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

Abstract

The present invention relates to a release agent composition for light irradiation release, the release agent composition containing: at least any one of a compound and a polymer having a structure represented by formula (1) and having a carbon content of 80% or less; and a solvent. (In formula (1), R1 and R2 each independently represent a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1-13 carbon atoms, a halogen atom,-COOR11 (R11 represents a hydrogen atom or an alkyl group having 1-4 carbon atoms) or-COO-. And R3 represents a methoxy group, an alkyl group having 1-13 carbon atoms, or a halogen atom. And n1 represents an integer of 0-4. And n2 represents 0 or 1. Wherein the total of n1 and n2 is 4 or less. And X1 represents an ether bond or an ester bond. And X2 represents an ether bond or an ester bond. * represents a bond. > # imgabs0 #

Description

Technical Field

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

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

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

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

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

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

[0007] Prior art literature

[0008] Patent Literature

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

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

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

[0012] Problems to be solved by the invention

[0013] In the method of stripping by light irradiation, after processing semiconductor substrates such as semiconductor wafers, the stripping agent layer is deteriorated by light irradiation, so that the semiconductor substrate is easy to be stripped from the supporting substrate. On the surface of the semiconductor substrate and / or the supporting substrate after stripping, foreign matter such as an adhesive layer, a stripping agent layer and their residues are sometimes attached, so the semiconductor substrate and / or the supporting substrate are cleaned. However, depending on the type of the stripping agent layer, foreign matter on the semiconductor substrate and the supporting substrate is sometimes not easy to be removed, and cleaning becomes difficult. In addition, if foreign matter remains in the cleaning agent in the form of contaminants, it will be attached to the semiconductor substrate and the supporting substrate again. If the foreign matter is not removed and remains on the semiconductor substrate, the problem of reduced yield of semiconductor products will occur. In addition, if the foreign matter is not removed and remains on the supporting substrate, it is difficult to reuse the supporting substrate. And, if the foreign matter remains in the cleaning agent in the form of contaminants, it is difficult to reuse the cleaning agent.

[0014] The present invention has been completed in view of the above situation, and its purpose is to provide a stripping agent composition for light irradiation stripping that can form a stripping agent layer with stripping properties and cleaning properties within a wide range of light irradiation doses, and a method for manufacturing a laminate and a processed semiconductor substrate using the stripping agent composition.

[0015] Solutions for solving problems

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

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

[0018] [1] A stripping agent composition for stripping by light irradiation,

[0019] The stripping agent composition contains: at least one of a compound having a structure represented by the following formula (1) and a carbon content of 80% or less and a polymer; and a solvent.

[0020]

[0021] (In formula (1), R 1 and R 2each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) or -COO-.

[0022] R 3 It represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom.

[0023] n1 represents an integer of 0 to 4. n2 represents 0 or 1. However, the total of n1 and n2 is 4 or less.

[0024] X 1 It represents an ether bond or an ester bond.

[0025] X 2 It represents an ether bond or an ester bond.

[0026] * indicates a bonding key. )

[0027] [2] The stripping agent composition according to [1], wherein at least any one of the compound and the polymer has at least any one of the structure represented by the following formula (2), the structure represented by the following formula (3), and the structure represented by the following formula (4).

[0028]

[0029] (In formula (2), X 11 Represents a divalent group. 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a bonding bond.

[0030] In formula (3), X 12 represents a divalent group. *, *1, and *1' represent a bond. Bond *1 is bonded to carbon atom *2 or carbon atom *3. Bond *1' is bonded to carbon atom *2' or carbon atom *3'.

[0031] In formula (4), X 13 and X 14 One of them represents a hydroxyl group, and the other represents a bond, X 15 and X 16 One of them represents a hydroxyl group, and the other represents a bond. m1 represents 0 or 1. )

[0032] [3] The stripping agent composition according to [2], wherein X in the formula (2) 11It is any of the structure represented by the following formula (2-1) and the structure represented by the following formula (2-2).

[0033]

[0034] (In formula (2-1), Q 1 represents a divalent acyclic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom, a divalent organic group represented by the following formula (2-1-1), a divalent organic group represented by the following formula (2-1-2), a divalent organic group represented by the following formula (2-1-3), or a divalent organic group represented by the following formula (2-1-4). n1 and n2 each independently represent 0 or 1. * represents a bonding bond.

[0035] In formula (2-2), X 21 Z represents a divalent group represented by any of the following formulae (2-2-1) to (2-2-4). 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (2-2-5).

[0036]

[0037] (In formulas (2-1-1) to (2-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a bonding bond.

[0038] In formula (2-1-1), 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 21 Optionally the same or different.

[0039] In formula (2-1-2), Z 11 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n12 and n13 each independently represent an integer of 0 to 4. 22 When there are two or more R 22 are optionally the same or different. 23 When there are two or more R 23 Optionally the same or different.

[0040] In formula (2-1-3), Z 12 and Z 13 Each independently represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms. n14 represents an integer of 0 to 4. 24 When there are two or more R 24 Optionally the same or different.

[0041] In formula (2-1-4), Z 14 Z represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. 15 and Z 16 Each independently represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. 25 When there are two or more R 25 are optionally the same or different. 26 When there are two or more R 26 Optionally the same or different. )

[0042]

[0043] (In formulas (2-2-1) to (2-2-3), R 1 ~R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a 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. 1 and R 2 They are optionally bonded to each other to form a ring having 3 to 6 carbon atoms. 3 and R 4 They are optionally bonded to each other to form a ring having 3 to 6 carbon atoms.

[0044] In formula (2-2-4), Z 3 represents a single bond or a divalent group represented by the following formula (2-2-5). 7 , A 8 and A 9 Each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0045] * represents a bond. *1 represents a bond to a carbon atom in formula (2-2). *2 represents a bond to a nitrogen atom in formula (2-2).

[0046]

[0047] (In formula (2-2-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to a nitrogen atom in formula (2-2) or formula (2-2-4). *4 represents a bond.)

[0048] [4] The stripping agent composition according to any one of [1] to [3], wherein the carbon content is 50% or more.

[0049] [5] The stripping agent composition according to any one of [1] to [4], wherein X in the formula (1) 1 represents an ether bond,

[0050] In the formula (1), R 1 represents cyano,

[0051] In the formula (1), R 2 Indicates -COO-,

[0052] n2 in the formula (1) represents 0.

[0053] [6] A laminated body, wherein:

[0054] The laminated body has:

[0055] Semiconductor substrate or electronic device layer;

[0056] a light-transmitting supporting substrate; and

[0057] a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate,

[0058] The release agent layer is a release agent layer formed from the release agent composition described in any one of [1] to [5].

[0059] [7] The laminate according to [6], wherein the laminate has an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0060] [8] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising:

[0061] A fifth step A of processing the semiconductor substrate of the laminated body described in [6] or [7]; or a fifth step B of processing the electronic device layer of the laminated body described in [6] or [7]; and

[0062] The sixth A step is to separate the semiconductor substrate processed in the fifth A step from the support substrate; or the sixth B step is to separate the electronic device layer processed in the fifth B step from the support substrate.

[0063] [9] The method for manufacturing a processed semiconductor substrate or electronic device layer according to [8], wherein the sixth step A or the sixth step B includes a step of irradiating the stacked body with laser light from the support substrate side.

[0064] Effects of the Invention

[0065] According to the present invention, there are provided a release agent composition for light irradiation release capable of forming a release agent layer having release properties and washability in a wide range of light irradiation doses, and a method for producing a laminate and a processed semiconductor substrate using the release agent composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is a schematic cross-sectional view of an example of the laminated body in the first embodiment.

[0067] Figure 2A This is a schematic cross-sectional view (part 1) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0068] Figure 2B This is a schematic cross-sectional view (part 2) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0069] Figure 2C This is a schematic cross-sectional view (part 3) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0070] Figure 3 This is a schematic cross-sectional view of an example of a laminated body in the second embodiment.

[0071] Figure 4 It is a schematic cross-sectional view of another example of the laminated body in the second embodiment.

[0072] Figure 5A This is a schematic cross-sectional view (part 1) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0073] Figure 5B This is a schematic cross-sectional view (part 2) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0074] Figure 5CThis is a schematic cross-sectional view (part 3) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0075] Figure 5D This is a schematic cross-sectional view (part 4) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0076] Fig. 6A This is a schematic cross-sectional view (part 1) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0077] Figure 6B This is a schematic cross-sectional view (part 2) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0078] Figure 6C This is a schematic cross-sectional view (part 3) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0079] Fig.6D This is a schematic cross-sectional view (part 4) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0080] Fig. 7A This is a schematic cross-sectional view (part 1) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0081] Figure 7B This is a schematic cross-sectional view (part 2) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0082] Figure 7C This is a schematic cross-sectional view (part 3) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0083] Fig.7D This is a schematic cross-sectional view (part 4) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0084] Fig. 7E This is a schematic cross-sectional view (part 5) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0085] Figure 7F This is a schematic cross-sectional view (part six) for explaining a method for processing a laminated body showing an example of the second embodiment. DETAILED DESCRIPTION

[0086] (Removal agent composition for light irradiation removal)

[0087] The stripping agent composition for light irradiation stripping of the present invention contains: at least one of a compound having a structure represented by the following formula (1) and a carbon content of 80% or less and a polymer; and a solvent.

[0088]

[0089] (In formula (1), R 1 and R 2 each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) or -COO-.

[0090] R 3 It represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom.

[0091] n1 represents an integer of 0 to 4. n2 represents 0 or 1. However, the total of n1 and n2 is 4 or less.

[0092] X 1 It represents an ether bond or an ester bond.

[0093] X 2 It represents an ether bond or an ester bond.

[0094] * indicates a bonding key. )

[0095] In the method of stripping by light irradiation, after processing semiconductor substrates such as semiconductor wafers, the stripping agent layer is deteriorated by light irradiation, so that the semiconductor substrate is easy to be stripped from the supporting substrate. On the surface of the semiconductor substrate and / or the supporting substrate after stripping, foreign matter such as an adhesive layer, a stripping agent layer and their residues are sometimes attached, so the semiconductor substrate and / or the supporting substrate are cleaned. However, depending on the type of the stripping agent layer, foreign matter on the semiconductor substrate and the supporting substrate is sometimes not easy to be removed, and cleaning becomes difficult. In addition, if foreign matter remains in the cleaning agent in the form of contaminants, it will be attached to the semiconductor substrate and the supporting substrate again. If the foreign matter is not removed and remains on the semiconductor substrate, the problem of reduced yield of semiconductor products will occur. In addition, if the foreign matter is not removed and remains on the supporting substrate, it is difficult to reuse the supporting substrate. And, if the foreign matter remains in the cleaning agent in the form of contaminants, it is difficult to reuse the cleaning agent.

[0096] On the other hand, when the release agent layer is irradiated with light, it is difficult to irradiate the entire surface of the release agent layer uniformly. When the local irradiation amount is observed, the irradiation amount has an in-plane deviation. In addition, the inventors of the present invention have conducted research and found that the peeling property and the cleaning property depend on the irradiation amount. The more the irradiation amount, the better the peeling property. On the other hand, the less the irradiation amount, the better the cleaning property.

[0097] Therefore, it is desirable to achieve both releasability and cleaning properties over a wide range of light irradiation doses.

[0098] Therefore, the present inventors have conducted intensive studies to provide a release agent composition for light irradiation release that can form a release agent layer having release properties and cleaning properties in a wide range of light irradiation doses.

[0099] As a result, the present invention was completed by discovering the following fact, namely, the following stripper composition can form a stripper layer having stripping and cleaning properties within a wide range of light irradiation, the stripper composition containing: at least any one of a compound and a polymer having a structure represented by formula (1) and a carbon content of less than 80%; and a solvent.

[0100] The present inventors have considered as follows that the release agent composition of the present invention can form a release agent layer having release properties and cleaning properties in a wide range of light irradiation doses.

[0101] By making the compound and the polymer have the structure shown in formula (1), the stripping agent layer is easily degraded by light irradiation, and as a result, a stripping agent layer having stripping properties within a wide range of light irradiation can be obtained. On the other hand, by making the carbon content of the compound and the polymer not too high, even if the stripping agent layer is degraded by light irradiation, it is easy to maintain cleaning properties. As degeneration, carbonization is considered, for example.

[0102] <Compound or polymer>

[0103] The compound and polymer contained in the release agent composition (hereinafter, sometimes referred to as "specific compound and polymer") have a structure represented by the following formula (1) and a carbon content of 80% or less.

[0104] It should be noted that, in the present invention, the difference between a compound and a polymer does not need to be particularly clear. For example, if it is a substance having a structure shown in formula (1) and a carbon content of 80% or less, it can be a low molecular weight, a high molecular weight, a single composition, or a molecular weight distribution (for example, the polydispersity (weight average molecular weight / number average molecular weight) can exceed 1).

[0105]

[0106] (In formula (1), R 1and R 2 each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) or -COO-.

[0107] R 3 It represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom.

[0108] n1 represents an integer of 0 to 4. n2 represents 0 or 1. However, the total of n1 and n2 is 4 or less.

[0109] X 1 It represents an ether bond (-O-) or an ester bond (-COO-).

[0110] X 2 It represents an ether bond (-O-) or an ester bond (-COO-).

[0111] * indicates a bonding key. )

[0112] As R in formula (1) 1 ~R 3 Examples of the alkyl group having 1 to 13 carbon atoms include alkyl groups having 1 to 6 carbon atoms.

[0113] Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, and a cyclohexyl group.

[0114] As R in formula (1) 11 Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an isopropyl group, and an n-butyl group.

[0115] As X in formula (1) 1 , preferably represents an ether bond.

[0116] As R in formula (1) 1 , preferably represents a cyano group.

[0117] As R in formula (1) 2 , preferably represents -COO-.

[0118] As n2 in formula (1), it is preferable that it represents 0.

[0119] The carbon content of the specific compound and polymer is not particularly limited as long as it is 80% or less, but is preferably 75% or less, and more preferably 70% or less.

[0120] The lower limit of the carbon content of the specific compound and polymer is not particularly limited, but the carbon content is preferably 45% or more, more preferably 50% or more, and particularly preferably 55% or more.

[0121] The carbon content of the compound and the polymer can be determined, for example, by the following method.

[0122] Determine the composition formula of the compound or polymer. When synthesizing a compound or polymer, the composition formula of the compound or polymer can be estimated based on the type of reaction raw materials, the amount of reaction raw materials used, reaction conditions, and the molecular weight of the product. In addition, when analyzing the compound or polymer to determine the composition formula of the compound or polymer, the composition formula can be determined using GPC (gel permeation chromatography), mass spectrometry, elemental analysis, infrared spectroscopy, etc.

[0123] The carbon content of the compound or polymer is calculated using the obtained composition formula of the compound or polymer. The carbon content represents the mass ratio of carbon in the compound or polymer. The carbon content can be obtained using the types of elements constituting the compound or polymer, the molar ratio of these elements, and the atomic weight of these elements. The carbon content can be obtained, for example, using the following formula.

[0124]

[0125] C atom : represents the molar ratio of carbon in the composition formula.

[0126] X 1，atom : represents the element X in the composition 1 The molar ratio of .

[0127] x 1 : represents element X 1 The atomic weight of .

[0128] X 2，atom : represents the element X in the composition 2 The molar ratio of .

[0129] x 2 : represents element X 2 The atomic weight of .

[0130] X n，atom : represents the element X in the composition n The molar ratio of .

[0131] x n : represents element X n The atomic weight of .

[0132] Here, as an example, the carbon atomic weight of benzene is determined.

[0133] The molecular formula of benzene is C 6 H 6 , the composition formula is CH. Therefore, the carbon atomic weight (%) of benzene is 100×12×1 / [12×1+1×1]=92.3%.

[0134] Next, as an example, the carbon atomic weight of the reaction product produced in Synthesis Example E described later was determined.

[0135] The reaction product produced in Synthesis Example E is composed of a structural unit of the following formula (A-5) except for the terminal.

[0136] Formula (A-5)

[0137]

[0138] The composition formula of the reaction product is composition formula C 21 H 23 O 7 N 3 Therefore, the carbon atomic weight (%) of the reaction product is 100×12×21 / [(12×21)+(1×23)+(16×7)+(14×3)]=58.7%.

[0139] It should be noted that in the case of certain compounds and polymers having a polysiloxane structure, the carbon content is reduced. This is because the ratio of silicon atoms to oxygen atoms in the polysiloxane structure is high. For example, -(Si(CH 2 ) 2 The carbon content of the -O)- unit is 33.3%.

[0140] The specific compound and polymer may or may not have a silicon atom.

[0141] The specific compound and polymer may or may not have a siloxane bond.

[0142] The specific compound and polymer may or may not have a polysiloxane structure.

[0143] The specific compound and polymer have a structure represented by formula (1), and preferably further have at least one of an alkylene group having 4 to 10 carbon atoms, an aliphatic hydrocarbon ring, a heterocyclic ring, and an aromatic hydrocarbon ring. From the viewpoint of appropriately obtaining the effects of the present invention, the specific compound and polymer more preferably have at least one of an alkylene group having 4 to 10 carbon atoms, an aliphatic hydrocarbon ring, and a heterocyclic ring.

[0144] The alkylene group having 4 to 10 carbon atoms may have a linear structure or a branched structure.

[0145] Examples of the aliphatic hydrocarbon ring include a five- to seven-membered aliphatic hydrocarbon ring.

[0146] The heterocyclic ring has, for example, a nitrogen atom, a carbon atom, an oxygen atom, and the like.

[0147] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring.

[0148] The specific compound and polymer preferably further have at least any one of the structure represented by the following formula (2), the structure represented by the following formula (3), and the structure represented by the following formula (4).

[0149]

[0150] (In formula (2), X 11 Represents a divalent group. 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group. * represents a bonding bond.

[0151] In formula (3), X 12 represents a divalent group. *, *1, and *1' represent a bond. Bond *1 is bonded to carbon atom *2 or carbon atom *3. Bond *1' is bonded to carbon atom *2' or carbon atom *3'.

[0152] In formula (4), X 13 and X 14 One of them represents a hydroxyl group, and the other represents a bond, and X 15 and X 16 One of them represents a hydroxyl group, and the other represents a bond. m1 represents 0 or 1. )

[0153] X in formula (2) 11 For example, it is any of the structure represented by the following formula (2-1) and the structure represented by the following formula (2-2).

[0154]

[0155] (In formula (2-1), Q 1 represents a divalent acyclic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom, a divalent organic group represented by the following formula (2-1-1), a divalent organic group represented by the following formula (2-1-2), a divalent organic group represented by the following formula (2-1-3), or a divalent organic group represented by the following formula (2-1-4). n1 and n2 each independently represent 0 or 1. * represents a bonding bond.

[0156] In formula (2-2), X21 Z represents a divalent group represented by any of the following formulae (2-2-1) to (2-2-4). 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (2-2-5).

[0157]

[0158] (In formulas (2-1-1) to (2-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. * represents a bonding bond.

[0159] In formula (2-1-1), 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 21 Optionally the same or different.

[0160] In formula (2-1-2), Z 11 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n12 and n13 each independently represent an integer of 0 to 4. 22 When there are two or more R 22 are optionally the same or different. 23 When there are two or more R 23 Optionally the same or different.

[0161] In formula (2-1-3), Z 12 and Z 13 Each independently represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms. n14 represents an integer of 0 to 4. 24 When there are two or more R 24 Optionally the same or different.

[0162] In formula (2-1-4), Z 14 Z represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. 15 and Z 16Each independently represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. 25 When there are two or more R 25 are optionally the same or different. 26 When there are two or more R 26 Optionally the same or different. )

[0163]

[0164] (In formulas (2-2-1) to (2-2-3), R 1 ~R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a 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. 1 and R 2 They are optionally bonded to each other to form a ring having 3 to 6 carbon atoms. 3 and R 4 They are optionally bonded to each other to form a ring having 3 to 6 carbon atoms.

[0165] In formula (2-2-4), Z 3 represents a single bond or a divalent group represented by the following formula (2-2-5). 7 , A 8 and A 9 Each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0166] * represents a bond. *1 represents a bond to a carbon atom in formula (2-2). *2 represents a bond to a nitrogen atom in formula (2-2).

[0167]

[0168] (In formula (2-2-5), m1 is an integer of 0 to 4, m2 is 0 or 1, m3 is 0 or 1, and m4 is an integer of 0 to 2. When m3 is 1, m1 and m2 are not simultaneously 0. *3 represents a bond to a nitrogen atom in formula (2-2) or formula (2-2-4). *4 represents a bond.)

[0169] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0170] In this specification, the alkyl group is not limited to a straight chain, and may be a branched chain or a cyclic chain. Examples of the straight chain or branched chain alkyl group include: methyl, ethyl, isopropyl, tert-butyl, n-hexyl, etc. Examples of the cyclic alkyl group (cycloalkyl group) include: cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0171] In the present specification, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-pentyloxy group, and an isopropoxy group.

[0172] In the present specification, examples of the alkylthio group include a methylthio group, an ethylthio group, a n-pentylthio group, an isopropylthio group, and the like.

[0173] In the present specification, examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl.

[0174] In the present specification, examples of the alkynyl group include groups in which the double bonds of the alkenyl groups exemplified above as the "alkenyl group" are replaced with triple bonds.

[0175] In the present specification, examples of the alkenyloxy group include a vinyloxy group, a 1-propenyloxy group, a 2-n-propenyloxy group (allyloxy group), a 1-n-butenyloxy group, and an isopentenyloxy group.

[0176] In the present specification, examples of the alkynyloxy group include a 2-propynyloxy group, a 1-methyl-2-propynyloxy group, a 2-methyl-2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.

[0177] In the present specification, examples of the acyl group include an acetyl group and a propionyl group.

[0178] In the present specification, examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0179] In the present specification, examples of the arylcarbonyl group include a phenylcarbonyl group and the like.

[0180] In the present specification, examples of the aralkyl group include a benzyl group and a phenethyl group.

[0181] In the present specification, examples of the alkylene group include a methylene group, an ethylene group, a 1,3-propylene group, a 2,2-propylene group, a 1-methylethylene group, a 1,4-butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2-ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2-ethyloctylene group, a 1,9-nonylene group, and a 1,10-decylene group.

[0182] As Q of formula (2-1) 1 The divalent acyclic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom may include, for example, an alkylene group having 2 to 10 carbon atoms, -CH 2 CH 2 -(OCH 2 CH 2 ) n -(n represents an integer from 1 to 9), -CH(CH 3 )CH 2 -(OCH(CH 3 )CH 2 ) n -(n represents an integer from 1 to 5), etc.

[0183] The alkylene group having 2 to 10 carbon atoms may be linear or branched.

[0184] As R in formulas (2-2-1) to (2-2-3) 1 ~R 5 Examples of the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkoxyalkoxyalkyl group having 3 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkylthioalkyl group having 2 to 10 carbon atoms.

[0185] Furthermore, the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom may contain two or more oxygen atoms or sulfur atoms.

[0186] Examples of the structure represented by formula (2-1) include the following structures.

[0187]

[0188] The above example is Q in formula (2-1) 1 This is an example of a divalent acyclic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom.

[0189]

[0190]

[0191]

[0192] (* indicates a bond.)

[0193] Examples of the structure represented by formula (2-2) include the following structures.

[0194]

[0195]

[0196]

[0197] (* indicates a bond.)

[0198] In formula (3), X 12 Represents a divalent group.

[0199] As X 12 Examples of divalent groups include: -C(=O)OCH 2 -, -NH-, -N=C=N-, etc.

[0200] Specific examples of the structure represented by formula (4) are as follows.

[0201]

[0202] (In formula (4-1) to formula (4-4), m1 represents 0 or 1. * represents a bonding bond.)

[0203] The specific compound and polymer preferably have at least any one of the structure represented by the following formula (1-2), the structure represented by the following formula (1-3), and the structure represented by the following formula (1-4) as the structure having the structure represented by the formula (1). The structure represented by the formula (1-2) may be a repeating unit in the polymer. The structure represented by the formula (1-3) may be a repeating unit in the polymer. The structure represented by the formula (1-4) may be a repeating unit in the polymer.

[0204]

[0205]

[0206] (In formula (1-2) to formula (1-4), X 1 , R 3 and n1 are each the same as X in formula (1) 1 , R3 And n1 have the same meaning.

[0207] In formula (1-2), X 11 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of them is the same as X in formula (2) 11 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Same meaning.

[0208] In formula (1-3), X 12 With X in formula (3) 12 Same meaning.

[0209] In formula (1-2) to formula (1-4), R 1 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[0210] In formulae (1-2) to (1-4), *, *1, *1', *4, and *5 represent bonds. Bond *1 is bonded to carbon atom *2 or carbon atom *3. Bond *1' is bonded to carbon atom *2' or carbon atom *3'.

[0211] In formula (1-4), X 13 and X 14 One of them represents a hydroxyl group, and the other represents a bond, X 15 and X 16 One of them represents a hydroxyl group and the other represents a bond. m1 represents 0 or 1. Formula (A) and Formula (B) are connected by the bond *4 or *5 in Formula (A) and X in Formula (B). 13 ~X 16 Any bond in the bond. )

[0212] Examples of the structure represented by formula (1-4) are as follows.

[0213]

[0214] (In formula (1-4-1) to formula (1-4-4), X 1 , R 1 , R 3 , m1 and n1 are respectively the same as X in formula (1-4)1 , R 1 , R 3 , m1 and n1 have the same meaning. * indicates a bonding bond. )

[0215] The weight average molecular weight of the compound or polymer is, for example, 300 to 100,000, preferably 800 to 50,000, more preferably 1,000 to 10,000, particularly preferably 1,200 to 5,000.

[0216] An example of a method for producing a specific compound and a polymer will be described.

[0217] An example of the specific compound and polymer can be obtained by, for example, the following reactions (I) to (II).

[0218] (I): Reaction of a compound represented by the following formula (1A) with at least one of a compound represented by the following formula (2A), a compound represented by the following formula (3A), and a compound represented by the following formula (4A).

[0219]

[0220] (In formula (1A), X 1A It represents a hydroxyl group or a carboxyl group.

[0221] In formula (1A), R 3 and n1 are respectively the same as R in formula (1) 3 Has the same meaning as n1.

[0222] In formula (1A), R 1 represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[0223] In formula (2A), X 11 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of them is the same as X in formula (2) 11 , A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Same meaning.

[0224] In formula (3A), X 12 With X in formula (3)12 The meanings are the same. *1 and *1' represent a bond. Bond *1 is bonded to carbon atom *2 or carbon atom *3. Bond *1' is bonded to carbon atom *2' or carbon atom *3'.

[0225] In formula (4A), m1 represents 0 or 1.

[0226] (II): Reaction of the compound represented by formula (1B) with at least any of the compound represented by formula (2A), the compound represented by formula (3A) and the compound represented by formula (4A).

[0227]

[0228] (In formula (1B), R 3 and n1 are respectively the same as R in formula (1) 3 Same meaning as n1. 1 and R 2 each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, or -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[0229] Examples of the compound represented by formula (1A) include the following compounds.

[0230]

[0231] Examples of the compound represented by formula (2A) include the following compounds.

[0232]

[0233] The above example is Q 1 This is an example of a divalent acyclic hydrocarbon group having 2 to 20 carbon atoms which may be interrupted by an oxygen atom.

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240] Examples of the compound represented by formula (3A) include the following compounds.

[0241]

[0242] Examples of the compound represented by formula (4A) include the following compounds.

[0243]

[0244] Examples of the compound represented by formula (1B) include the following compounds.

[0245]

[0246] In the formula, Me represents a methyl group.

[0247] Reactions (I) to (II) can be carried out in the presence of a catalyst. The catalyst is, for example, a quaternary phosphonium salt such as tetrabutylphosphonium bromide or ethyltriphenylphosphonium bromide; or a quaternary ammonium salt such as benzyltriethylammonium chloride. The amount of the catalyst used can be selected from a range of 0.1 to 10% by mass relative to the total mass of the reaction raw materials used in the reaction. The temperature and time of the reaction can be selected from the range of 80 to 160° C. and 2 to 50 hours for the best conditions.

[0248] The content of the specific compound and polymer in the release agent 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 constituent components in the release agent composition.

[0249] The film-constituting components refer to the components other than the solvent in the release agent composition.

[0250] <Cross-linking agent>

[0251] The release agent composition may also contain a crosslinking agent.

[0252] The crosslinking agent may also cause a crosslinking reaction by self-condensation. However, when a crosslinkable substituent exists in a specific compound or polymer, the crosslinking agent may cause a crosslinking reaction with the crosslinkable substituent.

[0253] Specific examples of crosslinking agents are not particularly limited, and typically include: phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, thiourea crosslinking agents, etc., which have crosslinking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl and other alkoxymethyl groups in the molecule. They can be low molecular weight compounds or high molecular weight compounds.

[0254] The crosslinking agent contained in the release agent composition generally has two or more crosslinking groups. From the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking groups contained in the compound as the crosslinking agent is preferably 2 to 10, more preferably 2 to 6.

[0255] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (eg, a benzene ring or a naphthalene ring) in the molecule. Typical examples of such a crosslinking agent include, but are not limited to, phenolic crosslinking agents.

[0256] The phenolic crosslinking agent having a crosslinking group refers to a compound having a crosslinking group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of such an alkoxy group derived from a phenolic hydroxyl group include, but are not limited to, a methoxy group and a butoxy group.

[0257] The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxyl group and / or the alkoxy group derived from the phenolic hydroxyl group is bonded are not limited to non-condensed aromatic rings such as benzene rings, but may be condensed aromatic rings such as naphthalene ring and anthracene ring.

[0258] When a plurality of aromatic rings are present in the molecule of the phenolic crosslinking agent, the crosslinking group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group may be bonded to the same aromatic ring in the molecule or to different aromatic rings.

[0259] The crosslinking group, the phenolic hydroxyl group, and the aromatic ring bonded to the alkoxy group derived from the phenolic hydroxyl group may be further substituted with a hydrocarbon group such as an alkyl group such as methyl, ethyl, or butyl; an aryl group such as phenyl; or a halogen atom such as a fluorine atom.

[0260] For example, specific examples of the phenolic crosslinking agent having a crosslinking-forming group include compounds represented by any of the formulae (L1) to (L4).

[0261]

[0262] In each formula, each R' independently represents a fluorine atom, an aryl group or an alkyl group, each R" independently represents a hydrogen atom or an alkyl group, and L 1 and L 2 Each independently represents a single bond, a methylene group or a propane-2,2-diyl group, L 3It is determined based on q1, represents a single bond, methylene, propane-2,2-diyl, methanetriyl or ethane-1,1,1-triyl, t11, t12 and t13 are integers satisfying 2≤t11≤5, 1≤t12≤4, 0≤t13≤3 and t11+t12+t13≤6, t21, t22 and t23 are integers satisfying 2≤t21≤4, 1≤t22≤3, 0≤t23≤2 and t21+t22+t23≤5, t24, t25 and t26 are integers satisfying 2≤t24≤4, 1≤t25≤3, 0≤t26≤2 and t24+t25+t26≤5, t27, t28 and t29 are integers satisfying 0 ≤t27≤4, 0≤t28≤4, 0≤t29≤4 and t27+t28+t29≤4, t31, t32 and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2 and t31+t32+t33≤5, t41, t42 and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1 and t41+t42+t43≤4, q1 is 2 or 3, q2 represents the number of repetitions and is an integer greater than 0. Specific examples of aryl and alkyl groups include the same groups as described below. As the aryl group, phenyl is preferred, and as the alkyl group, methyl and tert-butyl are preferred.

[0263] Specific examples of the compounds represented by formulae (L1) to (L4) are listed below, but are not limited thereto. It should be noted that these compounds can be synthesized by known methods, or can be obtained as products of, for example, Asahi Organic Materials Industries, Ltd. or Honshu Chemical Industries, Ltd.

[0264]

[0265]

[0266]

[0267] The melamine-based crosslinking agent having a crosslinking group refers to a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative or a 2-amino-1,3,5-triazine derivative in which at least one of the hydrogen atoms of the amino group bonded to the triazine ring is substituted with a crosslinking group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group.

[0268] Specific examples of melamine-based crosslinking agents having a crosslinking-forming group include, but are not limited to, mono-, di-, tri-, tetra-, penta- or hexa-alkoxymethyl melamines such as N,N,N',N',N",N"-hexa(methoxymethyl)melamine and N,N,N',N',N",N"-hexa(butoxymethyl)melamine; and mono-, di-, tri- or tetra-alkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N'-tetra(butoxymethyl)benzoguanamine.

[0269] The urea-based crosslinking agent having a crosslinking group refers to a derivative of a urea bond-containing compound having a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is substituted with a crosslinking group.

[0270] Specific examples of the urea crosslinking agent having a crosslinking group include, but are not limited to, mono-, di-, tri- or tetra-alkoxymethyl glycolurils such as 1,3,4,6-tetra(methoxymethyl) glycoluril and 1,3,4,6-tetra(butoxymethyl) glycoluril; and mono-, di-, tri- or tetra-alkoxymethyl ureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetramethoxymethylurea.

[0271] The thiourea-based crosslinking agent having a crosslinking group refers to a derivative of a thiourea bond-containing compound having a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is substituted with a crosslinking group.

[0272] Specific examples of the thiourea crosslinking agent having a crosslinking group include mono-, di-, tri- or tetra-alkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetramethoxymethylthiourea, but are not limited thereto.

[0273] The amount of the crosslinking agent contained in the stripping agent composition varies depending on the coating method adopted, the desired film thickness, etc., and therefore cannot be generally specified. It is usually 0.01 to 50% by mass relative to the specific compound and polymer. From the viewpoint of achieving appropriate curing and obtaining a laminate in which the semiconductor substrate or electronic device layer and the supporting substrate can be well separated with good reproducibility, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, further preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and further preferably 30% by mass or less.

[0274] <Acid generator and acid>

[0275] The release agent composition may contain an acid generator or an acid for the purpose of promoting a crosslinking reaction or the like.

[0276] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0277] The thermal acid generator is not particularly limited as long as it generates an acid by heat. Specific examples thereof include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG-2689, K-PURE TAG-2700 (manufactured by King Industries), SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters, but the present invention is not limited to these.

[0278] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0279] Specific examples of the onium salt compound include: iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, but are not limited to these.

[0280] Specific examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited thereto.

[0281] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0282] Specific examples of the acid include: p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid and other arylsulfonic acids, pyridinium salts, and their salts; salicylic acid, benzoic acid, hydroxybenzoic acid, naphthoic acid and other arylcarboxylic acids, and their salts; trifluoromethanesulfonic acid, camphorsulfonic acid and other chain or cyclic alkylsulfonic acids, and their salts; citric acid and other chain or cyclic alkylcarboxylic acids, and their salts, but are not limited to these.

[0283] The amounts of the acid generator and acid contained in the release agent composition vary depending on the type of crosslinking agent used, the heating temperature during film formation, etc., and therefore cannot be generally specified, but are usually 0.01 to 5% by mass based on the film constituent components.

[0284] <Surfactant>

[0285] The stripping agent composition may contain a surfactant for the purpose of adjusting the liquid properties of the composition itself, the film properties of the obtained film, or preparing a stripping agent composition with high uniformity with good reproducibility.

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

[0287] The surfactant may be used alone or in combination of two or more.

[0288] The amount of the surfactant is usually 2% by mass or less based on the film-constituting components of the release agent composition.

[0289] <Solvent>

[0290] The stripper composition contains a solvent.

[0291] As the solvent, for example, a high polarity solvent that can dissolve the above-mentioned specific compound and the film constituent components such as polymers and cross-linking agents well can be used. As required, a low polarity solvent can also be used for the purpose of adjusting the viscosity, surface tension, etc. It should be noted that in the present invention, a low polarity solvent refers to a solvent whose relative dielectric constant is less than 7 under a frequency of 100kHz, and a high polarity solvent refers to a solvent whose relative dielectric constant is more than 7 under a frequency of 100kHz. The solvent can be used alone or in combination of two or more.

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

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

[0294] The content of the solvent is appropriately determined in consideration of the desired viscosity of the composition, the coating method to be adopted, the thickness of the film to be produced, etc., and is less than 99% by mass of the entire composition, preferably 70 to 99% by mass relative to the entire composition, and more preferably 80 to 97% by mass relative to the entire composition. That is, the amount of the film constituent components in this case is preferably 1 to 30% by mass relative to the entire composition, and more preferably 3 to 20% by mass relative to the entire composition.

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

[0296] In one embodiment of the present invention, the release agent composition contains a glycol solvent from the viewpoint of obtaining a composition with high uniformity with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition providing a film with high uniformity with good reproducibility, etc. It should be noted that the "glycol solvent" referred to herein is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

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

[0298]

[0299] In formula (G), R G1 Each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, and R G2 and R G3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms, n g An integer from 1 to 6.

[0300] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, and hexamethylene.

[0301] Among them, from the viewpoint of obtaining a composition with high uniformity with good reproducibility, the viewpoint of obtaining a composition with high storage stability with good reproducibility, the viewpoint of obtaining a composition providing a film with high uniformity with good reproducibility, etc., a straight-chain or branched alkylene group having 2 to 3 carbon atoms is preferred, and a straight-chain or branched alkylene group having 3 carbon atoms is more preferred.

[0302] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl, The present invention includes, but is not limited to, n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl.

[0303] Among them, from the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, etc., a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0304] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same groups as mentioned above.

[0305] Among them, from the viewpoint of obtaining a composition having high uniformity with good reproducibility, from the viewpoint of obtaining a composition having high storage stability with good reproducibility, from the viewpoint of obtaining a composition providing a film having high uniformity with good reproducibility, etc., a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0306] From the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a highly stable composition with good reproducibility, obtaining a composition providing a highly uniform film with good reproducibility, etc., n g It is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and most preferably 1 or less.

[0307] From the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a highly stable composition with good reproducibility, obtaining a composition providing a highly uniform film with good reproducibility, etc., in formula (G), R is preferably G2 and R G3 At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R G2 and R G3One of them is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0308] From the viewpoint of obtaining a highly uniform composition with good reproducibility, the viewpoint of obtaining a composition with high storage stability with good reproducibility, the viewpoint of obtaining a composition that provides a highly uniform film with good reproducibility, etc., the content of the diol solvent is preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, further preferably 90 mass % or more, and further preferably 95 mass % or more, relative to the solvent contained in the stripping agent composition.

[0309] From the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition providing a highly uniform film with good reproducibility, etc., in the release agent composition, the film constituent components are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0310] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the release agent composition or after all components are mixed.

[0311] (Laminated body)

[0312] The laminated body of the present invention comprises a semiconductor substrate or an electronic device layer, a supporting substrate, and a release agent layer for release by light irradiation.

[0313] Preferably, the laminate of the present invention further has an adhesive layer, and has a structure including a semiconductor substrate or an electronic device layer, a supporting substrate, a release agent layer for release by light irradiation, and an adhesive layer.

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

[0315] The supporting substrate has light-transmitting properties.

[0316] The release agent layer for light irradiation release is provided between the semiconductor substrate or the electronic device layer and the support substrate.

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

[0318] The release agent layer for light irradiation removal is a layer formed of the above-mentioned release agent composition for light irradiation removal of the present invention.

[0319] The laminate of the present invention is used for temporary bonding in order to process a semiconductor substrate or an electronic device layer, and can be suitably used for processing such as thinning of a semiconductor substrate or an electronic device layer.

[0320] During the thinning process of the semiconductor substrate, the semiconductor substrate is supported by the supporting substrate. On the other hand, after the processing of the semiconductor substrate, the stripping agent layer is irradiated with light, and then the supporting substrate is separated from the semiconductor substrate. By the specific compounds and polymers contained in the stripping agent composition, in the stripping agent layer formed by the stripping agent composition, the specific compounds and polymers absorb light (such as laser) and cause the stripping agent layer to deteriorate (such as separate or decompose). As a result, after the stripping agent layer is irradiated with light, it is easy to peel off the semiconductor substrate from the supporting substrate.

[0321] Furthermore, the electronic device layer is supported by the support substrate while the electronic device layer is being processed such as being thinned. On the other hand, after the processing of the electronic device layer, the release agent layer is irradiated with light, and then the support substrate and the electronic device layer are separated.

[0322] The stripping agent layer of the present invention makes it easy to strip the semiconductor substrate or the electronic device layer from the supporting substrate after irradiation with light. Furthermore, after the semiconductor substrate or the electronic device layer and the supporting substrate are stripped, the residue of the stripping agent layer and the adhesive layer remaining on the semiconductor substrate, the electronic device layer, or the supporting substrate can be removed, for example, by a cleaning agent composition for cleaning the semiconductor substrate.

[0323] The wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the specific compound and polymer, such as decomposition.

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

[0325] The case where the laminated body has a semiconductor substrate and the case where the laminated body has an electronic device layer are described in detail below according to each case.

[0326] In the following <First Embodiment>, a case where the laminated body has a semiconductor substrate will be described, and in the following <Second Embodiment>, a case where the laminated body has an electronic device layer will be described.

[0327] <First embodiment>

[0328] The laminated body having the semiconductor substrate is used for processing the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to the support substrate. After the processing of the semiconductor substrate, the release agent layer is irradiated with light, and the semiconductor substrate is separated from the support substrate.

[0329] <<Semiconductor substrate>>

[0330] The main material constituting the entire semiconductor substrate is not particularly limited as long as it is a material used for such applications, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0331] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc. It should be noted that the surface of the disc-shaped semiconductor substrate does not need to be a perfect circle, and for example, the periphery of the semiconductor substrate may have a straight portion called an orientation flat, or may have a cutout called a notch.

[0332] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1000 μm.

[0333] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 100 to 1000 mm.

[0334] The semiconductor substrate may have a bump. A bump is a protruding terminal.

[0335] In the laminated body, when the semiconductor substrate has the bump, the semiconductor substrate has the bump on the supporting substrate side.

[0336] In a semiconductor substrate, bumps are usually formed on the surface where a circuit is formed. The circuit may be a single layer or a multilayer. There is no particular limitation on the shape of the circuit.

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

[0338] The material, size, shape, structure, and density of the bumps included in the semiconductor substrate are not particularly limited.

[0339] Examples of the bump include a ball bump, a printed bump, a stud bump, and a plated bump.

[0340] Normally, the height, radius, and pitch of the bumps are appropriately determined from conditions such as a bump height of about 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm.

[0341] Examples of materials for the bumps include low melting point solder, high melting point solder, tin, indium, gold, silver, copper, etc. The bumps may be made of a single component or a plurality of components. More specifically, SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy platings based on Sn may be included.

[0342] Furthermore, the bump may have a stacked structure including a metal layer made of at least any one of these components.

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

[0344] <<Support substrate>>

[0345] The supporting substrate is not particularly limited as long as it is a member that is light-transmissive to the light irradiated to the release agent layer and can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include glass supporting substrates.

[0346] The shape of the support substrate is not particularly limited, and an example thereof may be a disk shape.

[0347] The thickness of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 500 to 1000 μm.

[0348] The diameter of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 100 to 1000 mm.

[0349] An example of the supporting substrate is a glass wafer having 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 of a release agent composition.

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

[0353] The release agent layer may be in contact with the supporting substrate or may be in contact with the semiconductor substrate.

[0354] The release agent layer is formed using the above-mentioned release agent composition for light irradiation release of the present invention.

[0355] The stripping agent composition of the present invention can be suitably used to form a stripping agent layer of a laminate having a semiconductor substrate, a supporting substrate, and a stripping agent layer disposed between the semiconductor substrate and the supporting substrate. The laminate is used to strip the semiconductor substrate from the supporting substrate after the stripping agent layer absorbs light irradiated from the supporting substrate side.

[0356] One of the characteristics of the release agent layer obtained from the release agent composition of the present invention is that the semiconductor substrate and the supporting substrate can be easily peeled off after light irradiation.

[0357] When forming a release agent layer from the release agent composition, the specific compound and polymer may crosslink by themselves or react with other components to form a crosslinked structure, or may not crosslink or react and maintain the structure, as long as the effects of the present invention can be obtained.

[0358] In other words, in the release agent layer, the specific compound and polymer may form a crosslinked structure by crosslinking themselves or reacting with other components, or may exist while maintaining the structure.

[0359] The thickness of the release agent layer is not particularly limited and is generally 0.01 to 10 μm. From the viewpoint of maintaining film strength, it is preferably 0.05 μm or more, more preferably 0.1 μm or more, and further preferably 0.2 μm or more. From the viewpoint of avoiding unevenness caused by a thick film, it is preferably 10 μm or less, more preferably 8 μm or less, further preferably 5 μm or less, and further preferably 2 μm or less.

[0360] The method of forming the release agent layer from the release agent composition is described in detail in the explanation section of "Method for producing an example of a laminated body in the first embodiment" described below.

[0361] <<Adhesive layer>>

[0362] The adhesive layer is provided between the support substrate and the semiconductor substrate.

[0363] The adhesive layer is in contact with, for example, a semiconductor substrate. The adhesive layer may be in contact with, for example, a support substrate.

[0364] The adhesive layer is not particularly limited, but is preferably a layer formed of an adhesive composition.

[0365] <<Adhesive composition>>

[0366] Examples of the adhesive composition include silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives, but are not limited thereto.

[0367] Among them, silicone-based adhesives are preferred as adhesive compositions because they exhibit appropriate adhesion during processing of semiconductor substrates and the like, can be appropriately peeled off after processing, have excellent heat resistance, and can be appropriately removed by a cleaning composition.

[0368] In a preferred embodiment, the adhesive composition contains polyorganosiloxane.

[0369] Furthermore, in another preferred embodiment, the adhesive composition contains a component that cures by a hydrosilylation reaction.

[0370] For example, the adhesive composition used in the present invention contains a cured component (A) that becomes an adhesive component. The adhesive composition used in the present invention may also contain a cured component (A) that becomes an adhesive component and a component (B) that does not undergo a curing reaction. Here, as a component (B) that does not undergo a curing reaction, for example, polyorganosiloxane can be cited. It should be noted that in the present invention, "no curing reaction occurs" does not mean that no curing reaction occurs, but refers to a curing reaction that does not occur in the cured component (A).

[0371] In a preferred embodiment, the component (A) may be a component that is cured by a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0372] In another preferred embodiment, component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2). The alkenyl group having 2 to 40 carbon atoms may be optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0373] In another preferred embodiment, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises a catalyst selected from the group consisting of SiO 2 The siloxane units (Q units), R 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit), R 4 R 5 SiO 2 / 2 The siloxane units (D units) and R 6 SiO 3 / 2The polysiloxane (A1) comprises a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises a polysiloxane selected from SiO 2 The siloxane units (Q' units), R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane units (M' units), R 4 'R 5 'SiO 2 / 2 The siloxane units (D' units) and R 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of SiO 2 The siloxane units (Q" units), R 1 ”R 2 ”R 3 "SiO 1 / 2 The siloxane units (M" units), R 4 ”R 5 "SiO 2 / 2 The siloxane units (D" units) and R 6 "SiO 3 / 2 The siloxane units (T" units) shown in the figure contain one or more units selected from the group consisting of M" units, D" units and T" units.

[0374] It should be noted that (a1′) is an example of (a1), and (a2′) is an example of (a2).

[0375] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0376] R 1 '~R 6 ' is a group bonded to a silicon atom, each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6At least one of ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0377] R 1 ”~R 6 " is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group or a hydrogen atom, R 1 ”~R 6 " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like.

[0378] The alkyl group may be any of linear, branched, or cyclic, preferably linear or branched. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0379] Specific examples of the optionally substituted linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1- The present invention is not limited to dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among them, methyl is particularly preferred.

[0380] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, and 2,4-dimethylcyclobutyl. Cycloalkyl groups such as cyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl; bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, bicyclononyl, and dicyclodecyl, but are not limited to these, and the number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0381] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0382] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, pentenyl, etc., and the number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0383] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0384] As described above, the polysiloxane (A1) includes the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl groups contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction using a platinum group metal catalyst (A2) and cure. As a result, a cured film is formed.

[0385] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and comprises at least one selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0386] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include: (Q' units and M' units), (D' units and M' units), (T' units and M' units), (Q' units, T' units and M' units), but are not limited to these.

[0387] In addition, when the polyorganosiloxane (a1') includes two or more polyorganosiloxanes, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited to these.

[0388] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units and T" units, and contains at least one selected from the group consisting of M" units, D" units and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0389] Preferred combinations of two or more selected from the group consisting of "Q" units, "M" units, "D" units and "T" units include, but are not limited to, (M" units and "D" units), (Q" units and "M" units), and (Q" units, "T" units and "M" units).

[0390] The polyorganosiloxane (a1′) is composed of siloxane units having alkyl and / or alkenyl groups bonded to silicon atoms. 1 '~R 6 The ratio of alkenyl groups in all substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be set to an alkyl group.

[0391] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. 1 ”~R 6The ratio of all substituents and hydrogen atoms in the substituent atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 ”~R 6 " can be set to an alkyl group.

[0392] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si—H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0393] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0394] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxane (excluding the above-mentioned organosiloxane polymer) can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH (Co., Ltd.)) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgelSuperMultiporeHZ-H manufactured by TOSOH (Co., Ltd.), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko (Co., Ltd.)) used as a standard sample.

[0395] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and is usually 10 to 1,000,000 (mPa·s) each, and is preferably 50 to 10,000 (mPa·s) from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured at 25° C. using an E-type rotational viscometer.

[0396] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other by a hydrosilylation reaction to form a film. Therefore, the curing mechanism is different from the mechanism by a silanol group, and therefore, all siloxanes do not need to contain a functional group that forms a silanol group by hydrolysis, such as a silanol group or an alkoxy group.

[0397] In a preferred embodiment of the present invention, the adhesive composition contains a polyorganosiloxane component (A') and a platinum group metal catalyst (A2).

[0398] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si—H group of the polyorganosiloxane (a2).

[0399] Specific examples of the platinum-based metal catalyst include platinum-based catalysts such as platinum black, platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and bisacetoacetate platinum, but are not limited thereto.

[0400] Examples of the complex of platinum and olefins include a complex of divinyltetramethyldisiloxane and platinum, but the complex is not limited thereto.

[0401] The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually within a range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0402] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.

[0403] The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0404] The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect thereof, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0405] In one example of the adhesive composition used in the present invention, a component (B) that does not undergo a curing reaction and serves as a release agent component may be included together with the cured component (A). By including such a component (B) in the adhesive composition, the obtained adhesive layer can be appropriately peeled off with good reproducibility.

[0406] As such a component (B), a non-curable polyorganosiloxane is typically mentioned, and specific examples thereof include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, etc., but it is not limited to these.

[0407] In addition, as component (B), polydimethylsiloxane can be listed. The polydimethylsiloxane is optionally modified. As the optionally modified polydimethylsiloxane, for example, epoxy-containing polydimethylsiloxane, unmodified polydimethylsiloxane, phenyl-containing polydimethylsiloxane, etc. can be listed, but it is not limited to these.

[0408] Preferred examples of the polyorganosiloxane as the component (B) include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, and the like, but are not limited thereto.

[0409] The weight average molecular weight of the polyorganosiloxane as component (B) is not particularly limited, but is usually 100,000 to 2,000,000. From the viewpoint of achieving the effect of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. In addition, the dispersity thereof is not particularly limited, but is usually 1.0 to 10.0. From the viewpoint of achieving appropriate peeling with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight average molecular weight and dispersity can be measured by the above-mentioned method related to polyorganosiloxane.

[0410] The viscosity of the polyorganosiloxane as component (B) is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 / s. It should be noted that the viscosity of the polyorganosiloxane as the component (B) is represented by the kinematic viscosity, which is centistoke (cSt) = mm 2 / s. You can also divide the viscosity (mPa·s) by the density (g / cm 3 That is, it can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer, or it can be obtained from the kinematic viscosity (mm 2 / s) = viscosity (mPa·s) / density (g / cm 3 ) is calculated using this formula.

[0411] Examples of the epoxy-containing polyorganosiloxane include: 11 R 12 SiO 2 / 2 The siloxane units (D 10 Unit) polyorganosiloxane.

[0412] R 11 is a group bonded to a silicon atom, represents an alkyl group, and R 12 It is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include those described above.

[0413] The epoxy group in the organic group including an epoxy group may be an independent epoxy group without being condensed with other rings, or may be an epoxy group forming a condensed ring with other rings such as 1,2-epoxycyclohexyl group.

[0414] Specific examples of the organic group containing an epoxy group include a 3-glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group, but are not limited to these.

[0415] In the present invention, a preferred example of the epoxy-containing polyorganosiloxane is an epoxy-containing polydimethylsiloxane, but the present invention is not limited thereto.

[0416] The epoxy-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 10 Unit), but except D 10 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0417] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: 10 Polyorganosiloxane composed of units; containing D 10 Units and Q units of polyorganosiloxane; containing D 10 Units and M units of polyorganosiloxane; containing D 10 Units and T units of polyorganosiloxane; containing D 10 Unit, Q unit and M unit of polyorganosiloxane; containing D 10 Unit, M unit and T unit of polyorganosiloxane; containing D 10 Unit, Q unit, M unit and T unit of polyorganosiloxane, etc.

[0418] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight is not particularly limited but is usually 1,500 to 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0419] Specific examples of the epoxy-containing polyorganosiloxane include polyorganosiloxanes represented by formulae (E1) to (E3), but are not limited to these.

[0420]

[0421] (m 1 and n 1 represents the number of each repeating unit, which is a positive integer. )

[0422]

[0423] (m 2 and n 2 represents the number of each repeating unit, which is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms.

[0424]

[0425] (m 3 、n 3 and 3 represents the number of each repeating unit, which is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms.

[0426] Examples of the methyl group-containing polyorganosiloxane include: 210 R 220 SiO 2 / 2 The siloxane units (D 200 Units), preferably comprising R 21 R 21 SiO 2 / 2 The siloxane units (D 20 Units) of polyorganosiloxane.

[0427] R 210 and R 220 is a group bonded to a silicon atom, each independently represents an alkyl group, but at least one of them is a methyl group. Specific examples of the alkyl group include those described above.

[0428] R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include the above examples. 21 , preferably methyl.

[0429] In the present invention, polydimethylsiloxane is mentioned as a preferred example of the methyl group-containing polyorganosiloxane, but the present invention is not limited to this.

[0430] The methyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 200 Unit or D 20 Unit), but except D 200 Unit and D 20 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0431] In one embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 200 Polyorganosiloxane composed of units; containing D 200 Units and Q units of polyorganosiloxane; containing D 200 Units and M units of polyorganosiloxane; containing D200 Units and T units of polyorganosiloxane; containing D 200 Unit, Q unit and M unit of polyorganosiloxane; containing D 200 Unit, M unit and T unit of polyorganosiloxane; containing D 200 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0432] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 20 Polyorganosiloxane composed of units; containing D 20 Units and Q units of polyorganosiloxane; containing D 20 Units and M units of polyorganosiloxane; containing D 20 Units and T units of polyorganosiloxane; containing D 20 Unit, Q unit and M unit of polyorganosiloxane; containing D 20 Unit, M unit and T unit of polyorganosiloxane; containing D 20 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0433] Specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane represented by formula (M1), but the present invention is not limited thereto.

[0434]

[0435] (n 4 Represents the number of repeating units, which is a positive integer. )

[0436] Examples of the phenyl group-containing polyorganosiloxane include: 31 R 32 SiO 2 / 2 The siloxane units (D 30 Units) of polyorganosiloxane.

[0437] R 31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group, R 32 It is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those described above, and a methyl group is preferred.

[0438] The phenyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 30 Unit), but except D 30 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0439] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include:30 Polyorganosiloxane composed of units; containing D 30 Units and Q units of polyorganosiloxane; containing D 30 Polyorganosiloxane containing D 30 Units and T units of polyorganosiloxane; containing D 30 Unit, Q unit and M unit of polyorganosiloxane; containing D 30 Unit, M unit and T unit of polyorganosiloxane; containing D 30 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0440] Specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes represented by the formula (P1) or (P2), but are not limited to these.

[0441]

[0442] (m 5 and n 5 represents the number of each repeating unit, which is a positive integer. )

[0443]

[0444] (m 6 and n 6 represents the number of each repeating unit, which is a positive integer. )

[0445] The polyorganosiloxane as the release agent component (B) may be a commercially available product or a synthesized polyorganosiloxane.

[0446] Examples of commercially available polyorganosiloxanes include Wacker Chemie products such as the Wackersilicon Fluid AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000), GENIOPLAST GUM, Shin-Etsu Chemical Co., Ltd. dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995); Gelest Co., Ltd. epoxy-containing polyorganosiloxanes (trade names: CMS-227, ECMS-327); Shin-Etsu Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343); and Dow Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-102, KF-103, KF-104, KF-1056, X-22-347). Epoxy-containing polyorganosiloxane manufactured by Corning (BY16-839); phenyl-containing polyorganosiloxane manufactured by Gelest (PMM-1043, PMM-1025, PDM-0421, PDM-0821), phenyl-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (KF50-3000CS), phenyl-containing polyorganosiloxane manufactured by Momentive (TSF431, TSF433), etc., but not limited to these.

[0447] In one embodiment, the adhesive composition used in the present invention contains a curable component (A) and a non-curing component (B). In another embodiment, the adhesive composition contains a polyorganosiloxane as the component (B).

[0448] An example of the adhesive composition used in the present invention may contain component (A) and component (B) in an arbitrary ratio. If the balance between adhesion and releasability is taken into consideration, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A):(B)].

[0449] That is, when the polyorganosiloxane component (A') that cures by hydrosilylation reaction is included, the ratio of component (A') to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A'):(B)].

[0450] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s at 25° C., and preferably 1,000 to 10,000 mPa·s.

[0451] One example of the adhesive composition used in the present invention can be produced by mixing the component (A), the component (B) when used, and a solvent.

[0452] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing an adhesive composition, for example, there can be cited: a method of dissolving component (A) and component (B) in a solvent; a method of dissolving a part of component (A) and component (B) in a solvent, dissolving the rest in a solvent, and mixing the resulting solutions, but the method is not limited to these. It should be noted that when preparing the adhesive composition, it can also be heated appropriately within a range in which the components are not decomposed or deteriorated.

[0453] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the preparation of the adhesive composition or after all the components are mixed.

[0454] The thickness of the adhesive layer of 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 further preferably 30 μm or more. From the viewpoint of avoiding unevenness caused by a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and further preferably 70 μm or less.

[0455] The method of forming the adhesive layer from the adhesive composition is described in detail in the explanation section of "Method for producing an example of a laminated body in the first embodiment" described below.

[0456] Hereinafter, an example of the structure of the laminated body according to the first embodiment will be described using drawings.

[0457] Figure 1 The laminated body includes a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order.

[0458] The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0459] <<Method for producing an example of a laminate in the first embodiment>>

[0460] In the laminated body of the first embodiment, Figure 1 The following method for producing the laminate will be described using the laminate shown in FIG. 1 as an example.

[0461] An example of the laminate of the present invention can be produced by, for example, a method including the following first to third steps.

[0462] First step: a step of applying an adhesive composition on a semiconductor substrate to form an adhesive coating layer.

[0463] Second step: a step of applying a release agent composition on a supporting substrate to form a release agent layer.

[0464] Third step: a step of heating the adhesive coating layer in a state where the adhesive coating layer and the release agent layer are in contact with each other to form an adhesive layer.

[0465] The method for applying the adhesive composition is not particularly limited, but is usually spin coating. It is also possible to form a coating film separately by spin coating or the like to form a sheet-like coating film, and to attach the sheet-like coating film as the adhesive coating layer.

[0466] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive components contained in the adhesive composition, whether a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., and therefore cannot be generally specified, but is usually 80 to 150° C., and the heating time is usually 30 seconds to 5 minutes.

[0467] When the adhesive composition contains a solvent, the adhesive composition after application is usually heated.

[0468] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it as needed is usually about 5 to 500 μm, and is appropriately determined so that the thickness of the adhesive layer finally falls within the above-mentioned range.

[0469] The coating method of the release agent composition is not particularly limited, but is usually a spin coating method.

[0470] The heating temperature of the stripper composition after coating varies according to the type and amount of the stripper component contained in the stripper composition, the thickness of the desired stripper layer, etc., and therefore cannot be generally specified. From the perspective of achieving an appropriate stripper layer with good reproducibility, it is 80°C or more and 300°C or less, and the heating time is appropriately determined in the range of 10 seconds to 10 minutes according to the heating temperature. The heating temperature is preferably 100°C or more and 280°C or less, more preferably 150°C or more and 250°C or less. The heating time is preferably 30 seconds or more and 8 minutes or less, more preferably 1 minute or more and 5 minutes or less.

[0471] Heating can be performed using a hot plate, an oven, or the like.

[0472] The film thickness of the release agent layer obtained by applying the release agent composition and heating it as needed is usually about 5 nm to 100 μm.

[0473] In the present invention, such coating layers can be put together in a mutually contacting manner, and a load in the thickness direction of the semiconductor substrate and the supporting substrate is applied to make the two layers close to each other while performing a heating treatment or a decompression treatment or both, and then a post-heating treatment is performed, thereby obtaining the laminate of the present invention. It should be noted that the treatment conditions of any of the heating treatment, the decompression treatment, and the combination of the two are appropriately determined based on various situations such as the type of the adhesive composition, the specific composition of the stripper composition, the phase of the film obtained from the two compositions, the film thickness, and the bonding strength obtained.

[0474] The heating treatment temperature is usually appropriately determined within the range of 20 to 150° C. from the viewpoint of removing the solvent from the composition, softening the adhesive coating layer and achieving appropriate bonding with the release agent layer, etc. In particular, from the viewpoint of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), it is preferably 130° C. or less, more preferably 90° C. or less. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, and is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably achieving appropriate bonding, and is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other members.

[0475] The reduced pressure treatment may be performed by exposing the adhesive coating layer and the release agent layer in contact with each other to a gas pressure of 10 to 10000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

[0476] From the viewpoint of obtaining a laminated body in which the substrates can be well separated with good reproducibility, the two layers in contact with each other are preferably bonded together by a reduced pressure treatment, more preferably a combined heating treatment and a reduced pressure treatment.

[0477] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the two layers therebetween and allows them to be firmly adhered to each other, but is usually in the range of 10 to 1000N.

[0478] From the viewpoint of achieving a sufficient curing speed, the post-heating temperature is preferably 120° C. or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260° C. or lower.

[0479] From the perspective of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually more than 1 minute, preferably more than 5 minutes. From the perspective of suppressing or avoiding the adverse effects of excessive heating on the layers, the post-heating time is usually less than 180 minutes, preferably less than 120 minutes.

[0480] Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, the semiconductor substrate and the support substrate of the stack can be heated with either side facing downward. From the perspective of achieving appropriate peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.

[0481] It should be noted that one of the purposes of the post-heat treatment is to achieve a more appropriate adhesive layer and release agent layer as a self-supporting film, and in particular, to appropriately achieve curing by a hydrosilylation reaction.

[0482] Below, use Figure 2A to Figure 2C About Manufacturing Figure 1 An example of a method for forming a laminated body will be described.

[0483] Figure 2A to Figure 2C This is a diagram for explaining one method of manufacturing a laminated body.

[0484] First, a laminated body ( Figure 2A ). The laminate can be obtained, for example, by applying the adhesive composition on the semiconductor substrate 1 and heating it.

[0485] In addition, a laminated body ( Figure 2B ). The laminate can be obtained, for example, by applying a release agent composition on the supporting substrate 4 and heating it.

[0486] Next, Figure 2A The stack shown is Figure 2B The laminate shown is bonded in such a manner that the adhesive coating layer 2a is in contact with the release agent layer 3. Then, after a load is applied in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; heating plate) is arranged on the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive coating layer 2a, and the adhesive coating layer 2a is heated and cured by the heating device, and converted into the adhesive layer 2 ( Figure 2C ).

[0487] pass Figure 2A to Figure 2C The steps shown can obtain a laminated body.

[0488] It should be noted that in Figure 1In the embodiment, the laminate is sequentially laminated with a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a supporting substrate 4, so the above-mentioned manufacturing method is cited as an example, but for example, in the case of manufacturing a laminate in which a semiconductor substrate 1, a release agent layer 3, an adhesive layer 2, and a supporting substrate 4 are sequentially laminated, it can be manufactured by a method including the following steps: a first step, coating a release agent composition on the surface of the semiconductor substrate, heating it as needed to form a release agent layer; a second step, coating a release agent composition on the surface of the supporting substrate, heating it as needed to form an adhesive coating layer; and a third step, while subjecting the release agent layer of the semiconductor substrate and the adhesive coating layer of the supporting substrate to at least one of a heating treatment and a decompression treatment, a load is applied in the thickness direction of the semiconductor substrate and the supporting substrate to make them fit together, and then a post-heating treatment is performed to form a laminate.

[0489] It should be noted that, as long as the effects of the present invention are not impaired, the coating and heating of the respective compositions may be performed sequentially on either substrate.

[0490] <Second Implementation Method>

[0491] The laminate having the electronic device layer is used for processing the electronic device layer. During the processing of the electronic device layer, the electronic device layer is adhered to the support substrate. After the processing of the electronic device layer, the release agent layer is irradiated with light, and the electronic device layer is separated from the support substrate.

[0492] <<Electronic device layer>>

[0493] The electronic device layer refers to a layer having electronic devices, and in the present invention, refers to a layer in which a plurality of semiconductor chip substrates are buried in a sealing resin, that is, a layer including a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.

[0494] Here, "electronic device" refers to a member that constitutes at least a part of an electronic component. There are no particular restrictions on the electronic device, and it can be an electronic device in which various mechanical structures and circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a member composed of a metal or semiconductor and a resin that seals or insulates the member. The electronic device can be an electronic device in which a redistribution layer and / or a semiconductor element or other element described later is sealed or insulated with a sealing material or an insulating material, and has a single-layer or multi-layer structure.

[0495] <<Support substrate>>

[0496] As the supporting substrate, the same supporting substrate as that described in the column of <<Supporting substrate>> in the <First embodiment> is exemplified.

[0497] <<Release agent layer>>

[0498] The release agent layer is formed using the above-mentioned release agent composition for light irradiation release of the present invention.

[0499] The details of the release agent layer are as described in the above-mentioned <<Release agent layer>> section of the <First embodiment>.

[0500] <<Adhesive layer>>

[0501] The adhesive layer is formed using the above-mentioned adhesive composition.

[0502] The details of the adhesive layer are as described in the section of <<Adhesive layer>> in the <First embodiment>.

[0503] Hereinafter, an example of the structure of the laminated body according to the second embodiment will be described using drawings.

[0504] Figure 3 A schematic cross-sectional view showing an example of a laminate according to the second embodiment.

[0505] Figure 3 The laminated body includes a supporting substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26 in this order.

[0506] The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .

[0507] The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0508] In addition, another example of the structure of the laminated body of the second embodiment is shown in Figure 4 .

[0509] When the release agent layer of the present invention is a release agent layer having adhesive properties having both release and adhesive functions, the laminate may be formed of a single layer of a release agent layer having adhesive properties instead of a double layer of a release agent layer and an adhesive layer.

[0510] Figure 4 A schematic cross-sectional view showing another example of the laminated body.

[0511] Figure 4 The laminated body has a supporting substrate 24, a release agent layer 27 having adhesive properties, and an electronic device layer 26 in this order.

[0512] The release agent layer 27 having adhesive properties is provided between the support substrate 24 and the electronic device layer 26. The release agent layer 27 having adhesive properties can be produced by mixing components of a release agent composition forming a release agent with components of an adhesive composition forming an adhesive layer.

[0513] <<Method for producing an example of a laminated body in the second embodiment>>

[0514] In the laminated body of the second embodiment, Figure 3 Taking the laminate shown in the figure as an example, a method for producing the laminate will be described below.

[0515] The laminate of the present invention can be produced, for example, by a method including the following first to fifth steps.

[0516] First step: a step of applying a release agent composition on the surface of the support substrate to form a release agent coating layer (if necessary, further heating to form a release agent layer).

[0517] Second step: a step of applying an adhesive composition to the release agent coating layer or the surface of the release agent layer to form an adhesive coating layer (if necessary, further heating to form an adhesive layer).

[0518] The third step is a step of placing a semiconductor chip substrate on the adhesive coating layer or the adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer while performing at least one of a heating treatment and a reduced pressure treatment.

[0519] Fourth step: a step of forming an adhesive layer by subjecting the adhesive coating layer to post-heat treatment to cure the adhesive coating layer.

[0520] Fifth step: a step of sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin.

[0521] When the third step is described in more detail, for example, the step of the following embodiment (i) can be cited.

[0522] (i) placing a semiconductor chip substrate on an adhesive coating layer or an adhesive layer, applying a load in the thickness direction of the semiconductor chip substrate and the supporting substrate to make them closely fit together while performing at least one of a heating treatment and a decompression treatment, thereby bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer.

[0523] It should be noted that the fourth step can be performed after the semiconductor chip substrate is bonded to the adhesive coating layer in the third step, or can be performed together with the third step. For example, the semiconductor chip substrate is placed on the adhesive coating layer, and a load in the thickness direction of the semiconductor chip substrate and the supporting substrate is applied while the adhesive coating layer is heated to cure it, thereby performing the bonding of the semiconductor chip substrate and the adhesive coating layer and the curing of the adhesive coating layer to the adhesive layer at the same time, and the adhesive layer can be bonded to the semiconductor chip substrate.

[0524] The fourth step may be performed before the third step, or the semiconductor chip substrate may be placed on the adhesive layer and the adhesive layer and the semiconductor chip substrate may be bonded together while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0525] The coating method, the release agent composition to be coated, the heating temperature and heating method of the adhesive composition are the same as those described in the above-mentioned <<Method for producing an example of a laminated body in the first embodiment>> of the above-mentioned <First embodiment>.

[0526] The manufacturing method of the laminated body of the second embodiment is described in more detail below using the drawings. Figure 3 The stack shown.

[0527] like Figure 5A As shown, a release agent coating layer 23' made of a release agent composition is formed on a support substrate 24. At this time, the release agent coating layer 23' may be heated to form the release agent layer 23.

[0528] Then, if Figure 5B As shown, an adhesive coating layer 22' made of an adhesive composition is formed on the release coating layer 23' or the release layer 23. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22.

[0529] Then, if Figure 5C As shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22', and a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to make them close while performing at least one of a heating treatment and a decompression treatment, so that the semiconductor chip substrate 21 is attached to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is attached to the adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heating to form an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0530] It should be noted that when the adhesive coating layer 22 ′ is subjected to post-heat treatment, the release agent coating layer 23 ′ may be subjected to post-heat treatment at the same time to form the release agent layer 23 .

[0531] Then, if Figure 5D As shown, the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed with a sealing resin 25 . Figure 5D In the embodiment, a plurality of semiconductor chip substrates 21 temporarily bonded to a support substrate 24 via an adhesive layer 22 are sealed by a sealing resin 25. An electronic device layer 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22, so that the electronic device layer 26 becomes a base material layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0532] <<<Sealing process>>>

[0533] The semiconductor chip substrate 21 is sealed using a sealing material.

[0534] As a sealing material for sealing the semiconductor chip substrate 21, a member capable of insulating or sealing a member made of metal or semiconductor is used.

[0535] In the present invention, as the sealing material, for example, a resin composition (sealing resin) is used. The type of the sealing resin is not particularly limited as long as it can seal and / or insulate a metal or a semiconductor, and for example, epoxy resins or silicone resins are preferably used.

[0536] The sealing material may contain other components such as fillers in addition to the resin component. Examples of the filler include spherical silica particles.

[0537] In the sealing process, the sealing resin heated to, for example, 130 to 170° C. is supplied to the adhesive layer 22 in a manner that covers the semiconductor chip substrate 21 while maintaining a high viscosity, and compression molding is performed, thereby forming a layer composed of the sealing resin 25 on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170° C. In addition, the pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm 2 .

[0538] (Method for manufacturing processed semiconductor substrate or electronic device layer)

[0539] By using the laminated body of the present invention, a method for producing a processed semiconductor substrate or a method for producing a processed electronic device layer can be provided.

[0540] The "processed semiconductor substrate manufacturing method" uses the laminate described in the column of the above <First Embodiment> of the above (laminated body). In addition, the "processed electronic device layer manufacturing method" uses the laminate described in the column of the above <Second Embodiment> of the above (laminated body).

[0541] The “method for producing a processed semiconductor substrate” will be described in the following <Third Embodiment>, and the “method for producing a processed electronic device layer” will be described in the following <Fourth Embodiment>.

[0542] <Third Implementation Plan>

[0543] The method for producing a processed semiconductor substrate of the present invention includes the following fifth step A and the following sixth step A. The method for producing a processed electronic device layer may further include the following seventh step A.

[0544] Here, the fifth step A is a step of processing the semiconductor substrate in the laminated body described in the column of the above-mentioned <First Embodiment>.

[0545] In addition, the sixth A step is a step of separating the semiconductor substrate processed in the fifth A step from the support substrate.

[0546] In addition, the seventh A step is a step of cleaning the processed semiconductor substrate after the sixth A step.

[0547] In the fifth A step, the processing performed on the semiconductor substrate refers to, for example, the processing on the opposite side of the circuit surface of the wafer, and the thinning of the wafer by grinding the back side of the wafer can be cited. Then, for example, through silicon vias (TSV) are formed, and then the thinned wafer is peeled off from the supporting substrate to form a stack of wafers for three-dimensional mounting. In addition, for example, the formation of electrodes on the back side of the wafer is also performed before and after three-dimensional mounting. In the thinning and TSV processes of the wafer, heat of about 250 to 350°C is applied in a state bonded to the supporting substrate. The stack of the present invention generally includes an adhesive layer and has heat resistance to the load.

[0548] It should be noted that the processing is not limited to the above processing, and includes, for example, a semiconductor component mounting process when temporary bonding with a support substrate is performed in order to support a base material for mounting a semiconductor component.

[0549] In the sixth step A, the method of separating (peeling off) the semiconductor substrate from the supporting substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the peeling agent layer with light, peeling by tearing between the supporting body and the semiconductor chip, etc.

[0550] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the semiconductor substrate from the support substrate.

[0551] It is not necessary to irradiate the release agent layer with light to the entire area of ​​the release agent layer. Even if the area irradiated with light and the area not irradiated with light are mixed, as long as the peeling ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the supporting substrate by a slight external force such as pulling up the supporting substrate. The ratio and positional relationship of the area irradiated with light and the area not irradiated with light vary depending on the type of adhesive used, its specific composition; the thickness of the adhesive layer; the thickness of the adhesive layer; the thickness of the release agent layer; the intensity of the irradiated light, etc., but if a person skilled in the art is skilled in the art, appropriate conditions can be set without excessive experiments. Due to such a situation, according to the method for manufacturing a processed semiconductor substrate of the present invention, for example, when the supporting substrate of the stacked body used is light-transmissive, the light irradiation time can be shortened when peeling is performed by irradiating light from the supporting substrate side. As a result, not only can an improvement in throughput be expected, but also physical stress used for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the supporting substrate only by irradiation with light.

[0552] Generally, the irradiation dose of light used for peeling is 50 to 3000 mJ / cm 2 The irradiation time is appropriately determined according to the wavelength and the irradiation amount.

[0553] As described above, the wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the specific compound and polymer, such as decomposition.

[0554] The light used for stripping can be laser or non-laser emitted from a light source such as ultraviolet lamp.

[0555] The cleaning composition may be sprayed on the surface of at least any one of the separated semiconductor substrate and the supporting substrate, or the separated semiconductor substrate or the supporting substrate may be immersed in the cleaning composition to clean the substrate.

[0556] In addition, the surface of a processed semiconductor substrate or the like can also be cleaned using a removal tape or the like.

[0557] As an example of cleaning the substrate, a seventh A step of cleaning the processed semiconductor substrate may be performed after the sixth A step.

[0558] Examples of the cleaning agent composition used for cleaning include the following.

[0559] Cleaner compositions typically contain a solvent.

[0560] Examples of the solvent include lactones, ketones, polyols, compounds having an ester bond, derivatives of polyols, cyclic ethers, esters, and aromatic organic solvents.

[0561] Examples of the lactones include γ-butyrolactone and the like.

[0562] Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, and 2-heptanone.

[0563] Examples of the polyols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.

[0564] As a compound which has an ester bond, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate etc. are mentioned, for example.

[0565] Examples of derivatives of polyols include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., of the above-mentioned polyols or compounds having an ester bond, or compounds having an ether bond such as monophenyl ether. Among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.

[0566] Examples of the cyclic ethers include dioxane and the like.

[0567] Examples of the esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.

[0568] Examples of the aromatic organic solvent include anisole, benzyl ethyl ether, methyl anisole, diphenyl ether, dibenzyl ether, phenethyl ether, phenbutyl ether, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropyl toluene, and mesitylene.

[0569] These can be used alone or in combination of two or more.

[0570] Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0571] In addition, a mixed solvent of PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined in consideration of the compatibility of PGMEA and the polar solvent, and is preferably within the range of 1:9 to 9:1, and more preferably within the range of 2:8 to 8:2.

[0572] For example, when EL is used as a polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. In addition, when PGME is used as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. In addition, when PGME and cyclohexanone are used as polar solvents, the mass ratio of PGMEA:(PGME+cyclohexanone) is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0573] The cleaning composition may or may not contain a salt, but preferably contains no salt from the viewpoint of improving versatility in processing a semiconductor substrate using the laminate and from the viewpoint of reducing costs.

[0574] As an example of the case where the cleaning composition contains a salt, there is a cleaning composition containing a quaternary ammonium salt and a solvent.

[0575] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for such a purpose.

[0576] As such quaternary ammonium cations, tetra(alkyl)ammonium cations are typically mentioned. On the other hand, as anions forming pairs with them, hydroxide ions (OH － );Fluoride ion (F － ), chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ion (BF 4 － );Hexafluorophosphate ion (PF 6 － ), etc., but are not limited to these.

[0577] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0578] In the quaternary ammonium salt, the halogen atom may be contained in the cation or in the anion, but is preferably contained in the anion.

[0579] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0580] Specific examples of the hydrocarbon group in tetrahydrocarbyl ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

[0581] In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.

[0582] Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Among them, tetrabutylammonium fluoride is preferred.

[0583] A quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used in the form of a hydrate. In addition, a quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used alone or in combination of two or more.

[0584] The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the cleaning composition, but is generally 0.1 to 30% by mass based on the cleaning composition.

[0585] When the cleaning composition contains a salt, the solvent used in combination is not particularly limited as long as it can be used for such an application and dissolves salts such as quaternary ammonium salts. However, from the viewpoint of obtaining a cleaning composition having excellent cleaning properties with good reproducibility, and from the viewpoint of dissolving salts such as quaternary ammonium salts well to obtain a cleaning composition with excellent uniformity, the cleaning composition preferably contains one or more amide solvents.

[0586] As a preferred example of the amide solvent, an amide derivative represented by formula (Z) can be mentioned.

[0587]

[0588] In the formula, R 0 R represents ethyl, propyl or isopropyl, preferably ethyl or isopropyl, more preferably ethyl. A and R B Each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be any of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl. A and R B , preferably methyl or ethyl, more preferably both are methyl or ethyl, further preferably both are methyl.

[0589] Examples of the amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutanamide, N,N-diethylbutanamide, N-ethyl-N-methylbutanamide, N,N-dimethylisobutanamide, N,N-diethylisobutanamide, and N-ethyl-N-methylisobutanamide. Among them, N,N-dimethylpropanamide and N,N-dimethylisobutanamide are particularly preferred, and N,N-dimethylpropanamide is more preferred.

[0590] The amide derivative represented by the formula (Z) can be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product can be used.

[0591] Another example of a preferred amide solvent includes a lactam compound represented by formula (Y).

[0592]

[0593] In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 It represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and n-butyl, and specific examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene, but are not limited thereto.

[0594] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, and the like, and these may be used alone or in combination of two or more.

[0595] In a preferred embodiment, the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, contains N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment, contains N-methylpyrrolidone (NMP).

[0596] It should be noted that the cleaning composition used in the present invention may also contain water as a solvent, but from the perspective of avoiding corrosion of the substrate, etc., it is generally intended to use only organic solvents as solvents. It should be noted that in this case, the cleaning composition may contain hydration water of salt and a trace amount of water contained in the organic solvent, but this is not to deny it. The water content of the cleaning composition used in the present invention is usually 5% by mass or less.

[0597] The constituent elements and method elements related to the above-mentioned steps of the method for manufacturing a processed semiconductor substrate of the present invention may be variously modified without departing from the gist of the present invention.

[0598] The method for producing a processed semiconductor substrate of the present invention may include steps other than the above-mentioned steps.

[0599] In the peeling method of the present invention, when the semiconductor substrate or the supporting substrate of the laminated body of the present invention is light-transmissive, the semiconductor substrate and the supporting substrate of the laminated body are separated by irradiating the peeling agent layer with light from the semiconductor substrate side or the supporting substrate side.

[0600] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and releasably by the adhesive layer and the release agent layer, so that, for example, when the support substrate is light-transmissive, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Usually, the peeling is performed after the semiconductor substrate of the laminate is processed.

[0601] use Figure 6A to Figure 6D An example of the third embodiment will be described. This example is an example of manufacturing a thinned semiconductor substrate.

[0602] First, prepare a laminate ( Fig. 6A ). The laminate is Figure 1 and Figure 2C The stack shown is the same stack.

[0603] Next, a polishing device (not shown) is used to polish the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2, so that the semiconductor substrate 1 is thinned ( Figure 6B ) It should be noted that the thinned semiconductor substrate 1 may be subjected to formation of through electrodes and the like.

[0604] Next, after the release agent layer 3 is irradiated with light from the support substrate 4 side, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4 ( Figure 6C ).

[0605] In this way, a thinned semiconductor substrate 1 ( Fig.6D ).

[0606] Here, residues of the adhesive layer 2 and the release agent layer 3 may remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 with a cleaning composition to remove the residues of the adhesive layer 2 and the release agent layer 3 from the semiconductor substrate 1.

[0607] <Fourth Implementation Plan>

[0608] The method for producing a processed electronic device layer of the present invention includes the following fifth step B and the following sixth step B. The method for producing a processed electronic device layer may further include the following seventh step B.

[0609] Here, the fifth step B is a step of processing the electronic device layer in the laminate described in the above-mentioned <Second embodiment> section.

[0610] In addition, the sixth B step is a step of separating the electronic device layer processed in the fifth B step from the support substrate.

[0611] In addition, the seventh B step is a step of cleaning the processed electronic device layer after the sixth B step.

[0612] Below, use Figure 7A to Figure 7F A specific example of the fourth embodiment will be described.

[0613] Examples of the processing performed on the electronic device layer in the fifth B step include a grinding step and a wiring layer forming step.

[0614] <<Grinding process>>

[0615] The grinding step is a step of grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 so that a portion of the semiconductor chip substrate 21 is exposed.

[0616] Grinding of sealing resin parts, for example Figure 7B As shown, by Fig. 7A The sealing resin 25 layer of the laminated body shown is ground to a thickness substantially the same as that of the semiconductor chip substrate 21. Fig. 7A The stack shown is with Figure 3 and Figure 5D The stack shown is the same stack.

[0617] <<Wiring layer formation process>>

[0618] The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding step.

[0619] Figure 7C In the embodiment, a wiring layer 28 is formed on an electronic device layer 26 including a semiconductor chip substrate 21 and a sealing resin 25 .

[0620] The wiring layer 28 is also called RDL (Redistribution Layer), which is a thin-film wiring body that constitutes wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer can be made of a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) on a dielectric (silicon oxide (SiO X ), photosensitive resin such as photosensitive epoxy, etc.) to form a wiring layer, but is not limited to this.

[0621] As a method of forming the wiring layer 28 , for example, the following method can be cited.

[0622] First, silicon oxide (SiO X ), photosensitive resin and other dielectric layers. The dielectric layer composed of silicon oxide can be formed by, for example, sputtering, vacuum evaporation, etc. The dielectric layer composed of photosensitive resin can be formed by, for example, applying photosensitive resin on the layer of sealing resin 25 by spin coating, dipping, roller blade, spray coating, slit coating, etc.

[0623] Next, wiring is formed on the dielectric layer using a conductor such as a metal. As a method for forming wiring, for example, a known semiconductor process method such as a lithography process such as photolithography (resist lithography) and an etching process can be used. As such a lithography process, for example, a lithography process using a positive resist material and a lithography process using a negative resist material can be listed.

[0624] In the method for manufacturing the laminated body of the fourth embodiment, bumps may be further formed or components may be mounted on the wiring layer 28. The components may be mounted on the wiring layer 28 using, for example, a chip mounter or the like.

[0625] The laminated body of the fourth embodiment may be a laminated body produced by a process based on a fan-out technology in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer extending outside a chip region.

[0626] In the sixth step B, the method of separating (peeling off) the electronic device layer from the supporting substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the peeling agent layer with light, peeling by tearing between the supporting body and the electronic device layer, etc.

[0627] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the electronic device layer from the support substrate.

[0628] Figure 7D to Figure 7Eis a schematic cross-sectional view for explaining a method for separating a laminated body. Figure 7F This is a schematic cross-sectional view for explaining a method for cleaning a laminated body after separation. Figure 7D to Figure 7F , which can illustrate an embodiment of a method for manufacturing a semiconductor package (electronic component).

[0629] like Fig.7D As shown in FIG. 1 , the step of separating the laminated body is a step of irradiating the release agent layer 23 with light (arrow) via the support substrate 24 to modify the release agent layer 23 , thereby separating the electronic device layer 26 from the support substrate 24 .

[0630] After the release agent layer 23 is irradiated with light (arrow) to deteriorate the release agent layer 23, Fig. 7E As shown, the support substrate 24 is separated from the electronic device layer 26 .

[0631] The conditions and method of irradiating the adhesive layer with light are the same as those described in the above-mentioned section of <Third Embodiment>.

[0632] The substrate may be cleaned by spraying the cleaning composition on the surface of at least any one of the separated electronic device layer and the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition.

[0633] In addition, the surface of the processed electronic device layer or the like can also be cleaned using a removal tape or the like.

[0634] For example, in Fig. 7E In the embodiment, after the separation step, the adhesive layer 22 and the release agent layer 23 are attached to the electronic device layer 26, but by using a cleaning agent composition such as an acid or an alkali to decompose the adhesive layer 22 and the release agent layer 23, the adhesive layer 22 and the release agent layer 23 can be removed. By removing the release agent layer and the adhesive layer, the following can be appropriately obtained: Figure 7F The processed electronic device layer (electronic component) is shown.

[0635] The constituent elements and method elements related to the above-mentioned steps of the method for producing a processed electronic device layer of the present invention may be variously modified without departing from the gist of the present invention.

[0636] The method for producing a processed electronic device layer of the present invention may include steps other than the above-mentioned steps.

[0637] In the laminate of the present invention, the electronic device layer and the supporting substrate are temporarily bonded appropriately and releasably by the adhesive layer, so that, for example, when the supporting substrate is light-transmissive, the electronic device layer and the supporting substrate can be easily separated by irradiating light to the release agent layer from the supporting substrate side of the laminate. Usually, the peeling is performed after the electronic device layer of the laminate is processed.

[0638] Example

[0639] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0640] [Device]

[0641] (1) Mixer: ARE-500, a rotary and revolving mixer manufactured by THINKY Co., Ltd.

[0642] (2) Viscometer: TVE-22H rotary viscometer manufactured by Toki Sangyo Co., Ltd.

[0643] (3) Vacuum bonding device: automatic bonding machine manufactured by SUSS MicroTec Co., Ltd.

[0644] (4) Film thickness measurement: DEKTAK XT-A manufactured by BRUKER.

[0645] (5) Laser irradiation device: IPEX-848 manufactured by Light Machinery Co., Ltd.

[0646] [Measurement conditions of molecular weight]

[0647] The weight average molecular weight of the resin composition was measured using a GPC apparatus (HLC-8320GPC manufactured by TOSOH Corporation) and a GPC column (TSKgel Super-Multipore HZ-N (2 columns)), with the column temperature set to 40°C, tetrahydrofuran (THF) used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) used as a standard sample.

[0648] [1] Preparation of adhesive composition

[0649] [Preparation Example 1]

[0650] Into a 600 mL container dedicated to the stirrer, 80 g of an MQ resin containing a polysiloxane skeleton and a vinyl group (manufactured by Wacker Chemie), 2.52 g of a SiH group-containing linear polydimethylsiloxane with a viscosity of 100 mPa·s (manufactured by Wacker Chemie), 5.89 g of a SiH group-containing linear polydimethylsiloxane with a viscosity of 70 mPa·s (manufactured by Wacker Chemie), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added, and the mixture was stirred for 5 minutes using the stirrer to obtain a mixture (I).

[0651] 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa·s were stirred for 5 minutes using the above stirrer to obtain a mixture (II).

[0652] 3.96 g of the obtained mixture (II) was added to the mixture (I), and the mixture was stirred for 5 minutes using the stirrer to obtain a mixture (III).

[0653] Finally, the obtained mixture (III) was filtered through a 300-mesh nylon filter to obtain an adhesive composition.

[0654] [2] Synthesis of resin composition

[0655] [Synthesis Example A]

[0656] 5.00 g of neopentyl glycol glycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOLEX-211L), 3.37 g of α-cyano-4-hydroxycinnamic acid, 0.29 g of tetrabutylphosphonium bromide and 34.65 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to the same mass of the solid matter of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-1), and the weight average molecular weight was 1923 when measured by the above method.

[0657] Formula (A-1)

[0658]

[0659] [Synthesis Example B]

[0660] 5.00 g of 1,4-cyclohexanedimethanol diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX-216L), 3.37 g of α-cyano-4-hydroxycinnamic acid, 0.29 g of tetrabutylphosphonium bromide and 34.65 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to the same mass of the solid matter of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-2), and the weight average molecular weight was 1810 when measured by the above method.

[0661] Formula (A-2)

[0662]

[0663] [Synthesis Example C]

[0664] 5.00 g of hydrogenated bisphenol A diglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOLEX-252), 2.34 g of α-cyano-4-hydroxycinnamic acid, 0.20 g of tetrabutylphosphonium bromide and 30.14 g of propylene glycol monomethyl ether PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to the same mass of the solid matter of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-3), and the weight average molecular weight was 2080 when measured by the above method.

[0665] Formula (A-3)

[0666]

[0667] [Synthesis Example D]

[0668] 5.00 g of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: CEL2021P), 2.34 g of α-cyano-4-hydroxycinnamic acid, 0.20 g of tetrabutylphosphonium bromide and 30.14 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 to obtain a solution containing the reaction product in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-4), and the weight average molecular weight was 1500 when measured by the above method.

[0669] Formula (A-4)

[0670]

[0671] [Synthesis Example E]

[0672] 15.00 g of a 30% by mass PGME solution of 5,5-dimethyl-1,3-bis(oxiranylmethyl)imidazolidine-2,4-dione, 3.78 g of α-cyano-4-hydroxycinnamic acid, 0.32 g of tetrabutylphosphonium bromide and 24.09 g of PGME were added to a flask to prepare a raw material mixture, which was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, followed by stirring 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 to obtain a solution containing the reaction product in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-5), and the weight average molecular weight was 1964 when measured by the above method.

[0673] Formula (A-5)

[0674]

[0675] [Synthesis Example F]

[0676] 5.00 g of diglycidyl terephthalate (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX711), 3.43 g of α-cyano-4-hydroxycinnamic acid, 0.29 g of tetrabutylphosphonium bromide and 34.90 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 to obtain a solution containing the reaction product in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product is equivalent to the following formula (A-6), and the weight average molecular weight was 2135 when measured by the above method.

[0677] Formula (A-6)

[0678]

[0679] [Synthesis Example G]

[0680] 5.00 g of 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl (Mitsubishi Chemical Co., Ltd., trade name: YX4000), 2.56 g of α-cyano-4-hydroxycinnamic acid, 0.23 g of tetrabutylphosphonium bromide and 31.16 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105° C. for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-7), and as a result of measurement by the above-mentioned method, the weight average molecular weight thereof was 2730.

[0681] Formula (A-7)

[0682]

[0683] [Synthesis Example H]

[0684] 5.00 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene (manufactured by DIC Corporation, trade name: HP-4032D), 2.56 g of α-cyano-4-hydroxycinnamic acid, 0.23 g of tetrabutylphosphonium bromide and 31.16 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105° C. for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 to obtain a solution containing the reaction product in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-8), and the weight average molecular weight was 2295 when measured by the above method.

[0685] Formula (A-8)

[0686]

[0687] [Synthesis Example 1]

[0688] 6.00 g of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel, trade name: CEL2021P), 3.90 g of trans-4-hydroxycinnamic acid, 0.38 g of tetrabutylphosphonium bromide and 41.11 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 to obtain a solution containing the reaction product in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-9), and the weight average molecular weight was 1532 when measured by the above method.

[0689] Formula (A-9)

[0690]

[0691] [Synthesis Example J]

[0692] 20.00 g of a 30% by mass PGME solution of 5,5-dimethyl-1,3-bis(oxiranylmethyl)imidazolidine-2,4-dione, 4.37 g of trans-4-hydroxycinnamic acid, 0.43 g of tetrabutylphosphonium bromide and 29.45 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to the same mass of the solid matter of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-10), and the weight average molecular weight was 3546 when measured by the above method.

[0693] Formula (A-10)

[0694]

[0695] [Synthesis Example K]

[0696] 5.00 g of diglycidyl terephthalate (manufactured by Nagase ChemteX Co., Ltd., trade name: DENACOL EX711), 2.98 g of trans-4-hydroxycinnamic acid, 0.29 g of tetrabutylphosphonium bromide and 33.08 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to the same mass of the solid matter of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-11), and the weight average molecular weight was 2728 when measured by the above method.

[0697] Formula (A-11)

[0698]

[0699] [Synthesis Example L]

[0700] 6.00 g of 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl (Mitsubishi Chemical Co., Ltd., trade name: YX4000), 2.80 g of trans-4-hydroxycinnamic acid, 0.28 g of tetrabutylphosphonium bromide and 36.30 g of PGME were added to a flask to prepare a raw material mixture, and the raw material mixture was heated to reflux at 105°C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, a cation exchange resin and an anion exchange resin were added to the obtained reaction mixture, and 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 to obtain a solution containing the reaction product in the form of a filtrate. It should be noted that the amount of the cation exchange resin and the amount of the anion exchange resin were each set to be the same as the solid mass of the raw material mixture initially prepared. The obtained reaction product corresponds to the following formula (A-12), and as a result of measurement by the above-mentioned method, the weight average molecular weight thereof was 4619.

[0701] Formula (A-12)

[0702]

[0703] [Synthesis Example M]

[0704] Into a flask were added 56.02 g of N-phenyl-1-naphthylamine, 50.00 g of 1-pyrenecarboxaldehyde, 6.67 g of 4-(trifluoromethyl)benzaldehyde and 2.46 g of methanesulfonic acid, and then 86.36 g of 1,4-dioxane and 86.36 g of toluene were added, followed by reflux stirring for 18 hours under a nitrogen atmosphere.

[0705] After the obtained reaction mixture was cooled, 96 g of tetrahydrofuran was added for dilution, and the obtained dilution solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was recovered by filtering, and the filtrate was washed with methanol and dried under reduced pressure at 60° C. to obtain 72.12 g of a reaction product. The obtained reaction product was equivalent to the following formula (A-13), and the weight average molecular weight was 1100 when measured by the above method.

[0706] Formula (A-13)

[0707]

[0708] [3] Preparation of stripping agent composition

[0709] [Example 1-1]

[0710] PGME was added so that the solid content of the resin solution obtained in Synthesis Example A would be 6% by mass, thereby obtaining a release agent composition.

[0711] [Example 1-2] to [Example 1-12]

[0712] A release agent composition having a solid content of 6% by mass was obtained by the same procedure as in Example 1-1 except that the resin solutions obtained in Synthesis Examples B to L were respectively used as the resin solution.

[0713] [Comparative Example 1-1]

[0714] The resin obtained in Synthesis Example M was dissolved in propylene glycol monomethyl ether acetate so that the solid content was 6% by mass, thereby obtaining a release agent composition.

[0715] [4] Manufacturing of laminated body

[0716] [Example 2-1] to [Example 2-12], [Comparative Example 2-1]

[0717] The release agent composition obtained in Examples 1-1 to 1-12 and Comparative Example 1-1 was spin-coated on a 300 mm glass wafer (EAGLE-SG, manufactured by Corning, thickness 700 μm) serving as a substrate on the carrier side so that the film thickness in the final laminate was 250 nm, and fired at 200° C. for 5 minutes to form a release agent coating layer on the glass wafer.

[0718] On the other hand, the adhesive composition obtained in Preparation Example 1 was spin-coated on a 300 mm silicon wafer (thickness 775 μm) serving as a substrate on the device side so that the film thickness in the final obtained laminate was 65 μm, thereby forming an adhesive coating layer on the silicon wafer serving as a semiconductor substrate.

[0719] Then, a laminating device was used to laminate the glass wafer and the silicon wafer in a manner of sandwiching the release agent coating layer and the adhesive coating layer, and then post-heating was performed at 200° C. for 10 minutes to produce a laminate. It should be noted that the laminating was performed at a temperature of 23° C., a reduced pressure of 1000 Pa, and a load of 30 N was applied. The obtained laminate was cut into 4 cm squares using a cutting device.

[0720] [5] Calculation of carbon content

[0721] The carbon content of the resin obtained in [Synthesis Example A] to [Synthesis Example M] was calculated by the following formula. The results are shown in Tables 1-1 to 1-5.

[0722] The composition formula of the resin is C i H ii N iii O iv F v hour,

[0723] (Carbon content) (%) = (12×i)×100 / (12×i+1×ii+14×iii+16×iv+19×v).

[0724] [6] Confirmation of peelability

[0725] Using a laser irradiation device, irradiate the release agent layer with a laser of a wavelength of 308 nm from the glass wafer side of the fixed laminate at various irradiation doses shown in Tables 1-1 to 1-3. Then, manually pull up the support substrate to confirm whether it can be peeled off. The case where the silicon wafer can be peeled off without damage is set as "0", and the case where it cannot be peeled off is set as "×". The results of peeling are shown in Tables 1-1 to 1-5.

[0726] [7] Confirmation of cleaning performance

[0727] The glass substrate (glass wafer) obtained after laser stripping was immersed in PGME 7 mL for 5 minutes, and the cleaned substrate was obtained by air drying. In order to judge whether it can be cleaned, the cleaned glass substrate was observed under an optical microscope, and the case where no residue of the stripping agent layer was observed was set as "0", and the case where the residue was observed was set as "×". In Comparative Example 2-1, PGMEA (propylene glycol monomethyl ether acetate) was used instead of PGME for cleaning. The results are shown in Tables 1-1 to 1-5.

[0728] [Table 1-1]

[0729]

[0730] [Table 1-2]

[0731]

[0732] [Table 1-3]

[0733]

[0734] [Table 1-4]

[0735]

[0736] [Table 1-5]

[0737]

[0738] As shown in the table, in a laminate consisting of a layer that exhibits releasability by irradiation with light (release agent layer), a semiconductor substrate, and a supporting substrate, by using a release agent composition containing a polymer having a structure similar to cinnamic acid and a low carbon content to form the release agent layer, good releasability and cleaning properties can be achieved even after light irradiation.

[0739] Description of Reference Numerals

[0740] 1: semiconductor substrate; 2: adhesive layer; 2a: adhesive coating layer; 3: release agent layer; 4: supporting substrate; 21: semiconductor chip substrate; 22: adhesive layer; 23: release agent layer; 24: supporting substrate; 25: sealing resin; 26: electronic device layer; 27: release agent layer with adhesive properties; 28: wiring layer.

Claims

1. A stripping agent composition, which is a stripping agent composition for light irradiation stripping, The stripping agent composition contains: at least one of a compound having a structure represented by the following formula (1) and a carbon content of 80% or less and a polymer; and a solvent. In formula (1), R 1 and R 2 each independently represents a hydrogen atom, a cyano group, a phenyl group, an alkyl group having 1 to 13 carbon atoms, a halogen atom, -COOR 11 , or -COO-, said -COOR 11 In, R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 3 represents a methoxy group, an alkyl group having 1 to 13 carbon atoms, or a halogen atom, n1 represents an integer from 0 to 4, and n2 represents 0 or 1, wherein, The sum of n1 and n2 is less than 4, X 1 represents an ether bond or an ester bond, X 2 represents an ether bond or an ester bond, * indicates a bonding key.

2. The stripping agent composition according to claim 1, wherein At least any one of the compound and the polymer has at least any one of the structure represented by the following formula (2), the structure represented by the following formula (3), and the structure represented by the following formula (4), In formula (2), X 11 Represents a divalent group; A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each independently represents a hydrogen atom, a methyl group or an ethyl group; * represents a bonding bond, In formula (3), X 12 represents a divalent group; *, *1 and *1' represent bonds; bond *1 is bonded to carbon atom *2 or carbon atom *3; bond *1' is bonded to carbon atom *2' or carbon atom *3', In formula (4), X 13 and X 14 One of them represents a hydroxyl group, and the other represents a bond, X 15 and X 16 One of them represents a hydroxyl group, and the other represents a bond; m1 represents 0 or 1.

3. The stripping agent composition according to claim 2, wherein X in the formula (2) 11 is any of the structures represented by the following formula (2-1) and the structures represented by the following formula (2-2), In formula (2-1), Q 1 represents a divalent acyclic hydrocarbon group having 2 to 20 carbon atoms which is optionally interrupted by an oxygen atom, a divalent organic group represented by the following formula (2-1-1), a divalent organic group represented by the following formula (2-1-2), a divalent organic group represented by the following formula (2-1-3), or a divalent organic group represented by the following formula (2-1-4); n1 and n2 each independently represent 0 or 1; * represents a bonding bond, In formula (2-2), X 21 represents a divalent group represented by any of the following formulae (2-2-1) to (2-2-4); Z 1 and Z 2 Each independently represents a single bond or a divalent group represented by the following formula (2-2-5), In formulas (2-1-1) to (2-1-4), R 21 ~R 26 Each independently represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an alkynyloxy group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylcarbonyl group having 7 to 13 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms; * represents a bonding bond, In formula (2-1-1), 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 21 optionally the same or different, In formula (2-1-2), Z 11 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms; n12 and n13 each independently represent an integer of 0 to 4; in R 22 When there are two or more R 22 are optionally the same or different; in R 23 When there are two or more R 23 optionally the same or different, In formula (2-1-3), Z 12 and Z 13 Each independently represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms; n14 represents an integer from 0 to 4; in R 24 When there are two or more R 24 optionally the same or different, In formula (2-1-4), Z 14 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms; Z 15 and Z 16 Each independently represents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms; n15 and n16 each independently represent an integer of 0 to 4; in R 25 When there are two or more R 25 are optionally the same or different; in R 26 When there are two or more R 26 optionally the same or different, In formulas (2-2-1) to (2-2-3), R 1 ~R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a 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 and R 2 Optionally bond to each other to form a ring having 3 to 6 carbon atoms; R 3 and R 4 optionally bonded to each other to form a ring having 3 to 6 carbon atoms, In formula (2-2-4), Z 3 represents a single bond or a divalent group represented by the following formula (2-2-5); A 7 , A 8 and A 9 each independently represents a hydrogen atom, a methyl group or an ethyl group, * represents a bond; *1 represents a bond bonded to a carbon atom in formula (2-2); *2 represents a bond bonded to a nitrogen atom in formula (2-2), In formula (2-2-5), 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; wherein, when m3 is 1, m1 and m2 are not simultaneously 0; *3 represents a bond to the nitrogen atom in formula (2-2) or formula (2-2-4); and *4 represents a bond.

4. The stripping agent composition according to claim 1, wherein The carbon content is above 50%.

5. The stripping agent composition according to claim 1, wherein X in the formula (1) 1 represents an ether bond, In the formula (1), R 1 represents cyano, In the formula (1), R 2 Indicates -COO-, n2 in the formula (1) represents 0.

6. A laminate, wherein: The laminated body has: Semiconductor substrate or electronic device layer; A light-transmitting supporting substrate; as well as a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate, The release agent layer is a release agent layer formed from the release agent composition according to any one of claims 1 to 5 .

7. The laminate according to claim 6, wherein: The laminated body has an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

8. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: A fifth step A of processing the semiconductor substrate of the stacked body according to claim 6; or a fifth step B of processing the electronic device layer of the laminate according to claim 6; and The sixth A step is to separate the semiconductor substrate processed in the fifth A step from the support substrate; or the sixth B step is to separate the electronic device layer processed in the fifth B step from the support substrate.

9. The method for manufacturing a processed semiconductor substrate or an electronic device layer according to claim 8, wherein: The sixth step A or the sixth step B includes the step of irradiating the laminated body with a laser beam from the support substrate side.

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