Method for manufacturing laminate and method for manufacturing semiconductor element

Abstract

A method for producing a laminate having a surface-modified layer and a semiconductor substrate, the method comprising: a first step for obtaining a surface-modified layer precursor by applying a surface-modifying agent containing a polymer and a solvent onto the semiconductor substrate and then firing the semiconductor substrate to crosslink the polymer; and a second step for obtaining a surface-modified layer having a film thickness of 5 nm or less by bringing the surface-modified layer precursor into contact with a thinning liquid to thin the surface-modified layer precursor.

Description

Technical Field

[0001] The present invention relates to a method for producing a laminated body, and more preferably to a method for producing a laminated body on which a resist pattern is formed. In addition, the present invention relates to a method for producing a semiconductor element. Background Art

[0002] In the manufacture of semiconductor devices, the photolithography process using a resist composition has been carried out. In recent years, with the high integration of semiconductor devices, the miniaturization of patterns such as wiring is required. Along with the miniaturization of patterns, far ultraviolet light, vacuum ultraviolet light, electron beam (EB), X-rays, etc. with shorter wavelengths are used as light sources. Especially recently, short-wavelength light such as KrF excimer laser (wavelength 248nm) and ArF excimer laser (wavelength 193nm) are adopted to form the operation of resist pattern.

[0003] Along with this, diffuse reflection of active light from the semiconductor substrate and the influence of standing waves have become a major problem. Therefore, in order to solve this problem, a method of providing an anti-reflective film (Bottom Anti-Reflective Coating: BARC) between the resist and the semiconductor substrate has been widely studied. As such an anti-reflective film, from the perspective of ease of use, a large number of studies have been conducted on organic anti-reflective films formed from a composition containing a polymer having a light-absorbing group (chromophore) (for example, Patent Document 1).

[0004] On the other hand, for EUV (extreme ultraviolet light, wavelength 13.5nm) and electron beams used in further micro-processing technology, although there is no problem of reflection from the semiconductor substrate, the collapse of the resist pattern accompanying the miniaturization of the pattern becomes a problem, so research has been conducted on resist underlayer films with high adhesion to the resist.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application No. 2008-501985 Summary of the invention

[0008] Problems to be solved by the invention

[0009] Conventional resist underlayer films have the problem of being prone to etching defects such as side etching in the etching process. Therefore, if the substrate surface can be modified by a surface modification layer having a thinner film thickness than conventional underlayer films, it can be expected that etching defects such as side etching will not occur, the adhesion of the photoresist will be improved, and the resolution of the photoresist in the advanced photolithography process will be improved.

[0010] However, it is not easy to uniformly form a thin surface modification layer.

[0011] The present invention has been made in view of such circumstances, and there is a demand for a method for producing a laminate that can form a thin surface modification layer, a method for producing a semiconductor element using the method, and a laminate having a thin surface modification layer.

[0012] Means for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, and have completed the present invention having the following gist.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A method for producing a laminate having a surface modification layer and a semiconductor substrate, the method comprising the following steps:

[0016] Step 1: coating a surface modifier containing a polymer and a solvent on a semiconductor substrate, and then firing the surface modifier to crosslink the polymer to obtain a surface modification layer precursor; and

[0017] Step 2: The surface modification layer precursor is brought into contact with a thinning liquid to thin the surface modification layer precursor, thereby obtaining a surface modification layer having a film thickness of 5 nm or less.

[0018] [2] The method for producing a laminate according to [1], wherein the polymer is polysiloxane.

[0019] [3] The method for producing a laminate according to [2], wherein the polysiloxane comprises a modified polysiloxane in which at least a part of the silanol groups is alcohol-modified or acetal-protected.

[0020] [4] The method for producing a laminate according to [2] or [3], wherein the polysiloxane comprises a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aromatic ring having 6 to 30 carbon atoms which may be substituted with a halogen atom, an alkenyl group, an alkynyl group, a norbornene ring, a phenol group, a protected phenol group, an amino group, an amide group, a cyclic amide group, an imide group, a cyclic imide group, a sulfonyl group, a sulfonamide group, a nitro group, a cyano group, a thiocyanate group, an isocyanate group, a halogen group, a carboxylic acid group, a carboxylate group, a sulfonic acid group, a sulfonic acid ester group, a phosphoric acid group, a phosphoric acid ester group, an ammonium group, At least one structure selected from the group consisting of a sulfonium group, an epoxy group, a glycidyloxy group, a cyclohexyloxy group, a ring-opened epoxy group, a ring-opened glycidyloxy group, a ring-opened cyclohexyloxy group, a hydroxyl group, a mercapto group, an acryloyloxy group, and a methacryloyloxy group.

[0021] [5] The method for producing a laminate according to [2] or [3], wherein the polysiloxane contains a group that is bonded to a silicon atom and has an ion bond.

[0022] [6] The method for producing a laminate according to [5], wherein the group having an ionic bond has an anionic group as a group bonded to a silicon atom, and a cation,

[0023] The anion in the anionic group is a sulfonic acid anion, a carboxylic acid anion, or a phosphate anion.

[0024] The above cations are sulfonium cations, iodine cations cation, cation, dihydroimidazolium cation, or ammonium cation.

[0025] [7] The method for producing a laminate according to [5], wherein the group having an ionic bond has a cationic group as a group bonded to a silicon atom, and an anion,

[0026] The cation in the above cationic group is a sulfonium cation, an iodine cation cation, cation, dihydroimidazolium cation, or ammonium cation,

[0027] The anion is a sulfonic acid anion, a carboxylic acid anion, or a phosphoric acid anion.

[0028] [8] The method for producing a laminate according to any one of [2] to [7], wherein the polysiloxane contains a Q unit.

[0029] [9] The method for producing a laminate according to any one of [1] to [8], wherein the solvent contains at least one selected from alcohols, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylates, and water.

[0030]

[10] The method for producing a laminate according to any one of [1] to [9], wherein the surface modifier contains an acid.

[0031]

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

[10] , wherein the surface modifier contains an acid generator.

[0032]

[12] According to the method for manufacturing a laminated body described in any one of [1] to

[11] , the thinning liquid is at least one selected from an organic solvent, water, an acidic solution, an alkaline aqueous solution, and a diluent used in a RRC (reducing resist comsumption) process or an EBR (edge ​​bead removing) process.

[0033]

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

[12] , wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having an inorganic or organic film.

[0034]

[14] According to the method for producing a laminated body described in

[13] , the above-mentioned inorganic substance is at least one selected from metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides.

[0035]

[15] According to the method for manufacturing a laminated body described in

[13] , the above-mentioned organic matter is at least one selected from amorphous carbon, graphite, fullerene, carbon nanotube, diamond, diamond-like carbon, polyimide and organic films thereof doped or partially replaced by boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen.

[0036]

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

[15] , wherein the laminate further has a resist underlayer film containing silicon.

[0037]

[17] According to the method for manufacturing a laminated body described in any one of [1] to

[16] , the second step is a step of thinning the surface modification layer precursor by spin coating a thinning liquid on the surface modification layer precursor to obtain a surface modification layer with a film thickness of less than 5 nm.

[0038]

[18] According to the method for producing a laminate according to any one of [1] to

[17] , the second step is a step of thinning the surface modification layer precursor together with the RRC step or the EBR step to obtain a surface modification layer with a film thickness of less than 5 nm.

[0039]

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

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

[0040]

[20] A method for manufacturing a semiconductor device, comprising the following steps:

[0041] A step of forming a resist film on the laminated body obtained by the method for producing a laminated body according to any one of [1] to

[19] ; ​​and

[0042] The resist film is exposed and developed to obtain a resist pattern.

[0043]

[21] A laminate comprising a semiconductor substrate and a surface modification layer having a thickness of 5 nm or less and containing a cross-linked polymer.

[0044]

[22] The laminate according to

[21] , which is used for EUV or electron beam lithography.

[0045]

[23] The laminate according to

[21] or

[22] , wherein the polymer is polysiloxane.

[0046]

[24] The laminate according to

[23] , wherein the polysiloxane contains a Q unit.

[0047]

[25] A surface modifier comprising a polymer and a solvent,

[0048] This is used in the method for producing a laminate according to any one of [1] to

[19] .

[0049] Effects of the Invention

[0050] According to the present invention, a method for producing a laminated body capable of forming a thin surface modified layer, a method for producing a semiconductor element using the production method, and a laminated body having a thin surface modified layer can be provided. DETAILED DESCRIPTION

[0051] (Method for producing laminate, and laminate)

[0052] 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.

[0053] The first step is a step of applying a surface modifier containing a polymer and a solvent onto a semiconductor substrate and then firing the surface modifier to crosslink the polymer to obtain a surface modification layer precursor.

[0054] The second step is a step of bringing the surface modification layer precursor into contact with a thinning liquid to thin the surface modification layer precursor and obtain a surface modification layer having a film thickness of 5 nm or less.

[0055] If a surface modifier containing a polymer and a solvent is applied and then calcined, a film having a cross-linked polymer is obtained. However, it is not easy to obtain a thin film (for example, a film with a thickness of 5 nm or less) without film defects such as pinholes and uneven coating by only this process, and it is necessary to fully control the coating conditions, calcination conditions, etc.

[0056] Therefore, the inventors of the present invention have conducted in-depth research on a method for manufacturing a laminate that can form a thin surface modification layer. As a result, they found that by forming a layer (surface modification layer precursor) having a film thickness thicker than the target film thickness as a first step, and bringing the layer into contact with a thinning liquid to thin the layer as a second step, a thin surface modification layer can be formed, thereby completing the present invention.

[0057] Note that, by cross-linking the polymer in the first step, it is possible to prevent the surface modification layer precursor from being excessively dissolved in the thinning solution in the second step.

[0058] The laminated body obtained by the method for producing a laminated body of the present invention comprises a surface modification layer and a semiconductor substrate.

[0059] The laminate of the present invention comprises a semiconductor substrate and a surface modification layer having a thickness of 5 nm or less. The surface modification layer contains a cross-linked polymer.

[0060] The laminate of the present invention is obtained, for example, by the method for producing a laminate of the present invention.

[0061] The laminate obtained by the method for producing a laminate of the present invention and the laminate of the present invention are suitable for use in EUV (extreme ultraviolet light, wavelength 13.5 nm) or electron beam lithography.

[0062] The laminate obtained by the manufacturing method of the laminate of the present invention and the laminate of the present invention may further have other layers or films. As other layers, for example, a resist underlayer film containing silicon can be cited. As the resist underlayer film containing silicon, there is no particular limitation as long as it is a resist underlayer film containing silicon used in a photolithography process.

[0063] It should be noted that in the present invention, there is no clear distinction between a film and a layer.

[0064] The thickness of the surface modification layer is 5 nm or less, preferably 3 nm or less. The lower limit of the thickness of the surface modification layer is not particularly limited, and the thickness of the surface modification layer may be 0.1 nm or more, or 0.2 nm or more.

[0065] In the present invention, the film thickness is measured as follows.

[0066] The film thickness was measured using an ellipsometer RE-3100 (manufactured by SCREEN).

[0067] <1st step>

[0068] The first step is a step of obtaining a surface modification layer precursor.

[0069] In the first step, a surface modifying agent is applied onto a semiconductor substrate and then fired to crosslink a polymer, thereby obtaining a surface modification layer precursor.

[0070] The semiconductor substrate used in the first step is not particularly limited as long as it is a substrate used for manufacturing a precision integrated circuit element, for example.

[0071] Examples of the semiconductor substrate include an inorganic substrate, an organic substrate, a substrate having an inorganic film, and a substrate having an organic film.

[0072] Examples of the inorganic substance include arsenic, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, metal carbonitrides, etc. These may be used alone or in combination of two or more.

[0073] Examples of the metal include silicon, germanium, titanium, tungsten, hafnium, zirconium, chromium, copper, aluminum, indium, gallium, palladium, iron, tantalum, iridium, molybdenum, and alloys thereof.

[0074] Examples of the metal oxide include SiO 2 , TiO 2 and the like.

[0075] Examples of the metal nitride include SiN, TiN, and TaN.

[0076] Examples of the metal carbide include SiC and TiC.

[0077] Examples of the metal oxynitride include SiON and TiON.

[0078] Examples of the metal oxycarbide include SiOC and TiOC.

[0079] Examples of the metal carbonitride include SiCN and TiCN.

[0080] As organic matter, for example, amorphous carbon, graphite, fullerene, carbon nanotube, diamond, diamond-like carbon, polyimide, etc. can be mentioned. These can be used alone or in combination of two or more. Regarding the above-mentioned organic matter, they can also be doped or partially replaced by boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen.

[0081] As semiconductor substrates, for example, semiconductor substrates such as silicon wafers coated with silicon oxide films, silicon nitride films or silicon oxynitride films, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates formed with ITO (indium tin oxide) films or IZO (indium zinc oxide) films, plastic (polyimide, PET, etc.) substrates, substrates coated with low dielectric constant materials (low-k materials), flexible substrates, and the like can be cited.

[0082] The method for applying the surface modifier on the semiconductor substrate is not particularly limited, and the surface modifier can be applied by, for example, a spin coater, a coater or the like.

[0083] The surface modifier may be applied onto the semiconductor substrate and then fired, for example, using a heating means such as a hot plate.

[0084] The calcination conditions are appropriately selected from a calcination temperature of 40°C to 400°C, or 80°C to 250°C, and a calcination time of 0.3 to 60 minutes, preferably a calcination temperature of 150°C to 250°C, and a calcination time of 0.5 to 2 minutes.

[0085] By firing, the solvent in the surface modifier evaporates and the polymer is cross-linked, thereby obtaining a layered surface modification layer precursor. The cross-linking includes partial cross-linking.

[0086] 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.

[0087] <<Surface Modifier>>

[0088] The surface modifier contains a polymer and a solvent. The surface modifier may further contain other components.

[0089] The surface modifier used in the method for producing the laminate of the present invention is also the subject of the present invention.

[0090] <<<Polymer>>>

[0091] The polymer is not particularly limited as long as it is a cross-linkable polymer, and can be appropriately selected according to the intended purpose.

[0092] The polymers may form a cross-linked structure only by the polymers themselves or may form a cross-linked structure together with a cross-linking agent.

[0093] The weight average molecular weight of the polymer is not particularly limited, and may be, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation in the surface modifier, the weight average molecular weight may be preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and coating properties, the weight average molecular weight may be preferably 500 or more, and more preferably 600 or more.

[0094] -Polysiloxane-

[0095] As the polymer, polysiloxane is preferred from the viewpoint of being able to satisfactorily prevent the pattern collapse of the resist in EUV or electron beam lithography.

[0096] The polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond.

[0097] The polysiloxane may include a modified polysiloxane in which a part of the silanol groups is modified, for example, a modified polysiloxane in which a part of the silanol groups is modified with alcohol or protected with acetal.

[0098] As another example, the polysiloxane may include a hydrolysis condensate of a hydrolyzable silane, including a modified polysiloxane in which at least a part of the silanol groups of the hydrolysis condensate are alcohol-modified or acetal-protected. The hydrolyzable silane involved in the hydrolysis condensate may include one or more hydrolyzable silanes.

[0099] The polysiloxane may have a cage-type, ladder-type, linear-type, or branched-type main chain structure. Commercially available polysiloxanes may be used as the polysiloxane.

[0100] It should be noted that in the present invention, the "hydrolysis condensate" of the hydrolyzable silane, i.e., the product of hydrolysis and condensation, includes not only polyorganosiloxane polymers as condensates in which the condensation is completely completed, but also polyorganosiloxane polymers as partially hydrolysis condensates in which the condensation is not completely completed. Such partially hydrolysis condensates are also polymers obtained by hydrolysis and condensation of the hydrolyzable silane, just like the condensates in which the condensation is completely completed, but some of them stop at hydrolysis and are not condensed, so Si-OH groups remain. In addition, in the surface modifier, in addition to the hydrolysis condensate, uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silanes) may also remain.

[0101] In addition, in this specification, "hydrolyzable silane" may also be simply referred to as "silane compound".

[0102] In addition, in this specification, "polysiloxane" may be referred to as "hydrolysis condensate".

[0103] The polysiloxane preferably contains a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a halogen atom, an aromatic ring having 6 to 30 carbon atoms which may be substituted with a halogen atom, an alkenyl group, an alkynyl group, a norbornene ring, a phenol group, a protected phenol group, an amino group, an amide group, a cyclic amide group, an imide group, a cyclic imide group, a sulfonyl group, a sulfonamide group, a nitro group, a cyano group, a thiocyanate group, an isocyanate group, a halogen group, a carboxylic acid group, a carboxylate group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoric acid ester group, an ammonium group, At least one structure selected from the group consisting of a sulfonium group, an epoxy group, a glycidyloxy group, a cyclohexyloxy group, a ring-opened epoxy group, a ring-opened glycidyloxy group, a ring-opened cyclohexyloxy group, a hydroxyl group, a mercapto group, an acryloyloxy group, and a methacryloyloxy group.

[0104] If the polysiloxane contains these structures, the pattern collapse of the resist formed on the surface modification layer in EUV or electron beam lithography can be more effectively prevented.

[0105] It should be noted that the ring-opened epoxy group refers to a -CH(OH)-CH2(OH) group.

[0106] In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

[0107] The polysiloxane preferably contains a group which is bonded to a silicon atom and has an ion bond.

[0108] The group having an ionic bond includes, for example, an anionic group as a group bonded to a silicon atom and a cation. Such a group having an ionic bond is represented by, for example, the following formula (I-1).

[0109] The group having an ionic bond includes, for example, a cationic group as a group bonded to a silicon atom and an anion. Such a group having an ionic bond is represented by, for example, the following formula (I-2).

[0110]

[0111] (In formula (I-1), * represents a bond to a silicon atom. Ra represents a single bond or a divalent organic group. Xa - Indicates a monovalent group having an anion. + Represents a cation.

[0112] In formula (I-2), * represents a bond to a silicon atom. Rb represents a single bond or a divalent organic group. Yb + It represents a monovalent group having a cation. - represents an anion.)

[0113] Examples of Ra and Rb include divalent organic groups having 1 to 10 carbon atoms.

[0114] Ra and Rb may have a hetero atom. Examples of the hetero atom include an oxygen atom and a nitrogen atom.

[0115] Examples of the anion or anion in the anionic group include a sulfonic acid anion, a carboxylic acid anion, and a phosphoric acid anion.

[0116] Examples of the cations in the cationic group include sulfonium cations, iodonium cations, cation, Cation, dihydroimidazolium cation, ammonium cation, etc.

[0117] As the sulfonium cation, a triarylsulfonium cation, a diarylmonoalkylsulfonium cation, a monoaryldialkylsulfonium, a trialkylsulfonium cation and the like are preferred.

[0118] As iodine Cation, preferably diaryliodonium cation.

[0119] As Cation, preferably tetraaryl Cationic, triaryl monoalkyl Cation, diaryldialkyl Cations, monoaryltrialkylsulfonium cations, and the like.

[0120] As the ammonium cation, a quaternary ammonium cation, a tertiary ammonium cation, a secondary ammonium cation, a primary ammonium cation, and the like are preferred.

[0121] As the anionic group as a group bonded to a silicon atom, the following groups can be mentioned, for example.

[0122]

[0123] (* indicates a bond to a silicon atom.)

[0124] As the cationic group as a group bonded to a silicon atom, the following groups can be mentioned, for example.

[0125]

[0126] (* indicates a bond to a silicon atom.)

[0127] As the anion, for example, the following anions can be mentioned.

[0128]

[0129] Examples of the cation include the following cations.

[0130]

[0131] As the group having an ionic bond, for example, the following groups can be mentioned.

[0132]

[0133] (* indicates a bond to a silicon atom.)

[0134] The polysiloxane contains, for example, at least any one of an M unit, a D unit, a T unit, and a Q unit.

[0135] The so-called M unit is R a R b R c SiO 1 / 2 The structural unit shown, the so-called D unit, is R a R b SiO 2 / 2 The structural unit shown, the so-called T unit, is R a SiO 1 / 2 The structural unit shown, the so-called Q unit, is SiO 4 / 2The structural units shown. R a , R b , and R c It represents a non-hydrolyzable monovalent organic group.

[0136] The polysiloxane contains, for example, Q units.

[0137] The polysiloxane preferably contains T units. As the ratio of T units in the polysiloxane, relative to the total of the M units, D units, T units, and Q units of the polysiloxane, it is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more. It should be noted that, in this case, the polysiloxane may or may not contain M units, D units, and Q units. If the polysiloxane contains T units, the surface modification layer obtained by the action of the monovalent organic group is easy to interact with the adjacent layer or film. As a result, for example, the pattern of the resist formed on the surface modification layer in EUV or electron beam lithography can be better prevented from collapsing. In addition, in the case where the polysiloxane can contain M units and D units, if the mass ratio of T units is more than the total of M units and D units in the polysiloxane, the film strength, film forming properties, etc. of the surface modification layer can be improved.

[0138] Examples of the polysiloxane include hydrolysis-condensation products of hydrolyzable silanes containing at least one type of hydrolyzable silane represented by the following formula (1).

[0139] --Formula (1)--

[0140] R 1 a Si(R 2 ) 4-a (1)

[0141] In formula (1), R 1 It is a group bonded to a silicon atom, and independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents 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 amino 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.

[0142] In addition, R 2 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.

[0143] a represents an integer of 0-3.

[0144] ---R 1 ---

[0145] The alkyl group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and further preferably 10 or less.

[0146] Specific examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl, Pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl, etc.

[0147] It should be noted that, in the present specification, "i" means "iso", "s" means "secondary", and "t" means "tertiary".

[0148] Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl. Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, and cross-linked cycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl and dicyclodecyl.

[0149] The aryl group may be any one of a phenyl group, a monovalent group derived by removing one hydrogen atom of a condensed ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom of a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0150] For example, the aryl group includes an aryl group having 6 to 20 carbon atoms, and as an example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 1-naphthyl, 2-naphthyl, 5-naphthyl, 2- 1-pyrenyl, 2-pyrenyl, pentacene, benzopyrenyl, benzo[9,10]phenanthryl; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (m-biphenyl), biphenyl-4-yl (p-biphenyl), p-terphenyl-4-yl, m-terphenyl-4-yl, o-terphenyl-4-yl, 1,1′-binaphthyl-2-yl, 2,2′-binaphthyl-1-yl, etc., but are not limited to these.

[0151] The aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups include the same as those mentioned 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.

[0152] Specific examples of the aralkyl group include, but are not limited to, phenylmethyl (benzyl), 2-phenylethylene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, and 10-phenyl-n-decyl.

[0153] The halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms, respectively. Specific examples of such alkyl groups, aryl groups, and aralkyl groups include the same as those mentioned above.

[0154] The number of carbon atoms in the haloalkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and further preferably 10 or less.

[0155] Specific examples of the halogenated alkyl group include, but are not limited to, 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-hexafluoropropane-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group.

[0156] 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.

[0157] Specific examples of the halogenated aryl group include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl , 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, heptafluoro-2-naphthyl, and the like. In addition, groups in which the fluorine atom (fluoro group) in these groups is arbitrarily substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be mentioned, but are not limited to these.

[0158] 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.

[0159] Specific examples of the halogenated aralkyl group include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl and 2,3,4,5,6-pentafluorobenzyl. In addition, examples include groups in which the fluorine atom (fluoro group) in these groups is arbitrarily substituted with a chlorine atom (chloro group), a bromine atom (bromo group) or an iodine atom (iodo group), but the present invention is not limited to these.

[0160] The alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more alkoxy groups, respectively. Specific examples of such alkyl groups, aryl groups, and aralkyl groups include the same ones as described above.

[0161] Examples of the alkoxy group as a substituent include an alkoxy group having at least one alkyl moiety in a linear, branched, or cyclic form having 1 to 20 carbon atoms.

[0162] Examples of the linear or branched alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-butoxy, Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy, etc.

[0163] Examples of the cyclic alkoxy group include cyclopropyloxy, cyclobutyloxy, 1-methyl-cyclopropyloxy, 2-methyl-cyclopropyloxy, cyclopentyloxy, 1-methyl-cyclobutyloxy, 2-methyl-cyclobutyloxy, 3-methyl-cyclobutyloxy, 1,2-dimethyl-cyclopropyloxy, 2,3-dimethyl-cyclopropyloxy, 1-ethyl-cyclopropyloxy, 2-ethyl-cyclopropyloxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutyloxy, 2-ethyl-cyclobutyloxy, 3-ethyl-cyclobutyloxy, 1,2-dimethyl-cyclobutyloxy, 1,3-dimethyl-cyclopentyloxy, Methyl-cyclobutyloxy, 2,2-dimethyl-cyclobutyloxy, 2,3-dimethyl-cyclobutyloxy, 2,4-dimethyl-cyclobutyloxy, 3,3-dimethyl-cyclobutyloxy, 1-n-propyl-cyclopropyloxy, 2-n-propyl-cyclopropyloxy, 1-isopropyl-cyclopropyloxy, 2-isopropyl-cyclopropyloxy, 1,2,2-trimethyl-cyclopropyloxy, 1,2,3-trimethyl-cyclopropyloxy, 2,2,3-trimethyl-cyclopropyloxy, 1-ethyl-2-methyl-cyclopropyloxy, 2-ethyl-1-methyl-cyclopropyloxy, 2-ethyl-2-methyl-cyclopropyloxy and 2-ethyl-3-methyl-cyclopropyloxy, etc.

[0164] Specific examples of the alkoxyalkyl group include lower (having about 5 or less carbon atoms) alkyloxy lower (having about 5 or less carbon atoms) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl, but are not limited to these.

[0165] Specific examples of the alkoxyaryl group 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-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, and 7-methoxynaphth-1-yl.

[0166] Specific examples of the alkoxyaralkyl group include 3-(methoxyphenyl)benzyl and 4-(methoxyphenyl)benzyl, but are not limited to these.

[0167] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and further preferably 10 or less.

[0168] Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 1-butylene, 3-methyl-1-butylene, 3-methyl-2-butylene, 3-methyl-3-butylene, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- -dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, and cross-linked ring alkenyl such as bicycloheptenyl (norbornyl) can also be mentioned.

[0169] In addition, as the substituents in the above-mentioned alkyl group, aryl group, aralkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group, for example, alkyl group, aryl group, aralkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, alkoxy group, aralkyloxy group and the like are mentioned, and their specific examples and their suitable carbon atom numbers are the same as those mentioned above or described below.

[0170] In addition, the aryloxy group mentioned in the substituent is a group in which an aryl group is bonded via an oxygen atom (-O-), and as a specific example of such an aryl group, the same as above can be mentioned. 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 more preferably 20 or less. As a specific example thereof, phenoxy, naphthyl-2-yloxy, etc. can be mentioned, but it is not limited to these.

[0171] When there are two or more substituents, the substituents may be bonded to each other to form a ring.

[0172] Examples of the organic group having a ring-openable epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, a glycidoxycyclohexyl group, and a group in which these epoxy groups are ring-opened.

[0173] Examples of the organic group having an acryloyl group include an acryloyloxymethyl group, an acryloyloxyethyl group, and an acryloyloxypropyl group.

[0174] Examples of the organic group having a methacryloyl group include a methacryloyloxymethyl group, a methacryloyloxyethyl group, and a methacryloyloxypropyl group.

[0175] Examples of the organic group having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group.

[0176] Examples of the organic group having an amino group include, but are not limited to, amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl. The organic group having an amino group will be described in further detail below.

[0177] Examples of the organic group 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.

[0178] Examples of the organic group having a sulfonyl group include a sulfonylalkyl group and a sulfonylaryl group, but the group is not limited to these.

[0179] Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.

[0180] As the organic group having an amino group, there can be mentioned an organic group having at least any one of a primary amino group, a secondary amino group, and a tertiary amino group. Preferably, a hydrolysis condensate of a counter cation having a tertiary ammonium group formed by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid can be used. In addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as an oxygen atom and a sulfur atom.

[0181] As a preferred example of the organic group having an amino group, a group represented by the following formula (A1) can be mentioned.

[0182]

[0183] In formula (A1), R 101 and R 102 Each of them independently represents a hydrogen atom or a hydrocarbon group, and each of L independently represents an alkylene group which may be substituted. * represents a bond.

[0184] Examples of the hydrocarbon group include, but are not limited to, alkyl, alkenyl, and aryl groups. 1 Same as above.

[0185] The alkylene group may be linear or branched, and the number of carbon atoms thereof is usually 1 to 10, preferably 1 to 5. Examples thereof include linear alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene.

[0186] Examples of the organic group having an amino group include an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group, but the group is not limited to these.

[0187] ---R 2 ---

[0188] As R 2 The alkoxy group in R 1 The alkoxy group exemplified in the description of .

[0189] As R 2 The halogen atoms in R 1 The halogen atoms exemplified in the description of .

[0190] The aralkyloxy group is a monovalent group derived by removing a hydrogen atom from a hydroxyl group of an aralkyl alcohol, and specific examples of the aralkyl group in the aralkyloxy group include the same ones as described above.

[0191] The number of carbon atoms in the aralkyloxy group is not particularly limited, but may be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less.

[0192] Specific examples of the aralkyloxy group include phenylmethyloxy (benzyloxy), 2-phenylethyleneoxy, 3-phenyl-n-propyloxy, 4-phenyl-n-butyloxy, 5-phenyl-n-pentyloxy, 6-phenyl-n-hexyloxy, 7-phenyl-n-heptyloxy, 8-phenyl-n-octyloxy, 9-phenyl-n-nonyloxy, and 10-phenyl-n-decyloxy, but are not limited to these.

[0193] The acyloxy group is a monovalent group derived from the carboxyl group (-COOH) of a carboxylic acid compound by removing a hydrogen atom, and typically, alkylcarbonyloxy, arylcarbonyloxy or aralkylcarbonyloxy derived from the carboxyl group of an alkylcarboxylic acid, an arylcarboxylic acid or an aralkylcarboxylic acid by removing a hydrogen atom can be cited, but it is not limited to these. As specific examples of the alkyl group, aryl group and aralkyl group in such alkylcarboxylic acids, arylcarboxylic acids and aralkylcarboxylic acids, the same as above can be cited.

[0194] Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, The invention also includes 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and tosylcarbonyloxy.

[0195] ---Specific examples of hydrolyzable silane represented by formula (1)---

[0196] Specific examples of the hydrolyzable silane represented by the formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltripenzyloxysilane, methyltriphenethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxy Ethyl triethoxysilane, α-glycidoxypropyl trimethoxysilane, α-glycidoxypropyl triethoxysilane, β-glycidoxypropyl trimethoxysilane, β-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl tripropoxysilane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyl triphenoxysilane, α-glycidoxybutyl trimethoxysilane, α-glycidoxybutyl triethoxysilane, β-glycidoxybutyl triethoxysilane, γ-glycidoxybutyl trimethoxysilane, γ-glycidoxybutyl triethoxysilane, δ-glycidoxybutyl trimethoxysilane, δ -Glycidoxybutyltriethoxysilane, (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)butyltriethoxy Silane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane,γ-Glycidoxypropylmethyldiphenoxysilane, γ-Glycidoxypropylethyldimethoxysilane, γ-Glycidoxypropylethyldiethoxysilane, γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane silane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenyl Methoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, 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, phenethylmethyldiethoxysilane,Phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyl Triacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane Alkane, methoxynaphthyl triacetoxysilane, methoxynaphthyl trichlorosilane, ethoxynaphthyl trimethoxysilane, ethoxynaphthyl triethoxysilane, ethoxynaphthyl triacetoxysilane, ethoxynaphthyl trichlorosilane, γ-chloropropyl trimethoxysilane, γ-chloropropyl triethoxysilane, γ-chloropropyl triacetoxysilane, 3,3,3-trifluoropropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, β-cyanoethyl triethoxysilane, thiocyanate propyl triethoxysilane, chloromethyl trimethoxysilane, chloromethyl triethoxysilane, triethoxysilylpropyl diallyl isocyanurate, bicyclo[2,2,1 ] heptenyl triethoxysilane, benzenesulfonylpropyl triethoxysilane, benzenesulfonamidopropyl triethoxysilane, dimethylaminopropyl trimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, silanes represented by the following formulas (A-1) to (A-41),The silanes represented by the following formulas (1-1) to (1-290) are not limited thereto.

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205] In formulae (1-1) to (1-290), T each independently represents an alkoxy group, an acyloxy group, or a halogen group, and preferably represents a methoxy group or an ethoxy group, for example.

[0206] Examples of the polysiloxane include hydrolysis-condensation products of hydrolyzable silanes containing a hydrolyzable silane represented by the following formula (2) together with or instead of the hydrolyzable silane represented by the formula (1).

[0207] --Formula (2)--

[0208] 〔R 3 b Si(R 4 ) 3-b 〕2R 5 c (2)

[0209] In formula (2), R 3 It is a group bonded to a silicon atom, and independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents 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 amino 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.

[0210] In addition, R 4is 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.

[0211] R 5 is a group bonded to a silicon atom, and each independently represents an alkylene group or an arylene group.

[0212] b represents 0 or 1, and c represents 0 or 1.

[0213] As R 3 Specific examples of the groups in and their suitable carbon number can be given as follows: 1 The above mentioned groups and carbon atom numbers.

[0214] As R 4 Specific examples of the groups and atoms in the formula (a) and their suitable carbon number can be given as follows: 2 The above mentioned groups and atoms and the number of carbon atoms.

[0215] As R 5 Specific examples of the alkylene group in the term include straight-chain alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene; branched-chain alkylene groups such as 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 1,1-dimethylethylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 1,1-dimethyl-1,3-propylene, 1,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, and 1-ethyl-1,3-propylene; and alkylene groups such as methanetriyl, ethane-1,1,2 The invention also includes, but is not limited to, alkanetriyl groups such as butane-1,1,1-triyl, ethane-1,2,2-triyl, ethane-2,2,2-triyl, propane-1,1,1-triyl, propane-1,1,2-triyl, propane-1,2,3-triyl, propane-1,2,2-triyl, propane-1,1,3-triyl, butane-1,1,1-triyl, butane-1,1,2-triyl, butane-1,1,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, butane-1,2,2-triyl, butane-2,2,3-triyl, 2-methylpropane-1,1,1-triyl, 2-methylpropane-1,1,2-triyl and 2-methylpropane-1,1,3-triyl.

[0216] As R 5Specific examples of the arylene group in include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene; groups derived by removing two hydrogen atoms from the aromatic ring of a condensed ring aromatic hydrocarbon compound, such as 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, 2,3-anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl; and groups derived by removing two hydrogen atoms from the aromatic ring of a ring-linked aromatic hydrocarbon compound, such as 4,4'-biphenyldiyl and 4,4"-p-terphenyldiyl, but are not limited thereto.

[0217] b is preferably 0.

[0218] c is preferably 1.

[0219] Specific examples of the hydrolyzable silane represented by formula (2) include methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane, the like, but the present invention is not limited to these.

[0220] Examples of the polysiloxane include hydrolysis condensates of hydrolyzable silanes, which contain other hydrolyzable silanes listed below together with or in place of the hydrolyzable silane represented by the formula (1) and / or the hydrolyzable silane represented by the formula (2).

[0221] As other hydrolyzable silanes, there are mentioned those having The silane compounds include, but are not limited to, silane compounds having a sulfone group, silane compounds having a sulfonamide group, and silane compounds having a cyclic urea skeleton in the molecule.

[0222] -- The molecule has Silane compounds (hydrolyzable organosilanes) -

[0223] Expected to have The silane compound containing the hydrolyzable silane can effectively and efficiently promote the crosslinking reaction of the hydrolyzable silane.

[0224] The molecule has A suitable example of the silane compound having a group is represented by formula (3).

[0225] R 11 f R 12 g Si(R 13 ) 4-(f+g) (3)

[0226] R 11 is a group bonded to a silicon atom and represents Base or with Organic base.

[0227] R 12 It is a group bonded to a silicon atom, and independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents 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 amino group, or an organic group having a cyano group, or a combination of two or more thereof.

[0228] R 13 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.

[0229] f represents 1 or 2, g represents 0 or 1, and 1≤f+g≤2 is satisfied.

[0230] Specific examples of alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organic groups having an epoxy group which may be ring-opened, organic groups having an acryloyl group, organic groups having a methacryloyl group, organic groups having a mercapto group, organic groups having an amino group and organic groups having a cyano group, alkoxy groups, aralkyloxy groups, acyloxy groups, and halogen atoms; specific examples of substituents for alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl, and suitable carbon atom numbers thereof; and R 12 , we can cite the following about R 1 The above-mentioned 13 , we can cite the following about R 2 And the above.

[0231] If more detailed, as Specific examples of the ammonium group include a cyclic ammonium group or a chain ammonium group, and a tertiary ammonium group or a quaternary ammonium group is preferred.

[0232] That is, as Base or with Preferred specific examples of the organic group of the amine group include a cyclic ammonium group or a chain ammonium group or an organic group having at least one of them, and preferably a tertiary ammonium group or a quaternary ammonium group or an organic group having at least one of them.

[0233] It should be noted that in When the group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there are cases where the nitrogen atom constituting the ring is directly or via a divalent linking group and the silicon atom is bonded, and there are cases where the carbon atom constituting the ring is directly or via a divalent linking group and the silicon atom is bonded.

[0234] In one embodiment of a suitable embodiment, R as a group bonded to a silicon atom is 11 It is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0235]

[0236] In formula (S1), A 1 , A 2 , A 3 and A 4 Each independently represents a group represented by any one of the following formulas (J1) to (J3), but A 1 ~A 4 At least one of them is a group represented by the following formula (J2), and according to the silicon atom in formula (3) and A 1 ~A 4 Which combination of A and B determines the aromaticity of the formed ring. 1 ~A 4 The bond between each atom and the atoms adjacent thereto and constituting the ring together is either a single bond or a double bond. * indicates a bonding bond.

[0237]

[0238] In formula (J1) to formula (J3), R 10 Each independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, the halogenated alkyl group, the halogenated aryl group, the halogenated aralkyl group and the alkenyl group and their suitable carbon number are the same as those mentioned above. * represents a bonding bond.

[0239] In formula (S1), R 14 Each of them independently represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxyl group. 14 If there are two or more, two R14 Can combine with each other to form a ring, 2 R 14 The formed ring may be a cross-linked ring structure, and in this case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.

[0240] Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups and alkenyl groups and their suitable carbon atom numbers are the same as those mentioned above.

[0241] In formula (S1), n 1 is an integer from 1 to 8, m 1 is 0 or 1, m 2 It is 0 or a positive integer from 1 to the maximum number that can be substituted on a single ring or multiple rings.

[0242] In m 1 When it is 0, the structure contains A 1 ~A 4 (4+n 1 )-membered ring. That is, in n 1 When it is 1, it forms a 5-membered ring. 1 When it is 2, it forms a 6-membered ring. 1 When it is 3, it forms a 7-membered ring. 1 When it is 4, it forms an 8-membered ring. 1 When it is 5, it forms a 9-membered ring. 1 When it is 6, it forms a 10-membered ring. 1 When it is 7, it forms an 11-membered ring. 1 When it is 8, it forms a 12-membered ring.

[0243] In m 1 When it is 1, a 1 ~A 3 (4+n 1 )-membered ring and containing A 4 A condensed ring formed by condensing 6-membered rings.

[0244] According to A 1 ~A 4 In any of the formulae (J1) to (J3), there may be a case where the atoms constituting the ring have hydrogen atoms or a case where the atoms do not have hydrogen atoms, but in A 1 ~A 4 When there is a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R 14 In addition, R 14 Can be in addition to A 1 ~A 4 Based on this situation, as described above, m 2is selected from 0 or an integer from 1 to the maximum number of substitutions possible on a single ring or multiple rings.

[0245] The heteroaromatic cyclic ammonium group represented by formula (S1) is bonded to any carbon atom or nitrogen atom present in such a monocyclic or condensed ring, and is directly bonded to the silicon atom, or is bonded to the silicon atom via a linker to form an organic group having cyclic ammonium, which is bonded to the silicon atom.

[0246] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group, but the linking group is not limited to these.

[0247] Specific examples of the alkylene group and the arylene group and their suitable carbon atom numbers are the same as those mentioned above.

[0248] In addition, the alkenylene group is a divalent group derived by further removing one hydrogen atom from the alkenyl group, and specific examples of such alkenyl groups include the same as those mentioned above. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0249] Specific examples thereof include vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene, but are not limited to these.

[0250] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a heteroaromatic cyclic ammonium group represented by formula (S1) include silanes represented by the following formulae (I-1) to (I-50), but are not limited thereto.

[0251]

[0252]

[0253]

[0254] In another example, R as the group bonded to the silicon atom in formula (3) is 11 It may be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0255]

[0256] In formula (S2), A 5 , A 6 , A 7 and A 8 Each independently represents a group represented by any one of the following formulas (J4) to (J6), but A 5 ~A 8At least one of them is a group represented by the following formula (J5). 5 ~A 8 Which combination of A determines the non-aromatic nature of the formed ring. 5 ~A 8 Each of the bonds with the atoms that form the ring together with the adjacent atoms is a single bond or a double bond. * indicates a bonding bond.

[0257]

[0258] In formula (J4) to formula (J6), R 10 Each independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, the halogenated alkyl group, the halogenated aryl group, the halogenated aralkyl group and the alkenyl group and their suitable carbon number are the same as those mentioned above. * represents a bonding bond.

[0259] In formula (S2), R 15 Each of them independently represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxyl group. 15 If there are two or more, two R 15 Can combine with each other to form a ring, 2 R 15 The formed ring may be a cross-linked ring structure, and in this case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.

[0260] Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and their suitable carbon atom numbers are the same as those mentioned above.

[0261] In formula (S2), n 2 is an integer from 1 to 8, m 3 is 0 or 1, m 4 It is 0 or a positive integer from 1 to the maximum number that can be substituted on a single ring or multiple rings.

[0262] In m 3 When it is 0, the structure contains A 5 ~A 8 (4+n 2 )-membered ring. That is, in n 2 When it is 1, it forms a 5-membered ring. 2 When it is 2, it forms a 6-membered ring. 2 When it is 3, it forms a 7-membered ring. 2 When it is 4, it forms an 8-membered ring. 2 When it is 5, it forms a 9-membered ring. 2 When it is 6, it forms a 10-membered ring.2 When it is 7, it forms an 11-membered ring. 2 When it is 8, it forms a 12-membered ring.

[0263] In m 3 When it is 1, the 5 ~A 7 (4+n 2 )-membered ring and containing A 8 A condensed ring formed by condensing 6-membered rings.

[0264] According to A 5 ~A 8 In any of the formulae (J4) to (J6), there are cases where the atoms constituting the ring have hydrogen atoms or cases where the atoms do not have hydrogen atoms, but in A 5 ~A 8 When there is a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R 15 In addition, R 15 Can be in addition to A 5 ~A 8 The substitution is carried out on a ring-constituting atom other than the ring-constituting atom in the formula (a).

[0265] Based on this situation, as mentioned above, m 4 is selected from 0 or an integer from 1 to the maximum number of substitutions possible on a single ring or multiple rings.

[0266] The bond of the heteroaliphatic cyclic ammonium group represented by formula (S2) exists on any carbon atom or nitrogen atom existing in such a monocyclic or condensed ring, and is directly bonded to the silicon atom, or is bonded to the silicon atom via a linker to form an organic group having cyclic ammonium, which is bonded to the silicon atom.

[0267] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group and their suitable carbon atom numbers are the same as those mentioned above.

[0268] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a heteroaliphatic cyclic ammonium group represented by formula (S2) include silanes represented by the following formulas (II-1) to (II-30), but are not limited thereto.

[0269]

[0270]

[0271] In still another example, R as the group bonded to the silicon atom in formula (3) 11 It may be a chain ammonium group represented by the following formula (S3).

[0272]

[0273] In formula (S3), R 10 Each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group, and specific examples of the alkyl group, the aryl group, the aralkyl group, the halogenated alkyl group, the halogenated aryl group, the halogenated aralkyl group and the alkenyl group and their suitable carbon number are the same as those mentioned above. * represents a bond.

[0274] The chain ammonium group represented by the formula (S3) is directly bonded to the silicon atom, or is bonded via a linker to form an organic group having a chain ammonium group, which is bonded to the silicon atom.

[0275] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group include the same as those mentioned above.

[0276] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a chain ammonium group represented by formula (S3) include silanes represented by the following formulas (III-1) to (III-28), but are not limited thereto.

[0277]

[0278]

[0279] --Silane compounds having sulfone groups or sulfonamide groups (hydrolyzable organosilanes)--

[0280] Examples of the silane compound having a sulfone group and the silane compound having a sulfoneamide group include compounds represented by the following formulas (B-1) to (B-36), but are not limited thereto.

[0281] In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[0282]

[0283]

[0284] --Silane compounds having a cyclic urea skeleton in the molecule (hydrolyzable organosilanes)--

[0285] Examples of the hydrolyzable organosilane having a cyclic urea skeleton in the molecule include hydrolyzable organosilane represented by the following formula (4-1).

[0286] R 401 x R 402 y Si(R 403 )4-(x+y) (4-1)

[0287] In formula (4-1), R 401 is a group bonded to a silicon atom, and each independently represents a group represented by the following formula (4-2).

[0288] R 402 It is a group bonded to a silicon atom and represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a halogenated alkyl group which may be substituted, a halogenated aryl group which may be substituted, a halogenated aralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents 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, or an organic group having a cyano group, or a combination of two or more thereof.

[0289] R 403 The groups or atoms bonded to the silicon atom each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom.

[0290] x is 1 or 2, y is 0 or 1, and x+y≤2.

[0291] R 402 alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, organic groups having an epoxy group that can be ring-opened, organic groups having an acryloyl group, organic groups having a methacryloyl group, organic groups having a mercapto group, and organic groups having a cyano group, and R 403 The alkoxy group, aralkyloxy group, acyloxy group and halogen atom, as well as specific examples of these substituents and suitable carbon number can be cited as those for R 1 and R 2 And the same as above.

[0292]

[0293] In formula (4-2), R 404 each independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an organic group having an epoxy group, or an organic group having a sulfonyl group, and R 405 Each independently represents an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-). * represents a bonding bond.

[0294] It should be noted that R 404Specific examples of the alkyl group which may be substituted, the alkenyl group which may be substituted, and the organic group having an epoxy group and suitable carbon number thereof can be given as those for R 1 The same as above, but in addition to these, as R 404 The alkyl group which may be substituted is preferably an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group, and specific examples thereof include allyl group, 2-vinylethyl group, 3-vinylpropyl group, 4-vinylbutyl group and the like.

[0295] The organic group having a sulfonyl group is not particularly limited as long as it contains a sulfonyl group, and examples thereof include an alkylsulfonyl group which may be substituted, an arylsulfonyl group which may be substituted, an aralkylsulfonyl group which may be substituted, a halogenated alkylsulfonyl group which may be substituted, a halogenated arylsulfonyl group which may be substituted, a halogenated aralkylsulfonyl group which may be substituted, an alkoxyalkylsulfonyl group which may be substituted, an alkoxyarylsulfonyl group which may be substituted, an alkoxyaralkylsulfonyl group which may be substituted, and an alkenylsulfonyl group which may be substituted.

[0296] The alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl groups in these groups, as well as specific examples of these substituents and suitable carbon number thereof, can be cited as those mentioned above for R. 1 And the same as above.

[0297] The alkylene group is a divalent group derived by further removing one hydrogen atom from the alkyl group, and can be any of a linear, branched, and cyclic group. As specific examples of such alkylene groups, the same as those mentioned above can be cited. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0298] In addition, R 405 The alkylene group may have one or more selected from the group consisting of a sulfide bond, an ether bond, and an ester bond at its terminal or in the middle, preferably in the middle.

[0299] Specific examples of the alkylene group include straight-chain alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene; branched-chain alkylene groups such as methylethylene, 1-methyl1,3-propylene, 2-methyl1,3-propylene, 1,1-dimethylethylene, 1-methyl1,4-butylene, 2-methyl1,4-butylene, 1,1-dimethyl1,3-propylene, 1,2-dimethyl1,3-propylene, 2,2-dimethyl1,3-propylene, and 1-ethyl1,3-propylene; and 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2- Cyclic alkylene groups such as cyclohexanediyl and 1,3-cyclohexanediyl, and alkylene groups containing ether groups such as -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2OCH2CH2SCH2CH2-, but are not limited to these.

[0300] The hydroxyalkylene group is a group in which at least one hydrogen atom of the above-mentioned alkylene group is replaced by a hydroxyl group. Specific examples thereof include hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxy1,3-propylene, 2-hydroxy1,3-propylene, 3-hydroxy1,3-propylene, 1-hydroxy1,4-butylene, 2-hydroxy1,4-butylene, 3-hydroxy1,4-butylene, 4-hydroxy1,4-butylene, 1,2-dihydroxy1,4-butylene, 1,3-dihydroxy1,4-butylene, 1,4-dihydroxy1,4-butylene, 2,3-dihydroxy1,4-butylene, 2,4-dihydroxy1,4-butylene, and 4,4-dihydroxy1,4-butylene, but are not limited thereto.

[0301] In formula (4-2), X 401 Each independently represents any one of the groups represented by the following formulae (4-3) to (4-5), and the carbon atom of the keto group in the following formulae (4-4) and (4-5) and R in the formula (4-2) 405 The bound nitrogen atoms are bound.

[0302]

[0303] In formula (4-3) to formula (4-5), R 406 ~R 410 Each of them independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an organic group having an epoxy group or a sulfonyl group. Specific examples of the alkyl group which may be substituted, the alkenyl group which may be substituted, and the organic group having an epoxy group or a sulfonyl group and suitable carbon number thereof can be given as those described above with respect to R. 1 In addition, specific examples of organic groups having a sulfonyl group and suitable carbon number can be given as those for R 404 The same as above. * indicates a bonding bond.

[0304] In particular, when the obtained laminate is used for EUV or electron beam lithography, from the viewpoint of achieving excellent lithographic properties with good reproducibility, X 401 Preferred is a group represented by formula (4-5).

[0305] When the obtained laminate is used for EUV or electron beam lithography, from the viewpoint of achieving excellent lithographic properties with good reproducibility, R 404 and R 406 ~R 410 At least one of the groups is preferably an alkyl group in which a terminal hydrogen atom is substituted with a vinyl group.

[0306] The hydrolyzable organosilane represented by formula (4-1) may be a commercially available product or may be synthesized by a known method described in International Publication No. 2011 / 102470 or the like.

[0307] Specific examples of the hydrolyzable organosilane represented by the formula (4-1) include silanes represented by the following formulae (4-1-1) to (4-1-29), but are not limited to these.

[0308]

[0309]

[0310] The polysiloxane may be a hydrolysis-condensation product of a hydrolyzable silane containing other silane compounds than those exemplified above, within a range not impairing the effects of the present invention.

[0311] As described above, as the polysiloxane, a modified polysiloxane in which at least a part of the silanol groups is modified can be used. For example, a modified polysiloxane in which a part of the silanol groups is modified with alcohol or a modified polysiloxane in which acetal protection is performed can be used.

[0312] Examples of the modified polysiloxane include a reaction product obtained by reacting at least a part of the silanol groups of the hydrolyzable silane hydrolysis condensate with a hydroxyl group of an alcohol, a dehydration reaction product of the condensate and an alcohol, and a modified product obtained by protecting at least a part of the silanol groups of the condensate with an acetal group.

[0313] As the alcohol, a monohydric alcohol may be used, and examples thereof include methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-pentanol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3 -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.

[0314] In addition, 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.

[0315] The reaction between the silanol group of the condensate and the hydroxyl group of the alcohol is carried out by contacting the polysiloxane with the alcohol and reacting them at a temperature of 40 to 160° C., for example, 60° C., for 0.1 to 48 hours, for example, 24 hours, to obtain a modified polysiloxane in which the silanol groups are blocked. In this case, the alcohol as a blocking agent can be used as a solvent in the composition containing the polysiloxane.

[0316] The dehydration reaction product of polysiloxane and alcohol composed of a hydrolysis condensate of a hydrolyzable silane can be produced by reacting polysiloxane with alcohol in the presence of an acid as a catalyst, capping the silanol groups with alcohol, and removing the generated water by dehydration to the outside of the reaction system.

[0317] As the acid, an organic acid having an acid dissociation constant (pka) of -1 to 5, preferably 4 to 5 can be used. For example, the acid can be trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., particularly benzoic acid, isobutyric acid, acetic acid, etc.

[0318] As the acid, an acid having a boiling point of 70 to 160° C. may be used, and examples thereof include trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid.

[0319] As such, the acid is preferably a substance having an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160° C. That is, a substance with weak acidity or a substance with strong acidity but low boiling point can be used.

[0320] Furthermore, as the acid, any one of the properties of the acid dissociation constant and the boiling point can be utilized.

[0321] Acetal protection of the silanol group of the condensate can be performed using vinyl ether, for example, vinyl ether represented by the following formula (5) can be used. By reacting these, a partial structure represented by the following formula (6) can be introduced into the polysiloxane.

[0322]

[0323] 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, and R 4a represents an alkyl group having 1 to 10 carbon atoms, R 2a With R 4a They may be bonded to each other to form a ring. Examples of the alkyl group include those exemplified above.

[0324]

[0325] In formula (6), R 1 '、R 2 ', and R 3 ' each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 4 ' represents an alkyl group having 1 to 10 carbon atoms, R 2 'With R 4 ' can be bonded to each other to form a ring. In formula (6), * represents 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, R derived from formula (1) 1 The alkyl group includes the ones exemplified above.

[0326] As the vinyl ether represented by formula (5), for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be particularly preferably used.

[0327] The acetal protection of the silanol group can be carried out using polysiloxane, vinyl ether, and propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, 1,4-dimethoxybenzene, etc. as a solvent. Aprotic solvents such as alkane, pyridine The reaction is carried out in the presence of a catalyst such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid or the like.

[0328] It should be noted that the blocking of the silanol groups with alcohols and the acetal protection can be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described later.

[0329] In a preferred embodiment of the present invention, the polysiloxane comprises a hydrolyzable silane represented by formula (1) and, if necessary, a hydrolyzable silane represented by formula (2) and other hydrolyzable silanes, and at least one of hydrolysis condensates of hydrolyzable silanes and modified products thereof.

[0330] In a preferred embodiment, the polysiloxane comprises a dehydration reaction product of a hydrolysis condensate and an alcohol.

[0331] The polysiloxane as the hydrolysis condensate of the hydrolyzable silane (which may also include a modified product) may have a weight average molecular weight of, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of the hydrolysis condensate in the composition, the weight average molecular weight may be 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 coating properties, the weight average molecular weight may be preferably 500 or more, and more preferably 600 or more.

[0332] It should be noted that the weight average molecular weight is the molecular weight obtained by polystyrene conversion obtained by GPC analysis. GPC analysis can be performed using, for example, a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), the column temperature is 40 ° C, tetrahydrofuran is used as an eluent (elution solvent), and the flow rate (flow velocity) is set to 1.0 mL / minute, and a standard sample is carried out using polystyrene (Shodex (registered trademark) manufactured by Showa Denko Co., Ltd.).

[0333] The hydrolysis-condensation product of the hydrolyzable silane is obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).

[0334] The silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, that is, an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halosilyl group (hereinafter referred to as a hydrolyzable group).

[0335] In the hydrolysis of these hydrolyzable groups, usually 0.1 to 100 mol, for example 0.5 to 100 mol, preferably 1 to 10 mol of water is used per 1 mol of the hydrolyzable group.

[0336] During the hydrolysis and condensation, a hydrolysis catalyst may be used for the purpose of promoting the reaction, or the hydrolysis and condensation may be carried out without using a hydrolysis catalyst. When a hydrolysis catalyst is used, usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per 1 mol of the hydrolyzable group can be used.

[0337] The reaction temperature for hydrolysis and condensation is usually in the range of room temperature or higher and below the reflux temperature of the organic solvent that can be used for hydrolysis at normal pressure, and may be, for example, 20 to 110°C, or 20 to 80°C.

[0338] The hydrolysis may be complete hydrolysis, that is, all hydrolyzable groups are converted into silanol groups, or partial hydrolysis, that is, unreacted hydrolyzable groups remain.

[0339] Examples of the hydrolysis catalyst that can be used in the hydrolysis condensation include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0340] Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-isopropoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-tert-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di-isopropoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium , di-sec-butoxy·bis(acetylacetonate)titanium, di-tert-butoxy·bis(acetylacetonate)titanium, monoethoxy·tri(acetylacetonate)titanium, mono-n-propoxy·tri(acetylacetonate)titanium, mono-isopropoxy·tri(acetylacetonate)titanium, mono-n-butoxy·tri(acetylacetonate)titanium, mono-sec-butoxy·tri(acetylacetonate)titanium, mono-tert-butoxy·tri(acetylacetonate)titanium, tetra(acetylacetonate)titanium, triethoxy·mono(ethyl acetoacetate)titanium, tri-n-propoxy·mono(ethyl acetoacetate)titanium, tri-isopropoxy ethyl acetoacetate titanium, tri-n-butoxy mono(ethyl acetoacetate titanium), tri-sec-butoxy mono(ethyl acetoacetate titanium), tri-tert-butoxy mono(ethyl acetoacetate titanium), diethoxy bis(ethyl acetoacetate titanium), di-n-propoxy bis(ethyl acetoacetate titanium), di-isopropoxy bis(ethyl acetoacetate titanium), di-n-butoxy bis(ethyl acetoacetate titanium), di-sec-butoxy bis(ethyl acetoacetate titanium), di-tert-butoxy bis(ethyl acetoacetate titanium, mono(ethyl acetoacetate) titanium, tri-n-butoxy mono(ethyl acetoacetate) titanium, tri-sec-butoxy mono(ethyl acetoacetate) titanium, tri-tert-butoxy mono(ethyl acetoacetate) titanium, Titanium chelates such as ethoxy tris(ethyl acetoacetate)titanium, mono-n-propoxy tris(ethyl acetoacetate)titanium, mono-isopropoxy tris(ethyl acetoacetate)titanium, mono-n-butoxy tris(ethyl acetoacetate)titanium, mono-sec-butoxy tris(ethyl acetoacetate)titanium, mono-tert-butoxy tris(ethyl acetoacetate)titanium, tetrakis(ethyl acetoacetate), mono(acetylacetonate) tris(ethyl acetoacetate)titanium, bis(acetylacetonate) bis(ethyl acetoacetate)titanium, tris(acetylacetonate) mono(ethyl acetoacetate)titanium;triethoxy zirconium mono(acetylacetonate), tri-n-propoxy zirconium mono(acetylacetonate), tri-isopropoxy zirconium mono(acetylacetonate), tri-n-butoxy zirconium mono(acetylacetonate), tri-sec-butoxy zirconium mono(acetylacetonate), tri-tert-butoxy zirconium mono(acetylacetonate), diethoxy zirconium bis(acetylacetonate), di-n-propoxy zirconium bis(acetylacetonate), di-isopropoxy zirconium bis(acetylacetonate), di-n-butoxy zirconium bis(acetylacetonate), di-sec-butoxy zirconium bis(acetylacetonate), di-tert-butoxy · Zirconium bis(acetylacetonate), zirconium monoethoxy tris(acetylacetonate), zirconium mono-n-propoxy tris(acetylacetonate), zirconium mono-isopropoxy tris(acetylacetonate), zirconium mono-n-butoxy tris(acetylacetonate), zirconium mono-sec-butoxy tris(acetylacetonate), zirconium mono-tert-butoxy tris(acetylacetonate), zirconium tetra(acetylacetonate), zirconium triethoxy mono(ethyl acetoacetate), zirconium tri-n-propoxy mono(ethyl acetoacetate), zirconium tri-isopropoxy mono(ethyl acetoacetate), zirconium tri-n-butoxy mono(ethyl acetoacetate) ester) zirconium, tri-sec-butoxy mono(ethyl acetoacetate) zirconium, tri-tert-butoxy mono(ethyl acetoacetate) zirconium, diethoxy bis(ethyl acetoacetate) zirconium, di-n-propoxy bis(ethyl acetoacetate) zirconium, di-isopropoxy bis(ethyl acetoacetate) zirconium, di-n-butoxy bis(ethyl acetoacetate) zirconium, di-sec-butoxy bis(ethyl acetoacetate) zirconium, di-tert-butoxy bis(ethyl acetoacetate) zirconium, monoethoxy tris(ethyl acetoacetate) zirconium, mono-n-propoxy tris(ethyl acetoacetate) Zirconium, zirconium mono-isopropoxy tris(ethyl acetoacetate), zirconium mono-n-butoxy tris(ethyl acetoacetate), zirconium mono-sec-butoxy tris(ethyl acetoacetate), zirconium mono-tert-butoxy tris(ethyl acetoacetate), zirconium tetra(ethyl acetoacetate), zirconium mono(acetylacetonate) tris(ethyl acetoacetate), zirconium bis(acetylacetonate) bis(ethyl acetoacetate), zirconium tris(acetylacetonate) mono(ethyl acetoacetate); aluminum chelates such as aluminum tris(acetylacetonate), aluminum tris(ethyl acetoacetate); etc., but not limited to these. ;

[0341] Examples of organic acids used as the hydrolysis catalyst include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric 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.

[0342] Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc., but the present invention is not limited to these.

[0343] Examples of the organic base as the hydrolysis catalyst include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picolinium, 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.

[0344] Examples of the inorganic base as the hydrolysis catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like, but the present invention is not limited to these.

[0345] Among these catalysts, metal chelates, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0346] Among them, in the present invention, nitric acid can be suitably used as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the molecular weight change of the hydrolysis condensate can be suppressed. The stability of the hydrolysis condensate in the known liquid depends on the pH of the solution. After in-depth research, it was found that by using nitric acid in an appropriate amount, the pH of the solution becomes a stable region.

[0347] In addition, as described above, nitric acid can also be used when obtaining a modified product of the hydrolysis condensate, for example, when blocking the silanol group with an alcohol. Therefore, it is also preferred from the viewpoint of being a substance that can contribute to the reactions of both the hydrolysis and condensation of the hydrolyzable silane and the alcohol blocking of the hydrolysis condensate.

[0348] In the case of hydrolysis and condensation, an organic solvent may be used as a solvent. Specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, and n-pentylnaphthalene; Hydrocarbon solvents; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol Monohydric alcohol solvents such as alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, etc.; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, etc.; acetone, methyl ethyl ketone, methyl-n-butylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, etc. Ketone solvents such as propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone acetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, di Alkane, dimethyl alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether solvents such as propylene glycol monomethyl 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, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethyl Benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol diacetate, methoxytriethylene glycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, propylene glycol monomethyl ether, Ester solvents such as isopentyl oxalate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; sulfur-containing solvents such as methyl sulfide, ethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, cyclopentane, and 1,3-propane sultone, but are not limited to these. These solvents can be used in combination of one or more.

[0349] After the hydrolysis and condensation reactions are completed, the reaction solution is either diluted or concentrated, neutralized, and treated with an ion exchange resin, thereby removing the hydrolysis catalyst such as the acid or alkali used for the hydrolysis and condensation. In addition, before or after such treatment, alcohol, water, the hydrolysis catalyst used, etc. as by-products can be removed from the reaction solution by vacuum distillation or the like.

[0350] The hydrolysis condensate obtained by such operation can be obtained as a polysiloxane varnish dissolved in an organic solvent, and it can be directly used for the preparation of the surface modifier. That is, the reaction solution can be directly (or diluted) used for the preparation of the surface modifier. In this case, the hydrolysis catalyst and by-products used for hydrolysis and condensation can remain in the reaction solution as long as they do not damage the effect of the present invention. For example, the nitric acid used when the hydrolysis catalyst and the alcohol blocking of the silanol group are used can remain in the polymer varnish solution at about 100ppm to 5,000ppm.

[0351] The obtained polysiloxane varnish may be solvent-exchanged or diluted with an appropriate solvent. It should be noted that if the obtained polysiloxane varnish has good storage stability, the organic solvent may be distilled off to make the concentration of the film-forming component 100%. It should be noted that the so-called film-forming component refers to the component from which the solvent component is removed from all the components of the composition.

[0352] The organic solvent used for solvent replacement and dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited and may be one or more and may be arbitrarily selected and used.

[0353] <<<Solvent>>>

[0354] The solvent contained in the surface modifier can be used without particular limitation as long as it can dissolve / mix the polymer (for example, polysiloxane) and other components contained in the surface modifier as required.

[0355] Examples of the solvent include organic solvents and water.

[0356] Examples of the solvent include alcohols, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylates, and water.

[0357] Examples of the alcohols include monoalcohol solvents, polyol solvents, etc. Specific examples thereof include the above-mentioned monoalcohol solvents and polyol solvents as solvents for hydrolysis and condensation.

[0358] Examples of the alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0359] Examples of the alkylene glycol monoalkyl ether 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.

[0360] Examples of the alkylene glycol dialkyl ether 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.

[0361] Examples of the alkylene glycol monoalkyl ether carboxylates include alkylene glycol monoalkyl ether acetates.

[0362] Examples of the alkylene glycol monoalkyl ether acetate 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.

[0363] Specific examples of other solvents include toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl acetate, ethyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, butyl propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, 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-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, 4-methyl-2-pentanol, γ-butyrolactone, etc.

[0364] These solvents may be used alone or in combination of two or more.

[0365] The surface modifier may contain water as a solvent. When water is contained as a solvent, its content may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, relative to the total mass of the solvent contained in the surface modifier.

[0366] <<<Curing catalyst>>>

[0367] The surface modifier may be a composition not containing a curing catalyst, but preferably contains a curing catalyst.

[0368] As the curing catalyst, ammonium salts, phosphines, Salt, sulfonium salt, iodine Salt, oxygen Salts, etc. The salts described below as examples of curing catalysts may be added in the form of salts, or may be any substance that forms a salt in the composition (a substance that is added as another compound and forms a salt in the system).

[0369] As ammonium salts, there can be mentioned quaternary ammonium salts having a structure represented by formula (D-1), quaternary ammonium salts having a structure represented by formula (D-2), quaternary ammonium salts having a structure represented by formula (D-3), quaternary ammonium salts having a structure represented by formula (D-4), quaternary ammonium salts having a structure represented by formula (D-5), and tertiary ammonium salts having a structure represented by formula (D-6).

[0370]

[0371] (In the formula, m a Integer from 2 to 11, n a represents an integer from 2 to 3, R 21 represents an alkyl group, an aryl group, or an aralkyl group, and Y- represents an anion. )

[0372] R 22 R 23 R 24 R 25 N + Y - Formula (D-2)

[0373] (Where R 22 , R 23 , R 24 and R 25 independently represent an alkyl group, an aryl group, or an aralkyl group, Y- represents an anion, and R 22 , R 23 , R 24 , and R 25 Combined with nitrogen atoms.)

[0374]

[0375] (Where R 26 and R 27 Each of them independently represents an alkyl group, an aryl group, or an aralkyl group, and Y- represents an anion. )

[0376]

[0377] (Where R 28 represents an alkyl group, an aryl group, or an aralkyl group, and Y- represents an anion. )

[0378]

[0379] (Where R 29 and R 30 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.)

[0380]

[0381] (In the formula, m a Integer from 2 to 11, n a represents an integer from 2 to 3, Y - represents an anion.)

[0382] In addition, as Salts include quaternary Salt.

[0383] R 31 R 32 R 33 R 34 P + Y - Formula (D-7)

[0384] (Where R 31 , R 32 , R 33 , and R 34 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 31 , R 32 , R 33 , and R 34 Combined with phosphorus atoms respectively.)

[0385] In addition, examples of the sulfonium salt include tertiary sulfonium salts represented by formula (D-8).

[0386] R 35 R 36 R 37 S + Y- Formula (D-8)

[0387] (Where R 35 , R 36 , and R 37 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 35 , R 36 , and R 37 Combined with sulfur atoms.)

[0388] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a Integer from 2 to 11, n a represents an integer of 2 to 3. 21 represents, 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 straight-chain alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) and other acid groups.

[0389] The compound of formula (D-2) is R 22 R 23 R 24 R 25 N + Y - The quaternary ammonium salt R 22 , R 23 , R 24 and R 25 For example, it is an alkyl group having 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms such as phenyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O -The quaternary ammonium salt can be obtained as a commercial product, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0390] The compound of formula (D-3) is preferably a quaternary ammonium salt derived from a 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, R 26 and R 27 The total number of carbon atoms is 7 or more. 26 Examples include alkyl groups such as methyl, ethyl, and propyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 27 Examples include aralkyl groups such as benzyl, alkyl groups such as octyl and octadecyl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - The compound can also be obtained as a commercial product, but can be produced by reacting an imidazole compound such as 1-methylimidazole and 1-benzylimidazole with an aralkyl halide, alkyl halide or aryl halide such as benzyl bromide, methyl bromide or bromobenzene.

[0391] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 For example, it is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 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 butyl, octyl, benzyl, and lauryl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) or the like. The compound can also be obtained as a commercial product, but can be produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or the like, or an aryl halide. The compound can be exemplified by, for example, N-laurylpyridinium chloride N-Benzylpyridinium bromide wait.

[0392] The compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picolinate, etc. 29 For example, it is 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 methyl, octyl, lauryl, and benzyl. 30 For example, it 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. For example, when the compound represented by formula (D-5) is a quaternary ammonium derived from picolinate, R 30 Methyl. Anion (Y - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) or the like. The compound can also be obtained as a commercial product, but can be prepared by, for example, reacting a substituted pyridine such as picolinate with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide. The compound can be exemplified by, for example, N-benzylpicolinate chloride N-Benzylpicoline bromide N-Laurylpicolinyl chloride wait.

[0393] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m a Integer from 2 to 11, n a Indicates 2 or 3. In addition, anions (Y - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) and other acid groups. The present compound can be prepared by the reaction of an amine with a weak acid such as a carboxylic acid or phenol. Examples of carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y - ) is (HCOO - ), when acetic acid is used, the anion (Y - ) is (CH3COO - ). In addition, when phenol is used, the anion (Y - ) is (C6H5O - ).

[0394] The compound of formula (D-7) is a compound having R 31 R 32 R 33 R 34 P + Y - The structure of the season Salt. 31 , R 32 , R 33 , and R 34 For example, it is an alkyl group having 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms such as phenyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl. 31 ~R 34 Among the four substituents, three are unsubstituted phenyl or substituted phenyl, such as phenyl and tolyl, 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. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) and the like. The compound can be obtained as a commercial product, and examples thereof include tetra-n-butyl halides. Tetra-n-propyl halide Tetraalkyl halides Triethylbenzyl halide Trialkylbenzyl halides Triphenylmethyl halides Triphenylethyl halide Triphenyl halogenated monoalkyl Triphenylbenzyl halides Tetraphenyl halides Trimethylphenyl halides or trimethylbenzene monoalkyl halides (In the above, the halogen atom is a chlorine atom or a bromine atom.) A halogenated triphenylmethyl Triphenylethyl halide Triphenyl halogenated monoalkyl Triphenylbenzyl halides Isohalogenated triphenyl monoaryl Halogenated trimethylphenyl monophenyl Isohalogenated trimethylphenyl monoaryl Trimethylol Halide Isohalogenated trimethylbenzyl monoalkyl (The halogen atom is a chlorine atom or a bromine atom).

[0395] In addition, examples of the phosphines include primary phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, isopropyl phosphine, isobutyl phosphine and phenyl phosphine, secondary phosphines such as dimethyl phosphine, diethyl phosphine, diisopropyl phosphine, diisopentyl phosphine and diphenyl phosphine, and tertiary phosphines such as trimethyl phosphine, triethyl phosphine, triphenyl phosphine, methyldiphenyl phosphine and dimethylphenyl phosphine.

[0396] The compound of formula (D-8) is a compound having R 35 R 36 R 37 S + Y - The structure of tertiary sulfonium salt. 35 , R 36 , and R 37 For example, it is an alkyl group having 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms such as phenyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl. 35 ~R 37 Two of the three substituents are unsubstituted phenyl or substituted phenyl, such as phenyl and tolyl, 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. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ), maleic acid anion, nitrate anion and other acid groups. The compound can be obtained as a commercial product, for example, trialkylsulfonium halides such as tri-n-butylsulfonium halides, tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmethylsulfonium halides, diphenylethylsulfonium halides and other diphenylmonoalkylsulfonium halides, triphenylsulfonium halides (above, the halogen atom is a chlorine atom or a bromine atom), tri-n-butylsulfonium carboxylates, trialkylsulfonium carboxylates such as tri-n-propylsulfonium carboxylates, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylates, diphenylmethylsulfonium carboxylates, diphenylethylsulfonium carboxylates and diphenylmonoalkylsulfonium carboxylates, triphenylsulfonium carboxylates. In addition, triphenylsulfonium halides and triphenylsulfonium carboxylates can be preferably used.

[0397] Furthermore, a nitrogen-containing silane compound may be added as a curing catalyst. Examples of the nitrogen-containing silane compound include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0398] 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, based on 100 parts by mass of the polymer.

[0399] <<<Acid>>

[0400] The surface modifier preferably contains an acid.

[0401] The acid can be added during the preparation of the surface modifier. However, when the surface modifier contains polysiloxane, it can also be used as a hydrolysis catalyst during the production of the polysiloxane or during the alcohol blocking of the silanol group, and the substance remaining in the polysiloxane varnish can be treated as an acid.

[0402] Examples of the acid include organic acids and inorganic acids.

[0403] Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric 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.

[0404] Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

[0405] The amount of the acid blended (residual acid amount) may be, for example, 0.0001 to 1% by mass, or 0.001 to 0.1% by mass, or 0.005 to 0.05% by mass based on the total mass of the surface modifier.

[0406] <<<Amines, hydroxides>>>

[0407] The surface modifier may contain at least one selected from the group consisting of amines and hydroxides.

[0408] Examples of the amine 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; cyclic amines such as pyridine and morpholine, and the like.

[0409] Examples of the hydroxide include inorganic alkali hydroxides and organic alkali hydroxides.

[0410] Examples of the inorganic alkali hydroxide include sodium hydroxide and potassium hydroxide.

[0411] Examples of the organic base hydroxide include tetraalkylammonium hydroxide, triarylsulfonium hydroxide, diaryliodonium Hydroxides, etc. Examples of tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Examples of triarylsulfonium hydroxides include triphenylsulfonium hydroxide and tri(tert-butylphenyl)sulfonium hydroxide. Examples of diaryliodonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Hydroxides, for example diphenyl iodide Hydroxide, bis(tert-butylphenyl) iodide Hydroxide, etc.

[0412] The content of the amine and hydroxide in the surface modifier is not particularly limited, but is 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, based on 100 parts by mass of the polysiloxane.

[0413] <<<Other additives>>>

[0414] The surface modifier may be compounded with various additives depending on the application of the composition.

[0415] Examples of the 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 modifiers, adhesion promoters, and the like, and known additives that are mixed with materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflective films, and pattern reversal films.

[0416] In addition, although various additives are illustrated below, they are not limited to these.

[0417] - Stabilizer -

[0418] When the surface modifier contains polysiloxane, the stabilizer can be added for the purpose of stabilizing the hydrolysis condensate of the hydrolyzable silane mixture, and specific examples thereof include organic acids, water, alcohols, or combinations thereof.

[0419] As organic acids, for example, oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid, etc. can be cited. Among them, oxalic acid and maleic acid are preferred. When an organic acid is added, its addition amount is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture. These organic acids can act as pH regulators.

[0420] As water, pure water, ultrapure water, ion-exchanged water or the like may be used. When used, the amount thereof added may be 0.1 to 20 parts by mass based on 100 parts by mass of the surface modifier.

[0421] The alcohol is preferably one that is easily dispersed by heating after coating, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount thereof added may be 0.1 to 20 parts by mass based on 100 parts by mass of the surface modifier.

[0422] -Organic polymers-

[0423] When the surface modifier contains polysiloxane, by adding an organic polymer to the surface modifier, the dry etching rate (the reduction of the film thickness per unit time), attenuation coefficient, refractive index, etc. of the surface modified layer formed by the surface modifier can be adjusted. There is no particular limitation on the organic polymer, and it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) according to the purpose of its addition.

[0424] Specific examples thereof include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate.

[0425] In the present invention, an organic polymer containing an aromatic ring or heteroaromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, a quinoxaline ring, etc., which functions as a light absorbing site, can also be suitably used when such a function is required. Specific examples of such an organic polymer include addition polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymers such as phenol novolac and naphthol novolac, but are not limited thereto.

[0426] When an addition polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer.

[0427] Addition polymerizable monomers are used in the production of addition polymers. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0428] Specific examples of the acrylate compound include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracenemethyl 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 acid-6-lactone, 3-acryloyloxypropyltriethoxysilane, and glycidyl acrylate, but are not limited to these.

[0429] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate, but are not limited to these.

[0430] Specific examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide, but are not limited to these.

[0431] Specific examples of the methacrylamide compound include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-benzyl methacrylamide, N-phenyl methacrylamide, N,N-dimethyl methacrylamide, and N-anthryl methacrylamide, but are not limited thereto.

[0432] Specific examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0433] Specific examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene, but are not limited to these.

[0434] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but the maleimide is not limited thereto.

[0435] When a polycondensate is used as a polymer, such a polymer may be, for example, a polycondensate of a diol compound and a dicarboxylic acid compound. As the diol compound, diethylene glycol, 1,6-hexanediol, butanediol, etc. may be mentioned. As the dicarboxylic acid compound, succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. may be mentioned. In addition, polyesters, polyamides, and polyimides such as poly-1,2,4,5-pyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate may be mentioned, but are not limited to these.

[0436] When the organic polymer contains a hydroxyl group, the hydroxyl group can undergo a cross-linking reaction with a hydrolysis condensate or the like.

[0437] The weight average molecular weight of the organic polymer can be generally 1,000 to 1,000,000. When the organic polymer is mixed, the weight average molecular weight can be, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000, from the viewpoint of fully obtaining the effect of the function as the polymer and suppressing precipitation in the composition.

[0438] Such organic polymers may be used alone or in combination of two or more.

[0439] When the surface modifier is used in combination with polysiloxane and contains an organic polymer, the content thereof cannot be generally specified because it is appropriately determined in consideration of the function of the organic polymer, but generally, it can be in the range of 1 to 200% by mass relative to the mass of the polysiloxane. 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, and more preferably 30% by mass or less. From the viewpoint of sufficiently obtaining the effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0440] -Acid Generators-

[0441] Examples of the acid generator include a thermal acid generator and a photoacid generator, and a photoacid generator can be preferably used.

[0442] Examples of the photoacid generator include sulfonium salts, Salt, ammonium salt, iodine Salt, oxygen Salt, etc. Salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc., but are not limited to these. Among salt compounds, carboxylates such as nitrates and maleates, and hydrochlorides can also function as curing catalysts depending on their types.

[0443] Examples of the thermal acid generator include tetramethylammonium nitrate, but the present invention is not limited thereto.

[0444] As Specific examples of salt compounds include diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyl iodide Nonafluorobutane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Trifluoromethanesulfonate and other iodine Sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate (nitrate), triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride are also included, but are not limited to these.

[0445] Specific examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited thereto.

[0446] Specific examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane, but are not limited thereto.

[0447] When the surface modifier contains an acid generator, the content thereof cannot be generally specified because it is appropriately determined in consideration of the type of the acid generator, etc., but is usually in the range of 0.01 to 5% by mass relative to the mass of the polymer. From the viewpoint of suppressing the precipitation of the acid generator in the composition, etc., it is preferably 3% by mass or less, more preferably 1% by mass or less. From the viewpoint of sufficiently obtaining the effect, etc., it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0448] The acid generator may be used alone or in combination of two or more. A photoacid generator and a thermal acid generator may be used in combination.

[0449] -Surfactant-

[0450] When the surface modifier is applied to the substrate, a surfactant is effective in suppressing the generation of pinholes, streaks, etc. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorine surfactants, UV curing surfactants, and the like. More specifically, examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monostearate. Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and other nonionic surfactants; commercial products Names: EF301, EF303, and EF352 (registered trademarks) (manufactured by Mitsubishi Microelectronics Co., Ltd. (formerly Mitsubishi Microelectronics Co., Ltd.)), trade names: EF301 (Note: Registered trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.), FC430, FC431 (manufactured by スリーエムジャパン Co., Ltd. )), trade name Asahigard (registered trademark) AG710 (manufactured by AGC Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Semichem Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these.

[0451] The surfactant may be used alone or in combination of two or more.

[0452] When the surface modifier contains a surfactant, the content thereof may be generally 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass, based on the mass of the polymer.

[0453] -Rheology modifiers-

[0454] The rheology modifier is mainly added to improve the fluidity of the surface modifier, especially in the baking process, to improve the uniformity of the film thickness of the formed film and to improve the filling property of the composition to the inside of the pores. As specific examples, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, adipic acid derivatives such as di-n-butyl adipate, di-isobutyl adipate, di-isooctyl adipate, octyldecyl adipate, maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, or stearic acid derivatives such as stearic acid n-butyl stearate and glyceryl stearate can be cited.

[0455] When these rheology modifiers are used, the amount added is usually less than 30% by mass based on the total film-forming components of the surface modifier.

[0456] - Adhesive additives -

[0457] The adhesion promoter is mainly added for the purpose of improving the adhesion between the substrate or the resist and the film (surface modification layer) formed by the surface modifier, and in particular, for the purpose of suppressing / preventing the 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; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole. Heterocyclic compounds such as azole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

[0458] When these adhesion promoters are used, the amount added is usually less than 5% by mass, preferably less than 2% by mass, based on the film-forming component of the surface modifier.

[0459] -pH Adjuster-

[0460] In addition, as the pH adjuster, there can be mentioned an acid having one or more carboxylic acid groups, such as the organic acid mentioned above as the stabilizer, etc. When the pH adjuster is used, the amount thereof added can be 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass relative to 100 parts by mass of the polymer.

[0461] -Metal Oxides-

[0462] In addition, examples of metal oxides that can be added to the surface modifier include, but are not limited to, oxides of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten) and metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0463] 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.

[0464] The content of the polymer in the film-forming component is generally 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, etc., the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and further preferably 80% by mass, and the upper limit is preferably 99% by mass, and the remainder may be the above-mentioned additives.

[0465] Furthermore, the surface modifier preferably has a pH of 1-5, and more preferably has a pH of 2-4.

[0466] The surface modifier can be produced by mixing a polymer, a solvent, and, if necessary, other components. In this case, a solution containing a polymer (eg, polysiloxane) can be prepared in advance, and the solution can be mixed with the solvent and other components.

[0467] In the preparation of the surface modifier, heating may be performed appropriately within a range in which the components do not decompose or deteriorate.

[0468] The surface modifier can be filtered at a mid-stage of manufacturing or after all the components have been mixed using a submicron filter or the like. It should be noted that the material type of the filter used at this time is not limited, but for example, a polyethylene filter, a nylon filter, a fluororesin filter, a polyimide filter, or the like can be used.

[0469] <Step 2>

[0470] The second step is a step of thinning the surface modification layer precursor by bringing the surface modification layer precursor into contact with a thinning liquid to obtain a surface modification layer having a film thickness of 5 nm or less.

[0471] In the second step, there is no particular limitation on the method of contacting the surface modification layer precursor with the thinning liquid, but spin coating is preferred in that uniform thinning can be achieved and the degree of thinning can be easily managed with high precision. That is, the second step is preferably a step of thinning the surface modification layer precursor by spin coating the thinning liquid on the surface modification layer precursor to obtain a surface modification layer having a film thickness of 5 nm or less.

[0472] The spin coating conditions are not particularly limited, and include, for example, a coating process of applying a thinning liquid to a semiconductor substrate on which a surface modification layer precursor is formed, and a spinning process of spinning the semiconductor substrate.

[0473] For coating treatment, for example, when the surface modification layer precursor is coated with the thinning liquid, the semiconductor substrate is not rotated or rotated at a low speed (for example, below 1000 rpm). For coating treatment, the thinning liquid is brought into contact with the surface modification layer precursor to move the components in the surface modification layer precursor to the thinning liquid.

[0474] In the spin treatment, for example, the semiconductor substrate is rotated at a high speed (for example, more than 1,000 rpm and 5,000 rpm or less) to remove the thinning liquid from the semiconductor substrate on which the surface modification layer precursor is formed.

[0475] In this way, the surface modification layer precursor is thinned according to the amount of the component that has moved into the thinning liquid, and as a result, a surface modification layer having a film thickness of 5 nm or less is obtained.

[0476] The coating treatment time may be, for example, 10 seconds to 2 minutes.

[0477] The time for the rotation treatment may be, for example, 5 seconds to 1 minute.

[0478] In addition, during the rotation, for example, an axis perpendicular to the surface of the semiconductor substrate is used as the rotation axis.

[0479] In the second step, the film thickness of the surface modification layer precursor is preferably thinned by 0.5 nm to 10 nm, and more preferably thinned by 1 nm to 5 nm.

[0480] <<Thinning liquid>>

[0481] As the thinning liquid, there is no particular limitation as long as it is a liquid that can make the surface modification layer precursor thinner by bringing the surface modification layer precursor into contact with the thinning liquid, and examples thereof include organic solvents, water, acidic solutions, alkaline aqueous solutions, etc. In addition, a diluent used in the RRC (reducing resist comsumption) process or the EBR (edge ​​bead removing) process can be used. These can be used alone or in combination of two or more.

[0482] Examples of the organic solvent include alcohols, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylates.

[0483] Examples of the alcohols include monoalcohol solvents, polyol solvents, etc. Specific examples thereof include the above-mentioned monoalcohol solvents and polyol solvents as solvents for hydrolysis and condensation.

[0484] Examples of the alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0485] Examples of the alkylene glycol monoalkyl ether 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.

[0486] Examples of the alkylene glycol dialkyl ether 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.

[0487] Examples of the alkylene glycol monoalkyl ether carboxylates include alkylene glycol monoalkyl ether acetates.

[0488] Examples of the alkylene glycol monoalkyl ether acetate 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.

[0489] Specific examples of other organic solvents include toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, Esters, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, pentyl formate, isoamyl formate, methyl acetate, ethyl acetate, pentyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate , butyl butyrate, isobutyl butyrate, ethyl 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-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, 4-methyl-2-pentanol, γ-butyrolactone, etc.

[0490] As the acidic solution, for example, an inorganic acid aqueous solution, an organic acid aqueous solution, and an organic acid solution can be cited. As the inorganic acid aqueous solution, hydrochloric acid aqueous solution, nitric acid aqueous solution, phosphoric acid aqueous solution, sulfuric acid aqueous solution, perchloric acid aqueous solution, etc. can be cited. As the organic acid aqueous solution, acetic acid aqueous solution, trifluoroacetic acid aqueous solution, camphorsulfonic acid aqueous solution, p-toluenesulfonic acid aqueous solution, trifluoromethanesulfonic acid aqueous solution, etc. can be cited. As the organic acid solution, a substance obtained by replacing the water in the above-mentioned organic acid aqueous solution with an organic solvent can be cited. As the organic solvent, for example, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylates, etc. can be cited.

[0491] Examples of the alkaline aqueous solution include a developer used in a photolithography process.

[0492] As the aqueous alkali solution, for example, an inorganic alkali aqueous solution and an organic alkali aqueous solution can be mentioned. As the aqueous inorganic alkali solution, for example, an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, an aqueous potassium carbonate solution, an aqueous sodium hydrogen carbonate solution, an aqueous potassium hydrogen carbonate solution, an aqueous sodium phosphate solution, an aqueous potassium phosphate solution, etc. As the aqueous organic alkali solution, for example, an aqueous tetramethylammonium hydroxide solution, an aqueous tetraethylammonium hydroxide solution, an aqueous tetrabutylammonium hydroxide solution, an aqueous monoethanolamine solution, an aqueous diethanolamine solution, an aqueous triethanolamine solution, etc. can be mentioned.

[0493] The concentration of the alkali in the aqueous alkali solution is not particularly limited.

[0494] The so-called RRC (reducing resist consumption) process is a process for reducing the amount of photoresist used, and is a process in which a small amount of photoresist is evenly applied to the entire surface of the substrate by treating the substrate surface with a diluent before applying the photoresist.

[0495] The EBR (edge ​​bead removing) process is a process for removing unnecessary photoresist residues and other contaminants applied to the edge or rear portion of the substrate during the coating process.

[0496] Examples of the diluent used in the RRC step and the EBR step 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.

[0497] In one embodiment of the present invention, an organic underlayer film may be provided between the semiconductor substrate and the surface modification layer in the laminate.

[0498] The organic underlayer film used here is not particularly limited and can be arbitrarily selected from those conventionally used in photolithography processes.

[0499] By providing an organic lower film on a substrate, providing a surface modification layer thereon, and further providing a resist film described later thereon, even when the pattern width of the resist film is narrowed and the resist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas described later. For example, by using a fluorine-based gas having a sufficiently fast etching rate with respect to the resist film as an etching gas, the resist lower film can be processed, and by using an oxygen-based gas having a sufficiently fast etching rate with respect to the resist lower film as an etching gas, the organic lower film can be processed, and by further using a fluorine-based gas having a sufficiently fast etching rate with respect to the organic lower film as an etching gas, the substrate can be processed.

[0500] In addition, the substrate and coating method which can be used at this time are the same as those mentioned above.

[0501] (Method for manufacturing semiconductor element)

[0502] The method for producing a semiconductor element of the present invention includes the steps of forming a resist film on the laminated body obtained by the method for producing a laminated body of the present invention, and exposing and developing the resist film to obtain a resist pattern.

[0503] 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 known method, that is, by applying a coating type resist material (resist film forming composition) on the surface modification layer and firing it.

[0504] 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.

[0505] The photoresist material used for 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 (for example, KrF excimer laser, ArF excimer laser, etc.), and both negative photoresist materials and positive photoresist materials can be used. For example, there are positive photoresist materials composed of novolac resin and 1,2-naphthoquinone diazosulfonic acid ester, chemically amplified photoresist materials composed of a binder having a group that increases the alkali dissolution rate by acid decomposition and a photoacid generator, chemically amplified photoresist materials composed of a low molecular compound that increases the alkali dissolution rate of the photoresist material by acid decomposition, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresist materials composed of a binder having a group that increases the alkali dissolution rate by acid decomposition, a low molecular compound that increases the alkali dissolution rate of the photoresist material by acid decomposition, and a photoacid generator, etc.

[0506] Specific examples of commercially available products include, but are not limited to, APEX-E manufactured by Shiplay Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. In addition, fluorine-containing polymer photoresist materials such as those described in, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0507] In addition, as the resist film formed on the surface modification layer, a resist film for electron beam lithography (also referred to as electron beam resist film) or a resist film for EUV lithography (also referred to as EUV resist film) may be used instead of the photoresist film.

[0508] As electron beam resist materials for forming electron beam resist films, both negative materials and positive materials can be used. As specific examples, there are chemically amplified resist materials composed of an acid generator and a binder having a group that changes the alkali dissolution rate by acid decomposition, chemically amplified resist materials composed of an alkali-soluble binder, an acid generator, and a low molecular compound that changes the alkali dissolution rate of the resist material by acid decomposition, chemically amplified resist materials composed of an acid generator and a binder having a group that changes the alkali dissolution rate by acid decomposition, and a low molecular compound that changes the alkali dissolution rate of the resist material by acid decomposition, non-chemically amplified resist materials composed of a binder having a group that changes the alkali dissolution rate by electron beam decomposition, non-chemically amplified resist materials composed of a binder having a portion that changes the alkali dissolution rate by being cut by electron beam, etc. In the case of using these electron beam resist materials, the irradiation source can also be electron beams to form a pattern of the resist film in the same way as when a photoresist material is used.

[0509] Furthermore, as an EUV resist material for forming an EUV resist film, a methacrylate resin-based resist material, a polyhydroxystyrene resin-based resist material, and a methacrylate / polyhydroxystyrene mixed resin-based resist material can be used.

[0510] The resist film may be a resist film containing metal.

[0511] The metal-containing resist film is not particularly limited, but preferably contains at least one element of Si, Ge, Sn, Ti, Zr, Hf, Al, and Co.

[0512] The metal-containing resist film is formed of, for example, a metal-containing resist.

[0513] A resist containing a metal is also called a metal oxide resist (metal oxide resist (MOR)), and a representative example thereof is a tin oxide-based resist.

[0514] As a metal oxide resist material, for example, a coating composition described in Japanese Patent Application Publication No. 2019-113855, which includes a metal oxygen-hydroxyl network having an organic ligand through a metal carbon bond and / or a metal carboxylate bond, can be mentioned.

[0515] An example of a metal-containing resist uses a peroxide ligand as a radiation sensitivity stabilizing ligand. Peroxide-based metal oxygen-hydroxy compounds are described in detail in the patent document described in paragraph

[0011] of the Japanese Publication No. 2019-532489. As such patent documents, for example, U.S. Patent No. 9,176,377B2, U.S. Patent Application Publication No. 2013 / 0224652A1, U.S. Patent No. 9,310,684B2, U.S. Patent Application Publication No. 2016 / 0116839A1, and U.S. Patent Application Publication No. 15 / 291738 can be cited.

[0516] Another example of a metal-containing resist includes compositions described in Japanese Unexamined Patent Application Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Unexamined Patent Application Publication No. 2020-122959, Japanese Unexamined Patent Application Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229.

[0517] These contents are incorporated into this specification to the same extent as if all were expressly stated.

[0518] The method of forming a metal-containing resist film from a metal-containing resist is not particularly limited, and an example thereof includes a method of applying a coating type resist material (metal-containing resist film-forming composition) as a metal-containing resist and firing the coating material.

[0519] In addition, the metal-containing resist film can be formed by evaporation. As a method for forming a metal-containing resist film using evaporation, for example, the method described in Japanese Patent Publication No. 2017-116923 can be cited. The contents of Japanese Patent Publication No. 2017-116923 are incorporated into this specification to the same extent as all are explicitly stated. It should be noted that in Japanese Patent Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a film containing a metal oxide.

[0520] Next, the resist film formed on the upper layer of the surface modification layer is exposed through a predetermined mask (photomask). For exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam, etc. can be used.

[0521] After the exposure, post-exposure baking may be performed as necessary. 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.

[0522] Next, development is performed using a developer (eg, an alkaline developer). Thus, for example, when a positive photoresist film is used, the exposed portion of the photoresist film is removed, thereby forming a pattern of the photoresist film.

[0523] As the developer (alkaline developer), 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 alkaline aqueous solutions (alkaline developers) such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine can be cited as examples. Furthermore, a surfactant can also be added to these developers. As the development conditions, they can be appropriately selected from a temperature of 5 to 50° C. and a time of 10 seconds to 600 seconds.

[0524] In the present invention, an organic solvent may be used as a developer, and development may be performed with the developer (solvent) after exposure. Thus, for example, when a negative photoresist film is used, the unexposed portion of the photoresist film is removed to form a pattern of the photoresist film.

[0525] Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxy Butyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate , propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. are exemplified. Furthermore, a surfactant or the like may be added to these developers. As the conditions for development, it is appropriately selected from a temperature of 5° C. to 50° C. and a time of 10 seconds to 600 seconds.

[0526] For example, the surface modification layer is removed using the pattern of the resist film (upper layer) formed in this way as a protective film, and then the substrate is processed using the patterned resist film and the patterned surface modification layer as protective films.

[0527] The removal (patterning) of the surface modification layer using the pattern of the resist film (upper layer) as a protective film is performed, for example, by dry etching, and gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used.

[0528] It should be noted that, in the dry etching of the surface modification layer, halogen-based gases are preferably used. For dry etching using halogen-based gases, the resist film (photoresist film) formed by organic substances is not easy to be removed. In contrast, a large number of surface modification layers containing silicon atoms are rapidly removed by halogen-based gases. Therefore, the reduction of the film thickness of the photoresist film accompanying the dry etching of the surface modification layer can be suppressed. And then, as a result, the photoresist film can be used as a thin film. Therefore, the dry etching of the surface modification layer preferably uses fluorine-based gases, and as fluorine-based gases, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc. can be cited, but are not limited to these.

[0529] 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.

[0530] Examples of the fluorine-based gas include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0531] After processing (patterning) the substrate, the surface modification layer can be removed. The surface modification layer can be removed by dry etching or wet etching.

[0532] The dry etching of the surface modification layer preferably uses fluorine-based gases as mentioned in the patterning, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but are not limited to these.

[0533] As the chemical solution used for wet etching of the surface modification layer, there can be mentioned alkaline solutions such as dilute hydrofluoric acid (hydrogen fluoride acid), buffered hydrofluoric acid (a mixed solution of HF and NH4F), 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). In addition, as the alkaline solution, in addition to the ammonia peroxide solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide water and water, there can be mentioned a chemical solution containing ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidine Hydroxide, 1-propyl-1-methylpyrrolidine Hydroxide, 1-butyl-1-methylpiperidinium Hydroxide, 1-propyl-1-methylpiperidinium Hydroxide, methylpiperidin Hydroxides, trimethylsulfonium hydroxides, hydrazines, ethylenediamines, or 1 to 99% by mass aqueous solutions of guanidine. These solutions may also be used in combination.

[0534] Example

[0535] Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0536] In addition, in the examples, the apparatus and conditions used for analyzing the physical properties of the samples are as follows.

[0537] (1) Molecular weight determination

[0538] The molecular weight of the polysiloxane used in the present invention is a molecular weight obtained in terms of polystyrene obtained by GPC analysis.

[0539] The measurement conditions of GPC can be, 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, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 1.0 mL / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.).

[0540] (2) 1 H-NMR

[0541] Use JEOL's NMR equipment 1 H-NMR (400 MHz) was used for evaluation using d6-acetone as a solvent.

[0542] (3) Residual nitric acid

[0543] The amount of nitric acid remaining in the system was measured by ion chromatography evaluation.

[0544] (4) AFM observation

[0545] The surface roughness was evaluated by observing an area of ​​10 μm×10 μm using AFM5500M manufactured by Hitachi High-Tech.

[0546] (5) Film thickness measurement

[0547] The material film thickness was measured using an ellipsometer RE-3100 (manufactured by SCREEN).

[0548] The film thickness of the surface modification layer precursor was measured as follows: After measuring the film thickness of the SiO2 oxide film formed on the substrate in advance, the surface modifier was applied, and the film thickness was measured after the surface modification layer precursor was formed, and the difference was set as the film thickness of the surface modification layer precursor.

[0549] The thickness of the surface modification layer was measured as follows: After measuring the thickness of the SiO2 oxide film formed on the substrate in advance, the surface modification agent was applied and thinned and the thickness was measured, and the difference was defined as the thickness of the surface modification layer.

[0550] [1] Synthesis of polymer (hydrolysis condensation product)

[0551] (Synthesis example 1)

[0552] 31.89 g of phenyltrimethoxysilane and 47.83 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 20.28 g of a 0.01 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0553] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0554] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0555] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 900 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.006%.

[0556]

[0557] (Synthesis example 2)

[0558] 35.65 g of diallyl isocyanurate propyltriethoxysilane and 53.48 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 10.87 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0559] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0560] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0561] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2300 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.07%.

[0562]

[0563] (Synthesis example 3)

[0564] 33.42 g of bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane and 50.13 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 16.44 g of a 1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0565] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0566] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0567] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1200 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.8%.

[0568]

[0569] (Synthesis Example 4)

[0570] 33.57 g of thiocyanatepropyltriethoxysilane and 50.36 g of propylene glycol monomethyl ether acetate were added to a 300 mL flask, and 16.07 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0571] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0572] Propylene glycol monomethyl ether acetate was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monomethyl ether acetate, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0573] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1800 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked by propylene glycol monoalkyl ether was 0 mol% relative to the Si atoms. Furthermore, the amount of residual nitric acid in the polymer solution was 0.08%.

[0574]

[0575] (Synthesis Example 5)

[0576] 34.89 g of triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane and 52.33 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 12.78 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0577] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0578] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0579] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1800 in terms of polystyrene. 1According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0580]

[0581] (Synthesis Example 6)

[0582] 33.11 g of 4-methoxybenzyltrimethoxysilane and 49.66 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 17.23 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0583] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0584] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0585] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1800 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 7 mol% relative to the Si atoms. Furthermore, the amount of residual nitric acid in the polymer solution was 0.07%.

[0586]

[0587] (Synthesis Example 7)

[0588] 34.92 g of phenylsulfonylpropyltriethoxysilane and 52.37 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 12.71 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0589] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0590] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0591] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1500 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.07%.

[0592]

[0593] (Synthesis Example 8)

[0594] 35.27 g of 4-methoxyphenylsulfonylpropyltriethoxysilane and 52.91 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 11.82 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0595] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0596] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0597] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1400 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0598]

[0599] (Synthesis Example 9)

[0600] 35.10 g of phenylsulfonylamidepropyltriethoxysilane and 52.65 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 12.25 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0601] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0602] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0603] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1600 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 4 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0604]

[0605] (Synthesis Example 10)

[0606] 35.41 g of 4-methoxyphenylsulfonylamidepropyltriethoxysilane and 53.12 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 11.47 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0607] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0608] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0609] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1800 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 4 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0610]

[0611] (Synthesis Example 11)

[0612] 35.21 g of p-nitrobenzamidopropyltriethoxysilane and 52.81 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 11.99 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0613] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0614] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0615] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1400 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0616]

[0617] (Synthesis Example 12)

[0618] 34.89 g of pentafluorophenylmethyltriethoxysilane and 52.33 g of propylene glycol monomethyl ether acetate were added to a 300 mL flask, and 12.78 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0619] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0620] Propylene glycol monomethyl ether acetate was further added to the obtained solution to adjust the concentration to 20 mass % as a solid residue at 140° C. with 100% of propylene glycol monomethyl ether acetate as the solvent ratio, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0621] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1100 in terms of polystyrene. 1According to H-NMR, the amount of the atoms blocked by propylene glycol monoalkyl ether was 0 mol% relative to the Si atoms. Furthermore, the amount of residual nitric acid in the polymer solution was 0.08%.

[0622]

[0623] (Synthesis Example 13)

[0624] 34.07 g of iodopropyltrimethoxysilane and 51.11 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 14.81 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0625] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0626] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0627] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1300 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.07%.

[0628]

[0629] (Synthesis Example 14)

[0630] 34.31 g of succinic anhydride propyltriethoxysilane and 51.47 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 14.22 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0631] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0632] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0633] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1600 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0634]

[0635] (Synthesis Example 15)

[0636] 32.96 g of glycidyloxypropyltrimethoxysilane and 49.44 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 17.59 g of a 1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0637] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0638] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0639] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1600 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 7 mol% relative to the Si atoms. Furthermore, the amount of residual nitric acid in the polymer solution was 0.8%.

[0640]

[0641] (Synthesis Example 16)

[0642] 31.25 g of mercaptopropyltrimethoxysilane and 46.88 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 21.87 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0643] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0644] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0645] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2500 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0646]

[0647] (Synthesis Example 17)

[0648] 31.75 g of hydroxymethyltriethoxysilane and 47.63 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 20.61 g of a 0.01 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0649] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0650] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0651] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2800 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 4 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.008%.

[0652]

[0653] (Synthesis Example 18)

[0654] 32.92 g of methylaminopropyltrimethoxysilane and 49.37 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 17.71 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0655] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0656] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0657] The obtained polymer includes a polysiloxane having a structure represented by the following formula, and the weight average molecular weight obtained by GPC is 1000 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0658]

[0659] (Synthesis Example 19)

[0660] 32.46 g of cyanoethyltriethoxysilane and 48.70 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 18.84 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0661] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0662] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0663] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1500 in terms of polystyrene. 1According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0664]

[0665] (Synthesis Example 20)

[0666] 33.25 g of methacryloxypropyltrimethoxysilane and 49.87 g of propylene glycol monoethyl ether were added to a 300-mL flask, and 16.89 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0667] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0668] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0669] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2400 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0670]

[0671] (Synthesis Example 21)

[0672] 34.30 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate and 51.44 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 14.26 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0673] After the dropwise addition, the flask was transferred to an oil bath adjusted to 120° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0674] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0675] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1400 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0676]

[0677] (Synthesis Example 22)

[0678] 15.49 g of diallyl isocyanurate propyltriethoxysilane, 18.21 g of tetraethoxysilane, and 50.55 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 15.75 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0679] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0680] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0681] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2500 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 8 mol% based on Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0682]

[0683] (Synthesis Example 23)

[0684] 17.76 g of (3-triethoxysilyl)propylsuccinic anhydride, 16.37 g of triphenylsulfonium hydroxide, and 51.17 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 14.72 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0685] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0686] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0687] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1200 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 3 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.07%.

[0688]

[0689] (Synthesis Example 24)

[0690] 12.89 g of 3-(trihydroxysilyl)-1-propanesulfonic acid, 20.68 g of triphenylsulfonium hydrogen carbonate, and 50.35 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 16.08 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0691] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, water as a reaction by-product was distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) solution.

[0692] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0693] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1800 in terms of polystyrene. 1According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 5 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0694]

[0695] (Synthesis Example 25)

[0696] 2-(((2-hydroxy-5-(2-trimethoxysilyl)ethylcyclohexyl)oxy)carbonyl)phenylphenyl iodide 37.38 g of trifluoromethanesulfonate and 56.07 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 6.54 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0697] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed by reduced pressure distillation, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) solution.

[0698] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0699] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1500 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 4 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.06%.

[0700]

[0701] (Synthesis Example 26)

[0702] 37.74 g of (3-((2-hydroxy-5-(2-(trimethoxysilyl)ethyl)cyclohexyl)oxy)phenyl)(4-hydroxyphenyl)(phenyl)sulfonium nonafluorobutanesulfonate and 56.60 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 5.66 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0703] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed by reduced pressure distillation, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) solution.

[0704] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0705] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2200 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoalkyl ether was 3 mol% based on Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0706]

[0707] (Synthesis Example 27)

[0708] 16.69 g of (3-triethoxysilyl)propylsuccinic anhydride and diphenyl iodide 17.77 g of -2-carboxylate and 51.70 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 12.78 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0709] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0710] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0711] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 1500 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 6 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.08%.

[0712]

[0713] (Synthesis Example 28)

[0714] 12.90 g of 3-(trihydroxysilyl)-1-propanesulfonic acid and diphenyl iodide 20.67 g of -2-carboxylate and 50.35 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 16.09 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0715] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, water as a reaction by-product was distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) solution.

[0716] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0717] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2000 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 3 mol% based on the Si atoms. The amount of residual nitric acid in the polymer solution was 0.06%.

[0718]

[0719] (Synthesis Example 29)

[0720] 5.99 g of N-(3-trihydroxysilylpropyl)-4,5-dihydroimidazole, 3.77 g of p-toluenesulfonic acid, and 87.87 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 2.37 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0721] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and reacted for 20 hours. Then, water as a reaction by-product was distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) solution.

[0722] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 5 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0723] The obtained polymer includes a polysiloxane having a structure represented by the following formula, and the weight average molecular weight obtained by GPC is 1000 in terms of polystyrene. 1According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 3 mol% relative to the Si atoms. The amount of residual nitric acid in the polymer solution was 0.07%.

[0724]

[0725] (Synthesis Example 30)

[0726] 38.4 g of triphenylsulfonium 2-(((2-hydroxy-5-(2-(trimethoxysilyl)ethyl)cyclohexyl)oxy)carbonyl)-3,4,5,6-tetraiodobenzenesulfonate and 57.6 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 3.99 g of a 0.1 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0727] After the dropwise addition, the flask was transferred to an oil bath adjusted to 100° C. and reacted for 20 hours. Then, methanol and water as reaction by-products were removed by reduced pressure distillation, and the mixture was concentrated to obtain a hydrolysis condensate (polymer) solution.

[0728] Propylene glycol monoethyl ether was further added to the obtained solution to adjust the concentration to 5 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0729] The obtained polymer contained polysiloxane having a structure represented by the following formula, and its weight average molecular weight obtained by GPC was 2200 in terms of polystyrene. 1 According to H-NMR, the amount of the atoms blocked with propylene glycol monoethyl ether was 4 mol% relative to the Si atoms. Furthermore, the amount of residual nitric acid in the polymer solution was 0.07%.

[0730]

[0731] (Comparative Synthesis Example 1)

[0732] 32.20 g of tetraethoxysilane and 48.3 g of propylene glycol monoethyl ether were added to a 300 mL flask, and 19.5 g of an aqueous nitric acid solution (0.1 mol / L) was added dropwise while the mixed solution was stirred with an electromagnetic stirrer.

[0733] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and refluxed for 20 hours. Then, ethanol and water as reaction by-products were removed under reduced pressure and concentrated to obtain a hydrolysis condensate (polymer) solution.

[0734] Propylene glycol monomethyl ether was further added to the solution to adjust the concentration to 20 mass % in terms of solid residue at 140° C. with a solvent ratio of 100% of propylene glycol monomethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm).

[0735] The obtained polymer contained polysiloxane having the structure shown in the following formula, and its weight average molecular weight obtained by GPC was Mw5,800 in terms of polystyrene. In addition, according to 1H-NMR, the amount blocked by propylene glycol monomethyl ether was 9 mol% relative to Si atoms. In addition, the amount of residual nitric acid in the polymer solution was 0.08%.

[0736]

[0737] [2] Preparation of surface modifier (coating liquid)

[0738] The polysiloxane (polymer) obtained in the above synthesis example, the acid (additive 1), the photoacid generator and the curing catalyst (additive 2), and the solvent were mixed in the ratio shown in Table 1-1, Table 1-2, or Table 1-3, and filtered with a 0.1 μm fluororesin filter to prepare the surface modifier (coating liquid). The amounts of each addition in Table 1-1 to Table 1-3 are expressed in parts by mass.

[0739] It should be noted that although the hydrolysis condensate (polymer) was prepared as a composition containing a solution obtained in the synthesis example, the addition ratio of the polymer in Table 1-1 to Table 1-3 does not refer to the addition amount of the polymer solution but indicates the addition amount of the polymer itself.

[0740] The meanings of the abbreviations in Tables 1-1 to 1-3 are as follows.

[0741] <Solvent>

[0742] DIW: Ultrapure Water

[0743] PGEE: Propylene glycol monoethyl ether

[0744] PGME: Propylene glycol monomethyl ether

[0745] PGMEA: Propylene glycol monomethyl ether acetate

[0746] <Additive 1>

[0747] MA: Maleic acid

[0748] <Additive 2>

[0749] TPSNO3: Triphenylsulfonium nitrate

[0750] TPSML: Triphenylsulfonium maleate

[0751] TPSTfAc: triphenylsulfonium trifluoroacetate

[0752] TPSAc: triphenylsulfonium acetate

[0753] BTEAC: benzyltriethylammonium chloride

[0754] ImidTEOS: N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole as described below

[0755] DAICATEOS: Diallyl isocyanurate propyl triethoxysilane as described below

[0756]

[0757] [Table 1-1]

[0758]

[0759] [Table 1-2]

[0760]

[0761] [Table 1-3]

[0762]

[0763] Coating liquids 1 to 22, 101 to 108 and comparative coating liquids 1 to 2 and 101 further contained nitric acid contained in the polymer solutions prepared in Synthesis Examples 1 to 30 and Comparative Synthesis Example 1. Comparative coating liquid 3 did not contain nitric acid.

[0764] [3-1] Thin film test

[0765] The prepared coating solutions 1 to 22 and comparative coating solutions 1 to 3 were applied to silicon wafers using a spin coater. The surface modification layer precursors were formed by heating at 120°C or 215°C on a hot plate for 1 minute. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V): thinning solution) was applied to each surface modification layer precursor and allowed to stand for 60 seconds. Then, the wafer was rotated to shake off the solvent and dried by baking at 100 degrees for 30 seconds. The film thickness of the surface modification layer after the thinning solution was applied was measured, and the film thickness was reduced to a value of The following surface modifiers are rated as "good", and the film thickness exceeds The case where the film could not be thinned was designated as “cannot be thinned”, and the case where film unevenness occurred in AFM observation was designated as “film unevenness”. The results are shown in Table 2-1.

[0766] [Table 2.1]

[0767] Coating liquid Firing temperature Film forming properties Example 1 Coating liquid 1 215 degrees good Example 2 Coating liquid 2 215 degrees good Example 3 Coating liquid 3 120 degrees good Example 4 Coating liquid 4 215 degrees good Example 5 Coating liquid 5 120 degrees good Example 6 Coating liquid 6 215 degrees good Example 7 Coating liquid 7 215 degrees good Example 8 Coating liquid 8 215 degrees good Example 9 Coating liquid 9 215 degrees good Example 10 Coating liquid 10 215 degrees good Embodiment 11 Coating liquid 11 215 degrees good Example 12 Coating liquid 12 215 degrees good Embodiment 13 Coating liquid 13 215 degrees good Embodiment 14 Coating liquid 14 120 degrees good Embodiment 15 Coating liquid 15 120 degrees good Example 16 Coating liquid 16 120 degrees good Embodiment 17 Coating liquid 17 120 degrees good Embodiment 18 Coating liquid 18 120 degrees good Embodiment 19 Coating liquid 19 215 degrees good Embodiment 20 Coating liquid 20 120 degrees good Embodiment 21 Coating liquid 21 215 degrees good Embodiment 22 Coating liquid 22 120 degrees good Comparative Example 1 Comparative coating solution 1 120 degrees Cannot be thin film Comparative Example 2 Comparative coating liquid 2 215 degrees Uneven film Comparative Example 3 Comparative coating solution 3 215 degrees Uneven film

[0768] In Comparative Examples 2 and 3, there was film unevenness, and no surface modification layer was obtained.

[0769] [3-2] Thin film test

[0770] The prepared coating solutions 101 to 108 and the comparative coating solution 101 were applied to silicon wafers using a spin coater. The surface modification layer precursors were formed by heating on a hot plate at the firing temperature listed in Table 2-2 for 1 minute. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V): thinning solution) was applied to each surface modification layer precursor and spin dried. The film thickness of the surface modification layer after the thinning solution was applied was measured, and the film thickness was reduced to 0.04 mm / s. The following surface modifiers are rated as "good", and the film thickness exceeds The case where the film could not be made thinner was designated as “failed to make thinner”, and the case where uneven coating occurred in AFM observation was designated as “uneven coating”. The results are shown in Table 2-2.

[0771] [Table 2-2]

[0772] Coating liquid Firing temperature Film forming properties Embodiment 101 Coating Liquid 101 215 degrees good Embodiment 102 Coating liquid 102 160 degrees good Embodiment 103 Coating liquid 103 215 degrees good Embodiment 104 Coating liquid 104 215 degrees good Embodiment 105 Coating liquid 105 215 degrees good Embodiment 106 Coating liquid 106 160 degrees good Embodiment 107 Coating liquid 107 160 degrees good Embodiment 108 Coating liquid 108 160 degrees good Comparative Example 101 Comparison of coating solutions 101 215 degrees Cannot be thin film

[0773] [4] Substrate surface modification test

[0774] Bare-Si was coated with coating solutions 1 to 22, 101 to 108, and comparative coating solutions 1, 2, and 101. Specifically, 1 ml of each of coating solutions 1 to 22, 101 to 108, and comparative coating solutions 1, 2, and 101 was applied to the wafer using CLEANTRACK (registered trademark) ACT8 (Tokyo Electron), and after spin coating at 1500 rpm for 60 seconds, it was sintered at the sintering temperature described in Table 3-1 or Table 3-2. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was coated on each surface modification precursor layer and spin dried to form a The surface modification layer has a film thickness of the following. Then, the contact angle of water was measured for the Bare-Si substrates on which the surface modification layers of coating liquids 1 to 22, 101 to 108 and comparative coating liquids 1, 2, and 101 were formed. The water contact angle was measured in a constant temperature and humidity environment (23°C ± 2°C, 45% RH ± 5%) using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) with a liquid volume of 3μl and the measurement was performed after the liquid was left to stand for 5 seconds. Since the water contact angle of Bare-Si is less than 20 degrees, a water contact angle of less than 30 degrees is considered to be impossible to modify the surface and is defined as "poor", and a water contact angle of more than 30 degrees is considered to be possible to modify the surface and is defined as "good". The measurement results are recorded in the following Tables 3-1 and 3-2.

[0775] [Table 3-1]

[0776]

[0777] [Table 3-2]

[0778]

[0779] [5] Formation of resist pattern using EUV exposure: positive solvent development

[0780] The coating solution 1 was spin-coated on the bare-Si substrate and heated at 215° C. for 1 minute. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was coated on the coating film and spin-dried to form a The surface modification layer has a thickness of 1 to 3 nm.

[0781] Furthermore, an EUV resist solution (methacrylate / PHS-based resist) was spin-coated thereon and heated at 110°C for 1 minute to form an EUV resist film (C layer), and then exposed using an EUV exposure device (NXE3400) manufactured by ASML under the conditions of NA=0.33, σ=0.63 / 0.84, and quadrupole.

[0782] After exposure, post-exposure heating (PEB, 105° C. for 1 minute) was performed, and the film was cooled to room temperature on a cooling plate, developed for 30 seconds using a TMAH 2.38% developer, and rinsed to form a resist pattern.

[0783] By the same procedure, a resist pattern was formed using a substrate having a surface modified layer obtained by coating liquids 2 to 22, and 101 to 108 and comparative coating liquids 1, 2, and 101. In addition, as Comparative Example 8, a resist pattern was formed on a Bare-Si wafer not coated with a surface modifier. It should be noted that the heating temperature (firing temperature) after spin coating the coating liquid was set to the firing temperature shown in Table 4-1 or Table 4-2. In Example 67, a Si substrate formed with SiON (50 nm) was used as a substrate.

[0784] Furthermore, regarding each of the obtained patterns, the pattern shape was confirmed by pattern cross-sectional observation to evaluate whether a line pattern with a pitch of 28 nm and a line length of 14 nm could be formed.

[0785] In the observation of the pattern shape, the shape from the footing to the undercut and the state without significant residue in the gap portion were evaluated as "good", and the unpreferable state of the resist pattern collapsing was evaluated as "collapsed". The obtained results are shown in Tables 4-1 and 4-2.

[0786] [Table 4-1]

[0787] substrate Coating liquid Firing temperature Resist pattern shape Embodiment 45 Bare-Si Coating liquid 1 215 degrees good Embodiment 46 Bare-Si Coating liquid 2 215 degrees good Embodiment 47 Bare-Si Coating liquid 3 120 degrees good Embodiment 48 Bare-Si Coating liquid 4 215 degrees good Embodiment 49 Bare-Si Coating liquid 5 120 degrees good Embodiment 50 Bare-Si Coating liquid 6 215 degrees good Embodiment 51 Bare-Si Coating liquid 7 215 degrees good Embodiment 52 Bare-Si Coating liquid 8 215 degrees good Embodiment 53 Bare-Si Coating liquid 9 215 degrees good Embodiment 54 Bare-Si Coating liquid 10 215 degrees good Embodiment 55 Bare-Si Coating liquid 11 215 degrees good Embodiment 56 Bare-Si Coating liquid 12 215 degrees good Embodiment 57 Bare-Si Coating liquid 13 215 degrees good Embodiment 58 Bare-Si Coating liquid 14 120 degrees good Embodiment 59 Bare-Si Coating liquid 15 120 degrees good Embodiment 60 Bare-Si Coating liquid 16 120 degrees good Embodiment 61 Bare-Si Coating liquid 17 120 degrees good Embodiment 62 Bare-Si Coating liquid 18 120 degrees good Embodiment 63 Bare-Si Coating liquid 19 215 degrees good Embodiment 64 Bare-Si Coating liquid 20 120 degrees good Embodiment 65 Bare-Si Coating liquid 21 215 degrees good Embodiment 66 Bare-Si Coating liquid 22 120 degrees good Embodiment 67 SiON Coating liquid 2 215 degrees good Comparative Example 6 Bare-Si Comparative coating solution 1 120 degrees collapse Comparative Example 7 Bare-Si Comparative coating liquid 2 215 degrees collapse Comparative Example 8 Bare-Si none No Bake collapse

[0788] [Table 4-2]

[0789] substrate Coating liquid Firing temperature Resist pattern shape Embodiment 117 Bare-Si Coating Liquid 101 215 degrees good Embodiment 118 Bare-Si Coating liquid 102 160 degrees good Embodiment 119 Bare-Si Coating liquid 103 215 degrees good Embodiment 120 Bare-Si Coating liquid 104 215 degrees good Embodiment 121 Bare-Si Coating liquid 105 215 degrees good Embodiment 122 Bare-Si Coating liquid 106 160 degrees good Embodiment 123 Bare-Si Coating liquid 107 160 degrees good Embodiment 124 Bare-Si Coating liquid 108 160 degrees good

[0790] [6] Formation of resist pattern using EUV exposure: Negative solvent development of metal resist

[0791] The coating solution 101 was spin-coated on the bare-Si substrate and heated at 215° C. for 1 minute. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was coated on the coating film and spin-dried to form a The surface modification layer has a thickness of 1 to 3 nm.

[0792] Furthermore, a metal resist solution for EUV (metal oxide resist) was spin-coated thereon and heated at 100°C for 1 minute to form an EUV metal resist film (C layer), and then exposed using an EUV exposure device (NXE3400) manufactured by ASML under the conditions of NA=0.33, σ=0.35 / 0.88, and dipole 90X.

[0793] After exposure, post-exposure heating (PEB, 180° C. for 1 minute) was performed, and the film was cooled to room temperature on a cooling plate, developed for 30 seconds using an organic solvent-based developer, rinsed, and baked at 250° C. for 60 seconds to form a resist pattern.

[0794] Resist patterns were formed by the same procedure using substrates having surface modified layers obtained from coating solutions 102 to 108 and comparative coating solution 101. The heating temperature (baking temperature) after spin coating the coating solution was set to the baking temperature shown in Table 5.

[0795] Furthermore, regarding each of the obtained patterns, the pattern shape was confirmed by pattern cross-sectional observation to evaluate whether a line pattern with a pitch of 32 nm and a line length of 16 nm could be formed.

[0796] In the observation of the pattern shape, the shape from the base to the undercut and the state without significant residue in the gap portion were evaluated as "good", and the state where the resist was not well applied and a hole was partially opened and was not preferred was evaluated as "pinhole". The obtained results are shown in Table 5.

[0797] [Table 5]

[0798] substrate Coating liquid Firing temperature Resist pattern shape Embodiment 125 Bare-Si Coating Liquid 101 215 degrees good Embodiment 126 Bare-Si Coating liquid 102 160 degrees good Embodiment 127 Bare-Si Coating liquid 103 215 degrees good Embodiment 128 Bare-Si Coating liquid 104 215 degrees good Embodiment 129 Bare-Si Coating liquid 105 215 degrees good Embodiment 130 Bare-Si Coating liquid 106 160 degrees good Embodiment 131 Bare-Si Coating liquid 107 160 degrees good Embodiment 132 Bare-Si Coating liquid 108 160 degrees good Comparative Example 103 Bare-Si Comparison of coating solutions 101 215 degrees Pinhole .

Claims

1. A method for producing a laminate, the laminate comprising a surface modification layer and a semiconductor substrate, the method comprising the following steps: Step 1: coating a surface modifier containing a polymer and a solvent on a semiconductor substrate, and then firing the surface modifier to crosslink the polymer to obtain a surface modification layer precursor; and Step 2: The surface modification layer precursor is brought into contact with a thinning liquid to thin the surface modification layer precursor, thereby obtaining a surface modification layer having a film thickness of 5 nm or less. 2 . The method for producing a laminate according to claim 1 , wherein the polymer is polysiloxane. 3 . The method for producing a laminate according to claim 2 , wherein the polysiloxane comprises a modified polysiloxane in which at least a part of the silanol groups is alcohol-modified or acetal-protected.

4. The method for producing a laminate according to claim 2, wherein the polysiloxane comprises a hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, an aromatic ring having 6 to 30 carbon atoms which may be substituted by a halogen atom, an alkenyl group, an alkynyl group, a norbornene ring, a phenol group, a protected phenol group, an amino group, an amide group, a cyclic amide group, an imide group, a cyclic imide group, a sulfonyl group, a sulfonamide group, a nitro group, a cyano group, a thiocyanate group, an isocyanate group, a halogen group, a carboxylic acid group, a carboxylate group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphoric acid ester group, an ammonium group, At least one structure selected from the group consisting of a sulfonium group, an epoxy group, a glycidyloxy group, a cyclohexyloxy group, a ring-opened epoxy group, a ring-opened glycidyloxy group, a ring-opened cyclohexyloxy group, a hydroxyl group, a mercapto group, an acryloyloxy group, and a methacryloyloxy group. 5 . The method for producing a laminate according to claim 2 , wherein the polysiloxane includes a group that is bonded to a silicon atom and has an ion bond.

6. The method for producing a laminate according to claim 5, wherein the group having an ionic bond has an anionic group as a group bonded to a silicon atom, and a cation, The anion in the anionic group is a sulfonic acid anion, a carboxylic acid anion or a phosphate anion, The cation is a sulfonium cation, an iodine cation cation, cation, dihydroimidazolium cation or ammonium cation.

7. The method for producing a laminate according to claim 5, wherein the group having an ionic bond has a cationic group as a group bonded to a silicon atom and an anion, The cation in the cationic group is a sulfonium cation, an iodine cation, cation, cation, dihydroimidazolium cation or ammonium cation, The anion is a sulfonic acid anion, a carboxylic acid anion or a phosphoric acid anion. The method for producing a laminate according to claim 2 , wherein the polysiloxane contains a Q unit. 9 . The method for producing a laminate according to claim 1 , wherein the solvent contains at least one selected from the group consisting of alcohols, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylates, and water. 10 . The method for producing a laminate according to claim 1 , wherein the surface modifier contains an acid. 11 . The method for producing a laminate according to claim 1 , wherein the surface modifier contains an acid generator.

12. According to the manufacturing method of the laminated body according to claim 1, the thinning liquid is at least one selected from organic solvents, water, acidic solutions, alkaline aqueous solutions, and diluents used in the RRC process for reducing the consumption of the resist or the EBR process for removing the edge beads. 13 . The method for producing a laminate according to claim 1 , wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having an inorganic or organic film. 14 . The method for producing a laminate according to claim 13 , 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.

15. The method for manufacturing a laminate according to claim 13, wherein the organic matter is at least one selected from amorphous carbon, graphite, fullerene, carbon nanotube, diamond, diamond-like carbon, polyimide and organic films thereof doped or partially replaced with boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen. 16 . The method for producing a laminate according to claim 1 , wherein the laminate further comprises a resist underlayer film containing silicon.

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

18. The method for producing a laminate according to claim 1, wherein the second step is a step of thinning the surface modification layer precursor together with the RRC step or the EBR step to obtain a surface modification layer with a film thickness of 5 nm or less.

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

20. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming a resist film on the laminated body obtained by the method for producing a laminated body according to any one of claims 1 to 19; and The resist film is exposed and developed to obtain a resist pattern.

21. A laminate comprising a semiconductor substrate and a surface modification layer having a thickness of 5 nm or less and containing a cross-linked polymer.

22. The laminate according to claim 21, which is used for EUV or electron beam lithography.

23. The laminate according to claim 21, wherein the polymer is polysiloxane. The laminate according to claim 23 , wherein the polysiloxane comprises a Q unit.

25. A surface modifier comprising a polymer and a solvent. The method is used for the method for producing a laminate according to any one of claims 1 to 19.

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