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

Abstract

A release agent composition for light irradiation release, the release agent composition containing a polymer having a first structure that absorbs light and imparts release properties to a release agent layer formed from the release agent composition, a second structure that absorbs light, and a third structure that imparts release properties to the release agent layer formed from the release agent composition, and a solvent. The second structure has a-Si-O-Si-structure in the main chain of the polymer, and the third structure has at least any one of an aromatic hydrocarbon ring and a heterocyclic ring.

Description

Technical Field

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

[0002] In contrast to semiconductor wafers traditionally integrated in a two-dimensional planar direction, semiconductor integration technology aims for further integration in a three-dimensional direction (layering). This three-dimensional layering is a technique that integrates multiple layers while simultaneously wiring through silicon vias (TSVs). During multi-layer integration, the side opposite to the circuit surface (i.e., the back side) of each wafer to be integrated is thinned by grinding, and the thinned semiconductor wafers are then layered.

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

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

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

[0006] The applicant proposes a laminate having an intermediate layer bonded in a peelable manner between a support and a workpiece, and for processing the workpiece. The intermediate layer includes at least a release layer attached to the support side, the release layer containing a phenolic varnish resin that deteriorates by absorbing light of wavelengths 190 nm to 600 nm irradiated by the support (see Patent Document 3).

[0007] Existing technical documents

[0008] Patent documents

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

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

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

[0012] The problem that the invention aims to solve

[0013] In photo-irradiation peeling methods, after processing semiconductor substrates such as semiconductor wafers, light irradiation degrades the release agent layer, making the semiconductor substrate easier to peel from the support substrate. After peeling, the surface of the semiconductor substrate and / or support substrate sometimes contains foreign matter such as adhesive layers, release agent layers, and their residues, necessitating cleaning of the semiconductor substrate and / or support substrate. However, depending on the type of release agent layer, sometimes these foreign matter on the semiconductor substrate and support substrate are difficult to remove, making cleaning challenging.

[0014] The present invention was made in view of the above circumstances, and its object is to provide a release agent composition for photo-irradiation release that can form a release agent layer with excellent peelability and cleanability, as well as a method for manufacturing a laminate using the release agent composition and a processed semiconductor substrate.

[0015] Solution for solving the problem

[0016] The inventors conducted in-depth research to solve the aforementioned technical problem and found that the technical problem could be solved, thus completing the present invention with the following main objectives.

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

[0018] [1] A stripping agent composition for photo-irradiation stripping, the stripping agent composition comprising a polymer and a solvent, the polymer having a first structure, a second structure and a third structure, the first structure having a structure that absorbs light and imparts stripping properties to a stripping agent layer formed by the stripping agent composition, the second structure having a -Si-O-Si- structure in the main chain of the polymer, and the third structure having at least any one of aromatic hydrocarbon rings and heterocycles.

[0019] [2] The stripping agent composition according to [1], wherein the first structure is a repeating unit as shown in the following formula (1).

[0020]

[0021] (In formula (1), X) 1 Represents -O-, -CO-, -NR a - (R) a(representing hydrogen atom, optionally substituted alkyl group or optionally substituted aryl group), -SO-, -SO2-, -N=N-, -CH=CH-CO- or -CH=CH-CO-CH2-CO-CH=CH-.

[0022] m1 and m2 represent 0 or 1 independently, respectively.

[0023] R 1 and R 2 Each can be used to independently represent a halogen atom or a monovalent group.

[0024] n1 and n2 represent integers from 0 to 4 independently.

[0025] R 1 When there are two or more R, two or more R 1 They can be either the same or different.

[0026] R 2 When there are two or more R, two or more R 2 (Optional: same or different)

[0027] [3] The stripping agent composition according to [1] or [2], wherein the second structure is a repeating unit shown in formula (2-1) or formula (2-2).

[0028]

[0029] (In equation (2-1), X) 11 This indicates a divalent group with a -Si-O-Si- structure.

[0030] A 1 A 2 A 3 A 4 A 5 And A 6 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

[0031] In equation (2-2), X 12 This indicates a divalent group with a -Si-O-Si- structure.

[0032] *1 and *1' represent bonded bonds. Bonded bond *1 is bonded to carbon atom *2 or carbon atom *3. Bonded bond *1' is bonded to carbon atom *2' or carbon atom *3'.

[0033] [4] The stripping agent composition according to [3], wherein X in formula (2-1) 11 and X in equation (2-2) 12 Each is independently represented by the structure shown in the following formula (S).

[0034]

[0035] (In formula (S), R) 101 ~R 106 Each can be independently represented as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

[0036] Y 1 and Y 2 Each of the following can be used to independently represent an alkylene group having 1 to 10 carbon atoms.

[0037] m represents an integer greater than or equal to 0 or 1.

[0038] p and q represent 0 or 1 independently, respectively.

[0039] When m is 2 or more, there are two or more R 103 and R 104 They can be either the same or different.

[0040] * indicates a bond.

[0041] [5] The stripping agent composition according to any one of [1] to [4], wherein the third structure is a repeating unit as shown in the following formula (3).

[0042]

[0043] (In formula (3), X) 21 It represents a divalent group having at least any of the following: an aromatic hydrocarbon ring and a heterocycle.

[0044] A 11 A 12 A 13 A 14 A 15 And A 16 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

[0045] [6] The stripping agent composition according to [5], wherein X in formula (3) 21 It can be any of the structures shown in equation (3-1) and equation (3-2) below.

[0046]

[0047] (In equation (3-1), Q) 1 This represents a divalent organic group as shown in formula (3-1-1) or a divalent organic group as shown in formula (3-1-2). n1 and n2 independently represent 0 or 1, respectively. * represents a bond.

[0048] In equation (3-2), X 31Z represents any of the divalent groups shown in equations (3-2-1) to (3-2-3) below. 1 and Z 2 Each can be used independently to represent a single bond or a divalent group as shown in formula (3-2-4) below. * indicates a bonded bond.

[0049]

[0050] (In equations (3-1-1) and (3-1-2), R) 21 ~R 23 Each of these groups independently represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkenyloxy group with 2 to 6 carbon atoms, alkynyloxy group with 2 to 6 carbon atoms, acyl group with 2 to 6 carbon atoms, aryloxy group with 6 to 12 carbon atoms, arylcarbonyl group with 7 to 13 carbon atoms, or aralkyl group with 7 to 13 carbon atoms. * indicates a bond.

[0051] In equation (3-1-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. 21 When there are two or more R, two or more R 21 They can be either the same or different.

[0052] In equation (3-1-2), Z 11 Indicates a single bond or an alkylene group having 1 to 6 carbon atoms. n12 and n13 independently represent integers from 0 to 4. R 22 When there are two or more R, two or more R 22 They can be either the same or different. R 23 When there are two or more R, two or more R 23 (Optional: same or different)

[0053]

[0054] (In equations (3-2-1) to (3-2-3), R) 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (optionally interrupted by an oxygen or sulfur atom), an alkenyl group having 2 to 10 carbon atoms (optionally interrupted by an oxygen or sulfur atom), an alkynyl group having 2 to 10 carbon atoms (optionally interrupted by an oxygen or sulfur atom), a benzyl group, or a phenyl group, wherein the phenyl group is optionally substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R 1 With R 2 They can optionally bond together to form rings with 3 to 6 carbon atoms. R3 With R 4 They can optionally bond together to form rings with 3 to 6 carbon atoms.

[0055] * indicates a bond. *1 indicates a bond bonded to a carbon atom in formula (3-2). *2 indicates a bond bonded to a nitrogen atom in formula (3-2).

[0056]

[0057] (In equation (3-2-4), m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer from 0 to 2. When m3 is 1, m1 and m2 are not both 0. *3 represents the bond bonded to the nitrogen atom in equation (3-2). *4 represents the bond bond.)

[0058] [7] A laminate comprising: a semiconductor substrate or an electronic device layer; a light-transmitting support substrate; and a release agent layer disposed between the semiconductor substrate or the electronic device layer and the support substrate, the release agent layer being a release agent layer formed of a release agent composition as described in any one of [1] to [6].

[0059] [8] The laminate according to [7], wherein the laminate has an adhesive layer disposed between the semiconductor substrate or the electronic device layer and the support substrate.

[0060] [9] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: a 5A step of processing the semiconductor substrate of a laminate as described in [7] or [8]; or a 5B step of processing the electronic device layer of a laminate as described in [7] or [8]; and a 6A step of separating the semiconductor substrate processed in the 5A step from the support substrate; or a 6B step of separating the electronic device layer processed in the 5B step from the support substrate.

[0061]

[10] The method for manufacturing a processed semiconductor substrate or electronic device layer according to [9], wherein the 6A step or the 6B step includes a step of irradiating the laminate with a laser from the support substrate side.

[0062] Invention Effects

[0063] According to the present invention, a release agent composition for photo-irradiation release that can form a release agent layer with excellent peelability and cleanability, as well as a laminate using the release agent composition and a method for manufacturing a processed semiconductor substrate, are provided. Attached Figure Description

[0064] Figure 1 This is a schematic cross-sectional view of an example of a laminate in the first embodiment.

[0065] Figure 2A This is a schematic cross-sectional view (1) used to illustrate a method of manufacturing a laminate representing an example of a first embodiment.

[0066] Figure 2B This is a schematic cross-sectional view (2) used to illustrate a method of manufacturing a laminate representing an example of a first embodiment.

[0067] Figure 2C This is a schematic cross-sectional view (3) used to illustrate a method of manufacturing a laminate representing an example of a first embodiment.

[0068] Figure 3 This is a schematic cross-sectional view of an example of a laminate in the second embodiment.

[0069] Figure 4 This is a schematic cross-sectional view of another example of a laminate in the second embodiment.

[0070] Figure 5A This is a schematic cross-sectional view (1) used to illustrate a method of manufacturing a laminate representing an example of a second embodiment.

[0071] Figure 5B This is a schematic cross-sectional view (2) used to illustrate a method of manufacturing a laminate representing an example of a second embodiment.

[0072] Figure 5C This is a schematic cross-sectional view (3) used to illustrate a method of manufacturing a laminate representing an example of a second embodiment.

[0073] Figure 5D This is a schematic cross-sectional view (4) used to illustrate a method of manufacturing a laminate representing an example of a second embodiment.

[0074] Figure 6A This is a schematic cross-sectional view (1) used to illustrate the processing method of a laminate representing an example of a first embodiment.

[0075] Figure 6B This is a schematic cross-sectional view (2) used to illustrate the processing method of a laminate representing an example of a first embodiment.

[0076] Figure 6C It is a schematic cross-sectional view (3) used to illustrate the processing method of a laminate representing an example of a first embodiment.

[0077] Figure 6D This is a schematic cross-sectional view (4) used to illustrate the processing method of a laminate representing an example of a first embodiment.

[0078] Figure 7A This is a schematic cross-sectional view (1) used to illustrate the processing method of a laminated body representing an example of a second embodiment.

[0079] Figure 7B This is a schematic cross-sectional view (2) used to illustrate the processing method of a laminated body representing an example of a second embodiment.

[0080] Figure 7C This is a schematic cross-sectional view (3) used to illustrate the processing method of a laminated body representing an example of a second embodiment.

[0081] Figure 7D This is a schematic cross-sectional view (4) used to illustrate the processing method of a laminated body representing an example of a second embodiment.

[0082] Figure 7E This is a schematic cross-sectional view (5) used to illustrate the processing method of a laminated body representing an example of a second embodiment.

[0083] Figure 7F This is a schematic cross-sectional view (6) used to illustrate the processing method of a laminate representing an example of a second embodiment. Detailed Implementation

[0084] (A release agent composition for photo-irradiated stripping)

[0085] The photo-irradiation stripping agent composition of the present invention contains a polymer and a solvent.

[0086] The stripping agent composition for light-induced stripping may contain other components.

[0087] <Polymer>

[0088] The polymer has a first structure, a second structure, and a third structure.

[0089] The first structure has a structure that absorbs light and imparts peelability to the release agent layer formed by the release agent composition.

[0090] The second structure has a -Si-O-Si- structure in the polymer backbone.

[0091] The third structure has at least any one of aromatic hydrocarbon rings and heterocycles.

[0092] It should be noted that the first structure, the second structure, and the third structure are all different structures.

[0093] <<First Structure>>

[0094] As for the first structure, there are no particular limitations as long as it has a structure that absorbs light and imparts peelability to the release agent layer formed by the release agent composition.

[0095] The wavelength of the light used for stripping is as described above, preferably 250–600 nm, more preferably 250–370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for stripping is an amount that causes appropriate alteration of the first structure, such as decomposition.

[0096] The light used for stripping can be a laser or a non-laser light source such as an ultraviolet lamp.

[0097] As the first structure, from the viewpoint of achieving the effects of the present invention with good reproducibility, the repeating unit shown in the following formula (1) is preferred.

[0098]

[0099] (In formula (1), X) 1 Represents -O-, -CO-, -NR a - (R) a (representing hydrogen atom, optionally substituted alkyl group or optionally substituted aryl group), -SO-, -SO2-, -N=N-, -CH=CH-CO- or -CH=CH-CO-CH2-CO-CH=CH-.

[0100] m1 and m2 represent 0 or 1 independently, respectively.

[0101] R 1 and R 2 Each can be used to independently represent a halogen atom or a monovalent group.

[0102] n1 and n2 represent integers from 0 to 4 independently.

[0103] R 1 When there are two or more R, two or more R 1 They can be either the same or different.

[0104] R 2 When there are two or more R, two or more R 2 (Optional: same or different)

[0105] It should be noted that "-CH=CH-CO-CH2-CO-CH=CH-" has tautomers and has the same meaning as "-CH=CH-CO-CH=C(OH)-CH=CH-" or "-CH=CH-C(OH)=CH-CO-CH=CH-".

[0106] As X in equation (1) 1 From the viewpoint of achieving the effects of the present invention with good reproducibility, -CO- and -NR are preferred. a -.

[0107] As in equation (1) -NR a - of R a The substituents in the alkyl group that are optionally substituted include, for example, halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups having 1 to 6 carbon atoms, etc.

[0108] As R a The number of carbon atoms in the alkyl group that is optionally substituted is preferably, for example, 1 to 6.

[0109] As R a With regard to the alkyl group that is optionally substituted, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred.

[0110] In this specification, examples of halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0111] As in equation (1) -NR a - of R a The substituents in the aryl group that are optionally substituted include, for example, halogen atoms, hydroxyl groups, carboxyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, etc.

[0112] As R a Regarding the aromatic ring in the optionally substituted aryl group, it can be an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferred. Examples of aromatic hydrocarbon rings include: benzene rings, naphthalene rings, anthracene rings, etc.

[0113] As R a With regard to the optionally substituted aryl group, the optionally substituted phenyl group is preferred.

[0114] As R in equation (1) 1 and R 2 Monovalent groups in the group can include, for example, halogen atoms, hydroxyl groups, carboxyl groups, optionally substituted alkyl groups, optionally substituted alkoxy groups, optionally substituted aryl groups, etc.

[0115] As R 1and R 2 Substituents in the optionally substituted alkyl group include, for example, halogen atoms, hydroxyl groups, carboxyl groups, alkoxy groups having 1 to 6 carbon atoms, etc.

[0116] As R 1 and R 2 With regard to the alkyl group that is optionally substituted, alkyl groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred.

[0117] As R 1 and R 2 The substituents in the alkoxy group that are optionally substituted include, for example, halogen atoms, hydroxyl groups, carboxyl groups, etc.

[0118] As R 1 and R 2 With regard to the alkoxy group that is optionally substituted, an alkoxy group having 1 to 6 carbon atoms is preferred, and an alkoxy group having 1 to 4 carbon atoms is more preferred.

[0119] As R 1 and R 2 Examples of substituents in the optionally substituted aryl group include halogen atoms, hydroxyl groups, carboxyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, etc.

[0120] As R 1 and R 2 Regarding the aromatic ring in the optionally substituted aryl group, it can be an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferred. Examples of aromatic hydrocarbon rings include: benzene rings, naphthalene rings, anthracene rings, etc.

[0121] As R 1 and R 2 With regard to the optionally substituted aryl group, but preferably the optionally substituted phenyl group.

[0122] m1 and m2 can represent 0 or 1 independently, but it is preferable that both m1 and m2 are 0.

[0123] In the repeating unit shown in formula (1), there is no particular restriction on the bonding position of the benzene ring, but the repeating unit shown in formula (1) is preferably the repeating unit shown in formula (1-1) below.

[0124]

[0125] (In equation (1-1), X) 1 R 1 R 2 m1, m2, n1 and n2 are respectively related to X in equation (1) 1 R 1R 2 (m1, m2, n1, and n2 have the same meaning.)

[0126] As repeating units as shown in equation (1), the following repeating units can be listed.

[0127]

[0128] <<Second Structure>>

[0129] As a second structure, there are no particular restrictions as long as the polymer backbone has a -Si-O-Si- structure.

[0130] The polymer has a second structure, thereby imparting cleaning properties to the release agent layer formed by the release agent composition.

[0131] As a second structure, from the viewpoint of achieving the effects of the present invention with good reproducibility, the repeating unit shown in formula (2-1) or formula (2-2) below is preferred.

[0132]

[0133] (In equation (2-1), X) 11 This indicates a divalent group with a -Si-O-Si- structure.

[0134] A 1 A 2 A 3 A 4 A 5 And A 6 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

[0135] In equation (2-2), X 12 This indicates a divalent group with a -Si-O-Si- structure.

[0136] *1 and *1' represent bonded bonds. Bonded bond *1 is bonded to carbon atom *2 or carbon atom *3. Bonded bond *1' is bonded to carbon atom *2' or carbon atom *3'.

[0137] As A 1 A 2 A 3 A 4 A 5 And A 6 Hydrogen atoms are preferred.

[0138] As X in equation (2-1) 11 In the sum of equation (2-2) X 12 From the viewpoint of achieving the effects of the present invention with good reproducibility, the structure shown in the following formula (S) is preferred.

[0139]

[0140] (In formula (S), R) 101 ~R 106 Each can be independently represented as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

[0141] Y 1 and Y 2 Each of the following can be used to independently represent an alkylene group having 1 to 10 carbon atoms.

[0142] m represents an integer greater than or equal to 0 or 1.

[0143] p and q represent 0 or 1 independently, respectively.

[0144] When m is 2 or more, there are two or more R 103 and R 104 They can be either the same or different.

[0145] * indicates a bond.

[0146] R in equation (S) 101 ~R 106 The "alkyl" in "substituted or unsubstituted alkyl" is preferably an alkyl group having 1 to 10 carbon atoms. Examples of "alkyl" include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, 2-cyclohexylmethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, etc.

[0147] R in equation (S) 101 ~R 106 The "alkenyl" in "substituted or unsubstituted alkenyl" is preferably an alkenyl with 2 to 10 carbon atoms. Examples of "alkenyl" include: vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl, etc.

[0148] R in equation (S) 101 ~R 106The substituents of the alkyl group in "substituted or unsubstituted alkyl" and the substituents of the alkenyl group in "substituted or unsubstituted alkenyl" are not particularly limited, and examples include: halogen atoms, cyano, nitro, alkyl-oxy, alkyl-carbonyl, alkyl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl-oxy, alkenyl-carbonyl, alkenyl-oxy-carbonyl, alkenyl-carbonyl-oxy, aryl, aryl-oxy, aryl-carbonyl, aryl-oxy-carbonyl, aryl-carbonyl-oxy, etc., or combinations thereof. The number of substituents is preferably 1 to 3, more preferably 1.

[0149] R in equation (S) 101 ~R 106 The "aryl" in "substituted or unsubstituted aryl" is preferably an aryl group with 6 to 14 carbon atoms. Examples of "aryl" include phenyl, 1-naphthyl, and 2-naphthyl.

[0150] As R 101 ~R 106 The substituents of the aryl group in "substituted or unsubstituted aryl" are not particularly limited, and examples include: halogen atoms, cyano, nitro, alkyl, alkyl-oxy, alkyl-carbonyl, alkyl-oxy-carbonyl, alkyl-carbonyl-oxy, alkenyl, alkenyl-oxy, alkenyl-carbonyl, alkenyl-oxy-carbonyl, alkenyl-carbonyl-oxy, aryl, aryl-alkyl, aryl-alkenyl, aryl-oxy, aryl-carbonyl, aryl-oxy-carbonyl, aryl-carbonyl-oxy, etc., or combinations thereof. The number of substituents is preferably 1 to 3, more preferably 1.

[0151] R in equation (S) 101 ~R 106 Preferably, substituted or unsubstituted alkyl or substituted or unsubstituted aryl groups are used, more preferably (unsubstituted) alkyl or (unsubstituted) aryl groups are used, even more preferably methyl, ethyl, propyl, isopropyl, or phenyl groups are used, and particularly preferably methyl or phenyl groups are used.

[0152] Y in equation (S) 1 and Y 2 It is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.

[0153] X is used as the variable in equation (2-1) 11 For example, the following structures can be listed for the formula (S).

[0154]

[0155] (In formula (S3), Y) 1 and Y 2 respectively with Y in equation (S) 1 and Y 2They have the same meaning. m represents an integer greater than or equal to 1.

[0156] In the formula, * represents a bond.

[0157] Let X be the value in equation (2-2) 12 For example, the following structures can be listed for the formula (S).

[0158]

[0159] (In the formula, * represents a bond.)

[0160] <<Third Structure>>

[0161] As a third structure, there are no particular restrictions as long as it has at least any of the aromatic hydrocarbon rings and heterocycles.

[0162] Examples of aromatic hydrocarbon rings include: benzene ring, naphthalene ring, anthracene ring, etc.

[0163] Examples of heteroatoms present in heterocycles include oxygen atoms and nitrogen atoms.

[0164] As for the elemental ring number of a heterocyclic ring, examples include 5-membered rings to 7-membered rings.

[0165] As a third structure, from the viewpoint of achieving the effects of the present invention with good reproducibility, the repeating unit shown in the following formula (3) is preferred.

[0166]

[0167] (In formula (3), X) 21 It represents a divalent group having at least any of the following: an aromatic hydrocarbon ring and a heterocycle.

[0168] A 11 A 12 A 13 A 14 A 15 And A 16 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

[0169] As X in equation (3) 21 , which is any of the structures shown in equation (3-1) and equation (3-2) below.

[0170]

[0171] (In equation (3-1), Q) 1This represents a divalent organic group as shown in formula (3-1-1) or a divalent organic group as shown in formula (3-1-2). n1 and n2 independently represent 0 or 1, respectively. * represents a bond.

[0172] In equation (3-2), X 31 Z represents any of the divalent groups shown in equations (3-2-1) to (3-2-3) below. 1 and Z 2 Each can be used independently to represent a single bond or a divalent group as shown in formula (3-2-4) below. * indicates a bonded bond.

[0173]

[0174] (In equations (3-1-1) and (3-1-2), R) 21 ~R 23 Each of these groups independently represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkenyloxy group with 2 to 6 carbon atoms, alkynyloxy group with 2 to 6 carbon atoms, acyl group with 2 to 6 carbon atoms, aryloxy group with 6 to 12 carbon atoms, arylcarbonyl group with 7 to 13 carbon atoms, or aralkyl group with 7 to 13 carbon atoms. * indicates a bond.

[0175] In equation (3-1-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. 21 When there are two or more R, two or more R 21 They can be either the same or different.

[0176] In equation (3-1-2), Z 11 Indicates a single bond or an alkylene group having 1 to 6 carbon atoms. n12 and n13 independently represent integers from 0 to 4. R 22 When there are two or more R, two or more R 22 They can be either the same or different. R 23 When there are two or more R, two or more R 23 (Optional: same or different)

[0177]

[0178] (In equations (3-2-1) to (3-2-3), R) 1 ~R 5Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (optionally interrupted by an oxygen or sulfur atom), an alkenyl group having 2 to 10 carbon atoms (optionally interrupted by an oxygen or sulfur atom), an alkynyl group having 2 to 10 carbon atoms (optionally interrupted by an oxygen or sulfur atom), a benzyl group, or a phenyl group, wherein the phenyl group is optionally substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R 1 With R 2 They can optionally bond together to form rings with 3 to 6 carbon atoms. R 3 With R 4 They can optionally bond together to form rings with 3 to 6 carbon atoms.

[0179] * indicates a bond. *1 indicates a bond bonded to a carbon atom in formula (3-2). *2 indicates a bond bonded to a nitrogen atom in formula (3-2).

[0180]

[0181] (In equation (3-2-4), m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer from 0 to 2. When m3 is 1, m1 and m2 are not both 0. *3 represents the bond bonded to the nitrogen atom in equation (3-2). *4 represents the bond bond.)

[0182] In this specification, alkyl groups are not limited to straight-chain, but can also be branched or cyclic. Examples of straight-chain or branched alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and n-hexyl. Examples of cyclic alkyl groups (cycloalkyl groups) include cyclobutyl, cyclopentyl, and cyclohexyl.

[0183] In this specification, alkoxy groups may be listed as, for example, methoxy, ethoxy, n-pentoxy, isopropoxy, etc.

[0184] In this specification, examples of alkylthio groups include: methylthio, ethylthio, n-pentylthio, isopropylthio, etc.

[0185] In this specification, examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.

[0186] In this specification, as an alkynyl group, the alkenyl groups listed above in which the double bonds are replaced with triple bonds can be described.

[0187] In this specification, examples of olefinic groups include, for example, vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, isopentenyloxy, etc.

[0188] In this specification, examples of alkyneoxy groups include 2-propynyloxy, 1-methyl-2-propynyloxy, 2-methyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, etc.

[0189] In this specification, examples of acyl groups include, for example, acetyl and propionyl groups.

[0190] In this specification, aryloxy groups may be listed as, for example, phenoxy, naphthoxy, etc.

[0191] In this specification, phenyl carbonyl groups, for example, can be listed as aryl carbonyl groups.

[0192] In this specification, aryl groups may be listed as, for example, benzyl, phenylethyl, etc.

[0193] In this specification, examples of alkylene compounds include: methylene, ethylene, 1,3-propylene, 2,2-propylene, 1-methylethylene, 1,4-butylene, 1-ethylethylene, 1-methylpropylene, 2-methylpropylene, 1,5-pentylene, 1-methylbutylene, 2-methylbutylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1-ethylpropylene, 2-ethylpropylene, 1,6-hexylene, 1,4-cyclohexylene, 1,8-octylene, 2-ethyloctylene, 1,9-nonylene, and 1,10-decylene.

[0194] R is the equation (3-2-1) to (3-2-3). 1 ~R 5 Alkyl groups having 1 to 10 carbon atoms that are optionally interrupted by an oxygen atom or a sulfur atom include, for example, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkoxyalkyl groups having 2 to 10 carbon atoms, alkoxyalkoxyalkyl groups having 3 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, alkylthioalkyl groups having 2 to 10 carbon atoms, etc.

[0195] Furthermore, the alkyl group having 1 to 10 carbon atoms optionally includes two or more oxygen or sulfur atoms.

[0196] As shown in equation (3-1), the following examples illustrate the structure.

[0197]

[0198]

[0199]

[0200] (* indicates a bonding bond.)

[0201] As shown in equation (3-2), the following examples illustrate the structure.

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] The polymer, for example, has repeating units as shown in the following formula (X-2-1) as repeating units formed by combining repeating units shown in formula (1) and repeating units shown in formula (2-1).

[0208] The polymer, for example, has repeating units as shown in the following formula (X-2-2) as repeating units formed by combining repeating units shown in formula (1) and repeating units shown in formula (2-2).

[0209] The polymer, for example, has repeating units as shown in the following formula (X-3) as repeating units formed by combining repeating units shown in formula (1) and repeating units shown in formula (3).

[0210]

[0211] (In equations (X-2-1), (X-2-2), and (X-3), X) 1 R 1 R 2 m1, m2, n1 and n2 are respectively related to X in equation (1) 1 R 1 R 2 (m1, m2, n1, and n2 have the same meaning.)

[0212] In equation (X-2-1), X 11 A 1 A 2 A 3 A 4 A 5 And A 6 respectively with X in equation (2-1) 11 A 1 A2 A 3 A 4 A 5 And A 6 They have the same meaning.

[0213] In equation (X-2-2), X 12 X in equation (2-2) 12 They have the same meaning.

[0214] In equation (X-3), X 21 A 11 A 12 A 13 A 14 A 15 And A 16 respectively with X in equation (3) 21 A 11 A 12 A 13 A 14 A 15 And A 16 (Same meaning.)

[0215] The polymer, for example, has repeating units as shown in formula (X-2-1) and repeating units as shown in formula (X-3).

[0216] The polymer, for example, has repeating units as shown in formula (X-2-2) and repeating units as shown in formula (X-3).

[0217] The molar ratio of the total (X-2) of repeating units (X-2-1) and (X-2-2) of formula (X-2-1) to the repeating unit (X-3) of formula (X-3) in the polymer [(X-2):(X-3)] is not particularly limited, but is preferably 10:90 to 80:20, more preferably 20:80 to 70:30, and particularly preferably 30:70 to 60:40.

[0218] The molar ratio of repeating unit (X-2-1) of formula (X-2-1) to repeating unit (X-3) of formula (X-3) in the polymer [(X-2-1):(X-3)] is not particularly limited, but is preferably 10:90 to 80:20, more preferably 20:80 to 70:30, and particularly preferably 30:70 to 60:40.

[0219] The molar ratio of repeating unit (X-2-2) of formula (X-2-2) to repeating unit (X-3) of formula (X-3) in the polymer [(X-2-2):(X-3)] is not particularly limited, but is preferably 10:90 to 80:20, more preferably 20:80 to 70:30, and particularly preferably 30:70 to 60:40.

[0220] The weight-average molecular weight of the polymer is, for example, 300 to 100,000, preferably 800 to 50,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 5,000.

[0221] An example of a method for manufacturing a polymer is described.

[0222] One example of a polymer is obtained, for instance, through the following reaction (I).

[0223] (I): The reaction of at least any one of the compounds shown in formula (1X) below with the compounds shown in formula (2-1X) below and the compounds shown in formula (2-2X) below with the compound shown in formula (3X) below.

[0224] In reaction (I), other compounds may be used in combination.

[0225]

[0226] (In formula (1X), X) 1 R 1 R 2 m1, m2, n1 and n2 are respectively related to X in equation (1) 1 R 1 R 2 The meanings of m1, m2, n1, and n2 are the same.

[0227] In equation (2-1X), X 11 A 1 A 2 A 3 A 4 A 5 And A 6 respectively with X in equation (2-1) 11 A 1 A 2 A 3 A 4 A 5 And A 6 They have the same meaning.

[0228] In equation (2-2X), X 12 X in equation (2-2) 12 They have the same meaning.

[0229] In equation (3X), X 21 A 11 A 12 A 13 A 14 A 15 And A 16 respectively with X in equation (3) 21 A 11 A 12 A 13 A 14 A 15 And A 16 (Same meaning.)

[0230] Examples of compounds represented by formula (1X) include the following compounds.

[0231]

[0232] Examples of compounds represented by formula (2-1X) include the following. It should be noted that the compounds also include polymers.

[0233]

[0234] Examples of compounds represented by formula (2-2X) include the following compounds.

[0235]

[0236] Examples of compounds represented by formula (3X) include the following compounds.

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] Reaction (I) can be carried out, for example, in the presence of a catalyst. The catalyst can be, for example, a quaternary phosphorus salt such as tetrabutylphosphine bromide or ethyltriphenylphosphine bromide; or a quaternary ammonium salt such as benzyltriethylammonium chloride. The amount of catalyst used can be selected from 0.1% to 10% by mass relative to the total mass of the reactants used in the reaction. The optimal conditions for the reaction can be selected from, for example, a range of 80 to 160°C and 2 to 50 hours.

[0247] The content of the polymer in the stripper composition is not particularly limited, but is preferably 60% to 100% by mass, more preferably 70% to 100% by mass, and particularly preferably 80% to 100% by mass, relative to the film-forming components in the stripper composition.

[0248] The components of a film composition refer to the components in a stripper composition other than the solvent.

[0249] <Cross-linking agent>

[0250] The stripper composition may also contain a crosslinking agent.

[0251] Crosslinking agents sometimes undergo crosslinking reactions based on self-condensation, but in the presence of crosslinking substituents in the polymers mentioned above, they can undergo crosslinking reactions with these crosslinking substituents.

[0252] Specific examples of crosslinking agents are not particularly limited, but typically include: phenolic crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, thiourea-based crosslinking agents, etc., which have crosslinking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl, etc. in their molecules. They can be low molecular weight compounds or high molecular weight compounds.

[0253] 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 the crosslinking agent is preferably 2 to 10, more preferably 2 to 6.

[0254] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the stripping agent composition preferably has an aromatic ring (e.g., benzene ring, naphthalene ring) in the molecule. Phenolic crosslinking agents are typical examples of such crosslinking agents, but are not limited thereto.

[0255] A phenolic crosslinking agent having a crosslinking forming group refers to a compound having a crosslinking forming group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of such alkoxy groups derived from the phenolic hydroxyl group include methoxy and butoxy, but are not limited to these.

[0256] The aromatic rings bonded by the cross-linking groups, as well as the aromatic rings bonded by phenolic hydroxyl groups and / or alkoxy groups derived from phenolic hydroxyl groups, are not limited to non-condensing ring aromatic rings such as benzene rings, but can also be condensing ring aromatic rings such as naphthalene rings and anthracene.

[0257] In the case of multiple aromatic rings within the molecule of a phenolic crosslinking agent, the crosslinking forming group, as well as the phenolic hydroxyl group and the alkoxy group derived from the phenolic hydroxyl group, can bond to the same aromatic ring within the molecule or to different aromatic rings.

[0258] The aromatic rings bonded by cross-linking groups, phenolic hydroxyl groups, and alkoxy groups derived from phenolic hydroxyl groups can be further replaced by hydrocarbon groups such as alkyl groups such as methyl, ethyl, and butyl, aryl groups such as phenyl, and halogen atoms such as fluorine atoms.

[0259] For example, as specific examples of phenolic crosslinking agents having crosslinking forming groups, compounds represented by any of the formulas (L1) to (L4) can be listed.

[0260]

[0261] In each formula, each R' independently represents a fluorine atom, aryl group, or alkyl group, and each R” independently represents a hydrogen atom or alkyl group. 1 and L 2 Each independently represents a single bond, methylene, or propane-2,2-diyl, L 3 Determined by q1, representing a single bond, methylene, propane-2,2-diyl, methane-triyl, or ethane-1,1,1-triyl, t11, t12, and t13 are integers satisfying 2≤t11≤5, 1≤t12≤4, 0≤t13≤3, and t11+t12+t13≤6; t21, t22, and t23 are integers satisfying 2≤t21≤4, 1≤t22≤3, 0≤t23≤2, and t21+t22+t23≤5; t24, t25, and t26 are integers satisfying 2≤t24≤4, 1≤t25≤3, 0≤t26≤2, and t24+t25+t26≤5; t27, t28, and t29 are integers satisfying 0 The integers ≤t27≤4, 0≤t28≤4, 0≤t29≤4, and t27+t28+t29≤4 are used. t31, t32, and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2, and t31+t32+t33≤5. t41, t42, and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1, and t41+t42+t43≤4. q1 is 2 or 3, and q2 represents the number of repetitions, which is an integer greater than or equal to 0. As specific examples of aryl and alkyl groups, the same groups as those listed below can be enumerated. Phenyl is preferred as an aryl group, and methyl or tert-butyl is preferred as an alkyl group.

[0262] The following are specific examples of compounds represented by formulas (L1) to (L4), but are not limited thereto. It should be noted that these compounds can be synthesized by known methods, or can be obtained as products of companies such as Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd.

[0263]

[0264]

[0265]

[0266]

[0267] A melamine-based crosslinking agent with a crosslinking-forming group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative, wherein at least one of the hydrogen atoms of the amino group bonded to its triazine ring is replaced by a crosslinking-forming group. The triazine ring may further have substituents such as phenyl or aryl groups.

[0268] Specific examples of melamine-based crosslinking agents with crosslinking-forming groups include: mono-, bis-, tri-, tetra-, penta-, or hexaalkoxymethyl melamines such as N,N,N',N',N",N"-hexa(methoxymethyl)melamine and N,N,N',N',N",N"-hexa(butoxymethyl)melamine; mono-, bis-, tri-, or tetraalkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N'-tetra(butoxymethyl)benzoguanamine, but not limited to these.

[0269] A urea-based crosslinking agent with a crosslinking-forming group refers to a derivative of a compound containing a urea bond, having at least one hydrogen atom of the NH group constituting the urea bond replaced by a crosslinking-forming group.

[0270] Specific examples of urea-based crosslinking agents having crosslinking-forming groups include: mono-, di-, tri-, or tetraalkoxymethyl ureas such as 1,3,4,6-tetra(methoxymethyl) urea and 1,3,4,6-tetra(butoxymethyl) urea; mono-, di-, tri-, or tetraalkoxymethyl ureas such as 1,3-bis(methoxymethyl) urea and 1,1,3,3-tetramethoxymethyl urea, but are not limited to these.

[0271] Thiourea-based crosslinking agents with crosslinking-forming groups refer to derivatives of compounds containing thiourea bonds, having a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is replaced by a crosslinking-forming group.

[0272] Specific examples of thiourea-based crosslinking agents with crosslinking-forming groups include mono-, di-, tri-, or tetra-alkoxymethyl thioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetramethoxymethylthiourea, but are not limited to these.

[0273] The amount of crosslinking agent contained in the release agent composition varies depending on the coating method used, the desired film thickness, etc., and therefore cannot be specified in general terms. It is usually 0.01 to 50% by mass relative to the polymer. From the viewpoint of achieving proper curing and obtaining a laminate in which the semiconductor substrate or electronic device layer and the support substrate can be well separated, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0274] <Acid-producing agents and acids>

[0275] For purposes such as promoting cross-linking reactions, the stripping agent composition may also contain an acid-producing agent or an acid.

[0276] Examples of acid-producing agents include thermal acid-producing agents and photoacid-producing agents.

[0277] There are no particular limitations on thermally generated acid-producing agents, as long as they produce acid through heat. Specific examples include: 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), as well as SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic alkyl sulfonic acid esters, but not limited to these.

[0278] Examples of photoacid-generating agents include: onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0279] Specific examples of onionium salt compounds include: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, etc.; sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, etc., but are not limited to these.

[0280] Specific examples of sulfonylimide compounds include: N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalenediformimide, etc., but are not limited to these.

[0281] Specific examples of disulfonyl diazonium methane compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyl diazonium methane, etc., but are not limited to these.

[0282] Specific examples of acids include: p-toluenesulfonic acid, pyridonium p-toluenesulfonic acid (pyridonium p-toluenesulfonate), pyridonium trifluoromethanesulfonate, pyridonium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and other aryl sulfonic acids, pyridonium 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.

[0283] The amount of acid-generating agent and acid contained in the stripping agent composition varies depending on the type of crosslinking agent used and the heating temperature during film formation, so it cannot be specified in general terms. It is usually 0.01 to 5% by mass relative to the film composition.

[0284] <surfactants>

[0285] For the purpose of adjusting the liquid properties of the composition itself, the membrane properties of the obtained film, or preparing a release agent composition with high uniformity and good reproducibility, the release agent composition may also contain a surfactant.

[0286] Examples of surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. EFTOP Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd., trade name), MEGAFACE F171, F173, R-30, R-30N (manufactured by DIC Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd., trade name); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0287] Surfactants can be used alone or in combination of two or more.

[0288] The amount of surfactant is typically less than 2% by mass relative to the film composition of the stripper composition.

[0289] <Solvent>

[0290] The stripping agent composition contains a solvent.

[0291] As solvents, for example, highly polar solvents that can effectively dissolve the aforementioned polymers, crosslinking agents, and other film-forming components can be used. Low-polarity solvents can also be used as needed, for purposes such as adjusting viscosity and surface tension. It should be noted that in this invention, a low-polarity solvent is defined as a solvent with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polarity solvent is defined as a solvent with a relative permittivity of 7 or higher at a frequency of 100 kHz. One solvent can be used alone, or two or more solvents can be used in combination.

[0292] In addition, examples of highly polar solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0293] Examples of low-polarity solvents include: chloroform, chlorobenzene, and other chlorine-based solvents; alkylbenzene solvents such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, and decylbenzene, and other aromatic hydrocarbon solvents; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, and 1-decanol; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, and triethylene glycol butyl methyl ether; and ester solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0294] The solvent content is appropriately determined taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is less than 99% by mass of the whole composition, preferably 70 to 99% by mass relative to the whole composition, more preferably 85 to 97% by mass relative to the whole composition, that is, in this case, the amount of film-forming components is preferably 1 to 30% by mass relative to the whole composition, more preferably 3 to 15% by mass relative to the whole composition.

[0295] The viscosity and surface tension of the stripping agent composition can be appropriately adjusted by taking into account various factors such as the coating method used, the desired film thickness, and by changing the type of solvent used, their ratio, and the concentration of film components.

[0296] In one aspect 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 provides a film with high homogeneity, the stripping agent composition comprises a glycol-based solvent. It should be noted that the term "glycol-based solvent" as used herein refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0297] An example of a preferred diol solvent is represented by formula (G).

[0298]

[0299] In formula (G), R G1 Each independently represents a straight-chain or branched alkylene group having 2 to 4 carbon atoms, R G2 and R G3 Each of the following groups independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 8 carbon atoms, or an alkyl acyl group having 1 to 8 carbon atoms in a straight-chain or branched alkyl group, where ng is an integer from 1 to 6.

[0300] Specific examples of straight-chain or branched alkylene groups with 2 to 4 carbon atoms include: ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, etc., but are not limited to these.

[0301] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, straight-chain or branched alkylene groups with 2 to 3 carbon atoms are preferred, and straight-chain or branched alkylene groups with 3 carbon atoms are more preferred.

[0302] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-propyl. n-Amyl, 4-methyln-amyl, 1,1-dimethyln-butyl, 1,2-dimethyln-butyl, 1,3-dimethyln-butyl, 2,2-dimethyln-butyl, 2,3-dimethyln-butyl, 3,3-dimethyln-butyl, 1-ethyln-butyl, 2-ethyln-butyl, 1,1,2-trimethyln-propyl, 1,2,2-trimethyln-propyl, 1-ethyl-1-methyln-propyl, 1-ethyl-2-methyln-propyl, etc., but not limited to these.

[0303] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl and ethyl are preferred, and methyl is more preferred.

[0304] Specific examples of alkyl acyl groups having 1 to 8 carbon atoms in a straight-chain or branched alkyl group having 1 to 8 carbon atoms can be listed as the same groups as the specific examples described above.

[0305] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, methyl carbonyl and ethyl carbonyl are preferred, and methyl carbonyl is more preferred.

[0306] From the perspectives of obtaining compositions with good reproducibility and high homogeneity, obtaining compositions with good reproducibility and high storage stability, and obtaining compositions with good reproducibility that provide highly uniform films, n g Preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0307] 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 provides a film with high homogeneity, R is preferred in formula (G). G2 and R G3 At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably R G2 and R G3 One of them is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, and the other is an alkyl acyl group with hydrogen atoms or an alkyl part having 1 to 8 carbon atoms in a straight-chain or branched alkyl group.

[0308] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the content of the glycol solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the solvent contained in the stripper composition.

[0309] From the viewpoints of obtaining a composition with good reproducibility and high uniformity, obtaining a composition with good reproducibility and high storage stability, and obtaining a composition with good reproducibility that provides a film with high uniformity, the film components in the stripper composition are preferably uniformly dispersed or dissolved in a solvent.

[0310] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the manufacturing of the stripping agent composition or after all the components have been mixed.

[0311] (Layered structure)

[0312] The laminate of the present invention comprises: a semiconductor substrate or electronic device layer, a support substrate, and a release agent layer for photo-irradiation release.

[0313] Preferably, the laminate of the present invention further includes an adhesive layer, and is composed of a semiconductor substrate or electronic device layer, a support substrate, a release agent layer for photo-irradiation release, and an adhesive layer.

[0314] It should be noted that when the release agent layer of the present invention is formed to have not only the release function of peeling the semiconductor substrate or electronic device layer from the support substrate by light irradiation, but also the bonding function of bonding the semiconductor substrate or electronic device layer to the support substrate (that is, when the release agent layer is formed using a release agent composition containing components that perform both functions), the laminate can be formed by a single layer of the release agent layer with adhesive properties, rather than by two layers of the release agent layer and the adhesive layer.

[0315] The supporting substrate is transparent.

[0316] The stripping agent layer for photo-irradiation stripping is disposed between the semiconductor substrate or electronic device layer and the support substrate.

[0317] The laminate is used to peel the semiconductor substrate or electronic device layer from the support substrate after the release agent layer has absorbed light irradiated from the support substrate side.

[0318] The stripping agent layer for photo-irradiation stripping is formed from the photo-irradiation stripping agent composition of the present invention described above.

[0319] The laminate of the present invention is used for temporary bonding in the processing of semiconductor substrates or electronic device layers, and is suitable for processing such as thinning of semiconductor substrates or electronic device layers.

[0320] During the thinning and other processing of the semiconductor substrate, the semiconductor substrate is supported by a support substrate. After the semiconductor substrate is processed, a release agent layer is irradiated with light, and then the support substrate is separated from the semiconductor substrate. Through the polymer contained in the release agent composition, the polymer (particularly the first structure) absorbs light (e.g., laser light) in the release agent layer formed by the release agent composition, causing the release agent layer to deteriorate (e.g., separate or decompose). As a result, after irradiating the release agent layer with light, the semiconductor substrate is easily peeled off from the support substrate.

[0321] Furthermore, during the thinning and other processing of the electronic device layer, the electronic device layer is supported by a support substrate. On the other hand, after the processing of the electronic device layer, the release agent layer is irradiated with light, and then the support substrate separates from the electronic device layer.

[0322] With the release agent layer of the present invention, the semiconductor substrate or electronic device layer can be easily peeled off from the support substrate after irradiation. Moreover, after the semiconductor substrate or electronic device layer is peeled off from the support substrate, the residue of the release agent layer and adhesive layer remaining on the semiconductor substrate, electronic device layer or support substrate can be removed, for example, by a cleaning agent composition used for cleaning semiconductor substrates, etc.

[0323] The wavelength of the light used for stripping is preferably 250–600 nm, more preferably 250–370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for stripping is an amount that causes appropriate alteration of the first structure in the stripping agent layer, such as causing decomposition.

[0324] The light used for stripping can be a laser or a non-laser light source such as an ultraviolet lamp.

[0325] The following will be explained in detail in two cases: the case where the laminate has a semiconductor substrate and the case where it has an electronic device layer.

[0326] The first embodiment described below describes the case where the laminate has a semiconductor substrate, and the second embodiment described below describes the case where the laminate has an electronic device layer.

[0327] <First Implementation Plan>

[0328] A laminate containing a semiconductor substrate is used for the processing of the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to a support substrate. After the processing of the semiconductor substrate, the semiconductor substrate is separated from the support substrate by irradiating a release agent layer with light.

[0329] <<Semiconductor Substrates>>

[0330] As the main material constituting the semiconductor substrate, there are no particular limitations on the material used for this purpose; examples include silicon, silicon carbide, and compound semiconductors.

[0331] The shape of the semiconductor substrate is not particularly limited; for example, it can be disc-shaped. It should be noted that a disc-shaped semiconductor substrate does not need to have a completely circular surface. For example, the outer periphery of the semiconductor substrate can have a straight section called an orientation flat, or it can have a notch.

[0332] The thickness of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate, and there is no particular limitation. For example, it can be 500 to 1000 μm.

[0333] The diameter of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate, and there is no particular limitation. For example, it can be 100 to 1000 mm.

[0334] Semiconductor substrates can also have bumps. Bumps refer to protruding terminals.

[0335] In a laminate, where the semiconductor substrate has bumps, the semiconductor substrate has bumps on the support substrate side.

[0336] In semiconductor substrates, bumps are typically formed on the surface where circuitry is formed. The circuitry can be single-layered or multi-layered. There are no particular restrictions on the shape of the circuitry.

[0337] In a semiconductor substrate, the side opposite to the side with bumps (the back side) is the side to be processed.

[0338] There are no particular limitations on the material, size, shape, structure, or density of bumps on a semiconductor substrate.

[0339] Examples of bumps include: spherical bumps, printed bumps, stud bumps, plated bumps, etc.

[0340] Typically, the height, radius, and spacing of the bumps are determined appropriately based on the conditions that the bump height is approximately 1–200 μm, the bump radius is approximately 1–200 μm, and the bump spacing is approximately 1–500 μm.

[0341] Materials used for bumps include, for example, low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. Bumps can be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy plating.

[0342] In addition, the bump can also have a stacked structure, which includes a metal layer composed of at least any of these components.

[0343] An example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0344] <<Support substrate>>

[0345] As a support substrate, there are no particular limitations on any component that can support the semiconductor substrate during the processing of the semiconductor substrate, as long as it is transparent to light irradiating the release agent layer. For example, glass support substrates can be listed.

[0346] The shape of the support substrate is not particularly limited; for example, a disc shape can be listed.

[0347] The thickness of the disk-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, and there is no particular limitation. For example, it can be 500 to 1000 μm.

[0348] The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and there is no particular limitation. For example, it can be 100 to 1000 mm.

[0349] An example of a support substrate is a glass wafer with a diameter of 300 mm and a thickness of about 700 μm.

[0350] <<Release Agent Layer>>

[0351] The release agent layer is a layer formed from the release agent composition.

[0352] The release agent layer is disposed between the semiconductor substrate and the support substrate.

[0353] The release agent layer can be bonded to either the support substrate or the semiconductor substrate.

[0354] The stripper layer is formed using the photo-irradiation stripper composition of the present invention described above.

[0355] The release agent composition of the present invention is suitable for forming a release agent layer of a laminate comprising: a semiconductor substrate, a support substrate, and a release agent layer disposed between the semiconductor substrate and the support substrate. The laminate is used to peel the semiconductor substrate from the support substrate after the release agent layer absorbs light irradiated from the support substrate side.

[0356] One of the characteristics of the release agent layer obtained from the release agent composition of the present invention is that it can easily peel the semiconductor substrate from the support substrate after light irradiation.

[0357] The thickness of the release agent layer is not particularly limited, and is usually 0.01 to 10 μm. From the viewpoint of maintaining film strength, it is preferably 0.03 μm or more, more preferably 0.05 μm or more, and even more preferably 0.1 μm or more. From the viewpoint of avoiding non-uniformity caused by thick film, it is preferably 8 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, and even more preferably 1 μm or less.

[0358] The method for forming a release agent layer from the release agent composition will be described in detail in the explanatory section of "A Method for Manufacturing an Example of a Laminate of the First Embodiment" described below.

[0359] <<Adhesive Layer>>

[0360] An adhesive layer is disposed between the support substrate and the semiconductor substrate.

[0361] The adhesive layer is, for example, bonded to a semiconductor substrate. The adhesive layer may also be bonded to a support substrate.

[0362] There are no particular limitations on the adhesive layer, but it is preferably a layer formed from an adhesive composition.

[0363] <<Adhesive Composition>>

[0364] Examples of adhesive compositions include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

[0365] Among them, the adhesive exhibits appropriate bonding ability during the processing of semiconductor substrates, etc., can be properly peeled off after processing, has excellent heat resistance, and can be properly removed by the cleaning agent composition. Therefore, as an adhesive composition, a polysiloxane-based adhesive is preferred.

[0366] In a preferred embodiment, the adhesive composition contains a polyorganosiloxane.

[0367] In another preferred embodiment, the adhesive composition comprises an ingredient that is cured by a hydrosilylation reaction.

[0368] For example, the adhesive composition used in this invention contains a cured component (A) that serves as an adhesive component. The adhesive composition used in this invention may also contain a cured component (A) that serves as an adhesive component and a component (B) that does not undergo a curing reaction. Here, polyorganosiloxanes can be listed as examples of the component (B) that does not undergo a curing reaction. It should be noted that in this invention, "does not undergo a curing reaction" does not mean that no curing reaction occurs, but rather that a curing reaction does not occur in the cured component (A).

[0369] In a preferred embodiment, component (A) may be a component cured by a hydrosilylation reaction, or it may be a polyorganosiloxane component (A') cured by a hydrosilylation reaction.

[0370] In another preferred embodiment, component (A) may contain, for example, 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). Here, the alkenyl group having 2 to 40 carbon atoms may optionally be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0371] In another preferred embodiment, the polyorganosiloxane component (A') cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises siloxane units (Q units) selected from SiO2, R... 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit) and R shown are shown. 4 R 5 SiO 2 / 2 The siloxane unit (D unit) and R shown are shown. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units from the group consisting of the shown siloxane units (T units), and the polysiloxane (A1) includes polyorganosiloxane (a1') and polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises siloxane units (Q' units) selected from SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane unit (M' unit) and R shown are shown. 4 'R 5 'SiO 2 / 2 The siloxane unit (D' unit) and R shown are shown. 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) shown, and includes at least one unit selected from the group consisting of M' units, D' units, and T' units; the polyorganosiloxane (a2') includes siloxane units (Q" units) selected from SiO2, R 1 R 2 R 3 "SiO" 1 / 2 The siloxane unit (M” unit) and R shown 4 R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R shown are shown. 6 "SiO" 3 / 2 The siloxane unit (T” unit) shown is one or more units from the group consisting of the siloxane unit (T” unit), and includes at least one unit selected from the group consisting of the M” unit, the D” unit and the T” unit.

[0372] It should be noted that (a1') is an example of (a1), and (a2') is an example of (a2).

[0373] R 1 ~R 6The groups or atoms bonded to silicon atoms are each independently represented by an optionally substituted alkyl group, an optionally 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.

[0374] R 1 '~R 6 'A group bonded to a silicon atom, each independently representing an optionally substituted alkyl or optionally substituted alkenyl group, but R 1 '~R 6 At least one of the groups is an alkenyl group that is optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0375] R 1 "~R 6 "A group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl or hydrogen atom, but R..." 1 "~R 6 At least one of the elements is a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0376] The alkyl group can be any type of straight-chain, branched, or cyclic, but is preferably a straight-chain or branched alkyl group. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0377] Specific examples of linear or branched alkyl groups that may be optionally substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1 The carbon atoms are typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Methyl groups are particularly preferred.

[0378] Specific examples of optionally substituted cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl Cycloalkyl groups such as 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl; and dicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, and dicyclodecyl, but not limited to these, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0379] The alkenyl group can be any type of linear or branched chain, and its number of carbon atoms is not particularly limited, usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0380] Specific examples of linear or branched alkenyl groups that may be optionally substituted include vinyl, allyl, butenyl, pentenyl, etc., but are not limited thereto. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, vinyl and 2-propenyl are particularly preferred.

[0381] Specific examples of cyclic alkenyl groups that may be optionally substituted include cyclopentenyl, cyclohexenyl, etc., but are not limited thereto. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0382] As described above, the polysiloxane (A1) comprises polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a cross-linked structure and are cured by a hydrosilylation reaction using a platinum group metal catalyst (A2). The result is the formation of a cured film.

[0383] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and includes at least one unit selected from the group consisting of M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying these conditions may also be used in combination as the polyorganosiloxane (a1').

[0384] Examples of preferred combinations of two or more selected from the group consisting of Q' unit, M' unit, D' unit and T' unit include: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.

[0385] Furthermore, when the polyorganosiloxane (a1') contains two or more polyorganosiloxanes, combinations of (Q' unit and M' unit) and (D' unit and M' unit), combinations of (T' unit and M' unit) and (D' unit and M' unit), and combinations of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited thereto.

[0386] The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and comprises at least one unit selected from the group consisting of M" units, D" units, and T" units. As a polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0387] Examples of preferred combinations of two or more selected from the group consisting of Q” units, M” units, D” units and T” units include: (M” units and D” units), (Q” units and M” units), (Q” units, T” units and M” units), but are not limited to these.

[0388] Polyorganosiloxanes (a1') are composed of siloxane units whose silicon atoms are bonded with alkyl and / or alkenyl groups, R 1 '~R 6 The proportion of alkenyl groups in all the substituents shown is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, with the remainder being R. 1 '~R 6 'It can be set as an alkyl group.'

[0389] Polyorganosiloxanes (a2') are composed of siloxane units whose silicon atoms are bonded to alkyl and / or hydrogen atoms, R 1 "~R 6The proportion of all substituents and hydrogen atoms in the substituted atoms shown is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, with the remainder being R. 1 "~R 6 "It can be set as an alkyl group."

[0390] When component (A) includes (a1) and (a2), in a preferred embodiment 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.

[0391] 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 effect of the present invention with good reproducibility, it is preferably 5,000 to 50,000.

[0392] It should be noted that, in this invention, the weight-average molecular weight, number-average molecular weight, and dispersity of polyorganosiloxanes (excluding the aforementioned organosiloxane polymers) can be determined, for example, using a GPC apparatus (TOSOH Corporation EcoSEC, HLC-8320GPC) and a GPC column (TOSOH Corporation TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Showa Denko Corporation, Shodex) used as the standard sample.

[0393] The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, and are typically 10 to 1,000,000 mPa·s each. From the viewpoint of achieving the effects of the present invention with good reproducibility, 50 to 10,000 mPa·s is preferred. It should be noted that the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values ​​measured using an E-type rotational viscometer at 25°C.

[0394] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film via a hydrosilylation reaction. Therefore, their curing mechanism is different from that of silanol groups. Consequently, all siloxanes do not need to contain functional groups such as silanol groups or alkoxy groups that are formed by hydrolysis to form silanol groups.

[0395] In a preferred embodiment of the invention, the adhesive composition comprises a polyorganosiloxane component (A') and a platinum group metal catalyst (A2).

[0396] Such platinum-based metal catalysts are used to promote the hydrosilylation reaction of the alkenyl group of polyorganosiloxane (a1) with the Si-H group of polyorganosiloxane (a2).

[0397] Specific examples of platinum-based metal catalysts include: platinum black, platinum tetrachloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, the complex of chloroplatinic acid and an olefin, and platinum diacetate, but are not limited to these.

[0398] Examples of platinum complexes with alkenes include, but are not limited to, complexes of divinyltetramethyldisiloxane with platinum.

[0399] The amount of platinum group metal catalyst (A2) is not particularly limited, but it is generally in the range of 1.0 to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0400] For the purpose of inhibiting the hydrosilylation reaction, the polyorganosiloxane component (A') may also contain a polymerization inhibitor (A3).

[0401] There are no particular limitations on polymerization inhibitors as long as they can inhibit the hydrosilylation reaction. Specific examples include 1-ethynyl-1-cyclohexanol, 1,1-diphenyl-2-propynyl-1-ol, and other alkynyl alcohols.

[0402] There is no particular limit to the amount of polymerization inhibitor, but it is generally considered to be above 1000.0 ppm from the point of view of obtaining its effect, and below 10000.0 ppm from the point of view of preventing excessive inhibition of the hydrosilanization reaction, relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0403] In one example of the adhesive composition used in this invention, a curing component (A) and a non-curing component (B) that serves as a release agent may also be included. By including such a component (B) in the adhesive composition, the resulting adhesive layer can be reproducibly and appropriately released.

[0404] As such a component (B), non-curable polyorganosiloxanes can be typically listed, and specific examples include: epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, phenyl-containing polyorganosiloxanes, etc., but are not limited to these.

[0405] Furthermore, as component (B), polydimethylsiloxane may be listed. The polydimethylsiloxane may optionally be modified. Examples of optionally modified polydimethylsiloxanes include, but are not limited to, epoxy-containing polydimethylsiloxanes, unmodified polydimethylsiloxanes, and phenyl-containing polydimethylsiloxanes.

[0406] Preferred examples of polyorganosiloxanes as component (B) include, but are not limited to, epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, and phenyl-containing polyorganosiloxanes.

[0407] While the weight-average molecular weight of the polyorganosiloxane as component (B) is not particularly limited, it is typically 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, while its dispersity is not particularly limited, it is typically 1.0 to 10.0. From the viewpoint of achieving appropriate exfoliation with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersity can be determined by the methods described above related to the polyorganosiloxane.

[0408] The viscosity of the polyorganosiloxane used as component (B) is not particularly limited, and is typically 1,000 to 2,000,000 mm. 2 / s. It should be noted that the viscosity of the polyorganosiloxane, which is component (B), is expressed as kinematic viscosity, cSt = mm. 2 / s. Alternatively, viscosity (mPa·s) can be divided by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be calculated from the kinematic viscosity (mm). 2 / s) = viscosity (mPa·s) / density (g / cm³) 3 This formula is used to calculate the result.

[0409] As epoxy-containing polyorganosiloxanes, examples include those containing R 11 R 12 SiO 2 / 2 The siloxane unit shown (D) 10 Polyorganosiloxane (unit).

[0410] R 11 The group that bonds to silicon atoms represents an alkyl group, R. 12 The group that bonds to silicon atoms represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be listed above.

[0411] The epoxy group in an organic group containing an epoxy group can be an independent epoxy group that does not condense with other rings, or it can be an epoxy group that forms a fused ring with other rings, such as 1,2-epoxycyclohexyl.

[0412] Specific examples of organic groups containing epoxy groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these.

[0413] In this invention, as a preferred example of an epoxy-containing polyorganosiloxane, an epoxy-containing polydimethylsiloxane can be listed, but is not limited thereto.

[0414] Epoxy-containing polyorganosiloxanes contain the aforementioned siloxane units (D 10 (unit), but except for containing D 10 In addition to the unit, it may also include Q units, M units and / or T units.

[0415] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: those consisting only of D 10 Polyorganosiloxanes composed of units; containing D 10 Polyorganosiloxanes containing D and Q units; 10 Polyorganosiloxanes containing D and M units; 10 Polyorganosiloxanes containing D and T units; 10 Polyorganosiloxanes containing D, Q, and M units; 10 Polyorganosiloxanes containing D, M, and T units; 10 Polyorganosiloxanes with units such as Q-unit, M-unit, and T-unit.

[0416] The epoxy-containing polyorganosiloxane is preferably a polydimethylsiloxane with an epoxy value of 0.1 to 5. Furthermore, while its weight-average molecular weight is not particularly limited, it is typically 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0417] Specific examples of epoxy-containing polyorganosiloxanes include, but are not limited to, the polyorganosiloxanes represented by formulas (E1) to (E3).

[0418]

[0419] (m1 and n1 represent the number of each repeating unit, which are positive integers.)

[0420]

[0421] (m2 and n2 represent the number of each repeating unit, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms.)

[0422]

[0423] (m3, n3, and o3 represent the number of each repeating unit, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms.)

[0424] Examples of methyl-containing polyorganosiloxanes include: those containing R 210 R 220 SiO 2 / 2 The siloxane unit shown (D) 200 Polyorganosiloxanes (units), preferably containing R 21 R 21 SiO 2 / 2 The siloxane unit shown (D) 20 Polyorganosiloxane (unit).

[0425] R 210 and R 220 The groups bonded to silicon atoms are each independently represented as alkyl groups, but at least one of them is methyl. The examples above can be listed as specific examples of alkyl groups.

[0426] R 21 The group that bonds to a silicon atom is represented by an alkyl group. Specific examples of alkyl groups can be listed above. Wherein, as R... 21 Methyl group is preferred.

[0427] In this invention, polydimethylsiloxane is a preferred example of a methyl-containing polyorganosiloxane, but it is not limited thereto.

[0428] Methyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D... 200 Unit or D 20 (unit), but except for containing D 200 Unit and D 20 In addition to the unit, it may also include Q units, M units and / or T units.

[0429] In one aspect of the present invention, as a specific example of a methyl-containing polyorganosiloxane, the following can be listed: consisting only of D 200 Polyorganosiloxanes composed of units; containing D 200 Polyorganosiloxanes containing D and Q units; 200 Polyorganosiloxanes containing D and M units; 200 Polyorganosiloxanes containing D and T units; 200 Polyorganosiloxanes containing D, Q, and M units; 200 Polyorganosiloxanes containing D, M, and T units; 200 Polyorganosiloxanes with units of Q, M, and T.

[0430] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: those consisting only of D 20 Polyorganosiloxanes composed of units; containing D 20 Polyorganosiloxanes containing D and Q units; 20 Polyorganosiloxanes containing D and M units; 20 Polyorganosiloxanes containing D and T units; 20 Polyorganosiloxanes containing D, Q, and M units; 20 Polyorganosiloxanes containing D, M, and T units; 20 Polyorganosiloxanes with units of Q, M, and T.

[0431] As specific examples of methyl-containing polyorganosiloxanes, polyorganosiloxanes represented by formula (M1) can be listed, but are not limited thereto.

[0432]

[0433] (n4 represents the number of repeating units, which is a positive integer.)

[0434] As phenyl-containing polyorganosiloxanes, examples include those containing R 31 R 32 SiO 2 / 2 The siloxane unit shown (D) 30 Polyorganosiloxane (unit).

[0435] R 31 The group that bonds to silicon atoms represents a phenyl or alkyl group, R. 32 The group that bonds to silicon atoms is represented by phenyl. Specific examples of alkyl groups can be listed above, with methyl being preferred.

[0436] Phenyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D 30 (unit), but except for containing D 30 In addition to the unit, it may also include Q units, M units and / or T units.

[0437] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include: those consisting only of D 30 Polyorganosiloxanes composed of units; containing D 30 Polyorganosiloxanes containing D and Q units; 30 Polyorganosiloxanes containing D and M units; 30 Polyorganosiloxanes containing D and T units; 30 Polyorganosiloxanes containing D, Q, and M units; 30Polyorganosiloxanes containing D, M, and T units; 30 Polyorganosiloxanes with units of Q, M, and T.

[0438] Specific examples of phenyl-containing polyorganosiloxanes include, but are not limited to, polyorganosiloxanes represented by formula (P1) or (P2).

[0439]

[0440] (m5 and n5 represent the number of each repeating unit, which are positive integers.)

[0441]

[0442] (m6 and n6 represent the number of each repeating unit, which are positive integers.)

[0443] The polyorganosiloxane used as the stripping agent component (B) can be a commercially available product or a synthetically produced polyorganosiloxane.

[0444] Commercially available polysiloxanes include, for example: the WACKERSILICONE FLUID AK series (AK50, AK350, AK1000, AK10000, AK1000000) manufactured by Wacker Chemie, GENIOPLASTGUM, dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) manufactured by Shin-Etsu Chemical Co., Ltd., and cyclic dimethyl silicone oil (KF-995); epoxy-containing polysiloxanes (trade names CMS-227, ECMS-327) manufactured by Gelest Co., Ltd., and epoxy-containing polysiloxanes (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd., and Dow... Corning manufactures epoxy-containing polysiloxanes (BY16-839); Gelest manufactures phenyl-containing polysiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821); Shin-Etsu Chemical Co., Ltd. manufactures phenyl-containing polysiloxanes (KF50-3000CS); and MOMENTIVE manufactures phenyl-containing polysiloxanes (TSF431, TSF433), etc., but is not limited to these.

[0445] In one embodiment, the adhesive composition used in this invention comprises both a curing component (A) and a component that does not undergo a curing reaction (B). In another embodiment, it comprises a polyorganosiloxane as component (B).

[0446] An example of the adhesive composition used in this invention may contain component (A) and component (B) in any ratio. Considering the balance between adhesion and peelability, the ratio of component (A) to component (B) by mass ratio [(A):(B)] is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0447] That is, when the polyorganosiloxane component (A') is included and cured by the hydrosilanization reaction, the ratio of component (A') to component (B) by mass ratio [(A'):(B)] is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0448] The viscosity of the adhesive composition used in this invention is not particularly limited, but is generally 500 to 20000 mPa·s at 25°C, preferably 1000 to 10000 mPa·s.

[0449] An example of the adhesive composition used in this invention can be manufactured by mixing component (A) with component (B) as used in the case of use and a solvent.

[0450] The mixing order is not particularly limited. Examples of methods for easily and reproducibly producing adhesive compositions include: dissolving components (A) and (B) in a solvent; dissolving a portion of components (A) and (B) in a solvent, dissolving the remainder in a solvent, and mixing the resulting solutions; however, this method is not limited to these. It should be noted that, during the preparation of the adhesive composition, appropriate heating may be applied within a range that does not cause the components to decompose or deteriorate.

[0451] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the manufacturing of the adhesive composition or after all the components have been mixed.

[0452] 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 preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity of the thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 70 μm or less.

[0453] The method for forming an adhesive layer from an adhesive composition will be described in detail in the explanatory section of "A Method for Manufacturing an Example of a Laminate of the First Embodiment" described below.

[0454] The following uses figures to illustrate an example of the structure of the laminate in the first embodiment.

[0455] Figure 1 The laminate sequentially comprises a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4.

[0456] Adhesive layer 2 and release agent layer 3 are disposed between semiconductor substrate 1 and support substrate 4. Adhesive layer 2 is in contact with semiconductor substrate 1. Release agent layer 3 is in contact with adhesive layer 2 and support substrate 4.

[0457] <>

[0458] The following describes the laminated body of the first embodiment. Figure 1 Taking the laminated body shown as an example, the manufacturing method of the laminated body will be explained.

[0459] An example of the laminate of the present invention can be manufactured by a method including the following steps 1 to 3.

[0460] Step 1: The process of coating an adhesive composition onto a semiconductor substrate to form an adhesive coating layer.

[0461] Step 2: The process of coating a release agent composition onto a support substrate to form a release agent layer.

[0462] Step 3: The process of heating the adhesive coating layer to form an adhesive layer while the adhesive coating layer and the release agent layer are in contact.

[0463] There are no particular limitations on the coating method of the adhesive composition; spin coating is the most common method. It should be noted that a separate coating film can be formed using spin coating or similar methods to create a sheet-like coating film, which can then be pasted as the adhesive coating layer.

[0464] 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, the desired thickness of the adhesive layer, etc., so it cannot be specified in general terms, but it is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0465] When the adhesive composition contains a solvent, the coated adhesive composition is typically heated.

[0466] The thickness of the adhesive coating layer obtained by coating the adhesive composition and heating it as needed is typically around 5 to 500 μm, appropriately determined in a way that ultimately results in the aforementioned range of adhesive layer thickness.

[0467] There are no particular limitations on the application method of the release agent composition; spin coating is the most common method.

[0468] The heating temperature of the applied release agent composition varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., and therefore cannot be specified in general. From the viewpoint of achieving a suitable release agent layer with good reproducibility, it is preferably 80°C or higher and 300°C or lower, and the heating time is appropriately determined based on the heating temperature, typically within the range of 10 seconds to 10 minutes. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds or higher and 8 minutes or lower, more preferably 1 minute or higher and 5 minutes or lower.

[0469] Heating can be done using heating plates, ovens, etc.

[0470] The thickness of the release agent film obtained by coating the release agent composition and heating it as needed is typically around 5 nm to 100 μm.

[0471] In this invention, such coating layers can be joined together in an adjoint manner. While performing heat treatment or depressurization treatment, or both, a load in the thickness direction of the semiconductor substrate and the support substrate is applied to bring the two layers into close contact. Then, a post-heat treatment is performed, thereby obtaining the laminate of this invention. It should be noted that any of the treatment conditions—heat treatment, depressurization treatment, or a combination of both—can be appropriately determined based on various factors such as the type of adhesive composition, the specific composition of the release agent composition, the phase properties of the films obtained from the two compositions, the film thickness, and the calculated adhesive strength.

[0472] From the viewpoint of removing the solvent from the composition and softening the adhesive coating layer to achieve proper adhesion with the release agent layer, the heat treatment is generally appropriately determined within the range of 20 to 150°C. In particular, from the viewpoint of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), it is preferably 130°C or lower, more preferably 90°C or lower, and the heating time is appropriately determined according to the heating temperature and the type of adhesive. From the viewpoint of reliably achieving proper adhesion, it is generally 30 seconds or more, preferably 1 minute or more, and from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is generally 10 minutes or less, preferably 5 minutes or less.

[0473] The decompression treatment simply involves exposing the adhesive coating layers and release agent layers that are in contact with each other to a pressure of 10–10000 Pa. The decompression treatment time is usually 1–30 minutes.

[0474] From the viewpoint of obtaining a laminate with good reproducibility and good separation of the substrate, it is preferable that the two layers in contact with each other are bonded by decompression treatment, and more preferably by a combination of heat treatment and decompression treatment.

[0475] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the two layers between them, and can make them firmly and tightly bonded. It is usually in the range of 10 to 1000 N.

[0476] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260°C or lower.

[0477] From the viewpoint of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or more, preferably 5 minutes or more. From the viewpoint of suppressing or avoiding adverse effects on each layer caused by excessive heating, the post-heating time is usually 180 minutes or less, preferably 120 minutes or less.

[0478] Heating can be performed using a heating plate, oven, or similar equipment. 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 peeling with good reproducibility, it is preferable to heat the substrate with the semiconductor substrate facing downwards.

[0479] It should be noted that one of the purposes of the post-heat treatment is to achieve a more suitable self-supporting film adhesive layer and release agent layer, especially to achieve proper curing based on the hydrosilanization reaction.

[0480] The following uses Figures 2A to 2C For manufacturing Figure 1 An example of the method of stacking is given to illustrate this.

[0481] Figures 2A to 2C This is a diagram used to illustrate a scheme for manufacturing a laminated body.

[0482] First, a laminate with an adhesive coating layer 2a is prepared on a semiconductor substrate 1. Figure 2A This laminate can be obtained, for example, by coating an adhesive composition onto a semiconductor substrate 1 and heating it.

[0483] In addition, a laminate in which a release agent layer 3 is formed on the support substrate 4 is prepared separately. Figure 2B This laminate can be obtained, for example, by coating a release agent composition onto a support substrate 4 and heating it.

[0484] Next, Figure 2AThe stacked bodies shown and Figure 2B The laminate shown is bonded in such a way that the adhesive coating layer 2a is bonded to the release agent layer 3. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; heating plate) is placed on the side of the semiconductor substrate 1 opposite to the side bonded to the adhesive coating layer 2a. The adhesive coating layer 2a is heated by the heating device to cure it, transforming it into adhesive layer 2 ( Figure 2C ).

[0485] pass Figures 2A to 2C The laminate is obtained by the process shown.

[0486] It should be noted that, in Figure 1 In the above-described manufacturing method, a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 are sequentially stacked. However, when manufacturing a laminate consisting of a semiconductor substrate 1, a release agent layer 3, an adhesive layer 2, and a support substrate 4, it can be manufactured by a method including the following steps: Step 1, applying a release agent composition to the surface of the semiconductor substrate and heating it as needed to form a release agent layer; Step 2, applying a release agent composition to the surface of the support substrate and heating it as needed to form an adhesive coating layer; and Step 3, applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them adhere while subjecting at least one of heat treatment and decompression treatment to the release agent layer of the semiconductor substrate and the adhesive coating layer of the support substrate, and then performing a post-heat treatment to form the laminate.

[0487] It should be noted that, as long as the effect of the present invention is not compromised, the substrates of either party may be coated and heated sequentially with each composition.

[0488] <Second Implementation Plan>

[0489] A laminate containing an electronic device layer is used for the fabrication of the electronic device layer. During the fabrication of the electronic device layer, the electronic device layer is bonded to a support substrate. After the fabrication of the electronic device layer, the electronic device layer is separated from the support substrate by irradiation with a release agent layer.

[0490] <<Electronic Devices Layer>>

[0491] The electronic device layer refers to a layer containing electronic devices. In this invention, it refers to a layer in which multiple semiconductor chip substrates are embedded in a sealing resin, that is, a layer including multiple semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.

[0492] Here, "electronic device" refers to a component that constitutes at least a part of an electronic component. There are no particular limitations on the electronic device; it can be a component with various mechanical structures and circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite of a component made of metal or semiconductor and a resin that seals or insulates the component. The electronic device can be an electronic device in which the redistribution layer and / or semiconductor elements or other components described later are sealed or insulated with sealing or insulating materials, and it has a single-layer or multi-layer structure.

[0493] <<Support substrate>>

[0494] As a support substrate, an example is shown that is the same support substrate described in the "Support Substrate" section of the above-described "First Embodiment".

[0495] <<Release Agent Layer>>

[0496] The stripper layer is formed using the photo-irradiation stripper composition of the present invention described above.

[0497] The detailed description of the stripping agent layer is as described in the "Stripping Agent Layer" section of the above-mentioned "First Embodiment".

[0498] <<Adhesive Layer>>

[0499] The adhesive layer is formed using the adhesive composition described above.

[0500] The adhesive layer is described in detail in the "Adhesive Layer" section of the aforementioned "First Embodiment".

[0501] The following uses figures to illustrate an example of the structure of the laminate in the second embodiment.

[0502] Figure 3 A schematic cross-sectional view showing an example of a stacked body according to the second embodiment.

[0503] Figure 3 The laminate sequentially comprises a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26.

[0504] The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25 disposed between the semiconductor chip substrates 21 as a sealing material.

[0505] An adhesive layer 22 and a release agent layer 23 are disposed between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with both the adhesive layer 22 and the support substrate 24.

[0506] Furthermore, another example of the structure of the laminate in the second embodiment is shown below. Figure 4 .

[0507] In the case where the release agent layer of the present invention is a release agent layer with adhesive properties that have both release and adhesive functions, the laminate may be formed not by two layers of release agent layer and adhesive layer, but by a single layer of release agent layer with adhesive properties.

[0508] Figure 4 A schematic cross-sectional view showing another example of a stacked body.

[0509] Figure 4 The laminate sequentially comprises a support substrate 24, a release agent layer 27 with adhesive properties, and an electronic device layer 26.

[0510] A release agent layer 27 with adhesive properties is disposed between the support substrate 24 and the electronic device layer 26. The release agent layer 27 with adhesive properties can be manufactured by mixing the components of the release agent composition forming the release agent with the components of the adhesive composition forming the adhesive layer.

[0511] <<Manufacturing Method of an Example of a Laminated Body in the Second Implementation Scheme>>

[0512] The following describes the laminated body of the second embodiment. Figure 3 Taking the laminated body shown as an example, the manufacturing method of the laminated body will be explained.

[0513] The laminate of the present invention can be manufactured, for example, by a method including the following steps 1 to 5.

[0514] Step 1: A step of coating a release agent composition onto the surface of the above-mentioned support substrate to form a release agent coating layer (further heating is required to form the release agent layer).

[0515] Step 2: Applying an adhesive composition to the surface of the above-mentioned release agent coating layer or release agent layer to form an adhesive coating layer (further heating is required to form an adhesive layer).

[0516] Step 3: A process of placing a semiconductor chip substrate on an adhesive coating layer or adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least one of heat treatment and depressurization treatment.

[0517] Step 4: The adhesive coating layer is cured by post-heat treatment to form an adhesive layer.

[0518] Step 5: The process of sealing the semiconductor chip substrate fixed to the adhesive layer with sealing resin.

[0519] If the third step is described in more detail, the steps of the following implementation (i) can be listed, for example.

[0520] (i) The semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of the heat treatment and the decompression treatment, a load in the thickness direction of the semiconductor chip substrate and the support substrate is applied to make them fit together, thereby attaching the semiconductor chip substrate to the adhesive coating layer or adhesive layer.

[0521] It should be noted that the fourth step can be performed after the semiconductor chip substrate is bonded to the adhesive coating layer in the third step, or it can be performed together with the third step. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer can be heated to cure it. This allows for simultaneous bonding of the semiconductor chip substrate and the adhesive coating layer, as well as curing from the adhesive coating layer to the adhesive layer, thus bonding the adhesive layer to the semiconductor chip substrate.

[0522] In addition, the fourth step can be performed before the third step, or the semiconductor chip substrate can be placed on the adhesive layer, and the adhesive layer can be bonded to the semiconductor chip substrate while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0523] The coating method, the release agent composition after coating, the heating temperature of the adhesive composition, the heating method, etc., are as described in the above-mentioned "Manufacturing Method of an Example of a Laminate of the First Embodiment" of the above-mentioned "First Embodiment".

[0524] Regarding the manufacturing method of the laminate according to the second embodiment, the sequence will be further explained in detail below using figures. The laminate is manufactured using this method. Figure 3 The layered structure shown.

[0525] like Figure 5A As shown, a release agent coating layer 23' formed of a release agent composition is formed on the support substrate 24. At this time, the release agent coating layer 23' may also be heated to form the release agent layer 23.

[0526] Next, as Figure 5B As shown, an adhesive coating layer 22' formed of an adhesive composition is formed on the release agent coating layer 23' or the release agent layer 23. At this time, the adhesive coating layer 22' can also be heated to form the adhesive layer 22.

[0527] Next, as Figure 5CAs shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22'. While performing at least one of heat treatment and depressurization treatment, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to bring them into close contact, thus bonding the semiconductor chip substrate 21 to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is bonded to the adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heat treatment to form the adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0528] It should be noted that, during the post-heat treatment of the adhesive coating layer 22', the release agent coating layer 23' can also be post-heat treated simultaneously to form the release agent layer 23.

[0529] Next, as Figure 5D As shown, the semiconductor chip substrate 21, which is fixed to the adhesive layer 22, is sealed using sealing resin 25. Figure 5D In this process, a plurality of semiconductor chip substrates 21 temporarily bonded to a support substrate 24 through an adhesive layer 22 are sealed with a sealing resin 25. An electronic device layer 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between semiconductor chip substrates 21 is formed on the adhesive layer 22, thus the electronic device layer 26 becomes a substrate layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0530] <<<Sealing Process>>>

[0531] The semiconductor chip substrate 21 is sealed using a sealing material.

[0532] As a sealing material for sealing the semiconductor chip substrate 21, a component capable of insulating or sealing components made of metal or semiconductor is used.

[0533] In this invention, a resin composition (sealing resin) is used as a sealing material. There are no particular limitations on the type of sealing resin, as long as it can seal and / or insulate a metal or semiconductor; for example, epoxy resins or silicone resins are preferred.

[0534] In addition to resin components, sealing materials may also contain other components such as fillers. Examples of fillers include spherical silica particles.

[0535] In the sealing process, sealing resin heated to, for example, 130–170°C to maintain a high viscosity is supplied onto the adhesive layer 22 to cover the semiconductor chip substrate 21, and compression molding is performed, thereby forming a layer of sealing resin 25 on the adhesive layer 22. The temperature conditions at this time are, for example, 130–170°C. Furthermore, the pressure applied to the semiconductor chip substrate 21 is, for example, 50–500 N / cm. 2 .

[0536] (Method for manufacturing processed semiconductor substrates or electronic device layers)

[0537] If the laminate of the present invention is used, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided.

[0538] The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the column of the aforementioned <First Embodiment> (laminate). Furthermore, the "method for manufacturing a processed electronic device layer" uses the laminate described in the column of the aforementioned <Second Embodiment> (laminate).

[0539] The "method of manufacturing the processed semiconductor substrate" will be described in the following "Third Embodiment" and the "method of manufacturing the processed electronic device layer" will be described in the following "Fourth Embodiment".

[0540] <Third Implementation Plan>

[0541] The method for manufacturing the processed semiconductor substrate of the present invention includes steps 5A and 6A as described below. The method for manufacturing the processed electronic device layer may further include step 7A as described below.

[0542] Here, step 5A is a process for processing the semiconductor substrate in the laminate described in the column of the above-mentioned <First Embodiment>.

[0543] In addition, step 6A is a process that separates the semiconductor substrate processed in step 5A from the support substrate.

[0544] In addition, step 7A is a process of cleaning the processed semiconductor substrate after step 6A.

[0545] In step 5A, the processing performed on the semiconductor substrate refers to, for example, processing on the side of the wafer opposite to the circuit surface, such as wafer thinning achieved by grinding the back side of the wafer. Then, for example, through-silicon vias (TSVs) are formed, and the thinned wafer is peeled from the support substrate to form a wafer stack for three-dimensional mounting. Furthermore, for example, back-side electrodes are formed before and after three-dimensional mounting. During the wafer thinning and TSV processes, the wafer is bonded to the support substrate and subjected to heat of approximately 250–350°C. The stack of the present invention typically includes an adhesive layer and possesses heat resistance to the load.

[0546] The processing performed on the semiconductor substrate in step 5A can also be a process of cutting (monolithizing) the semiconductor substrate.

[0547] It should be noted that the processing is not limited to the above-mentioned processing, and also includes, for example, the mounting process of semiconductor components in which a temporary bonding is performed with a support substrate to support the substrate used for mounting semiconductor components.

[0548] In process 6A, methods for separating (peeling) the semiconductor substrate from the support substrate may include: mechanical peeling using a device with a sharp point after irradiating the release agent layer with light, peeling by tearing between the support and the semiconductor wafer, etc., but are not limited to these.

[0549] By irradiating the release agent layer with light from the support substrate side, the release agent layer deteriorates as described above (e.g., the release agent layer separates or decomposes). Then, for example, by pulling up either substrate, the semiconductor substrate can be easily separated from the support substrate.

[0550] Irradiation of the release agent layer by light does not necessarily require irradiation of the entire release agent layer. Even if irradiated and unirradiated areas are mixed, as long as the overall release agent layer's peeling ability is sufficiently improved, the semiconductor substrate can be separated from the support substrate by a slight 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 agent layer; the intensity of the irradiated light, etc., but those skilled in the art can set appropriate conditions without excessive experimentation. Because of this, the method for manufacturing the processed semiconductor substrate according to the present invention, for example, when the support substrate of the laminate used is light-transmitting, can shorten the light irradiation time when peeling by light irradiation from the support substrate side. As a result, not only can improved throughput be expected, but physical stress for peeling can also be avoided, and the semiconductor substrate can be easily and efficiently separated from the support substrate solely by light irradiation.

[0551] Typically, the light dose used for stripping is 50–3000 mJ / cm². 2 The irradiation time should be determined appropriately based on the wavelength and the amount of irradiation.

[0552] The wavelength of the light used for stripping is preferably, for example, 250–600 nm, more preferably 250–370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for stripping is an amount that causes appropriate alteration of the first structure in the stripping agent layer, for example, an amount that causes decomposition.

[0553] The light used for stripping can be a laser or a non-laser light source such as an ultraviolet lamp.

[0554] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least any one of the separated semiconductor substrate and support substrate, or by immersing the separated semiconductor substrate or support substrate in the cleaning agent composition.

[0555] In addition, the surface of processed semiconductor substrates can also be cleaned using tools such as tape removers.

[0556] As an example of cleaning the substrate, a 7A step can be performed after the 6A step to clean the processed semiconductor substrate.

[0557] The following substances are examples of cleaning agent compositions used for cleaning.

[0558] Cleaning agent compositions typically contain solvents.

[0559] The cleaning agent composition may contain salt.

[0560] As a suitable example of a cleaning agent composition, a cleaning agent composition comprising a quaternary ammonium salt and a solvent can be cited.

[0561] Quaternary ammonium salts are composed of quaternary ammonium cations and anions, and there are no particular limitations as long as they are used for this purpose.

[0562] Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, examples of their paired anions include hydroxide ions (OH-). － ); Fluoride ions (F) － ), chloride ions (Cl) － ), bromide ions (Br) － ), iodide ions (I － Halogen ions such as tetrafluoroborate ions (BF4) － ); hexafluorophosphate ions (PF6) － (etc.), but not limited to these.

[0563] The quaternary ammonium salt is preferably a halogenated quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.

[0564] In quaternary ammonium salts, halogen atoms can be contained in cations or anions, preferably in anions.

[0565] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0566] Specific examples of hydrocarbon groups 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, and aryl groups with 6 to 20 carbon atoms.

[0567] In a more preferred embodiment, the tetra(hydrocarbon) fluoride comprises tetraalkyl ammonium fluoride.

[0568] 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 preferred.

[0569] Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can also be used in hydrate form. In addition, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can be used alone or in combination of two or more.

[0570] There is no particular limitation on the amount of quaternary ammonium salt as long as it is dissolved in the solvent contained in the cleaning agent composition, and it is usually 0.1 to 30% by mass relative to the cleaning agent composition.

[0571] The solvent contained in the cleaning agent composition 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 cleaning agent composition with excellent cleaning properties and good reproducibility, and from the viewpoint of obtaining a cleaning agent composition with excellent uniformity by good dissolution of salts such as quaternary ammonium salts, the cleaning agent composition preferably contains one or more amide solvents.

[0572] As a suitable example of an amide solvent, the amide derivative shown in formula (Z) can be listed.

[0573]

[0574] In the formula, R 0 The symbol represents ethyl, propyl, or isopropyl, with ethyl or isopropyl being preferred, and ethyl being more preferred. R A and R B Each alkyl group independently represents an alkyl group having 1 to 4 carbon atoms. Alkyl groups having 1 to 4 carbon atoms can be any type of linear, branched, or cyclic form; specifically, examples include: methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, etc. Among these, R...A and R B Preferably, methyl or ethyl, more preferably both are methyl or ethyl, and even more preferably both are methyl.

[0575] Examples of amide derivatives represented by formula (Z) include: N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, and N-ethyl-N-methylisobutyramide. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0576] The amide derivatives shown in formula (Z) can be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or by using commercially available products.

[0577] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0578]

[0579] In equation (Y), R 101 R represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 102 This refers to alkylene groups 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 alkylene groups having 1 to 6 carbon atoms include: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited to these.

[0580] Specific examples of the lactam compounds represented by formula (Y) include: α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used alone or in combination of two or more.

[0581] In a preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment it comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment it comprises N-methylpyrrolidone (NMP).

[0582] The cleaning agent composition may also contain one or more other organic solvents that are different from the amide compounds described above.

[0583] There are no particular limitations on other organic solvents, as long as they are used for this purpose and are compatible with the aforementioned amide compounds.

[0584] Other preferred solvents include, but are not limited to, alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, and ether compounds containing cyclic structures.

[0585] Regarding the amount of other organic solvents different from the amide compounds mentioned above, it is generally appropriate to determine the amount as 95% by mass or less in the solvents contained in the cleaning agent composition, provided that the quaternary ammonium salt contained in the cleaning agent composition does not precipitate or separate, and is uniformly mixed with the amide compounds mentioned above.

[0586] It should be noted that cleaning agent compositions may also contain water as a solvent, but from the perspective of avoiding substrate corrosion, it is generally intended to use only organic solvents. It should also be noted that in this case, the cleaning agent composition may contain hydrated water of salt, and trace amounts of water contained in the organic solvent; this is not to negate the possibility of these components being present. The water content of the cleaning agent composition is typically 5% by mass or less.

[0587] Regarding the constituent elements and method elements related to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention, various modifications may be made as long as they do not depart from the spirit of the present invention.

[0588] The manufacturing method of the processed semiconductor substrate of the present invention may also include steps other than those described above.

[0589] The peeling method of the present invention, when the semiconductor substrate or support substrate of the laminate of the present invention is transparent, separates the semiconductor substrate and support substrate of the laminate by irradiating the peeling agent layer with light from the semiconductor substrate side or the support substrate side.

[0590] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are appropriately and peelably temporarily bonded by an adhesive layer and a release agent layer. Therefore, for example, if the support substrate is light-transmitting, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer from the support substrate side of the laminate. Typically, the peeling is performed after the semiconductor substrate of the laminate has been processed.

[0591] use Figures 6A to 6D An example of the third embodiment will be described. This example is an example of the fabrication of a thinned semiconductor substrate.

[0592] First, prepare the stacked body ( Figure 6A This laminate is with Figure 1 and Figure 2C The stack shown is the same as the stack shown.

[0593] Next, a polishing apparatus (not shown) is used to polish the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1. Figure 6B It should be noted that through-electrodes can be formed on the thinned semiconductor substrate 1.

[0594] Next, after irradiating the release agent layer 3 with light from the support substrate 4 side, a release device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4. Figure 6C ).

[0595] Thus, a thinned semiconductor substrate 1 is obtained. Figure 6D ).

[0596] Here, residues of adhesive layer 2 and release agent layer 3 may sometimes remain on the thinned semiconductor substrate 1. Therefore, it is preferable to use a cleaning agent composition to clean the thinned semiconductor substrate 1 to remove the residues of adhesive layer 2 and release agent layer 3 from the semiconductor substrate 1.

[0597] <Fourth Implementation Plan>

[0598] The method for manufacturing the processed electronic device layer of the present invention includes steps 5B and 6B as described below. The method for manufacturing the processed electronic device layer may further include step 7B as described below.

[0599] Here, step 5B is the process of processing the electronic device layer in the laminate described in the column of the above-mentioned <Second Implementation Scheme>.

[0600] In addition, step 6B is a process that separates the electronic device layer processed in step 5B from the support substrate.

[0601] In addition, step 7B is the process of cleaning the processed electronic device layer after step 6B.

[0602] The following uses Figures 7A to 7F A specific example of the fourth implementation plan is provided.

[0603] The processing performed on the electronic device layer in process 5B can include, for example, grinding and wiring layer formation.

[0604] <<Grinding Process>>

[0605] The grinding process is a process of grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 in such a way that a part of the semiconductor chip substrate 21 is exposed.

[0606] Grinding of the sealing resin portion, for example, Figure 7B As shown, by Figure 7AThe sealing resin 25 of the laminate shown is ground to approximately the same thickness as the semiconductor chip substrate 21. It should be noted that... Figure 7A The stacked body shown is with Figure 3 and Figure 5D The stack shown is the same as the stack shown.

[0607] <<Wireline Layer Formation Process>>

[0608] The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding process.

[0609] exist Figure 7C In this process, a wiring layer 28 is formed on an electronic device layer 26 that includes a semiconductor chip substrate 21 and a sealing resin 25.

[0610] The wiring layer 28, also known as the RDL (Redistribution Layer), is a thin film of wiring that forms the wiring connected to the substrate. It can have a single-layer or multi-layer structure. The wiring layer can utilize a conductor (such as metals like aluminum, copper, titanium, nickel, gold, and silver, as well as alloys like silver-tin alloys) on a dielectric (silicon oxide (SiO2)). X Layers of wiring are formed between photosensitive resins such as photosensitive epoxy, but are not limited to these.

[0611] The following methods can be listed as examples of methods for forming the wiring layer 28.

[0612] First, silicon oxide (SiO2) is formed on the layer of sealing resin 25. X Dielectric layers such as photosensitive resins are also present. Dielectric layers composed of silicon oxide can be formed, for example, by sputtering or vacuum evaporation. Dielectric layers formed of photosensitive resins can be formed by coating the sealing resin 25 layer with photosensitive resin using methods such as spin coating, dip coating, roller blade coating, spray coating, or slot coating.

[0613] Next, wiring is formed on the dielectric layer using a conductive material such as a metal. Methods for forming the wiring include, for example, well-known semiconductor processes such as photolithography (resist lithography) and etching. Examples of such lithography processes include lithography using a positive resist material and lithography using a negative resist material.

[0614] In the manufacturing method of the laminate according to the fourth embodiment, bumps can be formed or components can be mounted on the wiring layer 28. The mounting of components on the wiring layer 28 can be performed, for example, using a pick-and-place machine.

[0615] The stack in the fourth embodiment may be a stack fabricated in a fan-out technology process, in which terminals located on a semiconductor chip substrate are mounted on a wiring layer extending beyond the chip area.

[0616] In process 6B, methods for separating (peeling) the electronic device layer from the support substrate may include: mechanical peeling using a tool with a sharp point after irradiating the release agent layer with light, peeling by tearing between the support and the electronic device layer, etc., but are not limited to these.

[0617] By irradiating the release agent layer with light from the support substrate side, the release agent layer deteriorates as described above (e.g., the release agent layer separates or decomposes). Then, for example, by pulling up either substrate, the electronic device layer can be easily separated from the support substrate.

[0618] Figures 7D to 7E This is a schematic cross-sectional view used to illustrate the separation method of laminated bodies. Figure 7F This is a schematic cross-sectional view used to illustrate the cleaning method after the separation of the laminated body. Figures 7D to 7F This describes one implementation of a method for manufacturing semiconductor packages (electronic components).

[0619] like Figure 7D As shown, the process of separating the laminate is to irradiate the release agent layer 23 with light (arrow) through the support substrate 24, causing the release agent layer 23 to deteriorate, thereby separating the electronic device layer 26 from the support substrate 24.

[0620] After the release agent layer 23 is irradiated with light (arrow) to deteriorate it, as... Figure 7E As shown, the support substrate 24 is separated from the electronic device layer 26.

[0621] Regarding the irradiation conditions and methods for irradiating the adhesive layer, please refer to the description in the section of the aforementioned "Third Implementation Scheme".

[0622] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least any of the separated electronic device layer and the support substrate, or by immersing the separated electronic device layer or the support substrate in the cleaning agent composition.

[0623] In addition, it can also be used to clean the surface of processed electronic device layers, etc., by removing adhesive tape.

[0624] For example, in Figure 7E In the process, after the separation step, an adhesive layer 22 and a release agent layer 23 are attached to the electronic device layer 26. However, by using a cleaning agent composition such as an acid or alkali, the adhesive layer 22 and the release agent layer 23 can be decomposed and removed. By removing the release agent layer and the adhesive layer, a suitable product can be obtained. Figure 7F The processed electronic device layer (electronic component) is shown.

[0625] Regarding the constituent elements and methodological elements related to the above-described steps of the method for manufacturing the processed electronic device layer of the present invention, various modifications may be made as long as they do not depart from the spirit of the present invention.

[0626] The manufacturing method of the processed electronic device layer of the present invention may also include processes other than those described above.

[0627] In the laminate of the present invention, the electronic device layer and the support substrate are appropriately and peelably temporarily bonded by an adhesive layer. Therefore, for example, when the support substrate is light-transmitting, the electronic device layer and the support substrate can be easily separated by irradiating the release agent layer from the support substrate side of the laminate. Typically, the release is performed after the electronic device layer of the laminate has been processed.

[0628] Example

[0629] The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that the apparatus used is as described below.

[0630] [Apparatus]

[0631] (1) Mixer: ARE-500 self-rotating and revolution-rotating mixer manufactured by THINKY Corporation.

[0632] (2) Viscometer: TVE-22H rotational viscometer manufactured by Toki Sangyo Co., Ltd.

[0633] (3) Vacuum bonding device: Automatic bonding machine manufactured by SUSS MicroTec Co., Ltd.

[0634] (4) Film thickness measurement: BRUKER DEKTAK XT-A.

[0635] (5) Laser irradiation device: IPEX-848 manufactured by Light Machinery Co., Ltd.

[0636] [Conditions for determining molecular weight]

[0637] Using a GPC apparatus (TOSOH Corporation HLC-8320GPC) and two GPC columns (TSKgel Super-MultiporeHZ-N), the column temperature was set to 40°C, THF (tetrahydrofuran) was used as the eluent (dissolution solvent), the flow rate was set to 0.35 mL / min, and polystyrene (Shodex, Showa Denko Corporation) was used as the standard sample. The weight-average molecular weight of the resin composition was determined.

[0638] [1] Preparation of adhesive composition

[0639] [Preparation Example 1]

[0640] 80 g of MQ resin (manufactured by Wacker Chemie) containing a polysiloxane backbone and vinyl groups, 2.52 g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing SiH groups with a viscosity of 100 mPa·s, 5.89 g of linear polydimethylsiloxane (manufactured by Wacker Chemie) containing SiH groups with a viscosity of 70 mPa·s, and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added to a 600 mL container for the mixer. The mixture was stirred for 5 minutes to obtain mixture (I).

[0641] Mixture (II) was obtained by stirring 0.147 g of platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s for 5 minutes using the aforementioned stirrer.

[0642] 3.96 g of the obtained mixture (II) was added to mixture (I), and the mixture was stirred for 5 minutes using the mixer to obtain mixture (III).

[0643] Finally, the resulting mixture (III) was filtered through a 300-mesh nylon filter to obtain the adhesive composition.

[0644] [2] Synthesis of resin composition

[0645] [Synthetic Example A]

[0646] A mixture of raw materials was prepared by adding 5.00 g of a 30% by mass solution of 5,5-dimethyl-1,3-bis(epoxyethylenemethyl)imidazoline-2,4-dione in propylene glycol monomethyl ether (hereinafter referred to as PGME), 3.57 g of 4,4-dihydroxybenzophenone, 3.82 g of 1,3-bis[2-(7-oxabicyclo[4.1.0]heptane-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane, 0.27 g of tetrabutylphosphine bromide, and 10.27 g of PGME to a flask. The mixture was then heated under nitrogen atmosphere at 105 °C under reflux for 24 hours. After cooling to room temperature, 20.00 g of PGME, a cation exchange resin, and an anion exchange resin were added to the resulting reaction mixture. The mixture was then stirred at room temperature for 4 hours to remove unreacted monomers and the catalyst used in the reaction. Finally, the ion exchange resin was removed by filtration, yielding a solution containing the reaction products as a filtrate. It should be noted that the amounts of cation exchange resin and anion exchange resin were set to be the same as the mass of the solid matter in the initially prepared raw material mixture. The resulting reaction product corresponds to the following formula (A-1), and its weight-average molecular weight was determined by the above method to be 2384.

[0647] Equation (A-1)

[0648]

[0649] [Synthetic Example B]

[0650] 4.00 g of bisphenol A diglycidyl ether, 2.65 g of 4,4-dihydroxybenzophenone, 0.20 g of tetrabutylphosphine bromide, and 10.27 g of cyclohexanone (hereinafter referred to as CY) were added to a flask to prepare a raw material mixture. The mixture was heated under nitrogen atmosphere at 105 °C and refluxed for 24 hours. After cooling to room temperature, 20.00 g of CY, a cation exchange resin, and an anion exchange resin were added to the resulting reaction mixture. The mixture was then stirred at room temperature for 4 hours to remove unreacted monomers and the catalyst used in the reaction. Finally, the ion exchange resin was removed by filtration, and a solution containing the reaction product was obtained as a filtrate. It should be noted that the amounts of cation exchange resin and anion exchange resin were set to be the same as the mass of the solid matter in the initially prepared raw material mixture. The obtained reaction product corresponds to the following formula (A-2), and its weight-average molecular weight was determined by the above method to be 15283.

[0651] Equation (A-2)

[0652]

[0653] [3] Preparation of the stripping agent composition

[0654] [Preparation Example 2]

[0655] 14.00 g of cyclohexanone was added to 6 g of the resin solution (solid content: 23.29 wt%) obtained in Synthesis Example A to dissolve it, thus obtaining a stripping agent composition.

[0656] [Comparative Preparation Example 1]

[0657] 12.39 g of cyclohexanone was added to 6 g of the resin solution (solid content: 18.39 wt%) obtained in Synthesis Example B to dissolve it, thus obtaining a stripping agent composition.

[0658] [4] Preparation of cleaning agent composition

[0659] [Preparation Example 3]

[0660] 6g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) was mixed with 94g of N,N-dimethylpropionamide and stirred thoroughly to obtain a cleaning agent composition.

[0661] [5] Confirmation of membrane removability

[0662] [Example 1-1]

[0663] The stripper composition obtained in Preparation Example 2 was spin-coated onto a 4-inch bare silicon wafer with a final film thickness of 250 nm. The wafer was then heated at 230°C for 30 minutes to form a film on the bare silicon wafer. Substrates with the film formed were fabricated in the required quantity for evaluation.

[0664] [Comparative Example 1-1]

[0665] The stripper composition obtained in Comparative Preparation Example 1 was spin-coated onto a 4-inch bare silicon wafer with a final film thickness of 250 nm. The wafer was then heated at 230°C for 30 minutes to form a film on the bare silicon wafer. Substrates with the film formed were fabricated in the required quantity for evaluation.

[0666] The film thickness (film thickness before immersion) of each membrane obtained in Examples 1-1 and Comparative Examples 1-1 was measured. Then, each membrane, along with its substrate, was immersed in 7 mL of the cleaning agent composition obtained in Preparation Example 3 for 5 minutes, dried with an air gun, and the film thickness (film thickness after immersion) of each membrane was measured again. Furthermore, the same procedure was performed using cyclohexanone instead of the cleaning agent composition, and the film thickness was measured. The residual film yield (%) based on immersion was calculated according to the following formula.

[0667] Residual film yield (%) = [film thickness after impregnation (nm) / film thickness before impregnation (nm)] × 100

[0668] The results are shown in Table 1.

[0669]

[0670] [6] Fabrication of laminates

[0671] [Examples 2-1, 2-2] and [Comparative Examples 2-1, 2-2]

[0672] The release agent compositions obtained in Preparation Example 2 and Comparative Preparation Example 1 were spin-coated onto a 300 mm thick silicon wafer (775 μm thick) serving as the device side substrate, with a final laminate thickness of 250 nm. The wafer was then fired at 230 °C for 30 minutes, thereby forming a release agent coating layer on the silicon wafer.

[0673] Next, the adhesive composition obtained in Preparation Example 1 was spin-coated onto the release agent coating layer in a manner that resulted in a thickness of 65 μm, thereby forming an adhesive coating layer.

[0674] Then, using a bonding apparatus, the glass wafer (EAGLE-SG, manufactured by Corning, 700 μm thick) and the silicon wafer are bonded together by clamping the release agent coating layer and the adhesive coating layer, followed by a post-heat treatment at 200°C for 10 minutes, thereby producing a laminate. It should be noted that the bonding is performed at a temperature of 23°C, a pressure reduction of 1000 Pa, and an applied load of 30 N.

[0675] Next, the obtained laminate is heat-treated at 300°C for 2 hours or at 350°C for 1 hour. The obtained laminate is then cut into 4cm square pieces using a cutting device.

[0676] [7] Confirmation of peeling

[0677] Using a laser irradiation device, the release agent layer was irradiated with a 308 nm laser from the glass wafer side of the fixed laminate at various irradiation doses shown in Tables 2-1 and 2-2. Then, the support substrate was manually lifted to confirm whether the peeling was successful. Cases where the silicon wafer could be peeled off without damage were marked as "0", and cases where the silicon wafer could not be peeled off were marked as "×". The peeling results are shown in Tables 2-1 and 2-2.

[0678] [8] Confirmation of cleanability

[0679] The silicon substrate obtained after laser ablation was immersed in 7 mL of the cleaning composition for 5 minutes, rinsed with isopropanol, and air-dried to obtain the cleaned substrate. To determine whether the cleaning was satisfactory, the cleaned silicon substrate was observed using an optical microscope. A "0" was marked as no residue observed, and a "×" was marked as residue observed. The results are shown in Tables 2-1 and 2-2.

[0680]

[0681]

[0682] [9] Preparation of the stripping agent composition

[0683] [Preparation Example 4]

[0684] 0.098 g of 1,3,4,6-tetra(methoxymethyl)glycourea (hereinafter referred to as PL), 0.014 g of pyridinium p-toluenesulfonate (hereinafter referred to as Py-PTS), and 17.29 g of PGME were added to 6 g of the resin solution (solid content: 23.29 wt%) obtained in Synthesis Example A to dissolve it, thereby obtaining a stripping agent composition.

[0685] [Comparative Preparation Example 2]

[0686] PGME 12.39g was added to 6g of the resin solution (solid content: 18.39 wt%) obtained in Synthesis Example B to obtain a stripping agent composition.

[0687] [Comparative Preparation Example 3]

[0688] 0.077 g of PL, 0.011 g of Py-PTS, and 12.39 g of PGME were added to 6 g of the resin solution (solid content: 18.39 wt%) obtained in Synthesis Example B to dissolve it, thereby obtaining a stripping agent composition.

[0689]

[10] Confirmation of membrane removal performance

[0690] [Examples 1-2]

[0691] The stripper composition obtained in Preparation Example 4 was spin-coated onto a 4-inch bare silicon wafer with a final film thickness of 250 nm. The wafer was then heated at 230°C for 30 minutes to form a film on the bare silicon wafer. Substrates with the film formed were fabricated in the required quantity for evaluation.

[0692] [Comparative Examples 1-2]

[0693] The stripper composition obtained in Comparative Preparation Example 2 was spin-coated onto a 4-inch bare silicon wafer with a final film thickness of 250 nm. The wafer was then heated at 230°C for 30 minutes to form a film on the bare silicon wafer. Substrates with the film formed were fabricated in the quantity required for evaluation.

[0694] [Comparative Examples 1-3]

[0695] The stripper composition obtained in Comparative Preparation Example 3 was spin-coated onto a 4-inch bare silicon wafer with a final film thickness of 250 nm. The wafer was then heated at 230°C for 30 minutes to form a film on the bare silicon wafer. Substrates with the film formed were fabricated in the required quantity for evaluation.

[0696] The film thickness (film thickness before immersion) of each membrane obtained in Examples 1-2, Comparative Examples 1-2, and Comparative Examples 1-3 was measured. Then, each membrane, along with its substrate, was immersed in 7 mL of the cleaning agent composition obtained in Preparation Example 3 for 5 minutes, dried with an air gun, and the film thickness (film thickness after immersion) was measured again. Furthermore, the same procedure was performed using PGME instead of the cleaning agent composition, and the film thickness was measured. The residual film yield (%) based on immersion was calculated according to the following formula.

[0697] Residual film yield (%) = [film thickness after impregnation (nm) / film thickness before impregnation (nm)] × 100

[0698] The results are shown in Table 3.

[0699]

[0700]

[11] Fabrication of laminates

[0701] [Examples 2-3], [Comparative Examples 2-3]

[0702] The release agent compositions obtained in Preparation Example 4 and Comparative Preparation Example 3 were spin-coated onto a 300 mm glass wafer (EAGLE-SG, manufactured by Corning, 700 μm thick) serving as the substrate on the carrier side, with a final laminate thickness of 250 nm. The wafers were then fired at 230 °C for 30 minutes, thereby forming a release agent coating layer on the glass wafer.

[0703] On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated onto a 300 mm thick silicon wafer (775 μm thick) serving as a substrate on the device side, such that the film thickness in the final laminate was 65 μm, thus forming an adhesive coating layer on the silicon wafer serving as a semiconductor substrate.

[0704] Then, using a bonding device, the glass wafer and the silicon wafer are bonded together by clamping the release agent coating layer and the adhesive coating layer, followed by a post-heat treatment at 200°C for 10 minutes to produce a laminate. It should be noted that the bonding is performed at a temperature of 23°C, a pressure reduction of 1000 Pa, and an applied load of 30 N. The resulting laminate is then cut into 4 cm square pieces using a cutting device.

[0705]

[12] Confirmation of peeling

[0706] Using a laser irradiation device, the release agent layer was irradiated with a 308 nm laser at various irradiation doses shown in Table 4 from the glass wafer side of the fixed laminate. Then, the support substrate was manually lifted to confirm whether the peeling was successful. Cases where the silicon wafer could be peeled off without damage were marked as "0", and cases where the silicon wafer could not be peeled off were marked as "×". The peeling results are shown in Table 4.

[0707]

[13] Confirmation of cleanliness

[0708] The silicon substrate (silicon wafer) obtained after laser ablation was immersed in 7 mL of the cleaning composition for 5 minutes and then air-dried to obtain the cleaned substrate. To determine whether the cleaning was satisfactory, the cleaned silicon substrate was observed using an optical microscope. A "0" was marked as no residue observed on the substrate, and a "×" was marked as residue observed. The results are shown in Table 4.

[0709]

[0710] As shown in Tables 1-4, it was confirmed that the release agent composition of the present invention, containing a siloxane structure, exhibits good cleaning properties. Furthermore, it was confirmed that by containing a crosslinking agent, it exhibits solvent resistance to common organic solvents, becomes soluble in the cleaning agent composition, and can be used for cleaning. In addition, it was confirmed that by providing light-absorbing sites in the release agent composition, the substrate can be easily peeled off after irradiation with light.

[0711] Explanation of reference numerals in the attached figures:

[0712] 1: Semiconductor substrate; 2: Adhesive layer; 2a: Adhesive coating layer; 3: Release agent layer; 4: Support substrate; 21: Semiconductor chip substrate; 22: Adhesive layer; 23: Release agent layer; 24: Support substrate; 25: Sealing resin; 26: Electronic device layer; 27: Release agent layer with adhesive properties; 28: Wiring layer.

Claims

1. A stripping agent composition, which is a stripping agent composition for photo-irradiation stripping. The stripping agent composition contains a polymer and a solvent. The polymer has a first structure, a second structure, and a third structure. The first structure has a structure that absorbs light and imparts peelability to the release agent layer formed by the release agent composition. The second structure has a -Si-O-Si- structure in the main chain of the polymer. The third structure has at least any one of aromatic hydrocarbon rings and heterocycles.

2. The stripping agent composition according to claim 1, wherein, The first structure is a repeating unit as shown in equation (1) below. In equation (1), X 1 Represents -O-, -CO-, -NR a -, -SO-, -SO2-, -N=N-, -CH=CH-CO- or -CH=CH-CO-CH2-CO-CH=CH-, where, R a Represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. m1 and m2 independently represent 0 or 1, R 1 and R 2 Each can be used independently to represent a halogen atom or a monovalent group. n1 and n2 independently represent integers from 0 to 4. R 1 When there are two or more R, two or more R 1 Either the same or different, R 2 When there are two or more R, two or more R 2 They can be either the same or different.

3. The stripping agent composition according to claim 1, wherein, The second structure is a repeating unit as shown in equation (2-1) or equation (2-2). In equation (2-1), X 11 This indicates a divalent group with a -Si-O-Si- structure. A 1 A 2 A 3 A 4 A 5 And A 6 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group. In equation (2-2), X 12 This indicates a divalent group with a -Si-O-Si- structure. *1 and *1' represent bonded bonds; bonded bond *1 is bonded to carbon atom *2 or carbon atom *3; bonded bond *1' is bonded to carbon atom *2' or carbon atom *3'.

4. The stripping agent composition according to claim 3, wherein, X in equation (2-1) 11 and X in equation (2-2) 12 Each is independently represented by the structure shown in the following formula (S). In formula (S), R 101 ~R 106 Each can be independently represented as a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. Y 1 and Y 2 Each can be independently represented as an alkylene group having 1 to 10 carbon atoms. m represents an integer greater than or equal to 0 or 1. p and q represent 0 or 1 independently, When m is 2 or more, there are two or more R 103 and R 104 The same or different, can be chosen. * indicates a bonding bond.

5. The stripping agent composition according to claim 1, wherein, The third structure is a repeating unit as shown in the following formula (3). In equation (3), X 21 A represents a divalent group having at least any of the following: an aromatic hydrocarbon ring and a heterocycle. 11 A 12 A 13 A 14 A 15 And A 16 Each can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group.

6. The stripping agent composition according to claim 5, wherein, X in equation (3) 21 This refers to any of the structures shown in equation (3-1) and equation (3-2) below. In equation (3-1), Q 1 The symbol represents a divalent organic group as shown in formula (3-1-1) or a divalent organic group as shown in formula (3-1-2); n1 and n2 independently represent 0 or 1 respectively; * represents a bond. In equation (3-2), X 31 Z represents any of the divalent groups shown in equations (3-2-1) to (3-2-3) below; 1 and Z 2 Each can be used independently to represent a single bond or a divalent group as shown in the following formula (3-2-4); * indicates a bonded bond. In equations (3-1-1) and (3-1-2), R 21 ~R 23 Each of the following groups independently represents a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkoxy group with 2 to 6 carbon atoms, an alkenyloxy group with 2 to 6 carbon atoms, an alkynyloxy group with 2 to 6 carbon atoms, an acyl group with 2 to 6 carbon atoms, an aryloxy group with 6 to 12 carbon atoms, an arylcarbonyl group with 7 to 13 carbon atoms, or an aralkyl group with 7 to 13 carbon atoms; * indicates a bond. In equation (3-1-1), n3 represents 0 or 1; when n3 is 0, n11 represents an integer from 0 to 4; when n3 is 1, n11 represents an integer from 0 to 6; R 21 When there are two or more R, two or more R 21 The same or different, can be chosen. In equation (3-1-2), Z 11 Indicates a single bond or an alkylene group having 1 to 6 carbon atoms; n12 and n13 independently represent integers from 0 to 4; R 22 When there are two or more R, two or more R 22 The same or different can be chosen arbitrarily; R 23 When there are two or more R, two or more R 23 Either the same or different, In equations (3-2-1) to (3-2-3), R 1 ~R 5 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, optionally interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms, optionally interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, wherein the phenyl group is optionally substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkathio group having 1 to 6 carbon atoms; R 1 With R 2 They can optionally bond together to form rings with 3 to 6 carbon atoms; R 3 With R 4 They can optionally bond together to form rings with 3 to 6 carbon atoms. * indicates a bond; *1 indicates a bond bonded to a carbon atom in formula (3-2); *2 indicates a bond bonded to a nitrogen atom in formula (3-2). In equation (3-2-4), m1 is an integer from 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer from 0 to 2; where m3 is 1, m1 and m2 are not both 0; *3 represents the bond bonded to the nitrogen atom in equation (3-2); *4 represents the bond bond.

7. A layered body, wherein, The laminate has: Semiconductor substrate or electronic device layer; Transparent support substrate; as well as A release agent layer is disposed between the semiconductor substrate or the electronic device layer and the support substrate. The release agent layer is a release agent layer formed from the release agent composition as described in any one of claims 1 to 6.

8. The laminate according to claim 7, wherein, The laminate has an adhesive layer disposed between the semiconductor substrate or the electronic device layer and the support substrate.

9. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: Step 5A involves processing the semiconductor substrate of the laminate as described in claim 7; Alternatively, in step 5B, the electronic device layer of the laminate as described in claim 7 is processed; as well as In step 6A, the semiconductor substrate processed in step 5A is separated from the support substrate; or in step 6B, the electronic device layer processed in step 5B is separated from the support substrate.

10. The method for manufacturing the processed semiconductor substrate or electronic device layer according to claim 9, wherein, The 6A or 6B process includes irradiating the laminate with a laser from the support substrate side.

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