Method for manufacturing laminated body and method for manufacturing semiconductor element

Abstract

A method for manufacturing a laminate, comprising: a first step of applying a surface modifier containing a polysiloxane and a solvent on a semiconductor substrate, and then performing a firing to crosslink the polysiloxane, thereby obtaining a surface modification layer precursor; and a second step of thinning the surface modification layer precursor by contacting the surface modification layer precursor with a thinning solution, thereby obtaining a surface modification layer having a film thickness of 5 nm or less, the polysiloxane having an aromatic hydrocarbon ring and an RO-group (R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having a total of 2 to 6 carbon atoms) bonded to the aromatic hydrocarbon ring, the laminate having the surface modification layer and the semiconductor substrate, the laminate being used for photolithography in which an unexposed portion of a resist film containing an organic resin is developed with an organic solvent.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a laminate on which a negative resist pattern is formed. Furthermore, this invention relates to a method for manufacturing semiconductor devices. Background Technology

[0002] Photolithography, using resist compositions, has been a standard technique in semiconductor device manufacturing. In recent years, with the increasing integration of semiconductor devices, there has been a demand for finer patterns, such as wiring. This miniaturization has led to the use of shorter wavelengths of light, including far-ultraviolet light, vacuum ultraviolet light, electron beams (EB), and X-rays. Most recently, however, operations have been conducted using short-wavelength light, such as KrF excimer lasers (248 nm wavelength) and ArF excimer lasers (193 nm wavelength), to form resist patterns.

[0003] Along with this, the diffuse reflection of active light from the semiconductor substrate and the effects of standing waves have become major problems. Therefore, in order to solve this problem, methods of setting an anti-reflective film (bottom anti-reflective coating: BARC) between the resist and the semiconductor substrate have been extensively studied. As such an anti-reflective film, considering its ease of use, organic anti-reflective films formed from compositions containing polymers with light-absorbing groups (chromophores) have been extensively studied (for example, Patent Document 1).

[0004] On the other hand, while EUV (extreme ultraviolet light, wavelength 13.5 nm) and electron beams used in further microfabrication techniques do not cause problems with reflection from the semiconductor substrate, the collapse of the resist pattern accompanying the pattern miniaturization becomes a problem. Therefore, research was conducted on a resist underlayer film with high adhesion to the resist.

[0005] In conventional photoresist underlayers, etching defects such as side etching during the etching process are prone to occur. Therefore, if the substrate surface can be modified by a surface modification layer that is thinner than conventional underlayers, etching defects such as side etching can be expected to be eliminated, the adhesion of the photoresist will be improved, and the photoresist resolution in advanced lithography processes will be improved.

[0006] However, it is not easy to form a thin surface modification layer uniformly.

[0007] Therefore, a method for manufacturing a laminate is proposed, comprising the following steps: a first step of coating a surface modifier containing a polymer and a solvent onto a semiconductor substrate and then firing it to crosslink the polymer to obtain a surface-modified layer precursor; and a second step of thinning the surface-modified layer precursor by contacting it with a thinning solution to obtain a surface-modified layer with a film thickness of 5 nm or less, wherein the laminate comprises the surface-modified layer and the semiconductor substrate (see Patent Document 2).

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Publication No. 2008-501985

[0011] Patent Document 2: International Publication No. 2024 / 009993 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] However, during their research, the inventors discovered that if a negative resist pattern is to be formed on the surface-modified layer by developing with an organic solvent, the pattern sometimes collapses.

[0014] The present invention is made in view of the following situation, and claims a method for manufacturing a stacked body for forming a thin surface-modified layer capable of forming a negative resist pattern thereon, a method for manufacturing a semiconductor device using the manufacturing method, and a stacked body having a thin surface-modified layer.

[0015] Methods for solving problems

[0016] 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 main points.

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

[0018] [1] A method for manufacturing a laminate, comprising the following steps: The first step involves coating a surface modifier containing polysiloxane and solvent onto a semiconductor substrate, followed by firing to crosslink the polysiloxane and obtain a surface-modified layer precursor; and The second step involves contacting the surface-modified layer precursor with a thinning solution to thin the precursor, thereby obtaining a surface-modified layer with a film thickness of less than 5 nm. The aforementioned polysiloxane has an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) bonded to the aromatic hydrocarbon ring. The aforementioned stacked body includes the aforementioned surface modification layer and the aforementioned semiconductor substrate. The aforementioned stack is used in photolithography to develop the unexposed resist film with organic solvents using a resist containing organic resin.

[0019] [2] According to the manufacturing method of the laminate described in [1], the above-mentioned polysiloxane is a hydrolytic condensate of a hydrolyzable silane. The above-mentioned hydrolyzable silanes include compounds represented by the following formula (1).

[0020]

[0021] (In equation (1), R) a This refers to a group having an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) bonded to the aforementioned aromatic hydrocarbon ring. Specifically, in Si-R... a In the middle, Si and R a The carbon atoms in it are combined.

[0022] R b This indicates a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonyl group, or an organogroup having a cyano group, or a combination of two or more thereof. Wherein, R b With R a different.

[0023] X represents an alkoxy, arylalkoxy, acyloxy, or halogen atom.

[0024] a represents an integer from 1 to 3. b represents an integer from 0 to 2. a + b is an integer from 1 to 3.

[0025] When a is 2 or more, there are 2 or more R a They can be the same or different.

[0026] When b is 2, there are 2 R b They can be the same or different.

[0027] When (4-ab) is 2 or more, two or more X's can be the same or different.

[0028] [3] According to the manufacturing method of the laminate described in [2], R in the above formula (1) a It is represented by the following formula (1-1).

[0029]

[0030] (In formula (1-1), R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms.)

[0031] R c This represents a monovalent base with 1 to 6 carbon atoms. Among them, R... c Unlike RO-based.

[0032] Ar represents a benzene ring, naphthalene ring, or biphenyl ring.

[0033] Y represents a single bond or a divalent group with 1 to 4 carbon atoms.

[0034] a1 represents an integer from 1 to 3. a2 represents an integer from 0 to 3.

[0035] When a1 is 2 or more, the two or more RO- groups can be the same or different.

[0036] When a2 is 2 or more, there are 2 or more R c They can be the same or different.

[0037] (This represents a bonding bond.)

[0038] [4] The method for manufacturing the laminate according to any one of [1] to [3], wherein the solvent comprises at least one selected from carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, monoalkylene glycol monoalkyl ethers, monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of monoalkylene glycol monoalkyl ethers.

[0039] [5] The method for manufacturing the laminate according to any one of [1] to [4], wherein the surface modifier contains two or more photoacid-generating agents.

[0040] [6] In the method for manufacturing the laminate according to any one of [1] to [5], the thinning solution is selected from at least one of organic solvents, water, acidic solutions, alkaline solutions and diluents used in the RRC (reducing resist consumption) process or the EBR (edge ​​bead removing) process.

[0041] [7] In the method for manufacturing the stacked body according to any one of [1] to [6], the semiconductor substrate is an inorganic or organic substrate, or a substrate having a film of inorganic or organic material.

[0042] [8] According to the manufacturing method of the laminate described in [7], the inorganic material is selected from at least one of metal, metal oxide, metal nitride, metal carbide, metal oxynitride, metal oxycarbide and metal carbonitride.

[0043] [9] According to the manufacturing method of the stacked body described in [7], the organic material is selected from at least one of amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, polyimide, and organic films obtained by doping or replacing a portion of them with boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen.

[0044]

[10] The method for manufacturing a laminate according to any one of [1] to [9] further comprises a resist underlayer film.

[0045]

[11] According to any one of [1] to

[10] , the second step is to thin the surface modification layer precursor by spin coating a thinning liquid onto the surface modification layer precursor to obtain a surface modification layer with a film thickness of 5 nm or less.

[0046]

[12] The stacked body is used in EUV or electron beam lithography according to any one of [1] to [3] manufacturing method.

[0047]

[13] A method for manufacturing a semiconductor device, comprising the following steps: The step of forming a resist film on a laminate obtained by the manufacturing method of any one of [1] to

[12] ; and The process of irradiating the above-mentioned resist film with an electron beam or light and developing it with an organic solvent to obtain a resist pattern.

[0048] The effects of the invention

[0049] According to the present invention, a method for manufacturing a stacked body for forming a thin surface-modified layer capable of forming a negative resist pattern thereon can be provided, a method for manufacturing a semiconductor device using the manufacturing method, and a stacked body having a thin surface-modified layer can be provided. Detailed Implementation

[0050] (Manufacturing method of laminated bodies and laminated bodies)

[0051] The method for manufacturing the laminate of the present invention includes a first step and a second step. The method for manufacturing the laminate of the present invention may further include other steps.

[0052] The first step involves coating a surface modifier containing polysiloxane and solvent onto a semiconductor substrate, followed by firing to crosslink the polysiloxane and obtain a surface-modified layer precursor.

[0053] The second step is to thin the surface modification layer precursor by contacting it with a thinning solution to obtain a surface modification layer with a film thickness of less than 5 nm.

[0054] Polysiloxanes have an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) bonded to the aromatic hydrocarbon ring.

[0055] The stacked body has a surface modification layer and a semiconductor substrate.

[0056] The laminate is used in photolithography to develop the unexposed resist film with organic solvents using a resist containing organic resin.

[0057] It should be noted that in this invention, photolithography can be optical photolithography or electron beam photolithography. The term "unexposed area" refers to the location not exposed to light in optical photolithography, and to the location not exposed to an electron beam in electron beam photolithography.

[0058] It should be noted that in photolithography, the unexposed areas are selectively developed with organic solvents, while the exposed areas remain undeveloped.

[0059] If a film with crosslinked polymer is obtained by coating a surface modifier containing polysiloxane and solvent and then firing it, a film can be obtained. However, it is not easy to obtain a thin film (e.g., a film thickness of less than 5 nm) without film defects such as pinholes and with uneven coating by this process alone. It is necessary to fully control the coating conditions, firing conditions, etc.

[0060] Therefore, for the technology described in Patent Document 2, as a manufacturing method for a laminate capable of forming a thin surface-modified layer, a first step is proposed to form a layer (surface-modified layer precursor) with a film thickness that is thicker than the target film thickness, and a second step is proposed to form a thin surface-modified layer by contacting the layer with a thinning solution to make the layer thinner.

[0061] It should be noted that by crosslinking the polymer in the first step, excessive dissolution of the surface-modified layer precursor in the thinning solution can be prevented in the second step.

[0062] In the course of studying the technology described in Patent Document 2 (International Publication No. 2024 / 009993), the inventors discovered that if a negative resist pattern is to be formed on a surface-modified layer by developing with an organic solvent, the pattern sometimes collapses.

[0063] Therefore, further research was conducted, and it was found that the polysiloxane contained in the surface modifier has an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) that is bonded to the aromatic hydrocarbon ring. As a result, when a negative resist pattern is formed by developing it with an organic solvent, the pattern is less likely to collapse.

[0064] The inventors conducted an investigation as follows.

[0065] When forming negative resist patterns using organic solvents, although the unexposed areas are developed with the organic solvent, the exposed areas are also subject to etching caused by the organic solvent. Etching includes, for example, swelling and reduction in film thickness. Therefore, the formation of negative resist patterns is more prone to resist pattern collapse compared to the formation of positive resist patterns.

[0066] On the other hand, if the polysiloxane contained in the surface modifier has an aromatic hydrocarbon ring with RO-groups, the interaction between the surface-modified layer and the resist film in the exposed section becomes stronger (e.g., chemical bonds are formed between the surface-modified layer and the resist film). As a result, the adhesion between the surface-modified layer and the resist film is considered to be improved, and pattern collapse is less likely to occur.

[0067] The laminate obtained by the manufacturing method of the present invention has a surface modification layer and a semiconductor substrate.

[0068] The laminate obtained by the manufacturing method of the present invention is suitable for use in EUV (extreme ultraviolet light, wavelength 13.5 nm) or electron beam lithography.

[0069] The laminate obtained by the manufacturing method of the laminate of the present invention may further have other layers or films. Examples of other layers include, for example, a photoresist underlayer. There are no particular limitations on the photoresist underlayer, as long as it is used in the photolithography process. The photoresist underlayer may be, for example, a silicon-containing photoresist underlayer or an organic underlayer. Examples of organic underlayers include, for example, organic underlayers with high carbon content. Organic underlayers with high carbon content are obtained, for example, from compositions containing a broad category of phenolic varnish resin. Examples of such compositions include, for example, compositions for forming photoresist underlayers described in International Publication No. 2010 / 147155, International Publication No. 2012 / 077640, International Publication No. 2013 / 005797, and International Publication No. 2017 / 094780.

[0070] The photoresist underlayer is, for example, the underlayer of the surface modification layer. The photoresist underlayer is disposed, for example, between the semiconductor substrate and the surface modification layer.

[0071] It should be noted that in this invention, there is no clear distinction between film and layer.

[0072] The thickness of the surface-modified layer is less than 5 nm, preferably less than 3 nm. There is no particular limitation on the lower limit of the thickness of the surface-modified layer; the thickness of the surface-modified layer can be greater than 0.1 nm or greater than 0.2 nm.

[0073] In this invention, the film thickness is measured as follows.

[0074] The film thickness was measured using an elliptic film thickness measuring device RE-3100 (manufactured by SCREEN).

[0075] <Step 1>

[0076] The first step is to obtain the precursor for the surface-modified layer.

[0077] In the first step, after the surface modifier is coated on the semiconductor substrate, it is fired to crosslink the polysiloxane and obtain the surface modified layer precursor.

[0078] There are no particular restrictions on the semiconductor substrate used in the first process, for example, as long as it is a substrate used in the manufacture of precision integrated circuit components.

[0079] Examples of semiconductor substrates include inorganic substrates, organic substrates, substrates with inorganic films, and substrates with organic films.

[0080] Examples of inorganic substances include arsenic, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides. They can be used individually or in combination of two or more.

[0081] Examples of metals include silicon, germanium, titanium, tungsten, hafnium, zirconium, chromium, copper, aluminum, indium, gallium, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0082] Examples of metal oxides include SiO2 and TiO2.

[0083] Examples of metal nitrides include SiN, TiN, and TaN.

[0084] Examples of metal carbides include SiC and TiC.

[0085] Examples of metal oxynitrides include SiON and TiON.

[0086] Examples of metal oxycarbides include SiOC and TiOC.

[0087] Examples of metal carbonitrides include SiCN and TiCN.

[0088] Examples of organic compounds include amorphous carbon, graphite, fullerenes, carbon nanotubes, diamond, diamond-like carbon, and polyimide. They can be used individually or in combination of two or more. These organic compounds can be partially doped or replaced with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogens.

[0089] Examples of semiconductor substrates include, for example, silicon wafers coated with silicon oxide, silicon nitride, or silicon oxynitride films; silicon nitride substrates; quartz substrates; glass substrates (including alkali-free glass, low-alkali glass, and crystal glass); glass substrates with ITO (indium tin oxide) or IZO (indium zinc oxide) films; plastic substrates (polyimide, PET, etc.); substrates coated with low-k materials; and flexible substrates.

[0090] There are no particular limitations on the method of applying surface modifiers to semiconductor substrates; for example, it can be carried out by appropriate coating methods such as spin coaters or coating machines.

[0091] The firing process after the surface modifier is applied to the semiconductor substrate can be carried out using heating methods such as a hot plate.

[0092] The firing conditions are appropriately selected from a firing temperature of 40℃~400℃ or 80℃~250℃ and a firing time of 0.3 minutes~60 minutes. Preferably, the firing temperature is 120℃~250℃ and the firing time is 0.5 minutes~2 minutes.

[0093] A layered surface-modified layer precursor is obtained by firing, which evaporates the solvent in the surface modifier and crosslinks the polysiloxane. The crosslinking includes partial crosslinking.

[0094] The thickness of the precursor film for the surface-modified layer formed here is, for example, 1 nm to 1,000 nm, or 1 nm to 500 nm, or 1 nm to 300 nm, or 1 nm to 200 nm, or 1 to 150 nm.

[0095] <<Surface Modifiers>>

[0096] Surface modifiers contain polysiloxanes and solvents. Surface modifiers may further contain other components.

[0097] The surface modifier used in the manufacturing method of the laminate of the present invention is also the subject of the present invention.

[0098] <<<Polysiloxane>>>

[0099] As a polysiloxane, there are no particular restrictions as long as it can be crosslinked, and it can be selected appropriately according to the purpose.

[0100] Polysiloxanes can form cross-linked structures by themselves alone, or they can form cross-linked structures together with a cross-linking agent.

[0101] There are no particular limitations on the weight-average molecular weight of the polysiloxane; for example, it can be 500 to 1,000,000. From the viewpoint of suppressing precipitation from surface modifiers, it is preferable to have a weight-average molecular weight of 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of combining storage stability and coatability, it is preferable to have a weight-average molecular weight of 500 or more, and more preferably 600 or more.

[0102] It should be noted that the weight-average molecular weight is the molecular weight obtained from GPC analysis and converted to polystyrene. GPC analysis can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Corporation) and a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Corporation), with the column temperature set at 40°C, using tetrahydrofuran as the eluent, and a flow rate set at 1.0 mL / min. The standard sample is polystyrene (Shodex (registered trademark) manufactured by Showa Denko Corporation).

[0103] There are no particular restrictions on polysiloxanes as long as they are polymers with siloxane bonds.

[0104] Polysiloxanes may include modified polysiloxanes in which a portion of the silanol group has been modified, such as polysiloxanes in which a portion of the silanol group has been modified with an alcohol or protected with an acetal.

[0105] As another example, the polysiloxane includes a hydrolysis condensate of a hydrolyzable silane, and may include a modified polysiloxane in which at least a portion of the silanol groups of the hydrolysis condensate are modified with an alcohol or protected with an acetal. The hydrolyzable silane involved in the hydrolysis condensate may include one or more hydrolyzable silanes.

[0106] Furthermore, polysiloxanes can have any main chain structure, including cage-like, ladder-like, linear, and branched types. Commercially available polysiloxanes can also be used as polysiloxanes.

[0107] It should be noted that in this invention, the "hydrolysis condensate" of the hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only the polyorganosiloxane polymer as a condensate with complete condensation, but also the polyorganosiloxane polymer as a partially hydrolyzed condensate with incomplete condensation. Such partially hydrolyzed condensates, like the fully condensed condensates, are polymers obtained through the hydrolysis and condensation of the hydrolyzable silane, but the hydrolysis is partially stopped, and no condensation occurs; therefore, Si-OH groups remain. Furthermore, in addition to the hydrolysis condensate, the surface modifier may also contain uncondensed hydrolysates (completely hydrolyzed products, partially hydrolyzed products) and monomers (hydrolyzable silanes).

[0108] It should be noted that in this specification, "hydrolyzable silane" is sometimes simply referred to as "silane compound".

[0109] In addition, in this specification, "polysiloxane" is sometimes referred to as "hydrolysis condensate".

[0110] Polysiloxanes have an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) bonded to the aromatic hydrocarbon ring.

[0111] Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and biphenyl rings.

[0112] As an alkyl group having 1 to 6 carbon atoms in R, it can be any of straight-chain, branched, or cyclic forms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl It includes 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0113] Examples of alkoxyalkyl groups with a total carbon number of 2 to 6 in R include methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, ethoxymethyl, etc.

[0114] There is no particular restriction on the number of RO- groups that bind to an aromatic hydrocarbon ring; there can be one or more. In the case of two or more, the RO- groups can be the same or different.

[0115] Polysiloxanes are, for example, hydrolytic condensates of hydrolyzable silanes.

[0116] From the viewpoint of achieving the effects of the present invention, the hydrolyzable silane preferably comprises a compound represented by the following formula (1).

[0117]

[0118] (In equation (1), R) a This indicates a group having an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) bonded to the aromatic hydrocarbon ring. Specifically, in Si-R... a In the middle, Si and R a The carbon atoms in it are combined.

[0119] R b This indicates a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonyl group, or an organogroup having a cyano group, or a combination of two or more thereof. Wherein, R b With R a different.

[0120] X represents an alkoxy, arylalkoxy, acyloxy, or halogen atom.

[0121] a represents an integer from 1 to 3. b represents an integer from 0 to 2. a + b is an integer from 1 to 3.

[0122] When a is 2 or more, there are 2 or more R a They can be the same or different.

[0123] When b is 2, there are 2 R b They can be the same or different.

[0124] When (4-ab) is 2 or more, two or more X's can be the same or different.

[0125] a is preferably 1.

[0126] b is preferably 0.

[0127] - R in equation (1) a -

[0128] R a This indicates a group having an aromatic hydrocarbon ring and an RO- group (R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms) bonded to the aromatic hydrocarbon ring. Specifically, in Si-R... a In the middle, Si and R a The carbon atoms in it are combined.

[0129] As R a Preferably, it contains the group represented by the following formula (1-1).

[0130]

[0131] (In formula (1-1), R represents an alkyl group with 1 to 6 carbon atoms or an alkoxyalkyl group with 2 to 6 total carbon atoms.)

[0132] R c This represents a monovalent base with 1 to 6 carbon atoms. Among them, R... c Unlike RO-based.

[0133] Ar represents a benzene ring, naphthalene ring, or biphenyl ring.

[0134] Y represents a single bond or a divalent group with 1 to 4 carbon atoms.

[0135] a1 represents an integer from 1 to 3. a2 represents an integer from 0 to 3.

[0136] When a1 is 2 or more, the two or more RO- groups can be the same or different.

[0137] When a2 is 2 or more, there are 2 or more R c They can be the same or different.

[0138] (This represents a bonding bond.)

[0139] R c The monovalent groups with 1 to 6 carbon atoms in the carbon atom may or may not have heteroatoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0140] As R c The monovalent group having 1 to 6 carbon atoms can be, for example, a hydrocarbon group or a non-hydrocarbon group. Examples of hydrocarbon groups include, for example, alkylene groups. Examples of non-hydrocarbon groups include, for example, alkoxyalkyl groups.

[0141] The divalent groups of carbon atoms 1 to 4 in Y may or may not have heteroatoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0142] Examples of divalent groups with 1 to 4 carbon atoms in Y include, for example, -R x -O-based (R x This indicates alkylene groups with 1 to 4 carbon atoms. (e.g., -R) It should be noted that -R x The oxygen atom of the -O- group combines with Ar.

[0143] The number of carbon atoms in a divalent group with 1 to 4 carbon atoms can be 1, 2, 3, or 4.

[0144] a1 can be 1, 2, or 3.

[0145] a2 can be 0, 1, 2, or 3.

[0146] Examples of groups that can be represented by formula (1-1) include the following groups.

[0147]

[0148] ( (This represents a bonding bond.)

[0149] - R in equation (1) b -

[0150] The alkyl group can be any of the straight-chain, branched, or cyclic forms, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0151] Specific examples of alkyl groups, specifically straight-chain or branched alkyl groups, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-... Amyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0152] It should be noted that in this specification, "i" refers to "different", "s" refers to "middle", and "t" refers to "uncle".

[0153] Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl- Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, as well as cross-linked cycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl and dicyclodecyl.

[0154] The aryl group can be any of the following: phenyl, a monovalent group derived from removing one hydrogen atom of a fused-ring aromatic hydrocarbon compound, or a monovalent group derived from removing one hydrogen atom of a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0155] For example, aryl groups with 6 to 20 carbon atoms can be cited as examples. Examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, 1-tetraphenyl, 2-tetraphenyl, 5-tetraphenyl, 2-phenanthyl, 1-pyrene, 2-pyrene, pentaphenyl, benzo[9,10]phenanthyl; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (meta-biphenyl), biphenyl-4-yl (p-biphenyl), p-terphenyl-4-yl, meta-terphenyl-4-yl, o-terphenyl-4-yl, 1,1'-binaphth-2-yl, 2,2'-binaphth-1-yl, etc., but are not limited to these.

[0156] Aryl alkyl is an alkyl group that has been substituted with an aryl group. Specific examples of such aryl and alkyl groups can be given as the same examples as those described above. The number of carbon atoms in the aryl alkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0157] Specific examples of aralkyl groups include phenylmethyl (benzyl), 2-phenylethylidene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, etc., but are not limited to these.

[0158] Haloalkyl, haloaryl, and haloaralkyl are each alkyl, aryl, and aralkyl groups that have been substituted with one or more halogen atoms. Examples of such alkyl, aryl, and aralkyl groups can be given as examples similar to those described above.

[0159] The number of carbon atoms in the haloalkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0160] Specific examples of haloalkyl groups include monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropane-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, etc., but are not limited to these.

[0161] The number of carbon atoms in the haloaryl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0162] Specific examples of halogenated aryl groups include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl. 4-Fluoro-1-naphthyl, 6-Fluoro-1-naphthyl, 7-Fluoro-1-naphthyl, 8-Fluoro-1-naphthyl, 4,5-Difluoro-1-naphthyl, 5,7-Difluoro-1-naphthyl, 5,8-Difluoro-1-naphthyl, 5,6,7,8-Tetrafluoro-1-naphthyl, Heptafluoro-1-naphthyl, 1-Fluoro-2-naphthyl, 5-Fluoro-2-naphthyl, 6-Fluoro-2-naphthyl, 7-Fluoro-2-naphthyl, 5,7-Difluoro-2-naphthyl, Heptafluoro-2-naphthyl, etc., and other groups obtained by arbitrarily replacing the fluorine atom (fluorine group) in these groups with a chlorine atom (chloride group), a bromine atom (bromine group), or an iodine atom (iodide group), but not limited to these.

[0163] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0164] Specific examples of haloaralkyl groups include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc. Furthermore, groups obtained by arbitrarily replacing the fluorine atom (fluoro group) in these groups with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be cited, but are not limited to these.

[0165] Alkoxyalkyl, alkoxyaryl, and alkoxyaralkyl are each alkyl, aryl, and aralkyl groups that have been substituted with one or more alkoxy groups. Examples of such alkyl, aryl, and aralkyl groups are the same as those described above.

[0166] Examples of alkoxy groups that can be used as substituents include, for example, alkoxy groups having at least one alkyl moiety among straight-chain, branched, and cyclic forms having 1 to 20 carbon atoms.

[0167] Examples of linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-propoxy, etc. Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc.

[0168] In addition, examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentoxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentoxy, 2-methyl-cyclopentoxy, 3-methyl-cyclopentoxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-dimethyl-cyclobutoxy Methyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3-dimethyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl-cyclopropoxy, 1-isopropyl-cyclopropoxy, 2-isopropyl-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1,2,3-trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1-methyl-cyclopropoxy, 2-ethyl-2-methyl-cyclopropoxy, and 2-ethyl-3-methyl-cyclopropoxy, etc.

[0169] Specific examples of alkoxyalkyl groups include methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, ethoxymethyl, and other lower (approximately 5 carbon atoms or less) alkoxyalkyl groups, but are not limited to these.

[0170] Specific examples of alkoxyaryl groups include 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, 7-methoxynaphth-1-yl, etc., but are not limited to these.

[0171] Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0172] The alkenyl group can be either linear or branched, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0173] Specific examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3- Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2-Methyl-3-cyclopentenyl Examples of alkenyl groups include 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl. Cross-linked cyclic alkenyl groups such as dicycloheptenyl (norbornyl) can also be cited.

[0174] Furthermore, examples of substituents among the aforementioned alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl groups include, for example, alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkoxyaralkyl, alkenyl, alkoxy, arylalkoxy, etc., and the same specific examples and suitable carbon number as those described above or below can be given.

[0175] Furthermore, the aryloxy group mentioned in the substituents is a group in which the aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups can be given as examples similar to those described above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include phenoxy and naphth-2-yloxy groups, but are not limited to these.

[0176] Furthermore, when there are two or more substituents, the substituents can combine with each other to form a ring.

[0177] Examples of organic groups having an epoxy group that can open a ring include epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, epoxycyclohexyl, or their epoxy group with an open ring.

[0178] Examples of organic groups containing an acryloyl group include acryloyloxymethyl, acryloyloxyethyl, and acryloyloxypropyl.

[0179] Examples of organic groups containing a methacryloyl group include methacryloyloxymethyl, methacryloyloxyethyl, and methacryloyloxypropyl.

[0180] Examples of organic groups containing a thiol group include thiol ethyl, thiol butyl, thiol hexyl, thiol octyl, and thiol phenyl.

[0181] Examples of amino groups include amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl, but they are not limited to these. The following describes amino groups in further detail.

[0182] Examples of organic groups containing an alkoxy group include, but are not limited to, methoxymethyl and methoxyethyl. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded.

[0183] Examples of organic groups having a sulfonyl group include sulfonylalkyl and sulfonylaryl groups, but are not limited to these.

[0184] Examples of organic groups containing a cyano group include cyanoethyl, cyanopropyl, cyanophenyl, and thiocyanate groups.

[0185] As an organic group containing an amino group, examples include organic groups containing at least one of primary, secondary, and tertiary amino groups. Preferably, a hydrolytic condensate containing a tertiary ammonium group is obtained by hydrolyzing a hydrolyzable silane containing a tertiary amino group with a strong acid to form a countercation. Furthermore, in addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as oxygen and sulfur atoms.

[0186] As a preferred example, an organic group having an amino group can be exemplified by the group shown in the following formula (A1).

[0187]

[0188] In equation (A1), R 101 and R 102 Each of the two groups represents a hydrogen atom or a hydrocarbon group independently, and each of the two groups represents a alkylene group that can be substituted. This represents a bonding bond.

[0189] Examples of hydrocarbon groups include alkyl, alkenyl, and aryl groups, but are not limited to these. Specific examples of these alkyl, alkenyl, and aryl groups include those related to R... 1 The same example as the one mentioned above.

[0190] Furthermore, as an alkylene group, it can be linear or branched, and its carbon number is typically 1 to 10, preferably 1 to 5. Examples of linear alkylene groups include methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene.

[0191] Examples of organic groups containing an amino group include amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl, but are not limited to these.

[0192] -X-

[0193] In equation (1), X is the so-called hydrolytic group.

[0194] As an alkoxy group in X, examples include, for instance, in R b The description illustrates alkoxy groups.

[0195] As halogen atoms in X, examples include those in R. b The description illustrates halogen atoms.

[0196] Arylalkoxy is a monovalent group derived from the hydroxyl group of an aralkyl alcohol by removing a hydrogen atom. As a specific example of an aralkyl group in arylalkoxy, the same examples as those described above can be given.

[0197] The number of carbon atoms in the arylalkoxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less.

[0198] Specific examples of arylalkoxy groups include phenylmethoxy (benzyloxy), 2-phenylethyloxy, 3-phenyl-n-propoxy, 4-phenyl-n-butoxy, 5-phenyl-n-pentoxy, 6-phenyl-n-hexoxy, 7-phenyl-n-heptoxy, 8-phenyl-n-octoxy, 9-phenyl-n-nonoxy, 10-phenyl-n-decoxy, etc., but are not limited to these.

[0199] An acyloxy group is a monovalent group derived from the carboxyl group (-COOH) of a carboxylic acid compound by removing a hydrogen atom. Typically, examples include alkylcarbonyloxy, arylcarbonyloxy, or aralkylcarbonyloxy derived from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid, but these are not limited to. Specific examples of alkyl, aryl, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids can be given as examples similar to those described above.

[0200] Specific examples of acyloxy groups include those with 2 to 20 carbon atoms, such as methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl-n-butyl carbonyloxy, 2-methyl-n-butyl carbonyloxy, 3-methyl-n-butyl carbonyloxy, 1,1-dimethyl-n-propyl carbonyloxy, 1,2-dimethyl-n-propyl carbonyloxy, 2,2-dimethyl-n-propyl carbonyloxy, 1-ethyl-n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl ...propyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl carbonyloxy, 2-methyl-n-pentyl The compounds include 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and toluenesulfonylcarbonyloxy, etc.

[0201] Examples of compounds represented by formula (1) include the following compounds.

[0202]

[0203] (X represents an alkoxy group. X can also represent, for example, a methoxy or ethoxy group.)

[0204] The molar percentage of the compound represented by formula (1) in the hydrolyzable silane is not particularly limited, but is preferably 50 mol% or more, more preferably 75 mol% or more, and particularly preferably 90 mol% or more.

[0205] The polysiloxane can be a hydrolytic condensate of a hydrolytic silane that includes other silane compounds besides those exemplified above, without impairing the effects of the invention.

[0206] As described above, modified polysiloxanes in which at least a portion of the silanol group has been modified can be used as polysiloxanes. For example, polysiloxanes in which a portion of the silanol group has been modified with an alcohol or polysiloxanes protected with an acetal can be used.

[0207] Examples of polysiloxanes that can be modified include reaction products obtained by reacting at least a portion of the silanol groups in the hydrolytic condensate of the above-mentioned hydrolytic silane with the hydroxyl groups of an alcohol, dehydration products of the condensate and an alcohol, and modified products in which at least a portion of the silanol groups in the condensate are protected with acetal groups.

[0208] As an alcohol, monohydric alcohols can be used, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-pentanol, neopentanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-prop ... -Dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol and cyclohexanol.

[0209] In addition, alcohols containing alkoxy groups, such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol), can be used.

[0210] The reaction of the silanol groups in the condensate with the hydroxyl groups of the alcohol is achieved by contacting the polysiloxane with the alcohol and reacting at a temperature of 40–160°C, for example 60°C, for 0.1–48 hours, for example 24 hours, thereby obtaining a modified polysiloxane with blocked silanol groups. In this case, the alcohol, acting as a blocking agent, can be used as a solvent in the composition containing the polysiloxane.

[0211] In addition, the dehydration reaction product of polysiloxane composed of hydrolytic condensate of hydrolytic silane and alcohol can be produced by reacting polysiloxane with alcohol in the presence of acid as a catalyst, blocking the silanol group with alcohol, and removing the generated water produced by dehydration from the reaction system.

[0212] The acid can be an organic acid with an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. Examples of acids include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., especially benzoic acid, isobutyric acid, acetic acid, etc.

[0213] In addition, acids with boiling points of 70 to 160°C can be used, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid.

[0214] The preferred acid is one having an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160 °C. That is, a weak acid or an acid with a strong acidity but a low boiling point can be used.

[0215] Furthermore, as an acid, it is also possible to utilize any of the properties of acid dissociation constant and boiling point.

[0216] The acetal protection of the silanol group of the condensate can be achieved by using vinyl ethers, such as the vinyl ether shown in formula (5) below, which can introduce part of the structure shown in formula (6) below into the polysiloxane through their reaction.

[0217]

[0218] In equation (5), R 1a R 2a and R 3a Each represents an alkyl group having 1 to 10 hydrogen atoms, R 4a R represents an alkyl group having 1 to 10 carbon atoms. 2a With R 4a They can combine with each other to form rings. Alkyl groups can be exemplified by the above examples.

[0219]

[0220] In equation (6), R 1 '、R 2 'and R 3 Each represents an alkyl group having 1 to 10 hydrogen atoms, R 4 'Represents an alkyl group with 1 to 10 carbon atoms, R 2 'With R 4 They can combine to form a ring. In equation (6) This indicates a bond with an adjacent atom. Examples of adjacent atoms include, for example, the oxygen atom in a siloxane bond, the oxygen atom in a silanol group, and R derived from formula (1). 1 The carbon atom. Alkyl groups can be exemplified by the above examples.

[0221] As the vinyl ether represented by formula (5), aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran are particularly preferred.

[0222] Silanol acetal protection can be achieved using polysiloxanes, vinyl ethers, and solvents such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, and 1,4-dimethylformamide. Aprotic solvents such as alkanes, using pyridine It is carried out using catalysts such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

[0223] It should be noted that the use of alcohol blocking and acetal protection for these silanol groups can be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silanes described later.

[0224] Hydrolyzable silane condensates can be obtained by hydrolyzing and condensing the above-mentioned silane compounds (hydrolyzable silanes).

[0225] The above-mentioned silane compounds (hydrolyzable silanes) contain alkoxy, arylalkoxy, acyloxy, or halogen atoms that are directly bonded to silicon atoms, that is, they contain alkoxysilyl, arylalkoxysilyl, acyloxysilyl, or halosilyl (hereinafter referred to as hydrolyzable groups).

[0226] In the hydrolysis of these hydrolyzable groups, 0.1 to 100 moles of water are typically used per mole of hydrolyzable group, for example, 0.5 to 100 moles, preferably 1 to 10 moles.

[0227] During hydrolysis and condensation, a hydrolysis catalyst may be used to promote the reaction, or the hydrolysis and condensation may be carried out without using one. When using a hydrolysis catalyst, 0.0001 to 10 moles of hydrolyzable group are typically used, preferably 0.001 to 1 mole of hydrolysis catalyst.

[0228] The reaction temperature for hydrolysis and condensation is typically above room temperature and below the reflux temperature of the organic solvent that can be used for hydrolysis at atmospheric pressure, for example, 20–110°C, or for example, 20–80°C.

[0229] Hydrolysis can be complete, meaning all hydrolyzable groups are converted into silanol groups, or it can be partial, meaning that unreacted hydrolyzable groups remain.

[0230] Examples of hydrolysis catalysts that can be used to induce condensation during hydrolysis include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0231] Metal chelates that can be used as hydrolysis catalysts include, for example, triethoxylated metal chelates. Mono(acetylacetone)titanium, tri-n-propoxy Mono(acetylacetone)titanium, tri-isopropoxy Mono(acetylacetone)titanium, tri-n-butoxy Mono(acetylacetone)titanium, tri-sec-butoxy Mono(acetylacetone)titanium, tri-tert-butoxy Mono(acetylacetone)titanium, diethoxy bis(acetylacetone)titanium, di-n-propoxy bis(acetylacetone)titanium, di-isopropoxy Bis(acetylacetone)titanium, di-n-butoxy Bis(acetylacetone)titanium, di-sec-butoxy bis(acetylacetone)titanium, di-tert-butoxy bis(acetylacetone)titanium, monoethoxy Tri(acetylacetone)titanium, mono-n-propoxy Tri(acetylacetone)titanium, mono-isopropoxy Tri(acetylacetone)titanium, mono-n-butoxy Tri(acetylacetone)titanium, mono-sec-butoxy Tri(acetylacetone)titanium, mono-tert-butoxy Tri(acetylacetone)titanium, Tetra(acetylacetone)titanium, Triethoxy Mono(ethyl acetoacetate)titanium, tri-n-propoxy Mono(ethyl acetoacetate)titanium, tri-isopropoxy Mono(ethyl acetoacetate)titanium, tri-n-butoxy Mono(ethyl acetoacetate)titanium, tri-sec-butoxy Mono(ethyl acetoacetate)titanium, tri-tert-butoxy Mono(ethyl acetoacetate)titanium, diethoxy bis(ethyl acetoacetate)titanium, di-n-propoxy bis(ethyl acetoacetate)titanium, di-isopropoxy bis(ethyl acetoacetate)titanium, di-n-butoxy bis(ethyl acetoacetate)titanium, di-sec-butoxy bis(ethyl acetoacetate)titanium, di-tert-butoxy bis(ethyl acetoacetate)titanium, monoethoxy Tri(ethyl acetoacetate)titanium, mono-n-propoxy Tri(ethyl acetoacetate)titanium, mono-isopropoxy Tri(ethyl acetoacetate)titanium, mono-n-butoxy Tri(ethyl acetoacetate)titanium, mono-sec-butoxy Tri(ethyl acetoacetate)titanium, mono-tert-butoxy Titanium chelates such as tri(ethyl acetoacetate)titanium, tetra(ethyl acetoacetate)titanium, mono(acetylacetone)tri(ethyl acetoacetate)titanium, bis(acetylacetone)bis(ethyl acetoacetate)titanium, and tri(acetylacetone)mon(ethyl acetoacetate)titanium; triethoxy Mono(acetylacetone)zirconium, tri-n-propoxy Mono(acetylacetone)zirconium, tri-isopropoxy Mono(acetylacetone)zirconium, tri-n-butoxy Mono(acetylacetone)zirconium, tri-sec-butoxy Mono(acetylacetone)zirconium, tri-tert-butoxy Mono(acetylacetone)zirconium, diethoxy bis(acetylacetone)zirconium, di-n-propoxy bis(acetylacetone)zirconium, di-isopropoxy bis(acetylacetone)zirconium, di-n-butoxy bis(acetylacetone)zirconium, di-sec-butoxy bis(acetylacetone)zirconium, di-tert-butoxy bis(acetylacetone)zirconium, monoethoxy Tri(acetylacetone)zirconium, mono-n-propoxy Tri(acetylacetone)zirconium, mono-isopropoxy Tri(acetylacetone)zirconium, mono-n-butoxy Tri(acetylacetone)zirconium, mono-sec-butoxy Tri(acetylacetone)zirconium, mono-tert-butoxy Tri-(acetylacetone)zirconium, Tetra-(acetylacetone)zirconium, Triethoxy Mono(ethyl acetoacetate)zirconium, tri-n-propoxy Mono(ethyl acetoacetate)zirconium, tri-isopropoxy Mono(ethyl acetoacetate)zirconium, tri-n-butoxy Mono(ethyl acetoacetate)zirconium, tri-sec-butoxy Mono(ethyl acetoacetate)zirconium, tri-tert-butoxy Mono(ethyl acetoacetate) zirconium, diethoxy bis(ethyl acetoacetate)zirconium, di-n-propoxy bis(ethyl acetoacetate)zirconium, di-isopropoxy bis(ethyl acetoacetate)zirconium, di-n-butoxy bis(ethyl acetoacetate)zirconium, di-sec-butoxy bis(ethyl acetoacetate)zirconium, di-tert-butoxy bis(ethyl acetoacetate)zirconium, monoethoxy Tri(ethyl acetoacetate)zirconium, mono-n-propoxy Tri(ethyl acetoacetate)zirconium, mono-isopropoxy Tri(ethyl acetoacetate)zirconium, mono-n-butoxy Tri(ethyl acetoacetate)zirconium, mono-sec-butoxy Tri(ethyl acetoacetate)zirconium, mono-tert-butoxy Zirconium chelates such as tri(ethyl acetoacetate)zirconium, tetra(ethyl acetoacetate)zirconium, mono(acetylacetone)tri(ethyl acetoacetate)zirconium, bis(acetylacetone)bis(ethyl acetoacetate)zirconium, tri(acetylacetone)mon(ethyl acetoacetate)zirconium; aluminum chelates such as tri(acetylacetone)aluminum, tri(ethyl acetoacetate)aluminum; etc., but not limited to these.

[0232] Organic acids that can serve as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0233] Inorganic acids that can act as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0234] Examples of organic bases that can serve as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picolinide, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0235] Inorganic bases that can act as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0236] Among these catalysts, metal chelates, organic acids, and inorganic acids are preferred. They can be used alone or in combination of two or more.

[0237] In this invention, nitric acid is suitable as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the molecular weight change of the hydrolysis condensate can be suppressed. It is known that the stability of hydrolysis condensates in liquids depends on the pH of the solution. In-depth studies have shown that by using an appropriate amount of nitric acid, the pH of the solution reaches a stable range.

[0238] Furthermore, as mentioned above, nitric acid is preferred from the viewpoint that it can be used to obtain modified hydrolysis condensates, for example, when the silanol group is blocked by an alcohol. It can also be used to obtain modified hydrolysis condensates, for example, when the silanol group is blocked by an alcohol.

[0239] During hydrolysis and condensation, organic solvents can be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; and aromatic solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, and n-pentylnaphthalene. Hydrocarbon solvents: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecane Monohydric alcohol solvents such as alcohols, phenols, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; acetone, methyl ethyl ketone, methyl- Ketone solvents including n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, fentanyl ketone, etc.; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, etc. Alkane, dimethyl di Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether Ether solvents include propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate. Benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, triethylene glycol methoxyacetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate Ester solvents such as isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonyl lactone, etc., but not limited to these. One or more of these solvents may be used.

[0240] After the hydrolysis and condensation reactions are completed, the reaction solution is neutralized by direct dilution or concentration, followed by treatment with an ion exchange resin. This removes hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation processes. Furthermore, byproducts such as alcohols, water, and the hydrolysis catalysts used can be removed from the reaction solution before or after this treatment by methods such as vacuum distillation.

[0241] The hydrolysis condensate obtained through this operation can be obtained as a polysiloxane varnish dissolved in an organic solvent and directly used to formulate a surface modifier. That is, the reaction solution can be used directly (or diluted) to formulate a surface modifier. In this case, the hydrolysis catalyst and byproducts used in the hydrolysis and condensation can remain in the reaction solution as long as they do not impair the effects of the invention. For example, the hydrolysis catalyst and the nitric acid used for silanol group alcohol blocking can remain in the polymer varnish solution at a concentration of approximately 100 ppm to 5,000 ppm.

[0242] The resulting polysiloxane varnish can be solvent-displaced and diluted with a suitable solvent. It should be noted that, provided the resulting polysiloxane varnish has good storage stability, the organic solvent can also be removed by distillation to achieve a 100% concentration of the film-forming component. It should be noted that the film-forming component refers to the component remaining after removing the solvent from all components of the composition.

[0243] The organic solvents used for solvent displacement and dilution of polysiloxane varnishes can be the same as or different from those used for the hydrolysis and condensation reactions of hydrolyzable silanes. There are no particular limitations on the dilution solvent; it can be one type, two or more types, or any combination thereof.

[0244] <<<Solvent>>>

[0245] The solvent contained in the surface modifier can be used without particular restrictions, as long as it is a solvent that can dissolve / mix the polysiloxane and other components that are included in the surface modifier as needed.

[0246] Examples of solvents include organic solvents and water.

[0247] Examples of organic solvents include alcohols, carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic esters (monocarboxylic esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic esters of alkylene glycol monoalkyl ethers).

[0248] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents.

[0249] Examples of monohydric alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.

[0250] Examples of polyol solvents include ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0251] Examples of carboxylic acids having a hydroxyl group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, etc.

[0252] Examples of linear or cyclic alkyl ketones include, for example, methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0253] Examples of cyclic lactones include, for instance, γ-butyrolactone.

[0254] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0255] Examples of monoalkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, and propylene glycol monobutyl ether.

[0256] Examples of alkylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc.

[0257] Examples of monoalkylene glycol monoalkyl ether carboxylic esters include, for example, monocarboxylic esters of monoalkylene glycol monoalkyl ethers and alkoxycarboxylic esters of monoalkylene glycol monoalkyl ethers.

[0258] Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include, for example, alkylene glycol monoalkyl ether acetates.

[0259] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0260] Examples of alkoxycarboxylic acid esters that are monoalkylene glycol ethers include, for example, 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0261] Specific examples of other solvents include toluene, xylene, ethyl ethoxylate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl pyruvate, ethyl formate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl glycolate, and ethyl glycolate. Esters, methyl 3-methoxy-2-methylpropionate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, etc.

[0262] These solvents can be used alone or in combination of two or more.

[0263] Furthermore, the surface modifier may contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the surface modifier may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0264] <<<Civilized Catalyst>>>

[0265] The surface modifier can be a composition that does not contain a curing catalyst, but preferably contains a curing catalyst.

[0266] As a curing catalyst, ammonium salts, phosphine compounds, etc. can be used. Salt, matte salt, iodine Salt, oxygen Salts, etc. It should be noted that the following salts, described as an example of a curing catalyst, may be added in the form of salts, or may be any of the substances that form salts in the composition (substances that are added as other compounds and form salts in the system).

[0267] Examples of ammonium salts include quaternary ammonium salts with the structure shown in formula (D-1), quaternary ammonium salts with the structure shown in formula (D-2), quaternary ammonium salts with the structure shown in formula (D-3), quaternary ammonium salts with the structure shown in formula (D-4), quaternary ammonium salts with the structure shown in formula (D-5), and tertiary ammonium salts with the structure shown in formula (D-6).

[0268]

[0269] (where m) a n represents an integer from 2 to 11. a R represents integers from 2 to 3. 21 Y represents alkyl, aryl, or aralkyl. - (This indicates anion.)

[0270] (where R is in the formula) 22 R 23 R 24 and R 25 Each can be represented independently as alkyl, aryl, or aralkyl, Y - Represents an anion, and R 22 R 23 R 24 and R 25 Each atom bonds with a nitrogen atom.

[0271] (where R is in the formula) 26 and R 27 Each can be represented independently as alkyl, aryl, or aralkyl, Y - (This indicates anion.)

[0272] (where R is in the formula) 28 Y represents alkyl, aryl, or aralkyl. - (This indicates anion.)

[0273] (where R is in the formula) 29 and R 30 Each can be represented independently as alkyl, aryl, or aralkyl, Y - (This indicates anion.)

[0274] (where m) a n represents an integer from 2 to 11. a Y represents an integer from 2 to 3. - (This indicates anion.)

[0275] In addition, as Salt, as exemplified by the quaternary salts shown in equation (D-7), can be used as a reference. Salt.

[0276]

[0277] (where R is in the formula) 31 R 32 R 33 and R 34 Each can be represented independently as alkyl, aryl, or aralkyl, Y - Represents an anion, and R 31 R 32 R 33 and R 34 Each atom bonds with a phosphorus atom.

[0278] In addition, as a matte salt, the tertiary matte salt shown in formula (D-8) can be cited as an example.

[0279]

[0280] (where R is in the formula) 35 R 36 and R 37 Each can be represented independently as alkyl, aryl, or aralkyl, Y - Represents an anion, and R 35 R 36 and R 37 Each atom bonds with a sulfur atom.

[0281] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a n represents an integer from 2 to 11. a Represents an integer from 2 to 3. The R of this quaternary ammonium salt... 21 This refers to, for example, alkyl groups with 1 to 18 carbon atoms, preferably 2 to 10, aryl groups with 6 to 18 carbon atoms, or aralkyl groups with 7 to 18 carbon atoms. Examples include straight-chain alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Furthermore, anionic (Y)- Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) - ) and other acid groups.

[0282] The compound of formula (D-2) is R. 22 R 23 R 24 R 25 N ＋ Y - The quaternary ammonium salt shown. The R of this quaternary ammonium salt... 22 R 23 R 24 and R 25 Examples include alkyl groups with 1-18 carbon atoms such as ethyl, propyl, butyl, cyclohexyl, and cyclohexylmethyl; aryl groups with 6-18 carbon atoms such as phenyl; and aralkyl groups with 7-18 carbon atoms such as benzyl. Anion (Y - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) - The quaternary ammonium salt is available commercially, such as tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0283] The compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, preferably R. 26 and R 27 The total number of carbon atoms is 7 or more. For example, R 26 Examples of possible compounds include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. 27 Examples include aryl groups such as benzyl, octyl, and octadecyl. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) -), alkoxide (-O) - The compound can also be obtained from commercially available products, such as by reacting imidazole compounds like 1-methylimidazole and 1-benzylimidazole with aralkyl halides, alkyl halides, and aryl halides like benzyl bromide, methyl bromide, and bromobenzene.

[0284] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 For example, it can be an alkyl group with 1 to 18 carbon atoms, preferably an alkyl group with 4 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Examples include butyl, octyl, benzyl, and lauryl. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) - This compound can also be obtained commercially, for example, by reacting pyridine with alkyl halides or aryl halides such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, and octyl bromide. An example of this compound is N-laurylpyridine chloride. N-Benzylpyridine bromide wait.

[0285] Compounds of formula (D-5) are quaternary ammonium salts derived from substituted pyridines, such as picolino, R 29 For example, it can be an alkyl group with 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms, such as methyl, octyl, lauryl, benzyl, etc. 30 For example, it can be an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. For example, in the case where the compound shown in formula (D-5) is a quaternary ammonium derived from picolino, R 30 It is a methyl group. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) -This compound can also be obtained commercially, for example, by reacting substituted pyridines such as picolinate with alkyl halides or aryl halides such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, and benzyl bromide. An example of this compound is N-benzylpicolinate. Chloride, N-benzylpicoline bromide, N-laurylpicoline Chlorides, etc.

[0286] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m a n represents an integer from 2 to 11. a It indicates 2 or 3. Additionally, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) - This compound can be produced by reacting amines with weak acids such as carboxylic acids and phenols. Examples of carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y)... - ) is (HCOO) - In the case of using acetic acid, the anion (Y) - (CH3COO) - Furthermore, in the case of using phenol, the anion (Y) - (C6H5O) - ).

[0287] The compound of formula (D-7) is a compound with R 31 R 32 R 33 R 34 P ＋ Y - The structure of the season Salt. R 31 R 32 R 33 and R 34 Examples include alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl. R is preferred. 31 ~R 34 Of the four substituents, three are unsubstituted phenyl groups or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Furthermore, the anion (Y...)- Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) - (e.g., acid groups). This compound is available as a commercially available product; examples include tetrabutyl halide. Tetrapropylhalogenated isohalogenated tetraalkyl , triethylbenzyl halide isohalogenated trialkylbenzyl , triphenylmethyl halogenated , triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide Tetraphenylhalide , Trimethylyl monoaryl halogenated Or halogenated tricresyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom). A particularly preferred option is triphenylmethyl halide. , triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide isohalogenated triphenyl monoaryl , Trimethylbenzene Halogenated Isohyetalized trimethylolyl monoaryl , Trimethylhalogenated Isohyetalized trimethylyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom).

[0288] In addition, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0289] The compound of formula (D-8) is a compound with R 35 R 36 R 37 S ＋ Y - Tertiary sulfonium salts with a structure of R. 35 R 36 and R 37Examples include alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl. R is preferred. 35 ~R 37 Two of the three substituents are unsubstituted phenyl groups or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Additionally, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alkoxide (-O) - The compound contains acid groups such as maleic acid anion and nitrate anion. Examples of commercially available compounds include tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, dialkylbenzylsulfonium halide, diphenylmethylsulfonium halide, diphenylethylsulfonium halide, triphenylmonoalkylsulfonium halide (where the halogen atom is a chlorine or bromine atom), tri-n-butylsulfonium carboxylates, trialkylsulfonium carboxylates, dialkylbenzylsulfonium carboxylates, diphenylmethylsulfonium carboxylates, diphenylethylsulfonium carboxylates, and triphenylmonoalkylsulfonium carboxylates. Triphenylsulfonium halide and triphenylsulfonium carboxylates are preferred.

[0290] In addition, nitrogen-containing silane compounds can be added as curing catalysts. Examples of nitrogen-containing silane compounds include silane compounds containing an imidazole ring, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0291] The content of the curing catalyst in the surface modifier is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of polysiloxane, more preferably 0.01 to 25 parts by mass, and even more preferably 0.01 to 20 parts by mass.

[0292] <<<Acid>>

[0293] The surface modifier preferably contains an acid.

[0294] Acids can be added when preparing surface modifiers, but when the surface modifier contains polysiloxanes, they can also be used as hydrolysis catalysts or in the manufacture of the aforementioned polysiloxanes during the blocking of silanol groups, treating the substances remaining in the polysiloxane varnish as acids.

[0295] Examples of acids include organic acids and inorganic acids.

[0296] Examples of organic acids include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.

[0297] Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0298] The amount of acid mixed (residual acid) is based on the total mass of the surface modifier and can be, for example, 0.0001% to 1% by mass, 0.001% to 0.1% by mass, or 0.005% to 0.05% by mass.

[0299] <<<Acid-producing agent>>>

[0300] Surface modifiers may contain acid-producing agents.

[0301] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents, with photo-producing acid-producing agents being preferred.

[0302] Examples of photoacid-producing agents include sulfonium salts, Salts, ammonium salts, iodine Salt, oxygen Salt, etc. Salt compounds, sulfonylimide compounds, disulfonyldiazomethane compounds, etc., but not limited to these. It should be noted that photoacid-generating agents, such as those described later, are also included. Salt compounds such as nitrates, maleates, and other carboxylates, as well as hydrochlorides, can also function as curing catalysts depending on their type. In this invention, when a photoacid-generating agent also functions as a curing catalyst, that curing catalyst is treated as a photoacid-generating agent.

[0303] In addition, examples of heat-generating acid agents include tetramethylammonium nitrate, but these are not limited to.

[0304] As A specific example of a salt compound is diphenyliodide. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate, bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, triphenylsulfonium nitrate (nitrate), triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, triphenylsulfonium chloride, and other sulfonate compounds, but not limited to these.

[0305] Specific examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide, but are not limited to these.

[0306] Specific examples of disulfonyl diazonium methane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyl diazonium methane, etc., but are not limited to these.

[0307] It should be noted that one type of acid-producing agent can be used alone or in combination with two or more types. In addition, photo-acid-producing agents and thermal acid-producing agents can be used together.

[0308] Furthermore, from the viewpoint of improving the sensitivity of the resist, the surface modifier preferably contains two or more photoacid-generating agents. In this case, from the viewpoint of improving the sensitivity of the resist, it is more preferable to use a combination of a photoacid-generating agent that also functions as a curing catalyst and a photoacid-generating agent that does not function as a curing catalyst.

[0309] When the surface modifier contains an acid-generating agent, its content is appropriately determined by considering the type of acid-generating agent, etc., and therefore cannot be specified in general terms. However, generally, it is in the range of 0.01% to 35% by mass relative to the mass of polysiloxane. From the viewpoint of suppressing the precipitation of the acid-generating agent in the composition, it is preferably 30% by mass or less, more preferably 25% by mass or less. From the viewpoint of fully obtaining this effect, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0310] <<<Amines, Hydroxides>>>

[0311] The surface modifier may contain at least one selected from amines and hydroxides.

[0312] Examples of amines include ammonia; primary amines such as monoethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine; secondary amines such as dimethylamine, ethylmethylamine, and diethylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, dimethylethylamine, methyldiisopropylamine, diisopropylethylamine, diethylethanolamine, and triethanolamine; amines such as ethylenediamine and tetramethylethylenediamine; and cyclic amines such as pyridine and morpholine.

[0313] Examples of hydroxides include inorganic base hydroxides and organic base hydroxides.

[0314] Examples of inorganic base hydroxides include sodium hydroxide and potassium hydroxide.

[0315] Examples of organic base hydroxides include, for example, tetraalkylammonium hydroxide, triarylsulfonium hydroxide, and diaryliodophosphate. Hydroxides, etc. Examples of tetraalkylammonium hydroxides include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Examples of triarylsulfonium hydroxides include, for example, triphenylsulfonium hydroxide and tris(tert-butylphenyl)sulfonium hydroxide. Examples of diaryliodocyanine hydroxides... Hydroxides, such as diphenyl iodide, can be cited as an example. Hydroxide, bis(tert-butylphenyl)iodine Hydroxides, etc.

[0316] There is no particular limitation on the content of amines and hydroxides in the surface modifier, but it is preferably 0.05 to 20 parts by weight relative to 100 parts by weight of polysiloxane, more preferably 0.1 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight.

[0317] <<<Other Additives>>>

[0318] In surface modifiers, various additives can be mixed according to the intended use of the composition.

[0319] Examples of additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology modifiers, and adhesive aids, which are known additives that are mixed into materials (compositions) that form resist underlayer films, antireflective films, pattern reversal films, etc., and can be used in the manufacture of semiconductor devices.

[0320] It should be noted that the following examples illustrate various additives, but are not limited to them.

[0321] -Stabilizer-

[0322] When the surface modifier contains polysiloxane, a stabilizer can be added for purposes such as stabilizing the hydrolytic condensate of the hydrolytic silane mixture. For example, an organic acid, water, alcohol, or a combination thereof can be added.

[0323] Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Oxalic acid and maleic acid are preferred. When an organic acid is added, its amount is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters.

[0324] As water, pure water, ultrapure water, ion-exchanged water, etc. can be used. When used, its addition amount can be 0.1 to 20 parts by mass relative to 100 parts by mass of surface modifier.

[0325] The preferred alcohol is one that is easily dispersed by heating after coating, such as methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount added can be 0.1 to 20 parts by mass relative to 100 parts by mass of the surface modifier.

[0326] -Organic polymers-

[0327] When the surface modifier contains polysiloxane, by adding an organic polymer to the surface modifier, the dry etching rate (the amount of reduction in film thickness per unit time), as well as the attenuation coefficient, refractive index, etc., of the surface-modified layer formed by the surface modifier can be adjusted. There are no particular restrictions on the organic polymer; it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on its intended use.

[0328] Specific examples include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenolic varnish, naphthol varnish, polyether, polyamide, and polycarbonate.

[0329] In this invention, organic polymers containing aromatic or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be used when such functionality is required. Specific examples of such organic polymers include addition polymers containing addition monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as their structural units, as well as condensation polymers such as phenolic varnishes and naphtholic varnishes, but are not limited to these.

[0330] When using an addition polymer as an organic polymer, the polymer can be either a homopolymer or a copolymer.

[0331] In the manufacture of addition polymers, addition polymerizable monomers are used. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0332] 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-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0333] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene 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-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0334] 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.

[0335] 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.

[0336] Specific examples of vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0337] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetystyrene, etc., but are not limited to these.

[0338] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0339] When using condensation polymers as the polymer, examples of such polymers include condensation polymers of diol compounds and dicarboxylic acid compounds. Examples of diol compounds include diethylene glycol, 1,6-hexanediol, and butanediol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Furthermore, examples of polyesters, polyamides, and polyimides include, but are not limited to, poly(pyromellitic terephthalamide), poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0340] When an organic polymer contains hydroxyl groups, these hydroxyl groups can undergo cross-linking reactions with hydrolytic condensates, etc.

[0341] The weight-average molecular weight of organic polymers is typically between 1,000 and 1,000,000. When organic polymers are blended, from the viewpoint of fully obtaining the function of the polymer while suppressing precipitation in the composition, their weight-average molecular weight can be, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000.

[0342] Such organic polymers can be used alone or in combination of two or more.

[0343] When the surface modifier contains both polysiloxane and organic polymer, its content is appropriately determined by considering the function of the organic polymer, etc., and therefore cannot be specified in general terms. However, it can generally be in the range of 1 to 200% by mass relative to the mass of polysiloxane. From the viewpoint of inhibiting precipitation in the composition, it can be, for example, 100% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less. From the viewpoint of fully obtaining the effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more.

[0344] -surfactant-

[0345] Surfactants are effective in suppressing pinholes and streaks when surface modifiers are applied to substrates. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, and UV-curable surfactants. More specifically, examples include 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 monolaurate, sorbitol monopalmitate, sorbitol monostearate, and sorbitol monostearate. Nonionic surfactants and commercial products including monooleate, sorbitol trioleate, sorbitol tristearate, and other sorbitol fatty acid esters; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, and other polyoxyethylene sorbitol fatty acid esters; and more. Names: EF301, EF303, and EF352 (registered trademarks) (manufactured by Mitsubishi Microelectronics Co., Ltd. (formerly Mitsubishi Technology Co., Ltd.)), trade names: EF301 (Note: Registered trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.), FC430, FC431 (スリーエムジャパン) Fluorinated surfactants such as those manufactured by AGC Corporation, and fluorinated surfactants such as Asahigard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimeike Mikaru Corporation), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), but not limited to these.

[0346] Surfactants can be used alone or in combination of two or more.

[0347] When the surface modifier contains a surfactant, its content relative to the mass of the polysiloxane is typically 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass.

[0348] -Rheology modifier-

[0349] Rheology modifiers are primarily added to improve the flowability of surface modifiers, especially during the baking process, to enhance the uniformity of film thickness and improve the filling ability of the composition into pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-isobutyl adipate, di-isooctyl adipate, and octyl decyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate.

[0350] When using these rheology modifiers, their addition amount is typically less than 30% by mass relative to the total film-forming component of the surface modifier.

[0351] -Adhesive Additives-

[0352] Adhesion aids are mainly added to improve the adhesion between the substrate or resist and the film (surface modified layer) formed by the surface modifier, especially to inhibit / prevent resist peeling during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; and benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, as well as urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea.

[0353] When using these adhesive aids, the amount added is typically less than 5% by mass relative to the film-forming component of the surface modifier, preferably less than 2% by mass.

[0354] pH adjuster-

[0355] Furthermore, examples of pH adjusters include organic acids and other acids having one or more carboxylic acid groups, as mentioned above as stabilizers. When using a pH adjuster, its addition amount relative to 100 parts by mass of polysiloxane can be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass.

[0356] -Metal oxides-

[0357] Furthermore, examples of metal oxides that can be added to surface modifiers include, but are not limited to, oxides of one or more of the following metals: tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and w (tungsten), and metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0358] The concentration of the film-forming component in the surface modifier relative to the total mass of the composition can be, for example, 0.01 to 50% by mass, 0.01 to 30% by mass, 0.01 to 25% by mass, or 0.01 to 20.0% by mass.

[0359] The content of polysiloxane in the film-forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, further preferably 80% by mass, and the upper limit is preferably 99% by mass, and the remainder may be the above-mentioned additives.

[0360] Furthermore, the surface modifier preferably has a pH of 1 to 5, and more preferably a pH of 2 to 4.

[0361] Surface modifiers can be manufactured by mixing polysiloxanes and solvents, and, if necessary, other components. In this case, a solution containing polysiloxanes can be prepared in advance, and this solution can be mixed with the solvent and other components.

[0362] In the preparation of surface modifiers, appropriate heating can be applied within a range that does not cause the components to decompose or deteriorate.

[0363] Filtration can be performed during the manufacturing process of the surface modifier or after all components have been mixed, using submicron-level filters or similar equipment. It should be noted that the type of filter material used is not limited; for example, filters made of polyethylene, nylon, fluoropolymer, or polyimide can be used.

[0364] <Second Process>

[0365] The second step is to thin the surface modification layer precursor by contacting it with a thinning solution to obtain a surface modification layer with a film thickness of less than 5 nm.

[0366] In the second step, there are no particular limitations on the method of contacting the surface-modified layer precursor with the thinning solution. Spin coating is preferred in terms of uniform thinning and easy high-precision management of the thinning degree. That is, the second step is preferably a step in which the surface-modified layer precursor is thinned by spin coating the surface-modified layer precursor with the thinning solution to obtain a surface-modified layer with a film thickness of 5 nm or less.

[0367] There are no particular limitations on the conditions for spin coating. For example, it may include a coating process for applying a thinning solution to a semiconductor substrate on which a surface-modified layer precursor has been formed, and a spin process for rotating the semiconductor substrate.

[0368] For coating processes, such as coating a surface-modified layer precursor with a thinning solution, the semiconductor substrate is not rotated or rotates at a low speed (e.g., below 1000 rpm). In the coating process, the thinning solution is brought into contact with the surface-modified layer precursor, causing components in the surface-modified layer precursor to move into the thinning solution.

[0369] For example, a semiconductor substrate is rotated at a high speed (e.g., more than 1,000 rpm and less than 5,000 rpm) to remove the thinning liquid from the semiconductor substrate from which the surface modification layer precursor has been formed.

[0370] By doing so, the surface modification layer precursor is thinned in accordance with the components that move into the thinning liquid, resulting in a surface modification layer with a film thickness of less than 5 nm.

[0371] Examples of coating treatment times include, for example, 10 seconds to 2 minutes.

[0372] Examples of rotation processing times include, for instance, 5 seconds to 1 minute.

[0373] It should be noted that during rotation, for example, an axis orthogonal to the surface of the semiconductor substrate is designated as the axis of rotation.

[0374] In the second step, it is preferable to reduce the film thickness of the surface modification layer precursor by 0.5 nm or more and 10 nm or less, and more preferably by 1 nm or more and 5 nm or less.

[0375] <<Thinning Solution>>

[0376] As a thinning solution, there are no particular limitations as long as it is a liquid that can thin the surface-modified layer precursor by contacting it with the thinning solution; examples include organic solvents, water, acidic solutions, and alkaline solutions. Furthermore, diluents used in the RRC (reducing resist consumption) or EBR (edge ​​bead removing) processes can be used. They can be used alone or in combination of two or more.

[0377] Examples of organic solvents include alcohols, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic esters.

[0378] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents.

[0379] Examples of monohydric alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.

[0380] Examples of polyol solvents include ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0381] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0382] Examples of monoalkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, and propylene glycol monobutyl ether.

[0383] Examples of alkylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc.

[0384] Examples of alkylene glycol monoalkyl ether carboxylic esters include, for example, alkylene glycol monoalkyl ether acetates.

[0385] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0386] Specific examples of other organic solvents include toluene, xylene, 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 lactate, propyl lactate, and lactic acid. Isopropyl acetate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyrate Esters, isobutyl butyrate, ethyl hydroxybutyrate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxyisobutyrate, methyl 3-hydroxyisobutyrate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-methoxybutylacetate, methyl 3-methoxypropylacetate, methyl 3-methoxybutylacetate, methyl 3-methoxybutylpropionate, methyl 3-methoxybutylbutyrate, methyl acetoacetate, methyl methylpropyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, etc.

[0387] Examples of acidic solutions include aqueous solutions of inorganic acids, aqueous solutions of organic acids, and solutions of organic acids. Examples of aqueous solutions of inorganic acids include aqueous solutions of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and perchloric acid. Examples of aqueous solutions of organic acids include aqueous solutions of acetic acid, trifluoroacetic acid, camphor sulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. Examples of solutions of organic acids are substances in which the water in the above-mentioned aqueous solutions of organic acids is replaced by an organic solvent. Examples of organic solvents include alkylene glycol alkyl ethers and alkylene glycol monoalkyl ether carboxylic esters.

[0388] Examples of alkaline aqueous solutions include, for instance, the developing solution used in photolithography processes.

[0389] Examples of alkaline aqueous solutions include, for example, inorganic alkaline aqueous solutions and organic alkaline aqueous solutions. Examples of inorganic alkaline aqueous solutions include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium phosphate aqueous solution, potassium phosphate aqueous solution, etc. Examples of organic alkaline aqueous solutions include tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, monoethanolamine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, etc.

[0390] There are no particular restrictions on the concentration of alkali in an alkaline aqueous solution.

[0391] The so-called RRC (reducing resist consumption) process is a process used to reduce the amount of photoresist used. It is a process of treating the substrate surface with a diluent before applying the photoresist, thereby uniformly coating a small amount of photoresist on the entire surface of the substrate.

[0392] The so-called EBR (edge ​​bead removing) process is a process used to remove unwanted photoresist residues and other contaminants that were coated on the ends or back of the substrate during the coating process.

[0393] Examples of diluents used in the RRC and EBR processes include, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, ethyl 3-ethoxypropionate or methyl hydroxyisobutyrate, and mixtures thereof.

[0394] In one embodiment of the present invention, an organic underlayer film may be disposed between the semiconductor substrate and the surface modification layer in the stack.

[0395] There are no particular restrictions on the organic underlying film used here; any material that has been conventionally used in photolithography processes to date can be selected.

[0396] By providing an organic underlayer film, a surface modification layer, and a resist film (described later) on a substrate, the substrate can be processed even when the pattern width of the resist film is narrowed and the resist film is thinly coated to prevent pattern collapse. This can be achieved by selecting an appropriate etching gas (described later). For example, using a fluorine-based gas with a sufficiently fast etching rate relative to the resist film as the etching gas allows for the processing of the underlayer film. Furthermore, using an oxygen-based gas with a sufficiently fast etching rate relative to the underlayer film allows for the processing of the organic underlayer film. Finally, using a fluorine-based gas with a sufficiently fast etching rate relative to the organic underlayer film as the etching gas allows for the processing of the substrate.

[0397] It should be noted that the substrate and coating method that can be used at this time are the same as those described above.

[0398] (Semiconductor device manufacturing methods)

[0399] The semiconductor device manufacturing method of the present invention includes the following steps: forming a resist film on a stack obtained by the manufacturing method of the present invention; and irradiating the resist film with an electron beam or light and developing it with an organic solvent to obtain a resist pattern.

[0400] A layer (resist film) of, for example, photoresist material is formed on the surface-modified layer. The formation of the resist film can be carried out using a well-known method, namely, by coating a coating-type resist material (resist film forming composition) on the surface-modified layer and then firing it.

[0401] The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0402] As a photoresist material used to form a resist film on a surface-modified layer, there are no particular limitations as long as it contains an organic resin, is photosensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and can develop the unexposed area with an organic solvent.

[0403] There are no particular limitations on the types of organic resins used; for example, the organic resins used in known corrosion-resistant materials can be cited.

[0404] It should be noted that the so-called resist containing organic resin refers to resists that are not metal oxide resists (MOR).

[0405] In addition, for the resist film formed on the surface modification layer, an electron beam lithography resist film (also known as an electron beam resist film) or an EUV lithography resist film (also known as an EUV resist film) can be used instead of a photoresist film.

[0406] There are no particular limitations on electron beam resist materials used to form electron beam resist films, as long as they contain organic resins and can be developed with organic solvents on the unexposed areas.

[0407] In addition, as EUV resist materials for forming EUV resist films, methacrylate resin-based resist materials, polyhydroxystyrene resin-based resist materials, and mixed methacrylate / polyhydroxystyrene resin-based resist materials can be used.

[0408] Next, the resist film formed on top of the surface-modified layer is exposed through a specified mask. During exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam, etc., can be used.

[0409] Post-exposure baking can also be performed as needed after exposure. Post-exposure baking is performed under conditions where appropriate is selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0410] Examples of organic solvents used as developers include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. Butyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate Examples of developing solutions include propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, surfactants may be added to these developing solutions. For developing conditions, the temperature is appropriately selected from 5°C to 50°C, and the time from 10 seconds to 600 seconds.

[0411] For example, the pattern of the resist film (upper layer) formed by such operation is used as a protective film to remove the surface modification layer. Then, the patterned resist film and the patterned surface modification layer are used as protective films to process the substrate.

[0412] The removal (patterning) of the surface modification layer, which uses the pattern of the resist film (upper layer) as a protective film, can be performed, for example, by dry etching, using gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane.

[0413] It should be noted that halogen-based gases are preferred for dry etching of the surface-modified layer. With halogen-based gases, the resist film (photoresist film), which is essentially formed of organic matter, is difficult to remove. In contrast, the surface-modified layer, which contains a large number of silicon atoms, is rapidly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film accompanying the dry etching of the surface-modified layer can be suppressed. Consequently, the photoresist film can be used as a thin film. Therefore, fluorine-based gases are preferred for dry etching of the surface-modified layer. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2), but are not limited to these.

[0414] The processing (patterning) of the (semiconductor) substrate, in which the patterned surface modification layer is used as a protective film, is preferably performed by dry etching using fluorine-based gases.

[0415] Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0416] After the substrate is processed (patterned), the surface modification layer can be removed. The removal of the surface modification layer can be carried out by dry etching or wet etching.

[0417] The dry etching of the surface modification layer preferably uses a fluorine-based gas, as exemplified in patterning, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but is not limited to these.

[0418] Examples of solutions used for wet etching of surface modification layers include dilute hydrofluoric acid, buffered hydrofluoric acid (a mixture of HF and NH4F), aqueous solutions containing hydrochloric acid and hydrogen peroxide (SC-2 solution), aqueous solutions containing sulfuric acid and hydrogen peroxide (SPM solution), aqueous solutions containing hydrofluoric acid and hydrogen peroxide (FPM solution), and alkaline solutions containing ammonia and hydrogen peroxide (SC-1 solution). In addition to the ammonia-hydrogen peroxide aqueous solution (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide water, and water, other alkaline solutions include those containing ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, and 1-butyl-1-methylpyrrolidine. Hydroxide, 1-propyl-1-methylpyrrolidine Hydroxide, 1-Butyl-1-methylpiperidine Hydroxide, 1-propyl-1-methylpiperidine Hydroxides, mepiquat chloride Aqueous solutions of hydroxides, trimethylsulfonium hydroxides, hydrazines, ethylenediamines, or guanidines, ranging from 1% to 99% by mass. These solutions can also be used in combination.

[0419] Example

[0420] The present invention will be described in more detail below with examples of synthesis and embodiments, but the present invention is not limited to the following embodiments.

[0421] It should be noted that, in the embodiments, the apparatus and conditions used for the analysis of the physical properties of the samples are as follows.

[0422] (1) Molecular weight determination

[0423] The molecular weight of the polysiloxane used in this invention is the molecular weight obtained by GPC analysis and converted to polystyrene.

[0424] The determination conditions for GPC can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Co., Ltd.), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), a column temperature of 40°C, a tetrahydrofuran eluent, a flow rate of 1.0 mL / min, and a polystyrene standard sample (manufactured by Showa Denko Co., Ltd.).

[0425] (2) 1 H-NMR

[0426] The NMR spectrometer was prepared by JEOL and the 1H-NMR spectrometer (400 MHz) was used. The solvent used was d6-acetone.

[0427] (3) Residual nitric acid

[0428] The amount of nitric acid remaining in the system was evaluated and determined by ion chromatography.

[0429] (4) AFM observation

[0430] The surface roughness was evaluated by observing a 10μm × 10μm area using a Hitachi Hightech AFM5500M microscope.

[0431] (5) Film thickness measurement

[0432] The film thickness was measured using an elliptic film thickness measuring device RE-3100 (manufactured by SCREEN).

[0433] The thickness of the surface-modified layer precursor was measured as follows. After the thickness of the SiO2 oxide film formed on the substrate was measured in advance, a surface modifier was applied to form the surface-modified layer precursor, and the thickness was measured after that. The difference between the two measurements was taken as the thickness of the surface-modified layer precursor.

[0434] The thickness of the surface-modified layer was measured as follows. After the thickness of the SiO2 oxide film formed on the substrate was measured in advance, the thickness was measured after the surface modifier was coated / thinned, and the difference was taken as the thickness of the surface-modified layer.

[0435] [1] Synthesis of polymers (hydrolysis condensates)

[0436] (Synthesis example 1)

[0437] 14.3 g of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane and 21.5 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C and allowed to react for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0438]

[0439] (Synthesis example 2)

[0440] 17.2 g of triethoxy((4-methoxymethyl-2-methoxyphenoxy)methyl)silane and 25.8 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and ethanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0441]

[0442] (Synthesis example 3)

[0443] 11.4 g of (4-methoxyphenyl)trimethoxysilane and 17.1 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C and allowed to react for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0444]

[0445] (Synthesis Example 4)

[0446] 12.1 g of (4-ethoxyphenyl)trimethoxysilane and 18.2 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C and allowed to react for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0447]

[0448] (Synthesis Example 5)

[0449] 13.6 g of (4-(2-methoxyethoxy)phenyl)trimethoxysilane and 20.4 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C and allowed to react for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0450]

[0451] (Synthesis Example 6)

[0452] 12.1 g of (4-methoxybenzyl)trimethoxysilane and 18.2 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0453]

[0454] (Comparative Synthesis Example 1)

[0455] 9.9 g of trimethoxyphenylsilane and 14.9 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C and allowed to react for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0456]

[0457] (Comparative Synthesis Example 2)

[0458] 10.4 g of tetraethoxysilane and 15.6 g of propylene glycol monoethyl ether were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 6.3 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 120 °C and allowed to react for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and ethanol (a reaction byproduct) were removed by distillation under reduced pressure, yielding a concentrated solution containing a polymer (hydrolyzed condensate) with the structure shown below, using 1-ethoxy-2-propanol as a solvent. It should be noted that the solids concentration of the obtained concentrated solution, calculated based on the solid residue after heating at 150 °C, exceeds 20% by mass.

[0459]

[0460] [2] Preparation of surface modifier (coating solution)

[0461] The polysiloxane (polymer), acid (additive 1), photoacid generator (additive 2), photoacid generator (additive 3), and solvent obtained in the above synthesis example were mixed in the proportions shown in Table 1 and filtered through a 0.1 μm fluoropolymer filter to prepare surface modifiers (coating solutions). The amounts added in Table 1 are expressed in parts by mass.

[0462] It should be noted that although the hydrolysis condensate (polymer) was used to prepare the composition as a solution containing the condensate obtained in the synthesis example, the polymer addition ratio in Table 1 does not represent the amount of polymer solution added, but rather the amount of polymer itself added.

[0463] The meanings of the abbreviations in Table 1 are as follows.

[0464] <Solvent>

[0465] PGME: Propylene Glycol Monomethyl Ether

[0466] PGEE: Propylene Glycol Monoethyl Ether

[0467] <Additive 1>

[0468] MA: Maleic acid

[0469] <Additive 2>

[0470] TPSNO3: Triphenylsulfonium nitrate

[0471] <Additive 3>

[0472] TPSTf: Triphenylsulfonium trifluoromethanesulfonate

[0473] [Table 1]

[0474] Coating solutions 1-8 and comparative coating solutions 1-3 further contain nitric acid contained in the polymer solutions prepared in synthetic examples 1-6 and comparative synthetic examples 1-2.

[0475] [3] Thin film formation test

[0476] The prepared coating solutions 1–8 and comparative coating solutions 1–3 were respectively coated onto silicon wafers using a spin coater. The wafers were heated on a hot plate at 140°C or 215°C for 1 minute to form surface modification layer precursors. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V): thinning solution) was coated onto each surface modification layer precursor and spin-dried. The film thickness of the surface modification layer after coating with the thinning solution was measured. Surface modifiers with a film thickness of less than 30 Å and a smooth surface obtained in the AFM evaluation were designated as "good," while surface modifiers with a film thickness exceeding 30 Å were designated as "poor." The results are shown in Table 2.

[0477] [Table 2]

[0478] [4] Substrate surface modification test

[0479] Coating solutions 1-8 and comparative coating solutions 1-3 were applied to bare silicon substrates. Specifically, coating solutions 1-8 and comparative coating solutions 1-3 were each applied to 1 ml wafers using CLEANTRACK ACT8 (registered trademark). After spin coating at 1500 rpm for 60 seconds, the wafers were calcined at 140°C or 215°C. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was applied to each surface modification layer precursor and spin-dried to form a surface modification layer with a thickness of less than 30 Å. The water contact angle was then measured on the bare silicon substrates for which the surface modification layers of coating solutions 1-8 and comparative coating solutions 1-3 were formed. The water contact angle was measured under constant temperature and humidity conditions (23℃±2℃, 45%RH±5%) using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). The measurement was taken after the liquid volume was 3 μl and the mixture had been allowed to stand for 5 seconds. Since the water contact angle of bare silicon is below 20 degrees, a water contact angle less than 30 degrees was defined as not suitable for surface modification ("poor"), and a water contact angle above 30 degrees was defined as suitable for surface modification ("good"). The measurement results are recorded in Table 3 below.

[0480] [Table 3]

[0481] [5] Formation of resist patterns using EB exposure: negative organic solvent development

[0482] Spin-coating solution 1 was applied to bare silicon and heated at 140°C for 1 minute. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was applied to each coated film and spin-dried to form a surface modified layer (1-3 nm) with a film thickness of less than 30 Å.

[0483] EUV resist solution (methacrylate / PHS-based resist) was further spin-coated onto it, and heated at 110°C for 1 minute to form an EUV resist film (C layer). Then, it was exposed using an ERIONIX EB painting apparatus (ELS-G130).

[0484] After exposure, post-exposure heating (PEB, 90°C for 1 minute) is performed, followed by cooling on a cooling plate to room temperature. The image is then developed with an organic solvent developer (butyl acetate) for 30 seconds and rinsed to form a resist pattern.

[0485] Using the same steps, a resist pattern was formed on a substrate having a surface-modified layer obtained from coating solutions 2-8 and comparative coating solutions 1-2. It should be noted that the heating temperature (firing temperature) after spin coating was set to the firing temperatures shown in Table 4.

[0486] Furthermore, regarding the obtained patterns, the ability to form a 50nm pitch, 25nm line pattern is evaluated by confirming the pattern shape observed from the pattern cross-section.

[0487] In observing the pattern shape, a condition where the shape extends from the foot to the bottom and there is no significant residue in the gaps is rated as "good," while an undesirable condition where the resist pattern is unresolved or collapsed is rated as "poor." The results are shown in Table 4.

[0488] [Table 4]

[0489] Furthermore, in the case of coating solutions 2 and 4 (surface modifiers) containing multiple photoacid generators, the desired pattern size can be obtained even with low exposure compared to coating solutions 1 and 3 (surface modifiers) which do not contain photoacid generators, demonstrating improved sensitivity of the resist.

Claims

1. A method for manufacturing a laminate, comprising the following steps: The first step involves coating a surface modifier containing polysiloxane and solvent onto a semiconductor substrate, followed by firing to crosslink the polysiloxane, thereby obtaining a surface-modified layer precursor; and The second step involves contacting the surface-modified layer precursor with a thinning solution to thin the precursor, thereby obtaining a surface-modified layer with a film thickness of less than 5 nm. The polysiloxane has an aromatic hydrocarbon ring and an RO- group bonded to the aromatic hydrocarbon ring, where R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 total carbon atoms. The stacked body has the surface modification layer and the semiconductor substrate. The laminate is used to perform photolithography on the unexposed resist film using an organic resin-containing resist, thereby developing it with an organic solvent.

2. The method for manufacturing the laminate according to claim 1, wherein the polysiloxane is a hydrolytic condensate of a hydrolyzable silane. The hydrolyzable silane comprises a compound represented by formula (1) below. In equation (1), R a The group represents a group having an aromatic hydrocarbon ring and an RO- group bonded to the aromatic hydrocarbon ring, where R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 total carbon atoms; wherein, In Si-R a , Si is bound to a carbon atom in R a . R b The term represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or represents an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonyl group, or an organogroup having a cyano group, or a combination of two or more thereof; wherein, R b With R a different; X represents an alkoxy, arylalkoxy, acyloxy, or halogen atom; a represents an integer from 1 to 3; b represents an integer from 0 to 2; a + b is an integer from 1 to 3; When a is 2 or more, there are 2 or more R a They can be the same or different; When b is 2, there are 2 R b They can be the same or different; When (4-ab) is 2 or more, two or more X's can be the same or different.

3. The method for manufacturing a laminate according to claim 2, wherein R in formula (1) a It is represented by the following equation (1-1), In formula (1-1), R represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms in total; R c Represents monovalent bases with 1 to 6 carbon atoms; among which, R c Unlike RO-based; Ar represents a benzene ring, naphthalene ring, or biphenyl ring; Y represents a single bond or a divalent group with 1 to 4 carbon atoms; a1 represents an integer from 1 to 3; a2 represents an integer from 0 to 3; When a1 is 2 or more, the two or more RO- groups can be the same or different; When a2 is 2 or more, there are 2 or more R's. c They can be the same or different; This represents a bonding bond.

4. The method for manufacturing a laminate according to claim 1, wherein the solvent comprises at least one selected from carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers.

5. The method for manufacturing a laminate according to claim 1, wherein the surface modifier contains two or more photoacid-generating agents.

6. The method for manufacturing a laminate according to claim 1, wherein the thinning solution is selected from at least one of organic solvents, water, acidic solutions, alkaline solutions, and diluents used in the Reduction of Resist Consumption (RRC) process or the Edge Bead Removal (EBR) process.

7. The method for manufacturing a stacked body according to claim 1, wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having a film of inorganic or organic material.

8. The method for manufacturing a laminate according to claim 7, wherein the inorganic material is selected from at least one of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides.

9. The method for manufacturing a multilayer according to claim 7, wherein the organic material is selected from at least one of amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, polyimide, and organic films obtained by doping or partially replacing them with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogen.

10. The method for manufacturing a laminate according to claim 1, wherein the laminate further comprises a resist underlayer film.

11. The method for manufacturing a laminate according to claim 1, wherein the second step is to thin the surface modification layer precursor by spin-coating a thinning liquid onto the surface modification layer precursor to obtain a surface modification layer with a film thickness of less than 5 nm.

12. The method for manufacturing a stack according to claim 1, wherein the stack is used for EUV or electron beam lithography.

13. A method for manufacturing a semiconductor device, comprising the following steps: The step of forming a resist film on a laminate obtained by the manufacturing method of any one of claims 1 to 12; and The process of irradiating the resist film with an electron beam or light and developing it with an organic solvent to obtain a resist pattern.

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