Method for producing layered body and method for producing semiconductor element

Abstract

Provided is a method for producing a layered body having a surface modification layer and a semiconductor substrate, the method comprising: a first step for obtaining a surface modification layer precursor by coating a semiconductor substrate with a surface modifier containing a polysiloxane (A) having organic groups having nitrogen atoms and a solvent (B), and then baking the semiconductor substrate with the surface modifier thereon; and a second step for obtaining a surface modification layer having a film thickness no greater than 5 nm by inducing contact between the surface modification layer precursor and a thinning solution (X) in order to thin the surface modification layer precursor.

Description

Method for manufacturing laminate and method for manufacturing semiconductor element

[0001] The present invention relates to a method for manufacturing a laminate, preferably a method for manufacturing a laminate on which a resist pattern is formed, and also to a method for manufacturing a semiconductor element.

[0002] Lithography processes using resist compositions have been conventionally performed in the manufacture of semiconductor devices. In recent years, with the increasing integration of semiconductor devices, there has been a demand for finer patterns, such as wiring. As patterns become finer, light sources with shorter wavelengths, such as far ultraviolet light, vacuum ultraviolet light, electron beams (EB), and X-rays, have begun to be used. In particular, short-wavelength light such as KrF excimer lasers (wavelength 248 nm) and ArF excimer lasers (wavelength 193 nm), have recently been used to form resist patterns.

[0003] Accordingly, the effects of diffuse reflection and standing waves of actinic rays from semiconductor substrates have become a major problem, and therefore, in order to solve this problem, a method of providing an anti-reflective coating (Bottom Anti-Reflective Coating: BARC) between the resist and the semiconductor substrate has been widely studied. As such an anti-reflective coating, many studies have been conducted on organic anti-reflective coatings formed from compositions containing polymers having light-absorbing groups (chromophores) because of their ease of use (for example, Patent Document 1).

[0004] On the other hand, with EUV (extreme ultraviolet, wavelength 13.5 nm) and electron beams, which are applied to further fine processing techniques, the problem of reflection from semiconductor substrates does not arise, but resist pattern collapse associated with pattern miniaturization becomes a problem, and therefore, resist underlayer films with high adhesion to resists are being investigated.

[0005] Special Publication No. 2008-501985

[0006] Conventional resist underlayer films have the problem of being prone to etching defects such as side etching during the etching process. Therefore, if it were possible to modify the substrate surface using a surface modification layer that is thinner than conventional underlayer films, it would be expected that the adhesion of the photoresist would be improved without causing etching defects such as side etching, and that the photoresist resolution in advanced lithography processes would be improved. Furthermore, it would be even more desirable if the surface modification layer could increase the sensitivity of the resist. However, it is not easy to form a thin surface modification layer uniformly.

[0007] The present invention has been made in consideration of such circumstances, and aims to provide a method for manufacturing a laminate capable of forming a thin surface modification layer that can increase the sensitivity of the resist, a method for manufacturing a semiconductor element using the manufacturing method, and a laminate having a thin surface modification layer.

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0009] That is, the present invention encompasses the following: [1] A method for producing a laminate having the surface modification layer and the semiconductor substrate, comprising: a first step of applying a surface modification agent containing polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B) onto a semiconductor substrate, followed by baking to obtain a surface modification layer precursor; and a second step of contacting the surface modification layer precursor with a thinning liquid (X) to thin the surface modification layer precursor to obtain a surface modification layer having a film thickness of 5 nm or less. [2] A method for producing a laminate having the surface modification layer and the semiconductor substrate, wherein the nitrogen atom is a nitrogen atom (N １ ), a nitrogen atom (N ２ ), a nitrogen atom (N ３ ), and the N １ ~ The above N ３ A nitrogen atom other than the nitrogen atom (N ４[3] The method for producing a laminate according to [1] or [2], wherein the organic group having a nitrogen atom is a group bonded to a silicon atom and is a monovalent group represented by any one of the following formulas (Z1) to (Z4): (In formulas (Z1) to (Z4), R ａ R each independently represents a single bond or a divalent group having 1 to 6 carbon atoms. ｂ R each independently represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. ｃ１ ~R ｃ３ each independently represents a monovalent group having 1 to 20 carbon atoms; X represents a single bond, —O—, or —N(R ｅ )-(R ｅ represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. ｅ )-, then R ｅ and R ｃ２ may be taken together to form a ring structure having 5 to 7 carbon atoms. ｄ each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. Each n independently represents 0 or a positive number. HX represents an acid. * represents a bond.) [4] The method for producing a laminate according to any one of [1] to [3], wherein the polysiloxane is a hydrolysis condensate of a hydrolyzable silane containing a compound represented by the following formula (A): (In formula (A), R １ are groups bonded to a silicon atom, and each independently represents an organic group having a nitrogen atom. ２are groups bonded to silicon atoms, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group having an epoxy group which may be ring-opened, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof. Y are groups or atoms bonded to silicon atoms, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to 2. a+b is 1 to 3.) [5] R in the formula (A) １ is a monovalent group represented by any one of the following formulas (Z1) to (Z4): (In formulas (Z1) to (Z4), R ａ R each independently represents a single bond or a divalent group having 1 to 6 carbon atoms. ｂ R each independently represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. ｃ１ ~R ｃ３ each independently represents a monovalent group having 1 to 20 carbon atoms; X represents a single bond, —O—, or —N(R ｅ )-(R ｅ represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. ｅ )-, then R ｅ and R ｃ２ may be taken together to form a ring structure having 5 to 7 carbon atoms. ｄeach independently represent a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. Each n independently represents 0 or a positive number. HX represents an acid. * represents a bond.) [6] The method for producing a laminate according to any one of [1] to [5], wherein the solvent (B) contains at least one selected from the group consisting of a carboxylic acid having a hydroxy group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether. [7] The method for producing a laminate according to any one of [1] to [6], wherein the thinning liquid (X) contains at least one of an organic solvent and water. [8] The method for producing a laminate according to any one of [1] to [7], wherein the surface modifier further contains a curing catalyst (C). [9] The method for producing a laminate according to any one of [1] to [8], wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having an inorganic or organic film.

[10] The method for producing a laminate according to [9], wherein the inorganic material is at least one selected from the group consisting of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides.

[11] The method for producing a laminate according to [9], wherein the organic material is at least one selected from the group consisting of amorphous carbon, graphite, fullerenes, carbon nanotubes, diamond, diamond-like carbon, polyimides, and organic films doped or partially substituted with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogen.

[12] The method for producing a laminate according to any one of [1] to

[11] , wherein the laminate further comprises a resist underlayer film.

[13] The method for producing a laminate according to any one of [1] to

[12] , wherein the second step is a step of spin-coating the thinning solution (X) on the surface-modified layer precursor to thin the surface-modified layer precursor to obtain a surface-modified layer having a thickness of 5 nm or less.

[14] The method for producing a laminate according to any one of [1] to

[13] , wherein the laminate is used for EUV or electron beam lithography.

[15] A method for producing a laminate according to any one of [1] to

[13] , wherein the laminate is used for EUV lithography using a metal-containing resist film.

[16] A method for producing a semiconductor element, comprising the steps of forming a resist film on a laminate obtained by the method for producing a laminate according to any one of [1] to

[15] , and exposing and developing the resist film to obtain a resist pattern.

[17] A method for producing a semiconductor element according to

[16] , wherein the resist film is a metal-containing resist film.

[18] A laminate comprising a semiconductor substrate and a surface-modified layer having a thickness of 5 nm or less, formed using a surface modifier containing polysiloxane (A) having an organic group containing a nitrogen atom and a solvent (B).

[19] The laminate according to

[18] , wherein the laminate is used for EUV or electron beam lithography.

[20] The laminate according to

[18] , wherein the laminate is used for EUV lithography using a metal-containing resist film.

[21] A surface modifier containing a polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B), the surface modifier being used in the method for producing a laminate according to any one of [1] to

[15] .

[22] A compound represented by the following formula (T1): (In formula (T1), Q represents a divalent group having 1 to 6 carbon atoms. R ｐ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ｑ is expressed by the following formula (R ｑ -1) or formula (R ｑ R represents a monovalent group represented by the formula (I)-2). ｓ each independently represents an alkyl group having 1 to 3 carbon atoms. (Formula (R ｑ -1) and formula (R ｑ -2), * represents a bond. ｑ -2) Medium, R ｒ represents a perfluoroalkyl group having 1 to 3 carbon atoms, a difluoromethyl group, an iodine atom, an OH group, or a nitro group.

[0010] According to the present invention, it is possible to provide a method for manufacturing a laminate capable of forming a thin surface modification layer that can increase the sensitivity of a resist, a method for manufacturing a semiconductor element using the manufacturing method, and a laminate having a thin surface modification layer.

[0011] (Method for producing a laminate, and laminate) The method for producing a laminate of the present invention includes a first step and a second step. The method for producing a laminate of the present invention may further include other steps. The first step is a step of applying a surface modifier containing a polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B) onto a semiconductor substrate, followed by baking to obtain a surface modified layer precursor. The second step is a step of thinning the surface modified layer precursor by contacting the surface modified layer precursor with a thinning liquid (X) to obtain a surface modified layer with a film thickness of 5 nm or less. A silicon-containing film is obtained by applying a surface modifier containing a polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B) and then baking. However, it is not easy to obtain a thin film (for example, a film with a film thickness of 5 nm or less) without film defects such as pinholes or coating unevenness through this step alone, and it is necessary to thoroughly control the coating conditions, baking conditions, etc. Therefore, the present inventors have intensively studied a method for manufacturing a laminate capable of forming a thin surface-modified layer, and have found that a thin surface-modified layer can be formed by forming a layer (surface-modified layer precursor) with a thickness greater than the target thickness in the first step, and then contacting the layer with a thinning liquid (X) to thin the layer in the second step. When the surface-modified layer precursor obtained from the surface modifier is contacted with the thinning liquid (X), the surface-modified layer precursor is not completely removed from the substrate, but remains on the substrate as a thin surface-modified layer. The present inventors believe that this is related to the interaction of the hydroxyl group of the polysiloxane (A) with the substrate. Furthermore, the present inventors have discovered that the sensitivity of the resist film disposed on the surface-modified layer can be increased by having a nitrogen atom in the organic group of the polysiloxane (A), which led to the present invention.

[0012] The laminate obtained by the laminate manufacturing method of the present invention has a surface modification layer and a semiconductor substrate.

[0013] The laminate obtained by the laminate manufacturing method of the present invention is suitable for use in EUV (extreme ultraviolet, wavelength 13.5 nm) or electron beam lithography. The laminate obtained by the laminate manufacturing method of the present invention may further comprise other layers or films. Examples of such other layers include a resist underlayer film. The resist underlayer film is not particularly limited as long as it is a resist underlayer film used in a lithography process. The resist underlayer film may be, for example, a silicon-containing resist underlayer film or an organic underlayer film. Examples of the organic underlayer film include an organic underlayer film having a high carbon content. An organic underlayer film having a high carbon content can be obtained, for example, from a composition containing a novolac resin in the broad sense. Examples of such compositions include the resist underlayer film-forming compositions described in WO 2010 / 147155, WO 2012 / 077640, WO 2013 / 005797, and WO 2017 / 094780. The resist underlayer film is, for example, a layer below the surface modification layer. The resist underlayer film is, for example, disposed between the semiconductor substrate and the surface modification layer. In the present invention, there is no clear distinction between a film and a layer.

[0014] The thickness of the surface modification layer is 5 nm or less, preferably 3 nm or less. There is no particular limitation on the lower limit of the thickness of the surface modification layer, and the thickness of the surface modification layer may be 0.1 nm or more, or 0.2 nm or more.

[0015] In the present invention, the film thickness is measured as follows: The film thickness is measured using an ellipsometric film thickness measuring device RE-3100 (manufactured by SCREEN).

[0016] <First Step> The first step is a step of obtaining a surface modification layer precursor. In the first step, a surface modification agent is applied onto a semiconductor substrate, and then the surface modification layer precursor is obtained by baking.

[0017] The semiconductor substrate used in the first step is not particularly limited as long as it is a substrate used in the manufacture of precision integrated circuit devices, and examples of the semiconductor substrate include inorganic substrates, organic substrates, substrates having an inorganic film, and substrates having an organic film.

[0018] Examples of inorganic substances include arsenic, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides. These may be used alone or in combination of two or more. Examples of metals include silicon, germanium, titanium, tungsten, hafnium, zirconium, chromium, copper, aluminum, indium, gallium, palladium, iron, tantalum, iridium, molybdenum, and alloys thereof. Examples of metal oxides include SiO ２ , TiO ２ Examples of metal nitrides include SiN, TiN, and TaN. Examples of metal carbides include SiC and TiC. Examples of metal oxynitrides include SiON and TiON. Examples of metal oxycarbides include SiOC and TiOC. Examples of metal carbonitrides include SiCN and TiCN.

[0019] Examples of organic materials include amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, and polyimide. These materials can be used alone or in combination of two or more. The organic materials described above may be doped or partially substituted with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogen.

[0020] Examples of the semiconductor substrate include semiconductor substrates such as silicon wafers coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low dielectric constant materials (low-k materials), and flexible substrates.

[0021] The method for applying the surface modifier to the semiconductor substrate is not particularly limited, and can be carried out by a suitable application method such as using a spinner or a coater.

[0022] After the surface modifier is applied to the semiconductor substrate, the substrate can be baked using a heating means such as a hot plate. Baking conditions are appropriately selected from a baking temperature of 40°C to 400°C or 80°C to 250°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 250°C and the baking time is 0.5 minutes to 2 minutes.

[0023] The baking evaporates the solvent in the surface modifier, yielding a layer-like surface-modified layer precursor. In some cases, the baking also induces a crosslinking reaction, yielding a crosslinked layer. Crosslinking includes partial crosslinking.

[0024] The film thickness of the surface modification layer precursor 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.

[0025] <<Surface Modifier>> The surface modifier contains a polysiloxane (A) having an organic group containing a nitrogen atom and a solvent (B). The surface modifier may further contain other components. The surface modifier used in the method for producing the laminate of the present invention is also within the scope of the present invention.

[0026] <<<Polysiloxane (A)>>> The polysiloxane (A) has an organic group having a nitrogen atom. The organic group having a nitrogen atom is bonded to, for example, a silicon atom. The number of carbon atoms in the organic group having a nitrogen atom is not particularly limited, but is, for example, 1 to 30.

[0027] In order to obtain the effects of the present invention, the nitrogen atom in the nitrogen-containing organic group is preferably the following N １ ~N ４ It is a nitrogen atom of any of the following. １ : Nitrogen atom constituting an amide bond N ２ : Nitrogen atom constituting the sulfonamide bond N ３ : Nitrogen atom constituting the guanidine structure N ４ :N １ ~N ３ A nitrogen atom other than the above, which is bonded to at least one carbon atom and the bond is a single bond. Note that the amide bond (-N(R)-C(=O)-: R represents a hydrogen atom or a monovalent group) in the description of polysiloxane (A) encompasses an amide bond that is a part of a urethane bond and an amide bond that is a part of a urea bond.

[0028] The organic group having a nitrogen atom may or may not have an ionic bond. Examples of the organic group having a nitrogen atom with an ionic bond include an ammonium group and a guanidium group.

[0029] From the viewpoint of suitably achieving the effects of the present invention, the organic group having a nitrogen atom is preferably a group bonded to a silicon atom and a monovalent group represented by any one of the following formulas (Z1) to (Z4): (In formulas (Z1) to (Z4), R ａ R each independently represents a single bond or a divalent group having 1 to 6 carbon atoms. ｂ R each independently represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. ｃ１ ~R ｃ３ each independently represents a monovalent group having 1 to 20 carbon atoms; X represents a single bond, —O—, or —N(R ｅ)-(R ｅ represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. ｅ )-, then R ｅ and R ｃ２ may be taken together to form a ring structure having 5 to 7 carbon atoms. ｄ each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms; each n independently represents 0 or a positive number; HX represents an acid; * represents a bond.

[0030] -R ａ -R ａ In the formula (R), examples of the divalent group having 1 to 6 carbon atoms include alkylene groups having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. ａ As the alkylene group, an alkylene group having 1 to 6 carbon atoms is preferred.

[0031] -R ｂ -R ｂ Examples of the monovalent group having 1 to 6 carbon atoms in R include alkyl groups having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl groups, ethyl groups, propyl groups, and butyl groups. ｂ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0032] -R ｃ１ ~R ｃ３ -R ｃ１ ~R ｃ３The monovalent group having 1 to 20 carbon atoms in the formula (I) may be linear, branched, or cyclic, or may be a combination of any two or more of these. The monovalent group having 1 to 20 carbon atoms may or may not have a heteroatom. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms. In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The monovalent group having 1 to 20 carbon atoms may or may not have a multiple bond. Examples of multiple bonds include double bonds and triple bonds. Examples of multiple bonds include carbon-carbon double bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, oxygen-nitrogen double bonds, sulfur-oxygen double bonds, carbon-carbon triple bonds, and carbon-nitrogen triple bonds. The monovalent group having 1 to 20 carbon atoms may or may not have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene, naphthalene rings, and anthracene rings. When a monovalent group having 1 to 20 carbon atoms has an aromatic ring, the aromatic ring may or may not have a substituent. Examples of substituents include a hydroxy group, a nitro group, a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. The monovalent group having 1 to 20 carbon atoms may or may not have an aliphatic ring. The monovalent group having 1 to 20 carbon atoms may be a residue obtained by removing one hydrogen atom from a terpene. Terpenes are compounds composed of isoprene as a basic unit. Terpenes may have an alcoholic hydroxyl group, a carbonyl group, a carboxy group, or the like. Examples of terpenes include myrcene, ocimene, limonene, terpineol, pinene, camphor, farnesol, nerolidol, elemene, caryophyllene, and nootkatone.

[0033] R ｃ１ and R ｃ２Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, a group represented by the following formula (C1), and a group represented by the following formula (C2). (In formula (C), R ｆ represents a single bond or an alkylene group having 1 to 4 carbon atoms. Ar represents a monovalent aromatic group which may have a substituent. * represents a bond.

[0034] Examples of the monovalent aromatic group for Ar include residues in which one hydrogen atom has been removed from the aromatic rings described above for the monovalent groups having 1 to 20 carbon atoms. Examples of the substituent for Ar include the substituents described above for the monovalent groups having 1 to 20 carbon atoms.

[0035] R ｃ３ Examples of the alkenyl group include an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group.

[0036] -R ｄ -R ｄ As the monovalent group having 1 to 20 carbon atoms in the formula (I), an alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.

[0037] -R ｅ -R ｅ Examples of the monovalent group having 1 to 6 carbon atoms in R include alkyl groups having 1 to 4 carbon atoms. ｅ As the alkyl group, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group or an ethyl group is more preferred, and a hydrogen atom or a methyl group is particularly preferred.

[0038] X is -N(R ｅ )-, then R ｅ and R ｃ２ may be combined with each other to form a ring structure having 5 to 7 carbon atoms. An example of the ring structure having 5 to 7 carbon atoms is a lactam ring having 5 to 7 carbon atoms.

[0039] -n and HX- In formula (Z3) and formula (Z4), n represents 0 or a positive number. The upper limit of n is, for example, 3 in formula (Z3) and 1 in formula (Z4). When n is a positive number and the acid is a monovalent acid (e.g., methacrylic acid), n represents a positive integer. When the acid is a divalent acid (e.g., oxalic acid), n represents a positive integer multiple of 1 / 2. When the acid is a trivalent acid, n represents a positive integer multiple of 1 / 3. HX is not particularly limited as long as it is an acid. Examples of acids include the acids listed in the section <<<Acids>>> described below. Examples of acids include organic acids. Examples of acid groups in organic acids include carboxy groups and sulfo groups. Examples of organic acids include sorbic acid, acrylic acid, methacrylic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, p-toluenesulfonic acid, phenolsulfonic acid, and 5-sulfosalicylic acid. In formulas (Z3) and (Z4), when n is not 0, formulas (Z3) and (Z4) have a salt structure. In other words, formulas (Z3) and (Z4) have an ionic bond.

[0040] Examples of methods for introducing a salt structure into the polysiloxane represented by formula (Z3) and formula (Z4) include the following methods (I) and (II). (I): A method for introducing a salt structure into the polysiloxane represented by formula (Z3) and formula (Z4) (where n is 0) by adding an acid to a composition containing a polysiloxane having a monovalent group represented by formula (Z3) or formula (Z4) (where n is 0). (II): A method for introducing a salt structure into the polysiloxane represented by formula (A) (where R １ represents a monovalent group represented by formula (Z3) or formula (Z4), and n represents a positive number.

[0041] Examples of formulas (Z1) to (Z4) include the following groups. * represents a bond. Me represents a methyl group.

[0042] The polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond. The polysiloxane may include a modified polysiloxane in which a portion of the silanol groups has been modified, for example, a polysiloxane modified product in which a portion of the silanol groups has been alcohol-modified or acetal-protected. Furthermore, the polysiloxane may include, for example, a hydrolysis condensation product of a hydrolyzable silane, and may include a modified polysiloxane in which at least a portion of the silanol groups of the hydrolysis condensation product have been alcohol-modified or acetal-protected. The hydrolyzable silane in the hydrolysis condensation product may contain one or more hydrolyzable silanes. The polysiloxane may have a structure having a cage-type, ladder-type, linear-type, or branched-type main chain. Furthermore, commercially available polysiloxanes may be used as the polysiloxane.

[0043] The polysiloxane is, for example, a hydrolysis condensate of a hydrolyzable silane containing a compound represented by the following formula (A). In the present invention, the "hydrolysis condensate" of a hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only polyorganosiloxane polymers, which are condensates in which condensation has been completely completed, but also polyorganosiloxane polymers, which are partial hydrolysis condensates in which condensation has not been completely completed. Like condensates in which condensation has been completely completed, such partial hydrolysis condensates are polymers obtained by the hydrolysis and condensation of a hydrolyzable silane, but they are partially hydrolyzed and not condensed, and therefore Si-OH groups remain. In addition to the hydrolysis condensate, the surface modifier may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) or monomers (hydrolyzable silanes). In this specification, "hydrolyzable silanes" may also be simply referred to as "silane compounds." In this specification, "polysiloxanes" may also be referred to as "hydrolysis condensates."

[0044] (In formula (A), R １ are groups bonded to a silicon atom, and each independently represents an organic group having a nitrogen atom. ２are groups bonded to silicon atoms, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group having an epoxy group which may be ring-opened, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof. Y is a group or atom bonded to silicon atoms, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to 2. a+b is 1 to 3.

[0045] In addition, R １ and R ２ is not a hydrolyzable group. ２ is R １ is a different group from

[0046] a is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. b is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0047] -R １ -R １ In order to obtain the effects of the present invention, the nitrogen atom in the organic group having a nitrogen atom is preferably the following N １ ~N ４ It is a nitrogen atom of any of the following. １ : Nitrogen atom constituting an amide bond N ２ : Nitrogen atom constituting the sulfonamide bond N ３ : Nitrogen atom constituting the guanidine structure N ４ :N １ ~N ３a nitrogen atom other than the above, which is bonded to at least one carbon atom and the bond is a single bond;

[0048] R １ In order to suitably obtain the effects of the present invention, the organic group having a nitrogen atom in the formula (Z1) is preferably a group bonded to a silicon atom and a monovalent group represented by any one of the formulas (Z1) to (Z4) above.

[0049] -R ２ The alkyl group may be linear, branched, or cyclic, and the number of carbon atoms therein 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. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl ... a 1,2-dimethyl-n-pentyl group, a 2,2-dimethyl- Examples of such alkyl groups include 1-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. In this specification, "i" means "iso", "s" means "sec", and "t" means "tert".

[0050] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 2,5-dimethylcyclobutyl group, a 2,6-dimethylcyclobutyl group, a 2,7-dimethylcyclobutyl group, a 2,8-dimethylcyclobutyl group, a 2,9-dimethylcyclobutyl group, a 2,10-dimethylcyclobutyl group, a 2,11-dimethylcyclobutyl group, a 2,12-dimethylcyclobutyl group, a 2,13-dimethylcyclobutyl group, a 2,14-dimethylcyclobutyl group, a 2,15-dimethylcyclobutyl group, a 2,16-dimethylcyclobutyl group, a 2,17-dimethylcyclobutyl group, a 2,18-dimethylcyclobutyl group, a 2,19-dimethylcyclobutyl group, a 2,20-dimethylcyclobutyl group, a 2,21-dimethylcyclobutyl group, a 2,222-dimethylcyclobutyl group, a 2,23-dimethylcyclobutyl group, a 2,41-dimethylcyclobutyl group, a 2,42-dimethylcyclobutyl group, a 2,19-dimethylcyclobutyl group, a 2,19-dimethylcyclobutyl group, a 2,19 Examples include cycloalkyl groups such as a methyl cyclobutyl group, a 3,3-dimethyl cyclobutyl group, a 1-n-propyl cyclopropyl group, a 2-n-propyl cyclopropyl group, a 1-i-propyl cyclopropyl group, a 2-i-propyl cyclopropyl group, a 1,2,2-trimethyl cyclopropyl group, a 1,2,3-trimethyl cyclopropyl group, a 2,2,3-trimethyl cyclopropyl group, a 1-ethyl-2-methyl cyclopropyl group, a 2-ethyl-1-methyl cyclopropyl group, a 2-ethyl-2-methyl cyclopropyl group, and a 2-ethyl-3-methyl cyclopropyl group; and bridged ring cycloalkyl groups such as a bicyclobutyl group, a bicyclopentyl group, a bicyclohexyl group, a bicycloheptyl group, a bicyclooctyl group, a bicyclononyl group, and a bicyclodecyl group.

[0051] The aryl group may be any of a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. For example, the aryl group may be an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-naphthacenyl group, a 2-naphthacenyl group, a 5-naphthacenyl group, a 2-chrysenyl group, a 1-pyrenyl group, a 2-pyrenyl group, Examples include, but are not limited to, a pentacenyl group, a benzopyrenyl group, a triphenylenyl group; a biphenyl-2-yl group (o-biphenylyl group), a biphenyl-3-yl group (m-biphenylyl group), a biphenyl-4-yl group (p-biphenylyl group), a para-terphenyl-4-yl group, a meta-terphenyl-4-yl group, an ortho-terphenyl-4-yl group, a 1,1'-binaphthyl-2-yl group, and a 2,2'-binaphthyl-1-yl group.

[0052] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups include those described above. The number of carbon atoms in the aralkyl 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 of aralkyl groups include, but are not limited to, a phenylmethyl group (benzyl group), a 2-phenylethylene group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group, an 8-phenyl-n-octyl group, a 9-phenyl-n-nonyl group, and a 10-phenyl-n-decyl group.

[0053] The halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups, respectively, substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups, and aralkyl groups include those mentioned above.

[0054] The number of carbon atoms in the halogenated alkyl group 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. Specific examples of halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group, but are not limited to these.

[0055] The number of carbon atoms in the halogenated aryl 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 of the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group, a 2,3,5,6-tetrafluorophenyl group, a pentafluorophenyl group, a 2-fluoro-1-naphthyl group, a 3-fluorophenyl group, a 2-fluoro-1-naphthyl ... Examples of the fluorocarbon include 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, and heptafluoro-2-naphthyl. Examples of the fluorocarbon include, but are not limited to, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group).

[0056] The number of carbon atoms in the halogenated aralkyl 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 of the halogenated aralkyl group include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,5-trifluorobenzyl group, 2,6 ... Examples of the fluorobenzyl group include a 2,4,6-trifluorobenzyl group, a 2,3,4,5-tetrafluorobenzyl group, a 2,3,4,6-tetrafluorobenzyl group, a 2,3,5,6-tetrafluorobenzyl group, and a 2,3,4,5,6-pentafluorobenzyl group, and also include groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but are not limited to these.

[0057] The alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more alkoxy groups, and specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those described above.

[0058] Examples of the alkoxy group as a substituent include linear, branched, and cyclic alkoxy groups having at least one alkyl moiety and having 1 to 20 carbon atoms. Examples of the linear or branched alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 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-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyl ... 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-pentyloxy, 1,1-dimethyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1, Examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy, cyclopentyloxy, 1-methylcyclobutoxy, 2-methylcyclobutoxy, 3-methylcyclobutoxy, 1,2-dimethylcyclopropoxy, 2,3-dimethylcyclopropoxy, 1-ethylcyclopropoxy, 2-ethylcyclopropoxy, cyclohexyloxy, 1-methylcyclopentyloxy, 2-methylcyclopentyloxy, 3-methylcyclopentyloxy, 1-ethylcyclobutoxy, 2-ethylcyclobutoxy, 3-ethylcyclobutoxy, 1,2-dimethylcyclobutoxy, 1,3 dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0059] Specific examples of alkoxyalkyl groups include, but are not limited to, lower (about 5 carbon atoms or less) alkyloxy-lower (about 5 carbon atoms or less) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl groups. Specific examples of alkoxyaryl groups include, but are not limited to, 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-methoxynaphthalen-1-yl, 3-methoxynaphthalen-1-yl, 4-methoxynaphthalen-1-yl, 5-methoxynaphthalen-1-yl, 6-methoxynaphthalen-1-yl, and 7-methoxynaphthalen-1-yl groups. Specific examples of the alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group and a 4-(methoxyphenyl)benzyl group.

[0060] The alkenyl group may be either linear or branched, and the number of carbon atoms therein 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. Specific examples of the alkenyl group include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1- butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group , 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl- 2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3, 3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl 1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentenyl group, Examples include a cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group, and also include bridged cyclic alkenyl groups such as a bicycloheptenyl group (norbornyl group).

[0061] Furthermore, examples of the substituents in the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group include alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, alkoxy group, and aralkyloxy group. Specific examples and their preferred carbon numbers are the same as those described above or below. Furthermore, the aryloxy group exemplified as a substituent is a group in which an aryl group is bonded via an oxygen atom (—O—). Specific examples of such aryl groups include the same as 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, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. Furthermore, when two or more substituents are present, the substituents may be bonded to each other to form a ring.

[0062] Examples of organic groups having an epoxy group, which may be ring-opened, include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, an epoxycyclohexyl group, or groups resulting from ring-opening of such epoxy groups. Examples of organic groups having an acryloyl group include an acryloyloxymethyl group, an acryloyloxyethyl group, and an acryloyloxypropyl group. Examples of organic groups having a methacryloyl group include a methacryloyloxymethyl group, a methacryloyloxyethyl group, and a methacryloyloxypropyl group. Examples of organic groups having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group. Examples of organic groups having an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which an alkoxy group is directly bonded to a silicon atom are excluded. Examples of organic groups having a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group. Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.

[0063] The alkoxy group in Y is, for example, R ２ Examples of the halogen atom in Y include the alkoxy groups exemplified in the description of R ２ Examples of the halogen atoms include those exemplified in the explanation of the above.

[0064] An aralkyloxy group is a monovalent group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol, and specific examples of the aralkyl group in the aralkyloxy group include the same as those described above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of the aralkyloxy group include, but are not limited to, a phenylmethyloxy group (benzyloxy group), a 2-phenylethyleneoxy group, a 3-phenyl-n-propyloxy group, a 4-phenyl-n-butyloxy group, a 5-phenyl-n-pentyloxy group, a 6-phenyl-n-hexyloxy group, a 7-phenyl-n-heptyloxy group, an 8-phenyl-n-octyloxy group, a 9-phenyl-n-nonyloxy group, and a 10-phenyl-n-decyloxy group.

[0065] An acyloxy group is a monovalent group derived by removing a hydrogen atom from a carboxyl group (—COOH) of a carboxylic acid compound, and typical examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, and aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid. Specific examples of the alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid are the same as those described above.Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentyl ...methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, a n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group Examples of the alkyl group include a phenylcarbonyloxy group, a 3-methyl-n-pentylcarbonyloxy group, a 4-methyl-n-pentylcarbonyloxy group, a 1,1-dimethyl-n-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-butylcarbonyloxy group, a 2,2-dimethyl-n-butylcarbonyloxy group, a 2,3-dimethyl-n-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl-n-propylcarbonyloxy group, a 1-ethyl-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group.

[0066] Examples of the compound represented by formula (A) include compounds (1) to (13) described in the examples below.

[0067] An example of the compound represented by formula (A) is a compound represented by the following formula (T1): The compound represented by formula (T1) is also within the scope of the present invention. (In formula (T1), Q represents a divalent group having 1 to 6 carbon atoms. Rｐ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ｑ is expressed by the following formula (R ｑ -1) or formula (R ｑ R represents a monovalent group represented by the formula (I)-2). ｓ each independently represents an alkyl group having 1 to 3 carbon atoms. (Formula (R ｑ -1) and formula (R ｑ -2), * represents a bond. ｑ -2) Medium, R ｒ represents a perfluoroalkyl group having 1 to 3 carbon atoms, a difluoromethyl group, an iodine atom, an OH group, or a nitro group.

[0068] Examples of the compound represented by formula (T1) include compounds (1) and (2) described in the Examples below.

[0069] The method for synthesizing the compound represented by formula (T1) is not particularly limited, and the compound can be produced by, for example, referring to synthesis examples [(Synthesis of Compound 1) to (Synthesis of Compound 4)] described in paragraphs

[0031] to

[0040] and examples of WO 2011 / 033965. The compound represented by formula (T1) can be obtained, for example, by reacting a compound represented by the following formula (T1-1) with a compound represented by the following formula (T1-2). (In formula (T1-1), Q, R ｐ , and R ｓ are Q and R in formula (T1). ｐ , and R ｓ In formula (T1-2), R ｑ is R in formula (T1) ｑ X represents a halogen atom.

[0070] The hydrolyzable silane used to obtain the polysiloxane may contain, in addition to the compound represented by formula (A), a compound represented by the following formula (1): In other words, the polysiloxane may be a hydrolysis condensate of a hydrolyzable silane containing the compound represented by formula (A) and the compound represented by formula (1): (In formula (1), R１１ are groups bonded to a silicon atom, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group which may be ring-opened, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof. １２ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom; and k represents an integer of 0 to 3.

[0071] In addition, R １１ is not a hydrolyzable group.

[0072] R １１ Specific examples of R in formula (A) include ２ Examples of the above are given in the explanation of R. １２ Specific examples of include those given in the description of Y in formula (A).

[0073] --Specific examples of hydrolyzable silanes represented by formula (1)--Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, and methyltribenzyloxysilane. , methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane butyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldimethoxysilane Glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyl Ethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane Sisilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane,Allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyl Nyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, dimethoxymethyl-3- (3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethyl methyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane,Methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, i-propoxyphenyltrimethoxysilane, i-propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane, i-propoxyphenyltrichlorosilane, i-propoxyphenyltrimethoxysilane propoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane, i-propoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyl Trimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy ... thiocyanatepropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidopropyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane,Examples of the silane include, but are not limited to, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silanes represented by the following formulas (A-1) to (A-41).

[0074] The polysiloxane that is a hydrolysis condensation product may be a hydrolysis condensation product of a hydrolyzable silane that contains a silane compound other than the above-mentioned examples, as long as the effects of the present invention are not impaired.

[0075] As described above, the polysiloxane can be a modified polysiloxane in which at least a portion of the silanol groups are modified. For example, a polysiloxane modified product in which a portion of the silanol groups is modified with alcohol or a polysiloxane modified product in which the silanol groups are protected with acetal can be used. Examples of the modified polysiloxane include a reaction product obtained by reacting at least a portion of the silanol groups in the hydrolysis condensation product of the hydrolyzable silane with hydroxy groups of an alcohol, a dehydration reaction product of the condensation product with an alcohol, and a modified product in which at least a portion of the silanol groups in the condensation product are protected with acetal groups.

[0076] The alcohol may be a monohydric alcohol, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, or 1-hexanol. Examples of suitable alcohols include 2-methyl-1-pentanol, 2-hexanol, 3-hexanol, 2,3-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. Further, for example, alkoxy group-containing alcohols 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.

[0077] The reaction between the silanol groups of the condensate and the hydroxyl groups of the alcohol can be carried out by contacting the polysiloxane with the alcohol and reacting for 0.1 to 48 hours, for example, 24 hours, at a temperature of 40 to 160° C., for example, 60° C., to obtain a modified polysiloxane in which the silanol groups are capped. In this case, the alcohol capping agent can be used as a solvent in the composition containing the polysiloxane.

[0078] Furthermore, a dehydration reaction product of a polysiloxane composed of a hydrolysis condensate of a hydrolyzable silane and an alcohol can be produced by reacting the polysiloxane with an alcohol in the presence of an acid catalyst, capping the silanol groups with the alcohol, and removing the water produced by dehydration from the reaction system. The acid can be an organic acid having an acid dissociation constant (pka) of -1 to 5, preferably 4 to 5. Examples of the acid include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, and acetic acid, among others. Furthermore, the acid can have a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. Thus, the acid preferably has an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160°C. In other words, either a weak acidity or a strong acidity but a low boiling point can be used. As the acid, any of the properties such as the acid dissociation constant and boiling point can be used.

[0079] Acetal protection of the silanol groups in the condensate can be achieved using a vinyl ether, for example, a vinyl ether represented by the following formula (5). By this reaction, a partial structure represented by the following formula (6) can be introduced into the polysiloxane.

[0080] In formula (5), R １ａ , R ２ａ , and R ３ａ each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ４ａ represents an alkyl group having 1 to 10 carbon atoms, and R ２ａ and R ４ａ may be bonded to each other to form a ring. Examples of the alkyl group include those mentioned above. In formula (6), R １ ', R ２ ', and R ３ Each of R ′ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, ４ ' represents an alkyl group having 1 to 10 carbon atoms, and R ２ ' and R ４In formula (6), * indicates a bond to an adjacent atom. The adjacent atom may be, for example, an oxygen atom of a siloxane bond, an oxygen atom of a silanol group, or R in formula (1). １ Examples of the alkyl group include the carbon atoms derived from the following.

[0081] Examples of the vinyl ether represented by formula (5) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, and 2,3-dihydrofuran are preferably used.

[0082] Acetal protection of silanol groups can be carried out using polysiloxane, vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, and using a catalyst such as pyridium paratoluenesulfonate, trifluoromethanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0083] The capping of the silanol groups with an alcohol or the acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described below.

[0084] In a preferred embodiment of the present invention, the polysiloxane comprises at least one of a hydrolysis condensate of a hydrolyzable silane and a modified product thereof, which contains a compound represented by formula (A), and optionally a compound represented by formula (1), and other hydrolyzable silanes. In a preferred embodiment, the polysiloxane comprises a dehydration reaction product of the hydrolysis condensate and an alcohol.

[0085] The weight-average molecular weight of polysiloxane, which is a hydrolysis condensation product (which may include modified products) of hydrolyzable silane, can be, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the hydrolysis condensation product in the composition, the weight-average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, the weight-average molecular weight is preferably 500 or more, more preferably 600 or more. The weight-average molecular weight is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC analysis can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (Shodex (registered trademark) manufactured by Showa Denko K.K.) as a standard sample.

[0086] The hydrolysis condensate of hydrolyzable silane can be obtained by hydrolyzing and condensing the aforementioned silane compound (hydrolyzable silane). The aforementioned silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, i.e., an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halogenated silyl group (hereinafter referred to as a hydrolyzable group). To hydrolyze these hydrolyzable groups, typically 0.1 to 100 moles, for example, 0.5 to 100 moles, and preferably 1 to 10 moles, of water are used per mole of hydrolyzable group. During the hydrolysis and condensation, a hydrolysis catalyst may be used, or the hydrolysis and condensation may be carried out without the use of a hydrolysis catalyst, for example, to promote the reaction. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of hydrolyzable group. The reaction temperature during hydrolysis and condensation is usually in the range of room temperature or higher and the reflux temperature at normal pressure of the organic solvent that can be used for hydrolysis, and can be, for example, 20 to 110°C, or, for example, 20 to 80°C. The hydrolysis may be complete, i.e., all hydrolyzable groups are converted to silanol groups, or partial, i.e., unreacted hydrolyzable groups may remain. Examples of hydrolysis catalysts that can be used during hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0087] Examples of metal chelate compounds as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di -i-propoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, di-sec-butoxy bis(acetylacetonate)titanium, di-t-butoxy bis(acetylacetonate)titanium, monoethoxy tris(acetylacetonate)titanium, mono-n-propoxy tris(acetylacetonate)titanium, mono-i-propoxy tris(acetylacetonate)titanium, mono-n-butoxy tris(acetylacetonate)titanium, mono-sec-butoxy tris(acetylacetonate) titanium acetate), mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethoxy di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethylacetoacetate)titanium, mono-sec-butoxy tris(ethylacetoacetate)titanium, mono-t-butoxy tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonate)tris(ethylacetoacetate)titanium, bis(acetylacetonate)bis(ethylacetoacetate)titanium, and tris(acetylacetonate)mono(ethylacetoacetate)titanium; triethoxy mono(acetylacetonate) tri-n-propoxy mono(acetylacetonate) zirconium, tri-i-propoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-t-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-i-propoxy bis(acetylacetonate) zirconium cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxy tris(acetylacetonate)zirconium, mono-t-butoxy tris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxy mono(ethylacetoacetate)zirconium, tri-i-propoxy mono(ethylacetoacetate)zirconium, tri-n-butoxy mono(ethylacetoacetate)zirconium, tri-sec-butoxy mono(ethylacetoacetate)zirconium,Tri-t-butoxy mono(ethylacetoacetate)zirconium, diethoxy bis(ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium, mono-i-propoxy tris(ethylacetoacetate)zirconium, mono-n-butoxy Examples of the chelate compounds include, but are not limited to, zirconium chelate compounds such as tris(ethylacetoacetate)zirconium, mono-sec-butoxy tris(ethylacetoacetate)zirconium, mono-t-butoxy tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato)tris(ethylacetoacetate)zirconium, bis(acetylacetonato)bis(ethylacetoacetate)zirconium, and tris(acetylacetonato)mono(ethylacetoacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.

[0088] Examples of organic acids that can be used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic 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, mellitic 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.

[0089] Examples of inorganic acids that can be used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0090] Examples of organic bases as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0091] Examples of inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

[0092] Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0093] Among these, in the present invention, nitric acid can be preferably used as the hydrolysis catalyst. The use of nitric acid can improve the storage stability of the reaction solution after hydrolysis and condensation, and in particular, can suppress changes in the molecular weight of the hydrolysis condensate. It has been found that the stability of the hydrolysis condensate in a liquid depends on the pH of the solution. As a result of extensive investigation, it has been found that the pH of the solution falls within a stable range when an appropriate amount of nitric acid is used. Furthermore, as described above, nitric acid can also be used when obtaining a modified product of the hydrolysis condensate, for example, when capping silanol groups with an alcohol, and is therefore preferred from the viewpoint of being able to contribute to both the hydrolysis and condensation of hydrolyzable silanes and the alcohol capping of the hydrolysis condensate.

[0094] When carrying out the hydrolysis and condensation, an organic solvent may be used as the solvent, and specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-propylbenzene, and the like. Aromatic hydrocarbon solvents such as butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, and 2-ethylbutanol , n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, Monoalcohol-based solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; and polyhydric alcohol-based solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 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 glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 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, and ethylene glycol dibutyl ether-based solvents such as 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, ethoxytriglycol, 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, 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, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol acetate Examples of solvents include, but are not limited to, ester-based solvents such as methyl ether, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglyceride, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl 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-propane sultone. These solvents can be used alone or in combination of two or more. ;

[0095] After completion of the hydrolysis and condensation reactions, the reaction solution can be used as is or after dilution or concentration, neutralized, and treated with an ion exchange resin to remove the hydrolysis catalyst, such as an acid or a base, used in the hydrolysis and condensation. Before or after such treatment, by-product alcohol and water, the hydrolysis catalyst, etc., can be removed from the reaction solution by vacuum distillation or the like.

[0096] The hydrolysis condensate thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, which can be used directly to prepare a surface modifier. That is, the reaction solution can be used directly (or diluted) to prepare a surface modifier. At this time, the hydrolysis catalyst used in the hydrolysis and condensation, as well as by-products, may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst or the nitric acid used in the alcohol capping of silanol groups may remain in the polymer varnish solution at approximately 100 ppm to 5,000 ppm. The resulting polysiloxane varnish may be subjected to solvent substitution or diluted with an appropriate solvent. If the resulting polysiloxane varnish has sufficient storage stability, the organic solvent can be distilled off to achieve a film-forming component concentration of 100%. The film-forming component refers to the components of the composition excluding the solvent. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited, and one or more kinds may be arbitrarily selected and used.

[0097] The content of polysiloxane (A) in the surface modifier is not particularly limited, but is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, and particularly preferably 0.1% by mass to 3% by mass.

[0098] <<<<Solvent (B)>>> The solvent (B) contained in the surface modifier can be any solvent that can dissolve and mix the polysiloxane (A) and, if necessary, other components contained in the surface modifier, without particular limitation.

[0099] Examples of the solvent include organic solvents, water, etc. Examples of the organic solvent include alcohols, carboxylic acids having a hydroxy group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).

[0100] Examples of the alcohol include monoalcohol solvents and polyhydric alcohol solvents. Examples of the monoalcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, and n-octanol. Examples of polyhydric alcohol solvents include ethanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc. Examples of polyhydric alcohol solvents include ethylene glycol, propylene glycol, 1,3-butylene glycol, 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, glycerin, etc.

[0101] Examples of carboxylic acids having a hydroxy group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.

[0102] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0103] An example of the cyclic lactone is γ-butyrolactone.

[0104] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include 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 carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include 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, and propylene glycol dibutyl ether.

[0105] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene glycol monoalkyl ether acetates. Examples of alkylene glycol monoalkyl ether acetates include 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. Examples of the alkoxycarboxylic acid ester of alkylene glycol monoalkyl ether include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0106] Specific examples of other solvents include toluene, xylene, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, 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, and ethyl hydroxyacetate. Examples of suitable solvents include methyl 3-methoxy-2-methylpropionate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, 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, and 4-methyl-2-pentanol. These solvents can be used alone or in combination of two or more.

[0107] The surface modifier may contain water as a solvent. When water is contained as a solvent, the content of water can be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the solvents contained in the surface modifier.

[0108] <<<<Curing Catalyst (C)>>> The surface modifier may be a composition that does not contain a curing catalyst, but preferably contains a curing catalyst.

[0109] Examples of the curing catalyst that can be used include ammonium salts, phosphines, phosphonium salts, sulfonium salts, iodonium salts, and oxonium salts. The salts listed below as examples of the curing catalyst may be added in the form of a salt, or may form a salt in the composition (a compound that is added as a separate compound and forms a salt in the system).

[0110] The ammonium salt includes those represented by formula (D-1): (In the formula, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3, R ２１ represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0111] Formula (D-2): (In the formula, R ２２ , R ２３ , R ２４ and R ２５ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion, and R ２２ , R ２３ , R ２４ , and R ２５ are each bonded to a nitrogen atom.)

[0112] Formula (D-3): (In the formula, R ２６ and R ２７ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0113] Formula (D-4): (In the formula, R ２８ represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0114] Formula (D-5): (In the formula, R２９ and R ３０ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0115] Formula (D-6): (In the formula, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3, and Y － represents an anion.

[0116] Furthermore, the phosphonium salt includes a compound of the formula (D-7): (In the formula, R ３１ , R ３２ , R ３３ , and R ３４ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion, and R ３１ , R ３２ , R ３３ , and R ３４ are bonded to a phosphorus atom.

[0117] Furthermore, the sulfonium salt includes a compound represented by formula (D-8): (In the formula, R ３５ , R ３６ , and R ３７ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion, and R ３５ , R ３６ , and R ３７ are each bonded to a sulfur atom.

[0118] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3. R of this quaternary ammonium salt ２１represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include linear alkyl groups such as ethyl, propyl, and butyl groups, as well as benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and the like.

[0119] The compound of formula (D-2) is R ２２ R ２３ R ２４ R ２５ N ＋ Y － The R of this quaternary ammonium salt is ２２ , R ２３ , R ２４ and R ２５ is, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, a cyclohexyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －The quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0120] The compound of formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R ２６ and R ２７ The number of carbon atoms in R is, for example, 1 to 18. ２６ and R ２７ The total number of carbon atoms in R is preferably 7 or more. ２６ can be exemplified by alkyl groups such as methyl, ethyl, and propyl, aryl groups such as phenyl, and aralkyl groups such as benzyl, and R ２７ Examples of the anion (Y) include aralkyl groups such as benzyl, and alkyl groups such as octyl and octadecyl. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － Although this compound is commercially available, it can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an aralkyl halide, alkyl halide, or aryl halide such as benzyl bromide, methyl bromide, or benzene bromide.

[0121] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ２８is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include a butyl group, an octyl group, a benzyl group, and a lauryl group. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and other acid groups. This compound is commercially available, but can also be produced by reacting pyridine with an alkyl halide or aryl halide, such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0122] The compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine, such as picoline, and R ２９ is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples of R include a methyl group, an octyl group, a lauryl group, and a benzyl group. ３０ is, for example, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. For example, when the compound represented by formula (D-5) is a quaternary ammonium derived from picoline, R ３０ is a methyl group. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －) and other acid groups. This compound is commercially available, but can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0123] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents 2 or 3. Also, an anion (Y － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － The compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, an anion (Y － ) is (HCOO － ) and when acetic acid is used, the anion (Y － ) is (CH ３ COO － ) When phenol is used, the anion (Y － ) is (C ６ H ５ O － )

[0124] The compound of formula (D-7) is R ３１ R ３２ R ３３ R ３４ P ＋ Y － It is a quaternary phosphonium salt having the structure: R ３１ , R ３２ , R ３３ , and R ３４is, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, and preferably R ３１ ~R ３４ Three of the four substituents are unsubstituted phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －) and other acid groups. This compound is commercially available, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halides, tetraphenylphosphonium halides, tritolylmonoarylphosphonium halides, and tritolylmonoalkylphosphonium halides (all of which the halogen atom is a chlorine atom or a bromine atom). In particular, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritolylmonoarylphosphonium halides such as tritolylmonophenylphosphonium halide, and tritolylmonoalkylphosphonium halides (the halogen atom is a chlorine atom or a bromine atom) are preferred.

[0125] Examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0126] The compound of formula (D-8) is R ３５ R ３６ R ３７ S ＋ Y － It is a tertiary sulfonium salt having the structure: R ３５ , R ３６ , and R ３７is, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, and preferably R ３５ ~R ３７ Two of the three substituents are unsubstituted phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － Examples of suitable acid groups include trialkylsulfonium halides such as tri-n-butylsulfonium halides and tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halides and diphenylethylsulfonium halides, triphenylsulfonium halides (all of which the halogen atom is a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. Furthermore, triphenylsulfonium halides and triphenylsulfonium carboxylates are preferably used.

[0127] Furthermore, a nitrogen-containing silane compound can be added as a curing catalyst, such as an imidazole ring-containing silane compound, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0128] The content of the curing catalyst in the surface modifier is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 25 parts by mass, and even more preferably 0.01 to 20 parts by mass, per 100 parts by mass of the polysiloxane (A).

[0129] <<<Acid>>> The surface modifier preferably contains an acid. The acid may be added during the preparation of the surface modifier, or may be used as a hydrolysis catalyst or during alcohol capping of silanol groups in the production of the above-mentioned polysiloxane (A), and the acid remaining in the polysiloxane varnish may be treated as the acid.

[0130] Examples of the acid include organic acids and inorganic acids. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, sorbic acid, acrylic acid, methacrylic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, phenolsulfonic acid, 5-sulfosalicylic acid, gallic acid, butyric acid, mellitic 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. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0131] The amount of acid (residual acid amount) can be, for example, 0.0001% by mass to 1% by mass, or 0.001% by mass to 0.1% by mass, or 0.005% by mass to 0.05% by mass, based on the total mass of the surface modifier.

[0132] <<<Amine, Hydroxide>>> The surface modifier may contain at least one selected from an amine and a hydroxide.

[0133] Examples of amines include ammonia; primary amines such as monomethanolamine, 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.

[0134] Examples of hydroxides include inorganic alkali hydroxides and organic alkali hydroxides. Examples of inorganic alkali hydroxides include sodium hydroxide and potassium hydroxide. Examples of organic alkali hydroxides include tetraalkylammonium hydroxide, triarylsulfonium hydroxide, diaryliodonium hydroxide, etc. Examples of tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Examples of triarylsulfonium hydroxides include triphenylsulfonium hydroxide and tris(t-butylphenyl)sulfonium hydroxide, etc. Examples of diaryliodonium hydroxides include diphenyliodonium hydroxide and bis(t-butylphenyl)iodonium hydroxide, etc.

[0135] The content of the amine and hydroxide in the surface modifier is not particularly limited, but can be preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polysiloxane (A).

[0136] <<<Other Additives>>> Various additives can be blended into the surface modifier depending on the application of the composition. Examples of additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology adjusters, adhesion aids, and other known additives blended into materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. Examples of various additives are listed below, but are not limited to these.

[0137] -Stabilizer- A stabilizer can be added for purposes such as stabilizing the hydrolysis condensate of the hydrolyzable silane mixture. Specific examples of stabilizers include organic acids, water, alcohols, and combinations thereof. 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. Among these, oxalic acid and maleic acid are preferred. When an organic acid is added, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters. Examples of water that can be used include pure water, ultrapure water, and ion-exchanged water. When used, the amount added can be 0.1 to 20 parts by mass per 100 parts by mass of the surface modifier. Preferred alcohols are those that easily evaporate when heated after application, such as methanol, ethanol, propanol, i-propanol, and butanol. When alcohol is added, the amount added can be 0.1 to 20 parts by mass per 100 parts by mass of the surface modifier.

[0138] -Organic Polymer- By adding an organic polymer to a surface modifier, it is possible to adjust the dry etching rate (amount of film thickness reduction per unit time) of the surface-modified layer formed from the surface modifier, as well as the attenuation coefficient and refractive index. There are no particular limitations on the organic polymer, and it can be appropriately selected from various organic polymers (condensation polymerization polymers and addition polymerization polymers) depending on the purpose of addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing moieties can also be suitably used when such functionality is required. Specific examples of such organic polymers include, but are not limited to, addition polymerization polymers containing, as structural units, addition-polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0139] When an addition polymerization polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer. An addition polymerizable monomer is used to produce the addition polymerization polymer, and specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0140] Specific examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, glycidyl acrylate, and the like, but are not limited to these.

[0141] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, and the like, but are not limited to these.

[0142] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0143] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0144] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0145] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0146] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0147] When a condensation polymerization polymer is used as the organic polymer, examples of such a polymer include a condensation polymerization polymer of a glycol compound and a dicarboxylic acid compound. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol, etc. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. Examples of polyesters, polyamides, and polyimides such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, but are not limited to these. When the organic polymer contains a hydroxy group, this hydroxy group may undergo a crosslinking reaction with a hydrolysis condensate or the like.

[0148] The weight-average molecular weight of the organic polymer can usually be 1,000 to 1,000,000. When an organic polymer is incorporated, from the viewpoint of suppressing precipitation in the composition while fully obtaining the functional effect of the polymer, the weight-average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000. Such organic polymers may be used alone or in combination of two or more.

[0149] When the surface modifier contains an organic polymer in combination with the polysiloxane (A), the content cannot be generally defined because it is determined appropriately taking into account the function of the organic polymer, etc., but can usually be in the range of 1 to 200% by mass relative to the mass of the polysiloxane (A). From the viewpoint of suppressing 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, and 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.

[0150] -Acid Generator- Examples of the acid generator include thermal acid generators and photoacid generators, and photoacid generators are preferably used. Examples of the photoacid generator include onium salt compounds such as sulfonium salts, phosphonium salts, ammonium salts, iodonium salts, and oxonium salts, sulfonimide compounds, and disulfonyldiazomethane compounds, but are not limited to these. Note that the photoacid generator may also function as a curing catalyst depending on its type, for example, carboxylates such as nitrates and maleates of the onium salt compounds described below, or hydrochlorides. Examples of the thermal acid generator include, but are not limited to, tetramethylammonium nitrate.

[0151] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride. However, the present invention is not limited to these.

[0152] Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited to these.

[0153] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0154] When the surface modifier contains an acid generator, its content cannot be generally defined because it is determined appropriately taking into account the type of acid generator, etc., but is usually in the range of 0.01 to 5 mass % relative to the mass of polysiloxane (A), and from the viewpoint of suppressing precipitation of the acid generator in the composition, it is preferably 3 mass % or less, more preferably 1 mass % or less, and from the viewpoint of fully obtaining its effects, it is preferably 0.1 mass % or more, more preferably 0.5 mass % or more. The acid generators can be used alone or in combination of two or more, and a photoacid generator and a thermal acid generator may be used in combination.

[0155] -Surfactant- A surfactant is effective in suppressing the occurrence of pinholes, striations, and the like when the surface modifier is applied to a substrate. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorine-based surfactants, and UV-curable surfactants. More specifically, examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate; Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names of EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade names of MEGAFAC (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad F Examples of suitable surfactants include, but are not limited to, fluorine-based surfactants such as C430 and FC431 (manufactured by 3M Japan Ltd.), Asahiguard (registered trademark) AG710 (manufactured by AGC Corporation), and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants can be used singly or in combination of two or more.

[0156] When the surface modifier contains a surfactant, the content thereof is usually 0.0001 to 5 mass%, preferably 0.001 to 4 mass%, and more preferably 0.01 to 3 mass%, relative to the mass of the polysiloxane (A).

[0157] - Rheology Modifier - Rheology modifiers are added primarily to improve the fluidity of the surface modifier, particularly during the baking process, to improve the film thickness uniformity of the formed film and the ability of the composition to fill holes. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyldecyl 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. When these rheology modifiers are used, their addition amount is typically less than 30% by mass based on the total film-forming components of the surface modifier.

[0158] -Adhesion promoter- Adhesion promoters are added mainly to improve the adhesion between the substrate or resist and the film (surface modification layer) formed from the surface modifier, and particularly to suppress or prevent peeling of the resist 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 trimethylsilylimidazole; γ-chloropropyltrimethoxysilane; Examples of such adhesive aids include other silanes such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. When these adhesive aids are used, the amount added is usually less than 5% by mass, and preferably less than 2% by mass, of the film-forming components of the surface modifier.

[0159] pH Adjuster: Examples of pH adjusters include acids having one or more carboxylic acid groups, such as the organic acids listed above as stabilizers. When a pH adjuster is used, the amount added may be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of the polysiloxane (A).

[0160] -Metal Oxide- Examples of metal oxides that can be added to the surface modifier include, but are not limited to, oxides of one or a combination of two or more of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0161] The concentration of the film-forming component in the surface modifier 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, relative to the total mass of the composition. The content of polysiloxane (A) in the film-forming component is usually 20% by mass to 100% by mass. From the viewpoint of reproducibly obtaining the effects of the present invention, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and even more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the aforementioned additive. The surface modifier preferably has a pH of 1 to 5, more preferably 2 to 4.

[0162] The surface modifier can be produced by mixing polysiloxane (A), solvent (B), and, if desired, other components. In this case, a solution containing polysiloxane (A) may be prepared in advance, and this solution may be mixed with solvent (B) and other components. In preparing the surface modifier, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components.

[0163] During the production of the surface modifier, or after all components have been mixed, the mixture may be filtered using a submicrometer filter or the like. The material of the filter used here is not critical, and examples that can be used include polyethylene filters, nylon filters, fluororesin filters, and polyimide filters.

[0164] <Second Step> The second step is a step of thinning the surface-modified layer precursor by bringing the surface-modified layer precursor into contact with a thinning liquid (X) to obtain a surface-modified layer having a film thickness of 5 nm or less.

[0165] In the second step, the method of contacting the surface-modified layer precursor with the thinning liquid (X) is not particularly limited, but spin coating is preferred because it allows uniform thinning and makes it easy to control the degree of thinning with high precision. That is, the second step is preferably a step of thinning the surface-modified layer precursor by spin-coating the thinning liquid (X) onto the surface-modified layer precursor to obtain a surface-modified layer with a film thickness of 5 nm or less.

[0166] The spin coating conditions are not particularly limited, but include, for example, a coating process in which a thinning liquid (X) is applied to a surface modification layer precursor formed on a semiconductor substrate, and a rotation process in which the semiconductor substrate is rotated. In the coating process, for example, when the thinning liquid (X) is applied to the surface modification layer precursor, the semiconductor substrate is not rotated or rotated at a low speed (e.g., 1000 rpm or less). In the coating process, the thinning liquid (X) is brought into contact with the surface modification layer precursor, and the components in the surface modification layer precursor are transferred to the thinning liquid (X). In the rotation process, for example, the semiconductor substrate is rotated at a high speed (e.g., greater than 1000 rpm and less than 5000 rpm), and the thinning liquid (X) is removed from the semiconductor substrate on which the surface modification layer precursor is formed. By doing so, the surface modification layer precursor becomes thinner by the amount of the components in the surface modification layer precursor transferred to the thinning liquid (X), resulting in a surface modification layer with a film thickness of 5 nm or less. The coating time may be, for example, 10 seconds to 2 minutes. The rotation time may be, for example, 5 seconds to 1 minute. During rotation, the axis perpendicular to the surface of the semiconductor substrate is used as the rotation axis.

[0167] In the second step, the film thickness of the surface modification layer precursor is preferably reduced by 0.5 nm to 10 nm, more preferably by 1 nm to 5 nm.

[0168] <<Thinning Liquid (X)>> The thinning liquid (X) is not particularly limited as long as it is a liquid that can thin the surface-modified layer precursor by contacting the surface-modified layer precursor with the thinning liquid (X), and examples thereof include organic solvents, water, acidic solutions, and alkaline aqueous solutions. Furthermore, thinners used in the RRC (reducing resist consumption) process or the EBR (edge ​​bead removing) process can be used. These can be used alone or in combination of two or more.

[0169] Examples of the organic solvent include alcohol, alkylene glycol alkyl ether, and alkylene glycol monoalkyl ether carboxylic acid ester.

[0170] Examples of the alcohol include monoalcohol solvents and polyhydric alcohol solvents. Examples of the monoalcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, and n-octanol. Examples of the polyhydric alcohol solvent include ethanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc. Examples of the polyhydric alcohol solvent include ethylene glycol, propylene glycol, 1,3-butylene glycol, 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, glycerin, etc.

[0171] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include 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 carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include 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, and propylene glycol dibutyl ether.

[0172] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include alkylene glycol monoalkyl ether acetates, such as 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.

[0173] Specific examples of other organic solvents include toluene, xylene, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, propyl lactate, isopropyl lactate, 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, and butyl butyrate. Examples of suitable solvents include methyl acetoacetate, isobutyl butyrate, ethyl hydroxyacetate, 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, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, 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, and 4-methyl-2-pentanol.

[0174] Examples of acidic solutions include inorganic acid aqueous solutions, organic acid aqueous solutions, and organic acid solutions. Examples of inorganic acid aqueous solutions include hydrochloric acid aqueous solutions, nitric acid aqueous solutions, phosphoric acid aqueous solutions, sulfuric acid aqueous solutions, and perchloric acid aqueous solutions. Examples of organic acid aqueous solutions include acetic acid aqueous solutions, trifluoroacetic acid aqueous solutions, camphorsulfonic acid aqueous solutions, p-toluenesulfonic acid aqueous solutions, and trifluoromethanesulfonic acid aqueous solutions. Examples of organic acid solutions include those in which the water in the above organic acid aqueous solutions has been replaced with an organic solvent. Examples of organic solvents include alkylene glycol alkyl ethers and alkylene glycol monoalkyl ether carboxylic acid esters.

[0175] Examples of alkaline aqueous solutions include developers used in lithography processes. Examples of alkaline aqueous solutions include 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, and potassium phosphate aqueous solution. 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, and triethanolamine aqueous solution. The concentration of alkali in the alkaline aqueous solution is not particularly limited.

[0176] The RRC (reducing resist consumption) process is a process for reducing the amount of photoresist used, in which a small amount of photoresist is uniformly applied over the entire surface of the substrate by treating the substrate surface with a thinner before applying the photoresist. The EBR (edge ​​bead removing) process is a process for removing unnecessary photoresist residue and other contaminants applied to the edge or rear surface of the substrate during the application process. Examples of thinners used in the RRC and EBR processes include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, ethyl 3-ethoxypropionate, methyl hydroxyisobutyrate, and mixtures thereof.

[0177] In one embodiment of the present invention, the laminate may include an organic underlayer film between the semiconductor substrate and the surface modification layer. The organic underlayer film used here is not particularly limited and can be selected from any of those commonly used in lithography processes. By providing an organic underlayer film on a substrate, a surface modification layer thereon, and a resist film (described below) on top of that, the pattern width of the resist film is narrowed. Even if the resist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas (described below). For example, the resist underlayer film can be processed using a fluorine-based gas having a sufficiently fast etching rate for the resist film as an etching gas. The organic underlayer film can also be processed using an oxygen-based gas having a sufficiently fast etching rate for the resist underlayer film as an etching gas. Furthermore, the substrate can be processed using a fluorine-based gas having a sufficiently fast etching rate for the organic underlayer film as an etching gas. The substrate and coating method that can be used in this case are the same as those described above.

[0178] (Method for manufacturing a semiconductor element) The method for manufacturing a semiconductor element of the present invention includes a step of forming a resist film on the laminate obtained by the method for manufacturing a laminate of the present invention, and a step of exposing and developing the resist film to obtain a resist pattern.

[0179] For example, a layer of a photoresist material (resist film) is formed on the surface modification layer. The resist film can be formed by a well-known method, i.e., by applying a coating-type resist material (resist film-forming composition) on the surface modification layer and baking it. The film 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.

[0180] The photoresist material used in the resist film formed on the surface modification layer is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative and positive photoresist materials can be used. Examples include positive photoresist materials consisting of a novolac resin and a 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresist materials consisting of a binder having a group that decomposes in acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresist materials consisting of a low molecular weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresist materials consisting of a binder having a group that decomposes in acid to increase the alkaline dissolution rate, a low molecular weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772JN (trade name) manufactured by JSR Corporation, and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Other examples include fluorine-containing polymer photoresist materials such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0181] In addition, instead of a photoresist film, a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) can be used as the resist film formed on the surface modification layer. As the electron beam resist material for forming the electron beam resist film, either a negative or positive material can be used. Specific examples include a chemically amplified resist material comprising an acid generator and a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate; a chemically amplified resist material comprising an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; a chemically amplified resist material comprising an acid generator, a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; a non-chemically amplified resist material comprising a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate; and a non-chemically amplified resist material comprising a binder having a moiety that is cleaved by an electron beam to change the alkaline dissolution rate. When these electron beam resist materials are used, a resist film pattern can be formed in the same way as when a photoresist material is used with an electron beam as the irradiation source. Furthermore, as the EUV resist material for forming the EUV resist film, a methacrylate resin-based resist material, a polyhydroxystyrene resin-based resist material, and a methacrylate-polyhydroxystyrene hybrid resin-based resist material can be used.

[0182] The resist film may be a metal-containing resist film. The metal-containing resist film is not particularly limited, but preferably contains at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0183] The metal-containing resist film is formed, for example, from a metal-containing resist. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include coating compositions containing metal oxo-hydroxo networks having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP 2019-113855 A. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in the patent document described in paragraph

[0011] of JP 2019-532489 A. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738. Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0184] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0185] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0186] Next, the resist film formed on the surface modification layer is exposed to light through a predetermined mask (reticle). For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F ２ Excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), electron beam, etc. can be used. After exposure, post-exposure baking can be performed as needed. The post-exposure baking is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0187] Next, development is carried out using a developer (e.g., an alkaline developer). As a result, when a positive photoresist film is used, for example, the exposed portions of the photoresist film are removed, forming a photoresist film pattern. Examples of the developer (alkaline developer) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0188] In the present invention, an organic solvent can be used as a developer, and development is carried out with the developer (solvent) after exposure. As a result, when a negative photoresist film is used, for example, the photoresist film in the unexposed areas is removed, and a photoresist film pattern is formed. Examples of the developer (organic solvent) 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, 4-methyl ... Butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate 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, 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,Examples of the developer include isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5°C to 50°C and a development time of 10 to 600 seconds.

[0189] For example, the surface modification layer is removed using the pattern of the resist film (upper layer) formed in this manner as a protective film, and then the substrate is processed using the patterned resist film and the patterned surface modification layer as protective films.

[0190] The removal (patterning) of the surface modification layer, which is performed using the pattern of the resist film (upper layer) as a protective film, is performed by, for example, dry etching, using tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ Gases such as fluorine, trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the surface modification layer. Resist films (photoresist films) made of organic substances are generally difficult to remove with dry etching using a halogen-based gas. In contrast, surface modification layers containing a large amount of silicon atoms are quickly removed with a halogen-based gas. Therefore, it is possible to suppress the reduction in the thickness of the photoresist film that accompanies dry etching of the surface modification layer. As a result, it becomes possible to use a thin photoresist film. Therefore, it is preferable to use a fluorine-based gas for dry etching of the surface modification layer, and examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like, but are not limited to these.

[0191] The processing (patterning) of the (semiconductor) substrate using the patterned surface modification layer as a protective film is preferably performed by dry etching using a fluorine-based gas. Examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, and difluoromethane (CH ２ F ２ ) etc.

[0192] After processing (patterning) the substrate, the surface modification layer can be removed. The removal of the surface modification layer can be performed by dry etching or wet etching. Dry etching of the surface modification layer is preferably performed using a fluorine-based gas, as mentioned in the patterning, such as tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like. Chemical solutions used for wet etching of the surface modification layer include, but are not limited to, diluted hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (HF and NH ４Examples of suitable alkaline solutions include an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution). Examples of alkaline solutions include the aforementioned ammonia hydrogen peroxide solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These chemical solutions can also be used in combination.

[0193] The present invention will be explained in more detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0194] In the examples, the apparatus and conditions used for analyzing the physical properties of samples are as follows. (1) Molecular Weight Measurement The molecular weight of the polysiloxane used in the present invention is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC measurement conditions were a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as the standard sample. (2) １ H-NMR JEOL nuclear magnetic resonance apparatus１ The evaluation was carried out using H-NMR (400 MHz) and d6-acetone as the solvent. (3) Film Thickness Measurement The material film thickness was measured using an ellipsometric film thickness measurement device RE-3100 (manufactured by SCREEN). The film thickness of the surface modification layer precursor was measured as follows. ２ After measuring the thickness of the oxide film, a surface modifying agent was applied, and the thickness of the surface modified layer precursor was measured. The difference between the thicknesses was taken as the thickness of the surface modified layer precursor. The thickness of the surface modified layer was measured as follows. ２ After measuring the thickness of the oxide film, the surface modifier was applied to thin the film, and the thickness was then measured. The difference between the thicknesses was taken as the thickness of the surface-modified layer.

[0195] [1] Monomer Synthesis (Monomer Synthesis Example A) 6.85 g of aminopropyltrimethoxysilane, 4.25 g of triethylamine, and 30 g of chloroform were placed in a 200 ml three-neck flask and stirred. Then, 9.58 g of camphorsulfonyl chloride was added dropwise at room temperature, and the mixture was stirred at room temperature for 12 hours. After the reaction, the solution was filtered, and water was added to the filtrate to separate the liquids. The organic layer was then dried over sodium sulfate and filtered, and the solvent was removed under reduced pressure to obtain the target compound (1) in a yield of 37%. １ H-NMR (400MHz): 0.69ppm (t, 2H), 0.88ppm (s, 3H), 1.01ppm (s, 3H), 1.38ppm (m, 1H), 1.69ppm (m, 2H), 1.87ppm (m, 2H), 1.98ppm (m, 1H) , 2.10ppm (m, 1H), 2.22ppm (t, 1H), 2.34ppm (d, 1H), 2.87ppm (d, 1H), 3.07ppm (m, 2H), 3.34ppm (d, 1H), 3.50ppm (s, 9H), 5.36ppm (s, 1H)

[0196] Compound (1) Me represents a methyl group.

[0197] (Monomer Synthesis Example B) 11.85 g of N-methylaminopropyltrimethoxysilane, 6.83 g of triethylamine, and 45 g of chloroform were placed in a 200 ml three-neck flask and stirred. Then, 15.00 g of 4-(trifluoromethyl)benzenesulfonyl chloride was added dropwise at room temperature, and the mixture was stirred at room temperature for 12 hours. After the reaction, the solution was filtered, and water was added to the filtrate to separate the layers. The organic layer was then dried over sodium sulfate and filtered, and the solvent was removed under reduced pressure to obtain the target compound (2) in a yield of 66%. １ H-NMR (400MHz): 0.53ppm (t, 2H), 1.51ppm (m, 2H), 2.70ppm (s, 3H), 2.97ppm (t, 2H), 3.45ppm (s, 9H), 7.66ppm (d, 2H), 7.72ppm (d, 2H)

[0198] Compound (2) Me represents a methyl group.

[0199] [2] Synthesis of Polymer (Hydrolyzed Condensation Product) Compounds (1) to (13) used in each synthesis are shown below. Me represents a methyl group, and Et represents an ethyl group.

[0200] Synthesis Example 1 1.97 g of compound (1) and 2.95 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 0.63 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise 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 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product methanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0201] Synthesis Example 2 2.01 g of compound (2) and 3.01 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 0.63 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise 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 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product methanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0202] Synthesis Example 3 5.42 g of compound (3) and 8.13 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.89 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise 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 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0203] Synthesis Example 4 3.92 g of compound (4) and 3.64 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 0.51 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise 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 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C. Me represents a methyl group.

[0204] Synthesis Example 5 3.26 g of compound (5) and 4.89 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.86 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product methanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0205] Synthesis Example 6 3.52 g of compound (6) and 5.28 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.20 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 12 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product methanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0206] Synthesis Example 7 3.41 g of compound (7) and 5.11 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.48 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 9 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0207] Synthesis Example 8 2.21 g of compound (8) and 3.32 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 0.76 g of water was added dropwise to the solution. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water and the reaction by-product, ethanol, were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as the solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0208] Synthesis Example 9 3.45 g of compound (9) and 5.18 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.37 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 9 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0209] Synthesis Example 10 3.41 g of compound (10) and 5.12 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.47 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 9 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as the solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0210] Synthesis Example 11 3.43 g of compound (11) and 5.14 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 1.43 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 9 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as a solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0211] Synthesis Example 12 6.94 g of compound (12) and 10.40 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 3.15 g of water was added dropwise to the solution. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°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 to the reaction solution. Water and the reaction by-product, methanol, were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as the solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0212] Synthesis Example 13 1.31 g of compound (13) and 1.96 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 0.63 g of water was added dropwise to the solution. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 10 g of 1-ethoxy-2-propanol was added to the reaction solution. Water and the reaction by-product, ethanol, were distilled off under reduced pressure to obtain a concentrated solution of a polymer (hydrolysis condensate) containing a structure represented by the following formula, using 1-ethoxy-2-propanol as the solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0213] Comparative Synthesis Example 1 32.20 g of compound (14) and 48.3 g of 1-ethoxy-2-propanol were placed in a 300 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 19.5 g of a 0.1 mol / L aqueous nitric acid solution was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C, and the reaction was allowed to proceed for 20 hours. The reaction solution was then cooled to room temperature, and 50 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and the reaction by-product ethanol were distilled off under reduced pressure to obtain a concentrated solution of polymer (hydrolysis condensate) using 1-ethoxy-2-propanol as the solvent. The solids concentration of the resulting concentrated solution exceeded 20% by mass, calculated as the solid residue when heated at 150°C.

[0214] [3] Preparation of surface modifier (coating liquid) The polymer (hydrolysis condensate) obtained in the above synthesis example was mixed with additives and solvents in the proportions shown in Table 1, and filtered through a 0.02 μm polyethylene filter to prepare a surface modifier (coating liquid). In Table 1, the 2 parts by mass of each synthesis example listed in the composition column means that the hydrolysis condensate is 2 parts by mass. In addition, in Table 1, MA means maleic acid, TPSNO3 means triphenylsulfonium nitrate, PTSA means paratoluenesulfonic acid, PGEE means propylene glycol monoethyl ether, and PGME means propylene glycol monomethyl ether, respectively.

[0215]

[0216] [4] Thinning Evaluation Coating Solutions 1 to 16 and Comparative Coating Solution 1 were each applied to a silicon wafer using a spinner and heated on a hot plate for 60 seconds at the baking temperature shown in Table 2 to form a surface-modified layer precursor. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was then applied to the surface-modified layer precursor and allowed to stand for 60 seconds. The wafer was then rotated to shake off the solvent, and the wafer was baked at 100°C for 30 seconds and dried. The film thickness of the resulting surface-modified layer was then measured, and a film thickness of 30 Å or less was evaluated as "good," while a film thickness of less than 30 Å was evaluated as "poor." The results are shown in Table 2.

[0217]

[0218] [5] Surface Modification Evaluation Coating Solutions 1 to 16 and Comparative Coating Solution 1 were each applied to Bare-Si using a spinner and heated on a hot plate at the baking temperature shown in Table 3 for 60 seconds to form a surface modification layer precursor. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was then applied to the surface modification layer precursor, followed by spin drying. The water contact angle of the resulting surface modification layer was measured to evaluate whether the substrate surface had been modified. The water contact angle was measured using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) with a liquid volume of 3 μL, and the sample was allowed to stand for 5 seconds after application. Since the water contact angle of Bare-Si was 20 degrees or less, if the water contact angle was less than 30 degrees, it was determined that the surface had not been modified and was rated as "poor." On the other hand, if the water contact angle was 30 degrees or more, it was determined that the partial structure of the surface modifier had rendered the surface hydrophobic, i.e., the surface had been modified, and it was rated as "good." The evaluation results are shown in Table 3.

[0219]

[0220] [6] EUV Patterning Evaluation Using Metal Resist [6-1] Evaluation of Pattern Shape Coating Solutions 1, 3 to 16, and Comparative Coating Solution 1 were each applied to a silicon wafer using a spinner and heated on a hot plate for 60 seconds at the baking temperature shown in Table 4 to form a surface modification layer precursor. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was then applied to the surface modification layer precursor, followed by spin drying. A metal resist (metal oxide resist) solution was then applied to the resulting surface modification layer, and the resulting layer was heated at 100°C for 60 seconds to form a metal resist film. An ASML EUV exposure system (NXE3400) was then used to perform exposure under conditions of NA = 0.33 and σ = 0.595 / 0.817. After exposure, post-exposure baking (PEB) was performed at 180°C for 60 seconds, and the resist was cooled to room temperature on a cooling plate, developed with an organic solvent developer, and rinsed. The resist was then heated at 250°C for 60 seconds to form a resist pattern. The resulting pattern was observed with a 14 nm line / 28 nm pitch (line and space (L / S) = 1 / 1). A state in which no pinholes or residues were observed in the patterned area or in the spaced area was evaluated as "good," and a state in which pattern errors such as pinholes were observed in the patterned area was evaluated as "poor." The evaluation results are shown in Table 4.

[0221] [6-2] Evaluation of Exposure Sensitivity In the EUV patterning evaluation in [6-1] above, the exposure dose required to form 14 nm lines / 28 nm pitch (line and space (L / S) = 1 / 1) was defined as the optimum exposure dose, and the exposure sensitivity was evaluated. When the optimum exposure dose when Comparative Coating Liquid 1 was used was defined as 100%, a case in which the optimum exposure dose decreased by 2% or more, i.e., a case in which the exposure sensitivity improved, was evaluated as "good". Furthermore, among those evaluated as "good", a case in which the decrease rate of the optimum exposure dose was 20% or more, i.e., a case in which a further improvement in exposure sensitivity was observed, was evaluated as "very good". The evaluation results are shown in Table 4.

[0222]

Claims

1. A method for manufacturing a laminate having the surface modification layer and the semiconductor substrate, comprising: a first step of applying a surface modifier containing a polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B) onto a semiconductor substrate and then baking to obtain a surface modification layer precursor; and a second step of thinning the surface modification layer precursor by bringing the surface modification layer precursor into contact with a thinning liquid (X) to obtain a surface modification layer having a film thickness of 5 nm or less.

2. The nitrogen atom is a nitrogen atom (N that forms an amide bond) １ ), a nitrogen atom (N that forms a sulfonamide bond) ２ ), a nitrogen atom (N that forms a guanidine structure) ３ ), and the N １ to the N ３ is a nitrogen atom other than the above and is bonded to at least one carbon atom, and the bond is a single bond (N ４ ). The method for producing a laminate according to claim 1, wherein the nitrogen atom is any one of the nitrogen atoms.

3. The method for manufacturing a laminate according to claim 1, wherein the organic group having a nitrogen atom is a group bonded to a silicon atom and is a monovalent group represented by any one of the following formulas (Z1) to (Z4). (In formulas (Z1) to (Z4), R ａ each independently represents a single bond or a divalent group having 1 to 6 carbon atoms. R ｂ each independently represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. R ｃ１ to R ｃ３ each independently represents a monovalent group having 1 to 20 carbon atoms. X represents a single bond, -O-, or -N(R ｅ )-(R ｅ represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms.). When X is -N(R ｅ )-, R ｅ and R ｃ２ may together form a ring structure having 5 to 7 carbon atoms. R ｄ each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. n each independently represents 0 or a positive number. HX represents an acid. * represents a bond.).

4. The method for producing a laminate according to claim 1, wherein the polysiloxane is a hydrolytic condensate of a hydrolyzable silane containing a compound represented by the following formula (A). (In formula (A), R １ is a group bonded to a silicon atom and independently represents an organic group having a nitrogen atom. R ２ is a group bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group which may be ring-opened, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof. Y is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to 2. a + b is 1 to 3.) 5. R in the formula (A) １ The method for producing a laminate according to claim 4, wherein is a monovalent group represented by any one of the following formulas (Z1) to (Z4). (In the formulas (Z1) to (Z4), R ａ each independently represents a single bond or a divalent group having 1 to 6 carbon atoms. R ｂ each independently represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms. R ｃ１ to R ｃ３ each independently represents a monovalent group having 1 to 20 carbon atoms. X represents a single bond, -O-, or -N(R ｅ )(R ｅ represents a hydrogen atom or a monovalent group having 1 to 6 carbon atoms.). When X is -N(R ｅ ), R ｅ and R ｃ２ may together form a ring structure having 5 to 7 carbon atoms. R ｄ each independently represents a hydrogen atom or a monovalent group having 1 to 20 carbon atoms. n each independently represents 0 or a positive number. HX represents an acid. * represents a bond.).

6. The method for manufacturing a laminate according to claim 1, wherein the solvent (B) contains at least one selected from the group consisting of carboxylic acids having a hydroxy group, linear 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.

7. The method for manufacturing a laminate according to claim 1, wherein the thinning liquid (X) contains at least one of an organic solvent and water.

8. The method for manufacturing a laminate according to claim 1, wherein the surface modifier further contains a curing catalyst (C).

9. The method for manufacturing a laminate according to claim 1, wherein the semiconductor substrate is a substrate having an inorganic or organic substrate, or a substrate having an inorganic or organic film.

10. The method for manufacturing a laminate according to claim 9, wherein the inorganic substance is at least one selected from the group consisting of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides.

11. The method for manufacturing a laminate according to claim 9, wherein the organic substance is at least one selected from the group consisting of amorphous carbon, graphite, fullerene, carbon nanotube, diamond, diamond-like carbon, polyimide, and an organic film doped with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogen or partially substituted therewith.

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

13. The method for manufacturing a laminate according to claim 1, wherein the second step is a step of thinning the surface modification layer precursor by spin-coating the thinning liquid (X) on the surface modification layer precursor to obtain a surface modification layer having a film thickness of 5 nm or less.

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

15. The method for producing a laminate according to claim 1, wherein the laminate is used for EUV lithography using a metal-containing resist film.

16. A method for manufacturing a semiconductor device, comprising: a step of forming a resist film on a laminate obtained by the method for manufacturing a laminate according to any one of claims 1 to 15; and a step of exposing and developing the resist film to obtain a resist pattern.

17. The method for manufacturing a semiconductor device according to claim 16, wherein the resist film is a metal-containing resist film.

18. A laminate having a semiconductor substrate and a surface modification layer with a thickness of 5 nm or less formed using a surface modifier containing a polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B).

19. The laminate according to claim 18, which is used for EUV or electron beam lithography.

20. The laminate according to claim 18, which is used for EUV lithography using a metal-containing resist film.

21. A surface modifier containing a polysiloxane (A) having an organic group having a nitrogen atom and a solvent (B), which is used in the method for producing a laminate according to any one of claims 1 to 15.

22. A compound represented by the following formula (T1). (In formula (T1), Q represents a divalent group having 1 to 6 carbon atoms. R ｐ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ｑ represents a monovalent group represented by the following formula (R ｑ -1) or formula (R ｑ -2). R ｓ each independently represents an alkyl group having 1 to 3 carbon atoms.) (In formula (R ｑ -1) and formula (R ｑ -2), * each represents a bond. In formula (R ｑ -2), R ｒ represents a perfluoroalkyl group having 1 to 3 carbon atoms, a difluoromethyl group, an iodine atom, an OH group, or a nitro group.)

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