peel the semiconductor substrate from the support substrate after absorbing light irradiated from the support substrate side; characterized in that the release layer is a layer formed by a release agent composition; and the release agent composition contains a compound having: a first structure that absorbs the light, thereby facilitating the peeling of the semiconductor substrate from the support substrate, and having two or more aromatic rings constituting a π-electron conjugation system; and a siloxane structure as a second structure. [2] The laminate as described in [1], wherein the aforementioned first structure has a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene, diphenylene, azobenzene, diphenylfuran, fumonisin, carbazole, anthraquinone, 9,9-diphenyl-9H-fumonisin, naphthalene, anthracene, phenanthrene, acridine, pyrene and phenylbenzotriazole. [3] A laminate as described in item [1] or item [2], wherein the aforementioned first structure is a structure represented by any one of the following formulas (1) to (7): [Chemical 1] (In formulas (1) to (7), R1 to R13 each independently represent a halogen atom or a monovalent group. X represents a single bond, -O-, -CO-, -NR31- (R31 represents a hydrogen atom, a substituted alkyl group, or a substituted aryl group), -SO-, -SO2-, or -N=N-. Y1 represents a single bond or -CO-. When Y1 is a single bond, Y2 represents -O-, -CO-, or -NR32- (R32 represents a hydrogen atom, a substituted alkyl group, or a substituted aryl group). When Y1 is -CO-, Y2 represents -CO-. n1 is an integer from 0 to 4. n2 is an integer from 0 to 5. n3 is an integer from 0 to 3. n4 is an integer from 0 to 4. n5 is an integer from 0 to 4. n6 is an integer from 0 to 5. n7 is an integer from 0 to 4. n8 is an integer from 0 to 4. n9 is an integer from 0 to 7. n10 is an integer from 0 to 9. n11 is an integer from 0 to 9. n12 is an integer from 0 to 4. n13 is an integer from 0 to 4. * indicates a bond. In the case where R1 to R13 are each multiple, the multiple R1 to R13 may be the same or different. ) [4]A laminate as described in any one of items [1] to [3], wherein the aforementioned first structure has at least one hydroxyl group.[5] A laminate as described in any one of items [1] to [4], wherein the aforementioned second structure contains at least one of the group consisting of a siloxane unit (Q unit) represented by SiO2, a siloxane unit (M unit) represented by R101R102R103SiO1 / 2, a siloxane unit (D unit) represented by R104R105SiO2 / 2, and a siloxane unit (T unit) represented by R106SiO3 / 2 (R101 to R106 each independently represents a hydrogen atom or monovalent group bonded to Si, or a single bond or linking group that bonds Si to the aforementioned first structure.) [6] A laminate as described in item [5], wherein the aforementioned first structure is bonded to Si of any one of the aforementioned M unit, the aforementioned D unit, and the aforementioned T unit via a single bond or linking group. [7] A laminate as described in item [6], wherein the first structure is Si-bonded to any one of the M unit, D unit, and T unit via a linker; the linker is selected from the group consisting of alkylene groups, ester bonds, ether bonds, amide bonds, ethyl carbamate bonds, urea bonds, and combinations thereof having 1 to 10 carbon atoms. [8] A laminate as described in any one of items [1] to [7], wherein the adhesive layer is a layer formed from an adhesive composition containing a compound having a siloxane structure. [9] A laminate as described in item [8], wherein the adhesive composition contains a curing component (A).

[10] A laminate as described in item [9], wherein the component (A) is a component that is cured by a hydrogenation reaction.

[11] A laminate as described in [9] or

[10] , wherein the aforementioned component (A) contains: a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms; a polyorganosiloxane (a2) having a Si-H group; and a platinum group metal catalyst (A2).

[12] A release agent composition for forming a release layer of a laminate, the laminate having: a semiconductor substrate, a support substrate, and an adhesive layer and the release layer disposed between the semiconductor substrate and the support substrate, and the release layer being used to peel the semiconductor substrate from the support substrate after absorbing light irradiated from the support substrate side; characterized in that the release agent composition contains a compound having: a first structure that absorbs the aforementioned light, thereby facilitating the peeling of the semiconductor substrate from the support substrate by absorbing the aforementioned light, and having two or more aromatic rings constituting a π-electron conjugation system; and a siloxane structure as a second structure.

[13] The stripping agent composition as described in item

[12] , wherein the aforementioned first structure has a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene oxide, diphenylene oxide, azobenzene, diphenylfuran, fumonisin, carbazole, anthraquinone, 9,9-diphenyl-9H-fumonisin, naphthalene, anthracene, phenanthrene, acridine, pyrene and phenylbenzotriazole.

[14] A stripping agent composition characterized in that it contains: a first structure having a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene, diphenylene, azobenzene, diphenylfuran, fumonisin, carbazole, anthraquinone, 9,9-diphenyl-9H-fumonisin, naphthalene, anthracene, phenanthrene, acridine, pyrene and phenylbenzotriazole; and a siloxane structure as a second structure.

[15] The stripping agent composition as described in any one of items

[12] to

[14] , wherein the aforementioned first structure is the structure shown in any one of the following formulas (1) to (7): [Chemical 2] (In formulas (1) to (7), R1 to R13 each independently represent a halogen atom or a monovalent group. X represents a single bond, -O-, -CO-, -NR31- (R31 represents a hydrogen atom, a substituted alkyl group, or a substituted aryl group), -SO-, -SO2-, or -N=N-. Y1 represents a single bond or -CO-. When Y1 is a single bond, Y2 represents -O-, -CO-, or -NR32- (R32 represents a hydrogen atom, a substituted alkyl group, or a substituted aryl group). When Y1 is -CO-, Y2 represents -CO-. n1 is an integer from 0 to 4. n2 is an integer from 0 to 5. n3 is an integer from 0 to 3. n4 is an integer from 0 to 4. n5 is an integer from 0 to 4. n6 is an integer from 0 to 5. n7 is an integer from 0 to 4. n8 is an integer from 0 to 4. n9 is an integer from 0 to 7. n10 is an integer from 0 to 9. n11 is an integer from 0 to 9. n12 is an integer from 0 to 4. n13 is an integer from 0 to 4. * indicates a bond. In the case where R1 to R13 are each multiple, the multiple R1 to R13 may be the same or different. )

[16] A stripping agent composition as described in any one of items

[12] to

[15] , wherein the aforementioned first structure has at least one hydroxyl group.

[17] The stripping agent composition as described in any one of items

[12] to

[16] , wherein the aforementioned second structure contains at least one of the group consisting of a siloxane unit (Q unit) represented by SiO2, a siloxane unit (M unit) represented by R101R102R103SiO1 / 2, a siloxane unit (D unit) represented by R104R105SiO2 / 2, and a siloxane unit (T unit) represented by R106SiO3 / 2 (R101 to R106 each independently represents a hydrogen atom or monovalent group bonded to Si, or a single bond or linking group that bonds Si to the aforementioned first structure.)

[18] The stripping agent composition as described in item

[17] , wherein the aforementioned second structure is bonded to Si of any one of the aforementioned M unit, the aforementioned D unit, and the aforementioned T unit via a single bond or linking group.

[19] The stripping agent composition as described in item

[18] , wherein the aforementioned second structure is Si-bonded to any one of the aforementioned M unit, the aforementioned D unit, and the aforementioned T unit via a linker; the aforementioned linker is selected from the group consisting of alkylene groups, ester bonds, ether bonds, amide bonds, ethyl carbamate bonds, urea bonds, and combinations thereof having 1 to 10 carbon atoms.

[20] A method for manufacturing a processed semiconductor substrate, characterized by comprising: a first step of processing the aforementioned semiconductor substrate of any one of items [1] to

[11] ; a second step of separating the aforementioned semiconductor substrate processed by the aforementioned first step from the aforementioned support substrate; and a third step of cleaning the separated aforementioned semiconductor substrate with a cleaning agent composition.

[21] The method for manufacturing a processed semiconductor substrate as described in item

[20] , wherein the aforementioned second step includes the step of irradiating the aforementioned stripping layer with light.

[22] A method for manufacturing a processed semiconductor substrate as described in item

[20] or

[21] , wherein the aforementioned cleaning agent composition contains a quaternary ammonium salt and a solvent.

[23] A method for manufacturing a processed semiconductor substrate as described in item

[22] , wherein the aforementioned quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

[24] A method for manufacturing a processed semiconductor substrate as described in item

[23] , wherein the aforementioned halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt. [Effects of the Invention]

[0011] According to the present invention, a laminate can be provided that allows for easy separation of a support substrate from a semiconductor substrate when the substrate is separated, and that a light-irradiated release layer can be dissolved by a cleaning agent composition when the semiconductor substrate is cleaned; a release agent composition that can impart an ideal film as such a release layer; and a method for manufacturing a processed semiconductor substrate using such a laminate.

Implementation Method

[0013] (Laminated Structure) The laminate of the present invention comprises: a semiconductor substrate, a support substrate, an adhesive layer, and a release layer. The support substrate is light-transmitting. The adhesive layer and the release layer are disposed between the semiconductor substrate and the support substrate. In the laminate, the release layer is used to peel the semiconductor substrate from the support substrate after absorbing light irradiated from the support substrate side. The release layer is a layer formed of a release agent composition. The release agent composition contains a compound having a first structure and a second structure. The first structure is a light-absorbing structure, and is a structure that helps to facilitate the peeling of the semiconductor substrate from the support substrate by absorbing light. The second structure is a siloxane structure.

[0014] The stacking system of the present invention can be suitably used in processes such as thinning of semiconductor substrates. In the stacking system of the present invention, during the thinning or other processing of the semiconductor substrate, the semiconductor substrate is supported on a support substrate via an adhesive layer and a release layer. On the other hand, by allowing the compound contained in the release agent composition used to form the release layer to have a first structure, the first structure absorbs light (e.g., laser light) in the release layer formed by the release agent composition, causing the release layer to deteriorate (e.g., separate or decompose). As a result, after irradiating the release layer with light, the semiconductor substrate and the support substrate become easier to separate. Furthermore, by allowing the compound contained in the release agent composition used to form the release layer to have a second structure, the release layer after light irradiation will exhibit solubility in the cleaning agent composition described later. If the release layer after light irradiation is soluble in the cleaning agent composition, then, for example, when separating the support substrate and the semiconductor substrate, if residue of the release layer remains on the semiconductor substrate side, it can also be cleaned by the cleaning agent composition, thereby easily removing the residue.

[0015] The wavelength of the light used for stripping is not particularly limited as long as it is absorbed by the first structure, and is generally in the range of 100 to 600 nm, such as ideal wavelengths of 308 nm, 343 nm, 355 nm, or 365 nm. The amount of light required for stripping is an amount that can cause appropriate degradation of the first structure, such as decomposition. The light used for stripping can be laser light or non-laser light emitted from a light source such as a lamp.

[0016] <Semiconductor Substrate> The main material constituting the semiconductor substrate is not particularly limited as long as it is used for this purpose; examples include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited; for example, it can be disc-shaped. Furthermore, the shape of the surface of the disc-shaped semiconductor substrate does not need to be perfectly circular. For example, the outer periphery of the semiconductor substrate may have a straight portion called an orientation plane, or it may have a notch. The thickness of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate and is not particularly limited; for example, it is 500~1,000 μm. The diameter of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate and is not particularly limited; for example, it is 100~1,000 mm.

[0017] Semiconductor substrates may also have bumps. A bump refers to a protruding terminal. In a multilayer assembly, when the semiconductor substrate has bumps, the bumps are located on the side supporting the substrate. In a semiconductor substrate, bumps are typically formed on the surface where a circuit is formed. The circuit can be single-layer or multi-layer. There are no particular restrictions on the shape of the circuit. In a semiconductor substrate, the side opposite to the bumped surface (back side) is the surface for processing. There are no particular restrictions on the material, size, shape, structure, or density of the bumps on the semiconductor substrate. Examples of bumps include: ball bumps, printed bumps, cylindrical bumps, plated bumps, etc. The height, radius, and spacing of the bumps are usually determined appropriately from the conditions of approximately 1-200 μm in height, 1-200 μm in radius, and 1-500 μm in spacing. Examples of bump materials include: low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, copper, etc. Bumps can be composed of a single component or a plurality of components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy plating. Furthermore, bumps can also have a multilayer structure, comprising a metal layer made of at least one of these components.

[0018] One example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0019] <Supporting substrate> The supporting substrate is not particularly limited as long as it is a component that is transparent to light irradiating the release layer and can support the semiconductor substrate during the processing of the semiconductor substrate. Examples include glass supporting substrates.

[0020] The shape of the support substrate is not particularly limited, and a disc shape can be cited as an example. The thickness of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, for example, 500~1,000 μm. The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, for example, 100~1,000 mm.

[0021] One example of a support substrate is a glass wafer with a diameter of 300 mm and a thickness of about 700 μm.

[0022] <Release Layer> The release layer is a layer formed from a release agent composition. The release layer is disposed between the semiconductor substrate and the support substrate. The release layer may be in contact with either the support substrate or the semiconductor substrate.

[0023] There is no particular limitation on the method of forming the release layer from the release agent composition, and examples of the forming methods described below can be cited.

[0024] <<Removing Agent Composition>> The removing agent composition shall contain at least compounds having a first structure and a second structure (hereinafter referred to as "specific compounds"), and further contain other components such as crosslinking agents, acid generating agents, acids, surfactants, and solvents as needed.

[0025] <<<Compounds with First and Second Structures>>> Specific compounds contained in the stripping agent composition have a first structure and a second structure. The first structure is a light-absorbing structure that facilitates the separation of the semiconductor substrate from the support substrate by means of light absorption. The second structure is a siloxane structure.

[0026] - First Structure - The first structure is a light-absorbing structure that facilitates the easy separation of the semiconductor substrate and the support substrate by absorbing light. The first structure deteriorates by absorbing light, causing the release layer to deteriorate. As a result, after irradiating the release layer with light, the semiconductor substrate and the support substrate become easier to separate.

[0027] The first structure has, for example, two or more aromatic rings constituting a conjugated π-electron conjugation system. The two or more aromatic rings may also form a condensation ring. A condensation ring refers to two or more rings that are united in a single entity by each sharing two (sometimes more) atoms. The aromatic rings contained in the condensation ring may be aromatic hydrocarbon rings or heteroaromatic rings. Examples of aromatic hydrocarbon rings include, for example, benzene rings. Examples of heteroaromatic rings include, for example, furan rings, thiophene rings, pyrrole rings, pyrazole rings, imidazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyrazine rings, etc.

[0028] The first structure, from the viewpoint of achieving good peelability between the semiconductor substrate and the support substrate by means of excellent light absorption, ideally has a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene, diphenylene, azobenzene, diphenylfuran, fentanyl, carbazole, anthraquinone, 9,9-diphenyl-9H-fentanyl, naphthalene, anthracene, phenanthrene, acridine, pyrene and phenylbenzotriazole.

[0029] The first structure may also have substituents. Examples of substituents in the first structure include alkyl, alkoxy, aryl, halogen atom, hydroxyl, nitro, cyano, acetamino, sulfonamide, aceimino, carboxyl, carboxylic acid ester, sulfonyl, sulfonate ester, alkylamine, and aromatic amine.

[0030] The first structure, from the viewpoint of achieving good peelability between the semiconductor substrate and the support substrate by means of excellent light absorption, is ideally the structure shown in any of the following formulas (1) to (7). [Chemistry 3] (In formulas (1) to (7), R1 to R13 each independently represent a halogen atom or a monovalent group. X represents a single bond, -O-, -CO-, -NR31- (R31 represents a hydrogen atom, a substituted alkyl group, or a substituted aryl group), -SO-, -SO2-, or -N=N-. Y1 represents a single bond or -CO-. When Y1 is a single bond, Y2 represents -O-, -CO-, or -NR32- (R32 represents a hydrogen atom, a substituted alkyl group, or a substituted aryl group). When Y1 is -CO-, Y2 represents -CO-. n1 is an integer from 0 to 4. n2 is an integer from 0 to 5. n3 is an integer from 0 to 3. n4 is an integer from 0 to 4. n5 is an integer from 0 to 4. n6 is an integer from 0 to 5. n7 is an integer from 0 to 4. n8 is an integer from 0 to 4. n9 is an integer from 0 to 7. n10 is an integer from 0 to 9. n11 is an integer from 0 to 9. n12 is an integer from 0 to 4. n13 is an integer from 0 to 4. * indicates a bond. In the case where R1 to R13 are each multiple, the multiple R1 to R13 can be the same or different.

[0031] The halogen atoms in R1 to R13 can be, for example, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The monovalent groups in R1 to R13 can be, for example, atomic groups composed of two or more atoms. Specifically, examples include substituted alkyl groups, substituted alkoxy groups, substituted aryl groups, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, sulfonyl groups, and -N(R21)(R22) (R21 and R22 independently represent hydrogen atoms, substituted alkyl groups, or substituted aryl groups, respectively).

[0032] Specific examples of substituted alkyl groups in R1 to R13 include, for example, substituted alkyl groups having 1 to 20 carbon atoms. Examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups, etc. Specific examples of substituted alkoxy groups in R1 to R13 include, for example, substituted alkoxy groups having 1 to 20 carbon atoms. Examples of substituents include halogen atoms, hydroxyl groups, carboxyl groups, alkyl groups, etc. Specific examples of substituted alkyl groups in R21, R22, R31, and R32 include specific examples of substituted alkyl groups in the specific examples of R1 to R13. Specific examples of substituted aryl groups in R21, R22, R31, and R32 can be cited as examples of substituted aryl groups in R1 to R13. Alkyl groups that are substitutable can be exemplified by alkyl groups having 1 to 6 carbon atoms. Alkoxy groups that are substitutable can be exemplified by alkoxy groups having 1 to 6 carbon atoms. Furthermore, in "substituted alkyl groups having 1 to 20 carbon atoms," "1 to 20 carbon atoms" refers to the number of carbon atoms after removing the carbon atoms from the substituents. The same applies to "substituted aryl groups having 6 to 20 carbon atoms" and "substituted alkoxy groups having 1 to 20 carbon atoms."

[0033] The first structure, based on the following points (A) to (C), ideally has at least one hydroxyl group. (A): Excellent light absorption (e.g., easily absorbs light in the high wavelength region such as 308~355nm) (B): Easily peels the semiconductor substrate from the support substrate by absorbing light (C): Contributes to crosslinking reactivity. In the case where the first structure is the structure shown in any of formulas (1) to (7), based on the points (A) to (C), ideally, in formulas (1) to (7), each of R1 to R13 has at least one hydroxyl group.

[0034] As a structure in formula (1) where X is -CO-, examples can be given of structures in which one hydrogen atom of the aromatic ring is removed from the following compounds and replaced with a monovalent group: • 2-hydroxybenzophenone • 2,4-dihydroxybenzophenone • 2,3,4-trihydroxybenzophenone • 2,2',4,4'-tetrahydroxybenzophenone • 2,2',5,6'-tetrahydroxybenzophenone • 2-hydroxy-4-methoxybenzophenone • 2-hydroxy-4-octyloxybenzophenone • 2-hydroxy-4-dodecyloxybenzophenone • 2,2'-dihydroxy-4-methoxybenzophenone • 2,6-dihydroxy-4 -Methoxybenzophenone・2,2'-dihydroxy-4,4'-dimethoxybenzophenone・4-amino-2'-hydroxybenzophenone・4-dimethylamino-2'-hydroxybenzophenone・4-diethylamino-2'-hydroxybenzophenone・4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone・4-dimethylamino-2',4'-dihydroxybenzophenone・4-dimethylamino-3',4'-dihydroxybenzophenone

[0035] As a structure in formula (1) where X is -SO-, examples can be given such as: the structure in which a hydrogen atom of an aromatic ring is removed from the following compounds and replaced with a monovalent group. • Bis(2,3-dihydroxyphenyl) ion • Bis(5-chloro-2,3-dihydroxyphenyl) ion • Bis(2,4-dihydroxyphenyl) ion • Bis(2,4-dihydroxy-6-methylphenyl) ion • Bis(5-chloro-2,4-dihydroxyphenyl) ion • Bis(2,5-dihydroxyphenyl) ion • Bis(3,4-dihydroxyphenyl) ion • Bis(3,5-dihydroxyphenyl) ion • Bis(2,3,4-trihydroxyphenyl) ion • Bis(2,3,4-trihydroxyphenyl-6-methylphenyl) ion • Bis(5-chloro-2,3,4-trihydroxyphenyl) ion • Bis(2,4,6-trihydroxyphenyl) ion • Bis(5-chloro-2,4,6-trihydroxyphenyl) ion

[0036] As a structure where X is -SO2- in formula (1), examples can be given of the following compounds with one hydrogen atom removed from the aromatic ring and replaced by a monovalent group: ・bis(2,4-dihydroxyphenyl) ⇌ ・bis(3,4-dihydroxyphenyl) ⇌ ・bis(3,5-dihydroxyphenyl) ⇌ ・bis(3,6-dihydroxyphenyl) ⇌ ・bis(4-hydroxyphenyl) ⇌ ・bis(3-hydroxyphenyl) ⇌ ・bis(2-hydroxyphenyl) ⇌ ・bis(3,5-dimethyl-4-hydroxyphenyl) ⇌

[0037] As a structure in formula (2) where Y1 is a single bond and Y2 is -CO-, examples can be given of structures obtained by removing one hydrogen atom from the aromatic ring and replacing it with a monovalent group from the following compounds: ・2,7-dihydroxy-9H-furan-9-one

[0038] As the structure shown in formula (3), examples can be listed such as: structures in which one hydrogen atom of the aromatic ring is removed from the following compounds and replaced with a monovalent group. ・9,9-bis(4-hydroxyphenyl) ⇌ 9,9-bis(4-hydroxy-3-methylphenyl) ⇌ 9,9-bis(4-hydroxy-3-ethylphenyl) ⇌ 9,9-bis(4-hydroxy-3-n-propylphenyl) ⇌ 9,9-bis(4-hydroxy-3-isopropylphenyl) ⇌ 9,9-bis(4-hydroxy-3-n-butylphenyl) ⇌ 9,9-bis(4-hydroxy-3-secondary butylphenyl) ⇌ 9,9-bis(4-hydroxy-3-tertiary butylphenyl) ⇌ 9,9-bis(4-hydroxy-3-cyclohexylphenyl) ⇌ 9,9-bis(4-hydroxy-3-phenylphenyl) ⇌

[0039] The first structure is, for example, Si directly or via a linker group bonded to the siloxane structure of the second structure. The linker group is, for example, selected from the group consisting of alkylene groups, ester bonds, ether bonds, amide bonds, ethyl carbamate bonds, urea bonds, and combinations thereof having 1 to 10 carbon atoms. Furthermore, regarding "combinations thereof", two or more groups of the same kind or bonds may be used, such as -O-CH2-O- or -CH2-O-CH2-.

[0040] -Second Structure- The second structure is not particularly limited as long as it is a siloxane structure. The second structure may be, for example, containing at least one of the following groups: a siloxane unit represented by SiO2 (Q unit), a siloxane unit represented by R101R102R103SiO1 / 2 (M unit), a siloxane unit represented by R104R105SiO2 / 2 (D unit), and a siloxane unit represented by R106SiO3 / 2 (T unit) (R101~R106 each independently represent a hydrogen atom or a monovalent group bonded to Si, or a single bond or linking group that bonds Si to the aforementioned first structure.).

[0041] Specific examples of the monovalent groups in R101 to R106 can be given by, for example, the specific examples illustrated in the description of the monovalent groups in R1 to R13. The monovalent groups in R101 to R106 are ideally alkyl groups that may have substituents, aryl groups that may have substituents, and more ideally alkyl groups with 1 to 6 carbon atoms, or phenyl groups.

[0042] The first structure, for example, is a Si bond to any of the aforementioned M unit, D unit, and T unit via a single bond or a linker group. The linker group is, for example, selected from the group consisting of alkylene groups, ester bonds, ether bonds, amide bonds, ethyl carbamate bonds, urea bonds, and combinations thereof having 1 to 10 carbon atoms. Furthermore, regarding "combinations thereof", two or more groups or bonds of the same type may also be used, such as -O-CH2-O- or -CH2-O-CH2-.

[0043] The specific compounds described above are organosiloxane polymers because their first structure contains a designated structure for absorbing light and a siloxane structure. Therefore, the weight-average molecular weight of such specific compounds is not particularly limited, and is typically 400 to 100,000. From the viewpoint of reproducibly formulating a release agent composition that can suppress polymer precipitation and maintain excellent stability, its upper limit is ideally 50,000, more ideally 30,000, even more ideally 20,000, even more ideally 10,000, and even more ideally 5,000. From the viewpoint of reproducibly formulating a release agent composition that can impart a release layer with excellent heat resistance, its lower limit is ideally 500, and even more ideally 1,000. The weight-average molecular weight of a specific compound can be determined, for example, by the following method. The weight-average molecular weight of specific compounds was determined using a gel permeation chromatography (GPC) apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (Shodex KF-801, KF-802, and KF-803L manufactured by Showa Denko Corporation). The column temperature was set to 40°C, the dissolution solution (dissolution solvent) was tetrahydrofuran (THF), and the flow rate was set to 0.1 mL / min. Polystyrene (Shodex manufactured by Showa Denko Corporation) was used as the standard sample.

[0044] The amount of specific compounds contained in the stripping agent composition varies depending on the coating method used, the required film thickness, etc., and therefore cannot be specified in general. Relative to the film composition, it is typically 1 to 100% by mass. From the viewpoint of obtaining a laminate with good reproducibility that allows for good separation between the semiconductor substrate and the support substrate, it is ideally 20% by mass or more, more ideally 30% by mass or more, even more ideally 40% by mass or more, even more ideally 50% by mass or more, and particularly ideally 60% by mass or more. Furthermore, in this invention, the film composition refers to components other than the solvent contained in the composition.

[0045] The method for obtaining a specific compound is not particularly limited, but examples of the following (i) or (ii) are given: (i) A method for obtaining a specific compound by hydrolysis and condensation of a hydrolyzable silane compound having a first structure alone, or by hydrolysis and condensation of a hydrolyzable silane compound having a first structure with other hydrolyzable silane compounds. (ii) A method for obtaining a specific compound by reacting the compound having the second structure with a compound having the first structure after obtaining a compound having a second structure through hydrolysis and condensation of a hydrolyzable silane compound.

[0046] There are no particular limitations on the method of hydrolysis condensation, and the general method for synthesizing polysiloxanes from hydrolyzable silane compounds can be used.

[0047] (i) The hydrolyzable silane compound having the first structure used may be a synthesized product or a commercially available product. Examples of commercially available products include 2-hydroxy-4-(3-triethoxysilylpropoxy)diphenyl ketone (manufactured by Gelest Corporation).

[0048] Other hydrolyzable silane compounds used in (i) and (ii) may include, for example, compounds shown in formula (11) and compounds shown in formula (12) below. R1aSi(R2)4-a… Formula (11) (wherein, R1 represents an organic group having alkyl, aryl, halogenated alkyl, halogenated aryl, alkenyl, or having acrylonitrile, methacrylonitrile, mercapto, or cyano, and represents a group bonded to silicon atoms by Si-C bonds; R2 represents an alkoxy, acetoxy, or halogen atom; a represents an integer from 0 to 3). [R3cSi(R4)3-c]Zb… Formula (12) (wherein, R3 represents an alkyl, R4 represents an alkoxy, acetoxy, or halogen atom, Z represents an alkyl or aryl, b represents an integer of 0 or 1, and c represents an integer of 0 or 1.) Compounds represented by formula (11) may include, for example, tetramethoxysilane, tetrachlorosilane, tetraethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriethoxysilane, methyltripropoxysilane, and methyltriethoxysilane. Acryloxysilane, methyltributoxysilane, methyltripropoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriacetoxy Silane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane Dimethyl diethoxysilane, phenylmethyl diethoxysilane, dimethyl diethoxysilane, γ-methylpropenoxypropylmethyldimethoxysilane, γ-methpropenoxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methyl vinyldimethoxysilane, methyl vinyldiethoxysilane, etc. Compounds represented by formula (12) can be listed as follows: methylene bis(trimethoxysilane), methylene bis(trichlorosilane), methylene bis(triethoxysilane), ethyl bis(triethoxysilane), ethyl bis(trichlorosilane), ethyl bis(triethoxysilane), propyl bis(triethoxysilane), butyl bis(trimethoxysilane), phenyl bis(trimethoxysilane), phenyl bis(triethoxysilane), phenyl bis(methyl)ethoxysilane, phenyl bis(methyl)methoxysilane, naphthyl bis(trimethoxysilane), bis(trimethoxy)silane, bis(triethoxy)silane, bis(ethyl)ethoxysilane, bis(methyl)methoxysilane, etc.

[0049] The hydrolysis catalysts used in the hydrolysis condensation in (i) and (ii) can be exemplified by metal chelate compounds, organic acids, inorganic acids, organic bases, inorganic bases, etc.

[0050] Examples of metal chelating compounds that serve as hydrolysis catalysts include: triethoxy-mono(acetyl acetone)titanium, tri-n-propoxy-mono(acetyl acetone)titanium, triisopropoxy-mono(acetyl acetone)titanium, tri-n-butoxy-mono(acetyl acetone)titanium, tri-dibutoxy-mono(acetyl acetone)titanium, tri-tertoxy-mono(acetyl acetone)titanium, diethoxy-bis(acetyl acetone)titanium, di-n-propoxy-bis(acetyl acetone)titanium, diisopropoxy-bis(acetyl acetone)titanium, di-n-butoxy-bis(acetyl acetone)titanium, and di-n-butoxy-bis(acetyl acetone)titanium. Acetone) Titanium, Di-di-butoxy-bis(acetyl acetone) Titanium, Di-tertoxy-bis(acetyl acetone) Titanium, Monoethoxy-tris(acetyl acetone) Titanium, Mono-n-propoxy-tris(acetyl acetone) Titanium, Mono-isopropoxy-tris(acetyl acetone) Titanium, Mono-n-butoxy-tris(acetyl acetone) Titanium, Mono-di-butoxy-tris(acetyl acetone) Titanium, Mono-tertoxy-tris(acetyl acetone) Titanium, Tetra(acetyl acetone) Titanium, Triethoxy-mono(acetyl ethyl acetate) Titanium, Tri-n-propoxy-mono(acetyl ethyl acetate) Titanium, Triisopropoxy-tris(acetyl acetone) Titanium, Oxy-mono(ethyl acetate) titanium, tri-n-butoxy-mono(ethyl acetate) titanium, tri-di-butoxy-mono(ethyl acetate) titanium, tri-tertiary-butoxy-mono(ethyl acetate) titanium, diethoxy-bis(ethyl acetate) titanium, di-n-propoxy-bis(ethyl acetate) titanium, diisopropoxy-bis(ethyl acetate) titanium, di-n-butoxy-bis(ethyl acetate) titanium, di-di-di-butoxy-bis(ethyl acetate) titanium, di-tertiary-butoxy-bis(ethyl acetate) titanium, monoethoxy Titanium chelate compounds including methyl-trimethyl-ethyl acetate titanium, mono-n-propoxy-trimethyl-ethyl acetate titanium, mono-isopropoxy-trimethyl-ethyl acetate titanium, mono-n-butoxy-trimethyl-ethyl acetate titanium, mono-di-butoxy-trimethyl-ethyl acetate titanium, mono-tertoxy-trimethyl-ethyl acetate titanium, tetra-ethyl acetate titanium, mono-(acetyl acetone)trimethyl-ethyl acetate titanium, bis(acetyl acetone)bis(acetyl acetone) titanium, and trimethyl-(acetyl acetone)mono-(acetyl acetone) titanium;Triethoxymono(acetylene)zirconium, Tri-n-propoxymono(acetylene)zirconium, Triisopropoxymono(acetylene)zirconium, Tri-n-butoxymono(acetylene)zirconium, Tri-dibutoxymono(acetylene)zirconium, Tri-tertoxymono(acetylene)zirconium, Diethoxybis(acetylene)zirconium, Di-n-propoxybis(acetylene)zirconium, Diisopropoxybis(acetylene)zirconium, Di-n-butoxybis(acetylene)zirconium, Di-dibutoxybis(acetylene)zirconium, Di-dibutoxybis(acetylene)zirconium, Di-tertoxy... Zirconium bis(acetophenone), Zirconium monoethoxy-tris(acetophenone), Zirconium mono-n-propoxy-tris(acetophenone), Zirconium monoisopropoxy-tris(acetophenone), Zirconium mono-n-butoxy-tris(acetophenone), Zirconium monodibutoxy-tris(acetophenone), Zirconium monotertoxy-tris(acetophenone), Zirconium tetra(acetophenone), Zirconium triethoxy-mono(acetyl ethyl acetate), Zirconium tri-n-propoxy-mono(acetyl ethyl acetate), Zirconium triisopropoxy-mono(acetyl ethyl acetate), Zirconium tri-n-butoxy-mono(acetyl ethyl acetate) Zirconium, tri-butoxy-mono(ethyl acetate)zirconium, tri-tertoxy-mono(ethyl acetate)zirconium, diethoxy-bis(ethyl acetate)zirconium, di-n-propoxy-bis(ethyl acetate)zirconium, diisopropoxy-bis(ethyl acetate)zirconium, di-n-butoxy-bis(ethyl acetate)zirconium, di-di-butoxy-bis(ethyl acetate)zirconium, di-tertoxy-bis(ethyl acetate)zirconium, monoethoxy-tris(ethyl acetate)zirconium, mono-n-propoxy-tris(ethyl acetate)zirconium Zirconium chelates include zirconium monoisopropoxy-triethyl(ethyl acetate)zirconium, zirconium mono-n-butoxy-triethyl(ethyl acetate)zirconium, zirconium mono-dibutoxy-triethyl(ethyl acetate)zirconium, zirconium tetra(ethyl acetate)zirconium, zirconium mono(ethyl acetone)triethyl(ethyl acetate)zirconium, zirconium triethyl(ethyl acetone)mono(ethyl acetate)zirconium, etc.; aluminum chelates include zirconium triethyl(ethyl acetone)aluminum, zirconium triethyl(ethyl acetate)aluminum, etc.

[0051] Organic acids that can be used as hydrolysis catalysts include, for example, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, melamine acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolenic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, trifluoromethanesulfonic acid, etc.

[0052] Inorganic acids that can be used as hydrolysis catalysts include, for example, hydrochloric acid, nitric acid, sulfuric acid, fluorinated acid, and phosphoric acid.

[0053] Organic bases that can be used as hydrolysis catalysts include, for example: pyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc.

[0054] Inorganic bases that can be used as hydrolysis catalysts include, for example, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc.

[0055] Organic solvents used for hydrolysis and condensation include, for example, aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isohexane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentane, and trimethylbenzene; and methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, and 2 Monool solvents including methylpentanol, hexanol, 2-ethylbutanol, heptanol, heptanol-3, n-octanol, 2-ethylhexanol, 2-octanol, n-nonanol, 2,6-dimethyl-heptanol-4, n-decanol, undecyl alcohol, trimethylnonanol, tetradecyl alcohol, heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.; ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol Polyol solvents such as tripropylene glycol and glycerol; ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone-based acetone, diacetone alcohol, acetophenone, and fentanyl ketone; diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, dioxane, and dimethyldioxane. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and other ether-based solvents;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, butyl acetate 2, n-pentyl acetate, methyl pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, di ... Ester solvents such as glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylmethoxylamine, N,N-dimethylmethoxylamine, N,N-diethylmethoxylamine, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionic acid, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfide, cyclobutane, and 1,3-propane sulpholol. These organic solvents may be used in one or in combination of two or more.

[0056] <<<Crosslinking Agent>>> The stripping agent composition may also contain a crosslinking agent. By containing a crosslinking agent, crosslinking between specific compounds can proceed appropriately, and appropriate curing can be achieved. As a result, a film with good reproducibility can be expected. Although the aforementioned film cannot be properly removed by organic solvents, acids, and solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.), it can still be properly removed by the cleaning agent composition. There are no particular limitations on specific examples of such crosslinking agents. Typical examples include phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, thiourea crosslinking agents, etc., which have alkoxymethyl, methoxymethyl, butoxymethyl, or other crosslinking-forming groups in the molecule. These can be low-molecular-weight compounds or high-molecular-weight compounds. The crosslinking agent contained in the stripping agent composition usually has two or more crosslinking-forming groups. From the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking-forming groups contained in the compound as a crosslinking agent is ideally 2 to 10, and more ideally 2 to 6. From the perspective of achieving higher heat resistance, the crosslinking agent contained in the stripping agent composition ideally has an aromatic ring (such as a benzene ring or a naphthalene ring) in the molecule. Phenolic crosslinking agents are typical examples of such crosslinking agents, although not limited to this.

[0057] A phenolic crosslinking agent having a crosslinking forming group refers to a compound having a crosslinking forming group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of alkoxy groups derived from the phenolic hydroxyl group include methoxy and butoxy groups, but are not limited to these. The aromatic ring bonded by the crosslinking forming group, and the aromatic ring bonded by the phenolic hydroxyl group and / or the alkoxy group derived from the phenolic hydroxyl group, are not limited to non-condensed ring aromatic rings such as benzene rings, but can also be condensed ring aromatic rings such as naphthalene rings and anthracene rings. When there are multiple aromatic rings within the molecule of a phenolic crosslinking agent, the crosslinking forming group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group can bond to the same aromatic ring within the molecule, or they can bond to different aromatic rings. The cross-linking group, phenolic hydroxyl group, and aromatic rings bonded by alkoxy groups derived from phenolic hydroxyl groups can be further replaced by alkyl groups such as methyl, ethyl, and butyl, hydrocarbon groups such as aryl groups such as phenyl, halogen atoms, etc.

[0058] For example, specific examples of phenolic crosslinking agents having crosslinking forming groups include compounds represented by any one of formulas (L1) to (L4). [Chemical 4]

[0059] 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; L1 and L2 independently represent a single bond, a methylene group, or a propan-2,2-diyl group; L3 is determined by q1 and represents a single bond, a methylene group, a propan-2,2-diyl group, a methyltriyl group, or an ethyl-1,1,1-triyl group; t11, t12, and t13 satisfy 2≦ The integers t11≦5, 1≦t12≦4, 0≦t13≦3, and t11+t12+t13≦6 satisfying 2≦t21≦4, 1≦t22≦3, 0≦t23≦2, and t21+t22+t23≦5 satisfying 5; the integers t24, t25, and t26 satisfying 2≦t24≦4, 1≦t25≦3, 0≦t2 6≦2 and t24+t25+t26≦5 are integers; 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 Integers ≤ 5; t41, t42, and t43 are integers satisfying 2 ≤ t41 ≤ 3, 1 ≤ t42 ≤ 2, 0 ≤ t43 ≤ 1, and t41 + t42 + t43 ≤ 4; q1 is 2 or 3; q2 represents the number of repetitions and is an integer greater than or equal to 0; specific examples of aryl and alkyl groups can be given as examples as those below, with aryl ideally being phenyl and alkyl ideally being methyl or tributyl.

[0060] Specific examples of the compounds represented by the formulas (L1) to (L4) are listed below, but are not limited thereto. Further, these compounds can be synthesized by known methods, or can be obtained as products from Asahi Organic Chemical Industry Co., Ltd. or Honshu Chemical Industry Co., Ltd.

[0061] [Chemical Formula 5]

[0062] [Chemical Formula 6]

[0063] [Chemical Formula 7]

[0064] [Chemical Formula 8]

[0065] A melamine-based crosslinking agent having a crosslink-forming group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative or a 2-amino-1,3,5-triazine derivative in which at least one of the hydrogen atoms of the amino group bonded to its triazine ring is substituted with a crosslink-forming group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group. Specific examples of the melamine-based crosslinking agent having a crosslink-forming group include: mono-, bis-, tris-, tetrakis-, pentakis- or hexakis-alkoxymethyl melamines such as N,N,N’,N’,N”,N”-hexakis(methoxymethyl)melamine, N,N,N’,N’,N”,N”-hexakis(butoxymethyl)melamine; mono-, bis-, tris- or tetrakis-alkoxymethyl phenylmelamines such as N,N,N’,N’-tetrakis(methoxymethyl)phenylmelamine, N,N,N’,N’-tetrakis(butoxymethyl)phenylmelamine, etc., but are not limited thereto.

[0066] A urea-based crosslinking agent having a crosslink-forming group refers to a derivative of a compound containing a urea bond and having a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is substituted with a crosslink-forming group. Specific examples of the urea-based crosslinking agent having a crosslink-forming group include: mono-, bis-, tris- or tetrakis-alkoxymethyl acetylureas such as 1,3,4,6-tetrakis(methoxymethyl)acetylurea, 1,3,4,6-tetrakis(butoxymethyl)acetylurea; mono-, bis-, tris- or tetrakis-alkoxymethyl ureas such as 1,3-bis(methoxymethyl)urea, 1,1,3,3-tetramethoxymethylurea, etc., but are not limited thereto.

[0067] A thiourea-based crosslinking agent having a crosslink-forming group refers to a derivative of a compound containing a thiourea bond and having a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is substituted with a crosslink-forming group. Specific examples of the thiourea-based crosslinking agent having a crosslink-forming group include: mono-, bis-, tris- or tetrakis-alkoxymethyl thioureas such as 1,3-bis(methoxymethyl)thiourea, 1,1,3,3-tetramethoxymethylthiourea, etc., but are not limited thereto.

[0068] The amount of crosslinking agent contained in the stripping agent composition varies depending on the coating method used, the required film thickness, etc., and therefore cannot be specified in general. Relative to a specific compound, it is usually 0.01 to 50% by mass. From the viewpoint of obtaining a laminate with good reproducibility that achieves proper curing and enables good separation between the semiconductor substrate and the support substrate, it is ideal to be 0.1% by mass or more, more ideal to be 1% by mass or more, even more ideal to be 3% by mass or more, and even more ideal to be 5% by mass or more; ideally, it is 45% by mass or less, more ideally 40% by mass or less, even more ideally 35% by mass or less, and even more ideally 30% by mass or less.

[0069] <<<Acid generating agent and acid>>> For the purpose of promoting cross-linking reactions, the composition of the stripping agent may also contain acid generating agent and acid.

[0070] Acid generating agents may include, for example, thermal acid generating agents and photosensitive acid generating agents. Thermal acid generating agents are not particularly limited as long as they generate acid by heat. Specific examples include: 2,4,4,6-tetrabromocyclohexadienone, benzoyl toluenesulfonate, 2-nitrobenzyl toluenesulfonate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters, but are not limited to these.

[0071] Examples of photoacid generating agents include: onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0072] Specific examples of onium salt compounds include: diphenylmenium hexafluorophosphate, diphenylmenium trifluoromethanesulfonate, diphenylmenium nonafluoron-butanesulfonate, diphenylmenium perfluoron-octanesulfonate, diphenylmenium camphor sulfonate, bis(4-tert-butylphenyl)menium camphor sulfonate, bis(4-tert-butylphenyl)menium trifluoromethanesulfonate, etc.; triphenylstrontium nitrate, triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butanesulfonate, triphenylstrontium camphor sulfonate, triphenylstrontium trifluoromethanesulfonate, etc., but are not limited to these.

[0073] Specific examples of sulfonamide compounds include, but are not limited to, N-(trifluoromethanesulfonoxy)succinimide, N-(nonafluorobutanoxy)succinimide, N-(camphorsulfonoxy)succinimide, and N-(trifluoromethanesulfonoxy)naphthalenedimethylimide.

[0074] Specific examples of disulfonyldiazomethane compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methanesulfonyl-p-toluenesulfonyldiazomethane, etc., but are not limited to these.

[0075] Specific examples of acids include: p-toluenesulfonic acid, pyridinium toluenesulfonate, pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonate, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid and other aryl sulfonic acids and pyridinium salts and their salts; salicylic acid, benzoic acid, hydroxybenzoic acid, naphthoic acid and other aryl carboxylic acids and their salts; trifluoromethanesulfonic acid, camphorsulfonic acid and other chain or cyclic alkyl sulfonic acids and their salts; citric acid and other chain or cyclic alkyl carboxylic acids and their salts, but are not limited to these.

[0076] The amount of acid generating agent and acid contained in the stripping agent composition varies depending on the type of crosslinking agent used together, the heating temperature during film formation, etc., so it cannot be specified in general. It is usually 0.01 to 5% by mass relative to the film composition.

[0077] <<<Surfactant>>> The release agent composition may also contain surfactants for the purpose of adjusting the liquid properties of the composition itself and the membrane properties of the obtained membrane, as well as for the purpose of reproducibly modifying the release agent composition with high uniformity. Examples of surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl allyl 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; and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters. (EFTOP) Fluorinated surfactants include EF301, EF303, EF352 (manufactured by Tohkem Products, Inc., trade name), MEGAFAC F171, F173, R-30, R-30N (manufactured by DIC Corporation, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Corporation, trade name), AsahiGuard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Surfactants can be used alone or in combination of two or more. The amount of surfactant, relative to the film composition of the stripper, is typically less than 2% by mass.

[0078] <<< Solvent>>> Ideally, the stripping agent composition contains a solvent. Such a solvent can be, for example, a highly polar solvent capable of effectively dissolving the aforementioned specific compounds, crosslinking agents, and other film-forming components. Alternatively, a low-polarity solvent can be used as needed to adjust viscosity, surface tension, etc. Furthermore, in this invention, a low-polarity solvent is defined as having a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polarity solvent is defined as having a relative permittivity of 7 or higher at a frequency of 100 kHz. One solvent can be used alone, or two or more can be used in combination.

[0079] In addition, examples of highly polar solvents include: amine solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolium ketone; ketone solvents such as methyl ethyl ketone, isophorone, and cyclohexanone; cyanide solvents such as acetonitrile and 3-methoxypropionitrile; polyol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and urethane solvents such as dimethyl urethane.

[0080] Examples of low polar solvents include: chloroform, chlorobenzene and other chlorine-based solvents; alkylbenzene and other aromatic hydrocarbon solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decanbenzene; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; ester solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, di(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.

[0081] The content of the solvent is appropriately determined by taking into account the viscosity of the required components, the coating method used, the thickness of the film to be made, etc., and is less than 99% by mass of the total components. Ideally, it is 70% to 99% by mass relative to the total components. That is, in this case, the amount of film components is 1% to 30% by mass relative to the total components.

[0082] The viscosity and surface tension of the stripping agent composition are adjusted appropriately by taking into account various factors such as the coating method used and the required film thickness, by changing the type of solvent used or its equivalent ratio, and the concentration of film components.

[0083] In a certain embodiment of the present invention, from the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that imparts a film with high homogeneity, the stripping agent composition contains a glycol-based solvent. Furthermore, the term "glycol-based solvent" here refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0084] One example of an ideal diol solvent is represented by formula (G). [Chemical 9]

[0085] In formula (G), RG1 independently represents a straight-chain or branched alkyl group having 2 to 4 carbon atoms; RG2 and RG3 independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 8 carbon atoms, or an alkyl acetyl group having a straight-chain or branched alkyl group having 1 to 8 carbon atoms; ng is an integer from 1 to 6.

[0086] Specific examples of linear or branched alkyl groups having 2 to 4 carbon atoms include: ethyl, trimethylene, 1-methylethyl, tetramethylene, 2-methylpropyl-1,3-diyl, pentamethylene, hexamethylene, etc., but are not limited to these. Among these, from the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that can impart a film with high homogeneity, linear or branched alkyl groups having 2 to 3 carbon atoms are ideal, and linear or branched alkyl groups having 3 carbon atoms are more ideal.

[0087] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary 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- Amyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these. Among these, from the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that can impart a film with high homogeneity, methyl or ethyl is ideal, and methyl is more ideal.

[0088] Specific examples of alkyl alkyl groups having 1 to 8 carbon atoms in a straight-chain or branched alkyl group can be given as the specific examples described above. Among these, from the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that can impart a film with high homogeneity, methyl carbonyl and ethyl carbonyl are ideal, and methyl carbonyl is more ideal.

[0089] From the viewpoint of obtaining a composition with high homogeneity with good reproducibility, the viewpoint of obtaining a composition with high preservation stability with good reproducibility, and the viewpoint of obtaining a composition with high homogeneity that can impart a membrane with good reproducibility, ng is ideally 4 or less, more ideally 3 or less, even more ideally 2 or less, and most ideally 1.

[0090] From the viewpoint of obtaining a composition with high homogeneity and good reproducibility, the viewpoint of obtaining a composition with high storage stability and good reproducibility, and the viewpoint of obtaining a composition that can impart a film with high homogeneity and good reproducibility, in formula (G), ideally at least one of RG2 and RG3 is a linear or branched alkyl group having 1 to 8 carbon atoms; more ideally, one of RG2 and RG3 is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is an alkyl acetyl group having a hydrogen atom or an alkyl part that is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0091] From the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that imparts a film with high homogeneity, the content of a glycol-based solvent relative to the solvent contained in the stripper composition is ideally 50% by mass or more, more ideally 70% by mass or more, even more ideally 80% by mass or more, even more ideally 90% by mass or more, and even more ideally 95% by mass or more. From the viewpoints of obtaining a composition with good reproducibility and high homogeneity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that imparts a film with high homogeneity, the film-forming components in the stripper composition are uniformly dispersed or dissolved in the solvent, ideally dissolved.

[0092] The stripping agent composition can be manufactured, for example, by mixing the aforementioned specific compound, solvent, and, if necessary, crosslinking agent. The mixing order is not particularly limited. Examples of methods for easily and reproducibly manufacturing the stripping agent composition include: dissolving the aforementioned specific compound and crosslinking agent in the solvent in one step; and dissolving a portion of the aforementioned specific compound and crosslinking agent in the solvent, dissolving the remaining portion separately in the solvent, and then mixing the resulting solutions. However, these methods are not limited to these. Furthermore, the solution of the aforementioned specific compound can be the reaction solution obtained from the preparation of the aforementioned specific compound, either directly, concentrated, or diluted. In addition, when preparing the stripping agent composition, heating can be appropriately applied within a range that does not cause the components to decompose or deteriorate. In this invention, for the purpose of removing foreign matter, the solvent or solution used can be filtered using a filter or the like during the manufacturing process of the stripping agent composition or after mixing all the components.

[0093] The thickness of the release layer in the laminate of the present invention is not particularly limited, and is generally 5nm to 100μm, 10nm to 10μm in one sample, and 50nm to 1μm in other samples. In another sample, it is 100nm to 700nm.

[0094] The aforementioned release agent composition is also the subject of this invention, and the relevant conditions (ideal conditions, manufacturing conditions, etc.) are as described above. By using the release agent composition of this invention, ideal films can be reproducibly manufactured as release layers that can be used in the manufacture of semiconductor devices.

[0095] The release agent composition of the present invention can be suitably used to form a release layer of a laminate comprising: a semiconductor substrate, a support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate. In the laminate, the release layer is used to peel the semiconductor substrate from the support substrate after absorbing light irradiated from the support substrate side. One characteristic of the release layer obtained by the release agent composition of the present invention is that although it cannot be properly removed by organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.), it can still be properly removed by a cleaning agent composition. Such specific and selective removal is due to the specific compounds contained in the release agent composition of the present invention, which can function as solubility enhancers or removal enhancers of the cleaning agent composition for the release layer, and can also function as solubility de-enhancing agents or removal de-enhancing agents of organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) in the release layer.

[0096] As described above, the release layer obtained by the release agent composition of the present invention is ideally not removable by organic solvents, acids, or solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.).Specific examples of such organic solvents typically include: straight-chain or branched aliphatic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, and isododecane; cyclic aliphatic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, isopropylcyclohexane, and p-menthane, and cyclic aliphatic unsaturated hydrocarbons such as limonene; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, p-xylene, symmetrical trimethylbenzene, 1,2,4-trimethylbenzene, cumene, 1,4-diisopropylbenzene, and p-isopropyltoluene; dialkyl ketones such as MIBK (methyl isobutyl ketone), methyl ethyl ketone, acetone, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone, and cyclohexanone; and cycloalkyl ketones such as cyclohexanone. Aliphatic saturated hydrocarbon ketones, isophorones and other alkenyl ketones, and other aliphatic unsaturated hydrocarbon ketones; dialkyl ethers such as diethyl ether, di(n-propyl) ether, di(n-butyl) ether, and di(n-pentyl) ether; cyclic alkyl ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbon sulfides such as diethyl sulfide, di(n-propyl) sulfide, and di(n-butyl) sulfide; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolium ketone; nitriles such as acetonitrile and 3-methoxypropionitrile; alkyl alcohols such as methanol, ethanol, and propanol (linear or branched), cyclic alkyl alcohols such as cyclohexanol, diacetone alcohol, benzyl alcohol, and 2-phenoxy... Monools other than alkyl monools such as alkyl ethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; diols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, triethylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol; diols such as ethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether, 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, diethylene glycol monomethyl ether, and tripropylene glycol monobutyl ether. Monoalkyl ethers, diethylene glycol monophenyl ether, and other diol monoaryl ethers, and other diol monoalkyl ethers; 2-phenoxyethanol and other diol monoaryl ethers, and other diol monoethers; ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, and other diol dialkyl ethers, and other diol diethers; dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and other diol monoalkyl ether acetates, and other diol ether acetates; cyclic carbonates such as ethyl carbonate, propyl carbonate, and vinyl carbonate; esters such as butyl acetate and amyl acetate, etc.

[0097] Such acids can be listed as: inorganic acids such as phosphoric acid, hydrochloric acid, perchloric acid, nitric acid, and sulfuric acid and their salts; aryl sulfonic acids such as p-toluenesulfonic acid, pyridinium p-toluenesulfonate, pyridinium phenolsulfonate, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid and their salts; aryl carboxylic acids such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthoic acid and their salts; chain or cyclic alkyl sulfonic acids such as trifluoromethanesulfonic acid and camphorsulfonic acid and their salts; chain or cyclic alkyl carboxylic acids such as citric acid and their salts, but not limited to these.

[0098] Examples of alkaline developing solutions include: aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and other quaternary ammonium hydroxides; alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine, etc., but are not limited to these.

[0099] The release layer obtained from the release agent composition of the present invention cannot be properly removed by organic solvents, acids, or solutions used in semiconductor device manufacturing (alkaline developer, hydrogen peroxide, etc.). This characteristic can be evaluated using the following method. That is, a 200 nm thick film formed on a 4 cm square silicon wafer can be immersed together with the silicon wafer in 7 mL of evaluation liquid. The film thickness before and after immersion is compared, and the evaluation is performed by the film thickness reduction rate (%) of the film thickness after immersion relative to the film thickness before immersion. The release layer obtained from the release agent composition of the present invention, according to this method, exhibits a low film reduction rate even after immersion in organic solvents, acids, or solutions used in semiconductor device manufacturing (alkaline developer, hydrogen peroxide, etc.), typically below 10%, below 6% in the ideal sample, below 5% in the more ideal sample, below 4% in the even more ideal sample, below 3% in the still more ideal sample, below 2% in the even more ideal sample, below 1% in the still more ideal sample, and 0% in the most ideal sample. Furthermore, the film reduction rate can be calculated using the following formula: Film reduction rate (%) = [1 - [film thickness after immersion (nm) / film thickness before immersion (nm)]] × 100

[0100] Furthermore, according to the above formula, for example, when the film thickness increases due to film swelling, the film thickness after impregnation is increased compared to the film thickness before impregnation, so the film reduction rate will be negative. However, the above formula does not deny this situation and exclude it from the present invention.

[0101] <<<Detergent Composition>>> The stripping layer obtained by the stripping agent composition of the present invention can be appropriately removed by a detergent composition, which typically contains salt and solvent. An ideal example of a detergent composition is a detergent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is not particularly limited as long as it is composed of a quaternary ammonium cation and anion for this purpose. Typically, a tetra(hydrocarbon)ammonium cation can be listed as such a quaternary ammonium cation. On the other hand, the paired anions can include, but are not limited to, hydroxyl ions (OH-); halogen ions such as fluoride ions (F-), chloride ions (Cl-), bromide ions (Br-), and iodide ions (I-); tetrafluoroborate ions (BF4-); hexafluorophosphate ions (PF6-); etc.

[0102] In this invention, the quaternary ammonium salt is ideally a halogen-containing quaternary ammonium salt, and more ideally a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in the cation or in the anion, and ideally in the anion.

[0103] In an ideal monostate sample, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include: alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, alkynyl groups with 2 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, etc. In a more ideal monostate sample, tetra(hydrocarbon)ammonium fluoride contains tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include: tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride), etc., but are not limited to these. Among them, tetrabutylammonium fluoride is ideal.

[0104] Quadrivalent ammonium salts such as tetra(hydrocarbon)ammonium fluoride can also be used in hydrate form. Furthermore, tetra(hydrocarbon)ammonium fluoride and other quadrivalent ammonium salts can be used alone or in combination of two or more. There is no particular limitation on the amount of the quadrivalent ammonium salt, as long as it is soluble in the solvent contained in the detergent composition; it is typically 0.1 to 30% by mass relative to the detergent composition.

[0105] The solvent contained in the detergent composition used in the present invention is not particularly limited as long as it is used for this purpose and can dissolve salts such as quaternary ammonium salts. From the viewpoint of obtaining a detergent composition with excellent detergency and good reproducibility, and from the viewpoint of obtaining a detergent composition with excellent uniformity by dissolving salts such as quaternary ammonium salts well, it is ideal that the detergent composition used in the present invention contains one or more amide-based solvents.

[0106] An ideal example of a amide-based solvent is an acidic amide derivative represented by formula (Z). [Chemistry 10]

[0107] In the formula, R0 represents ethyl, propyl, or isopropyl, ideally ethyl or isopropyl, and more ideally ethyl. RA and RB each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms can be linear, branched, or cyclic. Specifically, examples include: methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, cyclobutyl, etc. Among these, RA and RB are ideally methyl or ethyl, more ideally both are methyl or ethyl, and even more ideally both are methyl.

[0108] Examples of acid amine derivatives represented by formula (Z) include: N,N-dimethylpropionic acid, N,N-diethylpropionic acid, N-ethyl-N-methylpropionic acid, N,N-dimethylbutyridine, N,N-diethylbutyridine, N-ethyl-N-methylbutyridine, N,N-dimethylisobutylamine, N,N-diethylisobutylamine, N-ethyl-N-methylisobutylamine, etc. In particular, among these, N,N-dimethylpropionic acid and N,N-dimethylisobutylamine are ideal, and N,N-dimethylpropionic acid is even more ideal.

[0109] The acid amine derivative represented by formula (Z) can be synthesized by substitution reaction of the corresponding carboxylic acid ester and amine, or commercially available products can be used.

[0110] Another example of an ideal acetylamine solvent can be cited by acetylamine compounds represented by formula (Y). [Chemistry 11]

[0111] In formula (Y), R101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R102 represents an alkyl group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, n-butyl, etc.; specific examples of alkyl groups having 1 to 6 carbon atoms include: methylene, ethyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited to these.

[0112] Specific examples of endoramine compounds represented by formula (Y) can be listed as: α-endoramine compounds, β-endoramine compounds, γ-endoramine compounds, δ-endoramine compounds, etc., which can be used alone or in combination of two or more.

[0113] In an ideal sample of the present invention, the endoamine compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolidone); in a more ideal sample, it contains N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP); in an even more ideal sample, it contains N-methylpyrrolidone (NMP).

[0114] The detergent composition used in this invention may also contain one or more other organic solvents different from the aforementioned acetamine compound. Such other organic solvents are not particularly limited as long as they are used for this purpose and are compatible with the aforementioned acetamine compound. Ideal other solvents include, but are not limited to, alkyl glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing cyclic structures. The amount of other organic solvents different from the aforementioned acetamine compound is generally determined to be less than 95% by mass of the solvent contained in the detergent composition, provided that the quaternary ammonium salt contained in the detergent composition does not precipitate or separate and can be uniformly mixed with the aforementioned acetamine compound. Furthermore, the detergent composition used in this invention may also contain water as a solvent; however, from the viewpoint of avoiding substrate corrosion, it is generally only intentional to use organic solvents as solvents. Furthermore, this does not negate the possibility that trace amounts of water contained in the hydrated salt or organic solvents are included in the detergent composition. The water content of the detergent composition used in this invention is typically 5% by mass or less.

[0115] The characteristic of the release layer obtained by the release agent composition of the present invention, which can be properly removed by the detergent composition, can also be evaluated by the film reduction rate (%) according to the above method. After being immersed in the detergent composition according to the above method, the release layer obtained by the release agent composition of the present invention exhibits a high film reduction rate, typically 90% or more, ideally 94% or more, more ideally 95% or more, even more ideally 96% or more, even more ideally 97% or more, even more ideally 98% or more, even more ideally 99% or more, and most ideally 100%.

[0116] <Adhesive Layer> An adhesive layer is disposed between a support substrate and a semiconductor substrate. The adhesive layer may, for example, be bonded to the semiconductor substrate. The adhesive layer may also, for example, be bonded to the support substrate.

[0117] The adhesive layer is not particularly limited, but ideally it is a layer formed by an adhesive composition.

[0118] <<Adhesive Composition>> Adhesive compositions may include, for example, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc., but are not limited to these. Among these, a polysiloxane-based adhesive composition is ideal because it exhibits appropriate adhesion when processing semiconductor substrates, can be properly peeled off after processing, has excellent heat resistance, and can be properly removed by a cleaning agent composition. Furthermore, the adhesive composition may be a thermosetting adhesive composition or a thermoplastic adhesive composition.

[0119] In an ideal embodiment, the adhesive composition contains a polyorganosiloxane. Furthermore, in other ideal embodiments, the adhesive composition contains a component that hardens via a hydrosilicification reaction. More specific embodiments of the thermosetting adhesive composition used in this invention can be exemplified, for example, from <<First Embodiment>> to <<Third Embodiment>> described below. Furthermore, more specific embodiments of the thermoplastic adhesive composition used in this invention can be exemplified, for example, from <<Fourth Embodiment>> described below.

[0120] <<First Embodiment>> As an ideal embodiment, the adhesive composition used in this invention contains a polyorganosiloxane. For example, the adhesive composition used in this invention contains a curing component (A) that becomes an adhesive component. The adhesive composition used in this invention may also contain a curing component (A) that becomes an adhesive component and a component (B) that does not undergo a curing reaction. Here, the component (B) that does not undergo a curing reaction can be exemplified by, for example, a polyorganosiloxane. Furthermore, in this invention, "does not undergo a curing reaction" does not mean that various curing reactions will not occur, but rather that a curing reaction will not occur on the curing component (A). In other ideal embodiments, component (A) may be a component that is cured by a hydrosiliconization reaction, or it may be a polyorganosiloxane component (A') that is cured by a hydrosiliconization reaction. In other ideal samples, component (A) may contain, for example, a polyorganosiloxane (a1) having an alkenyl group with 2 to 40 carbon atoms bonded to silicon atoms, a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2). Here, the alkenyl group with 2 to 40 carbon atoms may also be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc. In other ideal samples, the polyorganosiloxane component (A') cured by hydrosilylation contains polysiloxane (A1) and platinum group metal catalyst (A2); the aforementioned polysiloxane (A1) contains: siloxane units (Q units) selected from SiO2, siloxane units (M units) selected from R1R2R3SiO1 / 2, and siloxane units selected from R4R5SiO2 / 2. (D unit), and one or more units selected from the group consisting of siloxane units (T unit) represented by R6SiO3 / 2; the polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'); the aforementioned polyorganosiloxane (a1') contains: siloxane units (Q' unit) selected from SiO2, and units selected from the group consisting of siloxane units (D unit) and siloxane units (T unit) represented by R1'R2'R3'SiO1 / 2. The aforementioned polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (M' units), siloxane units represented by R4'R5'SiO2 / 2 (D' units), and siloxane units represented by R6'SiO3 / 2 (T' units), and contains at least one unit selected from the group consisting of M' units, D' units, and T' units;Furthermore, (a1') is an example of (a1), and (a2') is an example of (a2).

[0121] R1~R6 are groups or atoms bonded to silicon atoms, and each independently represents a substituted alkyl group, a substituted alkenyl group, or a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0122] R1'~R6' are groups bonded to silicon atoms, each independently representing a substituted alkyl or substituted alkenyl group, but at least one of R1'~R6' is a substituted alkenyl group. Examples of substituents include: halogen atom, nitro, cyano, amino, hydroxyl, carboxyl, aryl, heteroaryl, etc.

[0123] R1”~R6” are groups or atoms bonded to silicon atoms, each independently representing a substituted alkyl or hydrogen atom, but at least one of R1”~R6” is a hydrogen atom. Examples of substituents include: halogen atoms, nitro, cyano, amino, hydroxyl, carboxyl, aryl, heteroaryl, etc.

[0124] The alkyl group can be any of the following: straight-chain, branched, or cyclic. Ideally, it is a straight-chain or branched alkyl group. There is no particular limitation on the number of carbon atoms. It is usually 1 to 40, ideally less than 30, more ideally less than 20, and even more ideally less than 10.

[0125] Specific examples of substituted linear or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1, 1-Dimethyl-n-butyl, 1,2-Dimethyl-n-butyl, 1,3-Dimethyl-n-butyl, 2,2-Dimethyl-n-butyl, 2,3-Dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl-n-propyl, 1,2,2-Trimethyl-n-propyl, 1-Ethyl-1-methyl-n-propyl, 1-Ethyl-2-methyl-n-propyl, etc., but not limited to these, typically have 1 to 14 carbon atoms, ideally 1 to 10, and more ideally 1 to 6. The methyl group is particularly ideal.

[0126] Specific examples of substituted cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl Cycloalkyl groups such as 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, and dicyclodecyl, but not limited to these, typically having 3 to 14 carbon atoms, ideally 4 to 10, and more ideally 5 to 6.

[0127] Alkenyl groups can be either linear or branched, and their number of carbon atoms is not particularly limited, usually 2 to 40, ideally less than 30, more ideally less than 20, and even more ideally less than 10.

[0128] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl, propenyl, butenyl, pentenyl, etc., and their carbon number is usually 2 to 14, ideally 2 to 10, and more ideally 1 to 6. Vinyl and 2-propenyl are particularly ideal. Specific examples of substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl, cyclohexenyl, etc., and their carbon number is usually 4 to 14, ideally 5 to 10, and more ideally 5 to 6.

[0129] As described above, the polysiloxane (A1) contains a polyorganosiloxane (a1') and a polyorganosiloxane (a2'). The alkenyl groups contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') undergo a hydrosilylation reaction via a platinum group metal catalyst (A2) to form a cross-linked structure and harden. As a result, a hardened film is formed.

[0130] The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q', M', D' and T' units, and contains at least one unit selected from the group consisting of M', D' and T' units. Two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0131] Two or more ideal combinations selected from the group of Q' unit, M' unit, D' unit and T' unit can be listed as: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but not limited to these.

[0132] Furthermore, when the polyorganosiloxane (a1') contains two or more polyorganosiloxanes, the ideal combinations are (Q' unit and M' unit) and (D' unit and M' unit), (T' unit and M' unit) and (D' unit and M' unit), and (Q' unit, T' unit and M' unit) and (T' unit and M' unit), but are not limited to these.

[0133] 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 unit selected from the group consisting of M" units, D" units and T" units. The polyorganosiloxane (a2') can also be used in combination with two or more polyorganosiloxanes that satisfy such conditions.

[0134] Two or more ideal combinations selected from the group of Q” unit, M” unit, D” unit and T” unit can be listed as: (M” unit and D” unit), (Q” unit and M” unit), (Q” unit, T” unit and M” unit), but not limited to these.

[0135] The polyorganosiloxane (a1') is composed of siloxane units with alkyl and / or alkenyl groups bonded to their silicon atoms. The proportion of alkenyl groups in all substituents represented by R1' to R6' is ideally 0.1 to 50.0 mol%, more ideally 0.5 to 30.0 mol%, and the remainder R1' to R6' may be alkyl groups.

[0136] The polyorganosiloxane (a2') is composed of siloxane units with alkyl and / or hydrogen atoms bonded to their silicon atoms. Ideally, the proportion of hydrogen atoms in all substituents represented by R1”~R6” is 0.1~50.0 mol%, more ideally 10.0~40.0 mol%, and the remaining R1”~R6” can be alkyl.

[0137] When component (A) contains (a1) and (a2), in the ideal state of the present invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0138] The weight-average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and is usually 500 to 1,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is ideal to be 5,000 to 50,000. Furthermore, in the present invention, the determination of the weight-average molecular weight, number-average molecular weight, and dispersibility of polyorganosiloxanes (except for certain compounds) can be performed, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation). The column temperature is set to 40°C, the dissolution solution (dissolution solvent) is tetrahydrofuran, the flow rate is set to 0.35 mL / min, and the standard sample is polystyrene (Shodex manufactured by Showa Denko Corporation).

[0139] The viscosities of the polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, and are generally 10 to 1,000,000 mPa·s, respectively. From the viewpoint of achieving the effects of the present invention with good reproducibility, ideally they are 50 to 10,000 mPa·s, respectively. Furthermore, the viscosities of the polyorganosiloxane (a1) and polyorganosiloxane (a2) are values ​​measured at 25°C using an E-type rotational viscometer.

[0140] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film through a hydrosilicification reaction. Therefore, its curing mechanism is different from that of, for example, via silanol groups. Thus, neither of the siloxanes needs to contain silanol groups or functional groups such as alkoxy groups that are formed by hydrolysis to form silanol groups.

[0141] In the ideal embodiment of the present invention, the adhesive composition contains a polyorganosiloxane component (A') and a platinum group metal catalyst (A2). Thus, the platinum group metal catalyst is used to promote the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si-H group of the polyorganosiloxane (a2).

[0142] Specific examples of platinum group metal catalysts include platinum black, platinum tetrachloride, chloroplatinic acid, reactants of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and alkenes, and platinum diacetate, but are not limited to these. Examples of platinum-alkene complexes include, for instance, complexes of divinyltetramethyldisiloxane and platinum, but are not limited to these. The amount of platinum group metal catalyst (A2) is not particularly limited, but is generally in the range of 1.0 to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0143] The polyorganosiloxane component (A') may also contain a polymerization inhibitor (A3) for the purpose of inhibiting the hydrosiliconization reaction. There are no particular limitations on the polymerization inhibitor as long as it can inhibit the hydrosiliconization reaction; specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol. There are no particular limitations on the amount of the polymerization inhibitor; from the viewpoint of achieving its effect, it is generally 1000.0 ppm or more relative to the total amount of the polyorganosiloxane (a1) and polyorganosiloxane (a2); from the viewpoint of preventing excessive inhibition of the hydrosiliconization reaction, it is generally 10000.0 ppm or less.

[0144] One example of the adhesive composition used in this invention may contain a curing component (A) and a component (B) that does not undergo a curing reaction and serves as a release agent. By containing such component (B) in the adhesive composition, the obtained adhesive layer exhibits good reproducibility and can be properly released. Typically, such component (B) may include non-curing polyorganosiloxanes, and specific examples include epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, phenyl-containing polyorganosiloxanes, etc., but are not limited to these. In addition, component (B) may include polydimethylsiloxanes. The polydimethylsiloxane may also be modified. Examples of polydimethylsiloxanes that can be modified include, for example, epoxy-containing polydimethylsiloxanes, unmodified polydimethylsiloxanes, phenyl-containing polydimethylsiloxanes, etc., but are not limited to these.

[0145] Ideal examples of polyorganosiloxanes as component (B) may be listed as: polyorganosiloxanes containing epoxy groups, polyorganosiloxanes containing methyl groups, polyorganosiloxanes containing phenyl groups, etc., but not limited to these.

[0146] The weight-average molecular weight of the polyorganosiloxane as component (B) is not particularly limited, but is generally 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is ideally 200,000 to 1,200,000, and more ideally 300,000 to 900,000. Furthermore, its dispersibility is not particularly limited, but is generally 1.0 to 10.0. From the viewpoint of achieving proper exfoliation with good reproducibility, it is ideally 1.5 to 5.0, and more ideally 2.0 to 3.0. The weight-average molecular weight and dispersibility can be determined using the methods described above related to the polyorganosiloxane as component (A). The viscosity of the polyorganosiloxane as component (B) is not particularly limited, but is generally 1,000 to 2,000,000 mm² / s. Furthermore, the viscosity of the polyorganosiloxane, which is component (B), is expressed as kinematic viscosity, centistokes (cSt) = mm² / s. It can also be obtained by dividing viscosity (mPa·s) by density (g / cm³). That is, its value can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer, and can be calculated using the formula: kinematic viscosity (mm² / s) = viscosity (mPa·s) / density (g / cm³).

[0147] Examples of epoxy-containing polyorganosiloxanes include, for example, those containing siloxane units (D10 units) represented by R11R12SiO2 / 2.

[0148] R11 is a group bonded to a silicon atom, representing an alkyl group; R12 is a group bonded to a silicon atom, representing an epoxy group or an epoxy-containing organic group; specific examples of alkyl groups can be listed above. The epoxy group in an epoxy-containing organic group may be an independent epoxy group without condensation with other rings, or it may be an epoxy group that forms a condensed ring with other rings, such as 1,2-epoxycyclohexyl. Specific examples of epoxy-containing organic groups include 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these. In this invention, an ideal example of an epoxy-containing polyorganosiloxane is epoxy-containing polydimethylsiloxane, but is not limited to this.

[0149] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D10 unit). However, in addition to the D10 unit, it may also contain Q unit, M unit and / or T unit. In an ideal embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include: polyorganosiloxane composed only of D10 units; polyorganosiloxane containing D10 units and Q units; polyorganosiloxane containing D10 units and M units; polyorganosiloxane containing D10 units and T units; polyorganosiloxane containing D10 units, Q units and M units; polyorganosiloxane containing D10 units, M units and T units; polyorganosiloxane containing D10 units, Q units, M units and T units, etc.

[0150] The epoxy group-containing polyorganosiloxane preferably is a polydimethylsiloxane containing an epoxy group with an epoxy value of 0.1 to 5. In addition, its weight average molecular weight is not particularly limited, and is usually 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0151] Specific examples of the epoxy group-containing polyorganosiloxane include, but are not limited to, those represented by formulas (E1) to (E3).

[0152] [Chemical formula 12] (m1 and n1 represent the numbers of each repeating unit, and are positive integers.)

[0153] [Chemical formula 13] (m2 and n2 represent the numbers of each repeating unit, and are positive integers; R is an alkylene group having 1 to 10 carbon atoms.)

[0154] [Chemical formula 14] (m3, n3 and o3 represent the numbers of each repeating unit, and are positive integers; R is an alkylene group having 1 to 10 carbon atoms.)

[0155] Examples of the methyl group-containing polyorganosiloxane include those containing a siloxane unit (D200 unit) represented by R210R220SiO2 / 2, and preferably those containing a siloxane unit (D20 unit) represented by R21R21SiO2 / 2.

[0156] R210 and R220 are groups bonded to the silicon atom, and each independently represents an alkyl group, but at least one of them is a methyl group; specific examples of the alkyl group include the above-mentioned examples. R21 is a group bonded to the silicon atom and represents an alkyl group; specific examples of the alkyl group include the above-mentioned examples. Among them, R21 is preferably a methyl group. In the present invention, an ideal example of the methyl group-containing polyorganosiloxane includes polydimethylsiloxane, but is not limited thereto.<​

[0157] The methyl-containing polyorganosiloxane contains the above siloxane units (D200 units or D20 units), but in addition to the D200 units and D20 units, it may also contain Q units, M units and / or T units.

[0158] In one aspect of the present invention, specific examples of the methyl-containing polyorganosiloxane include: a polyorganosiloxane composed only of D200 units; a polyorganosiloxane containing D200 units and Q units; a polyorganosiloxane containing D200 units and M units; a polyorganosiloxane containing D200 units and T units; a polyorganosiloxane containing D200 units, Q units and M units; a polyorganosiloxane containing D200 units, M units and T units; a polyorganosiloxane containing D200 units, Q units, M units and T units.

[0159] In a preferred aspect of the present invention, specific examples of the methyl-containing polyorganosiloxane include: a polyorganosiloxane composed only of D20 units; a polyorganosiloxane containing D20 units and Q units; a polyorganosiloxane containing D20 units and M units; a polyorganosiloxane containing D20 units and T units; a polyorganosiloxane containing D20 units, Q units and M units; a polyorganosiloxane containing D20 units, M units and T units; a polyorganosiloxane containing D20 units, Q units, M units and T units. 【0×160】Specific examples of the methyl-containing polyorganosiloxane include, but are not limited to, the examples represented by formula (M1).

[0161] [Chemical formula 15] (n4 represents the number of repeating units and is a positive integer.)

[0162] The phenyl-containing polyorganosiloxane may include, for example, a siloxane unit (D30 unit) represented by R31R**32SiO2 / 2. [[ID=**********]] [[ID=**********]]

[0163] R31 is a group bonded to the silicon atom, representing a phenyl group or an alkyl group; R32 is a group bonded to the silicon atom, representing a phenyl group; specific examples of the alkyl group include the above examples, and preferably it is a methyl group.

[0164] The phenyl-containing polyorganosiloxane contains the above siloxane unit (D30 unit), but in addition to the D30 unit, it may also contain Q units, M units and / or T units. It should be noted that there seems to be an error in the "0×160" in item . It is assumed to be "0160" for the translation. If this is not the case, please correct it according to the actual situation.

[0165] In an ideal aspect of the present invention, specific examples of the phenyl-containing polyorganosiloxane include: polyorganosiloxanes composed only of D30 units; polyorganosiloxanes containing D30 units and Q units; polyorganosiloxanes containing D30 units and M units; polyorganosiloxanes containing D30 units and T units; polyorganosiloxanes containing D30 units, Q units and M units; polyorganosiloxanes containing D30 units, M units and T units; polyorganosiloxanes containing D30 units, Q units, M units and T units.

[0166] Specific examples of the phenyl-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0167] [Chemical Formula 16] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0168] [Chemical Formula 17] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0169] The polyorganosiloxane as the release agent component (B) can be a commercially available product or a synthetic product. Commercially available products of polyorganosiloxane include, for example: products of WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM manufactured by Wacker Chemie AG; dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-9, manufactured by Shin-Etsu Chemical Co., Ltd. 968), cyclic dimethyl silicone oil (KF-995); epoxy group-containing polyorganosiloxane (trade name CMS-227, ECMS-327) manufactured by Gelest Inc., epoxy group-containing polyorganosiloxane (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd., epoxy group-containing polyorganosiloxane (BY16-839) manufactured by Dow Corning Corporation; phenyl group-containing polyorganosiloxane (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest Inc., phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group-containing polyorganosiloxane (TSF431, TSF433) manufactured by Momentive Performance Materials Inc., etc., but are not limited to these.

[0170] In one state, the adhesive composition used in this invention contains a curing component (A) and a component (B) that does not undergo a curing reaction; in other states, component (B) contains a polyorganosiloxane.

[0171] One example of the adhesive composition used in this invention is that it can contain component (A) and component (B) in any ratio. However, considering the balance between adhesion and peelability, the ratio of component (A) to component (B) by mass [(A):(B)] is ideally 99.995:0.005 to 30:70, and more ideally 99.9:0.1 to 75:25. That is, when it contains a polyorganosiloxane component (A') that is cured by hydrosilicification, the ratio of component (A') to component (B) by mass [(A'):(B)] is ideally 99.995:0.005 to 30:70, and more ideally 99.9:0.1 to 75:25.

[0172] The viscosity of the adhesive composition used in this invention is not particularly limited, but at 25°C it is typically 500~20,000 mPa·s, and ideally 1,000~10,000 mPa·s.

[0173] <<Second Embodiment>> As an ideal embodiment, the adhesive composition used in this invention contains, for example, a curable adhesive material as described below, or contains the curable adhesive material and a release additive. The curable adhesive material is selected, for example, from: polyaryl oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof. The release additive may be, for example, a polyether compound. The polyether compound ideally contains a terminal group selected from the group consisting of hydroxyl, alkoxy, aryloxy, and mixtures thereof. The polyether compound ideally is selected from: polyethylene glycol, polypropylene glycol, poly(1,3-propanediol), polybutanediol, poly(tetrahydrofuran), ethylene glycol-propylene glycol copolymer, and mixtures thereof. The release additive is ideally selected from the group consisting of polyepoxide homopolymers and polyepoxide copolymers. The adhesive composition of the second embodiment may, for example, be a temporary bonding composition as described in Japanese Patent Application Publication No. 2014-150239. The adhesive composition of the second embodiment will be further described in detail below.

[0174] The adhesive composition used in the present invention contains a curable adhesive material and a release additive. Generally, the curable adhesive material has a modulus > 1 GPa when cured. Exemplary curable adhesive materials are not limited to the following, and may include: polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof. In order to provide additional hydrophobicity, the curable adhesive material can be partially replaced by some suitable groups, such as fluorine-containing groups, provided that such parts do not have a negative impact on the mechanical properties of the cured adhesive material. The curable adhesive material is preferably selected from polyarylene oligomers, cyclic olefin oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof, more preferably selected from one or more of arylcyclobutene oligomers, vinyl aromatic oligomers, and mixtures thereof. When different mixtures of curable adhesive materials are used in the present invention, such materials will be selected to cure with each other during the curing step. When different mixtures of curable materials are used, such curable materials are used in a mass ratio of 99:1 to 1:99, preferably 95:5 to 5:95, more preferably 90:10 to 10:90, and even more preferably 75:25 to 25:75.

[0175] A variety of polyarylene oligomers can be used in the present invention. For the purposes of this specification, the term "polyarylene" includes polyarylene ethers. Desirable polyarylene oligomers can also be synthesized from precursors, such as ethynyl aromatic compounds of the following formula.

[0176] In [Chemical Formula 18], each Ar is an aromatic group or an inertly substituted aromatic group; each R is independently hydrogen, an alkyl group, an aryl group, or an inertly substituted alkyl or aryl group; L is a covalent bond or a group that links one Ar to at least another Ar; n and m are integers of at least 2; and q is an integer of at least 1. Thus, the ethynyl aromatic compound usually has four or more ethynyl groups (e.g., tetraethynyl aromatic compounds).

[0177] Among the desirable polyarylene oligomers for the adhesive composition as a second embodiment for the temporary bonding composition, polymers containing the following as polymerization units can also be included.

[0178] In [Chemical Formula 19], Ar' is the residue of the (C≡C)n-Ar or Ar-(C≡C)m part of the reaction product; R, L, n, and m are as defined above. The polyarylene copolymer useful for the present invention contains a monomer of the following formula as a polymerization unit.

[0179] In [Chemical Formula 20] and the formula, Ar' and R are as defined above.

[0180] Exemplary polyaryl groups, Ar-L-Ar, include: biphenyl; 2,2-diphenylpropane; 9,9'-diphenyl benzoyl; 2,2-diphenylhexafluoropropane; diphenyl sulfide; diphenyloxonyl oxy; diphenyl ether; bis(phenyl)diphenylsilane; bis(phenyl)phosphine oxide; bis(phenyl)benzene; bis(phenyl)naphthalene; bis(phenyl)anthracene; dithiophenylene; 1,1,1-triphenylethane; 1,3,5-triphenylbenzene; 1,3,5-(2-phenyl-2-propyl)benzene; 1,1,1-triphenylmethane; 1,1,2,2-tetraphenyl-1,2-diphenylethane. Bis(1,1-diphenylethyl)benzene; 2,2'-diphenyl-1,1,1,3,3,3-hexafluoropropane; 1,1-diphenyl-1-phenylethane; naphthalene; anthracene; or bis(diphenyl)tetraphenyl; more preferably biphenylene; naphthylene; p,p'-(2,2-diphenylpropane) (or C6H4-C(CH3)2-C6H4-); p,p'-(2,2-diphenyl-1,1,1,3,3,3-hexafluoropropene) and (-C6H4-C(CF3)2-C6H4-), but not limited to these. Useful diphenyl derivatives include: 2,2-diphenylpropane; 9,9'-diphenylpropane; 2,2-diphenylhexafluoropropane; diphenyl sulfide; diphenyl ether; bis(phenyl)diphenylsilane; bis(phenyl)phosphorus oxide; bis(phenyl)benzene; bis(phenyl)naphthalene; bis(phenyl)anthracene; or bis(phenyl)tetraphenyl.

[0181] The polyaryl precursor monomer can also be prepared by various methods known in the art, for example by the following steps: step (a) in a solvent, selectively halogenating the polyphenol (ideally bisphenol) and selectively brominating it (wherein, each phenolic ring is halogenated at one of the two ortho positions relative to the phenolic hydroxyl group); step (b) converting the phenolic hydroxyl group on the obtained poly(ortho-halophenol) into a detachable group, such as a sulfonate ester (e.g., from trifluoromethyl ether). The synthesis involves a sulfonyl halide or a trifluoromethanesulfonate ester prepared from a trifluoromethanesulfonic anhydride, ideally substituted in a solvent by reactivity with a terminal acetylene compound; and step (c), in the presence of an arylacetylation catalyst, ideally a palladium catalyst and an acid acceptor, reacting an acetylenic compound or acetylenic synthon with the reaction product of step (b), thereby simultaneously substituting the halogen and the trifluoromethanesulfonate ester with an acetylenic group (e.g., acetylene, phenylacetylene, substituted phenylacetylene, or substituted acetylene). Further description of this synthesis is provided in International Publication No. WO97 / 10193 (Babb).

[0182] The acetylenic aromatic monomer of formula (I) is useful in the formulation of polymers of any formula (II) or (III). The polymerization of acetylenic aromatic monomers is entirely within the capabilities of those skilled in the art. Although the specific conditions of polymerization depend on various factors, including the specific acetylenic aromatic monomer (one or more) being polymerized and the desired properties of the resulting polymer, the general conditions of polymerization are detailed in International Publication No. WO97 / 10193 (Babb).

[0183] Particularly desirable polyarylates for use in this invention are exemplified by those sold from SiLK (trademark) semiconductor dielectrics (available from Dow Electronic Materials, Inc., Marlborough, Massachusetts). Other particularly desirable polyarylates include those disclosed in the following publications: International Publication No. 00 / 31183, International Publication No. 98 / 11149, International Publication No. 97 / 10193, International Publication No. 91 / 09081, European Patent Application Publication No. 755957, U.S. Patent No. 5,115,082, U.S. Patent No. 5,155,175, U.S. Patent No. 5,179,188, U.S. Patent No. 5,874,516, and U.S. Patent No. 6,093,636.

[0184] The ideal cyclic olefin material is a poly(cyclic olefin), which can be thermoplastic and ideally has a weight average molecular weight (Mw) of 2,000 to 200,000 Daltons, more ideally 5,000 to 100,000 Daltons, and even more ideally 2,000 to 50,000 Daltons. The ideal poly(cyclic olefin) system has a softening temperature of at least 100°C (melt viscosity at 3,000 PaS), more ideally at least 140°C. The ideal poly(cyclic olefin) system also has a glass transition temperature (Tg) of at least 60°C, more ideally 60 to 200°C, and most ideally 75 to 160°C.

[0185] Desirable poly(cyclic olefins) are composed of repeating monomers containing cyclic olefins and acyclic olefins, or ring-opening polymers based on cyclic olefins. Desirable cyclic olefins for use in the present invention can be selected from: norbornene-based olefins, tetracyclododecene-based olefins, dicyclopentadiene-based olefins, Diels-Alder polymers such as those derived from furan and maleimide, and derivatives thereof. Examples of derivatives include: alkyl (desirably C1-C20 alkyl, more desirably C1-C10 alkyl), alkylene (desirably C1-C20 alkylene, more desirably C1-C10 alkylene), aralkyl (desirably C6-C30 aralkyl, more desirably C6-C18 aralkyl), cycloalkyl (desirably C3-C30 cycloalkyl, more desirably C3-C18 cycloalkyl), ether, acetyl, aromatic, ester, hydroxyl, alkoxy, cyano, amide group, imide group, and silyl-substituted derivatives. Particularly desirable cyclic olefins for use in the present invention include the following and combinations selected therefrom.

[0186] [Chemical Formula 21]

[0187] [Chemical Formula 22] In the formula, each R1 and R2 is independently selected from H and alkyl (desirably C1-C20 alkyl, more desirably C1-C10 alkyl); and each R3 is independently selected from H, substituted and unsubstituted aryl (desirably C6-C18 aryl), alkyl (desirably C1-C20 alkyl, more desirably C1-C10 alkyl), cycloalkyl (desirably C3-C30 cycloalkyl, more desirably C3-C18 cycloalkyl), aralkyl (desirably C6-C30 aralkyl, more desirably C6-C18 aralkyl such as benzyl, phenethyl, phenylpropyl, etc.), ester group, ether group, acetyl, alcohol (desirably C1-C10 alcohol), aldehyde group, ketone, nitrile, and combinations thereof.

[0188] Desirable acyclic olefins can be selected from branched and unbranched C2-C20 olefins (desirably C2-C10 olefins). The acyclic olefin is more desirably of the structure (R4)2C=C(R4)2, wherein each R4 is independently selected from H and alkyl (desirably C1-C20 alkyl, more desirably C1-C10 alkyl). Particularly desirable acyclic olefins for use in the present invention include those selected from ethylene, propylene, and butene, and most desirably ethylene.

[0189] Methods for manufacturing cyclic olefin copolymers are known in the art. For example, cyclic olefin copolymers can be manufactured by chain polymerization of cyclic monomers and acyclic monomers. When norcamphene is reacted with ethylene under such conditions, an ethylene-norcamphene copolymer containing alternating norcamphenidine and ethyl units can be obtained. Examples of copolymers manufactured by this method include those from the brands TOPAS (trademark) (manufactured by Topas Advanced Polymers) and APEL (trademark) (manufactured by Mitsui Chemicals, Inc.). A preferred method for manufacturing such copolymers is disclosed in U.S. Patent No. 6,008,298. Cyclic olefin copolymers can also be manufactured by ring-opening metathesis polymerization of various cyclic monomers and subsequent hydrogenation. Polymers obtained by this type of polymerization can conceptually be considered as copolymers of ethylene and cyclic olefin monomers (e.g., alternating units of ethyl and cyclopentane-1,3-dimethyl). Examples of copolymers produced by this ring-opening method are provided by the brands ZEONOR (trademark) (from Zeon Chemicals) and ARTON (trademark) (manufactured by JSR Corporation). A preferred method for producing such copolymers by this ring-opening method is disclosed in U.S. Patent No. 5,191,026.

[0190] Useful arylcyclobutene oligomers as curable adhesive materials of the present invention are known in the art. Ideal arylcyclobutene oligomers include, but are not limited to, those having the following formula.

[0191] 〔Chemical 23〕 In the formula, B is an n-valent linking group; Ar is a polyvalent aryl group, and the carbon atom of the cyclobutene ring is bonded to the adjacent carbon atom on the same aromatic ring in Ar; m is an integer of 1 or more; n is an integer of 1 or more; and R5 is a monovalent group. The ideal polyvalent aryl Ar can be composed of 1 to 3 aromatic carbon rings or heteroaromatic rings. The ideal aryl system contains a single aromatic ring, and the more ideal system contains a benzene ring. Depending on the situation, the aryl group may be substituted with one to three groups selected from (C1-C6)alkyl, tri(C1-C6)silyl, (C1-C6)alkoxy, and halogen; ideally, one or more of (C1-C6)alkyl, tri(C1-C3)silyl, (C1-C3)alkoxy, and chlorine; more ideally, one or more of (C1-C3)alkyl, tri(C1-C3)silyl, and (C1-C3)alkoxy. The aryl group is ideally unsubstituted. Ideally, n = 1 or 2; more ideally, n = 1. Ideally, m = 1-4; more ideally, m = 2-4; even more ideally, m = 2. R5 ideally selected from H and (C1-C6)alkyl; more ideally selected from H and (C1-C3)alkyl. B ideally contains one or more carbon-carbon double bonds (vinyl unsaturation). Ideally, a monovalent β-aryl group has the formula -[C(R10)=CR11]xZ, where R10 and R11 are independently selected from hydrogen, (C1-C6)alkyl, and aryl; Z is selected from hydrogen, (C1-C6)alkyl, aryl, siloxyalkyl, and -CO2R12; each R12 is independently selected from H, (C1-C6)alkyl, aryl, aralkyl, and alkylaryl; and x = 1 or 2. R10 and R11 are ideally independently selected from H, (C1-C3)alkyl, and aryl, and more ideally independently selected from H and (C1-C3)alkyl. R12 is ideally (C1-C3)alkyl, aryl, and aralkyl. Z is ideally siloxyalkyl. Ideal siloxane systems have the formula -[Si(R13)2-O]p-Si(R13)2-, where each R13 is independently selected from H, (C1-C6)alkyl, aryl, aralkyl, and alkylaryl; p is an integer greater than or equal to 1. The R13 system is selected from (C1-C3)alkyl, aryl, and aralkyl. Ideal aralkyl groups include benzyl, phenethyl, and phenylpropyl.

[0192] The arylcyclobutene oligomer physical system contains one or more oligomers of the following formula.

[0193] In the formula, each R6 is independently selected from H and (C1-C6) alkyl, preferably selected from H and (C1-C3) alkyl; each R7 is independently selected from (C1-C6) alkyl, tris(C1-C6) alkylsilyl, (C1-C6) alkoxy, and halogen; each R8 is independently a divalent ethylenically unsaturated organic group; each R9 is independently selected from H, (C1-C6) alkyl, aralkyl, and phenyl; p is an integer of 1 or more; and q is an integer from 0 to 3. Each R6 is preferably independently selected from H and (C1-C3) alkyl, and each R6 is more preferably independently H. Each R7 is preferably independently selected from (C1-C6) alkyl, tris(C1-C3) alkylsilyl, (C1-C3) alkoxy, and chlorine, and more preferably independently selected from (C1-C3) alkyl, tris(C1-C3) alkylsilyl, and (C1-C3) alkoxy. Each R8 is preferably independently selected from (C2-C6) alkenyl, and each R8 is more preferably independently -CH=CH-. Each R9 is preferably selected from (C1-C3) alkyl, and each R9 is more preferably methyl. Preferably, p = 1 to 5, more preferably p = 1 to 3, and even more preferably p = 1. Preferably, q = 0. A particularly preferred arylcyclobutene oligomer, 1,3-bis(2-bicyclo[4.2.0]octa-1,3,5-trien-3-ylvinyl)-1,1,3,3-tetramethyldisiloxane ("DVS-bisBCB") has the following formula.

[0194] 〔Chemical formula 25〕

[0195] The arylcyclobutene oligomer can also be prepared by any of the following suitable means: for example, the means described in U.S. Patent No. 4,812,588, U.S. Patent No. 5,136,069, U.S. Patent No. 5,138,081, and International Publication No. WO94 / 25903. A preferred arylcyclobutene oligomer is also available under the commercial brand CYCLOTENE (trademark) from Dow Electronic Materials. The arylcyclobutene oligomer can be used directly, or it can also be further purified by some suitable means.

[0196] Curable vinyl aromatic oligomers can be used as curable adhesive materials in this invention. Such vinyl aromatic oligomers are generally oligomers of one or more reactive vinyl unsaturated comonomers and vinyl aromatic monomers. The vinyl aromatic monomer ideally contains one vinyl group. The ideal vinyl aromatic monomer is an unsubstituted vinyl aromatic monomer and a substituted vinyl aromatic monomer, wherein one or more hydrogen atoms are substituted by substituents selected from the group consisting of (C1-C6)alkyl, (C1-C6)alkoxy, halogen, and amino groups. Exemplary vinyl aromatic monomers are not limited to, but may include: styrene, vinyltoluene, vinylxylene, vinyl anisole, vinyl dimethoxybenzene, vinyl aniline, halostyrene, such as fluorostyrene, α-methylstyrene, β-methoxystyrene, ethyl vinylbenzene, vinylpyridine, vinyl imidazole, vinyl pyrrole, and mixtures thereof. Ideal vinyl aromatic monomers are styrene, vinyltoluene, vinylxylene, vinyl anisole, ethyl vinylbenzene, and mixtures thereof. Ideally, a reactive comonomer, in addition to the olefin (or vinyl unsaturated) moiety used to form the vinyl aromatic oligomer, also contains a reactive moiety—that is, a moiety that can be further polymerized (or crosslinked) after the formation of the vinyl aromatic oligomer, such as an allyl moiety or vinyl group. Such a reactive comonomer is ideally an asymmetric diene or triene that can be further polymerized via a Diels-Alder reaction after oligomerization with a vinyl aromatic monomer. More ideally, the reactive comonomer contains an allyl moiety in addition to the vinyl unsaturated moiety used to form the vinyl aromatic oligomer; even more ideally, it contains an allyl ester moiety in addition to the vinyl unsaturated moiety. Examples of illustrative reactive comonomers useful in forming vinyl aromatic oligomers include: vinylcyclohexene, vinyl ethers, asymmetric dienes or trienes such as terpene monomers, dicyclopentadiene, diallyl maleate, allyl acrylate, allyl methacrylate, allyl cinnamate, diallyl fumarate, allyl tiglate, divinylbenzene, and mixtures thereof, but not limited to these. Reactive comonomers are ideally diallyl maleate, allyl acrylate, allyl methacrylate, allyl cinnamate, diallyl fumarate, and mixtures thereof, more preferably diallyl maleate, allyl methacrylate, and mixtures thereof. Illustrative terpene monomers are not limited to the following, but may include: limonene, dipentene, laurylene, etc. Those skilled in the art will understand that one or more second comonomers can also be used to form vinyl aromatic oligomers. Such second comonomers, although vinyl unsaturated, do not contain a reactive moiety. Examples of second comonomers include: (meth)acrylic acid, (meth)acrylamide, (C1-C10)alkyl (meth)acrylates, aromatic (meth)acrylates, substituted ethylene monomers, and poly(epoxide)monomers, but are not limited to these.

[0197] The ideal molar ratio of vinyl aromatic monomer to comonomer in such vinyl aromatic oligomers is 99:1 to 1:99, more ideally 95:5 to 5:95, and even more ideally 90:10 to 10:90. Such vinyl aromatic oligomers can be formulated by any suitable method, for example, by any method known in the art. Typically, vinyl aromatic oligomers are formulated by free radical polymerization of vinyl aromatic monomers and comonomers. Ideally, vinyl aromatic oligomers contain an unreacted allyl moiety that allows for further hardening of such oligomers.

[0198] A wide variety of materials can be used as release additives in temporary bonded compositions, provided that such materials do not react with the adhesive material under storage and use conditions, and are non-curing under conditions used to cure the adhesive material. Furthermore, the release additive should be suitable for the temporary bonded composition; that is, the release additive should be dispersible and miscible with respect to the adhesive material and some other components used in the temporary bonded composition, such as organic solvents, or otherwise substantially suitable. When organic solvents (or mixed solvent systems) are used in the temporary bonded composition, the release additive and the curing adhesive material must be soluble in such solvents. In this invention, the release additive is sufficiently non-volatile so that it does not substantially evaporate under use conditions; that is, it does not substantially evaporate during stacking steps such as spin coating, or during any subsequent heating steps such as removing organic solvents or curing the adhesive material. When the film or layer of the temporary bonded composition is cast by, for example, spin coating, most (or all) of the solvent evaporates. While the release additive is soluble in any organic solvent used, it is ideally not completely soluble in the cured adhesive material. The release additive has the advantage of being more hydrophilic than the cured adhesive material. Although not bound by theory, it should be considered that during the curing of the adhesive material, the release additive phase will separate and preferentially migrate to the active surface of the wafer (a surface with higher hydrophilicity than the carrier surface). Using an appropriate hydrophilic portion in the release additive allows for complete dispersion, or ideally, dissolution in the temporary bond composition, and enables the release additive to migrate to the more hydrophilic surface, thus facilitating phase separation during the curing process of the adhesive material. Any material that cannot separate from the adhesive material phase during curing cannot function as a release additive according to the present invention.

[0199] Generally, stripping additives contain one or more relatively hydrophilic moieties, such as one or more moieties containing oxygen, nitrogen, phosphorus, and sulfur. Ideal stripping additives are not limited to, but may include: ethers, esters, carboxylic acid esters, alcohols, thioethers, thiols, amines, imines, amides, phosphate esters, sulfonates, and mixtures thereof. Ideally, stripping additives contain one or more polar terminal groups containing one or more oxygen, nitrogen, and sulfur moieties, with oxygen being the most desirable component. Examples of illustrative polar terminal groups include: alkoxy, aryloxy, hydroxyl, carboxylic esters, alkoxycarbonyl, mercapto, alkylthio, primary amines, secondary amines, and tertiary amines; ideal terminal groups may be selected from: (C1-C6)alkoxy, (C6-C10)aryloxy, hydroxyl, carboxylic esters, (C1-C6)alkoxycarbonyl, mercapto, (C1-C6)alkylthio, amino, (C1-C6)alkylamino, and di(C1-C6)alkylamino; more ideally, they may be selected from: (C1-C6)alkoxy, (C6-C10)aryloxy, hydroxyl, carboxylic esters, and (C1-C6)alkoxycarbonyl; even more ideally, they may be selected from: (C1-C6)alkoxy, hydroxyl, carboxylic esters, and (C1-C6)alkoxycarbonyl. Particularly ideal polar terminal groups may be selected from: hydroxyl, methoxy, ethoxy, propoxy, butoxy, carboxyl, and acetoxy. Ideally, the stripping additive should be silicone-free.

[0200] An ideal stripping additive has a number average molecular weight (Mn) of ≤10,000 Daltons, ideally ≤7,500 Daltons, and more ideally ≤7,000 Daltons. Under operating conditions, the stripping additive must have a sufficiently low molecular weight (Mn) to be substantially non-volatile (i.e., <5%, ideally <3%, and more ideally ≤1% volatilization during use). Ideally, the stripping additive has an Mn of ≥500 Daltons. The ideal range for Mn is 500–10,000 Daltons, more ideally 500–7,500 Daltons, and even more ideally 500–7,000 Daltons. Stripping additives can be linear polymers, branched polymers such as dendritic polymers and star polymers, polymer particles, etc. Ideally, the stripping additive is a linear polymer or polymer particles, and more ideally, a linear polymer. Although not bound by theory, it should be considered that linear polymers can migrate more effectively to the hydrophilic wafer surface through the curing adhesive material phase compared to branched polymers.

[0201] Polyethers are ideal stripping additives. Examples of polyether compounds include alkylene oxide homopolymers and copolymers, such copolymers being random or block copolymers. Polyalkylene oxide stripping additives can also have various polar terminal groups, ideally hydroxyl, (C1-C6)alkoxy, and (C1-C6)alkoxycarbonyl, more ideally hydroxyl, (C1-C3)alkoxy, and acetoxy. Ideal polyether compounds are polyethylene glycol (or polyalkylene oxides), such as poly(C1-C4)alkylene oxide compounds, which may contain a single type of repeating alkylene oxide unit or two or more different repeating alkylene oxide units. Ideal polyether compounds include: polyethylene glycol, polypropylene glycol, poly(1,3-propanediol), poly(tetrahydrofuran), ethylene oxide-propylene oxide copolymers, ethylene oxide-butane copolymers, and mixtures thereof. Ideally, when the stripping additive contains butylene oxide as a repeating unit, it is a copolymer of one or more different alkylene oxide repeating units. Those skilled in the art will understand that mixtures of stripping additives are suitable as temporary bonding compositions for use in this invention. Ideal stripping additives include polyethers such as PLURONIC (registered trademark), TETRONIC, and POLYTHF (available from BASF in Ludwigshafen, Germany); FORTEGRA (The Dow Chemical Company in Midland, Michigan); and TERATHANE (available from Invista in Wichita, Kansas), all of which can be used without further purification.

[0202] <<Third Embodiment>> As an ideal embodiment, the adhesive composition used in this invention contains, for example, a thermosetting polymer as described below. The adhesive composition of the third embodiment may be, for example, a thermosetting polymer described in Japanese Patent No. 6528747. The thermosetting polymer is not particularly limited, but ideal examples include a siloxane-containing polymer (hereinafter also referred to as silicone A) with a weight average molecular weight of 3,000 to 500,000, consisting of repeating units represented by the following formula (3) and, if necessary, repeating units represented by the following formula (4).

[0203] 〔Chemical 26〕[In the formula, R6~R9 each independently represent a monovalent hydrocarbon group with 1~8 carbon atoms. In addition, m represents an integer from 1 to 100. A and B are positive numbers that satisfy 0 < A < 1, 0 < B < 1, and A + B = 1. T1 and T2 are divalent organic groups represented by the following formula (5).

[0204] 〔Chemical Formula 27〕(In the formula, A1 is a single bond or a divalent organic group selected from the groups represented by the following formulas. R10 and R11 are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms. h is each independently 0, 1, or 2.)

[0205] 〔Chemical Formula 28〕,,, and

[0206] Examples of the monovalent hydrocarbon group represented by R6 to R9 include: alkyl groups such as methyl and ethyl; aryl groups such as phenyl. m is preferably an integer of 3 to 60, more preferably an integer of 8 to 40. In addition, A is preferably 0.3 to 0.8, B is preferably 0.2 to 0.7, and the ratio of A / B preferably satisfies 0.1 to 20, more preferably satisfies 0.5 to 5.

[0207] In addition, preferred examples of the thermosetting polymer include a polymer containing a siloxane bond (hereinafter also referred to as silicone B) having a weight average molecular weight of 3,000 to 500,000, which is composed of a repeating unit represented by the following formula (6) and, if necessary, a repeating unit represented by the following formula (7).

[0208] 〔Chemical Formula 29〕[In the formula, R12 to R15 each independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms. In addition, p represents an integer of 1 to 100. C and D are positive numbers satisfying 0 < C ≤ 1, 0 ≤ D < 1, and C + D = 1. T3 and T4 are divalent organic groups represented by the following formula (8).

[0209] 〔Chemical Formula 30〕(In the formula, A2 is a single bond or a divalent organic group selected from the groups represented by the following formulas. R16 and R17 are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms. k is each independently 0, 1, or 2.)

[0210] 〔Chemical Formula 31〕,,, and

[0211] In this case, examples of the monovalent hydrocarbon group represented by R11 to R14 are the same as those represented by R5 to R8. p is preferably an integer of 3 to 60, more preferably an integer of 8 to 40. In addition, C is preferably 0.3 to 1, D is preferably 0 to 0.7, and C + D = 1.

[0212] The adhesive composition of the third embodiment uses an adhesive layer formed of a thermosetting polymer, which is preferably a layer of a cured product of a thermosetting resin composition having silicone A or silicone B as a main component. Silicone A and silicone B can be used in combination. In this case, the ratio (polymerization ratio) is preferably silicone A: silicone B = 0.1:99.9 to 99.9:0.1, more preferably silicone A: silicone B = 20:80 to 80:20.

[0213] A thermosetting resin composition with silicone A as the main component, wherein, in order to thermoset, it contains one or more crosslinking agents selected from amine condensates, phenolic compounds and epoxy compounds; the aforementioned amine condensates are modified by formalin or formalin-ethanol; the aforementioned phenolic compounds have an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule; the aforementioned epoxy compounds have an average of two or more epoxy groups in one molecule.

[0214] On the other hand, the thermosetting resin composition with silicone B as the main component contains one or more crosslinking agents selected from phenolic compounds and epoxy compounds in order to thermoset it; the aforementioned phenolic compounds have an average of two or more phenolic groups in one molecule; the aforementioned epoxy compounds have an average of two or more epoxy groups in one molecule.

[0215] Furthermore, the thermosetting resin composition containing silicone A and silicone B contains one or more crosslinking agents selected from epoxy compounds in order to thermoset it; the aforementioned epoxy compounds have an average of two or more epoxy groups in one molecule.

[0216] Examples of the aforementioned amino condensates include melamine resins and urea resins. Melamine resins modified with formalin or formalin alcohol include those obtained by conventional methods, in which a modified melamine monomer (e.g., trimethoxymethyl monohydroxymethyl melamine) or its polymer (e.g., dimer, trimer, or other oligomers) is added to formaldehyde and polymerized to achieve the desired molecular weight. Furthermore, one of these can be used alone, or two or more can be used in combination.

[0217] Examples of urea resins modified with formalin or formalin-ethanol include: methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates, etc. Furthermore, one of these can be used alone, or two or more can be used in combination. For example, urea resins modified with formalin or formalin-ethanol can be modified by: according to conventional methods, using formalin to hydroxymethylate a urea condensate with the desired molecular weight, or further using ethanol to alkoxylate a urea condensate with the desired molecular weight.

[0218] Furthermore, examples of phenolic compounds having an average of two or more hydroxymethyl or alkoxyhydroxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A. Also, these compounds can be used alone or in combination of two or more.

[0219] The epoxy compound having two or more epoxy groups on average in one molecule is not particularly limited, and examples thereof include: polyfunctional epoxy resins having bifunctional, trifunctional or tetrafunctional or higher functions, such as EOCN-1020 (refer to the following formula), EOCN-102S, XD-1000, NC-2000-L, EPPN-201, GAN, NC6000, manufactured by Nippon Kayaku Co., Ltd., and examples represented by the following formula.

[0220] [Chemical formula 32]

[0221] Examples of the phenolic compound having two or more phenolic groups on average in one molecule include: m- or p-cresol novolak resins (for example, EP-6030G manufactured by Asahi Organic Chemical Industry Co., Ltd.), trifunctional phenolic compounds (for example, Tris-P-PA manufactured by Honshu Chemical Industry Co., Ltd.), tetrafunctional phenolic compounds (for example, TEP-TPA manufactured by Asahi Organic Chemical Industry Co., Ltd.), and the like.

[0222] The blending amount of the crosslinking agent in the thermosetting resin composition is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and even more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the thermosetting polymer. The crosslinking agent can be used alone or in combination of two or more. 【0​​​​​​​​​​

[0227] In formula (I), X is selected from the group consisting of benzene, aromatic compounds (ideally C6-C60, more ideally C6-C30, even more ideally C6-C24), aliphatic compounds (C2-C15, more ideally C2-C10, even more ideally C2-C6), and alicyclic compounds (ideally C4-C60, more ideally C4-C20, even more ideally C4-C12).

[0228] In one embodiment, X may be the above-mentioned aromatic group, the above-mentioned aliphatic group, or the above-mentioned alicyclic group. In other embodiments, X may contain: an aromatic group having an ether cross-bridge (as discussed in Z), or an aromatic group having a linking group and / or a -NH2 group at the meta position.

[0229] The particularly desirable X-based system is selected from the group consisting of alkyl-substituted phenyl, isopropylidene diphenyl, and hexafluoroisopropylidene (as described above).

[0230] In formula (II), Z is in the embodiment of a siloxane, and the ideal siloxane is represented by the following formula. [Chemical 37] [In the formula, each R3 is selected from the group consisting of hydrogen, alkyl (ideally C1-C10, more ideally C1-C2), and phenyl; m is 1 to 6; p is 1 to 50, ideally 1 to 20, more ideally 1 to 10.]

[0231] In formula (II), the ideal portion of Z with ether-bridged structure is selected from the group consisting of: [Chemical 38], ..., and

[0232] In embodiments of formula (I) or (II), the polymer or oligomer ideally further comprises end-capping groups. Ideally, the end-capping groups are derived from compounds selected from the group consisting of aromatic monoamines, aliphatic monoamines, alicyclic monoamines, and phthalic anhydrides. Particularly ideally, the end-capping groups comprise groups selected from the group consisting of alkyl groups (ideally C1-C15, more ideally C1-C10, even more ideally C1-C6) and the group consisting of [Chemical 39], [wherein R4 is an alkyl group (ideally C1-C15, more ideally C1-C10, even more ideally C1-C6); R5 is an alicyclic group (ideally C3-C12, even more ideally C5-C6); k is 0-20, ideally 0-10, even more ideally 0-5.]

[0233] Polymers or oligomers of amides, amides, and amides-siloxanes are thermoplastic and ideally have a weight-average molecular weight of about 3,000 Daltons to about 300,000 Daltons, more ideally about 6,000 Daltons to about 50,000 Daltons. Ideally, the compounds (at a melt viscosity of 3,000 Pa·s) have a softening temperature of at least about 150°C, more ideally at least about 200°C, and even more ideally about 200°C to about 250°C.

[0234] The adhesive composition used in this invention may also contain solvents for the purpose of adjusting viscosity, etc., and specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0235] More specifically, solvents may include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, symmetrical trimethylbenzene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. One such solvent may be used alone, or two or more may be used in combination.

[0236] When the adhesive composition used in this invention contains a solvent, its content is appropriately determined by taking into account the viscosity of the required composition, the coating method used, the thickness of the film produced, etc., and is in the range of about 10 to 90% by mass relative to the composition as a whole.

[0237] The viscosity of the adhesive composition used in this invention is not particularly limited, but is typically 500~20,000 mPa·s at 25°C, ideally 1,000~5,000 mPa·s. The viscosity of the adhesive composition used in this invention can be adjusted by changing the type or ratio of the solvent used, the concentration of the film components, etc., taking into account various factors such as the coating method used and the required film thickness.

[0238] One example of the adhesive composition used in this invention is that it can be manufactured by mixing component (A), component (B) if applicable, and a solvent. The mixing order is not particularly limited. Examples of methods for easily and reproducibly manufacturing the adhesive composition include: dissolving component (A) and component (B) in a solvent; dissolving a portion of component (A) and component (B) in a solvent, dissolving the remaining portion in a solvent, and then mixing the resulting solutions; but these are not limited to these methods. Furthermore, when preparing the adhesive composition, heating can be appropriately applied within a range that will not decompose or deteriorate the components. In this invention, for the purpose of removing foreign matter, the solvent and solution used can be filtered using a filter or the like during the manufacturing process of the adhesive composition or after mixing all the components.

[0239] The thickness of the adhesive layer in the laminate of the present invention is not particularly limited, and is generally 5 to 500 μm; from the viewpoint of maintaining film strength, it is ideal to be 10 μm or more, more ideal to be 20 μm or more, and even more ideal to be 30 μm or more; from the viewpoint of avoiding non-uniformity caused by the thick film, it is ideal to be 200 μm or less, more ideal to be 150 μm or less, even more ideal to be 120 μm or less, and even more ideal to be 70 μm or less.

[0240] The laminate of the present invention can be suitably manufactured, for example, by the following method of manufacturing laminate of the present invention.

[0241] An example of a multilayer is illustrated below using figures. Figure 1 is a schematic cross-sectional view of an example of a multilayer. The multilayer in Figure 1 sequentially comprises: a semiconductor substrate 1, an adhesive layer 2, a release layer 3, and a support substrate 4. The adhesive layer 2 and the release layer 3 are disposed between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release layer 3 is in contact with both the adhesive layer 2 and the support substrate 4.

[0242] <Method for Manufacturing a Laminate> The laminate of the present invention can be manufactured, for example, by a method comprising the following steps: a first step, coating an adhesive composition onto the surface of a semiconductor substrate, and heating it if necessary to form an adhesive coating layer; a second step, coating a release agent composition onto the surface of a support substrate, and heating it if necessary to form a release agent coating layer; and a third step, subjecting the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate to at least one of a heat treatment and a decompression treatment, while applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere closely, and then performing a post-heat treatment to form a laminate.

[0243] Furthermore, the laminate of the present invention can be manufactured, for example, by a method comprising the following steps: a first step, coating a release agent composition onto the surface of a semiconductor substrate, and heating it if necessary to form a release agent coating layer; a second step, coating an adhesive composition onto the surface of a support substrate, and heating it if necessary to form an adhesive coating layer; and a third step, subjecting the release agent coating layer of the semiconductor substrate and the adhesive coating layer of the support substrate to at least one of a heat treatment and a decompression treatment, while applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere closely, and then performing a post-heat treatment to form the laminate. Also, as long as the effect of the present invention is not impaired, the coating and heating of each composition can be performed sequentially on any substrate.

[0244] There are no particular limitations on the coating method, but spin coating is usually used. Alternatively, a coating film can be formed by spin coating or other methods, and then a sheet-like coating film can be attached as an adhesive coating layer or a release agent coating layer.

[0245] The heating temperature of the coated adhesive composition varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the boiling point of the solvent used, and the required thickness of the adhesive layer, etc., and therefore cannot be uniformly specified. It is usually 80~150°C; the heating time is usually 30 seconds to 5 minutes. When the adhesive composition contains solvent, the coated adhesive composition is usually heated.

[0246] The heating temperature of the coated release agent composition varies depending on the type and amount of acid-generating agent, the boiling point of the solvent used, and the required thickness of the release layer, and therefore cannot be uniformly specified. From the viewpoint of achieving an ideal release layer with good reproducibility, it is above 80°C; from the viewpoint of inhibiting the decomposition of acid-generating agents, it is below 300°C; the heating time is usually appropriately determined within the range of 10 seconds to 10 minutes, depending on the heating temperature. When the release agent composition contains solvent, the coated release agent composition is usually heated.

[0247] Heating can be performed using a heating plate, oven, etc.

[0248] The thickness of the adhesive coating obtained by coating the adhesive composition and heating it if necessary is usually around 5 to 500 μm, and it is ultimately appropriate to set it to the above-mentioned thickness range of the adhesive layer.

[0249] The thickness of the release agent coating layer obtained by coating the release agent composition and heating it if necessary is usually around 5 nm to 100 μm, and it is ultimately appropriate to set it to the above-mentioned thickness range of the release layer.

[0250] In this invention, the coating layers are bonded together so that they are in contact with each other, and then a heat treatment or a depressurization treatment, or both of these treatments, are performed. At the same time, a load is applied in the thickness direction of the semiconductor substrate and the support substrate to make the two layers adhere closely. Subsequently, a post-heat treatment is performed, thereby obtaining the laminate of this invention. Furthermore, whether to use any of the treatment conditions of heat treatment, depressurization treatment, or a combination of both treatments is appropriately determined after considering various factors such as the type of adhesive composition, the specific composition of the release agent composition, the phase properties of the film obtained from the two compositions, the film thickness, and the required adhesion strength.

[0251] From the perspective of removing solvents when the composition contains solvents, and from the perspective of softening the adhesive coating layer to achieve proper adhesion with the release agent coating layer, the heat treatment is generally suitable within the range of 20 to 150°C. In particular, from the perspective of suppressing or avoiding excessive hardening or unnecessary deterioration of the adhesive component (A), it is ideal to be below 130°C, and more ideally below 90°C. Although the heating time depends on the heating temperature and the type of adhesive, from the perspective of ensuring proper adhesion, it is generally 30 seconds or more, and ideally 1 minute or more. From the perspective of suppressing deterioration of the adhesive layer and other components, it is generally 10 minutes or less, and ideally 5 minutes or less.

[0252] The depressurization treatment involves exposing the adhesive coating layers and release agent coating layers that are in contact with each other to an air pressure of 10 to 10,000 Pa. The depressurization treatment time is usually 1 to 30 minutes.

[0253] From the viewpoint of obtaining a laminate with good reproducibility and good separation of substrates, it is ideal to bond two adjacent layers by decompression treatment, and even more ideally to bond two adjacent layers by heat treatment and decompression treatment.

[0254] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not have a negative impact on the semiconductor substrate, the support substrate and the two layers between the two substrates and is a load that can reliably adhere to the substrate. It is usually in the range of 10 to 1000 N.

[0255] The post-heating temperature is ideally 120°C or higher from the viewpoint of achieving sufficient curing speed; and ideally 260°C or lower from the viewpoint of preventing deterioration of the substrate and layers. The post-heating time is typically 1 minute or more, ideally 5 minutes or more, from the viewpoint of ensuring proper bonding of the substrate and layers constituting the laminate; and typically 180 minutes or less, ideally 120 minutes or less, from the viewpoint of suppressing or avoiding negative effects on the layers due to overheating. Heating can be performed using a heating plate, oven, etc. When using a heating plate for post-heating, either the semiconductor substrate or the support substrate of the laminate can be heated with the substrate facing downwards; however, from the viewpoint of achieving proper release with good reproducibility, it is ideal to heat with the semiconductor substrate facing downwards. Furthermore, one purpose of the post-heating process is to achieve proper curing of the adhesive layer and release layer as a more ideal self-supporting film, especially through hydrosiliconization.

[0256] (Method for manufacturing a processed semiconductor substrate) The method for manufacturing a processed semiconductor substrate of the present invention includes a first step, a second step, and a third step. The first step involves processing the semiconductor substrate of the multilayer of the present invention. The second step involves separating the semiconductor substrate processed in the first step from the support substrate. The third step involves cleaning the separated semiconductor substrate with a cleaning agent composition.

[0257] In the first step, the processing performed on the semiconductor substrate refers to, for example, processing performed on the opposite side of the circuit surface in a wafer, such as thinning the wafer by grinding the back side of the wafer. Subsequently, through-silicon via (TSV) electrodes are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. In addition, back-side electrodes are also formed before and after this process. During the wafer thinning and TSV processes, the wafer is subjected to heat of approximately 250 to 350°C while attached to the support substrate. The stack of the present invention, including the adhesive layer and the release layer, generally has heat resistance to this load. Furthermore, the processing is not limited to the above, and also includes, for example, performing a semiconductor component assembly process when the substrate is temporarily attached to the support substrate to support the substrate for mounting semiconductor components.

[0258] In the second step, methods for separating (peeling) the semiconductor substrate from the support substrate may include: mechanical peeling by means of a material with sharp edges after irradiating the release layer with light, tearing peeling between the support and the wafer, etc., but are not limited to these. By irradiating the release layer with light from the support substrate side, the release layer will deteriorate as described above (e.g., the release layer will separate or decompose), and then, for example, by pulling up either substrate, the semiconductor substrate and the support substrate can be easily separated.

[0259] When irradiating the release layer with light, it is not necessary to irradiate all areas of the release layer. Even if the irradiated and unirradiated areas are mixed together, if the overall release ability of the release layer can still be sufficiently improved, the semiconductor substrate and the support substrate can be separated by a small external force, such as pulling up the support substrate. The ratio and positional relationship between the irradiated and unirradiated areas vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release layer, the intensity of the irradiated light, etc. Those skilled in the art can set suitable conditions without excessive experimentation. Therefore, according to the method for manufacturing the processed semiconductor substrate of the present invention, for example, when the support substrate of the laminate used is light-transmitting, the irradiation time can be shortened when irradiating with light from the support substrate side for release. As a result, not only can the yield be increased, but the physical stress used for release can also be avoided, and the semiconductor substrate and the support substrate can be easily and efficiently separated by irradiation alone. The irradiation dose used for stripping is typically between 50 and 3,000 mJ / cm². The irradiation time depends on the wavelength and irradiation dose. Irradiation can be performed using laser light or non-laser light from sources such as ultraviolet lamps.

[0260] In the third step, the surface of the separated semiconductor substrate is sprayed with a cleaning agent composition, or the separated semiconductor substrate is immersed in the cleaning agent composition and then washed. After that, it is usually cleaned with a solvent and dried. The cleaning agent composition can be exemplified above.

[0261] In the manufacturing method of the processed semiconductor substrate of the present invention, the processed semiconductor substrate manufactured in the third step is cleaned well by the cleaning agent composition, but the use of removal tape to further clean the surface of the processed semiconductor substrate is not hindered. If necessary, removal tape or the like can also be used to further clean the surface.

[0262] The constituent elements and method elements related to the above-described steps in the method for manufacturing the processed semiconductor substrate of the present invention can be modified in various ways as long as they do not depart from the spirit of the present invention. The method for manufacturing the processed semiconductor substrate of the present invention may also include steps other than those described above.

[0263] When the semiconductor substrate or support substrate of the stacked body of the present invention is light-transmitting, the release method of the present invention separates the semiconductor substrate and support substrate of the stacked body by irradiating the release layer with light from the semiconductor substrate side or the support substrate side. In the stacked body of the present invention, the semiconductor substrate and support substrate are temporarily bonded in a manner that allows for appropriate peeling by means of the adhesive layer and the release layer. Therefore, for example, when the support substrate is light-transmitting, the semiconductor substrate and support substrate can be easily separated by irradiating the release layer with light from the support substrate side of the stacked body. Typically, the release is performed after the semiconductor substrate of the stacked body has been processed. [Example]

[0264] The present invention will be described in more detail below with examples, but the present invention is not limited to the following examples. Furthermore, the apparatus used is described below.

[0265] [Apparatus] (1) Mixer: ARE-500 self-rotating and revolution-rotating mixer manufactured by Shin-Ki Corporation. (2) Viscometer: TVE-22H rotational viscometer manufactured by Toki Industries, Ltd. (3) Vacuum bonding device: Automatic bonding machine manufactured by Hughes Microtechnology Co., Ltd. (4) Optical film thickness gauge (film thickness measurement): F-50 manufactured by Filmetrics Co., Ltd. (5) Laser irradiation device: IPEX-848 manufactured by Light Machinery Co., Ltd.

[0266] 〔Determination conditions of molecular weight of polypropylene polymer〕 The weight average molecular weight of polypropylene polymer was determined using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel Super-MultiporeHZ-N (two columns)). The column temperature was set to 40°C, tetrahydrofuran was used as the dissolution solution, the flow rate was set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko Corporation) was used as the standard sample.

[0267] [Determination conditions for the molecular weight of specific compounds (organosiloxane polymers)] The weight-average molecular weight of specific compounds was determined using a GPC apparatus (HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-801, Shodex KF-802, Shodex KF-803L manufactured by Showa Denko Corporation). The column temperature was set to 40°C, tetrahydrofuran was used as the dissolution solution, the flow rate was set to 1.0 mL / min, and polystyrene (Shodex manufactured by Showa Denko Corporation) was used as the standard sample.

[0268] [1]Preparation of Adhesive Composition[Preparation Example 1] 80g of MQ resin (manufactured by Wacker Chemie) containing a polysiloxane backbone and vinyl groups, 2.52g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing SiH groups with a viscosity of 100mPa·s, 5.89g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing SiH groups with a viscosity of 70mPa·s, and 0.22g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added to a 600mL container for a mixer as described above. The mixture was stirred for 5 minutes to obtain mixture (I). 0.147g of platinum catalyst (manufactured by Wacker Chemie) and 5.81g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing vinyl groups with a viscosity of 1000mPa·s were stirred for 5 minutes to obtain mixture (II). Add 3.96 g of the obtained mixture (II) to mixture (I) and stir for 5 minutes using the aforementioned mixer to obtain mixture (III). Finally, filter the obtained mixture (III) through a 300-mesh nylon filter to obtain the adhesive composition.

[0269] [2]Preparation of detergent composition[Preparation Example 2] 6g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) was mixed with 94g of N,N-dimethylpropionic acid and stirred thoroughly to obtain a detergent composition.

[0270] 〔3〕Synthesis of allyl propylene polymer〔Synthesis Example 1〕 9.80 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) was added to a flask, followed by 14.00 g of 4-allyloxy-2-hydroxybenzophenone, 0.70 g of 2,2'-azobis(isobutyronitrile), and 34.54 g of PGMEA. The mixture was stirred at 60°C under nitrogen atmosphere for 18 hours to obtain a reaction mixture. After cooling, the obtained reaction mixture was added dropwise to methanol to obtain a precipitate. After removing the methanol, the precipitate was dried under reduced pressure at 60°C to obtain 0.91 g of allyl propylene polymer. The obtained allyl propylene polymer corresponds to the following formula (B-1), with a weight average molecular weight of 860. 〔Chemical 40〕

[0271] [4]Synthesis of Organosiloxane Polymer[Example A] A raw material mixture was prepared by adding 20.93 g of 2-hydroxy-4-(3-triethoxysilylpropoxy)diphenyl ketone (manufactured by Gelest) and 28.69 g of acetone to a flask. While stirring the raw material mixture, 2.70 g of 0.01 mol / L hydrochloric acid and 2.70 g of acetone were added dropwise to the raw material mixture. After the addition, the resulting mixture was stirred at room temperature for 30 minutes, and then stirred at 85°C for 4 hours. After cooling to room temperature, 90.0 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) was added to the resulting reaction mixture. Acetone and water were removed by vacuum distillation to obtain a solution containing an organosiloxane polymer. The organosiloxane polymer is equivalent to the following formula (A-1), with a weight average molecular weight of 1,690. [Chemical 41]

[0272] [Example B] A raw material mixture was prepared by adding 18.84 g of 2-hydroxy-4-(3-triethoxysilylpropoxy)diphenyl ketone (manufactured by Gelest) 3.13 g of tetraethoxysilane and 29.43 g of acetone to a flask. While stirring the raw material mixture, 3.51 g of 0.01 mol / L hydrochloric acid and 3.51 g of acetone were added dropwise. After the addition, the resulting mixture was stirred at room temperature for 30 minutes, and then stirred at 85°C for 4 hours. After cooling to room temperature, 90.0 g of PGME was added to the obtained reaction mixture, and acetone and water were removed by vacuum distillation to obtain a solution containing an organosiloxane polymer. The obtained organosiloxane polymer is equivalent to the following formula (A-2), with a weight average molecular weight of 1,570. [Chemical 42]

[0273] [Example C] A raw material mixture was prepared by adding 12.56 g of 2-hydroxy-4-(3-triethoxysilylpropoxy)diphenyl ketone (manufactured by Gelest) 5.95 g of phenyltrimethoxysilane and 24.51 g of acetone to a flask. While stirring the raw material mixture, 3.24 g of 0.01 mol / L hydrochloric acid and 3.24 g of acetone were added dropwise. After the addition, the resulting mixture was stirred at room temperature for 30 minutes, and then stirred at 85°C for 4 hours. After cooling to room temperature, 90.0 g of PGME was added to the obtained reaction mixture, and acetone and water were removed by vacuum distillation to obtain a solution containing an organosiloxane polymer. The obtained organosiloxane polymer is equivalent to the following formula (A-3), with a weight average molecular weight of 1,150. [Chemical 43]

[0274] [5]Preparation of the stripping agent composition[Comparative Example 1-1] The following were added to the threaded tube: 0.28 g of the allyl propylene polymer obtained in Synthesis Example 1, 0.06 g of 1,3,4,6-tetra(methoxymethyl)ethynyl urea as a crosslinking agent, 0.14 g of pyridinium trifluoromethanesulfonate 5% by mass PGME solution as a crosslinking catalyst, 0.10 g of PGME, and 4.42 g of PGMEA. The obtained solution was then filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain the stripping agent composition.

[0275] [Example 1-1] Add and mix the following into a threaded tube: 10.24 g of a solution containing an organosiloxane polymer of formula (A-1) obtained in Example A (polymer concentration 25.15% by mass), 2.57 g of a 1% by mass solution of triphenylsilane nitrate as a crosslinking catalyst, and 7.19 g of PGME. The resulting solution is then filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition.

[0276] [Examples 1-2] Add and mix the following into a threaded tube: 7.97 g of a solution containing an organosiloxane polymer of formula (A-2) obtained in Example B (polymer concentration 32.28% by mass), 2.57 g of a 1% by mass solution of triphenylsilane nitrate as a crosslinking catalyst, and 9.45 g of PGME. The resulting solution is then filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition.

[0277] [Examples 1-3] Add and mix the following into a threaded tube: 9.44 g of a solution containing an organosiloxane polymer equivalent to the previously described formula (A-3) obtained in Example C (polymer concentration 27.26% by mass), 2.57 g of a 1% by mass solution of triphenylsilane nitrate as a crosslinking catalyst, and 7.98 g of PGME. The resulting solution is then filtered using a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition.

[0278] [6]Confirmation of film removal performance (film reduction rate)[Examples 2-1~2-3] The stripping agent composition obtained in Examples 1-1 to 1-3 was spin-coated onto a silicon wafer cut to 4 cm square with a final film thickness of 500 nm, and heated at 190°C for 1 minute to form a film on the wafer. Only the required number of wafers with film formation were produced.

[0279] [Comparative Example 2-1] The stripping agent composition obtained in Comparative Example 1-1 was spin-coated onto a silicon wafer cut to 4 cm square with a final film thickness of 500 nm. The wafer was heated at 250°C for 5 minutes to form a film on the wafer. Only the required number of wafers with film were produced.

[0280] The film thickness (film thickness before immersion) of each film obtained in Examples 2-1 to 2-3 and Comparative Example 2-1 was measured. Then, each film was immersed in 7 mL of the cleaning agent composition obtained in Preparation Example 2 for 5 minutes on each substrate (wafer), dried with an air gun, and the film thickness (film thickness after immersion) of each film was measured again. In addition, except that OK73 thinner (composed of 70% propylene glycol monomethyl ether and 30% propylene glycol monomethyl ether acetate) (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and N-methyl-2-pyrrolidone (NMP) were used to replace the cleaning agent composition, the same operation was performed to measure the film thickness. The film reduction rate (%) of immersion was calculated by the following formula: Film reduction rate (%) = [1 - [film thickness after immersion (nm) / film thickness before immersion (nm)]] × 100 The results are shown in Table 1.

[0281] 〔Table 1〕

[0282] As shown in Table 1, the membrane reduction rate of the membrane obtained in Comparative Example 2-1 was less than 5% when immersed in the detergent composition, OK73 thinner, and NMP. This means that the membrane obtained in Comparative Example 2-1 does not dissolve well in any of the detergent composition, OK73 thinner, or NMP. Although the membrane reduction rate of each membrane obtained in Examples 2-1 to 2-3 was less than 5% when immersed in various solvents, the membrane reduction rate was 100% when immersed in the detergent composition. That is, although the membranes obtained in Examples 2-1 to 2-3 cannot be properly removed by various solvents, they can be properly removed by the detergent composition.

[0283] [7] Fabrication of the stack and confirmation of its peelability by light irradiation[Example 3-1] With a final stack thickness of 500 nm, the release agent composition obtained in Example 1-1 was spin-coated onto a 100 mm glass wafer (EAGLE-XG, Corning, 700 μm thick) serving as the carrier side substrate, thereby forming a release agent coating layer on the glass wafer serving as the support substrate. On the other hand, with a final stack thickness of 65 μm, the adhesive composition obtained in Modulation Example 1 was spin-coated onto a 100 mm silicon wafer (775 μm thick) serving as the device side substrate, thereby forming an adhesive coating layer on the silicon wafer serving as the semiconductor substrate. Then, using a bonding device, the glass wafer and silicon wafer were bonded together by clamping the release agent coating layer and the adhesive coating layer. The laminate was then heated at 200°C for 10 minutes to create a multilayer. The bonding was performed at 23°C, a pressure reduction of 1000 Pa, and without load. Using a laser irradiation device, the release layer was irradiated with a 308nm laser from the glass substrate side of the fixed multilayer. The minimum irradiation dose that would cause peeling was set as the optimal irradiation dose. Then, the entire surface of the release layer was irradiated with a 308nm laser from the glass substrate side of the fixed multilayer at the optimal irradiation dose, and the support substrate was manually lifted to confirm peelability. If the silicon wafer was undamaged and peelable, it was considered peelable. The results are shown in Table 2. The values ​​in parentheses are the optimal irradiation doses.

[0284] [Examples 3-2~3-3] Except for using the release agent composition obtained in Examples 1-2~1-3 to replace the release agent composition obtained in Example 1-1, the laminate was manufactured in the same way as in Example 3-1, and it was confirmed whether it could be peeled off.

[0285] [Comparative Example 3-1] Except for using the release agent composition obtained in Comparative Example 1-1 to replace the release agent composition obtained in Example 1-1, the laminate was manufactured in the same way as in Example 3-1, and it was confirmed whether it could be peeled off.

[0286] 〔Table 2〕

[0287] As shown in Table 2, when a film obtained using a release agent composition containing a specific compound is used as a release layer, and the semiconductor substrate of the laminate having the release layer is separated from the support substrate by irradiating the release layer with light, good release properties are confirmed in the same way as when a release agent composition containing an acrylic polymer is used. [Industrial Applicability]

[0288] According to the present invention, the laminate of the present invention can be easily separated when separating the support substrate from the semiconductor substrate, and the stripping layer after light irradiation can be dissolved by the cleaning agent composition when cleaning the semiconductor substrate, thus it is useful in the manufacturing of the processed semiconductor substrate. [Simplified Explanation of the Diagram]

[0012] [Figure 1] is a schematic cross-sectional view of an example of a layered body.

Claims

1. A laminate comprising: a semiconductor substrate, a light-transmitting support substrate, and an adhesive layer and a release layer disposed between the semiconductor substrate and the support substrate; the release layer being used to peel the semiconductor substrate from the support substrate after absorbing light irradiated from the support substrate side; characterized in that the release layer is a layer formed of a release agent composition; and the release agent composition contains a compound having: a first structure, which is a structure that absorbs the light, thereby facilitating the peeling of the semiconductor substrate from the support substrate by absorbing the light, and having two or more aromatic rings constituting a π-electron conjugation system; and a siloxane structure as a second structure; the first structure having at least one hydroxyl group.

2. The stack as described in claim 1, wherein, The first structure has a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene, diphenylene, azobenzene, diphenylfuran, fumonisin, carbazole, anthraquinone, 9,9-diphenyl-9H-fumonisin, naphthalene, anthracene, phenanthrene, acridine, pyrene and phenylbenzotriazole.

3. The stack as described in claim 1, wherein, The first structure is the structure shown in any of the following formulas (1) to (7): [Chemical 1] (In formulas (1) to (7), R1 to R13 each independently represent a halogen atom or a monovalent group; X represents a single bond, -O-, -CO-, -NR31- (R31 represents a hydrogen atom, a substituted alkyl group or a substituted aryl group), -SO-, -SO2-, or -N=N-; Y1 represents a single bond or -CO-; when Y1 is a single bond, Y2 represents -O-, -CO- or -NR32- (R32 represents a hydrogen atom, a substituted alkyl group or a substituted aryl group); when Y1 is -CO-, Y2 represents -CO-; n1 is an integer from 0 to 4; n2 is an integer from 0 to 5; n3 is an integer from 0 to 3; n4 is an integer from 0 to 4; n5 is an integer from 0 to 4; n6 is an integer from 0 to 5; n7 is an integer from 0 to 4; n8 is an integer from 0 to 4; n9 is an integer from 0 to 7; n10 is an integer from 0 to 9; n11 is an integer from 0 to 9; n12 is an integer from 0 to 4; n13 is an integer from 0 to 4; However, each of formulas (1) to (7) has at least one hydroxyl group as any one of R1 to R13; * indicates a bond; in the case where R1 to R13 are multiple, the multiple R1 to R13 can be the same or different).

4. The stack as described in claim 1, wherein, The second structure contains at least one of the following groups: a siloxane unit represented by SiO2 (Q unit), a siloxane unit represented by R101R102R103SiO1 / 2 (M unit), a siloxane unit represented by R104R105SiO2 / 2 (D unit), and a siloxane unit represented by R106SiO3 / 2 (T unit) (R101 to R106 each independently represent a hydrogen atom or a monovalent group bonded to Si, or a single bond or a linking group that bonds Si to the first structure).

5. The stack as described in claim 4, wherein, The first structure is Si-bonded to any one of the M-unit, the D-unit, and the T-unit via a single bond or a linker.

6. The stack as described in claim 5, wherein, The first structure is Si-bonded to any one of the M unit, the D unit, and the T unit via a linker group; the linker group is selected from the group consisting of alkylene groups, ester groups, ether groups, amide groups, ethyl carbamate groups, urea groups, and combinations of two or more of the above, having 1 to 10 carbon atoms.

7. The stack as described in claim 1, wherein, The adhesive layer is formed from an adhesive composition containing compounds with a siloxane structure.

8. The stack as described in claim 7, wherein, The adhesive composition contains a hardening component (A).

9. The stack as described in claim 8, wherein, Component (A) is a component that is hardened by a silicon hydrogenation reaction.

10. The stack as described in claim 8, wherein, The component (A) contains: a polyorganosiloxane having an alkenyl group with 2 to 40 carbon atoms bonded to silicon atoms (a1); a polyorganosiloxane having a Si-H group (a2); and a platinum group metal catalyst (A2).

11. A release agent composition for forming a release layer of a laminate comprising: a semiconductor substrate, a support substrate, and an adhesion layer and the release layer disposed between the semiconductor substrate and the support substrate, wherein the release layer is used to peel the semiconductor substrate from the support substrate after absorbing light irradiated from the support substrate side; characterized in that the release agent composition contains a compound having: a first structure that absorbs the light, thereby facilitating the peeling of the semiconductor substrate from the support substrate, and having two or more aromatic rings constituting a π-electron conjugation system; and a siloxane structure as a second structure; the first structure having at least one hydroxyl group.

12. The stripping agent composition as described in claim 11, wherein, The first structure has a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene, diphenylene, azobenzene, diphenylfuran, fumonisin, carbazole, anthraquinone, 9,9-diphenyl-9H-fumonisin, naphthalene, anthracene, phenanthrene, acridine, pyrene and phenylbenzotriazole.

13. A stripping agent composition, characterized in that it comprises: a first structure having a structure selected from the group consisting of benzophenone, diphenylamine, diphenylene oxide, diphenylene oxide, azobenzene, diphenylfuran, genistein, carbazole, anthraquinone, 9,9-diphenyl-9H-genistein, naphthalene, anthracene, phenanthrene, acridine, pyrene, and phenylbenzotriazole; and a siloxane structure as a second structure; the first structure having at least one hydroxyl group.

14. The stripping agent composition as described in claim 11 or 13, wherein, The first structure is the structure shown in any of the following formulas (1) to (7): [Chemical 2] (In formulas (1) to (7), R1 to R13 each independently represent a halogen atom or a monovalent group; X represents a single bond, -O-, -CO-, -NR31- (R31 represents a hydrogen atom, a substituted alkyl group or a substituted aryl group), -SO-, -SO2-, or -N=N-; Y1 represents a single bond or -CO-; when Y1 is a single bond, Y2 represents -O-, -CO- or -NR32- (R32 represents a hydrogen atom, a substituted alkyl group or a substituted aryl group); when Y1 is -CO-, Y2 represents -CO-; n1 is an integer from 0 to 4; n2 is an integer from 0 to 5; n3 is an integer from 0 to 3; n4 is an integer from 0 to 4; n5 is an integer from 0 to 4; n6 is an integer from 0 to 5; n7 is an integer from 0 to 4; n8 is an integer from 0 to 4; n9 is an integer from 0 to 7; n10 is an integer from 0 to 9; n11 is an integer from 0 to 9; n12 is an integer from 0 to 4; n13 is an integer from 0 to 4; However, each of formulas (1) to (7) has at least one hydroxyl group as any one of R1 to R13; * indicates a bond; in the case where R1 to R13 are multiple, the multiple R1 to R13 can be the same or different).

15. The stripping agent composition as described in claim 11 or 13, wherein, The second structure contains at least one of the following groups: a siloxane unit represented by SiO2 (Q unit), a siloxane unit represented by R101R102R103SiO1 / 2 (M unit), a siloxane unit represented by R104R105SiO2 / 2 (D unit), and a siloxane unit represented by R106SiO3 / 2 (T unit) (R101 to R106 each independently represent a hydrogen atom or a monovalent group bonded to Si, or a single bond or a linking group that bonds Si to the first structure).

16. The stripping agent composition as described in claim 15, wherein, The second structure is Si-bonded to any one of the M-unit, D-unit, and T-unit via a single bond or a linker.

17. The stripping agent composition as described in claim 16, wherein, The second structure is Si-bonded to any one of the M unit, the D unit, and the T unit via a linker group; the linker group is selected from the group consisting of alkylene groups, ester groups, ether groups, amide groups, ethyl carbamate groups, urea groups, and combinations of two or more of the above, having 1 to 10 carbon atoms.

18. A method for manufacturing a processed semiconductor substrate, characterized by comprising: a first step of processing the semiconductor substrate of a multilayer as described in any one of claims 1 to 10; a second step of separating the semiconductor substrate processed in the first step from the support substrate; and a third step of cleaning the separated semiconductor substrate with a cleaning agent composition.

19. A method for manufacturing a processed semiconductor substrate as described in claim 18, wherein, The second step includes irradiating the release layer with light.

20. A method for manufacturing a processed semiconductor substrate as described in claim 18, wherein, The detergent composition contains quaternary ammonium salts and solvents.

21. A method for manufacturing a processed semiconductor substrate as described in claim 20, wherein, This quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

22. A method for manufacturing a processed semiconductor substrate as described in claim 21, wherein, This halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt.

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