Composition for forming coating film for foreign substance removal, and semiconductor substrate

Abstract

This composition for forming a coating film for foreign substance removal can form a coating film that can be removed using a remover liquid. The composition contains a film structural component and a solvent, and the film structural component contains a coordination compound.

Description

Coating film-forming composition for removing foreign matter and semiconductor substrate

[0001] The present invention relates to a coating film-forming composition for removing foreign matter, which can prevent foreign matter from remaining on a substrate in a simple manner, a coating film for removing foreign matter, a semiconductor substrate, and a method for producing a processed semiconductor substrate.

[0002] In the manufacture of semiconductor devices, particularly in the so-called post-processing, a process has been considered in which a semiconductor substrate (e.g., a wafer) is attached to a support substrate, and then back-grinding (grinding), wiring formation processes, etc. are carried out, and then the support substrate is peeled off to obtain a desired semiconductor substrate.

[0003] In such a process, foreign matter may be generated and must be removed. For example, Patent Documents 1 and 2 disclose a composition for forming a substrate processing film and a substrate processing method that can efficiently remove fine particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface in a process of forming a substrate processing film on the surface of a semiconductor substrate and removing foreign matter from the substrate surface.

[0004] International Publication No. WO 2017 / 056746 International Publication No. WO 2020 / 008965

[0005] On the other hand, when attaching a semiconductor substrate to a support substrate, the semiconductor substrate is attached using an adhesive layer (e.g., a liquid composition containing a polymer, a backgrinding tape, a dicing tape, etc.) that is resistant to subsequent processes (e.g., a heating process, a chemical treatment process, etc.). Alternatively, a support substrate having a pressure-sensitive adhesive layer is used. Then, a process of peeling the semiconductor substrate is performed. During this process, the adhesive layer or the pressure-sensitive adhesive layer of the support substrate may remain on the substrate as foreign matter (residue). This occurs particularly when an adhesive layer is formed directly on the surface of a semiconductor substrate on which wiring or the like has already been formed, or when a support substrate having a pressure-sensitive adhesive layer is directly attached. This foreign matter may not be completely removed even by cleaning with known organic solvents, liquid chemicals, etc. Therefore, a simple method is required to prevent peeling residues generated from the adhesive layer, pressure-sensitive adhesive layer, etc. from remaining on the semiconductor substrate. On the other hand, when a film (foreign matter removal coating film) is used for this purpose, the film is required to be easily removable from the semiconductor substrate after the process of peeling the semiconductor substrate has been performed (easy removability).

[0006] Therefore, an object of the present invention is to provide a coating film-forming composition for removing foreign matter, which can provide a coating film for removing foreign matter that is easily removable, and a method for producing a coating film for removing foreign matter, a semiconductor substrate, and a processed semiconductor substrate using the composition.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0008] That is, the present invention encompasses the following: [1] A coating film-forming composition for removing foreign matter, capable of forming a coating film removable by a removal solution, comprising film constituent components and a solvent, wherein the film constituent components include a coordinating compound. [2] The composition according to [1], wherein the coordinating compound is a compound capable of coordinating to copper. [3] The composition according to [1] or [2], wherein the coordinating compound is at least one of: (I) a compound having two or more hydroxy groups; (II) a compound having two or more carboxy groups; (III) a compound having a heterocycle; and (IV) an acetylene glycol compound. [4] The compound according to any one of [1] to [3], wherein the film constituent components include a compound or a polymer as a component other than the coordinating compound. [5] The composition according to [4], wherein the compound or polymer has at least one of a hydroxy group, a carboxy group, and a heterocycle. [6] The composition according to any one of [1] to [5], wherein the content of the coordinating compound is 1% by mass to 10% by mass relative to the film constituent components. [7] The composition according to any one of [4] to [6], wherein the content of the compound or polymer is 90% by mass to 99% by mass relative to the film constituent components. [8] The composition according to any one of [1] to [7], wherein the removal liquid is an alkaline removal liquid. [9] The composition according to any one of [1] to [8], wherein the coating film is in contact with copper.

[10] A coating film for removing foreign matter formed from the composition according to any one of [1] to [9].

[11] A semiconductor substrate having the coating film for removing foreign matter according to

[10] .

[12] The semiconductor substrate according to

[11] , wherein the coating film for removing foreign matter is in contact with copper.

[13] A method for manufacturing a processed semiconductor substrate, comprising: a first step of manufacturing a laminate by bonding the semiconductor substrate according to

[11] and a supporting substrate with the foreign matter removal coating film interposed therebetween; a second step of processing the laminate; a third step of peeling the supporting substrate from the laminate; and a fourth step of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the foreign matter removal coating film.

[14] The method for producing a processed semiconductor substrate according to

[13] , wherein the foreign matter removal coating film is in contact with copper in the laminate.

[15] The method for producing a processed semiconductor substrate according to

[13] or

[14] , wherein foreign matter is removed together with the foreign matter removal coating film in the fourth step.

[16] The method for producing a processed semiconductor substrate according to any of

[13] to

[15] , wherein the first step is a step of bonding the semiconductor substrate and the support base with the foreign matter removal coating film and adhesive layer interposed therebetween to produce a laminate.

[17] The method for producing a semiconductor substrate according to

[16] , wherein foreign matter, which is a peeling residue of the adhesive layer, is removed together with the foreign matter removal coating film in the fourth step.

[18] The method for producing a processed semiconductor substrate according to any of

[13] to

[17] , wherein the processing includes connecting the semiconductor substrate and a second semiconductor substrate.

[0009] Furthermore, according to the present invention, it is possible to provide a coating film-forming composition for removing foreign matter, which can provide a coating film for removing foreign matter that is easily removable, as well as a method for producing a coating film for removing foreign matter, a semiconductor substrate, and a processed semiconductor substrate using the composition.

[0010] FIG. 1A is a schematic cross-sectional view (part 1) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 1B is a schematic cross-sectional view (part 2) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 1C is a schematic cross-sectional view (part 3) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 1D is a schematic cross-sectional view (part 4) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 1E is a schematic cross-sectional view (part 5) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 1F is a schematic cross-sectional view (part 6) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 1G is a schematic cross-sectional view (part 7) illustrating an example of a method for manufacturing a processed semiconductor substrate. FIG. 2A is a schematic cross-sectional view (part 1) illustrating another example of a method for manufacturing a processed semiconductor substrate. FIG. 2B is a schematic cross-sectional view (part 2) illustrating another example of a method for manufacturing a processed semiconductor substrate. FIG. 2C is a schematic cross-sectional view (part 3) illustrating another example of a method for manufacturing a processed semiconductor substrate. FIG. 2D is a schematic cross-sectional view (part 4) illustrating another example of a method for manufacturing a processed semiconductor substrate. FIG. 2E is a schematic cross-sectional view (part 5) illustrating another example of a method for manufacturing a processed semiconductor substrate. Figure 2F is a schematic cross-sectional view (No. 6) for explaining another example of a method for manufacturing a processed semiconductor substrate. Figure 2G is a schematic cross-sectional view (No. 7) for explaining another example of a method for manufacturing a processed semiconductor substrate. Figure 2H is a schematic cross-sectional view (No. 8) for explaining another example of a method for manufacturing a processed semiconductor substrate. Figure 2I is a schematic cross-sectional view (No. 9) for explaining another example of a method for manufacturing a processed semiconductor substrate. Figure 2J is a schematic cross-sectional view (No. 10) for explaining another example of a method for manufacturing a processed semiconductor substrate. Figure 2K is a schematic cross-sectional view (No. 11) for explaining another example of a method for manufacturing a processed semiconductor substrate.

[0011] (Coating film-forming composition for removing foreign matter) The coating film-forming composition for removing foreign matter of the present invention contains film-constituting components and a solvent. The film-constituting components include a coordinating compound. The coating film-forming composition for removing foreign matter is preferably capable of forming a coating film that can be removed by a removal liquid. The film-constituting components refer to components other than the solvent in the coating film-forming composition for removing foreign matter.

[0012] The present inventors have found that when attempting to remove a coating film formed from a coating film-forming composition for removing foreign matter using a remover, the film may remain and be difficult to remove with the remover. The present inventors conducted further research and found that this difficulty in removal with the remover is more likely to occur when the coating film is in contact with a metal (e.g., copper). Further research led the present inventors to find that by incorporating a coordinating compound into the coating film-forming composition for removing foreign matter, the film can be prevented from remaining when attempting to remove the coating film with a remover, thereby maintaining the easy removability of the coating film. The present inventors have speculated as follows: When a metal (e.g., copper) in contact with the film diffuses (migrates) into the film and interacts (e.g., forms a complex) with the main component of the film, the film becomes difficult to remove with the remover. On the other hand, by incorporating a coordinating compound into the coating film-forming composition for removing foreign matter, the interaction between the main component of the film and the metal can be prevented, thereby maintaining the easy removability of the film. The reason why a coordinating compound can prevent the interaction between the main component of the film and the metal is unclear. Possible reasons include, for example, the uneven distribution of the coordinating compound at the interface between the film and the metal, preventing the metal from diffusing into the film, or the preferential interaction between the metal diffused into the film and the coordinating compound. Furthermore, metals in contact with the film can migrate to the film surface and form a thin oxide film, making them difficult to remove with a removal solution. On the other hand, when a coordinating compound is contained in a coating film-forming composition for removing foreign matter, the coordinating compound can trap the metal and inhibit the formation of an oxide film. Therefore, easy removability can be maintained.

[0013] Considering the above points, in order to more suitably obtain the effects of the present invention, it is preferable that the coating film be in contact with a metal. Examples of the metal include the "coordination-capable metals" described below. The metal in contact with the coating film is, for example, a metal present on a semiconductor substrate. Such a metal is, for example, a metal serving as an electrode. Examples of the electrode include bumps.

[0014] <Film Constituent Components> The film constituent components include a coordinating compound. Preferably, the film constituent components further include a compound or a polymer. In the present invention, the "compound or polymer" refers to a component different from the coordinating compound, the crosslinking agent described below, the additives described below, and the like. The "compound or polymer" is, for example, the main component of the film constituent components. The main component of the film constituent components means, for example, that it accounts for 50% by mass or more of the film constituent components.

[0015] <<Coordinating Compounds>> Coordinating compounds are capable of coordinating with metals. Coordinating compounds are also called complex-forming compounds. Coordinating compounds form complexes by coordinating with metals or metal ions. Examples of metals capable of coordinating include copper, aluminum, chromium, iron, nickel, zinc, molybdenum, cobalt, manganese, tantalum, titanium, tungsten, ruthenium, gold, silver, and platinum, with copper being preferred.

[0016] The coordinating compound has, for example, a functional group, such as a hydroxy group, a carboxy group, or a mercapto group.

[0017] In the present invention, the OH in the =N-OH group is considered to be one form of a hydroxy group, and the OH in the -COOH group (carboxy group) is not considered to be one form of a hydroxy group.

[0018] When the coordinating compound has a hydroxy group, the number of the hydroxy groups may be one, two, three, four, five, or six.

[0019] When the coordinating compound has a hydroxy group, the hydroxy group may or may not be a phenolic hydroxy group.

[0020] When the coordinating compound has a carboxy group, the number of the carboxy groups may be one, two, three, four, five, or six.

[0021] The coordination compound may have a ring structure. The ring structure may be, for example, a 5-membered ring, a 6-membered ring, a 7-membered ring, or a condensed ring of two or more of these. When the coordination compound has a ring structure, the number of ring structures is not particularly limited and may be one, two, three, or four.

[0022] The coordination compound may or may not have an aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocycle. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring. Examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a thiophene ring, and a pyridine ring.

[0023] The atoms constituting the coordination compound are not particularly limited, and the coordination compound may be a compound composed only of carbon atoms, hydrogen atoms, and oxygen atoms, a compound composed only of carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen atoms, or a compound composed only of carbon atoms, hydrogen atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.

[0024] The coordinating compound may or may not have a halogen atom, and may or may not have a carbonyl bond (CO).

[0025] Examples of the heterocycle in the compound having a heterocycle include a 5-membered ring, a 6-membered ring, and a 7-membered ring. Examples of the heteroatom contained in the heterocycle include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the heterocycle include an isocyanuric ring, a pyrazolone ring, a pyridine ring, and a thiazole ring.

[0026] The molecular weight of the coordinating compound (for example, the molecular weight of the following compounds (I) to (III)) is not particularly limited, and may be, for example, 100 to 500.

[0027] Examples of coordinating compounds include the following compounds: (I) Compounds having two or more hydroxy groups, (II) Compounds having two or more carboxy groups, (III) Compounds having a heterocycle, and (IV) Acetylene glycol compounds. Note that some compounds may fall into both (I) and (II). For example, tartaric acid (structure below) is a compound of both (I) and (II).

[0028] Examples of the compounds (I) to (III) include the following compounds:

[0029] (IV) The acetylene glycol compound is an oxyalkylene adduct of acetylene diol, which is obtained by adding an oxyalkylene having 2 or 3 carbon atoms to an acetylene diol.

[0030] Examples of acetylene diols include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 2-butyne-1,4-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 3-hexyne-2,5-diol.

[0031] The oxyalkylene having 2 or 3 carbon atoms is ethylene oxide (oxyethylene) or propylene oxide (oxypropylene), preferably ethylene oxide.

[0032] The average number of moles of oxyalkylene added in the oxyalkylene adduct of acetylene diol is, for example, 1 to 20, preferably 2 to 20, and more preferably 4 to 10.

[0033] The acetylene glycol compound is represented, for example, by the following formula (IV-1): (In formula (IV-1), R １ , R ２ , R ３ , and R ４ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m and n each represent an integer of 0 or greater.

[0034] The sum of n and m is, for example, 1 to 20, preferably 2 to 20, and more preferably 4 to 10. １ ~R ４ As for R ２ and R ３ is a methyl group, and R １ and R ４ is an isobutyl group (-CH ２ CH (CH ３ ) ２ ) is preferred.

[0035] The acetylene glycol compound may be a commercially available product. Examples of commercially available acetylene glycol compounds include Surfynol (registered trademark) and Olfine (registered trademark) manufactured by Nissin Chemical Industry Co., Ltd., and Acetylenol (registered trademark) manufactured by Kawaken Fine Chemicals Co., Ltd.

[0036] The content of the coordinating compound is not particularly limited, but is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass, based on the film constituent components.

[0037] The content of the coordinating compound in the coating film-forming composition for removing foreign matter is not particularly limited, but is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass, based on the "compound or polymer."

[0038] <<Compound or Polymer>> The compound or polymer that is the main component of the membrane constituent is not particularly limited, but the compound or polymer has, for example, a polar group. Examples of the polar group include a hydroxy group and a carboxy group.

[0039] The compound or polymer has, for example, a heterocycle. Examples of the heterocycle include a lactam ring.

[0040] Polymers (A) to (I) and compound (A) are introduced below as examples of the compounds or polymers.

[0041] <<<Polymer (A)>>> The polymer (A) is a polymer having at least one of a phenolic hydroxy group and a carboxy group.

[0042] The sum of the numbers of phenolic hydroxy groups and carboxy groups contained in the polymer (A) is, for example, 2 or more. In this case, the polymer (A) may have 2 or more phenolic hydroxy groups and no carboxy groups, or may have 2 or more carboxy groups and no phenolic hydroxy groups.

[0043] The polymer (A) is not particularly limited as long as it has at least one of a phenolic hydroxy group and a carboxy group, and examples thereof include phenol novolac, cresol novolac, polyhydroxystyrene, polyamic acid, and polyacrylic acid.

[0044] As the polymer (A), a polymer in which all of the units (repeating unit structures) constituting the polymer have a phenolic hydroxy group or a carboxyl group can be used. Alternatively, a polymer composed of a unit having a phenolic hydroxy group or a carboxyl group and a unit not having a phenolic hydroxy group or a carboxyl group can also be used. When such a polymer composed of a unit having a phenolic hydroxy group or a carboxyl group and a unit not having a phenolic hydroxy group or a carboxyl group is used, the molar ratio of the unit having a phenolic hydroxy group or a carboxyl group in the polymer is preferably 1% or more, for example, 10% or more, particularly 20% or more, but is 5% to 100%, for example, 10% to 100%, preferably 20% to 100%, more preferably 30% to 100%, based on the total units constituting the polymer.

[0045] Examples of the polymer (A) include polymers represented by the following formulas (4) to (23) and (26) to (35). １ , p ２ , p ３ and p ４ Each represents the molar proportion of each unit in the polymer, and the sum of these represents a value that is 100%.

[0046] Examples of polymer (A) include polymers (e.g., polyhydroxystyrene) containing hydroxystyrene units (repeating units derived from hydroxystyrene). Polymer (A) also includes polymers produced by copolymerization of hydroxystyrene with compounds having addition-polymerizable double bonds, such as acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, and vinyl ether compounds, for example, polymers of formulas (8) to (11). The hydroxystyrene units are preferably contained in a molar ratio of 10% or more relative to all units constituting the polymer. The molar ratio of hydroxystyrene units in the polymer is 10% or more, preferably 20% or more, for example, 10% to 100%, preferably 20% to 100%, and more preferably 30% to 100%, relative to all units constituting the polymer.

[0047] The polymer (A) also includes a polymer containing an acrylic acid unit or a methacrylic acid unit (e.g., a polyacrylic acid or polymethacrylic acid polymer). Furthermore, the polymer (A) also includes a polymer produced from a compound having an addition-polymerizable double bond, such as an acrylic acid ester compound, a methacrylic acid ester compound, or a styrene compound, and acrylic acid or methacrylic acid, for example, the polymers of formulas (10), (12) to (15). The acrylic acid unit or methacrylic acid unit is preferably contained in a molar ratio of 10% or more relative to all units constituting the polymer. The molar ratio of the acrylic acid unit or methacrylic acid unit in the polymer is 10% or more, preferably 20% or more, for example, 10% to 100%, preferably 20% to 90%, and more preferably 30% to 70%, relative to all units constituting the polymer.

[0048] The polymer (A) may also include polyimides. The polyimides used in the present invention can be produced from a tetracarboxylic dianhydride compound and a diamine compound having a phenolic hydroxy group or a carboxyl group. Examples of such polyimides include polyimides represented by formulas (31) to (35). For example, the polyimide represented by formula (31) can be obtained by reacting a 1,2,4,5-benzenetetracarboxylic dianhydride compound with 3,5-diaminobenzoic acid and 2,2-bis(3-amino-4-toluyl)hexafluoropropane.

[0049] The polymer (A) may also include polyamic acids. Polyamic acids can be produced by reacting a diamine compound with a tetracarboxylic acid or its derivatives, such as a tetracarboxylic acid dianhydride compound or a dicarboxylic acid dihalide. Polyamic acids can also be produced by synthesizing a polyamic acid silyl ester by polymerization of a bis-silylated diamine compound with a tetracarboxylic acid dianhydride compound, followed by decomposition of the silyl ester moiety with an acid. Examples of polyamic acids used in the present invention include polyamic acids represented by formulas (16) to (23) and (26) to (30). For example, polyamic acid represented by formula (20) can be obtained by reacting a 1,2,4,5-benzenetetracarboxylic acid dianhydride compound with 3,5-diaminobenzoic acid and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl.

[0050] Polymer (A) also includes polymers prepared from a compound having at least two epoxy groups and a compound having at least two phenolic hydroxy or carboxyl groups. Examples of such polymers include those prepared from a compound having at least two, e.g., two to six, epoxy groups and a compound having at least two, e.g., two to six, phenolic hydroxy or carboxyl groups. Such polymers can be prepared by reacting a compound having at least two epoxy groups with a compound having at least two phenolic hydroxy or carboxyl groups in an approximately equimolar amount relative to the epoxy groups in the presence of a catalyst such as a quaternary ammonium salt. Examples of compounds having at least two epoxy groups include 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.Examples of the compound having at least two phenolic hydroxy groups or carboxyl groups include 1,2,3-anthracenetriol, 2,7,9-anthracenetriol, 2-hydroxy-1-naphthoic acid, 7-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2,6-naphthoic acid, 1-hydroxy-4-phenyl-3-naphthoic acid, 6-ethoxy-2,3-naphthalenediol, 4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 2,4-dihydroxy-5-methylbenzoic acid, Examples of the polymers produced from a compound having at least two epoxy groups and a compound having at least two phenolic hydroxy groups or carboxyl groups include 3-hydroxybenzoic acid, 5-hydroxyisophthalic acid, 2,5-dihydroxybenzoic acid, terephthalic acid, 2-nitroterephthalic acid, 3,5-dibromo-4-hydroxybenzoic acid, 3,5-dibromo-2,4-dihydroxybenzoic acid, 3-iodo-5-nitro-4-hydroxybenzoic acid, 3,5-diiodo-2-hydroxybenzoic acid, 2,4,6-triiodo-3-hydroxybenzoic acid, 2,4,6-tribromo-3-hydroxybenzoic acid, and 2-bromo-4,6-dimethyl-3-hydroxybenzoic acid.

[0051]

[0052] The polymer (A) may also be a polymer represented by the following formula (1): (In formula (1), R １ represents a hydrogen atom or a methyl group. X represents —O— or —N(R ３ )-(R ３ represents a hydrogen atom or a methyl group. ２ represents a single bond or an alkylene group having 1 to 6 carbon atoms. １１ represents an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, two or more R １１may be the same or different. A polymer having a unit represented by the formula (1) can be used. The unit of formula (1) is contained in a molar ratio of, for example, 10% or more relative to all units constituting the polymer. The molar ratio of the unit of formula (1) in the polymer is 10% or more, preferably 20% or more, for example, 10% to 100%, preferably 15% to 80%, more preferably 20% to 70%, and most preferably 25% to 50%.

[0053] Examples of the monomer that provides the unit represented by formula (1) include the monomer represented by the following formula (1-1). (In formula (1-1), R １ represents a hydrogen atom or a methyl group. X represents —O— or —N(R ３ )-(R ３ represents a hydrogen atom or a methyl group. ２ represents a single bond or an alkylene group having 1 to 6 carbon atoms. １１ represents an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 4. When m is 2 or more, two or more R １１ may be the same or different.)

[0054] Examples of the monomer represented by formula (1-1) include the following monomers.

[0055] A polymer having a unit represented by formula (1) can be produced by polymerizing a monomer represented by formula (1-1) using a polymerization initiator such as N,N'-azobisisobutyronitrile.

[0056] A polymer having a unit represented by formula (1) can contain other units as long as the ratio of formula (1) in the polymer satisfies the above-mentioned value. The other units can be introduced into the polymer by using a polymerizable compound such as acrylic acid, methacrylic acid, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, or a vinyl compound during the production of the polymer.

[0057] Examples of the acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, and methoxytrifluoroethyl acrylate. Examples of the acrylate include ethylene glycol acrylate, mono-(2-(acryloyloxy)ethyl)phthalate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0058] Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxyethyl methacrylate, methyl ... Examples of suitable methacryloyloxyalkylene copolymers include triethylene glycol methacrylate, mono-(2-(methacryloyloxy)ethyl)phthalate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0059] Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

[0060] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and hydroxystyrene.

[0061] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0062] Examples of polymers having a unit represented by formula (1) include polymers represented by formulas (44) to (49). １ , q ２ , q ３ and q ４Each of q1 and q2 represents the molar proportion of each unit in the polymer, and q2 is 10% or more, and the sum of these represents a value that is 100%.

[0063]

[0064] The polymer (A) may be a polyamic acid having a structural unit derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group, as described in International Publication No. 2018 / 159665. The polymer (A) may also be a phenolic hydroxyl group-containing polymer or a carboxyl group-containing polymer, as described in International Publication No. 2022 / 019287. The contents of these publications are incorporated herein by reference to the same extent as if expressly set forth herein.

[0065] The polymer (A) may be a commercially available product, such as polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.).

[0066] <<<Polymer (B)>>> Polymer (B) is a polymer containing a structural unit represented by the following formula (1). [In formula (1), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group for an imide group that can be deprotected by alkali.]

[0067] Examples of the protecting group for the imide group in R that can be deprotected by an alkali include a methyl group, a cyclohexyl group, a hydroxyethyl group, a benzyl group, a phenyl group, etc. Examples of the alkali include alkalis contained in the alkaline removal solution.

[0068] The polymer (B) may have a structural unit other than the structural unit represented by formula (1). Such a structural unit is not particularly limited, and examples thereof include a structural unit derived from a compound having a polymerizable unsaturated bond.

[0069] The proportion of the structural units represented by formula (1) in polymer (B) is not particularly limited, but is preferably 50 mol % or more of all structural units, more preferably 70 mol % or more, even more preferably 80 mol % or more, and particularly preferably 90 mol % or more.

[0070] The weight-average molecular weight of the polymer (B) 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 a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0071] The polymer (B) can be obtained, for example, by polymerizing a monomer containing a compound represented by the following formula (1A). [In formula (1A), X has the same meaning as X in formula (1)]

[0072] Examples of the compound represented by formula (1A) include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-hydroxyethylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and maleic anhydride.

[0073] The polymerization method is not particularly limited, and examples thereof include radical polymerization. For example, a polymer can be obtained by homopolymerization of a compound represented by formula (1A), such as maleimide, or copolymerization with other monomers.

[0074] The monomer used in the polymerization may contain a monomer other than the compound represented by formula (1A). Examples of such a monomer include a compound having a polymerizable unsaturated bond. 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.

[0075] Specific examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl 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, glycidyl acrylate, and the like, but are not limited to these.

[0076] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl 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, bromophenyl methacrylate, and the like, but are not limited to these.

[0077] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0078] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0079] 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 acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0080] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0081] Polymer (B) may also be a polymer described in WO 2023 / 248946, the contents of which are incorporated herein by reference in their entirety.

[0082] <<<Polymer (C)>>> Polymer (C) is a polymer containing a structure represented by the following formula (1). [In formula (1), R １ represents a hydrogen atom, an imide-protecting group that can be deprotected by alkali, or an imide-protecting group that can be deprotected by acid, and * represents a bond.

[0083] R １In the formula (R), examples of the protecting group for the imide group that can be deprotected by alkali include a methyl group, a cyclohexyl group, a hydroxyethyl group, a benzyl group, and a phenyl group. １ In the formula (1), examples of the protecting group for the imide group that can be deprotected by an acid include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a methoxymethyl group, an ethoxymethyl group, a tetrahydropyranyl group, an acetyl group, a benzyl group, and a p-methoxybenzyl group. Examples of the alkali include alkalis contained in alkaline removal solutions. Examples of the acid include acids contained in acidic removal solutions.

[0084] Deprotection of the protecting group of the imide group that is deprotected by alkali can be carried out, for example, when a coating film formed from the coating film-forming composition for removing foreign matter is brought into contact with an alkaline removal solution. Deprotection of the protecting group of the imide group that is deprotected by acid can be carried out, for example, when a coating film formed from the coating film-forming composition for removing foreign matter is brought into contact with an acidic removal solution. Deprotection of the protecting group of the imide group that is deprotected by acid can be carried out, for example, by using an acid generated from an acid generator when a coating film is formed from a coating film-forming composition for removing foreign matter that contains an acid generator.

[0085] R in formula (1) １ is preferably a hydrogen atom.

[0086] The polymer (C) preferably further contains a structure represented by the following formula (2): [In formula (2), R １１ and R １２ each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted phenoxy group, and * represents a bond.

[0087] In the present invention, examples of substituents in the optionally substituted alkyl group having 1 to 10 carbon atoms include a halogen atom, a hydroxy group, and a carboxy group. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms.

[0088] In the present invention, examples of substituents in the optionally substituted phenyl group and the optionally substituted phenoxy group include a halogen atom, an alkyl group of 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group of 1 to 6 carbon atoms which may be substituted with a halogen atom. The number of substituents in the phenyl group and the phenoxy group may be one or two or more. When the number of substituents in the phenyl group and the phenoxy group is two or more, they may be the same type of substituent or different types of substituents.

[0089] R in formula (2) １１ and R １２ As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

[0090] For example, in polymer (C), the structure represented by formula (1) and the structure represented by formula (2) are linked as in the structure represented by the following formula (11): In other words, for example, polymer (C) contains a structure represented by the following formula (11): [In formula (11), R １ represents a hydrogen atom, a protecting group for an imide group that can be deprotected by alkali, or a protecting group for an imide group that can be deprotected by acid. ２ represents a divalent group having 1 to 6 carbon atoms. １１ and R １２ R each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted phenoxy group. ａ represents a hydrogen atom or a methyl group. * represents a bond.

[0091] R in formula (11) ２ Examples of the group include a divalent group represented by the following formula (L). (In formula (L), Y １ represents a single bond or an alkylene group having 1 to 6 carbon atoms. ２ represents a single bond, —C(═O)—, —O—, —C(═O)O—, —OC(═O)—, or —OCH ２ represents CH(OH)-. ３ represents a single bond or an alkylene group having 1 to 6 carbon atoms. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom. However, Y １ , Y ２ , and Y ３ The total number of carbon atoms is 1 to 6.

[0092] Examples of the divalent group represented by formula (L) include the following groups. (In the formula, * represents a bond. *1 represents a bond bonding to a carbon atom. *2 represents a bond bonding to a nitrogen atom.)

[0093] In the present invention, examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,5-pentylene group, and a 1,6-hexylene group.

[0094] R in formula (11) ２ As R in formula (11), a methylene group is preferred. １１ and R １２ As the alkyl group, an alkyl group having 1 to 10 carbon atoms and an optionally substituted phenyl group are preferred, an alkyl group having 1 to 6 carbon atoms and a phenyl group are more preferred, and a methyl group and a phenyl group are particularly preferred.

[0095] The polymer (C) is preferably a polymer obtained by a hydrosilylation reaction between a compound having a Si—H group and a compound having a carbon-carbon unsaturated bond capable of undergoing a hydrosilylation reaction.

[0096] The hydrosilylation reaction is carried out, for example, in the presence of a platinum group metal catalyst. Such a platinum group metal catalyst is a catalyst for promoting the hydrosilylation reaction between the Si—H group of a compound having an Si—H group and the carbon-carbon unsaturated bond (e.g., a carbon-carbon double bond) of a compound having a carbon-carbon unsaturated bond.

[0097] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum (e.g., Karstedt's catalyst). The amount of platinum-based metal catalyst used in the hydrosilylation reaction is not particularly limited.

[0098] -Compound Having Si-H Group- The compound having an Si-H group is not particularly limited as long as it is a compound having at least one Si-H group. The number of Si-H groups in the compound having an Si-H group may be one or two or more. As the compound having an Si-H group, a compound represented by the following formula (2A), a cyclic siloxane compound represented by the following formula (2B), or a silsesquioxane having an Si-H group is preferred. [In formula (2A), R １１ and R １２ X each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted phenoxy group. １ represents a single bond, an organic group having 1 to 10 carbon atoms, or a group represented by the following formula (2A-1): [In formula (2A-1), R １３ and R １４ each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted phenoxy group; n represents an integer of 0 to 10; * represents a bond. [In formula (2B), R １５each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted phenoxy group, and m represents an integer of 3 to 6.

[0099] R in formula (2A) １１ and R １２ As the alkyl group, an alkyl group having 1 to 10 carbon atoms and an optionally substituted phenyl group are preferred, an alkyl group having 1 to 6 carbon atoms and a phenyl group are more preferred, and a methyl group and a phenyl group are particularly preferred.

[0100] X in formula (2A) １ Examples of the organic group having 1 to 10 carbon atoms in the formula (I) include alkylene groups and phenylene groups having 1 to 6 carbon atoms.

[0101] R in formula (2A-1) １３ and R １４ As the alkyl group, an alkyl group having 1 to 10 carbon atoms and an optionally substituted phenyl group are preferred, an alkyl group having 1 to 6 carbon atoms and a phenyl group are more preferred, and a methyl group and a phenyl group are particularly preferred.

[0102] Examples of n in formula (2A-1) include 0, 1, 2, 3, and 4.

[0103] Examples of the compound represented by formula (2A) include the following compounds.

[0104] R in formula (2B) １５ As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and a methyl group is particularly preferred.

[0105] Examples of the cyclic siloxane compound represented by formula (2B) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexasiloxane, and 2,4,6,8,10,12,14-heptamethylcycloheptasiloxane.

[0106] 2,4,6,8-tetramethylcyclotetrasiloxane is represented by the following formula:

[0107] Silsesquioxanes are network polymers or polyhedral clusters obtained by hydrolysis of trifunctional silanes. Silsesquioxanes are known to have random, ladder, and cage structures. Cage structures include complete cage structures and incomplete cage structures.

[0108] The number of Si—H groups in the silsesquioxane having Si—H groups may be one or two or more.

[0109] Examples of silsesquioxanes having a Si—H group include cage silsesquioxanes represented by the following formulae (SQ1) to (SQ7). [In formulas (SQ1) to (SQ7), each R is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or —O—Si(R １０１ ) (R １０２ ) H (R １０１ and R １０２ each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. However, each of formulas (SQ1) to (SQ7) has at least one Si—H group.]

[0110] Examples of silsesquioxanes having a Si—H group include the following compounds:

[0111] The molecular weight of the compound having an Si—H group is not particularly limited, but may be, for example, 100 to 1,500.

[0112] Compound Having a Carbon-Carbon Unsaturated Bond The compound having a carbon-carbon unsaturated bond has a carbon-carbon unsaturated bond capable of undergoing a hydrosilylation reaction. Examples of carbon-carbon unsaturated bonds capable of undergoing a hydrosilylation reaction include carbon-carbon double bonds and carbon-carbon triple bonds.

[0113] The number of carbon-carbon unsaturated bonds capable of undergoing a hydrosilylation reaction in a compound having a carbon-carbon unsaturated bond is not particularly limited, and may be one or two or more.

[0114] The compound having a carbon-carbon unsaturated bond preferably includes a compound represented by the following formula (1A): [In formula (1A), R １ represents a hydrogen atom, a protecting group for an imide group that can be deprotected by alkali, or a protecting group for an imide group that can be deprotected by acid. ２ represents a divalent group having 1 to 6 carbon atoms. ３ represents a hydrogen atom, a protecting group for an imide group that can be deprotected by an alkali, a protecting group for an imide group that can be deprotected by an acid, or a group represented by the following formula (1A-1): ａ represents a hydrogen atom or a methyl group. [In formula (1A-1), R ４ represents a divalent group having 1 to 6 carbon atoms. ｂ represents a hydrogen atom or a methyl group. * represents a bond.

[0115] R in formula (1A) １ and R ３ Specific examples of the protecting group for the imide group that can be deprotected by alkali include R １ Specific examples of the protecting group for the imide group that can be deprotected by alkali include the following: １ and R ３ Specific examples of the protecting group for the imide group that can be deprotected by an acid include R １ Specific examples of the protecting group for the imide group that can be deprotected by an acid include:

[0116] R in formula (1A) ２ Examples of R in formula (1A) include a divalent group represented by formula (L). ２ Specific examples of R in formula (11) include ２ Examples include the specific examples given in the explanation of .

[0117] R in formula (1A-1) ４Examples of R in formula (1A-1) include the divalent group represented by formula (L). ４ Specific examples of R in formula (11) include ２ Examples include the specific examples given in the explanation of .

[0118] R in formula (1A) ２ As R in formula (1A), a methylene group is preferred. ３ represents a group represented by formula (1A-1), R ４ As the alkyl group, a methylene group is preferred.

[0119] Examples of the compound represented by formula (1A) include the following compounds:

[0120] When polymer (C) is obtained by utilizing a hydrosilylation reaction, the compound having a carbon-carbon unsaturated bond may contain, in addition to the compound represented by formula (1A), a compound having a carbon-carbon unsaturated bond other than the compound represented by formula (1A). Examples of the compound having a carbon-carbon unsaturated bond other than the compound represented by formula (1A) include compounds represented by the following formula (X): [In formula (X), R ２１ represents a hydrogen atom or a methyl group. ２ represents an m-valent organic group, and m represents an integer of 1 to 3.

[0121] X in formula (X) ２ The molecular weight of the copolymer is not particularly limited, and may be, for example, 100 to 500.

[0122] X in formula (X) ２ does not have the following isocyanuric acid structure, for example. [In the formula, * represents a bond.]

[0123] From the viewpoint of the heat resistance of the polymer (C), it is preferable that the compound represented by formula (X) does not have an ester bond.

[0124] X in formula (X) ２It is preferable that the aromatic ring has an aromatic ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.

[0125] Examples of the compound represented by formula (X) include compounds represented by the following formula (X1). [In formula (X1), R ２１ each independently represents a hydrogen atom or a methyl group. ２ represents a divalent organic group having an aromatic ring.

[0126] Examples of the compound represented by formula (X) include the following compounds:

[0127] The polymer (C) has, for example, a unit structure represented by the following formula (Y): The polymer having the unit structure represented by formula (Y) can be obtained, for example, by a hydrosilylation reaction between a compound having an Si—H group, including a compound represented by formula (2A), and a compound having a carbon-carbon unsaturated bond, including a compound represented by formula (1A). [In formula (Y), R １ represents a hydrogen atom, a protecting group for an imide group that can be deprotected by alkali, or a protecting group for an imide group that can be deprotected by acid. ２ represents a divalent group having 1 to 6 carbon atoms. １１ and R １２ R each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted phenoxy group. ａ represents a hydrogen atom or a methyl group.

[0128] R in formula (Y) １ is R in formula (1) and formula (11). １ R in formula (Y) has the same meaning as ２ is R in formula (11). ２ R in formula (Y) has the same meaning as １１ , R １２ , and X １ are R in formula (2) and formula (2A), respectively. １１ , and R １２ , and X in formula (2A)１ is synonymous with.

[0129] The weight-average molecular weight of the polymer (C) 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 a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0130] The polymer (C) may be a polymer described in International Publication No. 2024 / 117235 [International Application (PCT / JP2023 / 42991)], the contents of which are incorporated herein by reference to the same extent as if set forth in full.

[0131] <<<Polymer (D)>>> Polymer (D) is a polymer containing 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 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 heteroatom other than the oxygen atom.

[0132] R １ Examples of the alkyl group having 1 to 3 carbon atoms in R include a methyl group, an ethyl group, and a propyl group. ２ Examples of the alkyl group having 1 to 4 carbon atoms in R include a methyl group, an ethyl group, a propyl group, and a butyl group. ３Examples of the substituent in the optionally substituted alkyl group having 1 to 10 carbon atoms in the formula (I) include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aromatic group. Examples of the aromatic group include an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. R ３ Examples of the substituent in the optionally substituted aromatic hydrocarbon group in the formula (I) include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, etc. In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0133] 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 heteroatom other than the oxygen atom. Examples of such rings include 4- 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 an oxygen atom, a nitrogen atom, and a sulfur atom.

[0134] R １ is preferably a hydrogen atom or a methyl group. ２ R is preferably a methyl group or an ethyl group. ３ As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

[0135] The present inventors believe that the acetal structure in formula (1) acts as a protecting group for the carboxy group, imparting solubility to the polymer (D) in a solvent while improving the applicability of the coating film-forming composition for removing foreign matter. Meanwhile, during the process of forming a coating film from the coating film-forming composition for removing foreign matter, the acetal structure is eliminated (e.g., eliminated by heat or a catalyst), generating a carboxy group. The generated carboxy groups react with each other or, in the presence of a crosslinking agent, with the crosslinking agent, thereby imparting solvent resistance to the coating film. Furthermore, the generated carboxy groups facilitate the removal of the coating film with a removal solution. Therefore, the coating film obtained from the coating film-forming composition for removing foreign matter exhibits good solvent resistance. In addition, the coating film obtained from the coating film-forming composition for removing foreign matter is removable with a removal solution. Therefore, the coating film-forming composition for removing foreign matter of the present invention is a composition that can simply prevent foreign matter from remaining on a substrate and is a composition that can produce a coating film with good solvent resistance and easy removability.

[0136] Examples of the structural unit represented by formula (1) include the following structural units: １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represents a hydrogen atom or a methyl group.

[0137] The structural unit represented by formula (1) is derived from, for example, a compound represented by the following formula (1A). [In formula (1A), R １ , R ２ , and R ３ are R in formula (1), respectively. １ , R ２ , and R ３ is equivalent to the above.]

[0138] The polymer (D) may contain a structural unit other than the structural unit represented by formula (1). Examples of such a structural unit include a structural unit derived from a (meth)acrylic acid ester compound, a (meth)acrylamide compound, or a styrene compound. In the present invention, the (meth)acrylic acid ester compound refers to an acrylic acid ester compound or a methacrylic acid ester compound. The same applies to a (meth)acrylamide compound.

[0139] Examples of structural units derived from (meth)acrylic ester compounds include structural units represented by the following formula (2-1): Examples of structural units derived from (meth)acrylamide compounds include structural units represented by the following formula (2-2): Examples of structural units derived from styrene compounds include structural units represented by the following formula (2-3): [In formulas (2-1) to (2-3), R １１ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R １２ represents a monovalent group having 1 to 20 carbon atoms. １３ represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. １４ each independently represents a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, or a monovalent group having 1 to 10 carbon atoms, and m represents an integer of 0 to 5.

[0140] R １２ and R １３ The number of carbon atoms in may be 1 to 20, or may be 1 to 10. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in R may have a heteroatom. Examples of the heteroatom include an oxygen atom and a nitrogen atom. １２ and R １３ The monovalent group having 1 to 20 carbon atoms in R may have an aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring. １２ and R １３The monovalent group having 1 to 20 carbon atoms in R may have, for example, a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an epoxy group, or the like. １２ and R １３ In the above formula, examples of the monovalent group having 1 to 20 carbon atoms include an optionally substituted alkyl group and an optionally substituted aromatic group. Examples of the substituent in the optionally substituted alkyl group include a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an epoxy group, and an optionally substituted aromatic group. Examples of the substituent in the optionally substituted aromatic group include a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an epoxy group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0141] R １４ The monovalent group having 1 to 10 carbon atoms in R may have a heteroatom. Examples of the heteroatom include an oxygen atom and a nitrogen atom. １４ The monovalent group having 1 to 10 carbon atoms in R may have, for example, a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an epoxy group, or the like. １４ In the formula (I), examples of the monovalent group having 1 to 10 carbon atoms include an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0142] Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, 4-hydroxyphenyl acrylate, anthrylmethyl 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, but are not limited to these.

[0143] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 4-hydroxyphenyl acrylate, anthrylmethyl 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, bromophenyl methacrylate, and the like, but are not limited to these.

[0144] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N-(4-hydroxyphenyl)acrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0145] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N-(4-hydroxyphenyl)methacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0146] Specific examples of styrene compounds include, but are not limited to, styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0147] The polymer (D) may further have other structural units. Examples of monomers that derive such structural units include, but are not limited to, acrylic acid, methacrylic acid, vinyl compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0148] 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 acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0149] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0150] The lower limit of the molar ratio of the structural unit represented by formula (1) to all structural units of polymer (D) is not particularly limited, but from the viewpoint of preferably obtaining the effects of the present invention, the molar ratio of the structural unit 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 the structural unit represented by formula (1) to all structural units of polymer (D) is not particularly limited, but from the viewpoint of preferably obtaining the effects of the present invention, the molar ratio of the structural unit represented by formula (1) is preferably 100 mol% or less, more preferably 95 mol% or less, and particularly preferably 90 mol% or less.

[0151] The lower limit of the molar ratio of the sum of the structural units derived from a (meth)acrylic acid ester compound, the structural units derived from a (meth)acrylamide compound, and the structural units derived from a styrene compound (hereinafter sometimes referred to as "total structural units (2)") relative to all structural units of polymer (D) is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, the molar ratio of the total structural units (2) is preferably more than 0 mol%, more preferably 10 mol% or more. The upper limit of the molar ratio of the total structural units (2) relative to all structural units of the polymer is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, the molar ratio of the total structural units (2) is preferably 60 mol% or less, more preferably 45 mol% or less.

[0152] The molar ratio of the total of the structural units represented by formula (1) and the total structural units (2) to all structural units of the polymer (D) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%.

[0153] The polymer (D) may be a homopolymer or a copolymer. If the polymer is a copolymer, it may be a random copolymer or a block copolymer.

[0154] The method for producing the polymer (D) is not particularly limited. The polymer (D) can be produced by polymerizing the monomers by a conventional method, for example, bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, and in this case, for example, the monomers can be polymerized using a polymerization initiator. As the polymerization initiator, an organic peroxide or a diazo compound can be used.

[0155] The weight-average molecular weight of the polymer (D) 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 a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0156] The polymer (D) may be a polymer described in Japanese Patent Application No. 2024-3840 and International Application No. PCT / JP2025 / 258, the contents of which are incorporated herein by reference to the same extent as if set forth in full.

[0157] <<<Polymer (E)>>> Polymer (E) has a partial structure represented by the following formula (A). [In formula (A), R １１ represents a single bond or a divalent group having 1 to 4 carbon atoms. １２ represents a hydrogen atom, a hydroxy group, or a methyl group. * represents a bond.

[0158] When the polymer (E) has the partial structure represented by formula (A), solvent resistance and easy removability are imparted to the coating film obtained from the composition for forming a coating film for removing foreign matter.

[0159] The polymer (E) preferably has a structural unit represented by the following formula (A-1): For example, the partial structure 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 ６R each independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q represents a divalent organic group. １１ represents a single bond or a divalent group having 1 to 4 carbon atoms. １２ represents a hydrogen atom, a hydroxy group, or a methyl group.

[0160] <<R １１ >> In formula (A) and formula (A-1), R １１ represents a single bond or a divalent group having 1 to 4 carbon atoms. １１ The number of carbon atoms contained in R is 1 to 4, and may be 1 to 3, 1 or 2, or 1. １１ Examples of R include divalent hydrocarbon groups having 1 to 4 carbon atoms which may be substituted with a hydroxy group. １１ When R has a hydroxy group, １１ The number of hydroxy groups in R １１ The number of carbon atoms contained in R １１ From the viewpoint of suitably obtaining the effects of the present invention, R preferably represents a divalent group having 1 to 4 carbon atoms, and the divalent group preferably has a hydroxy group. １１ From the viewpoint of suitably obtaining the effects of the present invention, it more preferably represents —CH(OH)—.

[0161] <<R １２ >> In formula (A) and formula (A-1), R １２ represents a hydrogen atom, a hydroxy group, or a methyl group, and preferably represents a hydrogen atom or a hydroxy group.

[0162] Examples of the partial structure represented by formula (A) include the following structures: * represents a bond.

[0163] <<Q>> In formula (A-1), Q represents a divalent organic group. The divalent organic group is not particularly limited, but is preferably a divalent organic group having a heteroatom, and more preferably a divalent organic group having a nitrogen atom and an oxygen atom. 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 is preferably 3 to 30, and more preferably 3 to 20.

[0164] From the viewpoint of suitably obtaining the effects of the present invention, Q is preferably represented by either formula (A-11) or formula (A-12) below. (In formula (A-11), X １ represents a divalent group represented by the following formula (A-11-1), (A-11-2) or (A-11-3). １ and Z ２ Each of Q 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 ５ R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. ３ and R ４may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom. *2 represents a bond bonded to a nitrogen atom. (In formula (A-11-4), m1 is an integer of 1 to 4, m2 is 0 or 1, *3 represents a bond bonded to a nitrogen atom, and *4 represents a bond bonded to a carbon atom.)

[0165] Q in formula (A-12) １ is preferably represented by any one 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 independently represents a halogen atom, a hydroxy 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 of 0 to 4. When n3 is 1, n11 represents an integer of 0 to 6. R ３１ When is 2 or more, R is 2 or more ３１ In formula (A-12-2), Z may be the same or different. １ represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n12 and n13 each independently represent an integer of 0 to 4. R ３２ When is 2 or more, R is 2 or more ３２ may be the same or different. ３３ When is 2 or more, R is 2 or more ３３ In formula (A-12-3), Y may be the same or different. １ and Y ２ each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms. n14 represents an integer of 0 to 4. R３４ When is 2 or more, R is 2 or more ３４ In formula (A-12-4), Z may be the same or different. ２ represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms. n15 and n16 each independently represent an integer of 0 to 4. R ３５ When is 2 or more, R is 2 or more ３５ may be the same or different. ３６ When is 2 or more, R is 2 or more ３６ may be the same or different.)

[0166] Examples of Q in formula (A-11) include the following structures. * represents a bond.

[0167] When the polymer (E) 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.

[0168] The method for producing polymer (E) is not particularly limited, but may include, for example, a method of reacting a dicarboxylic acid represented by formula (A1) below with a diepoxy compound represented by formula (A2) below, in which case a polymer having a structural unit represented by formula (A-1) is obtained.

[0169] Examples of catalysts that activate epoxy groups include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected appropriately from the range of 0.1 to 10% by mass based on the total mass of the polymer raw materials used in the reaction. Optimal conditions for the temperature and time of the polymerization reaction can be selected, for example, from the ranges of 80 to 160°C and 2 to 50 hours.

[0170] (In formula (A1), R １１ and R １２ respectively represent R in formula (A-1). １１ and Ｒ１２ It is synonymous with

[0171] Examples of the dicarboxylic acid represented by formula (A1) include tartaric acid, malic acid, tartronic acid, citramalic acid, dioxymalonic acid, and mucic acid.

[0172] (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 ５ , A ６ and Q.)

[0173] The weight-average molecular weight of the polymer (E) is not particularly limited, but is preferably 700 to 15,000, and more preferably 900 to 10,000. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0174] The polymer (E) may be a polymer described in Japanese Patent Application No. 2024-3808 and International Application No. PCT / JP2025 / 273, the contents of which are incorporated herein by reference to the same extent as if set forth in full.

[0175] <<<Polymer (F)>>> Polymer (F) is cellulose or a derivative thereof. Cellulose is a polysaccharide in which D-glucose units are bonded via β-1,4 glucoside bonds. Examples of cellulose and derivatives thereof include cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose. Of these, hydroxypropyl cellulose is preferred.

[0176] An example of the structure of hydroxypropyl cellulose is shown below.

[0177] <<<Polymer (G)>>> Polymer (G) is cyclodextrin or a derivative thereof. Cyclodextrin is a cyclic oligosaccharide in which D-glucose units are linked together via α-1,4 glucoside bonds to form a cyclic structure, and examples include cyclodextrins containing 6 to 12 glucose units. Specific examples of cyclodextrin include α-cyclodextrin in which six D-glucose units are cyclic, β-cyclodextrin in which seven D-glucose units are cyclic, and γ-cyclodextrin in which eight D-glucose units are cyclic, as well as derivatives of these cyclodextrins and polymers in which a cyclodextrin structure is partially or partially arranged.

[0178] The cyclodextrin derivatives are compounds in which some or all of the hydroxyl groups at the 2-, 3-, and 6-positions of glucose in the above cyclodextrin are substituted with other functional groups, and examples thereof include alkyl derivatives, hydroxyalkyl derivatives, alkoxy derivatives, sulfoalkyl ether derivatives, and sugar-bound derivatives.Specific examples of the cyclodextrin derivatives include hydroxymethyl cyclodextrin, hydroxyethyl cyclodextrin, hydroxypropyl cyclodextrin, hydroxybutyl cyclodextrin, dimethyl cyclodextrin, trimethyl cyclodextrin, diethyl cyclodextrin, triethyl cyclodextrin, carboxymethyl cyclodextrin, glucosyl cyclodextrin, maltosyl cyclodextrin, dimaltosyl cyclodextrin, monochlorotriazinyl cyclodextrin, and cyclodextrin epichlorohydrin polymers.

[0179] More specific examples of the compounds include sugar-binding derivatives, alkylated cyclodextrins, hydroxyalkylated cyclodextrins, sulfoalkyl ether derivatives, alkoxylated cyclodextrins, etc. Examples of sugar-binding derivatives include glucosyl-α-cyclodextrin, glucosyl-β-cyclodextrin, glucosyl-γ-cyclodextrin, etc. Examples of alkylated cyclodextrins include 2,6-di-O-methyl-α-cyclodextrin, 2,3,6-tri-O-methyl-α-cyclodextrin, 2,6-di-O-methyl-β-cyclodextrin, 2,3,6-tri-O-methyl-β-cyclodextrin, 2,6-di-O-methyl-γ-cyclodextrin, and 2,3,6-tri-O-methyl-γ-cyclodextrin. Examples of hydroxyalkylated cyclodextrins include 2-hydroxyethyl-α-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-γ-cyclodextrin, etc. Examples of carboxyalkylated cyclodextrins include O-carboxymethyl-α-cyclodextrin, O-carboxymethyl-β-cyclodextrin, O-carboxymethyl-γ-cyclodextrin, etc. Examples of sulfoalkyl ether derivatives include sulfobutyl ether-α-cyclodextrin, sulfobutyl ether-β-cyclodextrin, sulfobutyl ether-γ-cyclodextrin, etc. Examples of alkoxylated cyclodextrins include methoxycyclodextrin, ethoxycyclodextrin, etc.

[0180] Among these, hydroxyalkylated cyclodextrins are preferred, and 2-hydroxypropyl-β-cyclodextrin is more preferred.

[0181] An example of the structure of 2-hydroxypropyl-β-cyclodextrin is shown below.

[0182] <<<Polymer (H)>>> Polymer (H) is a polymer having a structural unit derived from a hydroxyalkyl (meth)acrylate. Examples of the polymer having a structural unit derived from a hydroxyalkyl (meth)acrylate include a homopolymer of a hydroxyalkyl (meth)acrylate and a copolymer of a hydroxyalkyl (meth)acrylate and another monomer.

[0183] The number of carbon atoms in the hydroxyalkyl group in the hydroxyalkyl (meth)acrylate is, for example, 1 to 6. Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. Note that the term "(meth)acrylate" refers to acrylate and / or methacrylate.

[0184] The other monomers used in the copolymerization are not particularly limited, and examples thereof include (meth)acrylic acid, (meth)acrylic acid ester compounds, (meth)acrylamide compounds, vinyl compounds, styrene compounds, and acrylonitrile.

[0185] Specific examples of the (meth)acrylic acid ester compound include methyl (meth)acrylate, ethyl (meth)acrylate, normal hexyl (meth)acrylate, i-propyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, anthrylmethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and glycidyl (meth)acrylate.

[0186] Specific examples of the (meth)acrylamide compound include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-phenyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N-anthryl(meth)acrylamide.

[0187] Specific examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0188] Specific examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0189] In the case of a copolymer, the proportion of other monomers is not particularly limited.

[0190] Among these, a homopolymer of 2-hydroxyethyl acrylate is preferred.

[0191] <<<Compound (A)>>> Compound (A) is tannic acid. Tannic acid is represented by the following structure.

[0192] <<<Polymer (I)>>> Polymer (I) is a polymer having a lactam structure. Examples of polymers having a lactam structure include polymers having a γ-lactam, which is a 5-membered cyclic lactam, in a side chain, and polymers having a δ-lactam, which is a 6-membered cyclic lactam, in a side chain. Examples of lactam structures include a pyrrolidone ring and an alkylated pyrrolidone ring in which at least some of the hydrogen atoms of the pyrrolidone ring are substituted with alkyl groups. Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms.

[0193] Examples of polymers having a lactam structure include polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, and vinylpyrrolidone-vinyl acetate copolymer.

[0194] Examples of structures of polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, and vinylpyrrolidone-vinyl acetate copolymer are shown below.

[0195] The polymer having a lactam structure may be a commercially available product. Commercially available polyvinylpyrrolidone products include, for example, K-30 and K-90 (Nippon Shokubai Co., Ltd.). Commercially available alkylated polyvinylpyrrolidone products include, for example, Ganex P-904 LC (Ashland Inc.). Commercially available vinylpyrrolidone-vinyl acetate copolymer products include, for example, PVP / VA S-630 (Ashland Inc.).

[0196] The weight-average molecular weight of the compound or polymer is not particularly limited, but is preferably 700 to 5,000,000, and more preferably 900 to 100,000. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0197] The content of the "compound or polymer" in the coating film-forming composition for removing foreign matter is not particularly limited, but is preferably 70% by mass to 99.9% by mass, more preferably 80% by mass to 99.5% by mass, and particularly preferably 90% by mass to 99% by mass, based on the film-constituting components.

[0198] <<Removal Liquid>> The removal liquid is not particularly limited as long as it can remove a coating film formed from the coating film-forming composition for removing foreign matter. 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 the removal include dissolution removal and peeling removal. Examples of peeling removal include peeling from the adherend by swelling.

[0199] The removal liquid may contain water or an organic solvent, and may contain 50% by mass or more of an organic solvent.

[0200] The remover may be water. There are no particular limitations on the water used, as long as it is water that is commonly used in semiconductor manufacturing, and examples thereof include pure water, ultrapure water, and ion-exchanged water.

[0201] 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.

[0202] Examples of the removal liquid include an alkaline removal liquid and an acid removal liquid.

[0203] The alkaline remover contains an alkali. Examples of alkalis include ammonia, inorganic alkaline compounds, quaternary ammonium hydroxides, amines, and hydrazine. The alkaline remover may be a developer or cleaning solution used in semiconductor manufacturing processes and exhibit alkaline properties. For example, an example of a developer is NMD-3 (a 2.38% aqueous solution of tetramethylammonium hydroxide, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Examples of inorganic alkaline 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, and potassium borate. 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 be SC-1 (ammonia-hydrogen peroxide solution).

[0204] The acidic removal solution contains an acid. Examples of the acid include inorganic acids and organic acids. Examples of the inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and hydrofluoric acid. The acidic removal solution is, for example, an aqueous solution containing dilute hydrofluoric acid. The acidic removal solution may also 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 the chelating agent include organic acids, salts of organic acids, amino acids, and amino acid derivatives.

[0205] <Solvent> Examples of the solvent contained in the coating film-forming composition for removing foreign matter 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, Examples of solvents that can be used include 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. These solvents can be used alone or in combination of two or more. Furthermore, high-boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed and used.

[0206] The coating film-forming composition for removing foreign matter can be easily prepared, for example, by uniformly mixing the components, and is used in the form of a solution by dissolving in a suitable solvent. The coating film-forming composition for removing foreign matter prepared in this manner is preferably filtered using a filter with a pore size of about 0.2 μm before use. The coating film-forming composition for removing foreign matter prepared in this manner also has excellent long-term storage stability at room temperature.

[0207] The proportion of solids in the coating film-forming composition for removing foreign matter is not particularly limited as long as each component is uniformly dissolved, but is, for example, 0.5 to 50 mass %, or, for example, 1 to 30 mass %. Here, the solids content is the total components of the coating film-forming composition for removing foreign matter excluding the solvent component.

[0208] In the present invention, foreign matter refers to substances other than the intended object that are attached to a substrate. In semiconductor device manufacturing, foreign matter is an unnecessary substance. Examples of foreign matter include particles attached to a wafer, metal impurities, post-etching residues, peeling residues of an adhesive layer, etc.

[0209] The coating film for removing foreign matter is particularly preferably used in a process in which wafers are bonded together with an adhesive and then the adhesive is peeled off, in which the coating film of the present invention is formed before the adhesive is applied, and then the coating film is used to remove foreign matter (residues of the adhesive layer) after the wafer bonding and peeling processes.

[0210] The coating film for removing foreign matter can also be used to remove foreign matter that is already present on the semiconductor substrate.

[0211] The dissolution of a foreign matter-removing coating film in a removal liquid means that, when immersed, washed, or the like in the removal liquid, the coating film dissolves in the removal liquid and disappears from the substrate or other adherend. Dissolution in the present invention means that the film formed on the substrate is removed, for example, by at least 90% or more of the initial thickness (i.e., the remaining film thickness is 10% or less of the initial thickness), or by at least 95% or more (i.e., the remaining film thickness is 5% or less of the initial thickness), or by at least 99% or more (i.e., the remaining film thickness is 1% or less of the initial thickness), and most preferably by 100% (i.e., the remaining film thickness is 0% of the initial thickness (no remaining film)).

[0212] The composition preferably contains at least one of a crosslinking agent and an additive.

[0213] <<Crosslinking Agent>> The film constituent components may contain, for example, a crosslinking agent. The crosslinking agent is not particularly limited. The crosslinking agent has a structure different from that of the coordinating compound or the "compound or polymer."

[0214] Preferred crosslinking agents are aminoplast crosslinking agents and phenoplast crosslinking agents. Aminoplast crosslinking agents are addition condensation products of a compound having an amino group, such as melamine or guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensation products of a compound having a phenolic hydroxy group with formaldehyde.

[0215] Examples of the crosslinking agent 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 bonded to, for example, a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0216] R １０１ is preferably 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 bond.

[0217] As the crosslinking agent, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, or a compound having a phenolic hydroxy group is preferred. These may be used alone or in combination of two or more.

[0218] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0219] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0220] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.

[0221] The glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E). (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0222] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0223] The glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0224] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0225] (In formula (3d), R １ represents a methyl group or an ethyl group.

[0226] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0227] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0228] Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (G-1) or (G-2). (In formula (G-1) and formula (G-2), Q １ represents a single bond or a monovalent organic group. １ and R ４ R represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ R represents a hydrogen atom or a methyl group. ３ and R ６ n 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 an integer ≦3, n ２ is 2≦n ２ an integer ≦5, n ３ is 0≦n ３ an integer ≦3, n ４ is 0≦n ４ an integer ≦3, 3≦(n １ +n ２ +n ３ +n ４ ) represents an integer ≦6. ５ is 1≦n５ an integer ≦3, n ６ is 1≦n ６ n is an integer ≦4 ７ is 0≦n ７ an integer ≦3, n ８ is 0≦n ８ an integer ≦3, 2≦(n ５ +n ６ +n ７ +n ８ ) represents an integer of ≦5. m1 represents an integer of 2 to 10.

[0229] Examples of compounds having a phenolic hydroxy group include compounds represented by the following formula (G-3) or formula (G-4): The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In formula (G-3) and formula (G-4), Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ R represents a hydrogen atom or a methyl group. ７ and R １０ n 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 an integer ≦3, n １０ is 2≦n １０ an integer ≦5, n １１ is 0≦n １１ an integer ≦3, n １２ is 0≦n １２ an integer ≦3, 3≦(n ９ +n １０ +n １１ +n １２ ) represents an integer ≦6. １３ is 1≦n １３ an integer ≦3, n １４ is 1≦n １４ n is an integer ≦4 １５ is 0≦n １５ an integer ≦3, n １６ is 0≦n １６an integer ≦3, 2≦(n １３ +n １４ +n １５ +n １６ ) represents an integer of ≦5. m2 represents an integer of 2 to 10. ２ In the above, the m2-valent organic group includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.

[0230] Examples of the compound represented by formula (G-1) or formula (G-2) include the following compounds:

[0231] Examples of the compound represented by formula (G-3) or formula (G-4) include the following compounds: The above compound is available as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of the product is TMOM-BP, a product name of Asahi Organic Chemicals Co., Ltd.

[0232] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which one to four methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which one to four methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being more preferred.

[0233] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 1,000 or less.

[0234] The content of the crosslinking agent is, for example, 5 to 70 parts by mass, or 5 to 60 parts by mass, and preferably 5 to 45 parts by mass, relative to 100 parts by mass of the "compound or polymer." From the viewpoints of the degree of curing of the coating film and preventing intermixing with the adhesive layer, the content of the crosslinking agent is preferably 5 parts by mass or more relative to 100 parts by mass of the "compound or polymer," and from the viewpoint of solubility in the removal liquid, it is preferably 70 parts by mass or less relative to 100 parts by mass of the "compound or polymer."

[0235] <<Additives>> The film constituent components may contain additives such as a curing catalyst, a surfactant, an adhesion promoter, a rheology modifier, and silica particles.

[0236] The curing catalyst may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of the thermal acid generator 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 p-phenolsulfonate salt), 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.

[0237] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0238] Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal 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 nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0239] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0240] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0241] The curing catalyst may be used alone or in combination of two or more.

[0242] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass, relative to the crosslinking agent.

[0243] The coating film-forming composition for removing foreign matter can contain a surfactant. Examples of the surfactant 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, polyoxyethylene sorbitan monopalmitate, and the like. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171 and F173 (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by AGC Inc.); and organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 0.2% by mass or less, and preferably 0.1% by mass or less, of the total components of the coating film-forming composition for removing foreign matter. These surfactants may be added alone or in combination of two or more.

[0244] The coating film-forming composition for removing foreign matter may contain silica particles. Examples of the silica particles include silicone powder having a predetermined average particle size and silica sol containing silica having a predetermined average particle size.

[0245] Specific examples of silicone powders include silicone powders KMP series KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these.

[0246] Specific examples of colloidal silica (silica sol) include MA-ST-S (methanol-dispersed silica sol), MT-ST (methanol-dispersed silica sol), MA-ST-UP (methanol-dispersed silica sol), trade 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, all manufactured by Nissan Chemical Industries, Ltd. Examples of silica sols include, but are not limited to, silica sols dispersed in 1-methoxy-2-propanol, DMAC-ST (silica sol dispersed in dimethylacetamide), XBA-ST (silica sol dispersed in a xylene / n-butanol mixed solvent), trade name EAC-ST (silica sol dispersed in ethyl acetate), PMA-ST (silica sol dispersed in propylene glycol monomethyl ether acetate), MEK-ST (silica sol dispersed in methyl ethyl ketone), MEK-ST-UP (silica sol dispersed in methyl ethyl ketone), MEK-ST-L (silica sol dispersed in methyl ethyl ketone), and MIBK-ST (silica sol dispersed in methyl isobutyl ketone).

[0247] (Coating Film for Removing Foreign Matter) The coating film for removing foreign matter of the present invention is formed from the coating film-forming composition for removing foreign matter of the present invention.

[0248] The coating film for removing foreign matter of the present invention can be formed, for example, as follows. The coating film-forming composition for removing foreign matter of the present invention is applied to a semiconductor substrate by an appropriate application method such as a spinner, coater, or immersion, and then baked to form a coating film for removing foreign matter. Baking conditions are appropriately selected from a baking temperature of 80°C to 300°C and a baking time of 0.3 to 60 minutes.

[0249] In order to more suitably obtain the effects of the present invention, it is preferable that the coating film for removing foreign matter be in contact with a metal. Examples of metals include the above-mentioned "coordination-capable metals." The metal that the coating film for removing foreign matter is in contact with is, for example, a metal present on a semiconductor substrate. Such a metal is, for example, a metal used as an electrode. Examples of electrodes include bumps.

[0250] The thickness of the coating film for removing foreign matter is usually 5 nm to 3 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0251] The dissolution rate of the formed coating film for removing foreign matter in the removal solution, in terms of the rate of film thickness reduction, is, for example, 0.1 to 50 nm per second, preferably 0.2 to 40 nm per second, and more preferably 0.3 to 20 nm per second. If the dissolution rate is lower than this range, the time required to remove the coating film for removing foreign matter will be longer, resulting in a decrease in productivity.

[0252] The dissolution rate of the coating film for removing foreign matter formed from the coating film-forming composition for removing foreign matter of the present invention in a removal solution can be controlled by changing the baking conditions during formation. For a given baking time, the higher the baking temperature, the lower the dissolution rate of the coating film for removing foreign matter in a removal solution that can be formed.

[0253] The foreign matter removal coating film may be exposed to light after the film is formed. The exposure may be performed by exposing the entire wafer or through a mask having a predetermined pattern. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), or the like can be used. After the exposure, post-exposure baking (PEB) may also be performed as necessary.

[0254] (Semiconductor Substrate) The semiconductor substrate of the present invention has thereon the coating film for removing foreign matter of the present invention.

[0255] In order to more suitably obtain the effects of the present invention, it is preferable that the coating film for removing foreign matter be in contact with a metal. Examples of metals include the above-mentioned "coordination-capable metals." The metal that the coating film for removing foreign matter is in contact with is, for example, a metal present on a semiconductor substrate. Such a metal is, for example, a metal used as an electrode. Examples of electrodes include bumps.

[0256] The main material constituting the entire semiconductor substrate is not particularly limited as long as it is suitable for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a straight portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0257] The semiconductor substrate may have electrodes. The electrodes are, for example, bumps. Bumps are protruding terminals. When a semiconductor substrate has electrodes, the electrodes are located on the support substrate side. In a semiconductor substrate, the electrodes are typically formed on the surface on which a circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface on which the electrodes are formed (the back surface) is the surface used for processing. The material, size, shape, structure, and density of the electrodes on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. The height, radius, and pitch of the bumps are typically determined appropriately based on the following conditions: a bump height of approximately 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 bump may be composed of only a single component or multiple components. More specifically, examples include alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bump may also have a laminate structure including a metal layer composed of at least one of these components.

[0258] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0259] (Method for manufacturing a processed semiconductor substrate) The method for manufacturing a processed semiconductor substrate of the present invention includes a first step, a second step, a third step, and a fourth step. The first step is a step of manufacturing a laminate by bonding the semiconductor substrate of the present invention (a semiconductor substrate having a foreign matter removal coating film of the present invention) and a supporting substrate via the foreign matter removal coating film. The second step is a step of processing the laminate. The third step is a step of peeling the supporting substrate from the laminate. The fourth step is a step of washing the semiconductor substrate or supporting material with a removing liquid to remove the foreign matter removal coating film. In the first embodiment, the heat-resistant foreign matter removal coating film of the present invention is used as the foreign matter removal coating film.

[0260] <First Step> The first step is a step of manufacturing a laminate by bonding the semiconductor substrate of the present invention (semiconductor substrate having the coating film for removing foreign matter of the present invention) and a supporting substrate via the coating film for removing foreign matter.

[0261] The supporting substrate is not particularly limited as long as it is a member that can support a semiconductor substrate when the laminate (e.g., semiconductor substrate) is processed, and examples thereof include a flexible supporting substrate and a glass supporting substrate.

[0262] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., but is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., but is not particularly limited, and is, for example, 100 to 1,000 mm.

[0263] An example of the support substrate is a glass wafer having a diameter of about 300 mm and a thickness of about 700 μm.

[0264] The first step is preferably a step of manufacturing a laminate by bonding a semiconductor substrate and a supporting base material together via a coating film for removing foreign matter and an adhesive layer.

[0265] The adhesive layer is not particularly limited as long as it allows the supporting substrate to be peeled off from the laminate in step 3. The adhesive layer can be formed using a known adhesive and method. Examples of adhesives that can be used include coating-type wafer temporary adhesives described in International Publication No. 2015 / 190438, temporary bonding materials from Thin Materials (Nissan Chemical Industries, Ltd.), semiconductor wafer temporary bonding materials from Toray Industries, Inc., WaferBOND (registered trademark) CR-200, HT-10.10 (manufactured by Brewer Science), and tape-like adhesives (for example, backgrinding tapes (for example, 3MTM temporary fixing adhesive tape ATT-4025 (manufactured by 3M Japan Ltd.), E series, P series, S series (manufactured by Lintec Corporation, trade names), ICROS Tape (manufactured by Mitsui Chemicals Tocello Co., Ltd.)), dicing tapes (for example, solvent-resistant dicing tape (manufactured by Nitto Denko Corporation, trade name), temperature-sensitive adhesive sheet Intelimer (registered trademark) tape (manufactured by Nitta Corporation), Intelimer (registered trademark) tape (manufactured by Anchor Techno Co., Ltd.), etc.) may also be used. Specific wafer handling systems (for example, Zero It may also be a wafer adhesive applied in Newton (registered trademark) (manufactured by Tokyo Ohka Kogyo Co., Ltd.). In addition, as the adhesive layer, what is called a pressure-sensitive adhesive layer, pressure-sensitive adhesive tape, or temporary fixing material may be used. Examples of such materials include the pressure-sensitive adhesive layer described in WO 2021 / 225163, the adhesive layer described in WO 2022 / 065376, and the photocurable adhesive layer described in WO 2022 / 065388.

[0266] For example, backgrinding tape is composed of a base film, an adhesive layer, and a release film. While soft thermoplastic films such as ethylene-vinyl acetate copolymer (EVA) have traditionally been used as base films, attempts have also been made to use rigid stretched films such as polyethylene terephthalate (PET) to improve wafer support. Further improvements have since been made, and laminate designs of two types of films with different elastic moduli, such as a laminate design of PET and an ethylene-based copolymer, or a laminate design of polypropylene (PP) and an ethylene-based copolymer, have been reported.

[0267] Acrylic adhesives are commonly used. Acrylic adhesives are known to be designed by crosslinking an acrylic copolymer, primarily made from a monomer with a low glass transition temperature, such as butyl acrylate, with a curing agent. Backgrinding tape is applied to the circuit surface of a wafer, raising concerns about contamination from the adhesive after tape removal. Some designs have been reported that use emulsion-based adhesives, with the expectation that any remaining adhesive can be removed by washing with water, but complete removal is difficult. Therefore, by forming an adhesive layer after forming the coating film for foreign matter removal on the circuit surface of the present application, foreign matter (residue from the adhesive layer) can be completely removed by washing with a removal solution during the subsequent peeling process, without causing damage to the wiring of the circuit or other components.

[0268] The thickness of the adhesive layer is not particularly limited, but is, for example, 5 μm to 500 μm, preferably 10 μm to 300 μm, more preferably 20 μm to 200 μm, and particularly preferably 30 μm to 150 μm.

[0269] Before carrying out the first step, the adhesive layer may be formed on a coating film for removing foreign matter, on a supporting substrate, or on a semiconductor substrate.

[0270] When no adhesive layer is used, the support substrate preferably has a pressure-sensitive adhesive layer. The support substrate has, for example, a flexible support and a pressure-sensitive adhesive layer. Examples of the flexible support include a polyimide film. The pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a layer formed from the above-mentioned pressure-sensitive adhesive.

[0271] The lamination is carried out, for example, under heating and pressure. The heating temperature is not particularly limited as long as it is at least room temperature (25°C), but is usually at least 50°C. From the viewpoint of avoiding excessive heating, it is usually at most 220°C, and in one embodiment, at most 170°C. The load is not particularly limited as long as it allows the substrates and layers to be bonded together and does not damage the substrates or layers, but is, for example, 0.5 to 50 kN. The pressure during lamination is, for example, 0.1 to 20 N / mm ２ The pressure is measured by the unit area (mm ２ The degree of reduced pressure is not particularly limited as long as it allows the substrate and layer to be bonded together and does not damage the substrate or layer, but is, for example, 10 to 10,000 Pa.

[0272] When an adhesive layer is used, the layer structure of the laminate produced in the first step may be semiconductor substrate / foreign-matter removal coating film / adhesive layer / supporting substrate, with the aim of removing foreign matter, which is the peeling residue of the adhesive layer, together with the foreign-matter removal coating film in the fourth step, and ensuring that no foreign matter is present on the semiconductor substrate. Furthermore, when an adhesive layer is used, the layer structure of the laminate produced in the first step may be semiconductor substrate / adhesive layer / foreign-matter removal coating film / supporting substrate, with the aim of removing foreign matter, which is the peeling residue of the adhesive layer, together with the foreign-matter removal coating film in the fourth step, and ensuring that no foreign matter is present on the supporting substrate. In this case, the supporting substrate can be easily reused. Furthermore, the layer structure of the laminate produced in the first step may be semiconductor substrate / foreign-matter removal coating film / adhesive layer / foreign-matter removal coating film / supporting substrate, with the aim of ensuring that no foreign matter is present on the semiconductor substrate and supporting substrate.

[0273] The laminate produced in the first step may have a laser peeling layer between the semiconductor substrate and the support substrate. If the laminate has a laser peeling layer, in the third step, the support substrate may be peeled off from the laminate, for example, by irradiating the laser peeling layer with a laser. The laser is irradiated, for example, onto the laser peeling layer from the side of the support substrate that is transparent to laser light. If the laminate has a laser peeling layer, in the fourth step, foreign matter, which is peel residue of the laser peeling layer and adhesive layer, is removed together with the foreign matter removal coating film, so that the semiconductor substrate is free of foreign matter. The layer structure of the laminate produced in the first step may be, for example, semiconductor substrate / foreign matter removal coating film / laser peeling layer / adhesive layer / support substrate. If the laminate has a laser peeling layer, in the fourth step, foreign matter, which is peel residue of the laser peeling layer and adhesive layer, is removed together with the foreign matter removal coating film, so that the support substrate is free of foreign matter. The layer structure of the laminate produced in the first step may be, for example, semiconductor substrate / adhesive layer / laser peeling layer / foreign matter removal coating film / support substrate. In this case, the support substrate can be easily reused. Furthermore, if a peeling residue of the laser peeling layer remains on the adhesive layer after peeling the support substrate from the laminate by irradiating the laser peeling layer with a laser, foreign matter originating from the laser peeling layer may re-adhere to the semiconductor substrate or the support substrate, or the cleaning time for the adhesive layer may become longer. In order to prevent these, the layer structure of the laminate produced in the first step for the purpose of removing the residue of the laser peeling layer on the adhesive layer may be semiconductor substrate / adhesive layer / coating film for removing foreign matter / laser peeling layer / support substrate, or semiconductor substrate / laser peeling layer / coating film for removing foreign matter / adhesive layer / support substrate.

[0274] <Second Step> The second step is a step of processing the laminate. The processing in the second step is not particularly limited, but examples thereof include polishing of the semiconductor substrate, forming a through electrode in the semiconductor substrate, and connecting the semiconductor substrate and a second semiconductor substrate. The processing in the second step may include one of these processes or two or more of them.

[0275] <<Polishing Treatment>> The polishing treatment of a semiconductor substrate is not particularly limited as long as it is a treatment for polishing the surface of the semiconductor substrate opposite to the surface on which the foreign matter removal coating film is formed and thinning the semiconductor substrate, and examples thereof include physical polishing using an abrasive or a grindstone. The polishing treatment can be performed using a general polishing device used for polishing semiconductor substrates (e.g., silicon wafers). The polishing treatment reduces the thickness of the semiconductor substrate, resulting in a semiconductor substrate that has been thinned to a desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, and may be, for example, 30 to 300 μm or 30 to 100 μm.

[0276] <<Through Electrode Formation Process>> For example, a through electrode may be formed in a polished semiconductor substrate to provide electrical continuity between thinned semiconductor substrates when multiple thinned semiconductor substrates are stacked. Therefore, a through electrode formation process in which a through electrode is formed in the polished semiconductor substrate may be performed after the polishing process and before the peeling process. Methods for forming through electrodes in a semiconductor substrate are not particularly limited, but examples include forming through holes and filling the formed through holes with a conductive material. The through holes are formed, for example, by photolithography. The conductive material is filled into the through holes by plating, for example. Note that the through electrode formation process may be performed in the second step without performing the polishing process.

[0277] <<Connection Processing>> The connection processing is, for example, processing for connecting a semiconductor substrate and a second semiconductor substrate. The second semiconductor substrate is not particularly limited, and examples thereof include those listed in the above description of the semiconductor substrate. The connection processing is, for example, performed under heating. Furthermore, the connection processing is, for example, performed under pressure. The heating temperature is not particularly limited, and examples thereof include 100°C to 350°C.

[0278] In the connection process, for example, the wiring on the semiconductor substrate and the wiring on the second semiconductor substrate are electrically connected. Such connection is performed, for example, by connecting the ends of the wiring. The material, shape, and structure of the wiring on the semiconductor substrate are not particularly limited. The material, shape, and structure of the wiring on the second semiconductor substrate are not particularly limited.

[0279] <Step 3> Step 3 is a step of peeling the support substrate from the laminate. Step 3 can be said to be a step in which the semiconductor substrate and the support substrate are separated. Peeling methods include, but are not limited to, solvent peeling, peeling by light irradiation (laser light, non-laser light), mechanical peeling using equipment with sharp parts (so-called debonders), and manual peeling between the semiconductor substrate and the support substrate. In particular, when the laminate includes an adhesive layer, and the adhesive layer is formed using an organic resin that absorbs light and undergoes the necessary alteration to improve peelability, the adhesive layer can be peeled, for example, by irradiating it with a laser from the support substrate side. Laser light irradiation is performed using, for example, ultraviolet light with a wavelength of 190 nm to 400 nm or 190 nm to 600 nm (e.g., 308 nm, 355 nm, 532 nm). Peeling is performed using a pulse laser with a processing energy density of 50 to 500 mJ / cm. ２ When the laminate contains an adhesive layer, peeling usually occurs within the adhesive layer or at the interface between the adhesive layer and an adjacent substrate or layer (e.g., a coating film for removing foreign matter). Peeling occurring within the adhesive layer means that the adhesive layer is cleaved.

[0280] <Fourth Step> The fourth step is a step of cleaning the semiconductor substrate or the support substrate with a remover to remove the foreign matter removal coating film. For example, the foreign matter removal coating film remains on the semiconductor substrate that has been peeled off from the support substrate. Therefore, the foreign matter removal coating film is removed with a remover. In the fourth step, for example, the foreign matter is removed together with the foreign matter removal coating film. In the fourth step, for example, the foreign matter, which is a peeled residue of the adhesive layer, is removed together with the foreign matter removal coating film.

[0281] Examples of the removal liquid include the removal liquids mentioned in the description of the coating film-forming composition for removing foreign matter of the present invention. The cleaning method is not particularly limited, but examples include a method of immersing the semiconductor substrate on which the coating film for removing foreign matter remains in the removal liquid, and a method of spraying the removal liquid onto the semiconductor substrate on which the coating film for removing foreign matter remains. The cleaning conditions are not particularly limited, but for example, the temperature of the cleaning liquid is 5°C to 50°C. The cleaning time is appropriately selected from 2 to 500 seconds, or 3 to 400 seconds.

[0282] For example, it is preferable that the foreign matter removal coating film can be easily peeled off at room temperature (for example, 25° C.) using a commonly used 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0283] An example of a method for manufacturing a processed semiconductor substrate is described below with reference to the drawings. First, a semiconductor substrate 11 is prepared ( FIG. 1A ). Next, a foreign matter removal coating film 12 is formed on the semiconductor substrate 11 ( FIG. 1B ). Next, the semiconductor substrate 11 with the foreign matter removal coating film 12 shown in FIG. 1B is bonded to a support substrate 14 having a flexible support 14A and an adhesive layer 14B, with the foreign matter removal coating film 12 and the adhesive layer 14B facing each other ( FIG. 1C ). Next, the surface of the semiconductor substrate 11 opposite the surface with the foreign matter removal coating film 12 is polished to thin the semiconductor substrate 11 ( FIG. 1D ). Next, the support substrate 14 is separated from the semiconductor substrate 11 ( FIGS. 1E and 1F ). After separation, a peeled residue 14C of the adhesive layer 14B remains on the foreign matter removal coating film 12 ( FIG. 1F ). Therefore, the foreign matter removal coating film 12 is removed using a remover ( FIG. 1G ). By doing so, it is possible to prevent the peeling residue 14C, which is a foreign substance, from remaining on the semiconductor substrate 11.

[0284] Another example of a method for manufacturing a processed semiconductor substrate is described below with reference to the drawings. First, a semiconductor substrate 1 having wiring 1A is prepared ( FIG. 2A ). Next, a foreign matter removal coating film 2 is formed on the semiconductor substrate 1 ( FIG. 2B ). Separately, a glass substrate 4 having an adhesive layer 3 formed on its surface is prepared ( FIG. 2C ). The semiconductor substrate 1 having the foreign matter removal coating film 2 shown in FIG. 2B and the glass substrate 4 having the adhesive layer 3 shown in FIG. 2C are then bonded together, with the foreign matter removal coating film 2 and the adhesive layer 3 facing each other ( FIGS. 2D and 2E ). Next, the surface of the semiconductor substrate 1 opposite the surface with the foreign matter removal coating film 2 is polished to thin the semiconductor substrate 1 ( FIG. 2F ). Finally, the wiring 1A is exposed. Next, the laminate shown in FIG. 2F and a second semiconductor substrate 5 having wiring 5A are bonded together, with the surface of the semiconductor substrate 1 opposite the surface of the foreign matter removal coating film 2 facing the surface of the second semiconductor substrate 5 on which the wiring 5A is exposed (FIGS. 2G and 2H). Next, the adhesive layer 3 and glass substrate 4 are separated from the semiconductor substrate 1 (FIG. 2I). Separation can be easily achieved, for example, by irradiating the adhesive layer 3 with a laser to reduce the adhesive strength of the adhesive layer 3. After separation, peeling residue 3A of the adhesive layer 3 remains on the foreign matter removal coating film 2 (FIGS. 2I and 2J). Therefore, the foreign matter removal coating film 2 is removed with a remover (FIG. 2K). This prevents the peeling residue 3A from remaining on the semiconductor substrate 1.

[0285] The method for manufacturing a processed semiconductor substrate of the present invention can be suitably used for hybrid bonding, which connects semiconductor substrates together.

[0286] <Other embodiments> One embodiment of the present invention may be a method for removing foreign matter already present on a semiconductor manufacturing substrate.For example, as described in International Publication No. 2017 / 056746 and International Publication No. 2020 / 008965, in the process of forming a substrate processing film on the surface of a semiconductor substrate and removing foreign matter from the substrate surface, a substrate processing film-forming composition and a substrate processing method are disclosed that can efficiently remove fine particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface.The coating film-forming composition for removing foreign matter of the present invention can also be used in the same methods and applications as above.

[0287] The above example will be specifically described below. In this application example, the coating film-forming composition for removing foreign matter of the present invention is used as a composition for forming a coating film on a semiconductor substrate. First, a coating film-forming step is performed. That is, the coating film-forming composition for removing foreign matter is applied to a semiconductor substrate to form a coating film. The semiconductor substrate may be in an unprocessed state or in a state where various films are formed, i.e., a solid substrate (flat), or may be processed to have a shape such as wiring for semiconductor device manufacturing. Examples of coating methods include spin coating, casting coating, and roll coating. Next, the coating film is heated (baked) and / or reduced pressure to efficiently remove part or all of the solvent contained in the coating film, thereby promoting solidification and / or hardening of the solid content contained in the coating film. Here, "solidification" refers to solidification, and "hardening" refers to the process in which molecules bond to each other and increase the molecular weight (e.g., crosslinking, polymerization, etc.). In this manner, a coating film is formed. During this process, for example, particles adhering to the circuitry of the semiconductor substrate are captured by the coating film and efficiently detached from the circuitry. Next, a coating film removal step is performed. That is, a remover that dissolves the coating film is supplied onto the coating film to remove the entire coating film from the semiconductor substrate. As a result, the particles are removed from the semiconductor substrate together with the coating film.

[0288] Next, the present invention will be explained in detail with reference to synthesis examples and examples, but the present invention is not limited to these.

[0289] Example 1 A coating film-forming composition for removing foreign matter was prepared by adding 0.04 g of 1,1,1-tris(4-hydroxyphenyl)ethane (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.36 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0290] Example 2 A coating film-forming composition for removing foreign matter was prepared by adding 0.09 g of salicylaldoxime (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.31 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0291] Example 3 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of tartaric acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0292] Example 4 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of citric acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0293] Example 5 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of 3-methyl-1-phenyl-5-pyrazolone (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0294] Example 6 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of L-ascorbic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0295] Example 7 To 1.33 g of poly-parahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), 0.06 g of pyrogallol FZ (Honshu Chemical Industry Co., Ltd., structure shown below) and 98.60 g of propylene glycol monomethyl ether were added, and the mixture was filtered using a PTFE syringe filter having a pore size of 0.20 μm to prepare a coating film-forming composition for removing foreign matter.

[0296] Example 8 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of curcumin (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0297] Example 9 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of malonic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0298] Example 10 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of meso-butane-1,2,3,4-tetracarboxylic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0299] Example 11 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of 1,2,3,4-cyclopentanetetracarboxylic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0300] Example 12 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of thiazole-4-carboxylic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0301] Example 13 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of gallic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0302] Example 14 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of methyl gallate (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0303] Example 15 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of picolinic acid (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0304] Example 16 A coating film-forming composition for removing foreign matter was prepared by adding 0.06 g of N,N'-bis(salicylidene)-1,3-propanediamine (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether to 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0305] Example 17 To 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), 0.06 g of tris(2-hydroxyethyl) isocyanurate (Tokyo Chemical Industry Co., Ltd.) and 98.60 g of propylene glycol monomethyl ether were added, and the mixture was filtered using a PTFE syringe filter having a pore size of 0.20 μm to prepare a coating film-forming composition for removing foreign matter.

[0306] Example 18 To 1.33 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.), 0.06 g of Olfine E1010 (Nissin Chemical Industry Co., Ltd., structure shown below) and 98.60 g of propylene glycol monomethyl ether were added, and the mixture was then filtered using a PTFE syringe filter having a pore size of 0.20 μm to prepare a coating film-forming composition for removing foreign matter. n, m: average number of added moles 10

[0307] Comparative Example 1 A coating film-forming composition for removing foreign matter was prepared by adding 98.60 g of propylene glycol monomethyl ether to 1.40 g of polyparahydroxystyrene (VP-8000, Nippon Soda Co., Ltd.) and then filtering the mixture using a PTFE syringe filter having a pore size of 0.20 μm.

[0308] [Alkali Solubility Test] To evaluate solubility in an alkaline solution, each of the coating film-forming compositions for removing foreign matter prepared in Examples 1 to 18 and Comparative Example 1 was applied to a copper vapor-deposited substrate with a thickness of 150 nm, and heated at 160°C for 1 minute to form a coating film with a thickness of 40 nm. The copper substrate coated with the coating film-forming composition for removing foreign matter was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds, washed with pure water, and then visually evaluated for the presence or absence of a coating film. The results of the solubility test in an alkaline solution are shown in Table 1. The evaluation criterion "◯" can be said to indicate good alkaline solubility and excellent removability in an alkaline solution. The evaluation criterion "△" can be said to indicate alkaline solubility and is at a pass level. (Evaluation Criteria) ◯: No coating film remains △: Only a portion of the coating film remains ×: The coating film remains

[0309]

[0310] REFERENCE SIGNS LIST 1 Semiconductor substrate 1A Wiring 2 Foreign matter removal coating film 3 Adhesive layer 4 Glass substrate 5 Second semiconductor substrate 5A Wiring 11 Semiconductor substrate 12 Foreign matter removal coating film 14 Support base 14A Flexible support 14B Pressure-sensitive adhesive layer 14C Peeling residue

Claims

1. A coating film-forming composition for removing foreign matter, capable of forming a coating film that can be removed by a removal liquid, the composition comprising film-constituting components and a solvent, wherein the film-constituting components comprise a coordinating compound.

2. The composition of claim 1, wherein the coordinating compound is a compound capable of coordinating to copper.

3. The composition according to claim 1, wherein the coordinating compound is at least one of: (I) a compound having two or more hydroxy groups; (II) a compound having two or more carboxy groups; (III) a compound having a heterocycle; and (IV) an acetylene glycol compound.

4. The compound according to claim 1, wherein the membrane constituent component includes a compound or a polymer as a component other than the coordinating compound.

5. The composition according to claim 4, wherein the compound or polymer has at least one of a hydroxy group, a carboxy group, and a heterocycle.

6. The composition according to claim 1, wherein the content of the coordinating compound is 1% by mass to 10% by mass based on the film constituent components.

7. The composition according to claim 4, wherein the content of said compound or polymer is 90% by mass to 99% by mass relative to the membrane constituent components.

8. The composition of claim 1, wherein the removal solution is an alkaline removal solution.

9. The composition of claim 1, wherein the coating film is in contact with copper.

10. A coating film for removing foreign matter formed from the composition according to any one of claims 1 to 9.

11. A semiconductor substrate having the coating film for removing foreign matter according to claim 10.

12. The semiconductor substrate according to claim 11, wherein the foreign matter removal coating film is in contact with copper.

13. A method for manufacturing a processed semiconductor substrate, comprising: a first step of manufacturing a laminate by bonding the semiconductor substrate described in claim 11 and a supporting substrate with the foreign matter removal coating film interposed therebetween; a second step of processing the laminate; a third step of peeling the supporting substrate from the laminate; and a fourth step of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the foreign matter removal coating film.

14. The method for producing a processed semiconductor substrate according to claim 13, wherein the foreign matter removal coating film is in contact with copper in the laminate.

15. The method for producing a processed semiconductor substrate according to claim 13, wherein the fourth step removes foreign matter together with the foreign matter removal coating film.

16. A method for producing a processed semiconductor substrate according to claim 13, wherein the first step is a step of producing a laminate by bonding the semiconductor substrate and the support base material together via the foreign matter removal coating film and adhesive layer.

17. The method for manufacturing a semiconductor substrate according to claim 16, wherein in the fourth step, foreign matter, which is a peeled residue of the adhesive layer, is removed together with the foreign matter removal coating film.

18. The method of claim 13, wherein said processing includes connecting said semiconductor substrate with a second semiconductor substrate.

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