Composition for forming coating film for foreign matter removal and semiconductor substrate

Abstract

A composition for forming a coating film for foreign matter removal, from which a coating film capable of being removed by a removal liquid can be formed, the composition containing a film-forming component and a solvent, the film-forming component containing a complexing compound.

Description

Technical Field

[0001] The present invention relates to a composition for forming a foreign matter removal coating that can easily prevent foreign matter residues on a substrate, a foreign matter removal coating, a semiconductor substrate, and a method for manufacturing the processed semiconductor substrate.

[0002] In the manufacture of semiconductor devices, especially in the so-called back-end processes, a process has been studied in which a semiconductor substrate (e.g., a wafer) is attached to a support substrate, and then back-side grinding (sharpening), wiring fabrication, etc. are performed, and then the support substrate is peeled off to obtain the desired semiconductor substrate.

[0003] In such processes, foreign matter may sometimes be generated, which needs to be removed. Therefore, for example, Patent Documents 1 and 2 disclose a substrate processing film forming composition and substrate processing method for efficiently removing small particles from the substrate surface and easily removing the formed substrate processing film from the substrate surface in a process of removing foreign matter from the surface of a semiconductor substrate by forming a substrate processing film on the surface of the substrate.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2017 / 056746

[0007] Patent Document 2: International Publication No. 2020 / 008965 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] 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, back-grinding tape, dicing tape, etc.) that is resistant to subsequent processes (e.g., heating processes, chemical treatment processes, etc.). Alternatively, a support substrate with an adhesive layer (pressure-sensitive adhesive layer) can be used. Then, a process of peeling off the semiconductor substrate is performed. At this time, the adhesive layer or the adhesive layer of the support substrate sometimes remains on the substrate as foreign matter (residue). This phenomenon is particularly pronounced when the adhesive layer is formed directly on the surface of the semiconductor substrate where wiring is pre-formed, or when a support substrate with an adhesive layer is directly attached. This foreign matter sometimes cannot be completely removed even by cleaning with known organic solvents, liquid chemicals, etc.

[0010] Therefore, there is a need for a simple method to prevent peeling residues from adhesive layers, etc., from remaining on the semiconductor substrate.

[0011] On the other hand, when using a film (foreign object removal coating) for this purpose, the film is required to be easily removable from the semiconductor substrate after the process of peeling off the semiconductor substrate (removability).

[0012] Therefore, the object of the present invention is to provide a composition for forming a foreign matter removal coating that yields a "foreign matter removal coating with easy removability", as well as a method for manufacturing a foreign matter removal coating using the composition, a semiconductor substrate, and a processed semiconductor substrate.

[0013] Methods for solving problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, thus completing the present invention with the following core points.

[0015] That is, the present invention includes the following solutions.

[0016] [1]. A composition for forming a coating film for foreign matter removal, wherein the composition can form a coating film removable by a removal liquid, the composition comprising film-forming components and a solvent,

[0017] The membrane components contain coordination compounds.

[0018] [2]. The composition as described in [1], wherein the coordinating compound is a compound capable of coordinating with copper.

[0019] [3]. In the composition described in [1] or [2], the coordinating compound is at least one of (I) to (IV) below.

[0020] (I) Compounds having two or more hydroxyl groups,

[0021] (II) Compounds having two or more carboxyl groups,

[0022] (III) Compounds with heterocyclic structures, and

[0023] (IV) Alkyne diol compounds.

[0024] [4]. The compound as described in any one of [1] to [3], wherein the membrane constituents contain a compound or polymer as a component other than the coordinating compound.

[0025] [5]. The composition as described in [4], wherein the compound or polymer has at least one of a hydroxyl group, a carboxyl group and a heterocycle.

[0026] [6]. The composition of any one of [1] to [5], wherein the content of the coordination compound is 1% to 10% by mass relative to the membrane constituents.

[0027] [7]. The composition of any one of [4] to [6], wherein the content of the compound or polymer is 90% to 99% by mass relative to the membrane constituents.

[0028] [8]. The composition as described in any one of [1] to [7], wherein the removal liquid is an alkaline removal liquid.

[0029] [9]. The composition as described in any of [1] to [8], wherein the coating is in contact with copper.

[0030]

[10] . A coating for removing foreign matter, which is formed from any one of the compositions described in [1] to [9].

[0031]

[11] . A semiconductor substrate having the foreign matter removal coating described in

[10] .

[0032]

[12] . The semiconductor substrate as described in

[11] , wherein the foreign matter removal coating is in contact with copper.

[0033]

[13] . A method for manufacturing a processed semiconductor substrate, comprising the following steps:

[0034] Step 1: The semiconductor substrate described in

[11] and the support substrate are bonded together by the foreign matter removal coating to manufacture a laminate;

[0035] Step 2: Processing the laminated body;

[0036] Step 3: Peeling the support substrate from the laminate; and

[0037] Step 4: Clean the semiconductor substrate or the support substrate with a removal solution to remove the foreign matter removal coating.

[0038]

[14] . In the method for manufacturing the processed semiconductor substrate as described in

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

[0039]

[15] . In the method for manufacturing the processed semiconductor substrate as described in

[13] or

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

[0040]

[16] . A method for manufacturing a processed semiconductor substrate as described in any of

[13] to

[15] , wherein the first step is a step of bonding the semiconductor substrate and the support substrate together via the foreign matter removal coating and adhesive layer to manufacture a laminate.

[0041]

[17] . In the semiconductor substrate manufacturing method described in

[16] , in the fourth step, foreign matter that serves as peeling residue of the adhesive layer is removed together with the foreign matter removal coating.

[0042]

[18] . A method for manufacturing a processed semiconductor substrate as described in any of

[13] to

[17] , wherein the processing includes the step of connecting the semiconductor substrate to a second semiconductor substrate.

[0043] Invention Effects

[0044] Furthermore, according to the present invention, a composition for forming a foreign matter removal coating that can produce a foreign matter removal coating with easy removability can be provided, as well as a method for manufacturing a foreign matter removal coating using the composition, a semiconductor substrate, and a processed semiconductor substrate. Attached Figure Description

[0045] [ Figure 1A ]: Figure 1A A schematic cross-sectional view (1) is provided for illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0046] [ Figure 1B ]: Figure 1B A schematic cross-sectional view (2) is provided to illustrate an example of a method for manufacturing a processed semiconductor substrate.

[0047] [ Figure 1C ]: Figure 1C A schematic cross-sectional view (3) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0048] [ Figure 1D ]: Figure 1D A schematic cross-sectional view (4) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0049] [ Figure 1E ]: Figure 1E A schematic cross-sectional view (5) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0050] [ Figure 1F ]: Figure 1F A schematic cross-sectional view (6) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0051] [ Figure 1G ]: Figure 1G A schematic cross-sectional view (7) is provided to illustrate an example of a method for manufacturing a processed semiconductor substrate.

[0052] [ Figure 2A ]: Figure 2AA schematic cross-sectional view (1) is provided to illustrate another example of a method for manufacturing a processed semiconductor substrate.

[0053] [ Figure 2B ]: Figure 2B A schematic cross-sectional view (2) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0054] [ Figure 2C ]: Figure 2C A schematic cross-sectional view (3) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0055] [ Figure 2D ]: Figure 2D A schematic cross-sectional view (4) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0056] [ Figure 2E ]: Figure 2E A schematic cross-sectional view (5) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0057] [ Figure 2F ]: Figure 2F A schematic cross-sectional view (6) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0058] [ Figure 2G ]: Figure 2G A schematic cross-sectional view (7) is provided to illustrate another example of a method for manufacturing a processed semiconductor substrate.

[0059] [ Figure 2H ]: Figure 2H A schematic cross-sectional view (8) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0060] [ Figure 2I ]: Figure 2I A schematic cross-sectional view (9) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0061] [ Figure 2J ]: Figure 2J A schematic cross-sectional view (10) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0062] [ Figure 2K ]: Figure 2K A schematic cross-sectional view (11) illustrating another example of a method for manufacturing a processed semiconductor substrate. Detailed Implementation

[0063] (Composition for forming a coating for foreign matter removal)

[0064] The composition of the present invention for forming a coating for foreign matter removal contains a film-forming component and a solvent.

[0065] The membrane's components contain coordination compounds.

[0066] The composition for forming a coating for removing foreign matter is preferably capable of forming a coating that can be removed by a removal liquid.

[0067] Membrane composition refers to components other than solvents in a composition used to form a coating for foreign matter removal.

[0068] The inventors have come to the insight that when a coating formed by a composition for forming a foreign matter removal film is to be removed using a removal liquid, sometimes the film remains and is difficult to remove with the removal liquid.

[0069] After conducting research, the inventors have come to the following conclusion: the phenomenon that is difficult to remove with a remover is prone to occur when the coating comes into contact with a metal (e.g., copper).

[0070] Therefore, the inventors conducted further repeated studies and found that by containing a coordination compound in the composition used to form a coating for foreign matter removal, film residue can be prevented when the coating is removed with a removal liquid, and the easy removability of the coating can be maintained.

[0071] The inventors conducted an investigation as follows.

[0072] Metals (e.g., copper) in contact with a membrane can diffuse (migrate) within the membrane. If this metal interacts with the main components of the membrane (e.g., forming coordination compounds), it can become difficult to remove with the removal solution. On the other hand, if the composition used to form a coating for foreign matter removal contains a coordination compound, the interaction between the main components of the membrane and the metal can be prevented, thus maintaining the membrane's removability. The reason why coordination compounds can prevent the interaction between the main components of the membrane and the metal is uncertain. Possible reasons include that coordination compounds are concentrated at the membrane-metal interface, preventing the metal from diffusing into the membrane, and that the metal that has diffused into the membrane preferentially interacts with the coordination compound.

[0073] Furthermore, metals in contact with the membrane can migrate to the membrane surface, forming a thin oxide film that is difficult to remove with the removal solution. On the other hand, when the composition used to form a coating for foreign matter removal contains a coordination compound, the coordination compound can capture the metal and hinder oxide film formation. Therefore, easy removal can be maintained.

[0074] In view of the above, and for the purpose of better achieving the effects of the present invention, the coating is preferably in contact with a metal. Examples of metals include, for instance, "coordinating metals" described later.

[0075] The metal that the coating contacts is, for example, a metal present on a semiconductor substrate. Such a metal could be, for example, a metal used as an electrode. Examples of electrodes include bumps.

[0076] <Membrane Constituents>

[0077] The membrane's components contain coordination compounds.

[0078] The membrane composition preferably further contains compounds or polymers.

[0079] In this invention, "compound or polymer" is a different component from coordination compounds, crosslinking agents (described later), additives (described later), etc.

[0080] "Compound or polymer" refers to a major component of the membrane structure, for example, a component that accounts for 50% or more by mass of the membrane structure.

[0081] <<Coordination Compounds>>

[0082] Coordination compounds are capable of coordinating with metals. Coordination compounds are also called coordination-forming compounds. They form by coordinating with metals or metal ions.

[0083] Metals capable of coordination include, for example, copper, aluminum, chromium, iron, nickel, zinc, molybdenum, cobalt, manganese, tantalum, titanium, tungsten, ruthenium, gold, silver, and platinum, with copper being a preferred example.

[0084] Coordinating compounds, for example, those possessing functional groups. Examples of functional groups include hydroxyl, carboxyl, and thiol groups.

[0085] Furthermore, in this invention, the OH group in the =N-OH group is considered as a form of hydroxyl group. The OH group in the -COOH group (carboxyl group) is not considered as a form of hydroxyl group.

[0086] When a coordinating compound has hydroxyl groups, the number of hydroxyl groups can be 1, 2, 3, 4, 5, or 6.

[0087] When a coordinating compound has a hydroxyl group, the hydroxyl group may or may not be a phenolic hydroxyl group.

[0088] When a coordination compound has a carboxyl group, the number of carboxyl groups can be 1, 2, 3, 4, 5, or 6.

[0089] Coordination compounds can also have ring structures. The ring structure can be, for example, a 5-membered ring, a 6-membered ring, a 7-membered ring, or a condensation ring of two or more of these.

[0090] When a coordination compound has a ring structure, there is no particular limitation on the number of rings; it can be one, two, three, or four.

[0091] Coordinating compounds may or may not have aromatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. Examples of aromatic heterocycles include furan rings, pyrrole rings, thiophene rings, and pyridine rings.

[0092] There are no particular restrictions on the atoms that constitute coordination compounds.

[0093] Coordination compounds can be compounds composed only of carbon, hydrogen, and oxygen atoms; compounds composed only of carbon, hydrogen, oxygen, and nitrogen atoms; or compounds composed only of carbon, hydrogen, oxygen, nitrogen, and sulfur atoms.

[0094] Coordination compounds may or may not have halogen atoms.

[0095] Coordination compounds may or may not have carbonyl bonds (CO).

[0096] Examples of heterocycles in compounds containing heterocycles include 5-membered rings, 6-membered rings, and 7-membered rings.

[0097] Examples of heteroatoms present in heterocycles include oxygen atoms, nitrogen atoms, and sulfur atoms.

[0098] Examples of heterocyclic rings include isocyanuric acid rings, pyrazolone rings, pyridine rings, and thiazole rings.

[0099] There is no particular limitation on the molecular weight of the coordination compound (e.g., the molecular weight of compounds (I) to (III) below), for example, 100 to 500.

[0100] Examples of coordination compounds include the following compounds.

[0101] (I) Compounds having two or more hydroxyl groups,

[0102] (II) Compounds having two or more carboxyl groups,

[0103] (III) Compounds with heterocycles

[0104] (IV) Acynylene diol compounds

[0105] Furthermore, sometimes a compound can be equivalent to both (I) and (II). For example, tartaric acid (with the structure below) is both a compound of (I) and a compound of (II).

[0106]

[0107] Examples of compounds that can be listed as (I) to (III) are the following compounds.

[0108]

[0109]

[0110] (IV) Acrylene diols are alkene oxide adducts of alkene diols formed by the addition of an alkene oxide with 2 or 3 carbon atoms to an alkene diol.

[0111] Examples of alkynyldiols include 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 2,5,8,11-tetramethyl-6-dodecyn-5,8-diol, 2-butyn-1,4-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 3-hexyn-2,5-diol.

[0112] The olefin oxide with 2 or 3 carbon atoms is ethylene oxide (ethylene oxide) or propylene oxide (propylene oxide), preferably ethylene oxide.

[0113] The average number of moles of olefin oxide added to the olefin oxide adduct of alkynyl diol is, for example, 1 to 20, preferably 2 to 20, and more preferably 4 to 10.

[0114] Alkyne diol compounds, for example, represented by the following formula (IV-1).

[0115]

[0116] (In formula (IV-1), R) 1 R 2 R 3 and R 4 Each can be independently represented by a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0117] m and n are integers greater than or equal to 0.

[0118] The sum of n and m is, for example, 1 to 20, preferably 2 to 20, and more preferably 4 to 10.

[0119] Regarding R 1 ~R 4 In this regard, R is preferred 2 and R 3 It is methyl, and R 1 and R 4It is isobutyl (-CH2CH(CH3)2).

[0120] Alkyne diols are also commercially available. Examples of commercially available alkynyl diols include Surfynol (registered trademark) or Olfine (registered trademark) manufactured by Nissin Chemical Industries, Ltd., and Acetylenol (registered trademark) manufactured by Kawaken Fine Chemicals Co., Ltd.

[0121] There is no particular limitation on the content of the coordination compound, but it is preferably 0.1% to 20% by mass, more preferably 0.5% to 15% by mass, and particularly preferably 1% to 10% by mass relative to the composition of the membrane.

[0122] There is no particular limitation on the content of the coordination compound in the composition used to form a coating for foreign matter removal, but it is preferably 0.1% to 20% by mass, more preferably 0.5% to 15% by mass, and particularly preferably 1% to 10% by mass, relative to "compound or polymer".

[0123] <<Compounds or Polymers>>

[0124] There are no particular restrictions on the compounds or polymers that are the main components of the membrane, provided that the compounds or polymers have polar groups. Examples of polar groups include hydroxyl and carboxyl groups.

[0125] The compound or polymer may have heterocycles, for example. Examples of heterocycles include lactam rings.

[0126] The following describes polymers (A) to (I) and compound (A) as examples of compounds or polymers.

[0127] <<<Polymer (A)>>>

[0128] Polymer (A) is a polymer having at least one of phenolic hydroxyl and carboxyl groups.

[0129] The polymer (A) contains, for example, two or more phenolic hydroxyl groups and carboxyl groups. In this case, it may contain two or more phenolic hydroxyl groups and no carboxyl groups, or it may contain two or more carboxyl groups and no phenolic hydroxyl groups.

[0130] As a polymer (A), there are no particular limitations as long as it has at least one of phenolic hydroxyl and carboxyl groups, such as phenolic varnish, cresol varnish, polyhydroxystyrene, polyamic acid, polyacrylic acid, etc.

[0131] As polymer (A), a polymer in which all the units (repeating structural units) constituting the polymer have phenolic hydroxyl or carboxyl groups can be used. Alternatively, a polymer composed of units having phenolic hydroxyl or carboxyl groups and units not having phenolic hydroxyl or carboxyl groups can also be used. When using such a polymer composed of units having phenolic hydroxyl or carboxyl groups and units not having phenolic hydroxyl or carboxyl groups, the molar proportion of units having phenolic hydroxyl or carboxyl groups in the polymer, relative to all the units constituting the polymer, is preferably 1% or more, for example 10% or more, particularly 20% or more, and is 5% to 100%, for example 10% to 100%, preferably 20% to 100%, and more preferably 30% to 100%.

[0132] As a polymer (A), examples of polymers represented by the following formulas (4)~(23), (26)~(35) can be cited. In the formulas, p1, p2, p3 and p4 represent the molar proportions of each unit in the polymer, and represent the values ​​that make their sum 100%.

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] Polymer (A) can be exemplified by polymers containing hydroxystyrene units (structural units derived from hydroxystyrene) (e.g., polyhydroxystyrene). Furthermore, polymer (A) can also be exemplified by polymers produced by copolymerizing hydroxystyrene with compounds having addition-polymerizable double bonds, such as acrylate compounds, methacrylate compounds, maleimide, and vinyl ether compounds, for example, polymers of formulas (8) to (11). The hydroxystyrene unit preferably contains 10% or more in a molar proportion relative to all units constituting the polymer. The molar proportion of the hydroxystyrene unit 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.

[0146] Furthermore, polymers (A) containing acrylic acid units or methacrylic acid units (e.g., polyacrylic acid or polymethacrylic acid polymers) can be listed as examples. Further, polymers (A) can also be listed as polymers made from compounds having addition polymerizable double bonds, such as acrylate compounds, methacrylate compounds, and styrene compounds, and polymers made with acrylic acid or methacrylic acid, such as polymers of formulas (10), (12) to (15). The acrylic acid units or methacrylic acid units preferably contain a molar proportion of 10% or more relative to all units constituting the polymer. The molar proportion of acrylic acid units or methacrylic acid units 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.

[0147] Furthermore, as polymer (A), polyimide can be cited as an example. The polyimide used in this invention can be manufactured by a tetracarboxylic acid dianhydride compound and a diamine compound having a phenolic hydroxyl group or a carboxyl group. Such polyimides can be cited as examples of polyimides of formulas (31) to (35). For example, the polyimide of formula (31) can be obtained by reacting a 1,2,4,5-benzenetetracarboxylic acid dianhydride compound with 3,5-diaminobenzoic acid and 2,2-bis(3-amino-4-toluamide)hexafluoropropane.

[0148] Furthermore, as polymer (A), polyamic acid can be cited as an example. Polyamic acid can be manufactured by reacting a diamine compound with a tetracarboxylic acid or a tetracarboxylic acid derivative, or a dicarboxylic acid dihalide, etc. In addition, polyamic acid can also be manufactured by polymerizing a dimethylsilylated diamine compound with a tetracarboxylic acid dianhydride compound to synthesize polyamic acid silyl ester, and then decomposing the silyl ester portion with an acid. The polyamic acid used in the present invention can be exemplified by, for example, polyamic acids of formulas (16) to (23), (26) to (30). In addition, for example, polyamic acid of 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.

[0149] Furthermore, polymer (A) can be exemplified by polymers made from compounds having at least two epoxy groups and compounds having at least two phenolic hydroxyl or carboxyl groups. Examples of such polymers include polymers made from compounds having at least two, for example, two to six epoxy groups and compounds having at least two, for example, two to six phenolic hydroxyl or carboxyl groups.

[0150] Such polymers can be manufactured by reacting a compound having at least two epoxy groups, a compound having at least two phenolic hydroxyl or carboxyl groups in approximately equimolar amounts with the epoxy groups, in the presence of a catalyst such as a quaternary ammonium salt.

[0151] 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-cyclohexane dicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid ester, trimethylolethane triglycidyl ether, bisphenol A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

[0152] Examples of compounds having at least two phenolic hydroxyl or carboxyl groups include 1,2,3-anthratriol, 2,7,9-anthratriol, 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-naphthodiol, 4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 2,4-dihydroxy-5-methylbenzoic acid, and 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, etc.

[0153] As a polymer made from a compound having at least two epoxy groups and a compound having at least two phenolic hydroxyl groups or carboxyl groups, examples of polymers of formula (43) can be cited.

[0154]

[0155] Furthermore, as polymer (A), a polymer having the following formula (1) can be used:

[0156]

[0157] (In equation (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). R 2 Indicates a single bond or an alkylene group having 1 to 6 carbon atoms. R 11 This indicates an alkyl group with 1 to 6 carbon atoms. m represents an integer from 0 to 4. When m is 2 or more, it indicates two or more R atoms. 11 Polymers of units that can be the same or different.

[0158] The unit of formula (1) contains, for example, a molar proportion of 10% or more relative to all units constituting the polymer. The molar proportion 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%.

[0159] Monomers that are given the unit represented by equation (1) can be exemplified by, for example, the monomers represented by equation (1-1) below.

[0160]

[0161] (In equation (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). R 2 Indicates a single bond or an alkylene group having 1 to 6 carbon atoms. R 11 This indicates an alkyl group with 1 to 6 carbon atoms. m represents an integer from 0 to 4. When m is 2 or more, it indicates two or more R atoms. 11 (They can be the same or different).

[0162] As the monomer represented by equation (1-1), the following monomers can be listed as examples.

[0163]

[0164] Polymers having units represented by formula (1) can be manufactured by polymerizing monomers represented by formula (1-1) using polymerization initiators such as N,N'-azobisisobutyronitrile.

[0165] A polymer having units represented by formula (1) may contain other units within the range where the proportion of formula (1) in the polymer satisfies the stated value. These other units may be introduced into the polymer during polymer manufacturing using polymers capable of polymerization, such as acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0166] Examples of acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthraceneyl methyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, mono-(2-(acryloyloxy)ethyl)phthalate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantane acrylate, 2-propyl-2-adamantane acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, etc.

[0167] Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthraceneyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, mono-(2-(methacryloyloxy)ethyl)phthalate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantane methacrylate, 2-propyl-2-adamantane methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, etc.

[0168] Examples of vinyl compounds include vinyl ethers, methyl vinyl ethers, benzyl vinyl ethers, 2-hydroxyethyl vinyl ethers, phenyl vinyl ethers, and propyl vinyl ethers.

[0169] Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene, and hydroxystyrene.

[0170] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0171] As a polymer having units represented by formula (1), examples include polymers of formulas (44) to (49). In the formulas, q1, q2, q3 and q4 represent the molar proportions of each unit in the polymer, q1 is 10% or more, and represents the value that makes their sum 100%.

[0172]

[0173]

[0174] In addition, as polymer (A), it may also be the polyamic acid described in International Publication No. 2018 / 159665, which has a "structural unit derived from (a) a tetracarboxylic acid dianhydride compound and (b) a diamine compound having at least one carboxyl group".

[0175] In addition, polymer (A) may also be a polymer containing phenolic hydroxyl groups or a polymer containing carboxyl groups as described in International Publication No. 2022 / 019287.

[0176] The contents of these public announcements are incorporated into this specification to the same extent as all explicit records.

[0177] Polymer (A) may also be a commercially available product. Examples of commercially available products include poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.).

[0178] <<<Polymer (B)>>>

[0179] Polymer (B) is a polymer containing the structural unit represented by the following formula (1).

[0180]

[0181] [In formula (1), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of an imide group that can be deprotected by a base].

[0182] Protecting groups in R that can be deprotected by a base include, for example, methyl, cyclohexyl, hydroxyethyl, benzyl, phenyl, etc.

[0183] Examples of alkalis include those contained in alkaline removal solutions.

[0184] Polymer (B) may also have structural units other than those represented by formula (1). There are no particular restrictions on such structural units. Structural units derived from compounds with polymerizable unsaturated bonds can be listed.

[0185] There is no particular limitation on the proportion of the structural unit represented by formula (1) in polymer (B), but it 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.

[0186] There are no particular limitations on the weight-average molecular weight of polymer (B), but it is preferably 1,000 to 50,000, more preferably 1,500 to 30,000. Furthermore, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0187] As a polymer (B), it is obtained, for example, by polymerizing a monomer containing a compound represented by the following formula (1A).

[0188]

[0189] [In equation (1A), X has the same meaning as X in equation (1).]

[0190] Examples of compounds represented by formula (1A) include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-hydroxyethylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and maleic anhydride.

[0191] There are no particular restrictions on the polymerization method; for example, free radical polymerization can be cited.

[0192] For example, polymers can be obtained by homopolymerization of compounds represented by formula (1A) such as maleimide, or by copolymerization with other monomers.

[0193] The monomers used in the polymerization may also include monomers other than those represented by formula (1A). Examples of such monomers include, for instance, compounds having polymerizable unsaturated bonds. Specific examples include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, and acrylonitrile.

[0194] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantane acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0195] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantane methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0196] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0197] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthraylmethacrylamide.

[0198] 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, vinylanthracene, etc.

[0199] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc., but are not limited to these.

[0200] In addition, as polymer (B), it may also be the polymer described in International Publication No. 2023 / 248946.

[0201] The contents of that public announcement are incorporated into this specification to the same extent as all explicit statements.

[0202] <<<Polymer (C)>>>

[0203] Polymer (C) is a polymer containing the structure represented by the following formula (1).

[0204]

[0205] In equation (1), R 1 * indicates a hydrogen atom, a protecting group of an imide group that can be deprotected by a base, or a protecting group of an imide group that can be deprotected by an acid; * indicates a linking bond.

[0206] As R 1 The protecting groups of imide groups that can be deprotected by a base include, for example, methyl, cyclohexyl, hydroxyethyl, benzyl, phenyl, etc.

[0207] As R 1Protecting groups of imide groups that can be deprotected by acids include, for example, tert-butoxycarbonyl, benzyloxycarbonyl, trimethylsilyl, tert-butyldimethylsilyl, methoxymethyl, ethoxymethyl, tetrahydropyranyl, acetyl, benzyl, p-methoxybenzyl, etc.

[0208] Examples of alkalis include those contained in alkaline removal solutions.

[0209] Examples of acids include those contained in acid removal solutions.

[0210] The protection of the imide group can be removed by alkali, for example, when the coating formed by the composition for forming a foreign matter removal film is brought into contact with an alkaline removal liquid.

[0211] The protection of the imide group can be removed by acid, for example, when the coating formed by the composition for forming a foreign matter removal film is brought into contact with an acidic removal solution.

[0212] The protection of the imide group can be deprotected by acid, for example, by using an acid generated by the acid-generating agent when forming a coating film from a composition containing an acid-generating agent for forming a foreign matter removal film.

[0213] R in equation (1) 1 Hydrogen atoms are preferred.

[0214] The polymer (C) preferably further comprises the structure represented by the following formula (2).

[0215]

[0216] In equation (2), R 11 and R 12 Each of the following independently represents a substituted alkyl group, a substituted phenyl group, or a substituted phenoxy group having 1 to 10 carbon atoms; * indicates a linking bond.

[0217] In this invention, examples of substituents in substituted alkyl groups having 1 to 10 carbon atoms include halogen atoms, hydroxyl groups, carboxyl groups, etc.

[0218] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0219] Examples of substituted alkyl groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms.

[0220] In this invention, the substituents in the substituted phenyl and substituted phenoxy groups can be, for example, halogen atoms, alkyl groups having 1 to 6 carbon atoms that can be substituted by halogen atoms, alkoxy groups having 1 to 6 carbon atoms that can be substituted by halogen atoms, etc.

[0221] The number of substituents in phenyl and phenoxy compounds can be one or more.

[0222] When there are two or more substituents in phenyl and phenoxy groups, they can be substituents of the same type or substituents of different types.

[0223] As R in equation (2) 11 and R 12 Preferably, it is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0224] For example, in polymer (C), the structure represented by formula (1) is connected to the structure represented by formula (2) as shown in formula (11) below. In other words, for example, polymer (C) contains the structure represented by formula (11) below.

[0225]

[0226] In equation (11), R 1 It represents a hydrogen atom, a protecting group of an imide group that can be deprotected by a base, or a protecting group of an imide group that can be deprotected by an acid.

[0227] R 2 It represents a divalent group with 1 to 6 carbon atoms.

[0228] R 11 and R 12 Each of the following can be independently represented as a substituted alkyl group, a substituted phenyl group, or a substituted phenoxy group having 1 to 10 carbon atoms.

[0229] R a It represents a hydrogen atom or a methyl group.

[0230] * indicates a connection key.

[0231] R in equation (11) 2 Examples of divalent groups can be listed, such as those represented by the following formula (L).

[0232]

[0233] (In formula (L), Y) 1 It indicates a single bond or an alkylene group having 1 to 6 carbon atoms.

[0234] Y 2It represents a single bond, -C(=O)-, -O-, -C(=O)O-, -OC(=O)-, or -OCH2CH(OH)-.

[0235] Y 3 It indicates a single bond or an alkylene group having 1 to 6 carbon atoms.

[0236] *1 indicates a bonding bond to a carbon atom.

[0237] *2 indicates a bonding bond connected to a nitrogen atom.

[0238] Among them, Y 1 Y 2 and Y 3 The total number of carbon atoms is 1 to 6.

[0239] Examples of divalent groups represented by formula (L) include the following groups.

[0240]

[0241] (In the formula, * represents a linking bond. *1 represents a linking bond with a carbon atom. *2 represents a linking bond with a nitrogen atom.)

[0242] In this invention, examples of alkylene groups having 1 to 6 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, and 1,6-hexylene.

[0243] R in equation (11) 2 The preferred form is methylene.

[0244] R in equation (11) 11 and R 12 Preferably, it is an alkyl group having 1 to 10 carbon atoms and a substituted phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms and a phenyl group, and particularly preferably a methyl group and a phenyl group.

[0245] The polymer (C) is preferably a polymer obtained by hydrosilylation reaction between a "compound having Si-H groups" and a "compound having carbon-carbon unsaturated bonds capable of hydrosilylation".

[0246] Hydrosilylation reactions, for example, are carried out in the presence of platinum group metal catalysts.

[0247] Such platinum-based metal catalysts are catalysts used to promote the hydrosilylation reaction between "the Si-H group of a compound having a Si-H group" and "the carbon-carbon unsaturated bond (e.g., carbon-carbon double bond) of a compound having a carbon-carbon unsaturated bond".

[0248] Specific examples of platinum-based metal catalysts include platinum black, platinum(IV) chloride, chloroplatinic acid, reactants of chloroplatinic acid with monohydric alcohols, coordination compounds of chloroplatinic acid with olefins, platinum diacetate, etc., but are not limited to these.

[0249] Examples of platinum-olefin coordination compounds include, for example, divinyltetramethyldisiloxane-platinum coordination compounds (e.g., Karstedt catalysts), but are not limited to these.

[0250] There is no particular limitation on the amount of platinum group metal catalyst used in the hydrosilylation reaction.

[0251] -Compounds with Si-H groups-

[0252] There are no particular restrictions on compounds having Si-H groups, as long as they have at least one Si-H group.

[0253] Compounds containing Si-H groups can have one or more Si-H groups.

[0254] As compounds having Si-H groups, the preferred compounds are those represented by formula (2A), cyclic siloxane compounds represented by formula (2B), and sesquioxanes having Si-H groups.

[0255]

[0256] In equation (2A), R 11 and R 12 Each of the following can be independently represented as a substituted alkyl group, a substituted phenyl group, or a substituted phenoxy group having 1 to 10 carbon atoms.

[0257] X 1 Represents a single bond, an organic group having 1 to 10 carbon atoms, or a group represented by the following formula (2A-1).

[0258]

[0259] In equation (2A-1), R 13 and R 14 Each of the following groups independently represents a substituted alkyl group, a substituted phenyl group, or a substituted phenoxy group with 1 to 10 carbon atoms. n represents an integer from 0 to 10. * represents a connecting bond.

[0260]

[0261] In equation (2B), R 15 Each of the following can independently represent a substituted alkyl group, a substituted phenyl group, or a substituted phenoxy group with 1 to 10 carbon atoms. m represents an integer from 3 to 6.

[0262] As R in equation (2A) 11 and R 12 Preferably, it is an alkyl group having 1 to 10 carbon atoms and a substituted phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms and a phenyl group, and particularly preferably a methyl group and a phenyl group.

[0263] As X in equation (2A) 1 Organic groups with 1 to 10 carbon atoms, such as alkylene groups with 1 to 6 carbon atoms, and phenylene groups, can be listed as examples.

[0264] As R in equation (2A-1) 13 and R 14 Preferably, it is an alkyl group having 1 to 10 carbon atoms and a substituted phenyl group, more preferably an alkyl group having 1 to 6 carbon atoms and a phenyl group, and particularly preferably a methyl group and a phenyl group.

[0265] For example, n in equation (2A-1) can be 0, 1, 2, 3, 4, etc.

[0266] Examples of compounds represented by formula (2A) include the following compounds.

[0267]

[0268] As R in equation (2B) 15 Preferably, it is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

[0269] Examples of cyclic siloxane compounds 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.

[0270] Furthermore, 2,4,6,8,-tetramethylcyclotetrasiloxane is represented by the following formula.

[0271]

[0272] Silsesquioxanes are network polymers or polyhedral atomic clusters obtained by hydrolyzing trifunctional silanes. Silsesquioxanes with random, ladder, or cage-like structures are known.

[0273] As for cage-like structures, examples include complete cage-like structures and incomplete cage-like structures.

[0274] The number of Si-H groups in a silsesquioxane with Si-H groups can be one or more.

[0275] Si-H group silsesquioxanes can be exemplified by cage-like silsesquioxanes represented by the following formulas (SQ1) to (SQ7).

[0276]

[0277]

[0278]

[0279] In formulas (SQ1) to (SQ7), R independently represents a hydrogen atom, an alkyl group with 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 or phenyl group with 1 to 6 carbon atoms).

[0280] Among them, each of formulas (SQ1) to (SQ7) has at least one Si-H group.

[0281] Examples of silsesquioxanes having Si-H groups include the following compounds.

[0282]

[0283] There are no particular restrictions on the molecular weight of compounds with Si-H groups; for example, 100 to 1500 can be listed.

[0284] -Compounds with carbon-carbon unsaturated bonds-

[0285] Compounds containing carbon-carbon unsaturated bonds possess carbon-carbon unsaturated bonds capable of undergoing hydrosilylation. Examples of carbon-carbon unsaturated bonds capable of undergoing hydrosilylation include carbon-carbon double bonds and carbon-carbon triple bonds.

[0286] There is no particular limitation on the number of carbon-carbon unsaturated bonds in compounds that can undergo hydrosilylation; there can be one or more.

[0287] Compounds having carbon-carbon unsaturated bonds, preferably compounds represented by the following formula (1A).

[0288]

[0289] In formula (1A), R 1 It represents a hydrogen atom, a protecting group of an imide group that can be deprotected by a base, or a protecting group of an imide group that can be deprotected by an acid.

[0290] R 2 It represents a divalent group with 1 to 6 carbon atoms.

[0291] R 3 It represents a hydrogen atom, a protecting group of an imide group that can be deprotected by a base, a protecting group of an imide group that can be deprotected by an acid, or a group represented by the following formula (1A-1).

[0292] R a [Represents a hydrogen atom or a methyl group].

[0293]

[0294] In formula (1A-1), R 4 R represents a divalent group with 1 to 6 carbon atoms. b * indicates a hydrogen atom or a methyl group. * indicates a connecting bond.

[0295] As R in equation (1A) 1 and R 3 Specific examples of the protecting groups of imide groups that can be deprotected by a base can be listed in formula (1) with R. 1 Specific examples of the protecting groups of imide groups that can be deprotected by a base.

[0296] As R in equation (1A) 1 and R 3 Specific examples of protecting groups of imide groups that can be deprotected by acid can be listed in formula (1) with R. 1 Specific examples of protecting groups of imide groups that can be deprotected by acids.

[0297] As R in equation (1A) 2 Examples of divalent groups can be cited, for instance, those represented by the formula (L).

[0298] As R in equation (1A) 2 For specific examples, one could cite R in equation (11) as an example. 2 The specific examples listed in the explanation.

[0299] As R in equation (1A-1) 4 Examples of divalent groups can be cited, such as those represented by the formula (L).

[0300] As R in equation (1A-1) 4 For specific examples, one could cite R in equation (11) as an example. 2 The specific examples listed in the explanation.

[0301] R in equation (1A) 2 The preferred form is methylene.

[0302] R in equation (1A) 3 When the basis is expressed in equation (1A-1), R in equation (1A-1) 4 The preferred component is methylene.

[0303] Examples of compounds represented by formula (1A) include the following compounds.

[0304]

[0305]

[0306] When polymer (C) is obtained by hydrosilylation, the compounds having carbon-carbon unsaturated bonds may include compounds other than those represented by formula (1A) that have carbon-carbon unsaturated bonds.

[0307] Compounds having carbon-carbon unsaturated bonds other than those represented by formula (1A) can be listed, for example, compounds represented by formula (X) below.

[0308]

[0309] In formula (X), R 21 It represents a hydrogen atom or a methyl group.

[0310] X 2 This indicates an m-valent organic group.

[0311] m represents an integer from 1 to 3.

[0312] For X in equation (X) 2 There are no particular restrictions on the molecular weight; examples include 100 to 500.

[0313] In formula (X) 2 For example, it does not have the following isocyanuric acid structure.

[0314]

[0315] [In the formula, * represents a connector].

[0316] The compound represented by formula (X) is preferably free of ester bonds from the viewpoint of the heat resistance of polymer (C).

[0317] In equation (X), X 2 Preferably, it has an aromatic ring. The aromatic ring can be an aromatic hydrocarbon ring or an aromatic heterocycle.

[0318] Compounds represented by formula (X) can be exemplified by compounds represented by formula (X1) below.

[0319]

[0320] In formula (X1), R 21 Each can be used independently to represent a hydrogen atom or a methyl group.

[0321] X 2 [This indicates a divalent organic group having an aromatic ring].

[0322] Examples of compounds represented by formula (X) include the following compounds.

[0323]

[0324] Polymer (C), for example, having structural units represented by the following formula (Y).

[0325] Polymers having structural units represented by formula (Y) can, for example, be obtained by hydrosilylation between a compound having Si-H groups comprising a compound represented by formula (2A) and a compound having carbon-carbon unsaturated bonds comprising a compound represented by formula (1A).

[0326]

[0327] In formula (Y), R 1 It represents a hydrogen atom, a protecting group of an imide group that can be deprotected by a base, or a protecting group of an imide group that can be deprotected by an acid.

[0328] R 2 It represents a divalent group with 1 to 6 carbon atoms.

[0329] R 11 and R 12 Each of the following can be independently represented as a substituted alkyl group, a substituted phenyl group, or a substituted phenoxy group having 1 to 10 carbon atoms.

[0330] R a [Represents a hydrogen atom or a methyl group].

[0331] R in equation (Y) 1 R in equations (1) and (11) 1 They have the same meaning.

[0332] R in equation (Y) 2 , and R in equation (11) 2 They have the same meaning.

[0333] R in equation (Y) 11 R 12 and X 1 R in equations (2) and (2A) respectively 11 and R 12and X in equation (2A) 1 They have the same meaning.

[0334] There are no particular limitations on the weight-average molecular weight of polymer (C), but it is preferably 1,000 to 50,000, more preferably 1,500 to 30,000. Furthermore, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0335] As polymer (C), it can also be the polymer described in International Publication No. 2024 / 117235 [International Application (PCT / JP2023 / 42991)].

[0336] The contents of this application are incorporated herein to the same extent as all explicit descriptions.

[0337] <<<Polymer (D)>>>

[0338] Polymer (D) is a polymer containing the structural unit represented by the following formula (1).

[0339]

[0340] In equation (1), R 1 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 2 R represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 3 R represents an alkyl group having 1 to 10 carbon atoms that can be substituted, or an aromatic hydrocarbon group that can be substituted. 2 and R 3 It can also be used with R 2 and R 3 The carbon atoms and oxygen atoms between them form a ring, which may also contain heteroatoms in addition to the oxygen atoms.

[0341] As R 1 Alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl.

[0342] As R 2 Alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl.

[0343] As R 3 Substituents in alkyl groups having 1 to 10 carbon atoms can be substituted, such as halogen atoms, alkoxy groups having 1 to 6 carbon atoms, aromatic groups, etc. Examples of aromatic groups include aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, etc.

[0344] As R 3Substituents in substituted aromatic hydrocarbon groups can be exemplified by, for example, halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, etc.

[0345] In this invention, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms can be listed as halogen atoms.

[0346] R 2 and R 3 It can also be used with R 2 and R 3 The carbon and oxygen atoms together form a ring, which may also contain heteroatoms in addition to the oxygen atoms.

[0347] Examples of such rings include 4-membered rings to 7-membered rings.

[0348] Examples of such rings include cyclic ethers, lactone rings, and cyclic carbonates.

[0349] Examples of heteroatoms that a ring can contain include, such as oxygen, nitrogen, and sulfur atoms.

[0350] As R 1 The preferred atoms are hydrogen atoms and methyl groups.

[0351] As R 2 Methyl or ethyl compounds are preferred.

[0352] As R 3 Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[0353] The inventors believe that the acetal structure of formula (1) acts as a protecting group for the carboxyl group, imparting solubility of the polymer (D) to the solvent, while improving the coatability of the composition used to form a coating for foreign matter removal.

[0354] On the other hand, during the formation of the coating film from the composition used to form a coating film for foreign matter removal, carboxyl groups are generated by deactivating the acetal structure (e.g., by heat or a catalyst). The generated carboxyl groups impart solvent resistance to the coating film by reacting with each other or by reacting with a crosslinking agent in the presence of a crosslinking agent. Furthermore, the generated carboxyl groups make the coating film easier to remove with a removal liquid.

[0355] Therefore, the coating film obtained from the composition for forming a foreign matter removal film exhibits good solvent resistance. Furthermore, the coating film obtained from the composition for forming a foreign matter removal film can be removed by a removal liquid.

[0356] Therefore, the composition of the present invention for forming a coating for foreign matter removal is a composition that can easily prevent foreign matter residues on a substrate, and is a composition that can obtain a coating with good solvent resistance and easy removability.

[0357] As structural units represented by equation (1), the following structural units can be listed as examples. In the following structural units, R... 1 The alkyl group represents 1 to 3 carbon atoms, preferably hydrogen atoms or methyl groups.

[0358]

[0359]

[0360]

[0361] The structural unit represented by formula (1) is derived from, for example, the compound represented by formula (1A) below.

[0362]

[0363] In formula (1A), R 1 R 2 and R 3 , respectively with R in equation (1) 1 R 2 and R 3 (Same meaning)

[0364] Polymer (D) may also contain structural units other than those represented by formula (1).

[0365] Examples of such structural units include those derived from (meth)acrylate compounds, (meth)acrylamide compounds, or styrene compounds.

[0366] Furthermore, in this invention, (meth)acrylate compounds refer to acrylate compounds or methacrylate compounds. The same applies to (meth)acrylamide compounds.

[0367] As structural units derived from (meth)acrylate compounds, examples of structural units represented by the following formula (2-1) can be cited.

[0368] As structural units derived from (meth)acrylamide compounds, examples of structural units represented by the following formula (2-2) can be cited.

[0369] As structural units derived from styrene compounds, examples of structural units represented by the following formulas (2-3) can be cited.

[0370]

[0371] In equations (2-1) to (2-3), R 11 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 12 R represents a monovalent group with 1 to 20 carbon atoms. 13 R represents a monovalent group consisting of 1 to 20 hydrogen or carbon atoms. 14 Each group independently represents a halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, or a monovalent group with 1 to 10 carbon atoms. m represents an integer from 0 to 5.

[0372] R 12 and R 13 The number of carbon atoms in it can be 1 to 20 or 1 to 10.

[0373] R 12 and R 13 Monovalent groups containing 1 to 20 carbon atoms may also contain heteroatoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0374] R 12 and R 13 The monovalent group containing 1 to 20 carbon atoms can also have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings.

[0375] As R 12 and R 13 The monovalent groups containing 1 to 20 carbon atoms may also include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, etc.

[0376] As R 12 and R 13 Monovalent groups with 1 to 20 carbon atoms, such as substituted alkyl groups and substituted aromatic groups, can be listed as examples.

[0377] Examples of substituents in substituted alkyl groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, and substituted aromatic groups.

[0378] Examples of substituents in substituted aromatic groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, alkyl groups with 1 to 6 carbon atoms that can be substituted by halogen atoms, and alkoxy groups with 1 to 6 carbon atoms that can be substituted by halogen atoms.

[0379] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, and butyl.

[0380] Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0381] R 14 The monovalent groups containing 1 to 10 carbon atoms can also have heteroatoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0382] R 14 The monovalent groups containing 1 to 10 carbon atoms may also include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, etc.

[0383] As R 14 The monovalent groups with 1 to 10 carbon atoms in the group can be exemplified by alkyl groups with 1 to 6 carbon atoms that can be substituted by halogen atoms, alkoxy groups with 1 to 6 carbon atoms that can be substituted by halogen atoms, etc.

[0384] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, and butyl.

[0385] Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0386] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, 4-hydroxyphenyl acrylate, anthracene methyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantane acrylate, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0387] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 4-hydroxyphenyl acrylate, anthracene methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantane methacrylate, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0388] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N-(4-hydroxyphenyl)acrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0389] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N-(4-hydroxyphenyl)methacrylamide, N,N-dimethylmethacrylamide, and N-anthraylmethacrylamide.

[0390] Specific examples of styrene compounds include styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc., but are not limited to these.

[0391] 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.

[0392] 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, vinylanthracene, etc.

[0393] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but these are not limited to.

[0394] The viewpoint is that the effects of the present invention can be well obtained without particularly limiting the lower limit of the molar ratio of the structural unit represented by formula (1) to all structural units of polymer (D). 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.

[0395] The viewpoint is that the effect of the present invention can be well obtained without particularly limiting the upper limit of the molar ratio of the structural unit represented by formula (1) to all structural units of polymer (D). 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.

[0396] The lower limit of the molar ratio of the total structural units derived from (meth)acrylate compounds, structural units derived from (meth)acrylamide compounds, and structural units derived from styrene compounds (hereinafter sometimes referred to as "total structural units (2)") relative to all structural units of polymer (D) is not particularly limited, and the effect of the present invention can be well obtained. The molar ratio of total structural units (2) is preferably greater than 0 mol%, more preferably 10 mol% or more.

[0397] From the viewpoint that the effects of the present invention can be well obtained without particularly limiting the upper limit of the molar ratio of the total structural unit (2) to all structural units of the polymer, the molar ratio of the total structural unit (2) is preferably 60 mol% or less, more preferably 45 mol% or less.

[0398] The view that the effect of the present invention can be well obtained without any particular limitation on the molar ratio of the total of the structural units represented by formula (1) and the total of the total structural units (2) relative to all structural units of polymer (D), is preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%.

[0399] Polymer (D) can be a homopolymer or a copolymer. When the polymer is a copolymer, it can be a random copolymer or a block copolymer.

[0400] There are no particular restrictions on the manufacturing method of polymer (D).

[0401] The polymer (D) can be manufactured by polymerizing monomers using conventional methods such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, in which a polymerization initiator can be used, for example, to polymerize the monomers.

[0402] Organic peroxides and diazo compounds can be used as polymerization initiators.

[0403] There are no particular limitations on the weight-average molecular weight of polymer (D), but it is preferably 5,000 to 75,000, more preferably 10,000 to 50,000. Furthermore, the weight-average molecular weight is the value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0404] As polymer (D), it may also be the polymer described in Japanese Patent Application 2024-3840 and International Application PCT / JP2025 / 258.

[0405] The contents of this application are incorporated herein to the same extent as all explicit descriptions.

[0406] <<<Polymer (E)>>>

[0407] The polymer (E) has a partial structure represented by the following formula (A).

[0408]

[0409] In formula (A), R 11 Represents a single bond, or a divalent group with 1 to 4 carbon atoms. R 12 * indicates a hydrogen atom, hydroxyl group, or methyl group. * indicates a connecting bond.

[0410] The polymer (E) imparts solvent resistance and easy removal to the coating obtained from the composition used to form a coating for foreign matter removal by having a partial structure represented by formula (A).

[0411] The polymer (E) preferably has structural units represented by the following formula (A-1). Furthermore, for example, a portion of the structure represented by formula (A) is a part of the structural unit represented by the following formula (A-1).

[0412]

[0413] (In formula (A-1), A) 1 A 2 A 3 A 4 A 5 and A 6 Each of these can be used independently to represent a hydrogen atom, a methyl group, or an ethyl group; Q represents a divalent organic group. R 11 Represents a single bond, or a divalent group with 1 to 4 carbon atoms. R 12 (Represents a hydrogen atom, hydroxyl group, or methyl group).

[0414] <<R 11 >>

[0415] In equations (A) and (A-1), R 11 It represents a single bond or a divalent group with 1 to 4 carbon atoms.

[0416] R 11 It has 1 to 4 carbon atoms, which can be 1 to 3, 1 or 2, or even 1.

[0417] R 11 Examples include divalent hydrocarbon groups with 1 to 4 carbon atoms that can be substituted by hydroxyl groups.

[0418] R 11 When it has a hydroxyl group, R 11 The number of hydroxyl groups, for example, R 11 The number of carbon atoms it possesses is below.

[0419] From the viewpoint that the effects of the present invention are well obtained, R 11It represents a divalent group with 1 to 4 carbon atoms, and the divalent group preferably has a hydroxyl group.

[0420] From the viewpoint that the effects of the present invention are well obtained, R 11 More preferred representation

[0421] -CH(OH)-.

[0422] <<R 12 >>

[0423] In equations (A) and (A-1), R 12 It represents a hydrogen atom, a hydroxyl group, or a methyl group, preferably a hydrogen atom or a hydroxyl group.

[0424] The partial structure represented by equation (A) can be exemplified by the following structures.

[0425]

[0426] * indicates a connection key.

[0427] <<Q>>

[0428] In formula (A-1), Q represents a divalent organic group. There are no particular limitations on the divalent organic group, but it is preferred to be 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 nitrogen atoms, oxygen atoms, sulfur atoms, etc.

[0429] There is no particular limitation on the number of carbon atoms in the divalent organic group, but it is preferred to have 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.

[0430] From the viewpoint of achieving the desired effect of the present invention, Q is preferably expressed as either of the following formulas (A-11) and (A-12).

[0431]

[0432] (In formula (A-11), X) 1 This represents a divalent group represented by the following formula (A-11-1), formula (A-11-2), or formula (A-11-3). 1 and Z 2 Each can be represented independently as a single bond or a divalent group as shown in the following formula (A-11-4). * indicates a linking bond.

[0433] In equation (A-12), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring. n1 and n2 independently represent 0 or 1, respectively. * indicates a connecting bond.

[0434]

[0435] (In formulas (A-11-1)~(A-11-3), R) 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms into which an oxygen or sulfur atom may be inserted, an alkenyl group with 2 to 10 carbon atoms into which an oxygen or sulfur atom may be inserted, an alkynyl group with 2 to 10 carbon atoms into which an oxygen or sulfur atom may be inserted, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from the group consisting of an alkyl group with 1 to 6 carbon atoms, a halogen atom, an alkoxy group with 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group with 1 to 6 carbon atoms. R 1 With R 2 They can also connect to each other to form rings with 3 to 6 carbon atoms. R 3 With R 4 They can also connect to form rings with 3 to 6 carbon atoms. * indicates a linking bond. *1 indicates a linking bond to a carbon atom. *2 indicates a linking bond to a nitrogen atom.

[0436]

[0437] (In formula (A-11-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. *3 represents a bonding bond to a nitrogen atom. *4 represents a bonding bond to a carbon atom.)

[0438] Q in equation (A-12) 1 It is preferred to be expressed by any of the following formulas (A-12-1) to (A-12-4).

[0439]

[0440] (In formulas (A-12-1)~(A-12-4), R) 31 ~R 36 Each of these groups independently represents a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkoxy group with 2 to 6 carbon atoms, an alkenyloxy group with 2 to 6 carbon atoms, an alkynyloxy group with 2 to 6 carbon atoms, an acyl group with 2 to 6 carbon atoms, an aryloxy group with 6 to 12 carbon atoms, an arylcarbonyl group with 7 to 13 carbon atoms, or an aralkyl group with 7 to 13 carbon atoms. * indicates a connecting bond.

[0441] In equation (A-12-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. R 31 When there are two or more R's 31 They can be the same or different.

[0442] In formula (A-12-2), Z 1This indicates a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group with 1 to 6 carbon atoms. n12 and n13 independently represent integers from 0 to 4. R 32 When there are two or more R's 32 They can be the same or different. R 33 When there are two or more R's 33 They can be the same or different.

[0443] In formula (A-12-3), Y 1 and Y 2 Each can be used independently to represent a single bond or an alkylene group with 1 to 6 carbon atoms. n14 represents an integer from 0 to 4. R 34 When there are two or more R's 34 They can be the same or different.

[0444] In formula (A-12-4), Z 2 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n15 and n16 independently represent integers from 0 to 4. R 35 When there are two or more R's 35 They can be the same or different. R 36 When there are two or more R's 36 (They can be the same or different).

[0445] The Q in equation (A-11) can be represented by, for example, the following structures.

[0446]

[0447]

[0448]

[0449]

[0450]

[0451]

[0452]

[0453]

[0454]

[0455] * indicates a connection key.

[0456] When the polymer (E) has a structural unit represented by formula (A-1), there is no particular limitation on the mass ratio of the structural unit represented by formula (A-1) in the polymer, but it is preferably 50% to 100% by mass, more preferably 75% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0457] There are no particular limitations on the manufacturing method of polymer (E). For example, a method can be listed that involves reacting a dicarboxylic acid represented by formula (A1) with a diepoxide represented by formula (A2). In this case, a polymer having the structural unit represented by formula (A-1) can be obtained.

[0458] Catalysts for activating epoxy groups include, for example, quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide; and quaternary ammonium salts such as benzyltriethylammonium chloride. Regarding the amount of catalyst used, an appropriate amount can be selected from 0.1% to 10% by mass relative to the total mass of the polymer feedstock used in the reaction. The optimal conditions for the polymerization reaction can be selected, for example, from 80 to 160°C and 2 to 50 hours.

[0459]

[0460] (In formula (A1), R) 11 and R 12 respectively with R in equation (A-1) 11 and R12 (Same meaning)

[0461] Dicarboxylic acids represented by formula (A1) can be exemplified by tartaric acid, malic acid, hydroxymalonic acid, citrate, dihydroxymalonic acid, mucin, etc.

[0462]

[0463] (In formula (A2), A) 1 A 2 A 3 A 4 A 5 A 6 And Q, respectively, are related to A in equation (A-1) 1 A 2 A 3 A 4 A 5 A 6 (Same meaning as Q).

[0464] There are no particular limitations on the weight-average molecular weight of the polymer (E), but it is preferably 700 to 15,000, more preferably 900 to 10,000. Furthermore, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0465] As a polymer (E), it may also be the polymer described in Japanese Patent Application 2024-3808 and International Application PCT / JP2025 / 273.

[0466] The contents of this application are incorporated herein to the same extent as all explicit descriptions.

[0467] <<<Polymer (F)>>>

[0468] Polymer (F) is cellulose and its derivatives.

[0469] Cellulose is a polysaccharide obtained by linking D-glucose through β-1,4 glycosidic bonds.

[0470] Examples of cellulose and its derivatives include cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, etc.

[0471] Hydroxypropyl cellulose is particularly preferred among these.

[0472] The structure of hydroxypropyl cellulose is shown below, for example.

[0473]

[0474] R=H or CH2CH(OH)CH3

[0475] <<<Polymer (G)>>>

[0476] Polymer (G) consists of cyclodextrin and its derivatives.

[0477] Cyclodextrins are cyclic oligosaccharides with a cyclic structure in which D-glucose is linked by α-1,4 glycosidic bonds. Examples of cyclodextrins include those containing 6 to 12 glucose units.

[0478] Specifically, examples of cyclodextrins include α-cyclodextrin with 6 D-glucose molecules forming a cyclic structure, β-cyclodextrin with 7 D-glucose molecules forming a cyclic structure, γ-cyclodextrin with 8 D-glucose molecules forming a cyclic structure, derivatives of these cyclodextrins, and polymers that partially or entirely incorporate cyclodextrin structures.

[0479] As derivatives of cyclodextrin, they are compounds in which some or all of the hydroxyl groups at the 2, 3, and 6 positions of glucose in the above-mentioned cyclodextrin are replaced by other functional groups. Examples include alkyl derivatives, hydroxyalkyl derivatives, alkoxy derivatives, sulfonyl alkyl ether derivatives, or sugar-linked derivatives.

[0480] As derivatives of cyclodextrin, specific examples include hydroxymethyl cyclodextrin, hydroxyethyl cyclodextrin, hydroxypropyl cyclodextrin, hydroxybutyl cyclodextrin, dimethyl cyclodextrin, trimethyl cyclodextrin, diethyl cyclodextrin, triethyl cyclodextrin, carboxymethyl cyclodextrin, glucosyl cyclodextrin, maltosyl cyclodextrin, dismaltosyl cyclodextrin, monochlorotriazine cyclodextrin, and cyclodextrin epichlorohydrin polymers.

[0481] More specific compounds include, for example, sugar-linked derivatives, alkylated cyclodextrins, hydroxyalkylated cyclodextrins, sulfonyl alkyl ether derivatives, and alkoxylated cyclodextrins.

[0482] Examples of sugar-linked derivatives include glucosyl-α-cyclodextrin, glucosyl-β-cyclodextrin, and glucosyl-γ-cyclodextrin.

[0483] 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.

[0484] 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, and 2,3-dihydroxypropyl-γ-cyclodextrin.

[0485] Examples of carboxyalkylated cyclodextrins include O-carboxymethyl-α-cyclodextrin, O-carboxymethyl-β-cyclodextrin, and O-carboxymethyl-γ-cyclodextrin.

[0486] Examples of sulfonyl alkyl ether derivatives include sulfonyl butyl ether-α-cyclodextrin, sulfonyl butyl ether-β-cyclodextrin, and sulfonyl butyl ether-γ-cyclodextrin.

[0487] Examples of alkoxylated cyclodextrins include methoxycyclodextrin and ethoxycyclodextrin.

[0488] Among these, hydroxyalkylated cyclodextrins are particularly preferred, and 2-hydroxypropyl-β-cyclodextrins are even more preferred.

[0489] The structure of 2-hydroxypropyl-β-cyclodextrin is shown below.

[0490]

[0491] <<<Polymer (H)>>>

[0492] Polymer (H) is a polymer having structural units derived from hydroxyalkyl esters of (meth)acrylate.

[0493] Polymers having structural units derived from hydroxyalkyl (meth)acrylates include, for example, homopolymers of hydroxyalkyl (meth)acrylates, copolymers of hydroxyalkyl (meth)acrylates with other monomers, etc.

[0494] Examples of carbon atoms in the hydroxyalkyl group of (meth)acrylate include 1 to 6.

[0495] Examples of hydroxyalkyl esters of (meth)acrylate include 2-hydroxyethyl ester of (meth)acrylate, 2-hydroxybutyl ester of (meth)acrylate, 3-hydroxypropyl ester of (meth)acrylate, 4-hydroxybutyl ester of (meth)acrylate, and 6-hydroxyhexyl ester of (meth)acrylate.

[0496] Furthermore, (meth)acrylates refer to acrylates and / or methacrylates.

[0497] There are no particular restrictions on other monomers used in copolymerization, such as (meth)acrylic acid, (meth)acrylate compounds, (meth)acrylamide compounds, vinyl compounds, styrene compounds, acrylonitrile, etc.

[0498] Specific examples of (meth)acrylate compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-hexyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, anthracene methyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantane (meth)acrylate, glycidyl (meth)acrylate, etc.

[0499] Specific examples of (meth)acrylamide compounds include, for example, (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-benzyl (meth)acrylamide, N-phenyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-anthrayl (meth)acrylamide, etc.

[0500] Specific examples of vinyl compounds 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, vinylanthracene, etc.

[0501] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc.

[0502] There are no particular restrictions on the composition ratio of other monomers when the copolymer is formed.

[0503] Among these, homopolymers of 2-hydroxyethyl acrylate are particularly preferred.

[0504] <<<Compound (A)>>>

[0505] Compound (A) is tannic acid.

[0506] Tannic acid is represented by the following structure.

[0507]

[0508] <<<Polymer (I)>>>

[0509] Polymer (I) is a polymer with a lactam structure.

[0510] Polymers having a lactam structure include, for example, polymers of γ-lactams with a 5-membered ring lactam in the side chain, or polymers of δ-lactams with a 6-membered ring lactam in the side chain.

[0511] Examples of lactam structures include pyrrolidone rings and alkylated pyrrolidone rings in which at least a portion of the hydrogen atoms are substituted by alkyl groups. Examples of alkyl groups include alkyl groups having 1 to 6 carbon atoms.

[0512] Examples of polymers with a lactam structure include polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, and vinylpyrrolidone-vinyl acetate copolymer.

[0513] The structures of polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, and vinylpyrrolidone-vinyl acetate copolymers are shown below, for example.

[0514]

[0515] Polymers with a lactam structure are also commercially available. Examples of commercially available polyvinylpyrrolidone include K-30 and K-90 (Nippon Shokubai Co., Ltd.). Examples of commercially available alkylated polyvinylpyrrolidone include Ganex P-904 LC (Ashland Inc.). Examples of commercially available vinylpyrrolidone-vinyl acetate copolymers include PVP / VA S-630 (Ashland Inc.).

[0516] There are no particular limitations on the weight-average molecular weight of the compound or polymer, but it is preferably 700 to 5,000,000, more preferably 900 to 100,000. Furthermore, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0517] There is no particular limitation on the content of "compound or polymer" in the composition used to form a coating for foreign matter removal, but it is preferably 70% to 99.9% by mass, more preferably 80% to 99.5% by mass, and particularly preferably 90% to 99% by mass, relative to the composition of the film.

[0518] <<Removal Solution>>

[0519] As a removal liquid, there are no particular limitations as long as it can remove the coating formed by the composition used to form a coating for foreign matter removal.

[0520] The coating is formed, for example, on a semiconductor substrate. Removal here refers to removal from the semiconductor substrate.

[0521] Here, methods of removal include dissolution removal and peeling removal. Peeling removal can be exemplified by, for example, peeling off from the adhered material by swelling.

[0522] The removal solution may contain water or organic solvents.

[0523] The removal solution can also be a removal solution containing more than 50% by mass of organic solvent.

[0524] The removal solution can also be water. As for water, there are no particular restrictions as long as it is water commonly used in semiconductor manufacturing, such as pure water, ultrapure water, and ion-exchanged water.

[0525] 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 ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0526] Examples of removal solutions include alkaline removal solutions and acidic removal solutions.

[0527] Alkaline removal solutions contain alkalis. Examples of alkalis include ammonia, inorganic alkali compounds, quaternary ammonium hydroxide, amines, and hydrazine.

[0528] Alkaline removal solutions can also be developing solutions or cleaning solutions used in semiconductor manufacturing processes, and they are alkaline. For example, NMD-3 (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be listed as a developing solution.

[0529] Examples of inorganic alkali compounds include potassium hydroxide, sodium hydroxide, lithium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, and potassium borate.

[0530] Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and choline.

[0531] Examples of amines include ethanolamine, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, ethylenediamine, etc.

[0532] Examples of hydrazine include hydrazine monohydrate.

[0533] In addition, the alkaline removal solution can also be SC-1 (ammonia-hydrogen peroxide solution).

[0534] Acid removal solutions contain acids. Examples of acids include inorganic acids and organic acids. Examples of inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and hydrofluoric acid.

[0535] Acid removal solutions can be, for example, aqueous solutions containing dilute hydrofluoric acid.

[0536] In addition, the acid removal solution may be, for example, an aqueous solution containing sulfuric acid and hydrogen peroxide, or an aqueous solution containing acetic acid or a chelating agent. Examples of chelating agents include organic acids, salts of organic acids, amino acids, and derivatives of amino acids.

[0537] <Solvent>

[0538] Solvents contained in the composition for forming a coating for removing foreign matter may include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0539] These solvents can be used alone or in combination of two or more.

[0540] Furthermore, it can be used in combination with high-boiling-point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate.

[0541] Compositions for forming coatings for foreign matter removal, for example, can be easily prepared by uniformly mixing the components and can be dissolved in a suitable solvent for use in solution form.

[0542] The composition for forming a coating film for foreign matter removal prepared in this manner is preferably filtered using a filter or the like with a pore size of about 0.2 μm before use. The composition for forming a coating film for foreign matter removal prepared in this manner also exhibits excellent long-term storage stability at room temperature.

[0543] The proportion of solid components in the composition used to form a coating for foreign matter removal is not particularly limited as long as all components dissolve uniformly, for example, 0.5 to 50% by mass, or, for example, 1 to 30% by mass. Here, solid components refer to the components remaining after removing the solvent components from all components of the composition used to form a coating for foreign matter removal.

[0544] In this invention, foreign matter refers to any substance other than the target object adhering to the substrate. In the manufacture of semiconductor devices, foreign matter is an unwanted substance. Examples of foreign matter include particles adhering to the wafer, metallic impurities, etching residue, and adhesive layer peeling residue.

[0545] The coating for removing foreign matter is particularly preferred in the process of bonding wafers together with an adhesive and then peeling off the adhesive. The coating of the present invention is formed in advance before the adhesive is applied, and is used to remove foreign matter (adhesive layer residue) after the wafer bonding and peeling process.

[0546] The coating for foreign matter removal can also be used to remove foreign matter that is already present on a semiconductor substrate.

[0547] The term "dissolution of the coating in the removal solution" refers to the coating dissolving in the removal solution and disappearing from the substrate or other adhered material when subjected to immersion, cleaning, or other processes. In this invention, "dissolution" refers to the removal of at least 90% (i.e., the remaining film thickness is less than 10% of the initial film thickness), or at least 95% (i.e., the remaining film thickness is less than 5% of the initial film thickness), or at least 99% (i.e., the remaining film thickness is less than 1% of the initial film thickness), and most preferably 100% (i.e., the remaining film thickness is 0% of the initial film thickness (no remaining film)).

[0548] The composition preferably contains at least one of a crosslinking agent and an additive.

[0549] <<Cross-linking agent>>

[0550] As a component of the membrane, it may also contain, for example, a cross-linking agent.

[0551] There are no particular restrictions on crosslinking agents.

[0552] Crosslinking agents have a structure different from coordination compounds, "compounds or polymers".

[0553] The preferred crosslinking agent is an amino resin crosslinking agent or a phenolic resin crosslinking agent.

[0554] Amino resin crosslinking agents are addition condensations of amino compounds such as melamine or guanidine with formaldehyde.

[0555] Phenolic resin crosslinking agents refer to the addition condensation products of compounds with phenolic hydroxyl groups and formaldehyde.

[0556] Examples of crosslinking agents include compounds having two or more of the following structures.

[0557]

[0558] (In the structure, R) 101 * indicates a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 2 to 6 carbon atoms. * indicates a connecting bond.

[0559] Connecting bonds include, for example, bonds to nitrogen atoms or carbon atoms that form aromatic hydrocarbon rings.

[0560] R 101 Preferably, it contains hydrogen atoms, methyl groups, ethyl groups, or groups represented by the following structures.

[0561]

[0562] (In the structure, R) 102 * indicates a hydrogen atom, methyl group, or ethyl group. * indicates a connecting bond.

[0563] The crosslinking agent is preferably a melamine compound, guanidine compound, glycourea compound, urea compound, or a compound with phenolic hydroxyl groups. These can be used alone or in combination of two or more.

[0564] Examples of melamine compounds include hexahydroxymethyl melamine, hexamethoxymethyl melamine, compounds of hexahydroxymethyl melamine in which 1 to 6 hydroxymethyl groups are methoxymethylated, or mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds of hexahydroxymethyl melamine in which 1 to 6 hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0565] Examples of guanidine compounds include tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds of tetrahydroxymethylguanidine with 1 to 4 hydroxymethyl groups methoxymethylated, or mixtures thereof, tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds of tetrahydroxymethylguanidine with 1 to 4 hydroxymethyl groups acyloxymethylated, or mixtures thereof.

[0566] Examples of glycourea compounds include tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds of tetrahydroxymethylglycourea with 1 to 4 hydroxymethyl groups methoxymethylated, or mixtures thereof, and compounds of tetrahydroxymethylglycourea with 1 to 4 hydroxymethyl groups acylmethylated, or mixtures thereof.

[0567] In addition, glycourea compounds, for example, may be glycourea derivatives represented by the following formula (1E).

[0568]

[0569] (In formula (1E), the four R1s independently represent methyl or ethyl, and R2 and R3 independently represent hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, or phenyl groups).

[0570] Examples of compounds represented by formula (1E-1) to (1E-6) below can be cited as glycourea derivatives represented by the formula (1E).

[0571]

[0572] The glycourea derivative represented by formula (1E) can be obtained, for example, by reacting the glycourea derivative represented by formula (2E) with at least one compound represented by formula (3d).

[0573]

[0574] (In formula (2E), R2 and R3 independently represent hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, or phenyl groups, respectively, and R4 independently represents alkyl groups with 1 to 4 carbon atoms).

[0575]

[0576] (In formula (3d), R1 represents methyl or ethyl).

[0577] Examples of compounds represented by formula (2E) as glycourea derivatives include those represented by formulas (2E-1) to (2E-4). Further examples of compounds represented by formula (3d) include those represented by formulas (3d-1) and (3d-2).

[0578]

[0579]

[0580] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds of tetrahydroxymethylurea with one to four hydroxymethyl groups methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0581] Examples of compounds having phenolic hydroxyl groups include compounds represented by formulas (G-1) or (G-2) below.

[0582]

[0583] In equations (G-1) and (G-2), Q 1 This indicates a single bond or an organic group with an m1 valence.

[0584] R 1 and R 4 They respectively represent alkyl groups having 2 to 10 carbon atoms, or alkyl groups having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms.

[0585] R 2 and R 5 These represent hydrogen atoms or methyl groups, respectively.

[0586] R 3 and R 6 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0587] n1 represents an integer 1 ≤ n1 ≤ 3, n2 represents an integer 2 ≤ n2 ≤ 5, n3 represents an integer 0 ≤ n3 ≤ 3, n4 represents an integer 0 ≤ n4 ≤ 3, and also represents an integer 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0588] n5 represents an integer 1 ≤ n5 ≤ 3, n6 represents an integer 1 ≤ n6 ≤ 4, n7 represents an integer 0 ≤ n7 ≤ 3, n8 represents an integer 0 ≤ n8 ≤ 3, and also represents an integer 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0589] m1 represents an integer from 2 to 10.

[0590] In addition, compounds having phenolic hydroxyl groups can be listed as, for example, compounds represented by the following formula (G-3) or formula (G-4).

[0591] The compound represented by formula (G-1) or formula (G-2) may be a compound obtained by reacting "the compound represented by formula (G-3) or formula (G-4) below" with "an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms".

[0592]

[0593] In equations (G-3) and (G-4), Q 2 This indicates a single bond or an m2 valence organic group.

[0594] R 8 R 9 R 11 and R 12 These represent hydrogen atoms or methyl groups, respectively.

[0595] R 7 and R 10 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0596] n9 represents an integer where 1 ≤ n9 ≤ 3, and n 10 It means 2≤n 10 Integers ≤ 5, n 11 It means 0≤n 11 Integers ≤3, n 12 It means 0≤n 12 Integers ≤ 3, where 3 ≤ (n ≤ 9 + n) 10 +n 11 +n 12 Integers ≤ 6.

[0597] n 13 This means 1 ≤ n 13 Integers ≤3, n 14 This means 1 ≤ n 14 Integers ≤ 4, n 15 It means 0≤n 15 Integers ≤3, n 16 It means 0≤n 16 Integers ≤ 3, and represent 2 ≤ (n 13 +n14 +n 15 +n 16 Integers ≤ 5.

[0598] m2 represents an integer from 2 to 10.

[0599] Q 2 The m2 valence organic groups in the text can be exemplified by, for example, m2 valence organic groups with 1 to 4 carbon atoms.

[0600] Compounds represented by formula (G-1) or formula (G-2) can be exemplified by the following compounds.

[0601]

[0602]

[0603]

[0604]

[0605]

[0606] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0607]

[0608]

[0609] The above-mentioned compounds are available as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. Examples of such products include, for instance, the trade name TMOM-BP of Asahi Organic Materials Co., Ltd.

[0610] Among these, glycourea compounds are particularly preferred, specifically tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, a compound of tetrahydroxymethylglycourea with 1 to 4 hydroxymethyl groups methoxymethylated, or a mixture thereof, a compound of tetrahydroxymethylglycourea with 1 to 4 hydroxymethyl groups acylmethylated, or a mixture thereof; more preferably tetramethoxymethylglycourea.

[0611] There are no particular restrictions on the molecular weight of the crosslinking agent, but it is preferably below 1,000.

[0612] The content of the crosslinking agent, relative to 100 parts by weight of the "compound or polymer", is, for example, 5 to 70 parts by weight, or 5 to 60 parts by weight, preferably 5 to 45 parts by weight. From the viewpoint of the curing degree of the coating film and the prevention of miscibility with the adhesive layer, the content of the crosslinking agent is preferably 5 parts by weight or more relative to 100 parts by weight of the "compound or polymer", and from the viewpoint of solubility in the removal liquid, it is preferably 70 parts by weight or less relative to 100 parts by weight of the "compound or polymer".

[0613] <<Additives>>

[0614] The membrane composition may include curing catalysts, surfactants, tackifiers, rheology modifiers, and silica particles as additives.

[0615] Curing catalysts, including thermal acid-generating agents and photo-acid-generating agents, can all be used, with thermal acid-generating agents being preferred.

[0616] Examples of heat-generating acid agents include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-hydroxybenzenesulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzene disulfonic 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.

[0617] Examples of photoacid-generating agents include onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0618] Examples of ononium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0619] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0620] Examples of disulfonyl diazonium compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium.

[0621] The solidification catalyst can be used alone or in combination of two or more.

[0622] When using a curing catalyst, the proportion of the curing catalyst relative to the crosslinking agent is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0623] Compositions used to form coatings for foreign matter removal may contain surfactants. Examples of surfactants include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and nonionic surfactants such as polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate. (Eftop) Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tokem Products Co., Ltd., trade name), Megaface F171, F173 (manufactured by DIC Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd., trade name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name). The amount of these surfactants added is typically 0.2% by mass or less, preferably 0.1% by mass or less, in the total composition used to form a coating for foreign matter removal. These surfactants can be added individually or in combination of two or more.

[0624] Compositions for forming coatings for foreign matter removal may contain silica particles. Examples of silica particles include, for instance, organosilicon powder having a specific average particle size value, or silica sol containing silica having a specific average particle size value.

[0625] Specific examples of silicone powders include, but are not limited to, the KMP series of silicone powders manufactured by Shin-Etsu Chemical Industry Co., Ltd., such as KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030.

[0626] 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), 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), and NPC-ST- 30 (n-propyl cellulose solvent dispersed silica sol), PGM-ST (1-methoxy-2-propanol dispersed silica sol), DMAC-ST (dimethylacetamide dispersed silica sol), XBA-ST (xylene-n-butanol mixed solvent dispersed silica sol), trade names EAC-ST (ethyl acetate dispersed silica sol), PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol), MEK-ST (methyl ethyl ketone dispersed silica sol), MEK-ST-UP (methyl ethyl ketone dispersed silica sol), MEK-ST-L (methyl ethyl ketone dispersed silica sol), MIBK-ST (methyl isobutyl ketone dispersed silica sol), etc., but not limited to these.

[0627] (Coating for foreign object removal)

[0628] The foreign matter removal coating of the present invention is formed from the "composition for forming a foreign matter removal coating" of the present invention.

[0629] The foreign matter removal coating of the present invention can be formed, for example, as follows.

[0630] The composition for forming a foreign matter removal film of the present invention is applied onto a semiconductor substrate using a suitable coating method such as a spinner, coater, or immersion apparatus, and then the foreign matter removal film is formed by baking. The 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.

[0631] From the viewpoint of better achieving the effects of the present invention, the coating for removing foreign matter is preferably in contact with a metal. Examples of metals include, for instance, "coordinating metals".

[0632] The metal that the coating contacts for removing foreign matter is, for example, a metal present on a semiconductor substrate. Such a metal can be, for example, a metal used as an electrode. Examples of electrodes include bumps.

[0633] The thickness of the coating for foreign matter removal is typically 5 nm to 3 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0634] The dissolution rate of the foreign matter removal coating to the removal solution, measured in terms of the rate of film thickness reduction, is, for example, 0.1 nm to 50 nm per second, preferably 0.2 nm to 40 nm per second, and more preferably 0.3 nm to 20 nm per second. If the dissolution rate is lower than this, the time required for the foreign matter removal coating to remove it increases, resulting in reduced productivity.

[0635] The foreign matter removal coating formed by the composition of the present invention for forming a foreign matter removal coating film can have its dissolution rate with the removal liquid controlled by changing the baking conditions during formation. Under a given baking time, a higher baking temperature results in a foreign matter removal coating film with a lower dissolution rate with the removal liquid.

[0636] After the film is formed, it can be exposed to remove foreign matter. Exposure can be performed on the entire wafer or through a mask with a specific pattern. Exposure can be performed using KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), and F2 excimer lasers (wavelength 157nm), etc. Post-exposure baking (PEB) can also be performed as needed after exposure.

[0637] (Semiconductor substrate)

[0638] The semiconductor substrate of the present invention has the foreign matter removal coating of the present invention thereon.

[0639] From the viewpoint of better achieving the effects of the present invention, the coating for removing foreign matter preferably comes into contact with a metal. Examples of metals include, for instance, "coordinating metals".

[0640] The coating removes foreign matter from the metal it contacts, such as a metal present on a semiconductor substrate. This metal could be, for example, a metal used as an electrode. Examples of electrodes include bumps.

[0641] As the main material constituting the entire semiconductor substrate, there are no particular limitations on any material that can be used for this purpose, such as silicon, silicon carbide, and compound semiconductors.

[0642] There are no particular limitations on the shape of the semiconductor substrate, such as a disk shape. Furthermore, the surface of a disk-shaped semiconductor substrate does not necessarily have to be perfectly circular. For example, the outer periphery of the semiconductor substrate may have a straight section called an orientation flat or a notch.

[0643] The thickness of the disc-shaped semiconductor substrate can be appropriately specified according to the intended use of the semiconductor substrate, and is not particularly limited, for example, 500~1,000 μm.

[0644] The diameter of the disc-shaped semiconductor substrate can be appropriately specified according to the intended use of the semiconductor substrate, and there is no particular limitation, for example, it is 100~1,000 mm.

[0645] Semiconductor substrates may also have electrodes. Electrodes are, for example, bumps. Bumps refer to protruding terminals.

[0646] When a semiconductor substrate has electrodes, the semiconductor substrate has electrodes on the supporting substrate side.

[0647] In semiconductor substrates, electrodes are typically formed on the surface where circuitry is formed. Circuitry can be single-layered or multi-layered. There are no particular restrictions on the shape of the circuitry.

[0648] In a semiconductor substrate, the side opposite to the side with electrodes (the back side) is the side to be processed.

[0649] There are no particular restrictions on the material, size, shape, structure, or density of the electrodes on a semiconductor substrate.

[0650] Examples of bumps include spherical bumps, printed bumps, stud bumps, and plated bumps.

[0651] The height, radius, and spacing of the bumps are usually determined by the conditions of bump height of about 1~200μm, bump radius of 1~200μm, and bump spacing of 1~500μm.

[0652] Materials used for bumps include, for example, low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. Bumps can be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy platings.

[0653] In addition, the bumps may also have a stacked structure comprising a metal layer consisting of at least any of these components.

[0654] An example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0655] (Manufacturing method of the processed semiconductor substrate)

[0656] The method for manufacturing the processed semiconductor substrate of the present invention includes a first step, a second step, a third step, and a fourth step.

[0657] The first step is to manufacture a laminate by bonding the semiconductor substrate of the present invention (a semiconductor substrate having the foreign matter removal coating of the present invention) and the support substrate through the foreign matter removal coating.

[0658] The second process is the process of processing the laminated body.

[0659] The third process is the process of peeling the supporting substrate from the laminate.

[0660] The fourth step is to clean the semiconductor substrate or support material with a removal solution and remove the coating used for foreign matter removal.

[0661] In the first embodiment, the heat-resistant coating of the present invention for removing foreign matter is used as the coating for removing foreign matter.

[0662] <Step 1>

[0663] The first step is to manufacture a laminate by bonding the semiconductor substrate of the present invention (a semiconductor substrate having the foreign matter removal coating of the present invention) and the support substrate through the foreign matter removal coating.

[0664] As a support substrate, any component that can support a semiconductor substrate when processing a laminate (such as a semiconductor substrate) is not particularly limited, and examples include flexible support substrates and glass support substrates.

[0665] There are no particular limitations on the shape of the supporting substrate; for example, a disc shape can be cited.

[0666] The thickness of the disc-shaped support substrate can be appropriately specified according to the size of the semiconductor substrate, and is not particularly limited, for example, 500~1,000 μm.

[0667] The diameter of the disc-shaped support substrate can be appropriately specified according to the size of the semiconductor substrate, and is not particularly limited, for example, 100~1,000 mm.

[0668] One example of a supporting substrate is a glass wafer with a diameter of 300 mm and a thickness of about 700 μm.

[0669] The first step is preferably a step of manufacturing a laminate by bonding a semiconductor substrate and a support substrate together with a foreign matter removal coating and an adhesive layer.

[0670] As an adhesive layer, there are no particular restrictions as long as the supporting substrate can be peeled off from the laminate in the third process.

[0671] The adhesive layer can be formed using known adhesives and methods. Examples of adhesives include coating-type temporary wafer adhesives as described in International Publication No. 2015 / 190438, temporary bonding materials from Thin Materials (Nissan Chemical Co., Ltd.), temporary wafer bonding materials for semiconductors manufactured by Toray Industries, Ltd., WaferBOND (registered trademark) CR-200, and HT-10.10 (manufactured by Brewer Science). Tape-type adhesives can also be used (e.g., back-side grinding tapes, such as 3M™ temporary fixing adhesive tape ATT-4025 (3M...). (Made by Japan Co., Ltd.), E series, P series, S series (Made by Lintec Co., Ltd., trade name), Icros tape (registered trademark) (Made by Mitsui Chemicals TOHCELLO Co., Ltd.), dicing tape (e.g., solvent-resistant dicing tape (Made by Nitto Denko Co., Ltd., trade name), temperature-sensitive adhesive tape Intelimer (registered trademark) (Made by Nitta Co., Ltd.), Intelimer (registered trademark) tape (Made by Anchor Techno Co., Ltd.), etc.).

[0672] It can also be a wafer adhesive used in specific wafer operating systems (such as Zero Newton (registered trademark) (manufactured by Tokyo Ohka Kogyo Co., Ltd.)).

[0673] In addition, the adhesive layer may be a layer referred to as an adhesive layer, adhesive tape, or temporary fixing material. Examples of such layers include the adhesive layer described in International Publication No. 2021 / 225163, the adhesive layer described in International Publication No. 2022 / 065376, and the photocurable adhesive layer described in International Publication No. 2022 / 065388.

[0674] For example, back-grinding tape consists of a substrate film, an adhesive layer, and a release film. Regarding the substrate film, soft thermoplastic films such as ethylene-vinyl acetate copolymer (EVA) have been used previously, but rigid stretch films such as polyethylene terephthalate (PET) have also been explored to improve wafer support. Further improvements have been made, with reports of laminated designs using two films with different elastic moduli, such as laminates of PET and ethylene-based copolymers, or laminates of polypropylene (PP) and ethylene-based copolymers.

[0675] Adhesives are generally acrylic-based. Acrylic adhesives are known to be cross-linked by reacting acrylic copolymers, primarily composed of monomers with low glass transition temperatures such as butyl acrylate, with a curing agent. Since back-grinding tapes are used to adhere to the circuit surface of a wafer, contamination from the adhesive after tape peeling is a concern. Therefore, it has been reported that emulsion-based adhesives were designed to remove adhesive residue even if it remains, but complete removal is difficult. Therefore, the foreign matter removal coating of this application, after forming on the circuit surface, forms an adhesive layer that allows for complete removal of foreign matter (adhesive layer residue) from subsequent peeling processes by cleaning with a removal solution, without damaging the wiring of the circuit or other components.

[0676] There are no particular limitations on the thickness of the adhesive layer, for example, it is 5μm to 500μm, preferably 10μm to 300μm, more preferably 20μm to 200μm, and particularly preferably 30μm to 150μm.

[0677] Before the first step, the adhesive layer may be formed on the foreign matter removal coating, on the support substrate, or on the semiconductor substrate.

[0678] When an adhesive layer is not used, the support substrate preferably has an adhesive layer. The support substrate may have, for example, a flexible support and an adhesive layer. Examples of flexible supports include polyimide films. The adhesive layer is not particularly limited and may include layers formed from the adhesive.

[0679] Bonding, for example, is performed under heat and pressure.

[0680] There are no special restrictions on heating temperature as long as it is above room temperature (25℃). Generally, it is above 50℃ to avoid overheating. It is usually below 220℃, and below 170℃ in a single state sample.

[0681] As long as the substrate and layers can be bonded together without damaging them, the load is not particularly limited, for example, 0.5~50kN.

[0682] In addition, the pressure applied during bonding can be, for example, 0.1~20 N / mm.2 Furthermore, pressure refers to the pressure per unit area (mm²) of the substrate adjacent to the tool applying the load. 2 The force (load) that is subjected to.

[0683] As long as the substrate and the layer can be bonded together without damaging the substrate or the layer, there is no particular limitation on the pressure reduction, for example, 10~10,000 Pa.

[0684] When using an adhesive layer, the layer structure of the laminate manufactured in the first step can be semiconductor substrate / foreign matter removal coating / adhesive layer / support substrate, with the aim of removing foreign matter from the semiconductor substrate together with the foreign matter removal coating and the foreign matter as peeling residue of the adhesive layer in the fourth step.

[0685] Furthermore, when using an adhesive layer, with the aim of removing foreign matter from the coating used for foreign matter removal along with the foreign matter that serves as peeling residue of the adhesive layer in the fourth step, so that the support substrate is free of foreign matter, the layer structure of the laminate manufactured in the first step can also be semiconductor substrate / adhesive layer / foreign matter removal coating / support substrate. In this case, the reuse of the support substrate becomes easy.

[0686] In addition, the layer structure of the laminate manufactured in the first process for the purpose of ensuring that there are no foreign objects on the semiconductor substrate and the support substrate can also be a semiconductor substrate / foreign object removal coating / adhesive layer / foreign object removal coating / support substrate.

[0687] The laminate manufactured in the first step may also have a laser release layer between the semiconductor substrate and the support substrate. When the laminate has a laser release layer, in the third step, for example, the support substrate can be peeled off from the laminate by irradiating the laser release layer with a laser. The laser irradiates the laser release layer, for example, from the support substrate side which is laser-transmissive.

[0688] When the laminate has a laser release layer, the layer structure of the laminate manufactured in the first step is such that the foreign matter removal coating and the foreign matter that is the release residue of the laser release layer and the adhesive layer are removed together in the fourth step, so that the semiconductor substrate is free of foreign matter. For example, the layer structure of the laminate can also be semiconductor substrate / foreign matter removal coating / laser release layer / adhesive layer / support substrate.

[0689] When the laminate has a laser release layer, the layer structure of the laminate manufactured in the first step is such that the foreign matter removal coating and the foreign matter, which are the release residues of the laser release layer and the adhesive layer, are removed together in the fourth step, so that the support substrate is free of foreign matter. For example, the laminate structure can be semiconductor substrate / adhesive layer / laser release layer / foreign matter removal coating / support substrate. In this case, the reuse of the support substrate becomes easy.

[0690] Furthermore, after the support substrate is peeled off from the laminate by irradiating the laser release layer with a laser, if laser release residue remains on the adhesive layer, foreign matter originating from the laser release layer may sometimes adhere to the semiconductor substrate or support substrate, or the cleaning time of the adhesive layer may become longer. To prevent these situations, the layer structure of the laminate manufactured in the first step for the purpose of removing laser release residue from the adhesive layer may be semiconductor substrate / adhesive layer / foreign matter removal coating / laser release layer / support substrate, or semiconductor substrate / laser release layer / foreign matter removal coating / adhesive layer / support substrate.

[0691] <Second Process>

[0692] The second process is the process of processing the laminated body.

[0693] There are no particular restrictions on the processing in the second step. Examples include polishing of the semiconductor substrate, forming of through electrodes on the semiconductor substrate, and connection processing between the semiconductor substrate and the second semiconductor substrate. The processing in the second step may include one or more of these processes.

[0694] <<Grinding Process>>

[0695] The polishing process of semiconductor substrates is not particularly limited, for example, any process that polishes the side of the semiconductor substrate opposite to the side of the coating for removing foreign matter, so as to make the semiconductor substrate thinner. Examples include physical polishing using abrasives or polishing stones.

[0696] The polishing process can be performed using a conventional polishing apparatus used in the polishing of semiconductor substrates (e.g., silicon wafers).

[0697] By grinding, the thickness of the semiconductor substrate is reduced, resulting in a semiconductor substrate that has been thinned to the desired thickness. There is no particular limitation on the thickness of the thinned semiconductor substrate; for example, it can be 30~300μm or 30~100μm.

[0698] <<Through-Electrode Formation Process>>

[0699] For example, sometimes through electrodes are formed on a polished semiconductor substrate to enable conduction between multiple thinned semiconductor substrates when stacking multiple thinned semiconductor substrates.

[0700] Therefore, a through electrode forming process can be included after the polishing process and before the stripping process to form a through electrode on the polished semiconductor substrate.

[0701] There are no particular limitations on the method of forming through electrodes on a semiconductor substrate. Examples include forming through holes and filling the formed through holes with conductive material.

[0702] Through-holes can be formed, for example, by photolithography.

[0703] The through-hole is filled with a conductive material, for example, by plating.

[0704] Furthermore, in the second process, a through electrode formation process can be performed instead of a grinding process.

[0705] <<Connection Processing>>

[0706] The connection process is, for example, the process of connecting a semiconductor substrate to a second semiconductor substrate.

[0707] There are no particular limitations on the second semiconductor substrate, and examples such as those listed in the description of the semiconductor substrate can be included.

[0708] The connection process can be performed, for example, under heating. Alternatively, the connection process can be performed, for example, under pressure.

[0709] There are no particular restrictions on the heating temperature; for example, 100℃ to 350℃.

[0710] In the connection process, for example, wiring on a semiconductor substrate is electrically connected to wiring on a second semiconductor substrate. Such a connection is performed, for example, by connecting the ends of the wiring to each other.

[0711] There are no particular restrictions on the material, shape, or structure of wiring in semiconductor substrates.

[0712] There are no particular restrictions on the material, shape, or structure of the wiring in the second semiconductor substrate.

[0713] <Step 3>

[0714] The third step is the process of peeling the support substrate from the laminate. This third step can be referred to as the process of separating the semiconductor substrate from the support substrate.

[0715] Peeling methods include, but are not limited to, solvent peeling, peeling by light irradiation (laser, non-laser), mechanical peeling by means of a tool with sharp points (so-called debonding machine), and peeling by manually pulling apart the semiconductor substrate and the support substrate.

[0716] In particular, when the laminate contains an adhesive layer, and the adhesive layer is formed by using an organic resin that absorbs light and produces a modified form necessary for improved peelability, the adhesive layer can be peeled off, for example, by irradiating a laser from the support substrate side.

[0717] Laser irradiation can be performed using ultraviolet light with wavelengths of 190nm to 400nm or 190nm to 600nm (e.g., 308nm, 355nm, 532nm).

[0718] Stripping can be achieved by setting the processing energy density of pulsed laser to 50~500 mJ / cm². 2 Proceed from left to right.

[0719] When a laminate contains an adhesive layer, delamination typically occurs within the adhesive layer or at the interface between the adhesive layer and an adjacent substrate or layer (e.g., a coating for foreign matter removal). Delamination within the adhesive layer refers to cracking of the adhesive layer.

[0720] <Step 4>

[0721] The fourth step involves cleaning the semiconductor substrate or support substrate with a cleaning solution and removing foreign matter with a coating.

[0722] On a semiconductor substrate that has been peeled off from a support substrate, for example, there may be a coating for removing foreign matter. Therefore, this coating for removing foreign matter is removed with a removal solution.

[0723] In the fourth step, for example, foreign matter is removed together with a foreign matter removal coating.

[0724] In the fourth step, for example, foreign matter that serves as peeling residue of the adhesive layer is removed together with a foreign matter removal coating.

[0725] The removal liquid can be exemplified by, for example, those listed in the description of the composition for forming a coating film for removing foreign matter according to the present invention.

[0726] There are no particular restrictions on the cleaning method. Examples include immersing a semiconductor substrate with a coating for removing foreign matter in a cleaning solution, and spraying a cleaning solution onto a semiconductor substrate with a coating for removing foreign matter.

[0727] There are no particular restrictions on cleaning conditions, such as the temperature of the cleaning solution being 5℃ to 50℃. Furthermore, the cleaning time can be appropriately selected from 2 to 500 seconds or 3 to 400 seconds.

[0728] For example, a coating for removing foreign matter is preferably easily peeled off at room temperature (e.g., 25°C) using a commonly used 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0729] The following diagram illustrates an example of a method for manufacturing a processed semiconductor substrate.

[0730] First, prepare the semiconductor substrate 11 ( Figure 1A ).

[0731] Next, a foreign matter removal coating 12 is formed on the semiconductor substrate 11. Figure 1B ).

[0732] Next, Figure 1B The "semiconductor substrate 11 having a foreign matter removal coating 12" and the "support substrate 14 having a flexible support 14A and an adhesive layer 14B" shown are configured such that the foreign matter removal coating 12 and the adhesive layer 14B are bonded together facing each other. Figure 1C ).

[0733] Next, the side of the semiconductor substrate 11 opposite to the side of the foreign matter removal coating 12 is ground to thin the semiconductor substrate 11. Figure 1D ).

[0734] Next, the support substrate 14 is separated from the semiconductor substrate 11. Figure 1E and Figure 1F ).

[0735] On the separated foreign matter removal coating 12, there is a peeling residue 14C of adhesive layer 14B remaining. Figure 1F Therefore, the foreign matter is removed by the removal solution using the coating 12. Figure 1G In this way, stripping residue 14C, which is a foreign object, can be prevented from remaining on the semiconductor substrate 11.

[0736] The following figure illustrates another example of a method for manufacturing a processed semiconductor substrate.

[0737] First, prepare a semiconductor substrate 1 with wiring 1A. Figure 2A ).

[0738] Next, a foreign matter removal coating 2 is formed on the semiconductor substrate 1. Figure 2B ).

[0739] On the other hand, a glass substrate 4 on which an adhesive layer 3 is formed is prepared. Figure 2C ).

[0740] Then, Figure 2B The semiconductor substrate 1 shown has a foreign matter removal coating 2 and Figure 2C The glass substrate 4 shown, which has an adhesive layer 3, is configured such that the foreign matter removal coating 2 and the adhesive layer 3 are bonded together facing each other. Figure 2D and Figure 2E ).

[0741] Next, the side of the semiconductor substrate 1 opposite to the side of the foreign matter removal coating 2 is ground to thin the semiconductor substrate 1. Figure 2F Then expose wiring 1A.

[0742] Next, Figure 2F The laminate shown and the second semiconductor substrate 5 having wiring 5A are configured such that the "side of the semiconductor substrate 1 opposite to the side of the foreign matter removal coating 2" and the "side of the second semiconductor substrate 5 exposing the wiring 5A" are facing each other for bonding. Figure 2G and Figure 2H ).

[0743] Next, the adhesive layer 3 and the glass substrate 4 are separated from the semiconductor substrate 1. Figure 2I Separation can be easily achieved, for example, by irradiating the adhesive layer 3 with a laser, thereby reducing the adhesion of the adhesive layer 3.

[0744] On the separated foreign matter removal coating 2, there is a peeling residue 3A of the adhesive layer 3 remaining. Figure 2I and Figure 2J Therefore, the foreign matter is removed by the removal solution using coating 2. Figure 2K In this way, stripping residue 3A, which is a foreign object, can be prevented from remaining on the semiconductor substrate 1.

[0745] The method for manufacturing the processed semiconductor substrate of the present invention is suitable for use in hybrid bonding of semiconductor substrates to connect each other.

[0746] <Other Implementation Forms>

[0747] One embodiment of the present invention is a method for removing foreign matter already present on a semiconductor manufacturing substrate. For example, as described in International Publications Nos. 2017 / 056746 and 2020 / 008965, a substrate processing film forming composition and substrate processing method are disclosed, which efficiently remove small particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface. The composition of the present invention for forming a coating film for foreign matter removal can also be used in the same methods and applications as described above.

[0748] A specific example of the above is explained below. In this applicable example, the composition of the present invention for forming a coating film for foreign matter removal is used as a composition for forming a coating film on a semiconductor substrate. First, a coating film forming process is performed. That is, the composition for forming a coating film for foreign matter removal is applied to the semiconductor substrate to form a coating film. The semiconductor substrate may be an unprocessed state or a so-called full-coverage substrate (planar) with various films formed on it. For manufacturing semiconductor devices, it may be shaped with wiring, etc. Examples of coating methods include spin coating, casting coating, roll coating, etc. Next, by heating (baking) and / or reducing pressure on the coating film, part or all of the solvent contained in the coating film is effectively removed, thereby promoting the curing and / or solidification of the solid components contained in the coating film. "Curement" as used here refers to solidification, and "curing" refers to the increase in molecular weight due to the linkage of molecules (e.g., crosslinking or polymerization). The coating film is thus formed. At this point, particles, such as those attached to circuits on a semiconductor substrate, are efficiently separated from the circuits by being encapsulated in the coating. Next, a coating removal process is performed. That is, the coating is completely removed from the semiconductor substrate by supplying a removal solution that dissolves the coating onto the coating. As a result, the particles are removed from the semiconductor substrate along with the coating.

[0749] Example

[0750] The following examples and embodiments illustrate the content of the present invention, but the present invention is not limited to these.

[0751] <Example 1>

[0752] 1.36 g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.) was added to 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, and then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a composition for forming a coating for foreign matter removal.

[0753] <Example 2>

[0754] A composition for forming a coating for foreign matter removal was prepared by adding 1.31g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.09g of salicylaldehyde oxime (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0755] <Example 3>

[0756] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of tartaric acid (Tokyo Kasei Corporation), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0757] <Example 4>

[0758] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of citric acid (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0759] <Example 5>

[0760] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of 3-methyl-1-phenyl-5-pyrazolone (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0761] <Example 6>

[0762] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of L-ascorbic acid (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0763] <Example 7>

[0764] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of gallophenol FZ (Honshu Chemical Industry Co., Ltd., structure below), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0765]

[0766] <Example 8>

[0767] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of curcumin (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0768] <Example 9>

[0769] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of malonic acid (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0770] <Example 10>

[0771] A composition for forming a coating for foreign matter removal was prepared by adding 1.33 g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 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, and then filtering it through a PTFE syringe filter with a pore size of 0.20 μm.

[0772] <Example 11>

[0773] A composition for forming a coating for foreign matter removal was prepared by adding 1.33 g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06 g of 1,2,3,4-cyclopentanetetracarboxylic acid (Tokyo Chemical Industry Co., Ltd.), and 98.60 g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20 μm.

[0774] <Example 12>

[0775] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of thiazole-4-carboxylic acid (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0776] <Example 13>

[0777] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of gallic acid (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0778] <Example 14>

[0779] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of methyl gallate (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0780] <Example 15>

[0781] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of pyridinecarboxylic acid (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0782] <Example 16>

[0783] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of N,N'-bis(salicylylene)-1,3-propanediamine (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0784] <Example 17>

[0785] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of tris(2-hydroxyethyl isocyanurate) (Tokyo Chemical Industry Co., Ltd.), and 98.60g of propylene glycol monomethyl ether, and then filtering it through a PTFE syringe filter with a pore size of 0.20μm.

[0786] <Example 18>

[0787] A composition for forming a coating for foreign matter removal was prepared by adding 1.33g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.), 0.06g of Olfine E1010 (Nikshin Chemical Industry Co., Ltd., structure below), and 98.60g of propylene glycol monomethyl ether, and then filtering it using a PTFE syringe filter with a pore size of 0.20μm.

[0788]

[0789] n, m: Average number of moles added (10)

[0790] <Comparative Example 1>

[0791] A composition for forming a coating for foreign matter removal was prepared by adding 98.60 g of propylene glycol monomethyl ether to 1.40 g of poly(p-hydroxystyrene) (VP-8000, Nippon Soda Co., Ltd.) and then filtering it using a PTFE syringe filter with a pore size of 0.20 μm.

[0792] [Alkali solubility test]

[0793] As an evaluation of the solubility in alkaline solutions, the compositions prepared in Examples 1 to 18 and Comparative Example 1 for forming a coating film for foreign matter removal were coated onto copper vapor-deposited substrates with a film thickness of 150 nm. The coatings were then heated at 160°C for 1 minute to form a film with a thickness of 40 nm. The copper substrates coated with the compositions for forming a coating film for foreign matter removal were immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds, rinsed with pure water, and the presence or absence of a coating film was visually evaluated. The results of the solubility test in alkaline solutions are shown in Table 1. Furthermore, the evaluation criterion "0" indicates good alkaline solubility and excellent removal performance in alkaline solutions. The evaluation criterion "△" indicates alkaline solubility and is considered acceptable.

[0794] (Evaluation Criteria)

[0795] 〇: No coating residue remains

[0796] △: Only a portion of the coating remains.

[0797] ×: Residual coating

[0798]

[0799] Explanation of symbols in attached drawings

[0800] 1: Semiconductor substrate

[0801] 1A: Wiring

[0802] 2: Coating for foreign matter removal

[0803] 3: Adhesive layer

[0804] 4: Glass substrate

[0805] 5: Second semiconductor substrate

[0806] 5A: Wiring

[0807] 11: Semiconductor substrate

[0808] 12: Coating for foreign matter removal

[0809] 14: Supporting substrate

[0810] 14A: Flexible support

[0811] 14B: Adhesive layer

[0812] 14C: Stripping residue

Claims

1. A composition for forming a coating film for foreign matter removal, wherein the composition can form a coating film removable by a removal liquid, the composition comprising film-forming components and a solvent. The membrane components contain coordination compounds.

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

3. The composition of claim 1, wherein the coordinating compound is at least one of (I) to (IV) below. (I) Compounds having two or more hydroxyl groups, (II) Compounds having two or more carboxyl groups, (III) Compounds with heterocyclic structures, and (IV) Alkyne diol compounds.

4. The compound of claim 1, wherein the membrane constituents contain a compound or polymer as a component other than the coordinating compound.

5. The composition of claim 4, wherein the compound or polymer has at least one of a hydroxyl group, a carboxyl group, and a heterocyclic group.

6. The composition of claim 1, wherein the content of the coordination compound is 1% to 10% by mass relative to the membrane constituents.

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

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

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

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

11. A semiconductor substrate having the foreign matter removal coating of claim 10.

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

13. A method for manufacturing a processed semiconductor substrate, comprising the following steps: Step 1: The semiconductor substrate and the support substrate as described in claim 11 are bonded together by the foreign matter removal coating to manufacture a laminate; Step 2: Processing the laminated body; Step 3: Peeling the support substrate from the laminate; and Step 4: Clean the semiconductor substrate or the support substrate with a removal solution to remove the foreign matter removal coating.

14. The method of manufacturing a processed semiconductor substrate as claimed in claim 13, wherein the foreign matter removal coating is in contact with copper in the laminate.

15. The method for manufacturing a processed semiconductor substrate as claimed in claim 13, wherein in the fourth step, foreign matter is removed together with the foreign matter removal coating.

16. The method for manufacturing a processed semiconductor substrate as claimed in claim 13, wherein the first step is a step of bonding the semiconductor substrate and the support substrate together via the foreign matter removal coating and adhesive layer to manufacture a laminate.

17. The method for manufacturing a semiconductor substrate as claimed in claim 16, wherein in the fourth step, foreign matter that serves as peeling residue of the adhesive layer is removed together with the foreign matter removal coating.

18. The method of manufacturing a processed semiconductor substrate as claimed in claim 13, wherein the processing includes the step of connecting the semiconductor substrate to a second semiconductor substrate.

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