Composition for forming coating film for adhesive removal, laminate, method for producing laminate, and method for producing processed semiconductor substrate or electronic device layer

Abstract

Provided is, inter alia, a composition for forming a coating film for adhesive removal that is used for easily and cleanly removing a peeling residue of an adhesive layer when the adhesive layer used for temporarily bonding a semiconductor substrate or an electronic device layer and a support substrate remains on the semiconductor substrate or the electronic device layer after separating the semiconductor substrate or the electronic device layer and the support substrate.　A composition for forming a coating film for adhesive removal that is used for removing a peeling residue of an adhesive layer present on a semiconductor substrate, an electronic device layer or a support substrate after the semiconductor substrate or the electronic device layer and the support substrate are temporarily bonded using the adhesive layer and the semiconductor substrate or the electronic device layer and the support substrate are then separated, wherein the composition for forming a coating film for adhesive removal contains a polymer and a solvent and can form a coating film removable by a removing liquid, the polymer satisfying any of the following conditions [I] to [V].　[I]: A polymer (I) having a partial structure represented by formula (A) [II]: A polymer (II) having a structural unit represented by formula (1) [III]: A polymer (III) having a cyclic hydrocarbon selected from among polystyrene resins, cyclic olefin resins, and polyarylate resins [IV]: A polymer (IV) having a structural unit represented by formula (J) [V]: A polymer (V) having a structural unit represented by formula (K).

Description

Composition for forming a coating film for adhesive removal, laminate, method for manufacturing the laminate, and method for manufacturing a processed semiconductor substrate or electronic device layer.

[0001] The present invention relates to a composition for forming a coating film for adhesive removal, a laminate, a method for manufacturing a laminate, and a method for manufacturing a processed semiconductor substrate or electronic device layer.

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional planar direction. To achieve even greater integration, there is a need for semiconductor integration technology that integrates (stacks) in a three-dimensional direction as well. This three-dimensional stacking is a technology that integrates in multiple layers while connecting them with through-silicon vias (TSVs). When integrating in multiple layers, the side opposite to the circuit surface (i.e., the back surface) of each wafer to be integrated is thinned by polishing, and the thinned semiconductor wafers are stacked.

[0003] Before thinning, the semiconductor wafer (also simply called a wafer here) is bonded to a support in order to be polished using a polishing device. This bonding is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying too much force during removal can cause the thinned semiconductor wafer to cut or deform. To prevent this, it must be easily removed. However, it is undesirable for the temporary bonding to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the required performance of the temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] With the recent advancements in the semiconductor field, new technologies related to such bonding and separation processes are constantly in demand.

[0006] International Publication No. 2017 / 221772 Brochure International Publication No. 2018 / 216732 Brochure

[0007] When attempting to separate the support from the semiconductor substrate or electronic device layer after processing semiconductor wafers, foreign matter such as adhesive residue may adhere to the surface of the semiconductor substrate or electronic device layer after delamination. Therefore, the surface of the semiconductor substrate or electronic device layer is cleaned. However, depending on the extent of adhesive residue, it may be difficult to remove the foreign matter from the semiconductor substrate or electronic device layer, making cleaning difficult.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a composition for forming an adhesive removal coating film used to easily and cleanly remove adhesive residue from a semiconductor substrate or electronic device layer when an adhesive layer used to temporarily bond a semiconductor substrate or electronic device layer to a support substrate remains on the semiconductor substrate or electronic device layer or support substrate after the semiconductor substrate or electronic device layer and the support substrate have been separated. The present invention also aims to provide a laminate having an adhesive removal coating film formed using the composition, a method for manufacturing the laminate, and a method for manufacturing a processed semiconductor substrate or electronic device layer.

[0009] The inventors of the present invention conducted diligent studies to solve the aforementioned problems and, as a result, found that they could solve the aforementioned problems, and completed the present invention having the following gist.

[0010] That is, the present invention includes the following. [1] A composition for forming an adhesive removal coating film for forming an adhesive removal coating film used for removing peeling residue of the adhesive layer present on the semiconductor substrate, the electronic device layer, or the support substrate after temporarily bonding a semiconductor substrate or an electronic device layer to a support substrate using an adhesive layer and then separating the semiconductor substrate or the electronic device layer from the support substrate, wherein The composition for forming an adhesive removal coating film is a composition that contains a polymer and a solvent and can form a coating film removable by a removal solution, The composition for forming an adhesive removal coating film, wherein the polymer is a polymer that satisfies any one of the following [I] to [V]. [I]: Polymer (I) having a partial structure represented by the following formula (A) [II]: Polymer (II) having a structural unit represented by the following formula (1) [III]: Polymer (III) having a cyclic hydrocarbon selected from at least one of polystyrene resins, cyclic olefin resins, and polyarylate resins [IV]: Polymer (IV) having a structural unit represented by the following formula (J) [V]: Polymer (V) having a structural unit represented by the following formula (K) (In formula (A), R １１ represents a single bond or a divalent group having 1 to 4 carbon atoms. R １２ represents a hydrogen atom, a hydroxy group, or a methyl group. * represents a bond.) (In formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ３ represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group, R ２ and R ３ is R ２ and R ３ may form a ring together with the carbon atom and oxygen atom between them, and the ring may contain a hetero atom in addition to the oxygen atom.) (In formula (J), Z １This represents a hydroxyl group-substituted arylene group with 6 to 40 carbon atoms derived from a polyhydroxy aromatic compound, Z ２ (This represents an arylene group with 6 to 40 carbon atoms.) (In formula (K), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of an imide group that is deprotected by an alkali.) [2] The adhesive removal coating film forming composition according to [1], wherein the polymer (I) has a structural unit represented by the following formula (A-1). (In formula (A-1), A １ A ２ A ３ A ４ A ５ and A ６ Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group. １１ R represents a single bond or a divalent group with 1 to 4 carbon atoms. １２(wherein represents a hydrogen atom, a hydroxyl group, or a methyl group.) [3] The adhesive composition for forming the adhesive layer, comprising an adhesive component (A) that hardens by a hydrosilylation reaction, according to [1] or [2]. [4] The adhesive composition for forming the adhesive layer, according to [3], comprising an adhesive component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, and a component (A-2) having a Si-H group. [5] A laminate comprising a semiconductor substrate or an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate, wherein the adhesive removal coating film is formed from the adhesive removal coating film forming composition according to any one of [1] to [4]. [6] A method for manufacturing a laminate having a semiconductor substrate or an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate, comprising the steps of: applying an adhesive removal coating film forming composition onto the semiconductor substrate or the electronic device layer, or onto the support substrate to form an adhesive removal coating film; and bonding the semiconductor substrate or the electronic device layer to the support substrate via the adhesive layer and the adhesive removal coating film. [7] A method for manufacturing a processed semiconductor substrate or an electronic device layer, comprising the steps of: processing the semiconductor substrate or the electronic device layer with respect to a laminate in which the semiconductor substrate or electronic device layer is bonded to a support substrate via an adhesive layer and an adhesive removal coating film; separating the processed semiconductor substrate or the electronic device layer from the support substrate; and washing the semiconductor substrate or the electronic device layer with a removal solution to remove the adhesive layer peeling residue present on the semiconductor substrate or the electronic device layer together with the adhesive removal coating film.

[0011] According to the present invention, a composition for forming an adhesive removal coating film is provided for easily and cleanly removing adhesive residue from a semiconductor substrate or electronic device layer when an adhesive layer used to temporarily bond a semiconductor substrate or electronic device layer to a support substrate remains on the semiconductor substrate or electronic device layer or support substrate after separation of the semiconductor substrate or electronic device layer and the support substrate. Furthermore, according to the present invention, a laminate having an adhesive removal coating film formed using the composition, a method for manufacturing the laminate, and a method for manufacturing a processed semiconductor substrate or electronic device layer are also provided.

[0012] Figure 1 is a schematic cross-sectional view of an example of a laminate in the first embodiment. Figure 2 is a schematic cross-sectional view of another example of a laminate in the first embodiment. Figure 3A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 1). Figure 3B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 2). Figure 3C is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the first embodiment (part 3). Figure 4 is a schematic cross-sectional view of an example of a laminate in the second embodiment. Figure 5 is a schematic cross-sectional view of another example of a laminate in the second embodiment. Figure 6A is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 1). Figure 6B is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 2). Figure 6C is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 3). Figure 6D is a schematic cross-sectional view illustrating a method for manufacturing a laminate in an example of the second embodiment (part 4). Figure 7A is a schematic cross-sectional view illustrating an example of a laminate processing method in the first embodiment (part 1). Figure 7B is a schematic cross-sectional view illustrating an example of a laminate processing method in the first embodiment (part 2). Figure 7C is a schematic cross-sectional view illustrating an example of a laminate processing method in the first embodiment (part 3). Figure 7D is a schematic cross-sectional view illustrating an example of a laminate processing method in the first embodiment (part 4). Figure 8A is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 1). Figure 8B is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 2). Figure 8C is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 3). Figure 8D is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 4). Figure 8E is a schematic cross-sectional view illustrating an example of a laminate processing method in the second embodiment (part 5). Figure 8F is a schematic cross-sectional view illustrating a method for processing a laminate, showing an example in the second embodiment (part 6).

[0013] (Composition for forming an adhesive removal coating film) The adhesive removal coating film composition of the present invention is a composition used to form an adhesive removal coating film. The adhesive removal coating film is a film used to remove the adhesive layer residue present on the semiconductor substrate, the electronic device layer, or the support substrate after temporarily bonding the semiconductor substrate or the electronic device layer to the support substrate using an adhesive layer, and then separating the semiconductor substrate or the electronic device layer from the support substrate. The adhesive removal coating film has the role of easily and cleanly removing the adhesive layer residue present on the semiconductor substrate, the electronic device layer, or the support substrate together with the adhesive removal coating film by washing the semiconductor substrate, the electronic device layer, or the support substrate with a removal solution.

[0014] The adhesive removal coating film forming composition comprises a polymer and a solvent, and is capable of forming a coating film that can be removed by a removal solution. The polymer is a polymer that satisfies any of the following conditions [I] to [V]. [I]: A polymer having a substructure represented by the following formula (A) (I) [II]: A polymer having a structural unit represented by the following formula (1) (II) [III]: A polymer having a cyclic hydrocarbon selected from at least one of polystyrene resin, cyclic olefin resin, and polyarylate resin (III) [IV]: A polymer having a structural unit represented by the following formula (J) (IV) [V]: A polymer having a structural unit represented by the following formula (K) (V)

[0015] [I]: Polymer (I) is a polymer having a substructure represented by the following formula (A).

[0016] In formula (A), R １１ R represents a single bond or a divalent group with 1 to 4 carbon atoms. １２ * represents a hydrogen atom, a hydroxyl group, or a methyl group. * represents a bonding bond.

[0017] [II]: Polymer (II) is a polymer having a structural unit represented by the following formula (1).

[0018] In formula (1), R １ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ３ R represents an alkyl group having 1 to 10 carbon atoms which may be substituted or an aromatic hydrocarbon group which may be substituted. ２ and R ３ R ２ and R ３ The carbon and oxygen atoms between them may form a ring, and this ring may contain heteroatoms other than the oxygen atoms.

[0019] [III]: Polymer (III) is a polymer having a cyclic hydrocarbon selected from at least one of polystyrene resin, cyclic olefin resin, and polyarylate resin.

[0020] [IV]: Polymer (IV) is a polymer having a structural unit represented by the following formula (J).

[0021] In formula (J), Z １ This represents a hydroxyl group-substituted arylene group with 6 to 40 carbon atoms derived from a polyhydroxy aromatic compound, Z ２ This represents an arylene group with 6 to 40 carbon atoms.

[0022] [V]: Polymer (V) is a polymer having a structural unit represented by the following formula (K).

[0023] (In formula (K), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of the imide group that is deprotected by an alkali.)

[0024] The polymers represented by [I] through [V] above will be described in detail below.

[0025] <[I]: Polymer (I)> Polymer (I) has a substructure represented by the following formula (A). [In formula (A), R １１ R represents a single bond or a divalent group with 1 to 4 carbon atoms. １２ * represents a hydrogen atom, a hydroxyl group, or a methyl group. * represents a bonding bond.

[0026] The polymer (I) having a substructure represented by formula (A) imparts solvent resistance and easy removal properties to the coating film obtained from the adhesive removal coating film forming composition.

[0027] The polymer (I) preferably has a structural unit represented by the following formula (A-1). For example, the substructure represented by formula (A) is a part of the structural unit represented by the following formula (A-1). (In formula (A-1), A １ A ２ A ３ A ４ A ５ and A ６ Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group. １１ R represents a single bond or a divalent group with 1 to 4 carbon atoms. １２ (This represents a hydrogen atom, a hydroxyl group, or a methyl group.)

[0028] <<R １１ >> In equations (A) and (A-1), R １１ R represents a single bond or a divalent group with 1 to 4 carbon atoms. １１ The number of carbon atoms in R is 1 to 4, and may be 1 to 3, 1 or 2, or 1. １１ Examples include divalent hydrocarbon groups having 1 to 4 carbon atoms, which may be substituted with a hydroxyl group. １１ If R has a hydroxyl group, １１ The number of hydroxyl groups it has is, for example, R １１ It is less than or equal to the number of carbon atoms it has. １１ From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the divalent group has 1 to 4 carbon atoms, and that the divalent group has a hydroxyl group. １１From the viewpoint of suitably obtaining the effects of the present invention, more preferably, it represents -CH(OH)-.

[0029] <<R １２ >> In equations (A) and (A-1), R １２ This represents a hydrogen atom, a hydroxyl group, or a methyl group, preferably a hydrogen atom or a hydroxyl group.

[0030] Examples of substructures represented by formula (A) include the following: * represents a combination.

[0031] <<Q>> In formula (A-1), Q represents a divalent organic group. The divalent organic group is not particularly limited, but a divalent organic group having a heteroatom is preferred, and a divalent organic group having a nitrogen atom and an oxygen atom is more preferred. Examples of heteroatoms include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of carbon atoms in the divalent organic group is not particularly limited, but 3 to 30 carbon atoms is preferred, and 3 to 20 carbon atoms is more preferred.

[0032] As for Q, from the viewpoint of suitably obtaining the effects of the present invention, it is preferable that it be represented by either formula (A-11) or formula (A-12) below. (In formula (A-11), X １ This represents a divalent group represented by the following formula (A-11-1), formula (A-11-2), or formula (A-11-3). １ and Z ２ Each of these independently represents a single bond or a divalent group represented by the following formula (A-11-4). * represents a bond. In formula (A-12), Q １ represents a divalent group having an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. * represents a bond. (In formulas (A-11-1) to (A-11-3), R １ ~R ５Each independently represents a C1-C10 alkyl group that may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom, a C2-C10 alkenyl group that may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group that may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from the group consisting of C1-C6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, nitro groups, cyano groups, and C1-C6 alkylthio groups. １ and R ２ These may be bonded to each other to form a ring with 3 to 6 carbon atoms. ３ and R ４ These atoms may bond to each other to form a ring with 3 to 6 carbon atoms. * represents a bond. *1 represents a bond to a carbon atom. *2 represents a bond to a nitrogen atom. (In formula (A-11-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. *3 represents a bond to the nitrogen atom. *4 represents a bond to the carbon atom.)

[0033] Q in equation (A-12) １ It is preferable that it be represented by any of the following formulas (A-12-1) to (A-12-4). (In formulas (A-12-1) to (A-12-4), R ３１ ~R ３６ Each of these 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 bond. In formula (A-12-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. R ３１ When R is 2 or more, ３１They may be the same or they may be different. In equation (A-12-2), Z １ n12 and n13 each independently represent integers from 0 to 4. ３２ When R is 2 or more, ３２ They may be the same or they may be different. ３３ When R is 2 or more, ３３ They may be the same or they may be different. In equation (A-12-3), Y １ and Y ２ Each of these independently represents a single bond or an alkylene group with 1 to 6 carbon atoms. n14 represents an integer from 0 to 4. ３４ When R is 2 or more, ３４ They may be the same or they may be different. In equation (A-12-4), Z ２ n15 and n16 each independently represent integers from 0 to 4. ３５ When R is 2 or more, ３５ They may be the same or they may be different. ３６ When R is 2 or more, ３６ They may be the same or they may be different.

[0034] Examples of Q represented by equations (A-11) and (A-12) include the following structures. * represents a coupling.

[0035] When the polymer has a structural unit represented by formula (A-1), the mass proportion of the structural unit represented by formula (A-1) in the polymer is not particularly limited, but is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.

[0036] The method for producing the polymer is not particularly limited, and examples thereof include a method of reacting a dicarboxylic acid represented by the following formula (A1) with a diepoxy compound represented by the following formula (A2). In this case, a polymer having a structural unit represented by formula (A-1) is obtained.

[0037] The catalyst that activates epoxy groups is, for example, quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. An appropriate amount of the catalyst can be selected and used from the range of 0.1 to 10% by mass relative to the total mass of the polymer raw materials used in the reaction. Optimal conditions can be selected for the polymerization temperature and time, for example, from the ranges of 80 to 160°C and 2 to 50 hours.

[0038] (In formula (A1), R １１ and R １２ are each R in formula (A-1) １１ and Ｒ１２ have the same meaning as above.)

[0039] Examples of the dicarboxylic acid represented by formula (A1) include tartaric acid, malic acid, tartronic acid, citramalic acid, dioxymalonic acid, mucic acid, etc.

[0040] (In formula (A2), A １ , A ２ , A ３ , A ４ , A ５ , A ６ and Q are each A in formula (A-1) １ , A ２ , A ３ , A ４ , A ５A ６ (And it is synonymous with Q.)

[0041] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 700 to 15,000, and more preferably 900 to 10,000. The weight-average molecular weight is the value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

[0042] The polymer content in the adhesive removal coating film-forming composition is not particularly limited, but is preferably 0.01% to 60% by mass, more preferably 0.1% to 40% by mass, and particularly preferably 0.5% to 30% by mass, relative to the solid content.

[0043] <<Removal Solution>> The removal solution for polymer (I) is not particularly limited as long as it can remove the coating film formed from the adhesive removal coating film forming composition. The coating film is formed, for example, on a semiconductor substrate. In this case, removal refers to removal from the semiconductor substrate. Here, examples of removal methods include dissolution removal and peeling removal. Peeling removal can be, for example, peeling from the adherend by swelling.

[0044] The removal solution may contain water or an organic solvent. The removal solution may also contain 50% by mass or more of an organic solvent.

[0045] Examples of organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0046] Examples of removal solutions include alkaline and acidic removal solutions.

[0047] The alkaline removal solution contains an alkali. Examples of alkalis include ammonia, inorganic alkali compounds, quaternary ammonium hydroxide, amines, and hydrazine. The alkaline removal solution may be a developer or cleaning solution used in semiconductor manufacturing processes, and may also be alkaline. For example, NMD-3 (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be used as a developer. Examples of inorganic alkali compounds include potassium hydroxide, sodium hydroxide, lithium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, etc. Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and choline. Examples of amines include ethanolamine, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, and ethylenediamine. Examples of hydrazines include hydrazine monohydrate. The alkaline removal solution may also be SC-1 (ammonia-hydrogen peroxide solution).

[0048] The acid removal solution contains an acid. Examples of acids include inorganic acids and organic acids. Examples of inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and hydrofluoric acid. The acid removal solution is, for example, an aqueous solution containing dilute hydrofluoric acid. Alternatively, the acid removal solution may be, for example, an aqueous solution containing sulfuric acid and hydrogen peroxide, or an aqueous solution containing acetic acid or a chelating agent. Examples of chelating agents include organic acids, salts of organic acids, amino acids, and derivatives of amino acids.

[0049] <[II]: Polymer (II)> Polymer (II) is a polymer comprising a structural unit represented by the following formula (1). [In formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ３ represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group, R ２ and R ３ , R ２ and R ３ may together with the carbon atom and oxygen atom between them form a ring, and the ring may contain a hetero atom in addition to the oxygen atom.]]

[0050] R １ examples of the alkyl group having 1 to 3 carbon atoms for include a methyl group, an ethyl group and a propyl group. R ２ examples of the alkyl group having 1 to 4 carbon atoms for include a methyl group, an ethyl group, a propyl group and a butyl group. R ３ examples of the substituent on the optionally substituted alkyl group having 1 to 10 carbon atoms for include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an aromatic group and the like. Examples of the aromatic group include an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group and the like. R ３ examples of the substituent on the optionally substituted aromatic hydrocarbon group for include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and the like. In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0051] R ２ and R ３ , R ２ and R ３The carbon and oxygen atoms between them may form a ring, and this ring may contain heteroatoms other than the oxygen atom. Examples of such rings include 4-membered to 7-membered rings. Examples of such rings include cyclic ethers, lactone rings, and cyclic carbonates. Examples of heteroatoms that the ring may contain include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0052] R １ Hydrogen atoms and methyl groups are preferred. ２ As such, methyl groups and ethyl groups are preferred. ３ Preferably, the alkyl group has 1 to 6 carbon atoms, and more preferably, an alkyl group has 1 to 4 carbon atoms.

[0053] The inventors believe that the acetal structure of formula (1) acts as a protecting group for carboxyl groups, imparting solubility to the polymer in solvents while improving the applicability of the adhesive removal coating film-forming composition. On the other hand, during the process of forming a coating film from the adhesive removal coating film-forming composition, the acetal structure is removed (for example, by heat or catalyst), generating carboxyl groups. The generated carboxyl groups, by reacting with each other or with the crosslinking agent in the presence of a crosslinking agent, impart solvent resistance to the coating film. Furthermore, the generated carboxyl groups facilitate the removal of the coating film by the removal solution. Therefore, the coating film obtained from the adhesive removal coating film-forming composition exhibits good solvent resistance. In addition, the coating film obtained from the adhesive removal coating film-forming composition can be removed by the removal solution. Therefore, the adhesive removal coating film-forming composition of the present invention is a composition that can easily prevent foreign matter from remaining on the substrate, and is a composition that can obtain a coating film with good solvent resistance and easy removal.

[0054] Examples of structural units represented by formula (1) include the following structural units. Among the following structural units, R １This represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.

[0055] The structural unit represented by formula (1) originates, for example, from the compound represented by the following formula (1A). [In formula (1A), R １ , R ２ , and R ３ These are R in equation (1), respectively. １ , R ２ , and R ３ This is synonymous with [the above].

[0056] The polymer may contain structural units other than the structural unit represented by formula (1). Examples of such structural units include structural units derived from (meth)acrylic acid ester compounds, (meth)acrylamide compounds, or styrene compounds. In this invention, (meth)acrylic acid ester compounds mean acrylic acid ester compounds or methacrylic acid ester compounds. The same applies to (meth)acrylamide compounds.

[0057] Examples of structural units derived from (meth)acrylic acid ester compounds include the structural unit represented by the following formula (2-1). Examples of structural units derived from (meth)acrylamide compounds include the structural unit represented by the following formula (2-2). Examples of structural units derived from styrene compounds include the structural unit represented by the following formula (2-3). [In formulas (2-1) to (2-3), R １１ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １２ R represents a monovalent group with 1 to 20 carbon atoms. １３ R represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. １４ Each of these independently represents a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, or a monovalent group with 1 to 10 carbon atoms. m represents an integer from 0 to 5.

[0058] R１２ and R １３ The number of carbon atoms in R may be 1 to 20 or 1 to 10. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in the compound may have a heteroatom. Examples of heteroatoms include oxygen atoms and nitrogen atoms. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in the compound may have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in R may, for example, have a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an epoxy group, etc. １２ and R １３ Examples of monovalent groups having 1 to 20 carbon atoms include optionally substituted alkyl groups and optionally substituted aromatic groups. Examples of substituents on optionally substituted alkyl groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, and optionally substituted aromatic groups. Examples of substituents on optionally substituted aromatic groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, optionally substituted C1 to C6 alkyl groups, and optionally substituted C1 to C6 alkoxy groups. Examples of C1 to C6 alkyl groups include methyl groups, ethyl groups, propyl groups, and butyl groups. Examples of C1 to C6 alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups.

[0059] R １４ The monovalent group having 1 to 10 carbon atoms in R may have a heteroatom. Examples of heteroatoms include oxygen atoms and nitrogen atoms. １４The monovalent group having 1 to 10 carbon atoms in R may, for example, have a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an epoxy group, etc. １４ Examples of monovalent groups having 1 to 10 carbon atoms include alkyl groups having 1 to 6 carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 1 to 6 carbon atoms that may be substituted with halogen atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl groups, ethyl groups, propyl groups, and butyl groups. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups.

[0060] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, 4-hydroxyphenyl acrylate, anthyl methyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

[0061] Specific examples of methacrylic acid ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 4-hydroxyphenyl acrylate, anthyl methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, and bromophenyl methacrylate.

[0062] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N-(4-hydroxyphenyl)acrylamide, N,N-dimethylacrylamide, and N-antrylcrylamide.

[0063] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N-(4-hydroxyphenyl)methacrylamide, N,N-dimethylmethacrylamide, and N-antlylmethacrylamide.

[0064] Specific examples of styrene compounds include, but are not limited to, styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0065] The polymer may further have other structural units. Examples of monomers that induce such structural units include, but are not limited to, acrylic acid, methacrylic acid, vinyl compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0066] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

[0067] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0068] The lower limit of the molar ratio of structural units represented by formula (1) to the total structural units of the polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the molar ratio of structural units represented by formula (1) is preferably 20 mol% or more, more preferably 45 mol% or more, and particularly preferably 65 mol% or more. The upper limit of the molar ratio of structural units represented by formula (1) to the total structural units of the polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the molar ratio of structural units represented by formula (1) is preferably 100 mol% or less, more preferably 95 mol% or less, and particularly preferably 90 mol% or less.

[0069] The lower limit of the molar ratio of the total structural units derived from (meth)acrylic acid ester compounds, (meth)acrylamide compounds, and styrene compounds (hereinafter sometimes referred to as "total structural units (2)") relative to the total structural units of the polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the molar ratio of total structural units (2) is preferably greater than 0 mol%, and more preferably 10 mol% or more. The upper limit of the molar ratio of total structural units (2) relative to the total structural units of the polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the molar ratio of total structural units (2) is preferably 60 mol% or less, and more preferably 45 mol% or less.

[0070] The molar ratio of the total structural units (2) represented by formula (1) to the total structural units of the polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, 80 mol% to 100 mol% is preferred, and 90 mol% to 100 mol% is more preferred.

[0071] The polymer may be a homopolymer or a copolymer. If the polymer is a copolymer, it may be a random copolymer or a block copolymer.

[0072] The method for producing the polymer is not particularly limited. The polymer can be produced by polymerizing monomers by conventional methods, such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, in which case monomers can be polymerized using, for example, a polymerization initiator. Organic peroxides and diazo compounds can be used as polymerization initiators.

[0073] Examples of organic peroxides include diacyl peroxides, peroxydicarbonates, peroxyesters, and sulfonate peroxides. Examples of diacyl peroxides include diacetyl peroxide, diisobutyl peroxide, didecanoyl peroxide, benzoyl peroxide, and succinate peroxide. Examples of peroxydicarbonates include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diallyl peroxydicarbonate. Examples of peroxyesters include tert-butyl peroxyisobutyrate, tert-butyl neodecanate, and cumene peroxyneodecanate. Examples of sulfonate peroxides include acetylcyclohexylsulfonyl peroxide.

[0074] Examples of diazo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(isobutyrate)dimethyl, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethoxyvaleronitrile), and 2,2'-azobis(2-cyclopropylpropionitrile).

[0075] If polymerization is to be completed in a short time, it is preferable to use a polymerization initiator that has a decomposition half-life of 10 hours or less at 80°C. Suitable polymerization initiators include benzoyl peroxide and 2,2'-azobisisobutyronitrile, with 2,2'-azobisisobutyronitrile being more preferred.

[0076] The amount of polymerization initiator used is, for example, 0.0001 to 0.2 equivalents, preferably 0.0005 to 0.1 equivalents, relative to the total amount of monomer used.

[0077] The solvent used for polymerization is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the resulting polymer. Examples include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, and polyhydric alcohol derivatives. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aliphatic hydrocarbons include n-hexane and n-octane. Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone. Examples of ethers include tetrahydrofuran and dioxane. Examples of esters include ethyl acetate and butyl acetate. Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide. Examples of sulfoxides include dimethyl sulfoxide. Examples of alcohols include methanol and ethanol. Examples of polyhydric alcohol derivatives include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. These can be used individually or in combination of two or more.

[0078] The polymerization temperature is not particularly limited as long as it is within a temperature range where side reactions such as transfer reactions and termination reactions do not occur, and the monomer is consumed and polymerization is completed. However, it is preferable that the polymerization is carried out in a temperature range of -100°C or higher and below the boiling point of the solvent. The concentration of monomer in the solvent is not particularly limited, but is usually 1 to 40% by mass, and preferably 10 to 30% by mass. The polymerization reaction time can be appropriately selected, but is usually in the range of 2 to 50 hours.

[0079] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 5,000 to 75,000, and more preferably 10,000 to 50,000. The weight-average molecular weight is the value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

[0080] The polymer content in the adhesive removal coating film-forming composition is not particularly limited, but is preferably 0.01% to 60% by mass, more preferably 0.1% to 40% by mass, and particularly preferably 0.5% to 30% by mass, relative to the solid content.

[0081] <<Removal Solution>> The removal solution for polymer (II) is the same as that described in the <<Removal Solution>> section above, which was used for polymer (I).

[0082] <[III]: Polymer (III)> Polymer (III) is a polymer having a cyclic hydrocarbon selected from at least one of polystyrene resin, cyclic olefin resin, and polyarylate resin. Only one polymer may be used, or two or more polymers may be used.

[0083] <<Polystyrene Resin>> Polystyrene in polystyrene resin refers to a polymer containing a styrene component. It is preferable that the polystyrene contains 10% by mass or more of the styrene component. The polystyrene resin of this embodiment may contain one type of polystyrene or two or more types. Here, the styrene component is a structural unit derived from a monomer having a styrene skeleton in its structure. It is more preferable that the polystyrene contains 20% by mass or more of the styrene component, and even more preferable that it contains 30% by mass or more. Furthermore, the polystyrene may be composed only of the styrene component.

[0084] Polystyrenes composed solely of styrene components include homopolymers of styrene compounds and copolymers of two or more styrene compounds. Here, a styrene compound is a compound having a styrene skeleton in its structure, and includes not only styrene but also compounds in which substituents have been introduced to the extent that the ethylenically unsaturated bond of styrene can act as a reactive (polymerizable) group. Specific styrene compounds include, for example, styrene; alkyl styrenes such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, and tert-butylstyrene; and substituted styrenes such as hydroxystyrene, tert-butoxystyrene, vinylbenzoic acid, o-chlorostyrene, and p-chlorostyrene, in which hydroxyl groups, alkoxy groups, carboxyl groups, and halogen atoms have been introduced to the benzene ring of styrene.

[0085] The components other than the styrene component that may be contained in polystyrene are not particularly limited. That is, the polystyrene may be a styrene-diene copolymer or a styrene-polymerizable unsaturated carboxylic acid ester copolymer, etc. Also, so-called styrene-based elastomers can be suitably used.

[0086] The polystyrene is preferably hydrogenated (hydrogenated polystyrene is preferred). While there are no particular limitations on the hydrogenated polystyrene, hydrogenated styrene-diene copolymers such as hydrogenated styrene-butadiene-styrene block copolymer (SEBS), which is obtained by hydrogenating SBS (styrene-butadiene-styrene block copolymer), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), which is obtained by hydrogenating SIS (styrene-isoprene-styrene block copolymer), are preferred. Only one type of hydrogenated polystyrene may be used, or two or more types may be used. By using a hydrocarbon polymer such as hydrogenated polystyrene as the polymer, the solubility in the removal solution described later can be increased, and the ease of removal of the adhesive removal coating film can be further improved. In addition, by using a hydrocarbon polymer as the polymer, selectivity of the removal solution can be obtained (selection of solutions that dissolve the adhesive removal coating film and solutions that do not dissolve it).

[0087] Polystyrene resins can be obtained by conventional methods such as anionic polymerization, bulk polymerization, suspension polymerization, emulsification, or solution polymerization. Furthermore, in polystyrene, at least a portion of the unsaturated double bonds of the benzene rings of the conjugated diene and styrene monomer may be hydrogenated. The hydrogenation rate can be measured by nuclear magnetic resonance (NMR) spectroscopy.

[0088] As for polystyrene resin, commercially available products may be used, for example, "Clearlen 530L" and "Clearlen 730L" from Denki Kagaku Kogyo Co., Ltd., "Toughprene 126S" and "Asaprene T411" from Asahi Kasei Corporation, "Krayton D1102A" and "Krayton D1116A" from Kraton Polymer Japan, "Styrolux S" and "Styrolux T" from Styroluxion, Inc., and "Asaflex 840" and "Asaflex 860" from Asahi Kasei Chemicals (all SBS). As for hydrogenated polystyrene resins, for example, "Toughtec H series" from Asahi Kasei Chemicals, "Krayton G series" from Shell Japan (both SEBS), "Dynalon" (hydrogenated styrene-butadiene random copolymer) from JSR Corporation, and "Septon" (hydrogenated styrene thermoplastic elastomer, SEPS) from Kuraray Co., Ltd.

[0089] <<Cyclic Olefin Resins>> Examples of cyclic olefin resins include norbornene polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene polymers are preferred. Examples of norbornene polymers include ring-opening polymers of norbornene monomers (hereinafter sometimes referred to as "COP") and norbornene copolymers obtained by copolymerizing norbornene monomers with olefins such as ethylene (hereinafter sometimes referred to as "COC"). Hydrogenated COP and COC are particularly preferred. By using hydrocarbon polymers such as hydrogenated COP and COC as polymers, solubility in the removal solution described later can be increased, and the ease of removal of the adhesive removal coating film can be further improved. In addition, by using hydrocarbon polymers as polymers, selectivity of the removal solution (selection of solutions that dissolve the adhesive removal coating film and solutions that do not) can be obtained.

[0090] Norbornene monomers used as raw materials for norbornene polymers are alicyclic monomers having a norbornene ring. Examples of such norbornene monomers include norbornene, tetracyclododecene, ethylidenenorbornene, vinylnorbornene, ethylidetetracyclododecene, dicyclopentadiene, dimethanotetrahydrofluorene, phenylnorbornene, methoxycarbonylnorbornene, and methoxycarbonyltetracyclododecene. One or more of these norbornene monomers may be used.

[0091] Norbornene copolymers (COCs) are obtained by copolymerizing the above-mentioned norbornene monomer with copolymerizable olefins. Examples of such olefins include olefins having 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene; cycloolefins, such as cyclobutene, cyclopentene, and cyclohexene; and non-conjugated dienes, such as 1,4-hexadiene. These olefins may be used individually or in combination of two or more.

[0092] The content ratio of norbornene monomers in the norbornene copolymer (COC) is preferably 40 to 90 mol%, and more preferably 50 to 80 mol%. A content ratio within this range enhances solubility in the removal solution described later, thereby improving the ease of removal of the adhesive removal coating film.

[0093] Examples of commercially available cyclic olefin resins include, as a ring-opening polymer (COP) of norbornene monomers, "ZEONOR" manufactured by Nippon Zeon Co., Ltd., and as a norbornene copolymer (COC), "APPEL" manufactured by Mitsui Chemicals, Inc. and "TOPAS" manufactured by Polyplastics Co., Ltd.

[0094] <<Polyarylate Resin>> Polyarylate resin is an aromatic polyester resin obtained from an aromatic dicarboxylic acid component (including its functional derivatives) and a divalent phenol component, and contains these components as monomer components. Therefore, it can also be said that polyarylate resin contains residues of aromatic dicarboxylic acid and divalent phenol components. Functional derivatives refer to organic compounds in which the carboxyl group of an aromatic dicarboxylic acid is replaced with a more reactive substituent, and include, for example, acid halides having an acid halide group as described below.

[0095] The aromatic dicarboxylic acid component used to introduce aromatic dicarboxylic acid residues into polyarylate resins is an organic compound containing an aromatic ring and two carboxyl groups per molecule. The carboxyl groups may also be acid halide groups. An acid halide group is a group in which the hydroxyl group of a carboxyl group is replaced by a halogen atom. Specific examples of such aromatic dicarboxylic acid components include, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorphthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methylterephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfondicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis(4-carboxyphenoxy)ethane, 5-sodium sulfisoisophthalic acid, diphenic acid, and their derivatives (e.g., acid halides). One or more of these aromatic dicarboxylic acids may be used. Among these, from the viewpoint of suitably obtaining the effects of the present invention, the polyarylate resin preferably contains at least one, preferably both, of terephthalic acid and isophthalic acid.

[0096] The total content of terephthalic acid and isophthalic acid in the polyarylate resin is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass, relative to the total amount of aromatic dicarboxylic acid components. The total content of terephthalic acid and isophthalic acid may also be the total content of terephthalic acid and isophthalic acid residues.

[0097] When the polyarylate resin contains terephthalic acid and isophthalic acid as aromatic dicarboxylic acid components, the proportion of these components is not particularly limited, and the mass ratio of terephthalic acid / isophthalic acid is preferably 0 / 100 to 100 / 0, more preferably 20 / 80 to 80 / 20, even more preferably 40 / 60 to 60 / 40, particularly preferably 45 / 55 to 55 / 45, and most preferably 50 / 50. The proportion of terephthalic acid and isophthalic acid may also be the proportion of residues of terephthalic acid and isophthalic acid.

[0098] The divalent phenol components used to introduce divalent phenol residues into polyarylate resins are organic compounds containing two phenolic hydroxyl groups per molecule. A phenolic hydroxyl group is a hydroxyl group that is directly bonded to an aromatic ring. Specific examples of such divalent phenol components include, for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dibromophenyl). Examples include propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybiphenyl [4,4'-biphenol], 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 4,4'-(1,3-dimethylbutylidene)diphenol, resorcinol, and the like. These compounds may be used individually or in combination of two or more. From the viewpoint of suitably obtaining the effects of the present invention, the polyarylate resin preferably contains one or more divalent phenol components selected from the group consisting of bisphenol A, bisphenol C, bisphenol Z, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, and bisphenol TMC, and more preferably contains bisphenol A.

[0099] The bisphenol A content in the polyarylate resin is not particularly limited, but is preferably 0 to 100% by mass, more preferably 40 to 100% by mass, even more preferably 60 to 100% by mass, particularly preferably 80 to 100% by mass, and most preferably 100% by mass, relative to the total amount of divalent phenol components. The bisphenol A content may also be the content of bisphenol A residues.

[0100] The polyarylate resin may contain, to the extent that it does not impair the properties and effects of the present invention, a portion of the divalent phenol component may be replaced with at least one divalent alcohol component selected from the group consisting of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, dodecanediol, neopentyl glycol, cyclohexanediol, 1,4-dihydroxymethylcyclohexane, etc.

[0101] The content of the dihydric alcohol component in the polyarylate resin is not particularly limited. For example, it may be 50% by mass or less relative to the total amount of dihydric phenol component, preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass. The content of the dihydric alcohol component may also be the content of residues of the dihydric alcohol component.

[0102] Examples of commercially available polyarylate resins include U-Powder D-type and L-type (both manufactured by Unitika Corporation).

[0103] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 5,000 to 75,000, and more preferably 10,000 to 50,000. The weight-average molecular weight is the value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

[0104] The polymer content in the adhesive removal coating film-forming composition is not particularly limited, but is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass, relative to the mass of the film-forming component. Here, the film-forming component refers to the component obtained by removing the solvent component from the adhesive removal coating film-forming composition.

[0105] <<Removal Solution>> The removal solution for polymer (III) is not particularly limited as long as it can remove the coating film formed from the adhesive removal coating film forming composition. The coating film is formed, for example, on a semiconductor substrate. In this case, removal refers to removal from the semiconductor substrate. Here, examples of removal methods include dissolution removal and peeling removal. Peeling removal can be, for example, peeling from the adherend by swelling.

[0106] The removal solution preferably contains 70% by mass or more of a hydrocarbon solvent, more preferably 80% by mass or more, and even more preferably 90% by mass or more. Examples of hydrocarbon solvents include linear aliphatic hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched aliphatic hydrocarbons having 3 to 15 carbon atoms; cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclopentene, and cyclohexene; monocyclic aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, and isopropyltoluene (4-isopropyltoluene); polycyclic aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, pyrene, coronene, and fluorene; and terpenes such as limonene and p-menthane.

[0107] Of these hydrocarbon solvents, those containing a cyclic structure are preferred. Examples of hydrocarbon solvents containing a cyclic structure include cyclic aliphatic hydrocarbons, monocyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, limonene, and p-menthane. Among the hydrocarbon solvents containing a cyclic structure, benzene, toluene, xylene, mesitylene, isopropyltoluene, 1,2,4-trimethylbenzene, cyclohexane, and limonene are preferred, with toluene, mesitylene, and 1,2,4-trimethylbenzene being more preferred.

[0108] A coating film with a thickness of 40 nm formed from the adhesive removal coating film-forming composition containing polymer (III) according to the present invention exhibits a film thickness reduction rate of 90% or more when immersed in mesitylene at 23°C for 1 minute as the immersion solution. Furthermore, a coating film with a thickness of 40 nm formed from the adhesive removal coating film-forming composition containing polymer (III) according to the present invention exhibits a film thickness reduction rate of 5% or less when immersed in propylene glycol monomethyl ether at 23°C for 1 minute as the immersion solution. The film thickness reduction rate is calculated using the following formula: Film thickness reduction rate (%) = ((A - B) ÷ A) × 100 A: Film thickness before immersion B: Film thickness after immersion Note that the film thickness is given by the arithmetic mean of four points measured near the center of the coating film using an optical interferometry film thickness gauge. Furthermore, heating conditions when forming the coating film include, for example, heating at 200°C for 1 minute.

[0109] <[IV]: Polymer (IV)> Polymer (IV) has a structural unit represented by the following formula (J). [In formula (J), Z １ This represents a hydroxyl group-substituted arylene group with 6 to 40 carbon atoms derived from a polyhydroxy aromatic compound, Z ２ This represents an arylene group with 6 to 40 carbon atoms.

[0110] The polymer (IV) having a substructure represented by formula (J) imparts solvent resistance and easy removal properties to the coating film obtained from the adhesive removal coating film forming composition.

[0111] Z １The hydroxyl group-substituted arylene group represented by can be a hydroxyl group-substituted arylene group derived from a benzenediol, benzenetriol, or naphthalenediol. And Z １ The hydroxyl group-substituted arylene group represented by can be, for example, a hydroxyl group-substituted phenylene group derived from catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, or phloroglucinol.

[0112] Z ２ The arylene group represented by can be an organic group based on a benzene ring, a naphthalene ring, or an anthracene ring.

[0113] Examples of substructures represented by formula (J) include the following substructures.

[0114] The method for producing the polymer is not particularly limited. For example, a novolac resin containing a repeating unit structure of formula (J), obtained by condensing a polyhydroxy aromatic compound and an aldehyde, can be used as the polymer. This novolac resin is obtained by condensing a polyhydroxy aromatic compound with an aryl compound having an aldehyde group and a carboxylic acid group using an acid.

[0115] Polyhydroxyaromatic compounds include benzenediols, benzenetriols, or naphthalenediols. More specifically, benzene-based compounds include catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, or phloroglucinol. Naphthalene-based compounds include 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 1,5-dihydroxynaphthalene.

[0116] Aryl compounds are compounds that have an aldehyde group and a carboxylic acid group. Examples of compounds that have an aldehyde group and a carboxyl group include terephthalaldehyde and isophthalaldehyde.

[0117] In this reaction, 0.1 to 10 moles, preferably 0.8 to 2.2 moles, and more preferably 1.0 mole of aldehydes can be reacted with 1 mole of phenols.

[0118] Examples of acid catalysts used in condensation reactions include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of acid catalyst used is selected depending on the type of acid used. Typically, it is 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.1 to 100 parts by mass, per 100 parts by mass of the total of the polyhydroxy aromatic compound and the aldehyde. However, when using terephthalaldehyde acid as the compound having an aldehyde group and a carboxyl group, the acid catalyst may not be used.

[0119] The above condensation reaction can be carried out without a solvent, but it is usually carried out with a solvent. Any solvent that does not inhibit the reaction can be used. Examples include cyclic ethers such as tetrahydrofuran and dioxane. Also, if the acid catalyst used is a liquid, such as formic acid, it can also serve as a solvent. The reaction temperature during condensation is usually between 40°C and 200°C. The reaction time is selected according to the reaction temperature, but is usually between 30 minutes and 50 hours.

[0120] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 3,000 to 75,000, and more preferably 5,000 to 30,000. The weight-average molecular weight is the value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

[0121] The polymer content in the adhesive removal coating film-forming composition is not particularly limited, but is preferably 0.01% to 60% by mass, more preferably 0.1% to 40% by mass, and particularly preferably 0.5% to 30% by mass, relative to the solid content.

[0122] <<Removal Solution>> The removal solution for polymer (IV) is the same as that described in the <<Removal Solution>> section above, which was used for polymer (I).

[0123] <[V]: Polymer (V)> Polymer (V) has a substructure represented by the following formula (K). [In formula (K), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of the imide group that is deprotected by an alkali.]

[0124] Examples of protecting groups for the imide group deprotected by alkali in R include methyl, cyclohexyl, hydroxyethyl, benzyl, and phenyl groups. Examples of alkalis include alkalis contained in alkali removal solutions.

[0125] The polymer (V) having a substructure represented by formula (K) imparts solvent resistance and easy removal properties to the coating film obtained from the adhesive removal coating film forming composition.

[0126] The polymer may have structural units other than the structural unit represented by formula (K). Such structural units are not particularly limited. Examples include structural units derived from compounds having polymerizable unsaturated bonds.

[0127] The proportion of structural units represented by formula (K) in the polymer is not particularly limited, but it is preferably 50 mol% or more of the total structural units, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0128] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 1,000 to 50,000, and more preferably 1,500 to 30,000. The weight-average molecular weight is the value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC).

[0129] Polymers can be obtained, for example, by polymerizing monomers containing a compound represented by the following formula (Ka). [In equation (Ka), X is equivalent to X in equation (K).]

[0130] Examples of compounds represented by formula (Ka) include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-hydroxyethylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and maleic anhydride.

[0131] The polymerization method is not particularly limited, and examples include radical polymerization. For example, polymers can be obtained by homopolymerization of a compound represented by formula (Ka), such as maleimide, or by copolymerization with other monomers.

[0132] The monomers used in polymerization may include monomers other than the compound represented by formula (Ka). Examples of such monomers include compounds having polymerizable unsaturated bonds. Specific examples include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, and acrylonitrile.

[0133] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthyl methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

[0134] Specific examples of methacrylic acid ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthyl methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate.

[0135] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-antrylcrylamide.

[0136] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-antrylmethacrylamide.

[0137] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

[0138] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0139] The polymer content in the adhesive removal coating film-forming composition is not particularly limited, but is preferably 0.01% to 60% by mass, more preferably 0.1% to 40% by mass, and particularly preferably 0.5% to 30% by mass, relative to the solid content.

[0140] <<Removal Solution>> The removal solution for polymer (V) is the same as that described in the <<Removal Solution>> section above, which was used for polymer (I).

[0141] When polymers (I) to (V) described above are used as the polymers contained in the composition for forming an adhesive removal coating film, the adhesive layer residue remaining on the semiconductor substrate, electronic device layer, or support substrate can be easily and cleanly removed together with the adhesive removal coating film. In particular, even after a high-temperature firing process has been performed on a laminate containing the adhesive removal coating film, using polymers (I) to (V) described above makes it easier to easily and cleanly peel off the adhesive removal coating film from the semiconductor substrate, electronic device layer, or support substrate.

[0142] <Solvents> Examples of solvents included in the adhesive removal coating film forming composition are as follows:

[0143] <<Suitable Solvents for Polymer (I) or Polymer (II)>> When using the above polymer (I) or polymer (II), the following solvents are suitably used for these polymers. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be used. These solvents can be used individually or in combination of two or more. Furthermore, they can be used in combination with high-boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate.

[0144] The adhesive removal coating film-forming composition can be easily prepared, for example, by uniformly mixing each component, and is used in solution by dissolving it in a suitable solvent. It is preferable to filter the adhesive removal coating film-forming composition prepared in this way using a filter with a pore size of about 0.2 μm before use. The adhesive removal coating film-forming composition prepared in this way also exhibits excellent long-term storage stability at room temperature.

[0145] The proportion of solids in the adhesive removal coating film-forming composition is not particularly limited as long as each component is uniformly dissolved, but is for example 0.5 to 50% by mass, or for example 1 to 30% by mass. Here, solids refer to the total components of the adhesive removal coating film-forming composition excluding the solvent components.

[0146] <<Suitable Solvents for Polymer (III)>> When using the above polymer (III), suitable solvents for this polymer are as follows: Solvents included in the adhesive removal coating film forming composition include, for example, branched aliphatic hydrocarbons having 3 to 15 carbon atoms; cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclopentene, and cyclohexene; monocyclic aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, and isopropyltoluene (4-isopropyltoluene); polycyclic aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, pyrene, coronene, and fluorene; geraniol, nerol, linalool, citral, citronellol, p-menthane, o-menthane, m-menthane, and diphthane. Examples of cyclic hydrocarbons (terpenes) include monoterpenes such as phenylmenthane, menthol, isomenthol, neomenthol, limonene, α-terpinene, β-terpinene, γ-terpinene, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, 1,4-terpine, 1,8-terpine, carbone, ionone, thujone, camphor, bornane, borneol, norbornane, pinan, α-pinene, β-pinene, thujone, α-thujone, β-thujone, karane, camphor, longifolene, 1,4-cineole, 1,8-cineole, and other monoterpenes, as well as diterpenes such as abietane and abietic acid. These solvents can be used individually or in combination of two or more.

[0147] Of these solvents, solvents containing a cyclic structure are preferred, with benzene, toluene, xylene, mesitylene, isopropyltoluene, 1,2,4-trimethylbenzene, cyclohexane, limonene, and p-menthane being more preferred, and toluene, mesitylene, limonene, and p-menthane being even more preferred.

[0148] <<Suitable Solvents for Polymer (IV)>> The solvents for polymer (IV) are the same as those described in the section <<Suitable Solvents for Polymer (I) or Polymer (II)>> above, which was explained as a solvent for polymer (I) or (II).

[0149] <<Suitable Solvents for Polymer (V)>> The solvents for polymer (V) are the same as those described in the section <<Suitable Solvents for Polymer (I) or Polymer (II)>> above, which was explained as a solvent for polymer (I) or (II).

[0150] The adhesive removal coating film-forming composition can be easily prepared, for example, by uniformly mixing each component, and is used in solution by dissolving it in a suitable solvent. It is preferable to filter the adhesive removal coating film-forming composition prepared in this way using a filter with a pore size of about 0.2 μm before use. The adhesive removal coating film-forming composition prepared in this way also exhibits excellent long-term storage stability at room temperature.

[0151] The proportion of solids in the adhesive removal coating film-forming composition is not particularly limited as long as each component is uniformly dissolved, but is for example 0.5 to 50% by mass, or for example 1 to 30% by mass. Here, solids refer to the total components of the adhesive removal coating film-forming composition excluding the solvent components.

[0152] In this invention, substances other than the target substance that adhere to the substrate are also referred to as "foreign matter." In semiconductor device manufacturing, foreign matter is an unwanted substance. Examples of foreign matter include, in addition to the adhesive residue of the temporary adhesive used for removal in this invention, particles, metal impurities, etching residues, etc. that adhere to the wafer.

[0153] The adhesive removal coating film is particularly preferred for use in the process of bonding wafers together with a temporary adhesive and then removing the adhesive. The coating film of the present invention is formed before the application of the adhesive, and then used to remove foreign matter (residue of the adhesive layer) after the wafer bonding and debonding processes are carried out.

[0154] Dissolution of the adhesive removal coating film in the removal solution means that when the coating film is immersed or washed in the removal solution, it dissolves in the removal solution and disappears from the substrate or other adherend. In this invention, dissolution means that the film formed on the substrate is removed by at least 90% of the initially formed film thickness (i.e., the thickness of the remaining film is 10% or less of the initial film thickness), or at least 95% (i.e., the thickness of the remaining film is 5% or less of the initial film thickness), or at least 99% (i.e., the thickness of the remaining film is 1% or less of the initial film thickness), and most preferably 100% (i.e., the thickness of the remaining film is 0% of the initial film thickness (no remaining film)).

[0155] The adhesive removal coating film-forming composition of the present invention preferably contains a crosslinking agent and additives.

[0156] <Crosslinking Agent> There are no particular restrictions on the crosslinking agent. The crosslinking agent has a structure different from that of the polymer.

[0157] As crosslinking agents, aminoplast crosslinking agents and phenoplast crosslinking agents are preferred. Aminoplast crosslinking agents are addition condensates of compounds having amino groups, such as melamine and guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensates of compounds having phenolic hydroxyl groups with formaldehyde.

[0158] Examples of crosslinking agents include compounds having two or more of the following structures. (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond. The bond is, for example, attached to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0159] R １０１ Preferably, the group is a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bonding bond.

[0160] Preferred crosslinking agents include melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, and compounds having a phenolic hydroxyl group. These can be used individually or in combination of two or more.

[0161] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0162] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0163] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof.

[0164] Furthermore, the glycoluryl compound may also be, for example, a glycoluryl derivative represented by the following formula (1E). (In equation (1E), four R１ Each of these independently represents either a methyl group or an ethyl group, R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.

[0165] Examples of glycoluryl derivatives represented by formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0166] A glycoluryl derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0167] (In formula (2E), R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

[0168] (In formula (3d), R １ (This represents a methyl group or an ethyl group.)

[0169] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0170] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0171] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-1) or (G-2). (In equations (G-1) and (G-2), Q１ R indicates a single bond or an m1-valent organic group. １ and R ４ Each of these represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ Each represents either a hydrogen atom or a methyl group. ３ and R ６ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. １ is 1 ≤ n １ n is an integer ≤ 3. ２ is 2 ≤ n ２ An integer n ≤ 5 ３ is 0 ≤ n ３ n is an integer ≤ 3. ４ is 0 ≤ n ４ integers ≤ 3, 3 ≤ (n １ +n ２ +n ３ +n ４ This shows integers n ≤ 6. ５ is 1 ≤ n ５ n is an integer ≤ 3. ６ is 1 ≤ n ６ An integer n ≤ 4 ７ is 0 ≤ n ７ n is an integer ≤ 3. ８ is 0 ≤ n ８ integers ≤ 3, 2 ≤ (n ５ +n ６ +n ７ +n ８ (This represents an integer between 5 and 2. m1 represents an integer between 2 and 10.)

[0172] Furthermore, examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-3) or (G-4). Compounds represented by formulas (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In equations (G-3) and (G-4), Q ２ R indicates a single bond or an m2 valent organic group. ８ , R９ , R １１ and R １２ Each represents either a hydrogen atom or a methyl group. ７ and R １０ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. ９ is 1 ≤ n ９ n is an integer ≤ 3. １０ is 2 ≤ n １０ An integer n ≤ 5 １１ is 0 ≤ n １１ n is an integer ≤ 3. １２ is 0 ≤ n １２ integers ≤ 3, 3 ≤ (n ９ +n １０ +n １１ +n １２ This shows integers n ≤ 6. １３ is 1 ≤ n １３ n is an integer ≤ 3. １４ is 1 ≤ n １４ An integer n ≤ 4 １５ is 0 ≤ n １５ n is an integer ≤ 3. １６ is 0 ≤ n １６ integers ≤ 3, 2 ≤ (n １３ +n １４ +n １５ +n １６ ) indicates an integer ≤ 5. m² indicates an integer between 2 and 10. ) Q ２ Examples of m2 valent organic groups in this context include m2 valent organic groups having 1 to 4 carbon atoms.

[0173] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0174] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. The above compound can be obtained as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of such a product is TMOM-BP, a trade name of Asahi Organic Chemicals Co., Ltd.

[0175] Among these, glycoluryl compounds are preferred, specifically tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof, and tetramethoxymethyl glycoluryl is more preferred.

[0176] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 500 or less.

[0177] The content of the crosslinking agent is, for example, 5 to 70 parts by mass, or 5 to 60 parts by mass, preferably 5 to 45 parts by mass, per 100 parts by mass of the polymer. From the viewpoint of the degree of hardening of the coating film and prevention of intermixing with the adhesive layer, the content of the crosslinking agent is preferably 5 parts by mass or more per 100 parts by mass of the polymer, and from the viewpoint of solubility in the removal solution, it is preferably 70 parts by mass or less per 100 parts by mass of the polymer.

[0178] <Additives> The adhesive removal coating film forming composition may contain, as additives, a curing catalyst, a light-absorbing compound, a surfactant, an adhesion aid, a rheology modifier, and silica particles.

[0179] The curing catalyst can be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of thermal acid generators include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0180] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0181] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0182] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0183] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0184] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0185] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% to 50% by mass relative to the crosslinking agent, preferably 1% to 30% by mass.

[0186] The absorbent compound is not particularly limited as long as it is a compound that absorbs at the exposure wavelength used. Compounds having aromatic ring structures such as anthracene rings, naphthalene rings, benzene rings, quinoline rings, and triazine rings are preferably used. Furthermore, from the viewpoint of not inhibiting the solubility of the adhesive removal coating film in the removal solution, compounds having a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group are preferably used.

[0187] Examples of light-absorbing compounds that exhibit high absorption for light at a wavelength of 248 nm include 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, 1-hydroxy-2-naphthalenecarboxylic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 6-bromo-2-hydroxynaphthalene, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Rubonic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene Hydroxynaphthalene, 6-hydroxy-1-naphthalenecarboxylic acid, 1-hydroxy-2-naphthalenecarboxylic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 6-hydroxy-2-naphthalenecarboxylic acid, 1-bromo-2-hydroxy-3-naphthalenecarboxylic acid, 1-bromo-4-hydroxy-3-naphthalenecarboxylic acid, 1,6-dibromo-2-hydroxy-3-naphthalenecarboxylic acid, 3-hydroxy-7-methoxy-2-naphthalenecarboxylic acid, 1-amino-2-naphthol, 1,5-dimercaptonaphtha Len, 1,4,5,8-naphthalenetetracarboxylic acid, 3,5-dihydroxy-2-naphthalenecarboxylic acid, 1,4-dihydroxy-2-naphthalenecarboxylic acid, 2-ethoxy-1-naphthalenecarboxylic acid, 2,6-dichloro-1-naphthol, 2-hydroxy-3-naphthalenecarboxylic acid methyl ester, 6-hydroxy-2-naphthalenecarboxylic acid methyl ester, 3-hydroxy-7-methoxy-2-naphthalenecarboxylic acid methyl ester, 3,7-dihydroxy-2-naphthalenecarboxylic acid methyl ester, 2,Examples include 4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphthalenchiol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphthalenecarboxylic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthalene, 1-acetyl-2-naphthol, 9-anthracenecarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, and 1,8,9-trihydroxyanthracene.

[0188] Furthermore, absorbent compounds that exhibit high absorption for light with a wavelength of 193 nm include, for example, benzoic acid, 4-methylbenzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, 2-methoxybenzoic acid, isophthalic acid, terephthalic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-acetoxybenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, trimesic acid, 1,4-benzenedicarboxylic acid, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-acetylbenzoic acid, and pyrome Examples include littic acid, trimesic anhydride, 2-s[bis-(4-hydroxyphenyl)-methyl]benzoic acid, 3,4,5-trihydroxybenzoic acid, 2-benzophenone carboxylic acid, m-phenylbenzoic acid, 3-(4'-hydroxyphenoxy)benzoic acid, 3-phenoxybenzoic acid, phenol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 2-methylphenol, 3-methylphenol, 4-methylphenol, 1,3,5-trihydroxybenzene, 2,2-bis-4-hydroxyphenylpropane, 2-hydroxybiphenyl, 2-aminophenol, 3-aminophenol, 4-aminophenol, and 4-benzyloxyphenol. Furthermore, these light-absorbing compounds can be used in reaction with polymers or compounds having one or more reactive groups to suppress sublimation during firing for adhesive removal coating film formation.

[0189] For example, in the case of absorbent compounds having carboxyl groups or phenolic hydroxyl groups, compounds obtained by reacting them with polyfunctional epoxy compounds such as tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris(p-(2,3-epoxypropoxy)phenyl)propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether, or polymers containing structures with epoxy groups such as glycidyl methacrylate, can be used.

[0190] The above light-absorbing compounds can be used alone or in combination of two or more. When light-absorbing compounds are used, their content is, for example, 1 to 300 parts by mass, or 1 to 200 parts by mass, or 1 to 100 parts by mass, or 5 to 100 parts by mass, per 100 parts by mass of polymer. When the content of the light-absorbing compound is 300 parts by mass or less per 100 parts by mass of polymer, the solubility of the adhesive removal coating film in the removal solution is excellent, and the adhesive removal coating film is less likely to intermix with the adhesive layer.

[0191] Compositions for forming adhesive-removing coating films may contain polyhydric phenol compounds or carboxyl group-containing compounds to accelerate the dissolution rate in the removal solution. Such compounds are not particularly limited, but examples include tris-hydroxyphenylethane, bisphenol-A, bisphenol-S, 4,4'-isopropylidene-di-o-cresol, 5-tert-butylpyrogallol, hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobisindan-5,5',6,6'-tetrol, 4,4'-(9-fluorenylidene)diphenol, and bisphenol. Polyhydric phenols such as 5,5'-AP, bisphenol-P, 5-α,α-dimethyl-4-hydroxybenzylsalicylic acid, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 5,5'-di-tert-butyl-2,2',4,4'-tetrahydroxybenzophenone, pyromellitic acid, phthalic acid, trimellitic acid, 4-sulfophthalic acid, benzenehexacarboxylic acid, 2,3-naphthalenedicarboxylic acid, 4- Examples include polycarboxylic acids such as hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3'-,4,4'-biphenyltetracarboxylic acid, 3,3'-,4,4'-benzophenonetetracarboxylic acid, 3,3'-,4,4'-diphenylethertetracarboxylic acid, 3,3'-,4,4'-diphenylsulfonetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclohexanetetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, as well as carboxylic acids or polymers containing carboxylic acids or carboxylic acid anhydrides such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. The amount of the above compound added is, for example, 20% by mass or less, preferably 10% by mass or less, of the solid content of the adhesive removal coating film forming composition, and is used as needed.

[0192] The adhesive removal coating film-forming composition may also contain compounds having a carboxyl group or phenolic hydroxyl group protected by a group that is readily decomposed in the presence of an acid, such as a tert-butyl group, a tetrahydropyranyl group, a 1-ethoxyethyl group, and a trimethylsilyl group, for the purpose of adjusting the dissolution rate in the removal solution.

[0193] Examples of such compounds include di-tert-butylmalonate, tert-butyl acetate, tert-butyl propionate, tert-butyl acetate, tert-amyl acetate, tert-butyl benzoate ester, and tert-butyl pivalate.

[0194] These compounds readily generate carboxyl groups or phenolic hydroxyl groups in the presence of acid, giving compounds with increased solubility in alkaline removal solutions. Therefore, it is preferable to add these compounds together with a photoacid generator to a composition for forming adhesive removal coating films. That is, in an adhesive removal coating film formed from a composition for forming adhesive removal coating films containing a compound having a carboxyl group or phenolic hydroxyl group protected by a group that readily decomposes in the presence of the above-mentioned acid, and a photoacid generator, the carboxyl group or phenolic hydroxyl group of the compound having a carboxyl group or phenolic hydroxyl group protected by a group that readily decomposes in the presence of acid is regenerated in the exposed portion by the acid generated from the photoacid generator upon exposure, and as a result, the solubility of the adhesive removal coating film in the exposed portion in alkaline removal solutions is increased.

[0195] When a compound having a carboxyl group or phenolic hydroxyl group protected by a group that is readily decomposed in the presence of the above-mentioned acid is used, its content is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or for example, 20 to 10 parts by mass, per 100 parts by mass of the polymer. When a photoacid generator is used together with a compound having a carboxyl group or phenolic hydroxyl group protected by a group that is readily decomposed in the presence of an acid, its content is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or for example, 1 to 10 parts by mass, per 100 parts by mass of the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is readily decomposed in the presence of an acid.

[0196] The adhesive removal coating film-forming composition may contain a surfactant. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as Eftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173 (manufactured by DIC Corporation, trade name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., trade name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name). The amount of these surfactants included is usually 0.2% by mass or less, preferably 0.1% by mass or less, of the total components of the adhesive removal coating film-forming composition. These surfactants may be added individually or in combination of two or more types.

[0197] The adhesive removal coating film-forming composition may contain silica particles. Examples of silica particles include silicone powder having a predetermined average particle diameter, or silica sol containing silica having a predetermined average particle diameter.

[0198] Specific examples of silicone powder include, but are not limited to, the KMP series silicone powders manufactured by Shin-Etsu Chemical Co., Ltd., such as KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030.

[0199] Specific examples of colloidal silica (silica sol) include Nissan Chemical Corporation's MA-ST-S (methanol-dispersed silica sol), MT-ST (methanol-dispersed silica sol), MA-ST-UP (methanol-dispersed silica sol), product names MA-ST-M (methanol-dispersed silica sol), MA-ST-L (methanol-dispersed silica sol), IPA-ST-S (isopropanol-dispersed silica sol), IPA-ST (isopropanol-dispersed silica sol), IPA-ST-UP (isopropanol-dispersed silica sol), IPA-ST-L (isopropanol-dispersed silica sol), IPA-ST-ZL (isopropanol-dispersed silica sol), NPC-ST-30 (n-propyl cellosolve-dispersed silica sol), and PGM-ST. Examples of silica sols include (1-methoxy-2-propanol dispersed silica sol), DMAC-ST (dimethylacetamide dispersed silica sol), XBA-ST (xylene / n-butanol mixed solvent dispersed silica sol), trade name EAC-ST (ethyl acetate dispersed silica sol), PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol), MEK-ST (methyl ethyl ketone dispersed silica sol), MEK-ST-UP (methyl ethyl ketone dispersed silica sol), MEK-ST-L (methyl ethyl ketone dispersed silica sol), MIBK-ST (methyl isobutyl ketone dispersed silica sol), etc., but are not limited to these.

[0200] (Adhesive-removing coating film) The adhesive-removing coating film of the present invention is formed from the adhesive-removing coating film forming composition of the present invention.

[0201] The adhesive-removing coating film of the present invention can be formed, for example, as follows: The adhesive-removing coating film-forming composition of the present invention is applied to a semiconductor substrate or electronic device layer by an appropriate coating method such as a spinner, coater, or immersion, and then the adhesive-removing coating film is formed by firing. The firing conditions are appropriately selected from a firing temperature of 80°C to 300°C and a firing time of 0.3 to 60 minutes.

[0202] The thickness of the adhesive removal coating film is typically 5 nm to 1 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0203] The dissolution rate of the adhesive-removing coating film formed in the removal solution is, for example, 0.1 nm to 50 nm per second, preferably 0.2 nm to 40 nm per second, and more preferably 0.3 to 20 nm per second, as a rate of decrease in film thickness. If the dissolution rate is lower than this, the time required to remove the adhesive-removing coating film will be longer, resulting in a decrease in productivity.

[0204] The adhesive-removing coating film formed from the adhesive-removing coating film-forming composition of the present invention allows for control over the dissolution rate of the adhesive-removing coating film in the removal solution by changing the firing conditions during formation. For a constant firing time, increasing the firing temperature results in the formation of an adhesive-removing coating film with a lower dissolution rate in the removal solution.

[0205] For adhesive removal coating films, exposure may be performed after film formation. Exposure may be performed on the entire wafer or through a mask having a predetermined pattern. For exposure, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm) can be used. After exposure, post-exposure baking (PEB) may be performed as needed.

[0206] (Laminated body) The laminated body of the present invention comprises: a semiconductor substrate or an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate.

[0207] In a more preferred embodiment, the laminated body of the present invention is obtained by laminating: a semiconductor substrate or an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate in this order.

[0208] The adhesive removal coating film is formed from the above-mentioned composition for forming an adhesive removal coating film of the present invention.

[0209] The adhesive layer is used for temporarily bonding the semiconductor substrate or electronic device layer and the support substrate. By forming the adhesive removal coating film between the semiconductor substrate or electronic device layer and the support substrate (more preferably between the adhesive removal coating film and the adhesive layer), as will be described in detail below, after the semiconductor substrate or electronic device layer and the support substrate are separated, peeling residues of the adhesive layer remaining on the semiconductor substrate or electronic device layer or peeling residues of the adhesive layer remaining on the support substrate can be easily and cleanly removed together with the adhesive removal coating film by, for example, a detergent composition for cleaning semiconductor substrates and the like.

[0210] As described above, the laminated body of the present invention only needs to have layers laminated in the following order: (X1) semiconductor substrate or electronic device layer / adhesive removal coating film / adhesive layer / support substrate. Furthermore, in the laminated body of the present invention, a release agent layer may be provided, or a plurality of adhesive removal coating films may be formed, in order to facilitate the separation of the semiconductor substrate or electronic device layer and the support substrate, or to cleanly remove peeling residues remaining on the semiconductor substrate or electronic device layer after the separation of the semiconductor substrate or electronic device layer and the support substrate. Examples of the layer structure of the laminated body of the present invention include the following patterns (X2) to (X6) in addition to the above-mentioned pattern (X1).

[0211] (X2) Semiconductor substrate or electronic device layer / Adhesive removal coating film / Release agent layer / Adhesive layer / Support substrate (X3) Semiconductor substrate or electronic device layer / Adhesive removal coating film / Adhesive layer / Release agent layer / Support substrate As in the above patterns (X2) and (X3), the release agent layer may be provided between the adhesive removal coating film and the adhesive layer, or between the adhesive layer and the support substrate.

[0212] (X4) Semiconductor substrate or electronic device layer / Adhesive removal coating film / Adhesive layer / Adhesive removal coating film / Support substrate As shown in the (X4) pattern above, if the adhesive removal coating film is provided between the semiconductor substrate or electronic device layer and the adhesive layer, an additional adhesive removal coating film (second layer) may be provided between the adhesive layer and the support substrate, depending on the purpose.

[0213] (X5) Semiconductor substrate or electronic device layer / Adhesive removal coating film / Release agent layer / Adhesive layer / Adhesive removal coating film / Support substrate (X6) Semiconductor substrate or electronic device layer / Adhesive removal coating film / Adhesive layer / Release agent layer / Adhesive removal coating film / Support substrate A laminate may also have a layer configuration in which multiple layers of adhesive removal coating films are formed and a release agent layer is also formed, as in the above (X5) pattern or the above (X6) pattern.

[0214] (X7) Semiconductor substrate or electronic device layer / adhesive layer / adhesive removal coating film / support substrate (X8) Semiconductor substrate or electronic device layer / release agent layer / adhesive layer / adhesive removal coating film / support substrate (X9) Semiconductor substrate or electronic device layer / adhesive layer / release agent layer / adhesive removal coating film / support substrate Even when an adhesive removal coating film is formed between the semiconductor substrate or electronic device layer and the support substrate, as in the patterns (X7) to (X9) above, it is easier to remove the residue of the adhesive layer after separating the semiconductor substrate or electronic device layer from the support substrate, so a laminate with such a configuration is also acceptable.

[0215] In the construction of the laminate, the adhesive layer will be explained first.

[0216] <Adhesive Layer> The adhesive layer according to the present invention is used to temporarily bond a semiconductor substrate or electronic device layer to a support substrate. The adhesive layer is formed from an adhesive composition. The adhesive composition is not particularly limited as long as it can temporarily bond the semiconductor substrate or electronic device layer to the support substrate, and can be selected according to the purpose. Examples include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenol resin-based adhesives, etc.

[0217] Among these, polysiloxane-based adhesives are preferred as adhesive compositions because they exhibit suitable adhesive properties during processing of semiconductor substrates and the like, can be readily peeled off after processing, have excellent heat resistance, and can be readily removed with cleaning agent compositions.

[0218] Examples of embodiments of the adhesive composition include the adhesive compositions shown in [i] to [vi] below. The adhesive compositions shown in [i] to [vi] will be described in detail below.

[0219] <<Adhesive composition represented by [i]>> The adhesive composition contains a polyorganosiloxane. In a preferred embodiment, the adhesive composition contains a component that hardens by a hydrosilylation reaction.

[0220] For example, the adhesive composition used in the present invention contains a curing component (A) that becomes an adhesive component. The adhesive composition used in the present invention may contain a curing component (A) that becomes an adhesive component and a component (B) that does not undergo a curing reaction. Here, an example of the component (B) that does not undergo a curing reaction is a polyorganosiloxane. In this invention, "does not undergo a curing reaction" does not mean that no curing reaction occurs at all, but rather that the curing reaction that occurs in the curing component (A) does not occur.

[0221] <<<Adhesive Component>>> In a preferred embodiment, adhesive component (A) may be a component that hardens by a hydrosilylation reaction, or a polyorganosiloxane component (A') that hardens by a hydrosilylation reaction. From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the adhesive component contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter sometimes referred to as "component (A-1)") and a component having a Si-H group (hereinafter sometimes referred to as "component (A-2)").

[0222] <<<<Components (A-1) and (A-2)>>>> Component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group with 2 to 40 carbon atoms bonded to a silicon atom. Component (A-2) preferably contains a polyorganosiloxane (a2) having a Si-H group. Here, the alkenyl group with 2 to 40 carbon atoms may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0223] In another preferred embodiment, the adhesive composition cured by a hydrosilylation reaction is SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) expressed as R ４ R ５ SiO ２／２ Siloxane units (D units) and R are represented by these units. ６ SiO ３／２ The polysiloxane (A1) comprises one or more units selected from the group consisting of siloxane units (T units) represented by , and a platinum group metal catalyst (A-3), wherein the polysiloxane (A1) is SiO ２ Siloxane units (Q' units) represented by R １ 'R ２ 'R ３ 'SiO １／２Siloxane units (M' units) expressed as R ４ 'R ５ 'SiO ２／２ Siloxane units (D' units) and R are represented by these units. ６ 'SiO ３／２ A polyorganosiloxane (a1') containing one or more units selected from the group consisting of siloxane units (T' units) represented by , and at least one unit selected from the group consisting of M' units, D' units and T' units, and SiO ２ Siloxane units (Q'' units) expressed as R １ "R ２ "R ３ "SiO １／２ Siloxane units (M'' units) expressed as R ４ "R ５ "SiO ２／２ Siloxane units (D'' units) and R ６ "SiO ３／２ The polyorganosiloxane (a2') contains one or more units selected from the group consisting of siloxane units (T'' units) represented by , and also contains at least one unit selected from the group consisting of M'' units, D'' units, and T'' units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0224] R １ ~R ６ This group or atom is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0225] R １ '~R ６ ' represents a group that bonds to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R １ '~R ６At least one of the ' groups is an alkenyl group which may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0226] R １ "~R ６ " represents a group or atom bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or hydrogen atom, R １ "~R ６ At least one of the atoms is a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0227] The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0228] Specific examples of substituted linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, and 4-methyl-n-pentyl group. Examples of methyl groups include, but are not limited to, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, the methyl group is particularly preferred.

[0229] Specific examples of cyclic alkyl groups, whether substituted or not, include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, and 3,3-dimethyl-cyclobutyl group. Examples of cycloalkyl groups include cycloalkyl groups such as 2-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl; bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl. However, the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0230] The alkenyl group may be linear or branched, and its number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0231] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl groups, allyl groups, buttenyl groups, and pentenyl groups. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, ethenyl groups and 2-propenyl groups are particularly preferred. Specific examples of substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl groups. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0232] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl groups in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) in polyorganosiloxane (a2') form a cross-linked structure through a hydrosilylation reaction with a platinum group metal catalyst (A-3), and then harden. As a result, a hardened film is formed.

[0233] Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As polyorganosiloxane (a1'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0234] Two or more preferred combinations selected from the group consisting of Q' units, M' units, D' units, and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units, and M' units).

[0235] Furthermore, when polyorganosiloxane (a1') contains two or more polyorganosiloxanes, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

[0236] Polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q'' units, M'' units, D'' units, and T'' units, and also contains at least one unit selected from the group consisting of M'' units, D'' units, and T'' units. As polyorganosiloxane (a2'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0237] Two or more preferred combinations 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).

[0238] Polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, R １ '~R ６ The proportion of alkenyl groups in the total 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 an alkyl group.

[0239] Polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom are bonded to the silicon atom, R １ "~R ６ The proportion of hydrogen atoms in all substituents and substituted 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 an alkyl group.

[0240] When the adhesive composition contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 0.5:1.0.

[0241] When the adhesive composition comprises component (A-1) and component (A-2), the mass ratio of component (A-1) to component (A-2) [(A-1):(A-2)] is not particularly limited, but is, for example, 99:1 to 50:50, preferably 95:5 to 80:20.

[0242] 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 for each, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxane can be measured, for example, using a GPC system (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as an eluent (elution solvent), a flow rate (flow velocity) of 0.35 mL / min, and polystyrene (Shodex, manufactured by Showa Denko K.K.) as a standard sample.

[0243] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 10 to 1000000 (mPa·s) for each, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 50 to 10000 (mPa·s). The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured with an E-type rotational viscometer at 25°C.

[0244] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction. Therefore, the curing mechanism thereof is different from that via, for example, silanol groups, and hence none of the siloxanes need to contain silanol groups or functional groups that form silanol groups via hydrolysis such as alkyloxy groups.

[0245] <<<<Platinum Complex Catalyst>>>> In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal catalyst (A-3) together with a polyorganosiloxane component (A'). Such a platinum group metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of polyorganosiloxane (a1) and the Si-H group of polyorganosiloxane (a2).

[0246] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinum-dic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetate. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum. The amount of platinum group metal catalyst (A-3) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0247] <<

[0248] <<<Release Agent Component>>> The adhesive composition of the present invention may or may not contain a release agent component. The release agent component is not particularly limited, but from the viewpoint of more favorably obtaining the effects of the present invention, polyorganosiloxane is preferred. Polyorganosiloxane as a release agent component does not usually react with adhesive components. For example, polyorganosiloxane as a release agent component is a component that does not undergo hydrosilylation reactions.

[0249] The polyorganosiloxane is not particularly limited and examples include polydimethylsiloxane, epoxy group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and carbinol-modified polyorganosiloxane.

[0250] <<<<<Polydimethylsiloxane>>>>> The "polydimethylsiloxane" in this invention differs from epoxy group-containing polydimethylsiloxane, phenyl group-containing polydimethylsiloxane, carbinol-modified polyorganosiloxane, etc., in that it is an unmodified polyorganosiloxane having a methyl group as an organic group bonded to a silicon atom.

[0251] Specific examples of polydimethylsiloxanes include those represented by formula (M1), but are not limited to these.

[0252] (n ４ (This indicates the number of repeating units and is a positive integer.)

[0253] The weight-average molecular weight of polydimethylsiloxane is not particularly limited, but is usually 100,000 to 2,000,000, and from the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. The degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, and from the viewpoint of reproducibly achieving suitable peeling, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and degree of dispersion can be measured by the method described above for polyorganosiloxane. The viscosity of polydimethylsiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm². ２ The viscosity is given by / s. Note that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0254] <<<<<Epoxy group-containing polyorganosiloxane>>>>> Epoxy group-containing polyorganosiloxanes that do not have epoxy groups at the terminals are preferred. Epoxy group-containing polyorganosiloxanes that have epoxy groups in their side chains are preferred. Examples of epoxy group-containing polyorganosiloxanes include R １１ R １２ SiO ２／２ Siloxane units (D) are represented by these units. １０ Examples include those containing units.

[0255] R １１ R is a group that bonds to a silicon atom and represents an alkyl group. １２The group is a group that bonds to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups include those mentioned above. The epoxy group in an organic group containing an epoxy group may be an independent epoxy group that does not condense with other rings, or it may be an epoxy group that forms a fused ring with other rings, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of an epoxy group-containing polyorganosiloxane is, but is not limited to, an epoxy group-containing polydimethylsiloxane.

[0256] Epoxy group-containing polyorganosiloxanes are the siloxane units (D) described above. １０ It includes units, but D １０ In addition to units, Q units, M units and / or T units may also be included. In a preferred embodiment of the present invention, a specific example of the epoxy group-containing polyorganosiloxane is D １０ Polyorganosiloxanes consisting only of units, D １０ Polyorganosiloxane containing units and Q units, D １０ Polyorganosiloxane containing units and M units, D １０ Polyorganosiloxanes containing units and T units, D １０ Polyorganosiloxane containing units, Q units, and M units, D １０ Polyorganosiloxane containing units, M units, and T units, D １０ Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0257] Epoxy group-containing polyorganosiloxanes may have epoxy groups in their side chains, or at one end, or at both ends.

[0258] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. Its 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.

[0259] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0260] (m １ and n １ (This indicates the number of each repeating unit and is a positive integer.)

[0261] (m ２ and n ２ R is a positive integer indicating the number of repeating units, and R is an alkylene group having 1 to 10 carbon atoms, which may be interrupted by at least one of the oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bond, carbon-carbon triple bond, -N=N-).

[0262] (m ３ , n ３ and o ３ R is a positive integer indicating the number of repeating units, and R is an alkylene group having 1 to 10 carbon atoms, which may be interrupted by at least one of the oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bond, carbon-carbon triple bond, -N=N-).

[0263] In the above general formula, m １ , m ２ , m ３ , and o ３ If there are two or more of these repeating units, they may be arranged adjacent to each other to form a block, or they may be arranged randomly.

[0264] Furthermore, the polyorganosiloxane represented by formula (E3) is an epoxy group-containing polyorganosiloxane and a phenyl group-containing polyorganosiloxane, since it has both an epoxy group and a phenyl group. The epoxy group-containing polyorganosiloxane may or may not have a phenyl group.

[0265] The weight-average molecular weight of the epoxy group-containing polyorganosiloxane is not particularly limited, but is usually 100,000 to 2,000,000, and is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, from the viewpoint of reproducibly achieving the effects of the present invention. The degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, and is preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of reproducibly achieving suitable peeling. The weight-average molecular weight and degree of dispersion can be measured by the method described above for polyorganosiloxane. The viscosity of the epoxy group-containing polyorganosiloxane is not particularly limited, but is usually 1,000 to 2,000,000 mm². ２ The viscosity is given by / s. Note that the viscosity of epoxy group-containing polyorganosiloxanes is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0266] <<<<<Phenyl group-containing polyorganosiloxane>>>>> Examples of phenyl group-containing polyorganosiloxanes include R ３１ R ３２ SiO ２／２ Siloxane units (D) are represented by these units. ３０ Examples include those containing units.

[0267] R ３１ R is a group that bonds to a silicon atom and represents a phenyl group or an alkyl group.３２ This is a group that bonds to a silicon atom, representing a phenyl group. Specific examples of alkyl groups include those mentioned above, but a methyl group is preferred.

[0268] Phenyl group-containing polyorganosiloxanes are the siloxane units (D) described above. ３０ It includes units, but D ３０ In addition to units, Q units, M units, and / or T units may also be included.

[0269] In a preferred embodiment, a specific example of a phenyl group-containing polyorganosiloxane is D ３０ Polyorganosiloxanes consisting only of units, D ３０ Polyorganosiloxane containing units and Q units, D ３０ Polyorganosiloxane containing units and M units, D ３０ Polyorganosiloxanes containing units and T units, D ３０ Polyorganosiloxane containing units, Q units, and M units, D ３０ Polyorganosiloxane containing units, M units, and T units, D ３０ Examples include polyorganosiloxanes containing units, Q units, M units, and T units.

[0270] Specific examples of phenyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (P1) or (P2).

[0271] (m5 and n5 represent the number of repeating units and are positive integers.)

[0272] (m6 and n6 are positive integers, representing the number of each repeating unit.)

[0273] In the above general formula, m ５ , and m ６ If there are two or more of these repeating units, they may be arranged adjacent to each other to form a block, or they may be arranged randomly.

[0274] <<<<Carbinol-modified polyorganosiloxane>>>>> There are no particular restrictions on the carbinol-modified polyorganosiloxane. A carbinol-modified polyorganosiloxane is a polyorganosiloxane having a hydroxyl group directly bonded to a carbon atom. Thus, the carbinol in "carbinol-modified polyorganosiloxane" is not limited to methanol in the narrow sense, but includes methanol derivatives.

[0275] Carbinol-modified polyorganosiloxanes are, for example, carbinol-modified polydimethylsiloxanes.

[0276] The number of hydroxyl groups directly bonded to carbon atoms in a carbinol-modified polyorganosiloxane is not particularly limited and may be one or two or more.

[0277] Carbinol-modified polyorganosiloxane may have hydroxyl groups directly bonded to carbon atoms in its side chains, or at one end, or at both ends. It is preferable that the carbinol-modified polyorganosiloxane has hydroxyl groups directly bonded to carbon atoms in its side chains. In this case, even a small amount of carbinol-modified polyorganosiloxane can impart good release properties to the adhesive layer formed from the adhesive composition.

[0278] Carbinol-modified polyorganosiloxanes, for example, have a group represented by the following formula (Cg) as a group directly bonded to a silicon atom.

[0279] (In formula (Cg), R １ The symbol (*) represents a group with one or more carbon atoms. The asterisk (*) represents a bond to a silicon atom. However, the hydroxyl group in formula (Cg) is directly bonded to a carbon atom.

[0280] The number of hydroxyl groups directly bonded to a carbon atom in the group represented by formula (Cg) may be one or more. Examples of two or more include two, three, four, and so on.

[0281] R １ The number of carbon atoms is not particularly limited; for example, it may be 1 to 30, 1 to 20, or 1 to 10.

[0282] Examples of groups represented by formula (Cg) include those represented by the following formulas (Cg-1) to (Cg-4). (In formula (Cg-1), R １１ R represents an alkylene group having 1 to 6 carbon atoms, which may be substituted with an alkoxy group having 1 to 3 carbon atoms. In formula (Cg-2), R １２ R represents an alkylene group with 1 to 6 carbon atoms. １３ R represents an alkylene group having 1 to 6 carbon atoms, which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group. In formula (Cg-3), R １４ R represents an alkylene group with 1 to 6 carbon atoms. １５ R represents an alkylene group with 1 to 3 carbon atoms. m represents an integer from 1 to 10. In formula (Cg-4), R １６ ~R １８ Each of these independently represents an alkylene group with 1 to 6 carbon atoms. In formulas (Cg-1) to (Cg-4), * represents a bond to a silicon atom.

[0283] R １１ ~R １８ The alkylene group may be linear, branched, or cyclic.

[0284] Examples of groups represented by formula (Cg) include the following: (In the formula, m1 represents an integer between 2 and 10. * represents a bond connecting to a silicon atom.)

[0285] Carbinol-modified polyorganosiloxanes are represented, for example, by the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R ５１ Each of these independently represents a hydrocarbon group. １ R represents the base represented by the above formula (Cg). n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1. In formula (CPS-2), R５２ Each of these independently represents a hydrocarbon group. ２ X represents the group represented by the above formula (Cg). ３ (where n3 represents a hydrocarbon group or a group represented by the above formula (Cg). n3 represents an integer of 0 or greater.)

[0286] R ５１ , R ５２ , and X ３ Examples of hydrocarbon groups in this include alkyl groups having 1 to 8 carbon atoms. A methyl group is preferred among the alkyl groups having 1 to 8 carbon atoms. That is, the carbinol-modified polyorganosiloxane is preferably a polydimethylsiloxane represented by the following formula (CPS-1a) or formula (CPS-2a). (In formula (CPS-1a), X １ represents the base represented by the above formula (Cg). n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1. In formula (CPS-2a), X ２ X represents the group represented by the above formula (Cg). ３ (where n3 represents a methyl group or a group represented by the above formula (Cg). n3 represents an integer of 0 or greater.)

[0287] Furthermore, the carbinol-modified polyorganosiloxane represented by formula (CPS-1) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a) have hydroxyl groups directly bonded to carbon atoms in their side chains. The carbinol-modified polyorganosiloxane represented by formula (CPS-2) and the carbinol-modified polydimethylsiloxane represented by formula (CPS-2a) have hydroxyl groups directly bonded to carbon atoms at one or both ends.

[0288] Furthermore, in the carbinol-modified polyorganosiloxane represented by formula (CPS-1), if n2 is 2 or more, -Si(R ５１ ) (X １ The siloxane units represented by formula (CPS-1a) -O- may be arranged adjacently to form blocks, or they may be arranged randomly. In addition, in the carbinol-modified polydimethylsiloxane represented by formula (CPS-1a), when n2 is 2 or more, -Si(CH ３ ) (X１ The siloxane units represented by )-O- may be arranged adjacent to each other to form blocks, or they may be arranged randomly.

[0289] The weight-average molecular weight of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 500 to 1,000,000, and is preferably 5,000 to 50,000 from the viewpoint of reproducibly achieving the effects of the present invention. Furthermore, the degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, and is preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of reproducibly achieving suitable peeling. The viscosity of the carbinol-modified polyorganosiloxane is not particularly limited, but is usually 100 to 200,000 mm². ２ The viscosity is given by / s. Note that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, centistokes (cSt) = mm². ２ It is / s. Viscosity (mPa·s) is compared to density (g / cm³). ３ It can also be obtained by dividing by ). In other words, the value can be obtained from the viscosity and density measured with an E-type rotational viscometer at 25°C, and the kinematic viscosity (mm²) ２ / s)=viscosity (mPa・s) / density (g / cm ３ It can be calculated using the formula:

[0290] The polyorganosiloxane, which is the release agent component, may be a commercially available product or a synthesized product. Examples of commercially available polyorganosiloxanes include the WACKERSILICONE FLUID AK series (AK50, AK350, AK1000, AK10000, AK1000000) and GENIOPLAST, both manufactured by Wacker Chemistry. GUM, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (product names CMS-227, ECMS-327, EMS-622) manufactured by Gellest; epoxy group-containing polyorganosiloxane (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (DOWSIL) manufactured by Dow-Toray. Examples include, but are not limited to, BY16-839, DOWSIL8413, DOWSIL8411; phenyl group-containing polyorganosiloxanes from Gellest (PMM-1043, PMM-1025, PDM-0421, PDM-0821); phenyl group-containing polyorganosiloxanes from Shin-Etsu Chemical Co., Ltd. (KF50-3000CS); and phenyl group-containing polyorganosiloxanes from Momentive (TSF431, TSF433).

[0291] Furthermore, commercially available carbinol-modified polyorganosiloxanes include, for example, KF6000, KF6001, KF6002, KF6003, X-22-4039, X-22-4015 from Shin-Etsu Silicone Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, MCR-C63 from Dow Toray Corporation. Examples include 16-201, DOWSIL SF 8427 Fluid, and DOWSIL SF 8428 Fluid.

[0292] When an adhesive composition contains a release agent component, the content of the release agent component in the adhesive composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the nonvolatile content of the adhesive composition. There is no particular upper limit, but for example, is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The nonvolatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0293] <<<Solvent>>> The adhesive composition may contain a solvent for purposes such as adjusting viscosity. Specific examples include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specifically, examples include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Such solvents can be used individually or in combination of two or more.

[0294] If the adhesive composition contains a solvent, its content is appropriately set considering the viscosity of the desired composition, the application method used, the thickness of the thin film to be produced, etc., but is typically in the range of about 10 to 90% by mass of the entire composition.

[0295] 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.

[0296] An example of an adhesive composition used in the present invention can be manufactured by mixing an adhesive component, a release agent component, and a solvent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly manufacture an adhesive composition include, for example, dissolving the adhesive component and the release agent component in the solvent, or dissolving a portion of the adhesive component and the release agent component in the solvent, dissolving the remainder in the solvent, and then mixing the resulting solutions. However, the invention is not limited to these methods. When preparing the adhesive composition, heating may be used as appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the manufacturing of the adhesive composition or after all components have been mixed.

[0297] <<Adhesive composition represented by [ii]>> As the adhesive composition, for example, a temporary adhesive described in publications such as International Patent Publication WO2021 / 220929 can be used, and more specifically, the photocurable silicone resin composition described below is an example. The adhesive composition according to the present invention consists of a photocurable silicone resin composition containing a non-functional organopolysiloxane.

[0298] Such a photocurable silicone resin composition preferably contains, for example, the following components (A) to (D): (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass; (B) Organohydrogenpolysiloxane containing two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: in an amount such that the total number of SiH groups in component (B) is 0.3 to 10 in molar ratio to the total number of alkenyl groups in component (A); (C) Non-functional organopolysiloxane: 0.1 to 200 parts by mass; and (D) Photoactive hydrosilylation reaction catalyst: 0.1 to 5,000 ppm in terms of metal atomic weight relative to the total mass of components (A), (B), and (C).

[0299] <<<Component (A)>>> Component (A) is an organopolysiloxane having two or more alkenyl groups in one molecule. Component (A) may be a linear or branched diorganopolysiloxane containing two or more alkenyl groups in one molecule, or a diorganopolysiloxane containing two or more alkenyl groups in one molecule and SiO ４／２ Examples include organopolysiloxanes with a three-dimensional network structure having siloxane units (Q units) expressed in units. Of these, diorganopolysiloxanes or organopolysiloxanes with a three-dimensional network structure having an alkenyl group content of 0.6 to 9 mol% are preferred. In this invention, the alkenyl group content is the ratio (mol%) of the number of alkenyl groups to the number of Si atoms in the molecule.

[0300] Examples of such organopolysiloxanes include those represented by formulas (A-1) to (A-3) described in paragraph

[0015] of publications such as International Patent Publication WO2021 / 220929.

[0301] <<<Component (B)>>> Component (B) is a crosslinking agent and is an organohydrogenpolysiloxane having at least two, preferably three or more, hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. The organohydrogenpolysiloxane may be linear, branched, or cyclic. Furthermore, the organohydrogenpolysiloxane may be used alone or in combination of two or more types.

[0302] The viscosity of component (B), organohydrogenpolysiloxane, at 25°C is preferably 1 to 5,000 mPa·s, and more preferably 5 to 500 mPa·s.

[0303] <<<Component (C)>>> Component (C) is a non-functional organopolysiloxane. Here, "non-functional" means that the molecule does not have reactive groups such as alkenyl groups, hydrogen atoms, hydroxyl groups, alkoxy groups, halogen atoms, epoxy groups, etc., that are directly or via any group attached to the silicon atom.

[0304] Examples of such non-functional organopolysiloxanes include unsubstituted or substituted organopolysiloxanes having monovalent hydrocarbon groups other than aliphatic unsaturated hydrocarbon groups, having 1 to 12, preferably 1 to 10 carbon atoms. Examples of such monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups. Furthermore, some or all of the hydrogen atoms of these groups may be substituted with halogen atoms such as chlorine, fluorine, and bromine atoms. Examples of such groups include halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl. The monovalent hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.

[0305] The molecular structure of the non-functional organopolysiloxane component (C) is not particularly limited and may be linear, branched, cyclic, etc., but a linear or branched organopolysiloxane is preferred, and a linear diorganopolysiloxane is preferred in which the main chain basically consists of repeating diorganosiloxane units and both ends of the molecular chain are sealed with triorganosiloxy groups.

[0306] Component (C), the non-functional organopolysiloxane, is preferably such that its viscosity (at 25°C) in a 30% by mass toluene solution is 100 to 500,000 mPa·s, and more preferably 200 to 100,000 mPa·s, from the viewpoint of the workability of the composition, the coatability on the substrate, the mechanical properties of the cured product, and the peelability of the support. Within this range, it has an appropriate molecular weight, so it does not volatilize when the silicone resin composition is heat-cured, making it difficult to obtain the desired effect, nor does it cause wafer cracking in wafer thermal processes such as CVD, and it is preferable because it has good workability and coatability.

[0307] The non-functional organopolysiloxanes include dimethylsiloxane polymers with trimethylsiloxy groups sealed at both ends of the molecular chain, phenylmethylpolysiloxanes with trimethylsiloxy groups sealed at both ends of the molecular chain, 3,3,3-trifluoropropylmethylsiloxane polymers with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylsiloxane / methylphenylsiloxane copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, dimethylsiloxane / 3,3,3-trifluoropropylmethyl copolymers with trimethylsiloxy groups sealed at both ends of the molecular chain, and trimethylsiloxy groups sealed at both ends of the molecular chain. Examples include lusiloxy group-sealed methylphenylsiloxane / 3,3,3-trifluoropropylmethyl copolymer, trimethylsiloxane / 3,3,3-trifluoropropylmethylsiloxane / methylphenylsiloxane copolymer, dimethylphenylsiloxane / dimethylpolysiloxane, dimethylphenylsiloxane, methylphenylpolysiloxane, and dimethylphenylsiloxane / methylphenylsiloxane copolymer.

[0308] <<<Component (D)>>> Component (D) is a photoactive hydrosilylation catalyst. This photoactive hydrosilylation catalyst is activated by irradiation with light, particularly ultraviolet light with a wavelength of 300-400 nm, and is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the Si-H group in component (B). This promoting effect is temperature-dependent, with higher promoting effects obtained at higher temperatures. Therefore, it is preferable to use the catalyst at an ambient temperature of 0-200°C, more preferably 10-100°C, after the preferred light irradiation, in order to complete the reaction within an appropriate reaction time.

[0309] Photoactive hydrosilylation catalysts mainly consist of platinum group metal catalysts or iron group metal catalysts. Platinum group metal catalysts include platinum, palladium, and rhodium-based metal complexes, while iron group metal catalysts include nickel, iron, and cobalt-based iron group complexes. Among these, platinum-based metal complexes are preferred and frequently used because they are relatively easy to obtain and exhibit good catalytic activity.

[0310] Furthermore, ligands that exhibit catalytic activity with UV light in the medium to long wavelength range of UV-B to UV-A are preferable in terms of minimizing damage to the wafer. Examples of such ligands include cyclic diene ligands and β-diketonate ligands.

[0311] Based on the above, a preferred example of a photoactive hydrosilylation reaction catalyst is a cyclic diene ligand type, for example, (η ５ Examples of β-diketonate ligand complexes include (methylcyclopentadienyl)tri(σ-alkyl)platinum(IV), (cyclopentadienyl)trimethylplatinum(IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum(IV), (cyclopentadienyl)dimethylethylplatinum(IV), (cyclopentadienyl)dimethylacetylplatinum(IV), (trimethylsilylcyclopentadienyl)trimethylplatinum(IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum(IV), (dimethylphenylsilylcyclopentadienyl)trimethylplatinum(IV), and β-diketonate ligand types. Examples include β-diketonatoplatinum(II) or platinum(IV) complexes, particularly trimethyl(acetylacetonato)platinum(IV), trimethyl(3,5-heptanedionate)platinum(IV), trimethyl(methylacetoacetate)platinum(IV), bis(2,4-pentanedionato)platinum(II), bis(2,4-hexanedionato)platinum(II), bis(2,4-heptanedionato)platinum(II), bis(3,5-heptanedionato)platinum(II), bis(1-phenyl-1,3-butanedionato)platinum(II), bis(1,3-diphenyl-1,3-propanedionato)platinum(II), and bis(hexafluoroacetylacetonato)platinum(II).

[0312] When using these catalysts, if they are solid catalysts, they can be used in solid form. However, to obtain a more uniform cured product, it is preferable to dissolve them in a suitable solvent and then use them in a way that makes them compatible with the organopolysiloxane having an alkenyl group (component A). Examples of solvents include isononane, toluene, and 2-(2-butoxyethoxy)ethyl acetate.

[0313] <<<Component (E)>>> The above photocurable silicone resin composition may further contain a reaction control agent as component (E). The reaction control agent is added as needed to prevent the composition from becoming thicker or gelling when preparing the composition or applying it to a substrate.

[0314] Examples of the reaction control agents include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. Of these, 1-ethynylcyclohexanol and 3-methyl-1-butyne-3-ol are preferred.

[0315] When the photocurable silicone resin composition contains component (E), its controllability differs depending on its chemical structure, so its content should be adjusted to the optimal amount. However, considering the effects on curability, storage stability, and post-curing properties, the content of component (E) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total of components (A), (B), and (C). When the content of component (E) is within the above range, the composition has a long usable time, long-term storage stability is obtained, and curability and workability are good.

[0316] The photocurable silicone resin composition may be used after being dissolved by adding a solvent to improve workability and mixability by lowering the viscosity of the composition, and to adjust the film thickness of the temporary adhesive layer. The solvent used is not particularly limited as long as it can dissolve the above components, but hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene are preferred.

[0317] Methods for solution formation include preparing the above-mentioned photocurable silicone resin composition and then adding a solvent to adjust it to the desired viscosity, or pre-diluting the high-viscosity components (A), (B), and / or (C) with a solvent to improve workability and mixability before mixing the remaining components.

[0318] <<Adhesive composition represented by [iii]>> As the adhesive composition, for example, a temporary adhesive described in publications such as International Patent Publication WO2021 / 112070 can be used, and more specifically, the thermosetting silicone resin composition described below is an example. The adhesive composition according to the present invention consists of a thermosetting silicone resin composition containing a non-functional organopolysiloxane.

[0319] Such a thermosetting silicone resin composition preferably contains, for example, the following components (A) to (D): (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass; (B) Organohydrogenpolysiloxane containing two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: in an amount such that the total number of SiH groups in component (B) is 0.3 to 10 in molar ratio to the total number of alkenyl groups in component (A); (C) Non-functional organopolysiloxane: 0.1 to 200 parts by mass; and (D) Hydrosilylation reaction catalyst: 0.1 to 5,000 ppm in terms of metal atomic weight relative to the total mass of components (A), (B), and (C).

[0320] <<<Component (A)>>> As component (A), the same as that described in the <<<Component (A)>>> section of the above <<[ii] adhesive composition>> may be used.

[0321] Examples of such organopolysiloxanes include those represented by formulas (A-1) to (A-3) described in paragraph

[0015] of publications such as International Patent Publication WO2021 / 112070 and International Patent Publication WO2021 / 220929.

[0322] <<<Component (B)>>> As component (B), the same as that described in the <<<Component (B)>>> section of the above <<[ii] adhesive composition>> may be used.

[0323] <<<Component (C)>>> As component (C), the same as that described in the <<<Component (C)>>> section of the above <<[ii] Adhesive Composition>> may be used. In addition, as a branched non-functional organopolysiloxane in component (C), the polysiloxane described in paragraphs

[0033] to

[0034] of International Patent Publication WO2021 / 112070 may also be suitably used.

[0324] <<<Component (D)>>> Component (D) is a hydrosilylation reaction catalyst, preferably a platinum group metal hydrosilylation reaction catalyst. Component (D) is a catalyst that promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). Since this hydrosilylation reaction catalyst is generally a compound of a precious metal and is expensive, platinum or platinum compounds, which are relatively easy to obtain, are often used.

[0325] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. Other platinum group metal catalysts besides platinum compounds include rhodium, ruthenium, iridium, and palladium-based compounds, for example, RhCl(PPh ３ ) ３ , RhCl(CO)(PPh ３ ) ２ Ru ３ (CO) １２ , IrCl(CO)(PPh ３ ) ２ , Pd(PPh ３ ) ４ Examples include the above. In the above formula, Ph is a phenyl group.

[0326] When using these catalysts, if they are solid catalysts, they can be used in solid form. However, to obtain a more uniform cured product, it is preferable to dissolve chloroplatinic acid or the complex in a suitable solvent and make it compatible with component (A).

[0327] The amount of component (D) added is an effective amount, which is usually 0.1 to 5,000 ppm in terms of metal atomic weight relative to the total mass of components (A), (B), and (C), but preferably 1 to 1,000 ppm. If it is 0.1 ppm or more, the curability of the composition will not decrease, the crosslinking density will not decrease, and the holding power will not decrease. If it is 5,000 ppm or less, side reactions such as dehydrogenation during curing can be suppressed, and the usable time of the treatment solution can also be extended.

[0328] <<<Component (E)>>> The above thermosetting silicone resin composition may further contain a reaction control agent as component (E). The reaction control agent is added as needed to prevent the composition from becoming thicker or gelling when preparing the composition or applying it to a substrate.

[0329] Examples of the reaction control agents include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane. Of these, 1-ethynylcyclohexanol and 3-methyl-1-butyne-3-ol are preferred.

[0330] When the thermosetting silicone resin composition contains component (E), its controllability differs depending on its chemical structure, so its content should be adjusted to the optimal amount. However, considering the effects on curability, storage stability, and post-curing properties, the content of component (E) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total of components (A), (B), and (C). When the content of component (E) is within the above range, the composition has a long usable time, long-term storage stability is obtained, and curability and workability are good.

[0331] Thermosetting silicone resin compositions may be used after being dissolved by adding a solvent to improve workability and mixability by lowering the viscosity of the composition, and to adjust the film thickness of the temporary adhesive layer. The solvent used is not particularly limited as long as it can dissolve the above components, but hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene are preferred.

[0332] Methods for solution formation include preparing the thermosetting silicone resin composition and then adding a solvent to adjust it to the desired viscosity, or pre-diluting the high-viscosity components (A), (B), and / or (C) with a solvent to improve workability and mixability before mixing the remaining components.

[0333] <<Adhesive composition represented by [iv]>> As the adhesive composition, for example, a temporary adhesive described in a publication such as Japanese Patent Publication No. 2024-507781 can be used, and more specifically, a composition for forming a thermoplastic bonding layer as described below is an example. The adhesive composition according to the present invention consists of a composition for forming a thermoplastic bonding layer.

[0334] When a thermoplastic bonding composition is used to form a bonding layer, one preferred method involves spin-coating the bonding composition at a speed of about 300 rpm to about 3,000 rpm, preferably about 750 rpm to about 1,500 rpm, for a period of about 30 seconds to about 240 seconds, preferably about 60 seconds to about 180 seconds. Alternatively, the composition may be applied by other methods, including lamination, spray coating, jetting, or screen printing. The applied composition is then heated to a temperature preferably about 50°C to about 250°C, more preferably about 60°C to about 200°C, for a period of about 1 second to about 6 minutes, preferably about 60 seconds to about 4 minutes. In some embodiments, depending on the composition used, it is preferable to subject the layer to a multi-stage bake process. The formed thermoplastic bonding layer has a softening point of at least about -50°C, preferably about -20°C to about 100°C, more preferably about 0°C to about 50°C. The thickness of the formed thermoplastic bonding layer is preferably about 5 μm to about 200 μm, more preferably about 10 μm to about 120 μm.

[0335] The thermoplastic bonding layer can be formed from any commercially available thermoplastic bonding composition that can form a layer having the above properties. Typical such compositions are organic and preferably contain polymers and / or oligomers dissolved or dispersed in a solvent system. The solvent system may include one or more solvents, which are organic solvents, inorganic solvents, or water. The polymers or oligomers are typically selected from the group consisting of one or more polymers, copolymers (including block copolymers), and oligomers of cyclic olefins (e.g., cyclic olefin copolymers ("COC"), cyclic olefin polymers ("COP")), epoxy, acrylic, siloxane, styrene, vinyl halide, or vinyl esters. Typical polymers also include one or more selected from polyamides, polyimides, polysulfones, polyethersulfones, polyolefins, polyisoprene, polyurethanes, polyamide esters, polyimide esters, or polyacetals.

[0336] The typical solid content of a thermoplastic bonding composition is in the range of about 1% to about 60% by weight, preferably about 3% to about 40% by weight, when the total weight of the composition is 100% by weight. Some suitable compositions include, for example, any thermoplastic compositions described in U.S. Patents 9,496,164, 10,103,048, and 10,968,348. The thermoplastic bonding composition used to form the bonding layer preferably has a storage modulus of less than about 1 GPa, more preferably less than about 100 MPa, and even more preferably less than about 10 MPa at a temperature of about 250°C.

[0337] <<Adhesive composition represented by [v]>> As the adhesive composition, for example, a temporary adhesive described in a publication such as Japanese Patent Publication No. 2024-507781 can be used, and more specifically, a composition for forming a thermosetting bonding layer as described below is an example. The adhesive composition according to the present invention consists of a composition for forming a thermosetting bonding layer.

[0338] When a thermosetting bonding composition is used to form a bonding layer, one preferred method involves spin-coating the bonding composition at a speed of about 300 rpm to about 5,000 rpm, preferably about 500 rpm to about 2,000 rpm, for a period of about 30 seconds to about 240 seconds, preferably about 60 seconds to about 180 seconds. Alternatively, the composition may be applied by other methods, including lamination, spray coating, jetting, or screen printing. After the composition has been applied, the composition is heated to a temperature of preferably about 60°C to about 200°C, more preferably about 80°C to about 150°C, for a period of about 60 seconds to about 3 minutes, preferably about 90 seconds to about 2 minutes. In some embodiments, depending on the composition used, it is preferable to subject the layer to a multi-stage bake process. This bake should not be at a temperature high enough to initiate the curing of the material. The thermosetting bonding layer has a softening point of at least about 40°C, preferably about 50°C to about 200°C, and more preferably about 60°C to about 150°C. The thickness of the formed thermosetting bonding layer is preferably about 5 μm to about 200 μm, more preferably about 10 μm to about 120 μm, and most preferably about 20 μm to about 60 μm.

[0339] Thermosetting bonding compositions can be chemically crosslinked by heat, light, or other means. That is, these compositions include photo- and thermosetting resin and polymer-containing compositions, preferably those that produce little to no volatile byproducts during curing. These include resin and polymer compositions containing at least two reactive epoxy, acrylate, benzoxazine, maleimide, benzocyclobutene, and / or cyanate ester moieties. The reactive moieties may also contain chalcone, stilbene, and / or other photodimerizable functional groups. Epoxy resin-containing compositions cured with a photoacid generator ("PAG") or a thermoacid generator ("TAG") are particularly useful for carrying out this embodiment. Processes for coating and drying the thermosetting composition prior to the bonding process should minimize, and preferably avoid, crosslinking of the composition so that it remains fluid during the bonding process and allows for the formation of a void-free bond line. Some suitable compositions include, for example, any thermosetting compositions described in U.S. Patent Applications Publication Nos. 2020 / 0234993 and 2021 / 0033975 and U.S. Patents Nos. 9,496,164, 10,103,048 and 10,968,348.

[0340] <<Adhesive composition represented by [vi]>> As the adhesive composition, for example, an adhesive composition described in a publication such as Japanese Patent Publication No. 2017-530206 can be used. The adhesive composition according to the present invention consists of a composition for forming an adhesive layer that can be removed by heat and / or solvent.

[0341] The composition used to form the adhesive layer can be selected from commercially available adhesive compositions that are removable by heat and / or solvents while simultaneously forming a layer with adhesive properties. These materials should be capable of forming a strong adhesive bond with the substrate. Any adhesive strength measured by ASTM D4541 / D7234 greater than about 50 psig, preferably about 80 psig to about 250 psig, and more preferably about 100 psig to about 150 psig, is desirable for use as an adhesive layer.

[0342] Typical such compositions are organic and contain polymers or oligomers that are dissolved or dispersed in a solvent system. The polymers or oligomers are usually selected from the group consisting of polymers and oligomers of cyclic olefins, epoxy, acrylic, silicone, styrene, vinyl halide, vinyl ester, polyamide, polyimide, polysulfone, polyethersulfone, cyclic olefins, polyolefin rubber, polyurethane, ethylene-propylene rubber, polyamide ester, polyimide ester, polyacetal, and polyvinyl butyral. The typical solvent system depends on the selection of the polymer or oligomer. The typical solids content of a composition is about 1 wt% to about 60 wt%, preferably about 3 wt% to about 40 wt%, based on 100 wt% of the total weight of the composition. Some suitable compositions include, for example, those described in U.S. Patent Publications No. 8,268,449, 7,713,835, 7,935,780, and 8,092,628.

[0343] As described above, the laminate of the present invention comprises at least a semiconductor substrate or electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate. As described above, the laminate of the present invention may further have a release agent layer. It may also have multiple adhesive removal coating films.

[0344] The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device layer, and is suitably used for processing such as thinning of the semiconductor substrate or electronic device layer. While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by a support substrate. On the other hand, after the semiconductor substrate has been processed, the support substrate and the semiconductor substrate are separated. Similarly, while the electronic device layer is being processed such as thinning, the electronic device layer is supported by a support substrate. On the other hand, after the electronic device layer has been processed, the support substrate and the electronic device layer are separated. After the semiconductor substrate or electronic device layer and the support substrate are separated, any adhesive residue remaining on the semiconductor substrate, electronic device layer, or support substrate can be removed, for example, by a cleaning agent composition for cleaning semiconductor substrates, etc., along with the adhesive removal coating film.

[0345] The following will be a detailed explanation, divided into two cases: when the laminate has a semiconductor substrate and when it has an electronic device layer. The case where the laminate has a semiconductor substrate will be described in <First Embodiment> below, and the case where the laminate has an electronic device layer will be described in <Second Embodiment> below.

[0346] <First Embodiment> A laminate having a semiconductor substrate is used for processing the semiconductor substrate. While the semiconductor substrate is being processed, the semiconductor substrate is bonded to a support substrate. After processing the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0347] <<Semiconductor Substrate>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, but examples include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resin. The shape of the semiconductor substrate is not particularly limited, but for example it is disc-shaped. Note that the surface shape of the disc-shaped semiconductor substrate does not need to be a perfect circle; for example the outer edge of the semiconductor substrate may have a straight section called an orientation flat or a notch. The thickness of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 500 to 1,000 μm. The diameter of the disc-shaped semiconductor substrate is not particularly limited and can be appropriately determined according to the intended use of the semiconductor substrate, but for example it is 100 to 1,000 mm.

[0348] A semiconductor substrate may have bumps. A bump is a protruding terminal. For example, a bump may be an electrode. In a laminate, if the semiconductor substrate has bumps, the bumps are located on the side of the support substrate. In a semiconductor substrate, bumps are usually formed on the surface on which the circuit is formed. The circuit may be single-layer or multi-layer. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface with bumps (the back surface) is the surface used for processing. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. Typically, 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. Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, examples include Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bumps may also have a laminated structure including a metal layer made of at least one of these components.

[0349] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0350] <<Support Substrate>> The support substrate is not particularly limited as long as it is a material that can support the semiconductor substrate when the semiconductor substrate is being processed, but examples include glass support substrates and silicon support substrates.

[0351] The shape of the support substrate is not particularly limited, but for example, it can be disc-shaped. The disc-shaped support substrate does not need to have a perfectly circular surface; for example, the outer circumference of the support substrate may have a straight section called an orientation flat, or a notch. The thickness of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 100 to 1,000 mm.

[0352] An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0353] Furthermore, when delamination in a laminate is performed by light irradiation, a substrate that is light-transmitting to the light used is used as the support substrate.

[0354] <<Adhesive Removal Coating Film>> The adhesive removal coating film is provided between the support substrate and the semiconductor substrate. The adhesive removal coating film is in contact with the semiconductor substrate and also in contact with the adhesive layer. The adhesive removal coating film is a layer formed from an adhesive removal coating film forming composition, and the composition used is the composition described above (Adhesive Removal Coating Film Forming Composition).

[0355] A method for forming an adhesive-removing coating film from an adhesive-removing coating film-forming composition will be described in detail below in the section titled "<<Manufacturing Method of an Example of a Laminate in the First Embodiment>>".

[0356] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is in contact with, for example, the adhesive removal coating film and also in contact with the support substrate. The adhesive layer is a layer formed from an adhesive composition, and as the adhesive composition, the adhesive compositions described in <<[i]>> to <<[vi]>> of the above <<Adhesive Layer>> are used.

[0357] The thickness of the adhesive layer in the laminate of the present invention is not particularly limited, but is usually 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick films, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and still more preferably 100 μm or less.

[0358] The method for forming an adhesive layer from the adhesive composition will be described in detail below in the section titled "<>".

[0359] <<Release Agent Layer>> The laminate may have a release agent layer. In a laminate having a release agent layer, separation of the semiconductor substrate and the support substrate is performed, for example, by light irradiation of the release agent layer. The release agent layer is formed, for example, from a release agent composition.

[0360] <<<Release Agent Composition>>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and optionally other components. The organic resin is preferably one that can exhibit suitable release ability, and when the semiconductor substrate and the support substrate are separated by light irradiation of the release agent layer, the organic resin preferably absorbs light and undergoes a change, such as decomposition, necessary to improve the release ability.

[0361] A laminate having a release agent layer formed from a release agent composition can be peeled off without applying excessive load for peeling by, for example, irradiating the release agent layer with a laser. The release agent layer of the laminate has a reduced adhesive strength compared to before irradiation, for example, when irradiated with a laser. That is, in the laminate, for example, while a semiconductor substrate is being processed such as thinning, the semiconductor substrate is suitably supported on a laser-transmitting support substrate via an adhesive layer and a release agent layer. After processing is complete, by irradiating a laser from the support substrate side, the laser that has passed through the support substrate is absorbed by the release agent layer, causing alteration (e.g., separation) of the release agent layer at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or within the release agent layer itself. As a result, suitable peeling (separation) can be achieved without applying excessive load for peeling.

[0362] Examples of organic resins include novolac resins. Further details will be provided later.

[0363] In a preferred embodiment, the release agent composition contains at least a novolac resin and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinking agent, and optionally other components such as an acid generator, an acid, a surfactant, or a solvent. In yet another preferred embodiment, the release agent composition contains at least an organic resin and a branched polysilane, and optionally other components such as a crosslinking agent, an acid generator, an acid, a surfactant, or a solvent.

[0364] <<<<<Novolac resin>>>> Novolac resin is a resin obtained by condensing at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound under acid catalyst.

[0365] Examples of phenolic compounds include phenols, naphthols, antrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of antrols include 9-antrol. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of carbazole compounds include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'bis(9H-carbazole-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, and 9-(1H-benzotriazole-1-ylmethyl Examples include (9-ethylcarbazole-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarboxyaldehyde, 9-benzylcarbazole-3-carboxyaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, potassium carbazole, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carboxyaldehyde, and N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-indolinylamine. Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These can be used individually or in combination of two or more. They may also have substituents.For example, these may have substituents on the aromatic ring.

[0366] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, caproaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanealdehyde, 7-methoxy-3,7-dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and azipi Examples of suitable aldehydes include saturated aliphatic aldehydes such as ammonium aldehydes, unsaturated aliphatic aldehydes such as acrolein and methacrolein, heterocyclic aldehydes such as furfural and pyridine aldehyde, and aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred. Examples of suitable ketone compounds include diaryl ketone compounds such as diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, and 5-vinylnorbornadiene. These can be used individually or in combination of two or more.

[0367] Novolac resin is a type of novolac resin that absorbs and alters upon exposure to light irradiated from the support substrate side. This alteration is, for example, photodegradation.

[0368] Novolac resin includes, for example, at least one of the structural units represented by the following formula (C1-1), the following formula (C1-2), and the following formula (C1-3).

[0369]

[0370] In the formula, C １ This represents a group derived from an aromatic compound containing a nitrogen atom, C ２ This represents a group containing a tertiary carbon atom having at least one selected from the group consisting of secondary carbon atoms, quaternary carbon atoms, and aromatic rings in its side chain, C ３ This represents a group derived from an aliphatic polycyclic compound, C ４ This represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0371] In other words, novolac resin contains, for example, one or more of the following structural units: • A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring as a side chain (Formula (C1-1)) • A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (Formula (C1-2)) • A structural unit having a bond between a group derived from phenol, bisphenol, naphthol, biphenyl, or biphenol and a group containing a tertiary carbon atom having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring as a side chain (Formula (C1-3))

[0372] In a preferred embodiment, the novolac resin comprises either or both of the following structural units: a structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain (formula (C1-1)); and a structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)).

[0373] C １ The group derived from an aromatic compound containing a nitrogen atom can be, for example, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, etc., but is not limited to these.２ A group comprising a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring as a side chain can be, for example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxyaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from acetaldehyde, etc., but is not limited to these. ３ The group derived from the aliphatic polycyclic compound may be, but is not limited to, a group derived from dicyclopentadiene. ４ This group is derived from phenol, bisphenol, naphthol, biphenyl, or biphenol.

[0374] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-1) as a structural unit represented by formula (C1-1-1).

[0375]

[0376] In formula (C1-1-1), R ９０１ and R ９０２ R represents a substituent that substitutes for the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０３ R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０４ R represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０５ R represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０４ The base and R ９０５The groups may bond with each other to form a divalent group. Examples of substituents on alkyl and alkenyl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, and heteroaryl groups. Examples of substituents on aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, alkyl groups, and alkenyl groups. １ and h ２ Each of these independently represents an integer between 0 and 3.

[0377] The number of carbon atoms in the optionally substituted alkyl groups and optionally substituted alkenyl groups is usually 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility. The number of carbon atoms in the optionally substituted aryl groups and heteroaryl groups is usually 40 or less, preferably 30 or less, and more preferably 20 or less, from the viewpoint of solubility.

[0378] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0379] Specific examples of substituted alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, and 3-methyl-n-pentyl group. Examples include, but are not limited to, the following groups: 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, etc.

[0380] Specific examples of alkenyl groups that may be substituted include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, and 1-methyl-3-butenyl group. Nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group Xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group Examples include, but are not limited to, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0381] Specific examples of aryl groups that may be substituted include, but are not limited to, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 1-naphthyl group, 2-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0382] Specific examples of heteroaryl groups that may be substituted include, but are not limited to, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl groups.

[0383] The following are specific examples of structural units represented by formula (C1-1-1), but are not limited to these.

[0384]

[0385] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by formula (C1-1-2) below, as a structural unit represented by formula (C1-1).

[0386]

[0387] In formula (C1-1-2), Ar ９０１ and Ar ９０２ Each of these independently represents an aromatic ring such as a benzene ring or a naphthalene ring, and R ９０１ ~R ９０５ and h １ and h ２ This expresses the same meaning as above.

[0388] The following are specific examples of structural units represented by formula (C1-1-2), but are not limited to these.

[0389]

[0390] In a preferred embodiment, the novolac resin includes structural units represented by formula (C1-2), for example, structural units represented by the following formulas (C1-2-1) or (C1-2-2).

[0391]

[0392] In the above formula, R ９０６ ~R ９０９ is a substituent bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Specific examples and preferred carbon numbers of the halogen atom, optionally substituted alkyl group, optionally substituted alkenyl group, and optionally substituted aryl group are the same as those described above. ３ ~h ６ Each of these independently represents an integer from 0 to 3, and R ９０１ ~R ９０３ and h １ and h ２ This expresses the same meaning as above.

[0393] The following are specific examples of structural units represented by formulas (C1-2-1) and (C1-2-2), but are not limited to these.

[0394]

[0395] The following are specific examples of structural units represented by formula (C1-3), but are not limited to these.

[0396]

[0397] As mentioned above, novolac resins are resins obtained by condensing at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound under an acid catalyst. In this condensation reaction, for example, an aldehyde compound or ketone compound is usually used in a ratio of 0.1 to 10 equivalents per equivalent of the benzene ring constituting the ring of the carbazole compound.

[0398] In the above condensation reaction, an acid catalyst is usually used. Examples of acid catalysts include, but are not limited to, mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of acid catalyst is determined appropriately depending on the type of acid used and cannot be specified in general terms, but it is usually set appropriately from the range of 0.001 to 10,000 parts by mass per 100 parts by mass of the carbazole compound.

[0399] The above condensation reaction can sometimes be carried out without a solvent if either the starting compound or the acid catalyst is a liquid, but it is usually carried out with a solvent. Such solvents are not particularly limited as long as they do not inhibit the reaction, but typical examples include ether compounds such as tetrahydrofuran and cyclic ether compounds such as dioxane.

[0400] The reaction temperature is usually determined appropriately within the range of 40°C to 200°C, and the reaction time cannot be specified in general terms as it varies depending on the reaction temperature, but it is usually determined appropriately within the range of 30 minutes to 50 hours.

[0401] After the reaction is complete, if necessary, the novolac resin is purified and isolated according to standard procedures and used in the preparation of the release agent composition. A person skilled in the art can determine the production conditions for the novolac resin without undue burden based on the above description and common technical knowledge, and therefore can produce the novolac resin.

[0402] The weight-average molecular weight of organic resins such as novolac resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in solvents and ensuring good mixing with branched polysilanes when formed into a film to obtain a uniform film, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 5,000 or less, and still more preferably 3,000 or less. From the viewpoint of improving the strength of the film, it is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, still more preferably 900 or more, and still more preferably 1,000 or more. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of organic resins such as novolac resins, which are polymers, can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample.

[0403] The organic resin contained in the above-mentioned release agent composition is preferably novolac resin. Therefore, the above-mentioned release agent composition preferably contains novolac resin alone as the organic resin. However, other polymers may be included together with the novolac resin for purposes such as adjusting the film properties. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, and polyacrylonitrile compounds.

[0404] The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 70% by mass or more relative to the total amount of polymer contained in the release agent composition. The content of novolac resin in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film constituent components. In this invention, film constituent components refer to components other than the solvent contained in the composition.

[0405] <<<<<Polynuclear phenol derivatives>>>> A polynuclear phenol derivative is represented, for example, by the following formula (P).

[0406] In formula (P), Ar represents an arylene group, and its carbon number is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release agent layer with higher flatness with good reproducibility, it is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0407] Specific examples of such arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples include, but are not limited to, groups derived by removing two hydrogen atoms from the aromatic ring of fused ring aromatic hydrocarbon compounds such as diyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from the aromatic ring of ring-linked ring aromatic hydrocarbon compounds such as biphenyl-4,4'-diyl group and paraterphenyl-4,4''-diyl group.

[0408] From the viewpoint of obtaining a laminate that exhibits good peelability as a release agent layer and allows for good separation of the support substrate with good reproducibility, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0409]

[0410] The content of the polynuclear phenol derivative in the release agent composition is not particularly limited, but it is preferably 50 to 100% by mass relative to the film components.

[0411] << Although the reason is not entirely clear, depending on the type of end groups (end substituents (atoms)) of the polysilane, the polysilane can react with organic resins and crosslink. Furthermore, since branched polysilanes have more end groups (end substituents (atoms)) than linear polysilanes, it is thought that branched polysilanes have more crosslinking points than linear polysilanes. It is presumed that moderate and suitable curing via these more crosslinking points in branched polysilanes makes it possible to achieve both the property of being unsuitably removed by organic solvents, acids, and chemicals used in the manufacture of semiconductor devices (alkaline developers, hydrogen peroxide, etc.) and the property of being suitablely removed by cleaning agent compositions.

[0412] The branched polysilane preferably contains a structural unit represented by formula (B).

[0413]

[0414] In formula (B), R Ｂ The group represents a hydrogen atom, a hydroxyl group, a silyl group, or an organic group. Specific examples of such organic groups include hydrocarbon groups (optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, optionally substituted aralkyl groups), and ether groups corresponding to these hydrocarbon groups (optionally substituted alkoxy groups, optionally substituted aryloxy groups, optionally substituted aralkyloxy groups, etc.). However, the organic group in question is usually a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group. Furthermore, hydrogen atoms, hydroxyl groups, alkoxy groups, silyl groups, etc., are often substituted at their terminal ends.

[0415] The substituted alkyl group may be linear, branched, or cyclic. Specific examples of substituted linear or branched alkyl groups include: methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group Examples include ethyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, etc., but are not limited to these, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.Specific examples of cyclic alkyl groups, whether substituted or not, include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3- Examples of cycloalkyl groups include dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, and other cycloalkyl groups, as well as bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0416] The alkenyl group may be linear, branched, or cyclic. Specific examples of linear or branched alkenyl groups that may be substituted include, but are not limited to, vinyl, allyl, butyl, and pentenyl groups. The number of carbon atoms is typically 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Specific examples of cyclic alkenyl groups that may be substituted include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms is typically 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0417] Specific examples of substituted aryl groups include, but are not limited to, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 1-naphthyl, and 2-naphthyl groups. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0418] Specific examples of substituted aralkyl groups include, but are not limited to, benzyl, phenethyl, and phenylpropyl groups. Preferably, a substituted aralkyl group is a group in which one hydrogen atom of a C1-C4 alkyl group is substituted with a C6-C20 aryl group.

[0419] The substituted alkoxy group may have a linear, branched, or cyclic alkyl moiety. Specific examples of substituted linear or branched alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, and pentyloxy groups, and their carbon number is typically 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Specific examples of substituted cyclic alkoxy groups include, but are not limited to, cyclopentyloxy and cyclohexyloxy, and their carbon number is typically 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0420] Specific examples of substituted aryloxy groups include, but are not limited to, phenoxy, 1-naphthyloxy, and 2-naphthyloxy. The number of carbon atoms is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0421] Specific examples of substituted aralkyloxy groups include, but are not limited to, benzyloxy, phenethyloxy, and phenylpropyloxy. Preferably, a substituted aralkyloxy group is a group in which one hydrogen atom of an alkyloxy group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0422] Specific examples of silyl groups include silyl groups, disilanyl groups, and trisilanyl groups, but are not limited to these. The silicon number is usually 1 to 10, preferably 1 to 6.

[0423] R Ｂ However, in the case of the above-mentioned organic group or silyl group, at least one of its hydrogen atoms may be substituted with a substituent. Specific examples of such substituents include hydroxyl groups, alkyl groups, aryl groups, and alkoxy groups.

[0424] From the viewpoint of suppressing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor devices (such as an alkaline developer or hydrogen peroxide), and from the viewpoint of suitably removing the residue of the release agent layer on the substrate when the semiconductor substrate and support substrate of the laminate are separated and then washed with a cleaning agent composition, R Ｂ The group is preferably an alkyl group or an aryl group, more preferably an aryl group, even more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and even more preferably a phenyl group.

[0425] The branched-chain polysilane may contain structural units represented by formula (B), as well as structural units represented by formula (S) and formula (N). However, from the viewpoint of suppressing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor devices (such as an alkaline developer or hydrogen peroxide), and from the viewpoint of suitably removing residue of the release agent layer on the substrate when the semiconductor substrate and support substrate of the laminate are separated and then washed with a cleaning agent composition, the content of structural units represented by formula (B) in the branched-chain polysilane is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more of the total structural units.

[0426] (R Ｓ１ and R Ｓ２ R Ｂ (This expresses the same meaning.)

[0427] The terminal groups (terminal substituents (atoms)) of branched polysilanes are usually hydrogen atoms, hydroxyl groups, halogen atoms (such as chlorine atoms), alkyl groups, aryl groups, alkoxy groups, silyl groups, etc. Among these, hydroxyl groups, methyl groups, and phenyl groups are most common, with methyl groups being preferred, and the terminal group may be a trimethylsilyl group.

[0428] In one embodiment, the average degree of polymerization of the branched polysilane is typically 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30, in terms of silicon atoms (i.e., the average number of silicon atoms per molecule). In another embodiment, the upper limit of the weight-average molecular weight of the branched polysilane is typically 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, still more preferably 2,000, and even more preferably 1,500, and the lower limit is typically 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500. The average degree of polymerization and weight-average molecular weight of branched polysilanes can be measured, for example, using a GPC instrument (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and a GPC column (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K., used in this order), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.00 mL / min, and polystyrene (manufactured by Sigma-Aldrich) as the standard sample. If the degree of polymerization and weight-average molecular weight of the branched polysilane used are too low, heating during the formation of the release agent layer or during processing of the laminate containing the obtained release agent layer may cause the branched polysilane to vaporize or lead to defects due to insufficient film strength. If the degree of polymerization and molecular weight of the branched polysilane used are too high, depending on the type of solvent used to prepare the release agent composition, sufficient solubility may not be ensured, leading to precipitation in the composition or insufficient mixing with the resin, which may prevent the reproducibility of a highly uniform film. Therefore, from the viewpoint of obtaining a laminate containing a release agent layer that contributes to the suitable manufacture of semiconductor devices with even greater reproducibility, it is desirable that the degree of polymerization and weight-average molecular weight of the branched polysilane meet the above-mentioned range.

[0429] The 5% weight loss temperature of branched polysilane is typically 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, even more preferably 380°C or higher, even more preferably 395°C or higher, and even more preferably 400°C or higher, from the viewpoint of obtaining a release agent layer with excellent heat resistance and good reproducibility. The 5% weight loss temperature of branched polysilane can be measured, for example, by using a NETZSCH 2010SR under air conditions and raising the temperature from room temperature (25°C) to 400°C at a rate of 10°C / min.

[0430] When the semiconductor substrate and support substrate of a laminate are separated and then each substrate is washed with a cleaning agent composition, from the viewpoint of suitably removing residue from the release agent layer on the substrate and from the viewpoint of preparing a release agent composition with excellent uniformity and reproducibility, it is preferable that the branched-chain polysilane dissolves in any of the following: ether compounds such as tetrahydrofuran, aromatic compounds such as toluene, glycol ether ester compounds such as propylene glycol monomethyl ether acetate, ketone compounds such as cyclohexanone and methyl ethyl ketone, and glycol ether compounds such as propylene glycol monomethyl ether. In this case, dissolution means that when dissolution is attempted using a shaker at room temperature (25°C) to obtain a 10% by mass solution, it can be visually confirmed that dissolution has occurred within one hour.

[0431] The branched polysilane may be in either a solid or liquid state at room temperature.

[0432] Branched-chain polysilanes can be manufactured by referring to known methods described in, for example, Japanese Patent Publication No. 2011-208054, Japanese Patent Publication No. 2007-106894, Japanese Patent Publication No. 2007-145879, WO2005 / 113648, etc., or they can be obtained as commercially available products. Specific examples of commercially available products include, but are not limited to, the silicon material polysilanes OGSOL SI-20-10 and SI-20-14 manufactured by Osaka Gas Chemical Co., Ltd.

[0433] Suitable examples of branched polysilanes include, but are not limited to, the following. (Ph represents the phenyl group, R ＥEach of these independently represents a terminal substituent, an atom or a group, and n ｂ (This indicates the number of repeating units.)

[0434] The branched polysilane content in the above-mentioned stripping agent composition is usually 10 to 90% by mass relative to the film components. However, from the viewpoint of reproducibly achieving a film that cannot be suitably removed by organic solvents, acids, or chemicals used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide, etc.) but can be suitably removed by the cleaning agent composition, the content is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.

[0435] <<<<<Crosslinking Agent>>>> The release agent composition may contain a crosslinking agent. The crosslinking agent may undergo a crosslinking reaction by self-condensation, but if crosslinkable substituents are present in the novolac resin, it can undergo a crosslinking reaction with those crosslinkable substituents.

[0436] Specific examples of crosslinking agents are not limited to those mentioned above, but typically include phenolic crosslinking agents, melamine crosslinking agents, urea crosslinking agents, thiourea crosslinking agents, etc., which have crosslinking groups such as hydroxymethyl groups, methoxymethyl groups, butoxymethyl groups, and other alkoxymethyl groups in their molecules. These may be low molecular weight compounds or high molecular weight compounds. The crosslinking agent contained in the release agent composition usually has two or more crosslinking groups, but from the viewpoint of achieving more suitable curing with good reproducibility, the number of crosslinking groups contained in the crosslinking agent compound is preferably 2 to 10, more preferably 2 to 6. From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (e.g., a benzene ring, a naphthalene ring) in its molecule, and typical examples of such crosslinking agents, though not limited to those mentioned above, include phenolic crosslinking agents.

[0437] A phenolic crosslinking agent having a crosslinking group is 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 a phenolic hydroxyl group. Examples of such alkoxy groups derived from a phenolic hydroxyl group include, but are not limited to, methoxy groups and butoxy groups. 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 a phenolic hydroxyl group are bonded are not limited to non-fused aromatic rings such as benzene rings, but may also be fused aromatic rings such as naphthalene rings and anthracene rings. When multiple aromatic rings exist within the molecule of a phenolic crosslinking agent, the crosslinking group and the phenolic hydroxyl group and the alkoxy group derived from a phenolic hydroxyl group may be bonded to the same aromatic ring or to different aromatic rings within the molecule. The aromatic ring to which the crosslinking group, the phenolic hydroxyl group and the alkoxy group derived from a phenolic hydroxyl group are bonded may be further substituted with alkyl groups such as methyl groups, ethyl groups and butyl groups, hydrocarbon groups such as aryl groups such as phenyl groups, halogen atoms such as fluorine atoms, etc.

[0438] For example, specific examples of phenolic crosslinking agents having crosslinking groups include compounds represented by any of the formulas (L1) to (L4).

[0439]

[0440] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, and each R'' independently represents a hydrogen atom or an alkyl group, L １ and L ２ Each of these independently represents a single bond, a methylene group, or a propane-2,2-diyl group, L ３t11, t12 and t13 are integers satisfying 2≦t11≦5, 1≦t12≦4, 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, and t27, t28 and t29 are integers satisfying 0≦t27≦4, 0≦t28≦ 4 is an integer satisfying 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 of 0 or more, specific examples of aryl groups and alkyl groups are the same as the specific examples below, but phenyl groups are preferred as aryl groups and methyl groups and t-butyl groups are preferred as alkyl groups.

[0441] The following are specific examples of compounds represented by formulas (L1) to (L4), but are not limited to these. These compounds may be synthesized by known methods, or they may be available as products from companies such as Asahi Organic Chemicals Co., Ltd. or Honshu Chemical Industry Co., Ltd.

[0442]

[0443]

[0444]

[0445]

[0446] A melamine-based crosslinking agent having a crosslinking group is 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 hydrogen atom of the amino group bonded to the triazine ring is substituted with a crosslinking group, and the triazine ring may further have substituents such as aryl groups such as phenyl groups. Specific examples of melamine-based crosslinking agents having crosslinking groups include, but are not limited to, mono, bis, tris, tetrakiss, pentakiss, or hexakisalkoxymethyl melamine such as N,N,N',N',N'',N''-hexakis(butoxymethyl)melamine, mono, bis, tris, or tetrakisalkoxymethyl benzoguanamine such as N,N,N',N'-tetrakis(methoxymethyl)benzoguanamine, and N,N,N',N'-tetrakis(butoxymethyl)benzoguanamine.

[0447] A urea-based crosslinking agent having a crosslinking group is a derivative of a urea bond-containing compound having a structure in which at least one hydrogen atom of the NH group constituting the urea bond is substituted with a crosslinking group. Specific examples of urea-based crosslinking agents having a crosslinking group include, but are not limited to, mono, bis, tris, or tetrakisalkoxymethyl glycoluryls such as 1,3,4,6-tetrakis(methoxymethyl) glycoluryl and 1,3,4,6-tetrakis(butoxymethyl) glycoluryl, and mono, bis, tris, or tetrakisalkoxymethylureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetrakismethoxymethylurea.

[0448] A thiourea-based crosslinking agent having a crosslinking group is a derivative of a thiourea bond-containing compound having a structure in which at least one hydrogen atom of the NH group constituting the thiourea bond is substituted with a crosslinking group. Specific examples of thiourea-based crosslinking agents having a crosslinking group include, but are not limited to, mono, bis, tris, or tetrakisalkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetrakismethoxymethylthiourea.

[0449] The amount of crosslinking agent contained in the release agent composition cannot be specified in general terms as it varies depending on the coating method adopted, the desired film thickness, etc. However, it is usually 0.01 to 50% by mass relative to the organic resin or polynuclear phenol derivative. From the viewpoint of achieving suitable curing and obtaining a laminate in which the semiconductor substrate and the support substrate can be separated well with good reproducibility, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and still more preferably 30% by mass or less.

[0450] <<

[0451] Examples of acid generators include thermal acid generators and photoacid generators. Thermal acid generators are not particularly limited as long as they generate acid with heat, and specific examples include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic alkyl sulfonates.

[0452] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0453] Specific examples of onium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0454] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0455] Specific examples of disulfonyl diazomethane compounds 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.

[0456] Specific examples of acids include, but are not limited to, aryl sulfonic acids and pyridinium salts such as 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, and 1-naphthalenesulfonic acid, as well as their salts; aryl carboxylic acids and their salts such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; linear or cyclic alkyl sulfonic acids and their salts such as trifluoromethanesulfonic acid and camphorsulfonic acid; and linear or cyclic alkyl carboxylic acids and their salts such as citric acid.

[0457] The amounts of acid generator and acid contained in the release agent composition cannot be specified in general terms, as they vary depending on the type of crosslinking agent used, the heating temperature when forming the film, etc., but are usually 0.01 to 5% by mass relative to the film components.

[0458] <<<<<Surfactants>>>>> The stripping agent composition may contain surfactants for purposes such as adjusting the liquid properties of the composition itself and the film properties of the resulting film, or for reproducibly preparing a highly uniform stripping agent composition. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl 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; polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30, R-30N (manufactured by DIC Corporation, trade name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Surfactants can be used individually or in combination of two or more. The amount of surfactant is usually 2% by mass or less relative to the film components of the stripping agent composition.

[0459] <<<<Solvent>>>> The release agent composition preferably contains a solvent. As such a solvent, for example, a highly polar solvent that can well dissolve the film components such as the aforementioned organic resins, polynuclear phenol derivatives, branched polysilanes, and crosslinking agents can be used, and if necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In this invention, a low-polarity solvent is defined as one with a relative permittivity of less than 7 at a frequency of 100 kHz, and a highly polar solvent is defined as one with a relative permittivity of 7 or more at a frequency of 100 kHz. The solvent can be used alone or in combination of two or more types.

[0460] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, 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; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0461] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene, and decylbenzene; aliphatic alcohol 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, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0462] The solvent content is determined appropriately considering the viscosity of the desired composition, the coating method used, the thickness of the film to be produced, etc., but is 99% by mass or less of the total composition, preferably 70 to 99% by mass of the total composition, that is, the amount of film components in that case is 1 to 30% by mass of the total composition.

[0463] The viscosity and surface tension of the release agent composition are appropriately adjusted by changing the type of solvent used, their ratios, and the concentration of film components, taking into consideration various factors such as the application method used and the desired film thickness.

[0464] In one aspect of the present invention, the release agent composition contains a glycol-based solvent, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility. The term "glycol-based solvent" as used herein refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0465] An example of a preferred glycol-based solvent is represented by formula (G).

[0466]

[0467] In formula (G), R Ｇ１ Each of these independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, R Ｇ２ and R Ｇ３ Each of these 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 portion is a linear or branched alkyl group having 1 to 8 carbon atoms, n ｇ is an integer between 1 and 6.

[0468] Specific examples of linear or branched alkylene groups having 2 to 4 carbon atoms include, but are not limited to, ethylene groups, trimethylene groups, 1-methylethylene groups, tetramethylene groups, 2-methylpropane-1,3-diyl groups, pentamethylene groups, and hexamethylene groups. In particular, linear or branched alkylene groups having 2 to 3 carbon atoms are preferred, and linear or branched alkylene groups having 3 carbon atoms are more preferred, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility.

[0469] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, and 3-methyl Examples of these groups include, but are not limited to, -n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. In particular, methyl groups and ethyl groups are preferred, and methyl groups are more preferred, from the viewpoint of obtaining a highly homogeneous composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly homogeneous film with good reproducibility.

[0470] Specific examples of linear or branched alkyl groups having 1 to 8 carbon atoms in alkylacyl groups, where the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms, are the same as the specific examples described above. Among these, methyl carbonyl groups and ethyl carbonyl groups are preferred, and methyl carbonyl groups are more preferred, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility.

[0471] n ｇ From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility, the ratio is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1.

[0472] From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with high storage stability with good reproducibility, and a composition that gives a highly uniform film with good reproducibility, in formula (G), preferably, R Ｇ２ and R Ｇ３ At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably R Ｇ２ and R Ｇ３ One of the members is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is an alkylacyl group in which the hydrogen atom or the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0473] From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility, the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the solvent contained in the release agent composition. From the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility, the film components in the release agent composition are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0474] A release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative with a solvent and, if necessary, a crosslinking agent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinking agent are dissolved in the solvent, the remainder is dissolved separately in the solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be appropriately applied, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the solvent or solution used may be filtered using a filter or the like during the production of the release agent composition or after all components have been mixed.

[0475] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, 10 nm to 10 μm in one embodiment, 50 nm to 1 μm in another embodiment, and 100 nm to 700 nm in yet another embodiment.

[0476] There are no particular limitations on the method for forming a release agent layer from a release agent composition, but one example is a method of forming a release agent layer by coating the release agent composition. There are no particular limitations on the method of coating the release agent composition, but it is usually a spin coating method. The heating temperature of the coated release agent composition cannot be specified in general terms as it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc. However, from the viewpoint of reproducibly achieving a suitable release agent layer, it is 80°C to 300°C, and the heating time is usually appropriately determined in the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C to 280°C, and more preferably 150°C to 250°C. The heating time is preferably 30 seconds to 8 minutes, and more preferably 1 minute to 5 minutes. Heating can be carried out using a hot plate, oven, etc.

[0477] The following describes an example of the configuration of the laminate according to the first embodiment, using the figures. Figure 1 shows a schematic cross-sectional view of an example of the laminate according to the first embodiment. The laminate in Figure 1 has a semiconductor substrate 1, an adhesive removal coating film 10, an adhesive layer 2, and a support substrate 4 in this order. That is, the adhesive removal coating film 10 and the adhesive layer 2 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive removal coating film 10 is in contact with the semiconductor substrate 1, and the adhesive layer 2 is in contact with the support substrate 4. The laminate in Figure 1 shows a laminate having the layer configuration (semiconductor substrate or electronic device layer / adhesive removal coating film / adhesive layer / support substrate) described as the (X1) pattern above.

[0478] Figure 2 shows a schematic cross-sectional view of another example of the laminate of the first embodiment. The laminate in Figure 2 has a semiconductor substrate 1, an adhesive removal coating film 10, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order. The adhesive removal coating film 10, the adhesive layer 2, and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive removal coating film 10 is in contact with the semiconductor substrate 1, the adhesive layer 2 is in contact with the adhesive removal coating film 10, and the release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4. The laminate in Figure 2 shows a laminate having the layer configuration (semiconductor substrate or electronic device layer / adhesive removal coating film / adhesive layer / release agent layer / support substrate) described as the (X3) pattern above.

[0479] <<Example of a manufacturing method for a laminate in the first embodiment>> The manufacturing method for a laminate according to the present invention is a method for manufacturing a laminate having a semiconductor substrate, an adhesive removal coating film, an adhesive layer, and a support substrate, comprising the steps of: applying an adhesive removal coating film forming composition onto the semiconductor substrate or the support substrate to form an adhesive removal coating film; and bonding the semiconductor substrate to the support substrate via the adhesive layer and the adhesive removal coating film.

[0480] In a more preferred embodiment, the method for manufacturing a laminate according to the present invention is a method for manufacturing a laminate comprising a semiconductor substrate, an adhesive removal coating film, an adhesive layer, and a support substrate, in this order, the method comprising the steps of: applying an adhesive removal coating film forming composition onto a semiconductor substrate to form an adhesive removal coating film; and bonding the semiconductor substrate with the adhesive removal coating film to a support substrate via the adhesive layer.

[0481] The manufacturing method of the laminate will be described below using the laminate shown in Figure 1 as an example from the laminate in the first embodiment. An example of the laminate of the present invention can be manufactured by a method including the following first and second steps. First step: Applying an adhesive removal coating film forming composition onto a semiconductor substrate to form an adhesive removal coating film. Second step: Bonding the semiconductor substrate with the adhesive removal coating film to a support substrate via an adhesive layer.

[0482] The method for applying the adhesive removal coating film-forming composition or adhesive composition is not particularly limited, but is usually done by spin coating. By spin coating, a coating film consisting of the adhesive removal coating film-forming composition or adhesive composition can be formed. Alternatively, a sheet-like coating film consisting of the adhesive removal coating film-forming composition or adhesive composition can be formed separately by spin coating or the like, and this sheet-like coating film can be applied as the adhesive removal coating film or adhesive coating layer.

[0483] After applying an adhesive-removing coating film-forming composition onto a semiconductor substrate, the coating film is subjected to heat treatment to evaporate the solvent in the coating film, thereby forming the adhesive-removing coating film. The heating temperature for the coating film of the adhesive-removing coating film-forming composition cannot be specified in general terms, as it varies depending on the type and amount of components contained in the adhesive-removing coating film-forming composition, whether or not a solvent is included, the boiling point of the solvent used, and the desired thickness of the adhesive-removing coating film. However, for example, the heating conditions can be considered in the section above (adhesive-removing coating film). If the adhesive-removing coating film-forming composition contains a solvent, the coating film of the adhesive-removing coating film-forming composition is usually subjected to heat treatment.

[0484] After applying the adhesive composition to the support substrate, it is preferable to perform a heat treatment (preheating treatment) to evaporate the solvent in the coated film. The heating temperature for the coated film of the adhesive composition cannot be specified in general, as it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc. However, it is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. If the adhesive composition contains a solvent, the coated film of the adhesive composition is usually heat-treated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is usually about 5 to 500 μm, and is ultimately determined appropriately so that it falls within the above-mentioned range of adhesive layer thickness.

[0485] Next, the semiconductor substrate with the adhesive removal coating film and the support substrate with the adhesive coating film are placed so that the adhesive removal coating film and the adhesive coating film are in contact with each other, and the semiconductor substrate, adhesive removal coating film, adhesive coating film, and support substrate are bonded together in that stacking order.

[0486] In the present invention, a laminate can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing heat treatment, vacuum treatment, or both, and then performing heat treatment (post-heat treatment). The choice of which treatment conditions to adopt—heat treatment, vacuum treatment, or a combination of both—is determined appropriately after considering various factors such as the type of adhesive removal coating film forming composition or adhesive composition, the film thickness, and the desired adhesive strength.

[0487] The bonded adhesive coating layers are then heat-treated (post-heat treatment) to form an adhesive layer in which the adhesive composition has hardened. As a result, the semiconductor substrate with the adhesive removal coating film is bonded to the support substrate via the adhesive layer. The adhesive layer can more firmly bond the semiconductor substrate with the adhesive removal coating film to the support substrate.

[0488] The heat treatment used when bonding a semiconductor substrate and a support substrate via an adhesive coating layer is usually determined appropriately from the range of 20 to 230°C. In particular, when using a warped semiconductor substrate, the temperature is preferably 90°C or higher, more preferably 110°C or higher, in order to mitigate the warping of the semiconductor substrate while preventing cracking. There is no particular upper limit to the heating temperature, but the heating temperature may be 200°C or lower, or 180°C or lower. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, but from the viewpoint of ensuring good adhesion, it is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is usually 10 minutes or less, preferably 5 minutes or less.

[0489] When bonding a semiconductor substrate and a support substrate via an adhesive coating layer, the reduced pressure treatment can be performed by exposing the adhesive coating layers in contact with each other to a pressure of 10 to 10,000 Pa. The duration of the reduced pressure treatment is usually 1 to 30 minutes.

[0490] 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, the support substrate and the layers between them, and can firmly adhere them together, but it is usually in the range of 10 to 50,000 N.

[0491] The heating temperature during post-heat treatment of the bonded adhesive coating layer is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, etc. When post-heating using a hot plate, heating may be done with either the semiconductor substrate or the support substrate of the laminate facing downwards, but it is preferable to post-heat with the semiconductor substrate facing downwards from the viewpoint of achieving suitable delamination with good reproducibility. One of the purposes of the post-heat treatment is to realize an adhesive layer that is a more suitable self-supporting film, and in particular to suitably achieve curing by hydrosilylation reaction.

[0492] Figures 3A to 3C illustrate one embodiment of the manufacturing process for a laminate. First, an adhesive removal coating film-forming composition is applied to a semiconductor substrate 1 to form a coating film of the adhesive removal coating film-forming composition. The coating film is then heat-treated to form an adhesive removal coating film 10. This prepares a semiconductor substrate 1 with an adhesive removal coating film 10 (Figure 3A). On the other hand, a support substrate 4 with an adhesive coating layer 2a is prepared (Figure 3B). This can be obtained, for example, by applying an adhesive composition to a support substrate 4 to form a coating film of the adhesive composition. Next, the coating film is heat-treated (preheating treatment). Next, the semiconductor substrate 1 with the adhesive removal coating film 10 shown in Figure 3A and the support substrate 4 with the adhesive coating layer 2a shown in Figure 3B are bonded together so that the adhesive removal coating film 10 and the adhesive coating layer 2a are in contact. Then, after applying a load in the thickness direction between the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; hot plate) is placed on the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive removal coating film 10, and the adhesive coating layer 2a is heated and cured by the heating device to convert it into the adhesive layer 2 (Figure 3C). The laminate shown in Figure 1 is obtained by the process shown in Figures 3A to 3C.

[0493] The above describes a method of preparing a semiconductor substrate 1 with an adhesive removal coating film 10 and a support substrate 4 with an adhesive coating layer 2a, and then bonding them together. However, for example, a semiconductor substrate 1 with an adhesive removal coating film 10 may be prepared, and an adhesive composition may be applied to the adhesive removal coating film 10 to form a coating film of the adhesive composition. Next, the coating film may be heat-treated (preheating treatment) to form a laminate on the semiconductor substrate 1 in which the adhesive removal coating film 10 and the adhesive coating layer 2a are laminated, and the support substrate 4 may be bonded to the laminate to form the laminate of the present invention shown in Figure 1.

[0494] <Second Embodiment> A laminate having an electronic device layer is used for processing the electronic device layer. While the electronic device layer is being processed, the electronic device layer is bonded to a support substrate. After processing the electronic device layer, the electronic device layer is separated from the support substrate.

[0495] <<Electronic Device Layer>> The electronic device layer refers to a layer having an electronic device, and in the present invention, it refers to a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a layer consisting of a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. Here, "electronic device" means a component that constitutes at least a part of an electronic component. The electronic device is not particularly limited and may have various mechanical structures or circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite of a component made of metal or semiconductor and a resin that seals or insulates the component. The electronic device may have a redistribution layer and / or semiconductor elements or other elements that are sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

[0496] <<Support Substrate>> An example of a support substrate is the same as the one described in the <<Support Substrate>> section of the <<First Embodiment>> above.

[0497] <<Adhesive Removal Coating Film>> Examples of adhesive removal coating films include those similar to those described in the <<Adhesive Removal Coating Film>> section of the <<First Embodiment>> above.

[0498] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above. A detailed description of the adhesive layer is as described in the <<Adhesive Layer>> section of the <<First Embodiment>> above.

[0499] <<Release Agent Layer>> The release agent layer is formed using the release agent composition described above. A detailed description of the release agent layer is as described in the <<Release Agent Layer>> section of the <<First Embodiment>> above.

[0500] The following describes an example of the configuration of the laminate according to the second embodiment, using the figures. Figure 4 shows a schematic cross-sectional view of an example of the laminate according to the second embodiment. The laminate in Figure 4 has a support substrate 24, an adhesive layer 22, an adhesive removal coating film 30, and an electronic device layer 26 in this order. The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25, which is a sealing material, disposed between the semiconductor chip substrates 21. The adhesive layer 22 and the adhesive removal coating film 30 are provided between the support substrate 24 and the electronic device layer 26. The adhesive removal coating film 30 is in contact with the electronic device layer 26, and the adhesive layer 22 is in contact with the support substrate 24. The laminate in Figure 4 shows a laminate having the layer configuration (semiconductor substrate or electronic device layer / adhesive removal coating film / adhesive layer / support substrate) described above as the (X1) pattern.

[0501] Figure 5 shows a schematic cross-sectional view of another example of the laminate of the second embodiment. The laminate in Figure 5 has a support substrate 24, a release agent layer 23, an adhesive layer 22, an adhesive removal coating film 30, and an electronic device layer 26 in this order. The electronic device layer 26 has a plurality of semiconductor chip substrates 21 and a sealing resin 25 which is a sealing material disposed between the semiconductor chip substrates 21. The adhesive removal coating film 30, 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 removal coating film 30 is in contact with the electronic device layer 26, the adhesive layer 22 is in contact with the adhesive removal coating film 30, and the release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24. The laminate in Figure 5 shows a laminate having the layer configuration (semiconductor substrate or electronic device layer / adhesive removal coating film / adhesive layer / release agent layer / support substrate) described as the (X3) pattern above.

[0502] <<Example of a manufacturing method for a laminate in the second embodiment>> The manufacturing method for a laminate according to the present invention is a method for manufacturing a laminate having an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate, comprising the steps of: applying an adhesive removal coating film forming composition on the electronic device layer or on the support substrate to form an adhesive removal coating film; and bonding the electronic device layer to the support substrate via the adhesive layer and the adhesive removal coating film.

[0503] In a more preferred embodiment, the method for manufacturing a laminate according to the present invention is a method for manufacturing a laminate comprising an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate, in this order, the method comprising the steps of: applying an adhesive removal coating film forming composition onto the electronic device layer to form an adhesive removal coating film; and bonding the electronic device layer with the adhesive removal coating film to the support substrate via the adhesive layer.

[0504] The manufacturing method of the laminate will be described below using the laminate shown in Figure 4, one of the laminates in the second embodiment, as an example. The laminate of the present invention can be manufactured, for example, by a method including the following first to fourth steps. First step: Applying an adhesive removal coating film forming composition onto a semiconductor chip substrate to form an adhesive removal coating film. Second step: Applying an adhesive composition to the surface of a support substrate to form an adhesive coating layer (and, if necessary, further heating to form an adhesive layer). Third step: Placing the semiconductor chip substrate with the adhesive removal coating film on the adhesive coating layer or adhesive layer on the support substrate, and bonding the semiconductor chip substrate to the support substrate via the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a vacuum treatment. When the semiconductor chip substrate with the adhesive removal coating film is bonded to the support substrate via the adhesive coating layer, after bonding, the adhesive coating layer is post-heat-treated to cure the adhesive composition and form an adhesive layer. Fourth step: Sealing the semiconductor chip substrate fixed on the adhesive layer using a sealing resin.

[0505] To explain the third step in more detail, for example, the step of the embodiment described in (i) below is taken. (i) A semiconductor chip substrate with an adhesive removal coating film is placed on the adhesive coating layer or adhesive layer, and while performing at least one of a heat treatment and a vacuum treatment, a load is applied in the thickness direction to the semiconductor chip substrate and the support substrate to bring them into close contact, thereby bonding the semiconductor chip substrate to the support substrate via the adhesive coating layer or adhesive layer.

[0506] Furthermore, in the third step, the process of bonding the semiconductor chip substrate and the support substrate and the process of post-heating the adhesive coating layer to form an adhesive layer may be performed together. For example, the semiconductor chip substrate with an adhesive removal coating film may be placed on the adhesive coating layer, and the adhesive coating layer may be heated and cured while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, thereby simultaneously achieving adhesion between the semiconductor chip substrate and the adhesive coating layer and curing from the adhesive coating layer to the adhesive layer, and bonding the semiconductor chip substrate and the support substrate. Alternatively, in the third step, after forming the adhesive layer from the adhesive coating layer, the semiconductor chip substrate with an adhesive removal coating film may be placed on the adhesive layer on the support substrate, 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.

[0507] The application method, the heating temperature of the coating film of the adhesive removal coating film forming composition, the heating means, etc., the heating temperature of the coating film of the adhesive composition, the heating means, etc., and the bonding conditions are as described in the section "<<Example of manufacturing method of a laminate in the first embodiment>>" in the section "<First embodiment>" above.

[0508] The method for manufacturing the laminate according to the second embodiment will be described in more detail below with reference to the figures. In this manufacturing method, the laminate shown in Figure 4 is produced. As shown in Figure 6A, a coating layer 30 made of a composition for forming an adhesive-removing coating film is formed on the semiconductor chip substrate 21, and a semiconductor chip substrate 21 with the adhesive-removing coating film 30 is prepared. As shown in Figure 6B, an adhesive coating layer 22' made of an adhesive composition is formed on the support substrate 24. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22. Next, as shown in Figure 6C, the semiconductor chip substrate 21 with the adhesive-removing coating film 30 is placed on the adhesive layer 22 or adhesive coating layer 22' on the support substrate 24, and while performing a heat treatment and a reduced pressure treatment, a load in the thickness direction is applied to the semiconductor chip substrate 21 and the support substrate 24 to bring them into close contact, and the semiconductor chip substrate 21 with the adhesive-removing coating film 30 is bonded to the adhesive layer 22 or adhesive coating layer 22' on the support substrate 24. When a semiconductor chip substrate 21 with an adhesive removal coating film 30 is bonded to an adhesive coating layer 22', the adhesive coating layer 22' is cured by post-heat treatment to form an adhesive layer 22, and the semiconductor chip substrate 21 with the adhesive removal coating film 30 is fixed to the adhesive layer 22 on the support substrate 24. Next, as shown in Figure 6D, the semiconductor chip substrate 21 with the adhesive removal coating film 30 fixed on the adhesive layer 22 is sealed using a sealing resin 25. In Figure 6D, multiple semiconductor chip substrates 21 temporarily bonded to the support substrate 24 via the adhesive removal coating film 30 and the adhesive layer 22 are sealed with the sealing resin 25. An electronic device layer 26 is formed on the adhesive layer 22 and the adhesive removal coating film 30, having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21. In this way, the electronic device layer 26 is a substrate layer in which multiple semiconductor chip substrates are embedded in the sealing resin.

[0509] <<<Sealing Process>>> The semiconductor chip substrate 21 is sealed using a sealing material. The sealing material used to seal the semiconductor chip substrate 21 is a material that can insulate or seal a component made of metal or semiconductor. In the present invention, for example, a resin composition (sealing resin) is used as the sealing material. The type of sealing resin is not particularly limited as long as it can seal and / or insulate metal or semiconductor, but for example, epoxy resin or silicone resin is preferred. In addition to the resin component, the sealing material may also contain other components such as fillers. Examples of fillers include spherical silica particles. In the sealing process, for example, a sealing resin heated to 130 to 170°C is supplied onto the adhesive removal coating film 30 and the adhesive layer 22 so as to cover the semiconductor chip substrate 21 while maintaining a high viscosity state, and is compression molded to form a layer made of sealing resin 25 on the adhesive removal coating film 30 and the adhesive layer 22. At that time, the temperature condition is, for example, 130 to 170°C. Furthermore, the pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm². ２ That is the case.

[0510] (Method for manufacturing a processed semiconductor substrate or electronic device layer) By using the laminate according to the present invention, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided. The "method for manufacturing a processed semiconductor substrate" can use the laminate described in the <First Embodiment> section of (Laminate) above. The "method for manufacturing a processed electronic device layer" can use the laminate described in the <Second Embodiment> section of (Laminate) above. The "method for manufacturing a processed semiconductor substrate" will be described in the <Third Embodiment> below, and the "method for manufacturing a processed electronic device layer" will be described in the <Fourth Embodiment> below.

[0511] <Third Embodiment> The present invention provides a method for manufacturing a processed semiconductor substrate, comprising: a step of processing a semiconductor substrate with respect to a laminate formed by bonding a semiconductor substrate to a support substrate via an adhesive layer and an adhesive removal coating film; a step of separating the processed semiconductor substrate from the support substrate; and a step of washing the semiconductor substrate with a removal solution to remove the adhesive layer residue present on the semiconductor substrate together with the adhesive removal coating film.

[0512] In a more preferred embodiment, the method for manufacturing a processed semiconductor substrate of the present invention includes the steps of: processing a semiconductor substrate with an adhesive-removing coating film bonded to a support substrate via an adhesive layer to form a laminate; separating the processed semiconductor substrate from the support substrate; and washing the semiconductor substrate with a removal solution to remove the adhesive layer residue present on the semiconductor substrate together with the adhesive-removing coating film.

[0513] The method for manufacturing a processed semiconductor substrate of the present invention may include the following steps 5A to 6A. The method for manufacturing a processed semiconductor substrate may further include the following step 7A. Step 5A: A step of processing a semiconductor substrate onto the laminate described in the section <First Embodiment> above. Step 6A: A step of separating the semiconductor substrate processed in step 5A from the support substrate. Step 7A: After step 6A, a step of washing the processed semiconductor substrate with a removal solution to remove the adhesive layer peeling residue present on the semiconductor substrate together with the adhesive removal coating film.

[0514] The processing performed on the semiconductor substrate in step 5A includes, for example, processing on the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface. Subsequently, for example, through-silicon electrodes (TSVs) are formed, and then the thinned wafer is peeled off the support substrate to form a wafer laminate for three-dimensional mounting. Alternatively, for example, back-side electrodes may be formed before or after this. During the wafer thinning and TSV processes, heat of approximately 250 to 350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention typically includes an adhesive layer and possesses heat resistance to this load. The processing is not limited to those described above and also includes, for example, the implementation of a semiconductor component mounting process when the substrate is temporarily bonded to the support substrate to support the substrate for mounting semiconductor components.

[0515] <<Separation (Delamination) Method>> In step 6A, the method for separating (delaminating) the semiconductor substrate and the support substrate is not particularly limited. For example, a method of mechanical delamination using equipment with a sharp part (a so-called debonder) can be used. Specifically, for example, the sharp part is inserted between the semiconductor substrate and the support substrate, and then the semiconductor substrate and the support substrate are separated. Also, if the laminate has a release agent layer, the method for separating (delaminating) the semiconductor substrate and the support substrate in step 6A may be delamination by irradiating the release agent layer with light and then pulling the semiconductor substrate and the support substrate apart. By irradiating the release agent layer with light from the support substrate side, the release agent layer is altered as described above (for example, separation or decomposition of the release agent layer), and then, for example, one of the substrates can be easily lifted up to separate the semiconductor substrate and the support substrate.

[0516] Irradiation of the release agent layer with light does not necessarily have to be performed over the entire area of ​​the release agent layer. Even if there is a mixture of irradiated and unirradiated areas, if the overall release ability of the release agent layer is sufficiently improved, the semiconductor substrate and the support substrate can be separated by a small external force, such as lifting the support substrate. The ratio and positional relationship between the irradiated and unirradiated areas will vary depending on the type and specific composition of the adhesive removal coating film forming composition and adhesive composition used, the thickness of the adhesive removal coating film, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the irradiated light, etc. However, those skilled in the art can set the conditions appropriately without requiring excessive testing. For these reasons, according to the manufacturing method of the processed semiconductor substrate of the present invention, for example, when the support substrate of the laminate used is light-transmitting, it is possible to shorten the light irradiation time when peeling is performed by light irradiation from the support substrate side. As a result, not only is an improvement in throughput expected, but the semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone, avoiding physical stress for peeling. Typically, the amount of light irradiation for peeling is 50 to 3,000 mJ / cm². ２ The irradiation time is determined appropriately according to the wavelength and irradiation dose.

[0517] The wavelength of light used for peeling is preferably, for example, 250 to 600 nm, and more preferably 250 to 370 nm. More preferred wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for peeling is an amount that can induce a suitable alteration, such as decomposition, of the specific compound and polymer. The light used for peeling may be laser light or non-laser light emitted from a light source such as an ultraviolet lamp.

[0518] <<<Method for Separation (Peeling) of Adhesive Layer by Laser Light>>> The above method of separation by light irradiation describes a method in which a release agent layer is used to separate (peel) the adhesive layer. However, this is just one example, and in the present invention, a release agent layer is not essential for the separation method by light irradiation, as long as the semiconductor substrate and the support substrate can be separated. By appropriately selecting the types of components of the adhesive composition that forms the adhesive layer, separation (peeling) of the adhesive layer by light irradiation can be made possible. For example, by appropriately selecting the types of components from the compositions described in the column <<[i]> of the above <adhesive layer>, separation (peeling) of the adhesive layer by an infrared laser can be made possible, such as the adhesive composition described in publications such as International Patent Publication WO2020 / 100966. Below, the infrared peeling adhesive composition described in International Patent Publication WO2020 / 100966 will be described from the viewpoint of a composition that forms an adhesive layer that can be suitably used in the present invention.

[0519] An infrared peelable adhesive composition can be formed from components including, for example, an adhesive component (A) that hardens by a hydrosilylation reaction and at least one component (B) selected from the group consisting of a component containing epoxy-modified polyorganosiloxane, a component containing methyl group-containing polyorganosiloxane, and a component containing phenyl group-containing polyorganosiloxane. This makes it possible to form an adhesive layer that can be peeled off by irradiation with an infrared laser. Regarding the adhesive component (A) that hardens by a hydrosilylation reaction and the polyorganosiloxane contained in the infrared peelable adhesive composition, reference can be given to the contents described in the section "<<[i] Adhesive Composition>>" of the above <Adhesive Layer> and the contents described in International Patent Publication No. WO2020 / 100966.

[0520] The infrared laser mentioned above may, for example, have a wavelength of 1 μm to 20 μm. In a preferred embodiment of the present invention, the wavelength of the infrared laser is 9.2 to 10.8 μm. When the adhesive layer is irradiated with an infrared laser, the adhesive layer is altered by thermal decomposition or the like, its adhesive strength is significantly reduced, and it becomes peelable. Since the adhesive layer has been altered and its adhesive strength has been significantly reduced, the adhesive layer and the support substrate can be easily separated by applying a slight external force and pulling it up, and as a result, the semiconductor substrate and the support substrate can be easily separated.

[0521] It should be noted that infrared laser irradiation does not necessarily need to be applied to the entire surface of the adhesive layer. Even if there is a mixture of areas irradiated and unirradiated by the infrared laser, if the overall strength of the adhesive layer is sufficiently reduced, the support substrate can be peeled off the laminate by applying a slight external force and pulling up the support substrate. The ratio and positional relationship between the areas irradiated and unirradiated by the infrared laser will vary depending on the infrared release adhesive composition forming the adhesive layer, the thickness of the adhesive layer, the intensity of the infrared laser used, etc. However, those skilled in the art can set the conditions appropriately without requiring excessive testing. For example, an area not irradiated by the infrared laser may be provided next to the area irradiated by the infrared laser, with the same width as the infrared line width.

[0522] In a method of separating (peeling off) an adhesive layer by irradiating it with an infrared laser, the adhesive layer does not need to be a single layer; it may consist of multiple layers. For example, as in the adhesive composition described in publications such as International Patent Publication WO2020 / 100965, the adhesive layer may consist of two layers, and one of these adhesive layers may be irradiated with an infrared laser to separate (peele) it. The components of each adhesive layer in the two-layer adhesive layer configuration may be determined by referring to the contents described in International Patent Publication WO2020 / 100965.

[0523] <<Cleaning Method>> The separated semiconductor substrate can be cleaned by spraying the cleaning agent composition onto its surface or by immersing the separated semiconductor substrate in the cleaning agent composition. Alternatively, the surface of the processed semiconductor substrate may be cleaned using a removal tape or the like. As an example of substrate cleaning, step 7A, in which the processed semiconductor substrate is cleaned, may be performed after step 6A. The following are examples of cleaning agent compositions that can be used for cleaning.

[0524] Detergent compositions typically contain a solvent. Examples of solvents include lactones, ketones, polyhydric alcohols, compounds having ester bonds, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of lactones include γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having ester bonds include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or compounds having ether bonds such as monophenyl ether, which are monomethyl ethers, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyhydric alcohols or compounds having ester bonds. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. These can be used individually or in combination of two or more.Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0525] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined considering the compatibility of PGMEA and the polar solvent, but it is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. For example, when EL is used as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is used as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are used as the polar solvent, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0526] The cleaning agent composition may or may not contain salt, but it is preferable that it does not contain salt in order to increase its versatility when processing semiconductor substrates using laminates and to reduce costs.

[0527] An example of a detergent composition containing a salt is a detergent composition containing a quaternary ammonium salt and a solvent. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, the anion that pairs with it is the hydroxide ion (OH) － ); fluoride ion (F － ), chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ions (BF４ － ); Hexafluorophosphate ion (PF ６ － Examples include, but are not limited to, these.

[0528] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt. 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.

[0529] In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of hydrocarbon groups in tetra(hydrocarbon)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. In a more preferred embodiment, tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also called tetrabutylammonium fluoride). Among these, tetrabutylammonium fluoride is preferred.

[0530] Quaternary ammonium salts such as tetraammonium fluoride may be used in hydrate form. Furthermore, quaternary ammonium salts such as tetraammonium fluoride may be used alone or in combination of two or more types. The amount of quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass relative to the detergent composition.

[0531] When a detergent composition contains a salt, the solvent used in combination is not particularly limited as long as it is used for this type of application and dissolves salts such as quaternary ammonium salts. However, from the viewpoint of obtaining a detergent composition with excellent cleaning properties with good reproducibility, and from the viewpoint of dissolving salts such as quaternary ammonium salts well and obtaining a detergent composition with excellent uniformity, the detergent composition preferably contains one or more amide-based solvents.

[0532] A suitable example of an amide solvent is an acid amide derivative represented by formula (Z).

[0533] In the formula, R ０ R represents an ethyl group, a propyl group, or an isopropyl group, with ethyl and isopropyl groups being preferred, and ethyl group being more preferred. Ａ and R Ｂ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and cyclobutyl groups. Of these, R Ａ and R Ｂ The groups are preferably methyl or ethyl, more preferably both are methyl or ethyl, and even more preferably both are methyl.

[0534] Examples of acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyrate amide, N,N-diethylbutyrate amide, N-ethyl-N-methylbutyrate amide, N,N-dimethylisobutyrate amide, N,N-diethylisobutyrate amide, and N-ethyl-N-methylisobutyrate amide. Of these, N,N-dimethylpropionamide and N,N-dimethylisobutylamide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0535] The acid amide derivative represented by formula (Z) may be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or a commercially available product may be used.

[0536] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0537] In equation (Y), R １０１ R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １０２ The symbol represents an alkylene group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and n-butyl groups, while specific examples of alkylene groups having 1 to 6 carbon atoms include, but are not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups.

[0538] Specific examples of lactam compounds represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used individually or in combination of two or more.

[0539] In one preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in one more preferred embodiment, comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in one even more preferred embodiment, comprises N-methylpyrrolidone (NMP).

[0540] The cleaning agent composition used in this invention may contain water as a solvent, but from the viewpoint of avoiding corrosion of the substrate, etc., only organic solvents are usually intentionally used as solvents. In this case, however, it is not ruled out that trace amounts of water contained in the salt's hydrated water or in the organic solvent may be included in the cleaning agent composition. The water content of the cleaning agent composition used in this invention is usually 5% by mass or less.

[0541] The components and method elements relating to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways, as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may also include steps other than those described above.

[0542] One example of the delamination method of the present invention involves separating the semiconductor substrate and the support substrate of a laminate by irradiating the release agent layer with light from either the semiconductor substrate side or the support substrate side, when the semiconductor substrate or support substrate of the laminate is light-transmitting. In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are suitably temporarily bonded together by an adhesive layer and a release agent layer. For example, if the support substrate is light-transmitting, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Typically, delamination is performed after processing has been carried out on the semiconductor substrate of the laminate.

[0543] An example of a third embodiment will be described using Figures 7A to 7D. This example is an example of manufacturing a thinned semiconductor substrate. First, a laminate is prepared (Figure 7A). This laminate is the same as the laminate shown in Figures 1 and 3C. 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 removal coating film 10, thereby thinning the semiconductor substrate 1 (Figure 7B). The thinned semiconductor substrate 1 may also be subjected to the formation of through electrodes, etc. Next, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4 (Figure 7C). At this point, there may be peeling residue of the adhesive layer 2 remaining on the thinned semiconductor substrate 1. Therefore, the thinned semiconductor substrate 1 is cleaned using a cleaning agent composition to remove the peeling residue of the adhesive layer 2 along with the adhesive removal coating film 10 from the semiconductor substrate 1. As a result, a thinned semiconductor substrate 1 is obtained in which the peeling residue of the adhesive layer has been easily and cleanly removed (Figure 7D).

[0544] <Fourth Embodiment> The present invention provides a method for manufacturing a processed electronic device layer, comprising the steps of: processing an electronic device layer on a laminate in which an electronic device layer is bonded to a support substrate via an adhesive layer and an adhesive removal coating film; separating the processed electronic device layer from the support substrate; and washing the electronic device layer with a removal solution to remove the adhesive layer peeling residue present on the electronic device layer together with the adhesive removal coating film.

[0545] In a more preferred embodiment, the method for manufacturing a processed electronic device layer of the present invention includes the steps of: processing an electronic device layer on a laminate in which an electronic device layer with an adhesive-removing coating film is bonded to a support substrate via an adhesive layer; separating the processed electronic device layer from the support substrate; and washing the electronic device layer with a removal solution to remove any adhesive residue present on the electronic device layer together with the adhesive-removing coating film.

[0546] The method for manufacturing a processed electronic device layer of the present invention may include the following steps 5B to 6B. The method for manufacturing a processed electronic device layer may further include the following step 7B. Step 5B: A step of processing an electronic device layer onto the laminate described in the section <Second Embodiment> above. Step 6B: A step of separating the electronic device layer processed in step 5B from the support substrate. Step 7B: After step 6B, a step of washing the processed electronic device layer with a removal solution to remove the adhesive layer peeling residue present on the electronic device layer together with the adhesive removal coating film.

[0547] The following describes a specific example of the fourth embodiment, using Figures 8A to 8F.

[0548] The processing applied to the electronic device layer in step 5B includes, for example, grinding and wiring layer formation processes.

[0549] <<Grinding Process>> The grinding process involves 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. The grinding of the sealing resin portion is performed, for example, as shown in Figure 8B, by grinding the sealing resin 25 layer of the laminate shown in Figure 8A until it is approximately the same thickness as the semiconductor chip substrate 21. Note that the laminate shown in Figure 8A is the same laminate as the laminates shown in Figures 4 and 6D.

[0550] <<Wiring Layer Formation Process>> The wiring layer formation process is a process in which a wiring layer is formed on the exposed semiconductor chip substrate 21 after the grinding process described above. In Figure 8C, a wiring layer 28 is formed on an electronic device layer 26 consisting of a semiconductor chip substrate 21 and a sealing resin 25 layer. The wiring layer 28 is also called an RDL (Reduction Layer) and is a thin film wiring body that constitutes wiring connected to the substrate, and may have a single-layer or multi-layer structure. The wiring layer is made of dielectric material (silicon oxide (SiO2) ｘ The wiring may be formed by a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) between layers of photosensitive resins such as photosensitive epoxy, etc., but is not limited to this. For example, the following method can be used to form the wiring layer 28. First, silicon oxide (SiO2) is formed on the layer of sealing resin 25. ｘ), a dielectric layer such as a photosensitive resin is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering or vacuum deposition. The dielectric layer made of a photosensitive resin can be formed by, for example, applying the photosensitive resin onto the layer of sealing resin 25 by methods such as spin coating, dipping...

Claims

1. A composition for forming an adhesive removal coating film used for removing peeling residues of the adhesive layer present on the semiconductor substrate, the electronic device layer, or the support substrate after temporarily bonding a semiconductor substrate or an electronic device layer to a support substrate using an adhesive layer and then separating said semiconductor substrate or said electronic device layer from said support substrate, wherein said composition for forming an adhesive removal coating film is a composition containing a polymer and a solvent and capable of forming a coating film removable by a removing solution, and said polymer is a polymer satisfying any one of the following [I] to [V], the composition for forming an adhesive removal coating film. [I]: Polymer (I) having a partial structure represented by the following formula (A) [II]: Polymer (II) having a structural unit represented by the following formula (1) [III]: Polymer (III) having a cyclic hydrocarbon selected from at least one of a polystyrene resin, a cyclic olefin-based resin, and a polyarylate resin [IV]: Polymer (IV) having a structural unit represented by the following formula (J) [V]: Polymer (V) having a structural unit represented by the following formula (K) (In formula (A), R １１ represents a single bond or a divalent group having 1 to 4 carbon atoms. R １２ represents a hydrogen atom, a hydroxy group, or a methyl group. * represents a bonding site.) (In formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ３ represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group, R ２ and R ３ may together with the carbon atom and the oxygen atom between R ２ and R ３ form a ring, and the ring may contain a hetero atom in addition to said oxygen atom.) (In formula (J), Z １ This represents a hydroxyl group-substituted arylene group with 6 to 40 carbon atoms derived from a polyhydroxy aromatic compound, Z ２ (This represents an arylene group with 6 to 40 carbon atoms.) (In formula (K), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of the imide group that is deprotected by an alkali.) 2. The adhesive removal coating film forming composition according to claim 1, wherein the polymer (I) has a structural unit represented by the following formula (A-1). (In formula (A-1), A １ A ２ A ３ A ４ A ５ and A ６ Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group. １１ R represents a single bond or a divalent group with 1 to 4 carbon atoms. １２ (This represents a hydrogen atom, a hydroxyl group, or a methyl group.) 3. The adhesive composition for forming the adhesive layer contains an adhesive component (A) that hardens by a hydrosilylation reaction, as described in claim 1.

4. The adhesive removal coating film forming composition according to claim 3, wherein the adhesive component (A) contains a component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, and a component (A-2) having a Si-H group.

5. A laminate comprising a semiconductor substrate or an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate, wherein the adhesive removal coating film is formed from an adhesive removal coating film forming composition according to any one of claims 1 to 4.

6. A method for manufacturing a laminate having a semiconductor substrate or an electronic device layer, an adhesive removal coating film, an adhesive layer, and a support substrate, comprising the steps of: applying an adhesive removal coating film forming composition onto the semiconductor substrate or the electronic device layer, or onto the support substrate to form an adhesive removal coating film; and bonding the semiconductor substrate or the electronic device layer to the support substrate via the adhesive layer and the adhesive removal coating film.

7. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: a step of processing a semiconductor substrate or electronic device layer on a laminate formed by bonding the semiconductor substrate or electronic device layer to a support substrate via an adhesive layer and an adhesive removal coating film; a step of separating the processed semiconductor substrate or electronic device layer from the support substrate; and a step of washing the semiconductor substrate or electronic device layer with a removal solution to remove the adhesive layer peeling residue present on the semiconductor substrate or electronic device layer together with the adhesive removal coating film.

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