Laminate, method for producing laminate, and photosensitive surface modifier

Abstract

A laminate which comprises a substrate and a surface-modified film that is formed from a photosensitive surface-modifying agent containing a photosensitive polymer and is irradiated with light or an electron beam, the surface-modified film having an exposed region irradiated with the light or the electron beam and an unexposed region, either the exposed region or the unexposed region is a selective upper layer formation region in which an upper layer is selectively formed.

Description

Technical Field

[0001] This invention relates to laminates, methods for manufacturing laminates, and photosensitive surface modifiers. Background Technology

[0002] Photolithography, which uses photoresist compositions, has been a standard technique in semiconductor device manufacturing for a long time. In recent years, with the increasing integration of semiconductor devices, there is a growing demand for finer patterns, such as wiring. Thin film formation technologies, including CVD and ALD, have been developed to create dense thin films with uniform thickness.

[0003] As the aforementioned thin film formation method, Patent Document 1 and Non-Patent Document 1 disclose a method for selectively forming a thin film on a specific area of ​​a substrate surface using the ALD method.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-14631

[0007] Non-patent literature

[0008] Non-patent literature 1: Journal of Photopolymer Science and Technology (2018), 31(3), 431-436 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The aforementioned methods for forming regionally selective thin films using methods such as ALD are currently under development, and technological improvements are expected in the future. For example, there is a need to develop substrates that can be formed using simple methods without requiring special raw materials or manufacturing processes, as substrates for forming regionally selective thin films.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, and completed the present invention with the following main points.

[0013] That is, the present invention includes the following solutions.

[0014] [1] A laminate having a substrate and a surface-modified film, the surface-modified film being formed from a photosensitive surface modifier containing a photosensitive polymer and irradiated with light or electron beams. The aforementioned surface-modified film has an exposed area that has been irradiated by the aforementioned light or electron beam, and an unexposed area. Either the exposed area or the unexposed area is a selective upper layer formation area for selectively forming the upper layer.

[0015] [2] According to the stacked body described in [1], the above-mentioned photosensitive polymer is polysiloxane.

[0016] [3] According to the laminate described in [2], the polysiloxane comprises a polysiloxane modified by alcohol modification or acetal protection of at least a portion of the silanol group.

[0017] [4] According to the laminate described in [2] or [3], the above-mentioned polysiloxane comprises a hydrocarbon group with 1 to 8 carbon atoms that can be substituted by a halogen atom, an aromatic ring with 6 to 30 carbon atoms that can be substituted by a halogen atom, an alkenyl group, an alkyne group, a norbornene ring, a phenolic group, a protected phenolic 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 carboxylic acid ester group, a sulfonic acid group, a sulfonate group, a phosphoric acid group, a phosphate ester group, an ammonium group, It has at least one structure selected from the following groups: alkyl, sulfonyl, epoxy, epoxypropoxy, cyclohexylepoxy, ring-opened epoxy, ring-opened epoxypropoxy, ring-opened cyclohexylepoxy, hydroxyl, mercapto, acryloyloxy, and methacryloyloxy.

[0018] [5] The laminate according to any one of [2] to [4], wherein the polysiloxane comprises a group that is bonded to silicon atoms and has an ionic bond.

[0019] [6] According to the stacked body described in [5], the above-mentioned groups having ionic bonds include anionic groups and cations that are groups that bond with silicon atoms. The anions in the above-mentioned anionic radicals are sulfonate anions, carboxylate anions, or phosphate anions. The above cations are sulfonium cations and iodine cations. cation, Cations, dihydroimidazole cations, or ammonium cations.

[0020] [7] According to the laminate described in [5] or [6], the groups having ionic bonds include cationic groups and anionic groups as groups that bond with silicon atoms. The cations in the above cationic groups are sulfonium cations and iodine cations. cation, Cations, dihydroimidazolium cations, or ammonium cations The anions mentioned above are sulfonate anions, carboxylate anions, or phosphate anions.

[0021] [8] The polysiloxane comprising any one of [2] to [7] in the laminate of any one of the following:

[0022] [9] The substrate of any one of [1] to [8] is made of a material containing inorganic or organic matter.

[0023]

[10] The laminate according to any one of [1] to [9], wherein the substrate has a film made of a material containing inorganic or organic matter.

[0024]

[11] According to the stacked body described in [9] or

[10] , the inorganic material is selected from at least one of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides and metal carbonitrides.

[0025]

[12] The stacked body according to any one of [9] to

[11] , wherein the organic material is selected from at least one of amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, polyimide and organic films thereof doped or partially replaced by boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen.

[0026] The method for manufacturing a laminate as described in any one of

[13] , [1] to

[12] includes the following steps: A film formation process in which a surface-modified precursor film is formed on the substrate by means of the photosensitive surface modifier containing the photosensitive polymer and solvent; and An exposure process in which the surface-modified precursor film is irradiated with the light or electron beam to form the surface-modified film having the exposed area and the unexposed area.

[0027]

[14] According to the manufacturing method of the stacked body described in

[13] , the stacked body further comprises a photoresist underlayer containing silicon or a photoresist underlayer containing carbon.

[0028]

[15] According to the manufacturing method of the stacked body described in

[13] or

[14] , the thickness of the surface modified film is less than 5 nm.

[0029]

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

[13] to

[15] further includes the following steps: contacting the surface-modified film with a thinning liquid to thin the film to a thickness of 5 nm or less.

[0030]

[17] In the method for manufacturing the laminate according to

[16] , the thinning liquid is selected from at least one of organic solvents, water and alkaline aqueous solutions.

[0031]

[18] According to the manufacturing method of the stacked body described in

[16] or

[17] , the above-mentioned thinning process is to thin the above-mentioned surface modified film by spin coating a thinning liquid to obtain a surface modified film with a film thickness of less than 5 nm.

[0032]

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

[13] to

[18] further includes the following step: a selective film forming step in which an upper layer is preferentially formed in either the exposed area or the unexposed area.

[0033]

[20] According to the manufacturing method of the stacked body described in

[19] , the above-mentioned selective film formation process is a process of forming the upper layer by any one of vacuum evaporation, CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition), and MLD (Molecular Layer Deposition).

[0034]

[21] A photosensitive surface modifier is the above-mentioned photosensitive surface modifier containing the above-mentioned photosensitive polymer and solvent. It is the material for forming the surface-modified film of the laminate as described in any one of [1] to

[12] .

[0035]

[22] According to the photosensitive surface modifier of

[21] , the solvent comprises at least one selected from alcohols, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylic esters and water.

[0036]

[23] The photosensitive surface modifier according to

[21] or

[22] contains an acid.

[0037]

[24] The photosensitive surface modifier according to any one of

[21] to

[23] , wherein the photosensitive surface modifier contains an acid-producing agent.

[0038] The effects of the invention

[0039] According to the present invention, a laminate formed by a simple process of creating multiple regions with different surface properties can be provided as a substrate for selectively forming thin films. Detailed Implementation

[0040] (Laminated structure)

[0041] The laminate of the present invention has a substrate and a surface-modified film, the surface-modified film being formed from a photosensitive surface modifier containing a photosensitive polymer and irradiated with light or an electron beam. The laminate of the present invention may further comprise other films or layers.

[0042] <<Surface Modified Film>>

[0043] The surface-modified film is formed from a photosensitive surface modifier and has exposed areas that are irradiated by light or an electron beam, and unexposed areas. The laminate of the present invention may further include other areas.

[0044] Either the exposed region or the unexposed region is a selectively formed upper layer region. That is, for the laminate of the present invention, the exposed region is surface modified by means of light irradiation or the like. The surface-modified exposed region and the unexposed region are regions where the ease of forming the upper layer differs from each other (different surface characteristics). Either the exposed region or the unexposed region is a region where the upper layer is easily selectively formed.

[0045] The exposed area is the region within the surface-modified film that has been irradiated with light or an electron beam. The unexposed area is the region within the surface-modified film that has not been irradiated with light or an electron beam, such as the region located under a specified mask when irradiated with light or an electron beam.

[0046] There are no particular restrictions on the upper layer; for example, a layer of photoresist material can be included.

[0047] The exposed and unexposed areas formed above are regions with different surface properties. Specifically, the exposed and unexposed areas preferably have different hydrophilicities. Examples of hydrophilicity include, for instance, the water contact angle. The difference in water contact angle between the exposed and unexposed areas is preferably 10 degrees or more, particularly preferably 15 degrees or more, and even more preferably 20 degrees or more.

[0048] The contact angle of water can be measured using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd. DM-701). The water volume is 3 μl, and the solution is allowed to stand for 5 seconds before measurement. The average value of 5 measurements is then used to calculate the contact angle.

[0049] Thus, by utilizing the different surface characteristics of the exposed and unexposed regions, when a surface-modified film is formed as the upper layer in a laminate, the deposition amount of the upper layer is more likely to increase in either the exposed or unexposed region, facilitating the selective formation of the upper layer. For example, when a layer forming a metallic material is used as the upper layer, the upper layer can be selectively formed in regions with higher hydrophilicity.

[0050] The thickness of the surface-modified film is less than 5 nm, preferably less than 3 nm. There is no particular limitation on the lower limit of the thickness of the surface-modified film; the thickness of the surface-modified film can be greater than 0.1 nm or greater than 0.2 nm.

[0051] It should be noted that in this invention, there is no clear distinction between film and layer.

[0052] In this invention, the film thickness is measured as follows.

[0053] The film thickness was measured using an elliptic film thickness measuring device RE-3100 (SCREEN).

[0054] <<<Photosensitive Polymers>>>

[0055] As a photosensitive polymer, there are no particular restrictions as long as it is photosensitive to light or electron beam irradiation, and it can be appropriately selected according to the purpose.

[0056] Photosensitive polymers are, for example, polymers that undergo photochemical reactions upon exposure to light or electron beams, resulting in structural changes such as crosslinking and decomposition (photoreactive polymers). Photosensitive polymers may also contain photoinitiators that react with the aforementioned photoreactive polymers, causing structural changes in the polymer. For example, a photoinitiator could be a photoacid generator (PAG).

[0057] It should be noted that, in the following text, photosensitive polymers will sometimes be referred to simply as polymers.

[0058] There are no particular limitations on the weight-average molecular weight of the photosensitive polymer; for example, it can be 500 to 1,000,000. From the viewpoint of suppressing precipitation from the photosensitive surface modifier, the weight-average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of combining storage stability and coatability, it is preferably 500 or more, and more preferably 600 or more.

[0059] -Polysiloxane-

[0060] As a photosensitive polymer, a polysiloxane having a portion of organic sites is preferred from the viewpoint that it can be firmly bonded to the substrate through chemical crosslinking, and is easy to undergo photodecomposition or photocrosslinking in EUV, ArF exposure or electron beam lithography.

[0061] There are no particular restrictions on polysiloxanes as long as they are polymers with siloxane bonds.

[0062] There are no particular limitations on the photosensitive reactions of polysiloxanes. For example, reactions can be considered where, under light or electron beam irradiation, the following reactions occur: photoacid generators (PAGs) of the polysiloxane side chains decompose halogens, the polymer undergoes structural changes, and sulfonic acids and carboxylic acids are generated, thus readily exhibiting hydrophilicity. Furthermore, as a photosensitive reaction for polysiloxanes, reactions can also be considered where, for example, the aromatic rings of the polymer are desorbed, and the hydrophilic portion (OH groups) is exposed through structural changes accompanying this desorption.

[0063] Polysiloxanes may also include modified polysiloxanes in which a portion of the silanol group has been modified, such as polysiloxanes in which a portion of the silanol group has been modified with an alcohol or protected with an acetal.

[0064] As another example, the polysiloxane includes a hydrolysis condensate of a hydrolyzable silane, and may also include a modified polysiloxane in which at least a portion of the silanol groups of the hydrolysis condensate are modified with an alcohol or protected with an acetal. The hydrolyzable silane involved in the hydrolysis condensate may include one or more hydrolyzable silanes.

[0065] Furthermore, polysiloxanes can have a main chain structure with any of the following: cage-like, ladder-like, linear, and branched. Commercially available polysiloxanes can also be used as polysiloxanes.

[0066] It should be noted that in this invention, the "hydrolysis condensate" of the hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only the polyorganosiloxane polymer as a condensate with complete condensation, but also the polyorganosiloxane polymer as a partially hydrolyzed condensate with incomplete condensation. Such partially hydrolyzed condensates, like the fully condensed condensates, are polymers obtained through the hydrolysis and condensation of the hydrolyzable silane, but the hydrolysis is partially stopped, and no condensation occurs; therefore, Si-OH groups remain. Furthermore, in the surface modifier, in addition to the hydrolysis condensate, uncondensed hydrolysates (completely hydrolyzed products, partially hydrolyzed products) and monomers (hydrolyzable silanes) may also remain.

[0067] It should be noted that in this specification, "hydrolyzable silane" is sometimes abbreviated as "silane compound".

[0068] In addition, in this specification, "polysiloxane" is sometimes referred to as "hydrolysis condensate".

[0069] Polysiloxanes preferably contain a hydrocarbon group with 1 to 8 carbon atoms that can be substituted by a halogen atom, an aromatic ring with 6 to 30 carbon atoms that can be substituted by a halogen atom, an alkenyl group, an alkynyl group, a norbornene ring, a phenolic group, a protected phenolic 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 carboxylic acid ester group, a sulfonic acid group, a sulfonate ester group, a phosphoric acid group, a phosphate ester group, or an ammonium group. It has at least one structure selected from the following groups: alkyl, sulfonyl, epoxy, epoxypropoxy, cyclohexylepoxy, ring-opened epoxy, ring-opened epoxypropoxy, ring-opened cyclohexylepoxy, hydroxyl, mercapto, acryloyloxy, and methacryloyloxy.

[0070] If polysiloxanes contain these structures, decomposition reactions occur after EUV or electron beam exposure, which can easily lead to hydrophilization.

[0071] It should be noted that the so-called ring-opening epoxy group refers to the -CH(OH)-CH2(OH) group.

[0072] In this invention, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0073] Polysiloxanes are particularly preferably composed of hydrocarbon groups with 1 to 8 carbon atoms that can be substituted by halogen atoms, or aromatic rings with 6 to 30 carbon atoms that can be substituted by halogen atoms. The more halogen atoms substituted, the more readily it becomes a photosensitive polymer that decomposes under light or electron beam irradiation during the exposure process. Furthermore, when aromatic rings are present, it is easier to form a surface-modified precursor film with a high water contact angle before the exposure process on the substrate during the film formation process; moreover, it is easier to become a photosensitive polymer that is easily decomposed under light or electron beam irradiation during the exposure process.

[0074] Examples of such groups include hydrocarbon groups with 1 to 8 carbon atoms that can be substituted by halogen atoms, or aromatic rings with 6 to 30 carbon atoms that can be substituted by halogen atoms.

[0075]

[0076] (* indicates a bond that binds to a silicon atom.)

[0077] Polysiloxanes preferably contain groups that are bonded to silicon atoms and have ionic bonds.

[0078] Groups with ionic bonds can be, for example, anionic groups that bond with silicon atoms, or cations. Such groups with ionic bonds are represented, for example, by the following formula (I-1).

[0079] Groups with ionic bonds can be, for example, cationic groups that bond with silicon atoms, and anionic groups. Such groups with ionic bonds are represented, for example, by the following formula (I-2).

[0080]

[0081] (In formula (I-1), * represents a bonding bond with a silicon atom. Ra represents a single bond or a divalent organic group. Xa) - This represents a monovalent group with an anion. Ya ＋ It represents a cation.

[0082] In formula (I-2), * represents a bonding bond with a silicon atom. Rb represents a single bond or a divalent organic group. Yb ＋ This indicates a monovalent group with a cation. Xb - (This indicates anion.)

[0083] Examples of Ra and Rb include divalent organic groups with 1 to 10 carbon atoms.

[0084] Ra and Rb can have heteroatoms. Examples of heteroatoms include oxygen and nitrogen atoms.

[0085] Examples of anions or anions that are part of anionic radicals include sulfonate anions, carboxylate anions, and phosphate anions.

[0086] Examples of cations or cations that can be categorized as cationic groups include sulfonium cations and iodine cations. cation, Cations, dihydroimidazolium cations, ammonium cations, etc. The cation in the cationic group, or preferably a sulfonium cation or iodine cation. Cationic. The reason is that it is a photosensitive polymer that is easily decomposed by light or electron beam irradiation during the exposure process.

[0087] Preferred sulfonium cations include triarylsulfonium cations, diarylmonalkylsulfonium cations, monoaryldialkylsulfonium, and trialkylsulfonium cations.

[0088] As iodine Cation, preferably diaryliodophosphate cation.

[0089] As Cation, preferably tetraaryl cationic, triaryl monoalkyl cationic, diaryldialkyl Cationic, monoaryltrialkylsulfonium cation, etc.

[0090] As ammonium cations, quaternary ammonium cations, tertiary ammonium cations, secondary ammonium cations, and primary ammonium cations are preferred.

[0091] Examples of anionic groups that can bond with silicon atoms include the following groups.

[0092]

[0093] (* indicates a bonding bond with a silicon atom.)

[0094] Examples of cationic groups that can be used to bond with silicon atoms include the following groups.

[0095]

[0096] (* indicates a bonding bond with a silicon atom.)

[0097] Examples of anions include the following.

[0098]

[0099] Examples of cations include the following.

[0100]

[0101] Examples of groups that have ionic bonds include the following groups.

[0102]

[0103] (* indicates a bonding bond with a silicon atom.)

[0104] Polysiloxanes contain, for example, at least one of M units, D units, T units, and Q units.

[0105] 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 3 / 2 The structural unit shown, the so-called Q unit, is SiO2. 4 / 2 The structural units shown. R in these structural units a R b and R c It represents a monovalent organic group that is not hydrolyzable.

[0106] Polysiloxanes contain, for example, Q units.

[0107] The polysiloxane preferably contains T units. The proportion of T units in the polysiloxane is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total of the M, D, T, and Q units of the polysiloxane. It should be noted that, in this case, the polysiloxane may or may not contain M, D, and Q units. If the polysiloxane contains T units, the surface-modified layer obtained through the action of monovalent organic groups readily interacts with adjacent layers or films. As a result, for example, it readily and efficiently generates the characteristics of organic groups, such as photoreaction, while maintaining close adhesion to the underlying substrate via SiO bonds. Furthermore, when the polysiloxane may contain M and D units, if the mass proportion of T units in the polysiloxane is higher than the total of the M and D units, the film strength and film-forming properties of the surface-modified layer can be improved.

[0108] Examples of polysiloxanes include hydrolytic condensates of hydrolytic silanes containing at least one hydrolytic silane as shown in formula (1) below.

[0109] --Formula (1)--

[0110] In equation (1), R 1 "R" represents a group bonded to a silicon atom, and independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonyl group, or an organogroup having a cyano group, or a combination of two or more thereof. 1 Preferably, it is an aryl group that can be substituted, an alkyl group that can be substituted, or an aryl group that can be substituted.

[0111] In addition, R 2 A group or atom bonded to a silicon atom, and independently representing an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0112] a represents an integer from 0 to 3.

[0113] ---R 1 ---

[0114] The alkyl group can be any of the straight-chain, branched, or cyclic forms, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0115] Specific examples of alkyl groups, specifically straight-chain or branched alkyl groups, include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-... Amyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0116] It should be noted that in this specification, "i" refers to "different", "s" refers to "middle", and "t" refers to "uncle".

[0117] Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl- Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, as well as cross-linked cycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl and dicyclodecyl.

[0118] The aryl group can be any of the following: phenyl, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from 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.

[0119] For example, aryl groups with 6 to 20 carbon atoms can be cited as examples. Other examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, 1-tetraphenyl, 2-tetraphenyl, 5-tetraphenyl, 2- 1-Pyrene, 2-Pyrene, pentaphenyl, benzo[9,10]phenanthrene; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (me-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 not limited to these.

[0120] Aryl alkyl is an alkyl group that has been substituted with an aryl group. Specific examples of such aryl and alkyl groups can be given as those described above. The number of carbon atoms in the aryl alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0121] Specific examples of aralkyl groups include phenylmethyl (benzyl), 2-phenylethylidene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, etc., but are not limited to these.

[0122] Haloalkyl, haloaryl, and haloaralkyl are each alkyl, aryl, and aralkyl groups that have been substituted with one or more halogen atoms. Specific examples of such alkyl, aryl, and aralkyl groups can be given as those described above.

[0123] 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 even more preferably 10 or less.

[0124] Specific examples of haloalkyl groups include monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropane-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, etc., but are not limited to these.

[0125] The number of carbon atoms in the haloaryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0126] Specific examples of halogenated aryl groups include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, and 3-fluoro-1-naphthyl. Examples of groups include 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, heptafluoro-2-naphthyl, etc. Furthermore, examples of groups in which the fluorine atom (fluoro group) is arbitrarily replaced by a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be cited, but these are not limited to these.

[0127] 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.

[0128] Specific examples of haloaralkyl groups include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc. Furthermore, examples of groups in which the fluorine atom (fluoro group) is arbitrarily replaced by a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be given, but these are not limited to these.

[0129] Alkoxyalkyl, alkoxyaryl, and alkoxyaralkyl are each alkyl, aryl, and aralkyl groups that have been substituted with one or more alkoxy groups. Specific examples of such alkyl, aryl, and aralkyl groups can be given as those similar to those described above.

[0130] Examples of alkoxy groups that can be used as substituents include, for example, alkoxy groups having at least one alkyl moiety among straight-chain, branched, and cyclic forms having 1 to 20 carbon atoms.

[0131] Examples of linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-propoxy, etc. Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc.

[0132] In addition, examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentoxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentoxy, 2-methyl-cyclopentoxy, 3-methyl-cyclopentoxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-dimethyl-cyclobutoxy Methyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3-dimethyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl-cyclopropoxy, 1-isopropyl-cyclopropoxy, 2-isopropyl-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1,2,3-trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1-methyl-cyclopropoxy, 2-ethyl-2-methyl-cyclopropoxy, and 2-ethyl-3-methyl-cyclopropoxy, etc.

[0133] Specific examples of alkoxyalkyl groups include methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, ethoxymethyl, and other lower (approximately 5 carbon atoms or less) alkyloxyalkyl groups, but are not limited to these.

[0134] Specific examples of alkoxyaryl groups include 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, 7-methoxynaphth-1-yl, etc., but are not limited to these.

[0135] Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0136] The alkenyl group can be either linear or branched, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0137] Specific examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3- Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2-Methyl-3-cyclopentenyl Examples of alkenyl groups include 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl. Cross-linked cyclic alkenyl groups such as dicycloheptenyl (norbornyl) can also be cited.

[0138] Furthermore, examples of substituents among the aforementioned alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl groups include, for example, alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkoxyaralkyl, alkenyl, alkoxy, aralkyloxy, etc., and examples of them and their suitable carbon number are the same as those described above or below.

[0139] Furthermore, the aryloxy group mentioned in the substituents is a group in which the aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups include those similar to those described above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include phenoxy and naphth-2-yloxy groups, but are not limited to these.

[0140] Furthermore, when there are two or more substituents, the substituents can combine with each other to form a ring.

[0141] Examples of organic groups having an epoxy group that can open a ring include epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, epoxycyclohexyl, or their epoxy group with an open ring.

[0142] Examples of organic groups containing an acryloyl group include acryloyloxymethyl, acryloyloxyethyl, and acryloyloxypropyl.

[0143] Examples of organic groups containing a methacryloyl group include methacryloyloxymethyl, methacryloyloxyethyl, and methacryloyloxypropyl.

[0144] Examples of organic groups containing a thiol group include thiol ethyl, thiol butyl, thiol hexyl, thiol octyl, and thiol phenyl.

[0145] Examples of amino groups include amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl, but are not limited to these. Amino groups will be described in further detail below.

[0146] Examples of organic groups having an alkoxy group include, but are not limited to, methoxymethyl and methoxyethyl. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded.

[0147] Examples of organic groups having a sulfonyl group include sulfonylalkyl and sulfonylaryl groups, but are not limited to these.

[0148] Examples of organic groups containing a cyano group include cyanoethyl, cyanopropyl, cyanophenyl, and thiocyanate groups.

[0149] As an organic group containing an amino group, examples include organic groups containing at least one of primary, secondary, and tertiary amino groups. Preferably, a hydrolytic condensate containing a tertiary ammonium group is formed by hydrolyzing a hydrolyzable silane containing a tertiary amino group with a strong acid. Furthermore, in addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as oxygen and sulfur atoms.

[0150] As a preferred example, an organic group having an amino group can be exemplified by the group shown in the following formula (A1).

[0151]

[0152] In equation (A1), R 101 and R 102 Each atom or hydrocarbon group can be represented independently, and each L can be represented independently as a substituted alkylene group. * indicates a bond.

[0153] Examples of hydrocarbon groups include alkyl, alkenyl, and aryl groups, but are not limited to these. Specific examples of these alkyl, alkenyl, and aryl groups include those related to R... 1 The same as the one mentioned above.

[0154] Furthermore, as an alkylene group, it can be either straight-chain or branched, and its carbon number is typically 1 to 10, preferably 1 to 5. Examples of straight-chain alkylene groups include methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene.

[0155] Examples of organic groups containing an amino group include amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl, but are not limited to these.

[0156] ---R 2 ---

[0157] As R 2 The alkoxy group in R can be exemplified by, for example, in R 1 The description illustrates alkoxy groups.

[0158] As R 2 Halogen atoms in R can be cited as an example. 1 The description illustrates halogen atoms.

[0159] Arylalkyloxy groups are monovalent groups derived from the hydroxyl group of aralkyl alcohols by removing a hydrogen atom. Specific examples of aralkyl groups in aryloxy groups can be the same as those described above.

[0160] The number of carbon atoms in the arylalkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less.

[0161] Specific examples of aralkyloxy groups include phenylmethyloxy (benzyloxy), 2-phenylethyloxy, 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, 10-phenyl-n-decyloxy, etc., but are not limited to these.

[0162] An acyloxy group is a monovalent group derived from the carboxyl group (-COOH) of a carboxylic acid compound by removing a hydrogen atom. Typically, examples include alkylcarbonyloxy, arylcarbonyloxy, or aralkylcarbonyloxy derived from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid, but these are not limited to. Specific examples of alkyl, aryl, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids are those identical to those described above.

[0163] Specific examples of acyloxy groups include those with 2 to 20 carbon atoms, such as methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl-n-butyl carbonyloxy, 2-methyl-n-butyl carbonyloxy, 3-methyl-n-butyl carbonyloxy, 1,1-dimethyl-n-propyl carbonyloxy, 1,2-dimethyl-n-propyl carbonyloxy, 2,2-dimethyl-n-propyl carbonyloxy, 1-ethyl-n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl ...propyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl carbonyloxy, 2-methyl-n-pentyl The compounds include 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and toluenesulfonylcarbonyloxy, etc.

[0164] ---Specific examples of hydrolyzable silanes shown in formula (1)---

[0165] Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethoxysilane, epoxypropoxymethyltrimethoxysilane, epoxypropoxymethyltriethoxysilane, α-epoxypropoxyethyltrimethoxysilane, α-epoxypropoxyethyltriethoxysilane, β-epoxypropoxyethyltrimethoxysilane, β-epoxypropoxyethyltrimethoxysilane, and β-epoxypropoxy... Ethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ -Epoxypropoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane 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-glycidoxypropylmethyldibutoxysilaneγ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane Allyl 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-Styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, 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, phenethylmethyldiethoxysilanePhenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenylethyltrimethoxysilane, methoxyphenylethyltriacetoxysilane, methoxyphenylethyltrichlorosilane, 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 ,Methoxynaphthyltriacetoxysilane,Methoxynaphthyltrichlorosilane,Ethoxynaphthyltrimethoxysilane,Ethoxynaphthyltriethoxysilane,Ethoxynaphthyltriacetoxysilane,Ethoxynaphthyltrichlorosilane,γ-chloropropyltrimethoxysilane,γ-chloropropyltriethoxysilane,γ-chloropropyltriacetoxysilane,3,3,3-trifluoropropyltrimethoxysilane,γ-methacryloyloxypropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane,β-cyanoethyltriethoxysilane,Thiocyanate-based propyltriethoxysilane,Chloromethyltrimethoxysilane,Chloromethyltriethoxysilane,Triethoxysilylpropyldiallylisocyanurate,Bicyclo[2,2,1] Heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidepropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silanes represented by formulas (A-1) to (A-41) below.The silanes shown in formulas (1-1) to (1-294) below, but not limited to these.

[0166]

[0167] In formulas (1-1) to (1-294), T independently represents an alkoxy, acyloxy, or halogen group, preferably a methoxy or ethoxy group.

[0168] Examples of polysiloxanes include hydrolytic condensates of hydrolytic silanes containing, together with or in place of, the hydrolytic silane shown in formula (1) or the hydrolytic silane shown in formula (1), the hydrolytic silane shown in formula (2).

[0169] --Equation (2)--

[0170] In equation (2), R 3 The group is a group bonded to a silicon atom and independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonyl group, or an organogroup having a cyano group, or a combination of two or more thereof.

[0171] In addition, R 4 A group or atom bonded to a silicon atom, and independently representing an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0172] R 5These are groups that bond with silicon atoms and represent alkylene or arylene groups independently of each other.

[0173] b represents 0 or 1, and c represents 0 or 1.

[0174] As R 3 Specific examples of the groups in R and their suitable number of carbon atoms can be given. 1 The above-mentioned groups and number of carbon atoms.

[0175] As R 4 Specific examples of the groups and atoms in R, and their suitable number of carbon atoms, can be given. 2 The aforementioned groups and atoms, as well as the number of carbon atoms.

[0176] As R 5 Specific examples of alkylene groups 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; branched 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 and ethane-1,1,2-ethyltriylylene. -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, 2-methylpropane-1,1,3-triyl alkane triyl, etc., but not limited to these.

[0177] As R 5Specific examples of arylene groups include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthodiyl, 1,8-naphthodiyl, 2,6-naphthodiyl, 2,7-naphthodiyl, 1,2-anthratriyl, 1,3-anthratriyl, 1,4-anthratriyl, 1,5-anthratriyl, 1,6-anthratriyl, 1,7-anthratriyl, 1,8-anthratriyl, 2,3-anthratriyl, 2,6-anthratriyl, 2,7-anthratriyl, 2,9-anthratriyl, 2,10-anthratriyl, 9,10-anthratriyl, etc., which are derived by removing two hydrogen atoms from the aromatic ring of a fused-ring aromatic hydrocarbon compound; 4,4'-biphenyldiyl, 4,4''-p-terphenyldiyl, etc., which are derived by removing two hydrogen atoms from the aromatic ring of a ring-linked aromatic hydrocarbon compound, etc., but are not limited to these.

[0178] b is preferably 0.

[0179] c is preferably 1.

[0180] Specific examples of the hydrolyzable silanes shown in formula (2) include methylene bis(trimethoxysilane), methylene bis(trichlorosilane), methylene bis(triacetoxysilane), ethylene bis(triethoxysilane), ethylene bis(trichlorosilane), ethylene bis(triacetoxysilane), propylene bis(triethoxysilane), butylene bis(trimethoxysilane), phenylene bis(trimethoxysilane), phenylene bis(triethoxysilane), phenylene bis(methyl)ethoxysilane, phenylene bis(methyl)methoxysilane, naphthylene bis(trimethoxysilane), bis(trimethoxyethyl)silane, bis(triethoxyethyl)silane, bis(ethyl)ethoxyethyl)silane, bis(methyl)methoxyethyl)silane, etc., but are not limited to these.

[0181] As a polysiloxane, examples include hydrolytic condensates of hydrolytic silanes that together with or in place of the hydrolytic silanes shown in formula (1) and / or the hydrolytic silanes shown in formula (2), or other hydrolytic silanes listed below.

[0182] Other hydrolyzable silanes include those with intramolecular properties... Silane compounds with a sulfone group, silane compounds with a sulfonamide group, silane compounds with a cyclic urea skeleton within the molecule, etc., but not limited to these.

[0183] --Intramolecular Silane compounds (hydrolyzable organosilanes) --

[0184] Expecting intramolecular properties Silane compounds can effectively and efficiently promote the cross-linking reaction of hydrolyzable silanes.

[0185] Intramolecular A suitable example of a silane compound is represented by formula (3).

[0186]

[0187] R 11 A group that bonds with silicon atoms, and represents... base or having Organic groups of radicals.

[0188] R 12 The group is a group that is bonded to a silicon atom and independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, an organogroup having an amino group, or an organogroup having a cyano group, or a combination of two or more thereof.

[0189] R 13 A group or atom bonded to a silicon atom, and independently representing an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0190] f represents 1 or 2, g represents 0 or 1, and 1 ≤ f + g ≤ 2 is satisfied.

[0191] Specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organogroups having ring-opening epoxy groups, organogroups having acryloyl groups, organogroups having methacryloyl groups, organogroups having mercapto groups, organogroups having amino groups and organogroups having cyano groups, alkoxy, aralkyloxy, acyloxy, halogen atoms, and further specific examples of substituents of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl, and their suitable number of carbon atoms, regarding R 12 Examples of R can be given. 1 Regarding R mentioned above... 13 Examples of R can be given. 2 And the above.

[0192] If described in more detail, then as Specific examples of the group include cyclic ammonium groups or chain ammonium groups, preferably tertiary ammonium groups or quaternary ammonium groups.

[0193] That is, as base or having Suitable specific examples of the organic group of the group may be cyclic ammonium group or chain ammonium group or organic group having at least one of them, preferably tertiary ammonium group or quaternary ammonium group or organic group having at least one of them.

[0194] It should be noted that, in When the group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as a ring-forming atom. In this case, there are cases where the nitrogen atom constituting the ring is bonded to the silicon atom directly or through a divalent linker, and cases where the carbon atom constituting the ring is bonded to the silicon atom directly or through a divalent linker.

[0195] In one example of a suitable scheme, R is a group that bonds with silicon atoms. 11 It is a heteroaromatic cyclic ammonium group as shown in the following formula (S1).

[0196]

[0197] In equation (S1), A 1 A 2 A 3 and A 4 Each of the groups represented independently 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), according to the silicon atom in formula (3) and A 1 ~A 4 Which combination, in the way the formed ring displays aromaticity, determines A. 1 ~A 4 The bonds between each atom and its adjacent atoms forming a ring are either single or double bonds. * indicates a bonding bond.

[0198]

[0199] In equations (J1) to (J3), R 10 The terms "single bond," "hydrogen atom," "alkyl," "aryl," "aralkyl," "haloalkyl," "haloaryl," "haloaralkyl," or "alkenyl" can be used independently to represent single bonds, hydrogen atoms, alkyl groups, aralkyl groups, haloalkyl groups, haloaryl groups, haloaralkyl groups, and alkenyl groups, and their suitable carbon numbers can be given as above. * indicates a bonding bond.

[0200] In equation (S1), R 14 Each of the following can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, or hydroxyl groups, in the presence of two or more R groups. 14 In the case of 2 R 14 They can combine to form a ring, 2 Rs 14The formed ring can be a cross-linked ring structure. In such cases, the cyclic ammonium group can have adamantane ring, norbornene ring, spiro ring, etc.

[0201] Specific examples of such alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl groups, and their suitable carbon numbers, can be given as those described above.

[0202] In equation (S1), n 1 m is an integer from 1 to 8. 1 m is 0 or 1 2 It is a positive integer ranging from 0 or 1 to the largest number that can be substituted on a single or multiple rings.

[0203] In m 1 When the value is 0, it constitutes a combination of A. 1 ~A 4 (4+n) 1 A ring of elements. That is, in n... 1 When the value is 1, a 5-membered ring is formed; in n... 1 When the number is 2, a 6-membered ring is formed. 1 When the number is 3, it forms a 7-membered ring, and in n 1 When the sum is 4, it forms an 8-membered ring, and in n 1 When the sum is 5, a 9-membered ring is formed, and in n... 1 When the sum is 6, a 10-membered ring is formed, and at n... 1 When 7 elements are formed, an 11-membered ring is formed. At n... 1 A 12-membered ring is formed when the number of elements is 8.

[0204] In m 1 When the value is 1, a structure containing A is formed. 1 ~A 3 (4+n) 1 ) Metacyclic rings and containing A 4 The 6-membered ring is fused with a fused ring.

[0205] According to A 1 ~A 4 Which of equations (J1) to (J3) has the case where the atoms constituting the ring have hydrogen atoms and the case where they do not? In A 1 ~A 4 When the atoms constituting the ring have hydrogen atoms, those hydrogen atoms can be replaced by R. 14 In addition, R 14 It can also be in addition to A 1 ~A 4 The rings in the ring are substituted on atoms other than the ring-forming atoms. Due to this situation, as described above, m 2 An integer selected from 0 or 1 up to the largest number that can be substituted on a single or multiple rings.

[0206] The bonding bonds of the heteroaromatic cyclic ammonium group shown in formula (S1) exist on any carbon or nitrogen atom present on such a monocyclic or fused ring, directly bonded to silicon atoms, or bonded to a linker group to form an organic group with cyclic ammonium, which is bonded to silicon atoms.

[0207] Examples of such linking groups include alkylene, arylene, and alkenylene, but they are not limited to these.

[0208] Specific examples of alkylene and arylene groups and their suitable carbon number can be given as above.

[0209] Furthermore, the alkenyl group is a divalent group derived by removing one hydrogen atom from the alkenyl group. Specific examples of such alkenyl groups include those similar to those described above. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0210] Specific examples include vinylidene, 1-methylvinylidene, propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, etc., but are not limited to these.

[0211] Specific examples of silane compounds (hydrolyzable organosilanes) having a heteroaromatic cyclic ammonium group as shown in formula (S1) can be silanes shown in formulas (I-1) to (I-50) below, but are not limited to these.

[0212]

[0213] In another example, R in formula (3) is a group that bonds with silicon atoms. 11 It can be a heteroaliphatic cyclic ammonium group as shown in the following formula (S2).

[0214]

[0215] In equation (S2), A 5 A 6 A 7 and A 8 Each of the groups represented independently by any one of the following formulas (J4) to (J6), but A 5 ~A 8 At least one of them is a group represented by the following formula (J5). Based on the silicon atom in formula (3) and A... 5 ~A 8 Which combination, in a way that the formed ring exhibits non-aromaticity, determines A. 5 ~A8 The bonds between each atom and its adjacent atoms forming a ring are either single or double bonds. * indicates a bonding bond.

[0216]

[0217] In equations (J4) to (J6), R 10 The terms "single bond," "hydrogen atom," "alkyl," "aryl," "aralkyl," "haloalkyl," "haloaryl," "haloaralkyl," or "alkenyl" can be used independently to represent single bonds, hydrogen atoms, alkyl groups, aralkyl groups, haloalkyl groups, haloaryl groups, haloaralkyl groups, and alkenyl groups, and their suitable carbon numbers can be given as above. * indicates a bonding bond.

[0218] In equation (S2), R 15 Each of the following can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, or hydroxyl groups, in the presence of two or more R groups. 15 In the case of 2 R 15 They can combine to form a ring, 2 Rs 15 The formed ring can be a cross-linked ring structure. In such cases, the cyclic ammonium group can have adamantane ring, norbornene ring, spiro ring, etc.

[0219] Specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl groups and their suitable carbon numbers can be given as above.

[0220] In equation (S2), n 2 m is an integer from 1 to 8. 3 m is 0 or 1 4 It is a positive integer ranging from 0 or 1 to the largest number that can be substituted on a single or multiple rings.

[0221] In m 3 When the value is 0, it constitutes a combination of A. 5 ~A 8 (4+n) 2 A ring of elements. That is, in n... 2 When the value is 1, a 5-membered ring is formed; in n... 2 When the number is 2, a 6-membered ring is formed. 2 When the number is 3, it forms a 7-membered ring, and in n 2 When the sum is 4, it forms an 8-membered ring, and in n 2 When the sum is 5, a 9-membered ring is formed, and in n... 2 When the sum is 6, a 10-membered ring is formed, and at n... 2 When 7 elements are formed, an 11-membered ring is formed. At n... 2 A 12-membered ring is formed when the number of elements is 8.

[0222] In m 3 When the value is 1, a structure containing A is formed.5 ~A 7 (4+n) 2 ) Metacyclic rings and containing A 8 The 6-membered ring is fused with a fused ring.

[0223] According to A 5 ~A 8 Which of equations (J4) to (J6) has the case where the atoms constituting the ring have hydrogen atoms and the case where they do not? In A 5 ~A 8 When the atoms constituting the ring have hydrogen atoms, those hydrogen atoms can be replaced by R. 15 In addition, R 15 In addition to A 5 ~A 8 The rings in the atom are substituted on the atom other than the rings that constitute the ring.

[0224] As a result of this situation, as mentioned above, m 4 An integer selected from 0 or 1 up to the largest number that can be substituted on a single or multiple rings.

[0225] The heteroaliphatic cyclic ammonium group shown in formula (S2) has a bonding bond that exists on any carbon or nitrogen atom present on such a monocyclic or fused ring, directly bonded to silicon atoms, or bonded to a linker group to form an organic group with cyclic ammonium, which is bonded to silicon atoms.

[0226] Examples of such linking groups include alkylene, arylene, or alkenylene, and examples of alkylene, arylene, and alkenylene, and their suitable carbon number, are the same as those described above.

[0227] Specific examples of silane compounds (hydrolyzable organosilanes) having a heteroaliphatic cyclic ammonium group as shown in formula (S2) as shown in formula (3) can be silanes shown in formulas (II-1) to (II-30) below, but are not limited to these.

[0228]

[0229] In another further example, R in formula (3) is a group that bonds with silicon atoms. 11 It can be a chain-like ammonium group as shown in the following formula (S3).

[0230]

[0231] In equation (S3), R 10The hydrogen atom, alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, or alkenyl can be represented independently of each other. Specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl, and their suitable number of carbon atoms, can be given as above. * indicates a bonding bond.

[0232] The chain-like ammonium group shown in formula (S3) is directly bonded to silicon atoms or bonded to a linker group to form an organic group with chain-like ammonium groups, which is bonded to silicon atoms.

[0233] Examples of such linking groups include alkylene, arylene, or alkenylene, and specific examples of alkylene, arylene, and alkenylene are those identical to those described above.

[0234] Specific examples of silane compounds (hydrolyzable organosilanes) of formula (3) having a chain-like ammonium group as shown in formula (S3) can be silanes of formulas (III-1) to (III-28) shown below, but are not limited to these.

[0235]

[0236] --Silane compounds with sulfone or sulfonamide groups (hydrolyzable organosilanes)--

[0237] Examples of silane compounds having a sulfone group and silane compounds having a sulfonamide group include, for example, compounds shown in formulas (B-1) to (B-36) below, but are not limited to these.

[0238] In the following formula, Me represents methyl and Et represents ethyl.

[0239]

[0240] --Silane compounds with an intramolecular cyclic urea skeleton (hydrolyzable organosilanes)--

[0241] Examples of hydrolyzable organosilanes having an intramolecular cyclic urea skeleton include, for example, the hydrolyzable organosilane shown in formula (4-1) below.

[0242]

[0243] In equation (4-1), R 401 The groups that bond with silicon atoms are represented independently of each other as shown in the following formula (4-2).

[0244] R 402The group that is bonded to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having a ring-opening epoxy group, an organogroup having an acryloyl group, an organogroup having a methacryloyl group, an organogroup having a mercapto group, or an organogroup having a cyano group, or a combination of two or more thereof.

[0245] R 403 These are groups or atoms that bond with silicon atoms, and are independently represented as alkoxy, aralkyloxy, acyloxy, or halogen atoms.

[0246] x is 1 or 2, y is 0 or 1, and x + y ≤ 2.

[0247] R 402 Alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl and organogroups having ring-opening epoxy groups, organogroups having acryloyl groups, organogroups having methacryloyl groups, organogroups having mercapto groups and organogroups having cyano groups, and R 403 Specific examples of alkoxy, aralkyloxy, acyloxy, and halogen atoms, as well as their substituents, suitable carbon numbers, etc., can be given in relation to R. 1 and R 2 The same applies to the above.

[0248]

[0249] In equation (4-2), R 404 Each of the following can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, an organogroup with an epoxy group, or an organogroup with a sulfonyl group. 405 Each can be represented independently as an alkylene group, hydroxyalkylene group, sulfur bond (-S-), ether bond (-O-), or ester bond (-CO-O- or -O-CO-). * indicates a bond.

[0250] It should be noted that R 404 Specific examples of substituted alkyl groups, substituted alkenyl groups, and organogroups with epoxy groups, and suitable carbon numbers, can be given in relation to R. 1 And the same as above, except for these, as R 404 The alkyl group can be replaced, preferably an alkyl group in which the terminal hydrogen atom is replaced by a vinyl group, such as allyl, 2-vinylethyl, 3-vinylpropyl, 4-vinylbutyl, etc.

[0251] As an organic group containing a sulfonyl group, there are no particular limitations as long as it contains a sulfonyl group. Examples include substituted alkyl sulfonyl groups, substituted aryl sulfonyl groups, substituted aralkyl sulfonyl groups, substituted haloalkyl sulfonyl groups, substituted haloaryl sulfonyl groups, substituted haloaralkyl sulfonyl groups, substituted alkoxyalkyl sulfonyl groups, substituted alkoxyaryl sulfonyl groups, substituted alkoxyaralkyl sulfonyl groups, and substituted alkenyl sulfonyl groups, etc.

[0252] Specific examples of these groups, including alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl and alkenyl, as well as their substituents and suitable carbon numbers, can be cited in relation to R. 1 The same applies to the above.

[0253] The alkylene group is a divalent group derived by removing one hydrogen atom from an alkyl group. It can be linear, branched, or cyclic. Specific examples of such alkylene groups are those similar to those described above. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0254] In addition, R 405 The alkylene group may have one or more of the following at its end or in the middle, preferably in the middle: a sulfur bond, an ether bond, and an ester bond.

[0255] Specific examples of alkylene compounds include straight-chain alkylene compounds 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 compounds such as methyl ethylene, 1-methyl 1,3-propylene, 2-methyl 1,3-propylene, 1,1-dimethyl ethylene, 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 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, and 1,2-... Cyclohexanediyl, 1,3-cyclohexanediyl and other cyclic alkylene groups, -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2CH2SCH2CH2CH2-, -CH2OCH2CH2SCH2- and other alkylene groups including ether groups, but not limited to these.

[0256] A hydroxyalkylene group is a group in which at least one hydrogen atom of the aforementioned alkylene group is replaced by a hydroxyl group. Specific examples include hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxy-1,3-propylene, 2-hydroxy-1,3-propylene, 3-hydroxy-1,3-propylene, 1-hydroxy-1,4-butylene, 2-hydroxy-1,4-butylene, 3-hydroxy-1,4-butylene, 4-hydroxy-1,4-butylene, 1,2-dihydroxy-1,4-butylene, 1,3-dihydroxy-1,4-butylene, 1,4-dihydroxy-1,4-butylene, 2,3-dihydroxy-1,4-butylene, 2,4-dihydroxy-1,4-butylene, 4,4-dihydroxy-1,4-butylene, etc., but are not limited to these.

[0257] In equation (4-2), X 401 Each of the groups represented independently by formulas (4-3) to (4-5) below, and the carbon atom of the ketone group in formulas (4-4) and (4-5) below is related to the R in formula (4-2). 405 The nitrogen atoms are bonded together.

[0258]

[0259] In equations (4-3) to (4-5), R 406 ~R 410 Each can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organogroup having an epoxy or sulfonyl group. Specific examples of substituted alkyl groups, substituted alkenyl groups, and organogroups having epoxy or sulfonyl groups, and suitable numbers of carbon atoms, can be given in relation to R. 1 The same applies to the above. Furthermore, specific examples of organogroups having sulfonyl groups and suitable carbon numbers can be cited in relation to R. 404 The same applies to the above. * indicates a bonding bond.

[0260] In the case of using the resulting stack for EUV or electron beam lithography, from the viewpoint of achieving excellent lithographic properties with good reproducibility, X 401 Preferably, it contains the group shown in formula (4-5).

[0261] When the resulting stack 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 preferred alkyl groups has a terminal hydrogen atom replaced by a vinyl group.

[0262] The hydrolyzable organosilanes shown in formula (4-1) can be commercially available or synthesized by known methods as described in International Publication No. 2011 / 102470, etc.

[0263] Hereinafter, as specific examples of hydrolyzable organosilanes represented by formula (4-1), examples may be given of silanes represented by formulas (4-1-1) to (4-1-29), but are not limited to these.

[0264]

[0265] Without impairing the effects of the invention, the polysiloxane may be a hydrolytic condensate of a hydrolytic silane containing other silane compounds besides those exemplified above.

[0266] As described above, as a polysiloxane, a modified polysiloxane in which at least a portion of the silanol group has been modified can be used. For example, a polysiloxane modified with a portion of the silanol group modified by an alcohol or a polysiloxane modified with acetal protection can be used.

[0267] Examples of polysiloxanes that can be modified include reaction products obtained by reacting at least a portion of the silanol groups in the hydrolytic condensate of the aforementioned hydrolytic silane with the hydroxyl groups of an alcohol, dehydration products of the condensate and an alcohol, and modified products in which at least a portion of the silanol groups in the condensate are protected with acetal groups.

[0268] As an alcohol, monohydric alcohols can be used, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-pentanol, neopentanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-prop ... -Dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol and cyclohexanol.

[0269] In addition, alcohols containing alkoxy groups, such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol), can be used.

[0270] The reaction of the silanol groups in the condensate with the hydroxyl groups of the alcohol is achieved by contacting the polysiloxane with the alcohol and reacting at a temperature of 40–160°C, for example, 60°C, for 0.1–48 hours, for example, 24 hours, thereby obtaining a modified polysiloxane with silanol groups capped. In this case, the alcohol, as the capping agent, can be used as a solvent in the composition containing the polysiloxane.

[0271] In addition, the dehydration reaction product of polysiloxane composed of hydrolytic condensate of hydrolyzable silane and alcohol can be produced by reacting polysiloxane with alcohol in the presence of acid as a catalyst, end-capping silanol groups with alcohol, and removing the water generated by dehydration from the reaction system.

[0272] The acid can be an organic acid with an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. Examples of acids include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., especially benzoic acid, isobutyric acid, acetic acid, etc.

[0273] In addition, acids with boiling points of 70 to 160°C can be used, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid.

[0274] Thus, as an acid, it is preferable to have an acid dissociation constant (pKa) of 4 to 5, or a boiling point of 70 to 160 °C, and to possess any of the following physical properties. That is, a substance with weak acidity, or a substance with strong acidity but a low boiling point, can be used.

[0275] Furthermore, as an acid, it can also utilize any of the properties, such as the acid dissociation constant and boiling point.

[0276] The acetal protection of the silanol group of the condensate can be achieved by using vinyl ethers, such as the vinyl ether shown in formula (5) below, which can introduce part of the structure shown in formula (6) below into the polysiloxane through their reaction.

[0277]

[0278] In equation (5), R 1a R 2a and R 3a Each represents an alkyl group having 1 to 10 hydrogen atoms, R 4a R represents an alkyl group having 1 to 10 carbon atoms. 2a With R 4a They can combine with each other to form rings. Alkyl groups can be exemplified by the above examples.

[0279]

[0280] In equation (6), R 1’ R 2’ and R 3’ Each represents an alkyl group having 1 to 10 hydrogen atoms, R 4’ R represents an alkyl group having 1 to 10 carbon atoms. 2’ With R 4’ They can combine to form rings. In formula (6), * represents a bond with an adjacent atom. Examples of adjacent atoms include, for example, the oxygen atom in a siloxane bond, the oxygen atom in a silanol group, and R derived from formula (1). 1 The carbon atom. Alkyl groups can be exemplified by the above examples.

[0281] As the vinyl ether represented by formula (5), aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. Ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran are particularly preferred.

[0282] Silanol acetal protection can be achieved using polysiloxanes, vinyl ethers, and solvents such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, and 1,4-dimethylformamide. Aprotic solvents such as alkanes, using pyridine It is carried out using catalysts such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

[0283] It should be noted that the use of alcohol-terminated and acetal-protected silanol groups can be carried out simultaneously with the hydrolysis and condensation of hydrolyzable silanes described later.

[0284] In a preferred embodiment of the invention, the polysiloxane contains at least one of the following: a hydrolyzable silane of formula (1), a hydrolyzable silane of formula (2) as needed, and other hydrolyzable silanes, a hydrolyzable condensate of hydrolyzable silane, and a modified thereof.

[0285] In a preferred embodiment, the polysiloxane comprises a dehydration reaction product of a hydrolysis condensate and an alcohol.

[0286] The weight-average molecular weight of the polysiloxane, which is a hydrolysis condensate (and may also include a modifier) ​​of a hydrolyzable silane, can be, 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 is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of combining storage stability and coatability, the weight-average molecular weight is preferably 500 or more, more preferably 600 or more.

[0287] It should be noted that the weight-average molecular weight is the molecular weight obtained by GPC analysis and converted to polystyrene. GPC analysis can be performed, for example, under the following conditions: GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Co., Ltd.), GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), column temperature at 40°C, tetrahydrofuran as eluent, flow rate at 1.0 mL / min, and polystyrene (Shodex (registered trademark) manufactured by Showa Denko Co., Ltd.).

[0288] Hydrolyzable silane hydrolysis condensates are obtained by hydrolyzing and condensing the above-mentioned silane compounds (hydrolyzable silanes).

[0289] The above-mentioned silane compounds (hydrolyzable silanes) contain alkoxy, aralkyloxy, acyloxy, or halogen atoms that are directly bonded to silicon atoms, that is, they contain alkoxysilyl, aralkyloxysilyl, acyloxysilyl, or halosilyl (hereinafter referred to as hydrolyzable groups).

[0290] In the hydrolysis of these hydrolyzable groups, for every 1 mole of the hydrolyzable group, 0.1 to 100 moles of water are typically used, for example, 0.5 to 100 moles, preferably 1 to 10 moles.

[0291] During hydrolysis and condensation, a hydrolysis catalyst may be used to promote the reaction, or the hydrolysis and condensation may be carried out without using one. When a hydrolysis catalyst is used, 0.0001 to 10 moles of hydrolytic group are typically used, preferably 0.001 to 1 mole of hydrolysis catalyst per mole of hydrolytic group.

[0292] The reaction temperature for hydrolysis and condensation is typically above room temperature and below the reflux temperature of the organic solvent that can be used for hydrolysis at atmospheric pressure, for example, 20–110°C, or, for example, 20–80°C.

[0293] Hydrolysis can be complete, meaning all hydrolyzable groups can be converted into silanol groups, or it can be partial, meaning that unreacted hydrolyzable groups remain.

[0294] Examples of hydrolysis catalysts that can be used in the hydrolysis and condensation process include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0295] Metal chelates that can be used as hydrolysis catalysts include, for example, triethoxylated metal chelates. Mono(acetylacetone)titanium, tri-n-propoxy Mono(acetylacetone)titanium, tri-isopropoxy Mono(acetylacetone)titanium, tri-n-butoxy Mono(acetylacetone)titanium, tri-sec-butoxy Mono(acetylacetone)titanium, tri-tert-butoxy Mono(acetylacetone)titanium, diethoxy bis(acetylacetone)titanium, di-n-propoxy bis(acetylacetone)titanium, di-isopropoxy Bis(acetylacetone)titanium, di-n-butoxy Bis(acetylacetone)titanium, di-sec-butoxy bis(acetylacetone)titanium, di-tert-butoxy bis(acetylacetone)titanium, monoethoxy Tri(acetylacetone)titanium, mono-n-propoxy Tri(acetylacetone)titanium, mono-isopropoxy Tri(acetylacetone)titanium, mono-n-butoxy Tri(acetylacetone)titanium, mono-sec-butoxy Tri(acetylacetone)titanium, mono-tert-butoxy Tri(acetylacetone)titanium, Tetra(acetylacetone)titanium, Triethoxy Mono(ethyl acetoacetate)titanium, tri-n-propoxy Mono(ethyl acetoacetate)titanium, tri-isopropoxy Mono(ethyl acetoacetate)titanium, tri-n-butoxy Mono(ethyl acetoacetate)titanium, tri-sec-butoxy Mono(ethyl acetoacetate)titanium, tri-tert-butoxy Mono(ethyl acetoacetate)titanium, diethoxy bis(ethyl acetoacetate)titanium, di-n-propoxy bis(ethyl acetoacetate)titanium, di-isopropoxy bis(ethyl acetoacetate)titanium, di-n-butoxy bis(ethyl acetoacetate)titanium, di-sec-butoxy bis(ethyl acetoacetate)titanium, di-tert-butoxy bis(ethyl acetoacetate)titanium, monoethoxy Tri(ethyl acetoacetate)titanium, mono-n-propoxy Tri(ethyl acetoacetate)titanium, mono-isopropoxy Tri(ethyl acetoacetate)titanium, mono-n-butoxy Tri(ethyl acetoacetate)titanium, mono-sec-butoxy Tri(ethyl acetoacetate)titanium, mono-tert-butoxy Titanium chelates such as tri(ethyl acetoacetate)titanium, tetra(ethyl acetoacetate)titanium, mono(acetylacetone)tri(ethyl acetoacetate)titanium, bis(acetylacetone)bis(ethyl acetoacetate)titanium, and tri(acetylacetone)mon(ethyl acetoacetate)titanium; triethoxy Mono(acetylacetone)zirconium, tri-n-propoxy Mono(acetylacetone)zirconium, tri-isopropoxy Mono(acetylacetone)zirconium, tri-n-butoxy Mono(acetylacetone)zirconium, tri-sec-butoxy Mono(acetylacetone)zirconium, tri-tert-butoxy Mono(acetylacetone)zirconium, diethoxy bis(acetylacetone)zirconium, di-n-propoxy bis(acetylacetone)zirconium, di-isopropoxy bis(acetylacetone)zirconium, di-n-butoxy bis(acetylacetone)zirconium, di-sec-butoxy bis(acetylacetone)zirconium, di-tert-butoxy bis(acetylacetone)zirconium, monoethoxy Tri(acetylacetone)zirconium, mono-n-propoxy Tri(acetylacetone)zirconium, mono-isopropoxy Tri(acetylacetone)zirconium, mono-n-butoxy Tri(acetylacetone)zirconium, mono-sec-butoxy Tri(acetylacetone)zirconium, mono-tert-butoxy Tri-(acetylacetone)zirconium, Tetra-(acetylacetone)zirconium, Triethoxy Mono(ethyl acetoacetate)zirconium, tri-n-propoxy Mono(ethyl acetoacetate)zirconium, tri-isopropoxy Mono(ethyl acetoacetate)zirconium, tri-n-butoxy Mono(ethyl acetoacetate)zirconium, tri-sec-butoxy Mono(ethyl acetoacetate)zirconium, tri-tert-butoxy Mono(ethyl acetoacetate)zirconium, diethoxy bis(ethyl acetoacetate)zirconium, di-n-propoxy bis(ethyl acetoacetate)zirconium, di-isopropoxy bis(ethyl acetoacetate)zirconium, di-n-butoxy bis(ethyl acetoacetate)zirconium, di-sec-butoxy bis(ethyl acetoacetate)zirconium, di-tert-butoxy bis(ethyl acetoacetate)zirconium, monoethoxy Tri(ethyl acetoacetate)zirconium, mono-n-propoxy Tri(ethyl acetoacetate)zirconium, mono-isopropoxy Tri(ethyl acetoacetate)zirconium, mono-n-butoxy Tri(ethyl acetoacetate)zirconium, mono-sec-butoxy Tri(ethyl acetoacetate)zirconium, mono-tert-butoxy Zirconium chelates such as tri(ethyl acetoacetate)zirconium, tetra(ethyl acetoacetate)zirconium, mono(acetylacetone)tri(ethyl acetoacetate)zirconium, bis(acetylacetone)bis(ethyl acetoacetate)zirconium, tri(acetylacetone)mon(ethyl acetoacetate)zirconium; aluminum chelates such as tri(acetylacetone)aluminum, tri(ethyl acetoacetate)aluminum; etc., but not limited to these.

[0296] Organic acids that can serve as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0297] Inorganic acids that can act as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0298] Examples of organic bases that can serve as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picolinide, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0299] Inorganic bases that can act as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0300] Among these catalysts, metal chelates, organic acids, and inorganic acids are preferred. They can be used alone or in combination of two or more.

[0301] In this invention, nitric acid is suitable as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, changes in the molecular weight of the hydrolyzed condensate can be suppressed. It is known that the stability of the hydrolyzed condensate in a liquid depends on the pH of the solution. Further research has revealed that by using an appropriate amount of nitric acid, the pH of the solution reaches a stable range.

[0302] Furthermore, as mentioned above, nitric acid is also preferred from the viewpoint that it can be used to obtain modified hydrolysis condensates, for example, when end-capping silanol groups with alcohols.

[0303] During hydrolysis and condensation, organic solvents can be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; and aromatic solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, and n-pentylnaphthalene. Aromatic 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 alkanols, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; acetone, methyl ethyl ketone, methyl- Ketone solvents including n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, fentanyl ketone, etc.; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, etc. Alkane, dimethyl di Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl Ethers, 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, and other ether-based solvents; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate. Benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, triethylene glycol methoxyacetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate Ester solvents such as isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonyl lactone, etc., but not limited to these. One or more of these solvents may be used in combination.

[0304] After the hydrolysis and condensation reactions are completed, the reaction solution is neutralized by either direct dilution or concentration, and then treated with an ion exchange resin. This removes hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation processes. Furthermore, before or after this treatment, byproducts such as alcohols, water, and the hydrolysis catalysts used can be removed from the reaction solution by means of vacuum distillation.

[0305] The hydrolysis condensate obtained through this process is obtained as a polysiloxane varnish dissolved in an organic solvent and can be directly used to formulate a surface modifier. That is, the reaction solution can be used directly (or diluted) to formulate a surface modifier. In this case, as long as the effects of the invention are not impaired, the hydrolysis catalyst, byproducts, etc., used in the hydrolysis and condensation can remain in the reaction solution. For example, the hydrolysis catalyst and the nitric acid used in the silanol end-capping process can remain in the polymer varnish solution at levels of approximately 100 ppm to 5,000 ppm.

[0306] The resulting polysiloxane varnish can be solvent-displaced and diluted with a suitable solvent. It should be noted that if the resulting polysiloxane varnish has good storage stability, the organic solvent can also be removed by distillation to achieve a film-forming component concentration of 100%. It should be noted that the film-forming component refers to the component remaining after removing the solvent from all components of the composition.

[0307] The organic solvents used for solvent displacement and dilution of polysiloxane varnishes can be the same as or different from those used for the hydrolysis and condensation reactions of hydrolyzable silanes. There are no particular limitations on the diluent; one or more solvents can be used, and any choice can be made.

[0308] <<Substrate>>

[0309] The substrate in the stack of the present invention is not particularly limited as long as it is a substrate used for manufacturing, for example, precision integrated circuit components.

[0310] Examples of substrates include those made of materials containing inorganic or organic matter.

[0311] The substrate may also have a film made of a material containing inorganic or organic matter.

[0312] Examples of inorganic materials constituting the aforementioned substrate and film include arsenic, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides. They can be used individually or in combination of two or more.

[0313] Examples of metals include silicon, germanium, titanium, tungsten, hafnium, zirconium, chromium, copper, aluminum, indium, gallium, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0314] Examples of metal oxides include SiO2 and TiO2.

[0315] Examples of metal nitrides include SiN, TiN, and TaN.

[0316] Examples of metal carbides include SiC and TiC.

[0317] Examples of metal oxynitrides include SiON and TiON.

[0318] Examples of metal oxycarbides include SiOC and TiOC.

[0319] Examples of metal carbonitrides include SiCN and TiCN.

[0320] Examples of organic materials constituting substrates and films include amorphous carbon, graphite, fullerenes, carbon nanotubes, diamond, diamond-like carbon, and polyimide. These can be used individually or in combination of two or more. The aforementioned organic materials can also be organic films doped or partially substituted with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogens.

[0321] Examples of substrates described above include, for instance, 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 crystal glass); glass substrates with ITO (indium tin oxide) films or IZO (indium zinc oxide) films formed on them; plastic substrates (polyimide, PET, etc.); substrates coated with low-k materials; and flexible substrates.

[0322] The substrate can be a substrate with a water contact angle of 50 degrees or less, and preferably a substrate with a water contact angle of 40 degrees or less.

[0323] (Manufacturing method of laminated bodies)

[0324] The method for manufacturing the laminate of the present invention includes a film formation step and an exposure step. The method for manufacturing the laminate of the present invention may further include a thinning step, or steps other than those described above.

[0325] The film formation process involves coating a photosensitive surface modifier containing a photosensitive polymer and a solvent onto a substrate, followed by firing to crosslink the photosensitive polymer and obtain a surface-modified precursor film.

[0326] The exposure process is a process of irradiating a surface-modified precursor film with light or an electron beam to form a surface-modified film having exposed and unexposed areas.

[0327] The laminate obtained by the manufacturing method of the present invention can have a semiconductor substrate and a surface-modified film with a thickness of less than 5 nm. The surface-modified film contains a cross-linked photosensitive polymer.

[0328] The laminate obtained by the manufacturing method of the present invention may also have other layers or films. Examples of other layers include, for example, a silicon-containing photoresist underlayer film and a carbon-containing photoresist underlayer film. There are no particular limitations on whether the silicon-containing or carbon-containing photoresist underlayer film is used in the photolithography process.

[0329] <<Photosensitive Surface Modifiers>>

[0330] Photosensitive surface modifiers contain photosensitive polymers and solvents.

[0331] The photosensitive polymer can be the substance described in the above-described surface-modified film.

[0332] <<<Solvent>>>

[0333] The solvent contained in the photosensitive surface modifier can be used without particular restriction as long as it is a solvent that can dissolve / mix the photosensitive polymer (e.g., polysiloxane) and other components contained in the photosensitive surface modifier as needed.

[0334] Examples of solvents include organic solvents and water.

[0335] Examples of solvents include alcohols, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylic esters, and water.

[0336] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents. Specific examples of these include the aforementioned monohydric alcohol solvents and polyhydric alcohol solvents used as solvents for hydrolysis and condensation.

[0337] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0338] Examples of monoalkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, and propylene glycol monobutyl ether.

[0339] Examples of alkylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc.

[0340] Examples of alkylene glycol monoalkyl ether carboxylic esters include, for example, alkylene glycol monoalkyl ether acetates.

[0341] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0342] Specific examples of other solvents include toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, etc. Acetic acid ester, 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, methyl 3-methoxybutylacetate, methyl 3-methoxypropylacetate, methyl 3-methoxybutylacetate, methyl 3-methoxybutylpropionate, methyl 3-methoxybutylbutyrate, methyl acetoacetate, methyl methylpropyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone, etc.

[0343] These solvents can be used alone or in combination of two or more.

[0344] Furthermore, the photosensitive surface modifier may contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the surface modifier may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0345] <<<Civilized Catalyst>>>

[0346] The photosensitive surface modifier can be a composition that does not contain a curing catalyst, but preferably contains a curing catalyst.

[0347] As a curing catalyst, ammonium salts, phosphine compounds, etc. can be used. Salt, matte salt, iodine Salt, oxygen Salts, etc. It should be noted that the following salts, described as an example of a solidification catalyst, can be added in the form of salts or as substances that form salts in the composition (substances that are added as other compounds and form salts in the system).

[0348] Examples of ammonium salts include quaternary ammonium salts with the structure shown in formula (D-1), quaternary ammonium salts with the structure shown in formula (D-2), quaternary ammonium salts with the structure shown in formula (D-3), quaternary ammonium salts with the structure shown in formula (D-4), quaternary ammonium salts with the structure shown in formula (D-5), and tertiary ammonium salts with the structure shown in formula (D-6).

[0349]

[0350] (where m) a n represents an integer from 2 to 11. a R represents integers from 2 to 3. 21 Y represents alkyl, aryl, or aralkyl. - (This indicates anion.)

[0351] (where R is in the formula) 22 R 23 R 24 and R 25 Each can be represented independently as alkyl, aryl, or aralkyl, Y - Represents an anion, and R 22 R 23 R 24 and R 25 Each atom bonds with a nitrogen atom.

[0352] (where R is in the formula) 26 and R 27 Each can be represented independently as alkyl, aryl, or aralkyl, Y - (This indicates anion.)

[0353] (where R is in the formula) 28 Y represents alkyl, aryl, or aralkyl. - (This indicates anion.)

[0354] (where R is in the formula) 29 and R 30 Each can be represented independently as alkyl, aryl, or aralkyl, Y - (This indicates anion.)

[0355] (where m) a n represents an integer from 2 to 11. a Y represents an integer from 2 to 3. - (This indicates anion.)

[0356] In addition, as Salt, as exemplified by the quaternary salts shown in equation (D-7), can be used as a reference. Salt.

[0357]

[0358] (where R is in the formula) 31 R 32 R 33 and R 34 Each can be represented independently as alkyl, aryl, or aralkyl, Y - Represents an anion, and R 31 R 32 R 33 and R 34 Each atom bonds with a phosphorus atom.

[0359] In addition, as a matte salt, the tertiary matte salt shown in formula (D-8) can be cited as an example.

[0360]

[0361] (where R is in the formula) 35 R 36 and R 37 Each can be represented independently as alkyl, aryl, or aralkyl, Y - Represents an anion, and R 35 R 36 and R 37 Each atom bonds with a sulfur atom.

[0362] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a n represents an integer from 2 to 11. a Represents an integer from 2 to 3. The R of this quaternary ammonium salt... 21 This refers to, for example, alkyl groups having 1 to 18 carbon atoms, preferably 2 to 10, aryl groups having 6 to 18 carbon atoms, or aralkyl groups having 7 to 18 carbon atoms. Examples include linear alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Furthermore, anions (Y...) -Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O) - ) and other acid groups.

[0363] The compound of formula (D-2) is R. 22 R 23 R 24 R 25 N ＋ Y - The quaternary ammonium salt shown. The R of this quaternary ammonium salt... 22 R 23 R 24 and R 25 Examples include alkyl groups with 1-18 carbon atoms such as ethyl, propyl, butyl, cyclohexyl, and cyclohexylmethyl; aryl groups with 6-18 carbon atoms such as phenyl; and aralkyl groups with 7-18 carbon atoms such as benzyl. Anion (Y - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O) - The quaternary ammonium salt is available commercially, such as tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0364] The compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, preferably R. 26 and R 27 The total number of carbon atoms is 7 or more. For example, R 26 Examples of possible compounds include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. 27 Examples include aryl groups such as benzyl, octyl, and octadecyl. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O)- The compound can be obtained commercially, but it can also be produced by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with aralkyl halides, alkyl halides, and aryl halides such as benzyl bromide, methyl bromide, and bromobenzene.

[0365] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 For example, it can be an alkyl group with 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms, such as butyl, octyl, benzyl, and lauryl. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O) - This compound is available as a commercially available product, but it can also be prepared by reacting pyridine with alkyl or aryl halides such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. An example of this compound is N-laurylpyridine chloride. N-Benzylpyridine bromide wait.

[0366] Compounds of formula (D-5) are quaternary ammonium salts derived from substituted pyridines, such as picolino, R 29 For example, it can be an alkyl group with 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms, such as methyl, octyl, lauryl, benzyl, etc. R 30 For example, it can be an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. For example, in the case where the compound shown in formula (D-5) is a quaternary ammonium derived from picolino, R 30 It is a methyl group. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O) - This compound is available as a commercially available product, but it can also be prepared by reacting substituted pyridines, such as picolinate, with alkyl or aryl halides such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, and benzyl bromide. An example of this compound is N-benzylpicolinate chloride. N-Benzylpicoline bromide N-Laurylpicoline chloride wait.

[0367] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m a n represents an integer from 2 to 11. a It indicates 2 or 3. Additionally, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O) - This compound can be produced by reacting amines with weak acids such as carboxylic acids and phenols. Examples of carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y)... - ) is (HCOO) - In the case of using acetic acid, the anion (Y) - (CH3COO) - Furthermore, in the case of using phenol, the anion (Y) - (C6H5O) - ).

[0368] The compound of formula (D-7) is a compound with R 31 R 32 R 33 R 34 P ＋ Y - The structure of the season Salt. R 31 R 32 R 33 and R 34 Examples include alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl. R is preferred. 31 ~R 34 Of the four substituents, three are unsubstituted phenyl groups or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Furthermore, the anion (Y...) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3)- ), alcohol radical (-O) - (e.g., acid groups). This compound is available as a commercially available product; examples include tetrabutyl halide. Tetrapropylhalogenated isohalogenated tetraalkyl , triethylbenzyl halide isohalogenated trialkylbenzyl , triphenylmethyl halogenated , triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide Tetraphenylhalide , Trimethylyl monoaryl halogenated Or halogenated tricresyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom). Triphenylmethyl halogenate is particularly preferred. , triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide isohalogenated triphenyl monoaryl , Trimethylbenzene Halogenated Isohyetalized trimethylolyl monoaryl , Trimethylhalogenated Isohyetalized trimethylyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom).

[0369] In addition, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0370] The compound of formula (D-8) is a compound with R 35 R 36 R 37 S ＋ Y - Tertiary sulfonium salts with a structure of R. 35 R 36 and R 37 Examples include alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl. R is preferred. 35 ~R 37Two of the three substituents are unsubstituted phenyl groups or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Additionally, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halide ions - ), sulfonate (-SO3) - ), alcohol radical (-O) - The compound contains acid groups such as maleate anions and nitrate anions. Examples of commercially available compounds include tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, dialkylbenzylsulfonium halide, diphenylmethylsulfonium halide, diphenylethylsulfonium halide, triphenylmonoalkylsulfonium halide (where the halogen atom is a chlorine or bromine atom), tri-n-butylsulfonium carboxylates, trialkylsulfonium carboxylates, dialkylbenzylsulfonium carboxylates, diphenylmethylsulfonium carboxylates, diphenylethylsulfonium carboxylates, and triphenylmonoalkylsulfonium carboxylates. Triphenylsulfonium halide and triphenylsulfonium carboxylates are preferred.

[0371] Furthermore, nitrogen-containing silane compounds can be added as curing catalysts. Examples of nitrogen-containing silane compounds include silane compounds containing an imidazole ring, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0372] The content of the curing catalyst in the photosensitive surface modifier is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the polymer, more preferably 0.01 to 25 parts by mass, and even more preferably 0.01 to 20 parts by mass.

[0373] <<<Acid>>

[0374] The preferred photosensitive surface modifier contains an acid.

[0375] Acids can be added during the preparation of photosensitive surface modifiers, but when the photosensitive surface modifier contains polysiloxanes, the portion remaining in the polysiloxane varnish can also be treated as an acid, either as a hydrolysis catalyst in the manufacture of the aforementioned polysiloxanes or during the alcohol-termining of silanol groups.

[0376] Examples of acids include organic acids and inorganic acids.

[0377] Examples of organic acids include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.

[0378] Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0379] The amount of acid mixed (residual acid content) is based on the total mass of the surface modifier and can be, for example, 0.0001% to 1% by mass, 0.001% to 0.1% by mass, or 0.005% to 0.05% by mass.

[0380] <<<Amines, Hydroxides>>>

[0381] The photosensitive surface modifier may contain at least one selected from amines and hydroxides.

[0382] Examples of amines include ammonia; primary amines such as monoethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine; secondary amines such as dimethylamine, ethylmethylamine, and diethylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, dimethylethylamine, methyldiisopropylamine, diisopropylethylamine, diethylethanolamine, and triethanolamine; amines such as ethylenediamine and tetramethylethylenediamine; and cyclic amines such as pyridine and morpholine.

[0383] Examples of hydroxides include inorganic base hydroxides and organic base hydroxides.

[0384] Examples of inorganic base hydroxides include sodium hydroxide and potassium hydroxide.

[0385] Examples of organic base hydroxides include, for example, tetraalkylammonium hydroxide, triarylsulfonium hydroxide, and diaryliodophosphate. Hydroxides, etc. Examples of tetraalkylammonium hydroxides include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Examples of triarylsulfonium hydroxides include, for example, triphenylsulfonium hydroxide and tris(tert-butylphenyl)sulfonium hydroxide. Examples of diaryliodocyanine hydroxides... Hydroxides, such as diphenyl iodide, can be cited as an example. Hydroxide, bis(tert-butylphenyl)iodine Hydroxides, etc.

[0386] The content of amines and hydroxides in the photosensitive surface modifier is not particularly limited, and can be 0.05 to 20 parts by weight relative to 100 parts by weight of polysiloxane, more preferably 0.1 to 15 parts by weight, and even more preferably 0.5 to 10 parts by weight.

[0387] <<<Other Additives>>>

[0388] In photosensitive surface modifiers, various additives can be mixed according to the intended use of the composition.

[0389] Examples of additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid-generating agents, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology modifiers, and adhesive aids, which are known additives that are mixed into materials (compositions) of various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflective films, and pattern reversal films.

[0390] It should be noted that the following examples illustrate various additives, but are not limited to these.

[0391] -Stabilizer-

[0392] When a photosensitive surface modifier contains polysiloxane, a stabilizer may be added for purposes such as stabilizing the hydrolysis condensate of the hydrolyzable silane mixture. For example, an organic acid, water, alcohol, or a combination thereof may be added.

[0393] Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Oxalic acid and maleic acid are preferred. When an organic acid is added, its amount is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters.

[0394] As water, pure water, ultrapure water, ion-exchanged water, etc. can be used. When used, its addition amount can be 0.1 to 20 parts by weight relative to 100 parts by weight of photosensitive surface modifier.

[0395] As the alcohol, it is preferred to be a substance that is easily dispersed by heating after coating, such as methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount added can be 0.1 to 20 parts by mass relative to 100 parts by mass of the photosensitive surface modifier.

[0396] -Organic polymers-

[0397] When a photosensitive surface modifier contains polysiloxane, the dry etching rate (the amount of film thickness reduction per unit time), attenuation coefficient, refractive index, etc., of the surface-modified film formed by the photosensitive surface modifier can be adjusted by adding an organic polymer to the photosensitive surface modifier. There are no particular restrictions on the organic polymer used; it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on its intended use.

[0398] Specific examples include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenolic varnish, naphthol varnish, polyether, polyamide, and polycarbonate.

[0399] In this invention, organic polymers containing aromatic or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be used when such functionality is required. Specific examples of such organic polymers include addition polymers containing addition monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as their structural units, as well as condensation polymers such as phenolic varnishes and naphtholic varnishes, but are not limited to these.

[0400] When using an addition polymer as an organic polymer, the polymer can be either a homopolymer or a copolymer.

[0401] In the manufacture of addition polymers, addition polymerizable monomers are used. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0402] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0403] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0404] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0405] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthraylmethacrylamide.

[0406] Specific examples of vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0407] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetystyrene, etc., but are not limited to these.

[0408] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0409] When using condensation polymers as the polymer, examples of such polymers include condensation polymers of diol compounds and dicarboxylic acid compounds. Examples of diol compounds include diethylene glycol, 1,6-hexanediol, and butanediol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Furthermore, examples of polyesters, polyamides, and polyimides include, but are not limited to, poly(1,2,4,5-pyromellitictetramethylimide), poly(terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0410] When an organic polymer contains hydroxyl groups, these hydroxyl groups can undergo cross-linking reactions with hydrolytic condensates, etc.

[0411] The weight-average molecular weight of organic polymers is typically between 1,000 and 1,000,000. When organic polymers are blended, from the viewpoint of fully obtaining the function of the polymer while suppressing precipitation in the composition, their weight-average molecular weight can be, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000.

[0412] Such organic polymers can be used alone or in combination of two or more.

[0413] When a photosensitive surface modifier contains polysiloxane and is used in conjunction with an organic polymer, its content should be appropriately determined considering the function of the organic polymer, etc., and therefore cannot be specified in general terms. However, it can generally be in the range of 1 to 200% by mass relative to the mass of polysiloxane. From the viewpoint of inhibiting precipitation in the composition, it can be, for example, 100% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less. From the viewpoint of fully obtaining its effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more.

[0414] -Acid-producing agents-

[0415] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents, with photo-producing acid-producing agents being preferred.

[0416] Examples of photoacid-producing agents include sulfonium salts, Salts, ammonium salts, iodine Salt, oxygen Salt, etc. Salt compounds, sulfonylimide compounds, disulfonyldiazomethane compounds, etc., but not limited to these. It should be noted that photoacid-generating agents, such as those described later, are also included. Salt compounds such as nitrates, maleates, and other carboxylates, as well as hydrochlorides, can also act as curing catalysts depending on their type.

[0417] In addition, examples of heat-generating acid agents include tetramethylammonium nitrate, but these are not limited to.

[0418] As A specific example of a salt compound is diphenyliodide. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate, bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, triphenylsulfonium nitrate (nitrate), triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, triphenylsulfonium chloride, and other sulfonate compounds, but not limited to these.

[0419] Specific examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide, but are not limited to these.

[0420] Specific examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, etc., but are not limited to these.

[0421] When the photosensitive surface modifier contains an acid-generating agent, its content is appropriately determined considering the type of acid-generating agent, etc., and therefore cannot be specified in general. However, it is generally in the range of 0.01 to 5% by mass relative to the polymer. From the viewpoint of suppressing the precipitation of the acid-generating agent in the composition, it is preferably 3% by mass or less, more preferably 1% by mass or less. From the viewpoint of fully obtaining its effect, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0422] It should be noted that one or more acid-producing agents can be used alone or in combination. In addition, photo-acid-producing agents can be used in combination with thermal acid-producing agents.

[0423] -surfactant-

[0424] When photosensitive surface modifiers are coated onto a substrate, surfactants are effective in suppressing the formation of pinholes, streaks, etc. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, and UV-curable surfactants. More specifically, examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, and sorbitol monostearate. Nonionic surfactants and commercial products including monooleate, sorbitol trioleate, sorbitol tristearate, and other sorbitol fatty acid esters; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, and other polyoxyethylene sorbitol fatty acid esters; and more. Names: EF301, EF303, and EF352 (registered trademarks) (manufactured by Mitsubishi Microelectronics Co., Ltd. (formerly Mitsubishi 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 (スリーエムジャパン) Fluorinated surfactants such as those manufactured by AGC Corporation, and fluorinated surfactants such as Asahigard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimeike Mikaru Corporation), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), but not limited to these.

[0425] Surfactants can be used alone or in combination of two or more.

[0426] When the photosensitive surface modifier contains a surfactant, its content can typically be 0.0001 to 5% by mass relative to the polymer, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass.

[0427] -Rheology modifier-

[0428] Rheology modifiers are primarily added to improve the flowability of photosensitive surface modifiers, particularly to enhance the uniformity of film thickness and improve the filling ability of the composition into pores during the baking process. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-isobutyl adipate, di-isooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate.

[0429] When using these rheology modifiers, their addition amount is typically less than 30% by mass relative to the total film-forming component of the photosensitive surface modifier.

[0430] -Adhesive additives-

[0431] Adhesion aids are mainly added to improve the adhesion between the substrate or resist and the film (surface modified layer) formed by the photosensitive surface modifier, especially to inhibit / prevent 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 trimethylsilylimidazolium; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; and benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, as well as urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea.

[0432] When using these adhesive aids, the amount added is typically less than 5% by mass relative to the film-forming component of the photosensitive surface modifier, preferably less than 2% by mass.

[0433] pH adjuster-

[0434] Furthermore, examples of pH adjusters include organic acids and other acids having one or more carboxylic acid groups, which are also used as stabilizers. When using a pH adjuster, its addition amount can be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass relative to 100 parts by mass of the polymer.

[0435] -Metal oxides-

[0436] In addition, as metal oxides that can be added to photosensitive surface modifiers, examples include oxides of one or more 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), but these are not limited to these.

[0437] The concentration of the film-forming component in the photosensitive surface modifier may be, for example, 0.01–50% by mass, 0.01–30% by mass, 0.01–25% by mass, or 0.01–20% by mass relative to the total mass of the composition.

[0438] The polymer content in the film-forming component is typically 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, further preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the aforementioned additives.

[0439] Furthermore, the photosensitive surface modifier preferably has a pH of 1 to 5, and more preferably a pH of 2 to 4.

[0440] Photosensitive surface modifiers can be manufactured by mixing a polymer and a solvent, and, if necessary, other components. In this case, a solution containing the polymer (e.g., polysiloxane) can be prepared in advance, and this solution can be mixed with the solvent and other components.

[0441] In the preparation of photosensitive surface modifiers, appropriate heating can be carried out within a range that does not decompose or deteriorate the components.

[0442] The photosensitive surface modifier can be filtered during the manufacturing process or after all components have been mixed using submicron-level filters. It should be noted that there are no restrictions on the type of filter material used; filters made of materials such as polyethylene, nylon, fluoropolymer, or polyimide can be used.

[0443] <Membrane Formation Process>

[0444] The film formation process is the process of obtaining a surface-modified precursor film.

[0445] For the film formation process, after the photosensitive surface modifier is coated on the substrate, it is fired to crosslink the polymer and obtain the surface modified layer precursor.

[0446] There are no particular restrictions on the substrate, as long as it is a substrate used for manufacturing, for example, precision integrated circuit components. The materials described in the above-described laminate can be used as the substrate.

[0447] There are no particular limitations on the method of applying a photosensitive surface modifier to a substrate, and it can be carried out by a suitable coating method such as a spin coater or a coating machine.

[0448] The firing process after the photosensitive surface modifier is applied to the substrate can be carried out using heating methods such as a hot plate.

[0449] The firing conditions are appropriately selected from a firing temperature of 40℃~400℃ or 80℃~250℃ and a firing time of 0.3 minutes~60 minutes. Preferably, the firing temperature is 150℃~250℃ and the firing time is 0.5 minutes~2 minutes.

[0450] Through firing, the solvent in the photosensitive surface modifier evaporates, and the polymer crosslinks, resulting in a layered surface-modified precursor film. The crosslinking includes partial crosslinking.

[0451] The thickness of the surface-modified precursor film 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.

[0452] In the film formation process, the water contact angle of the surface-modified precursor film formed is preferably large relative to the contact angle of the substrate. The water contact angle of the surface-modified precursor film is preferably 20 degrees or more larger than the contact angle of the substrate, more preferably 30 degrees or more, and particularly preferably 40 degrees or more.

[0453] When the water contact angle of the surface-modified precursor film is greater than that of the substrate, the contact angle between the exposed and unexposed areas tends to differ in the surface-modified film after the exposure process described below. Furthermore, if the difference in contact angle between the exposed and unexposed areas is large, the upper layer tends to be selectively deposited in only one area during the selective film deposition process.

[0454] <Exposure Process>

[0455] Exposure processes, such as those used on surface-modified precursor films, create exposed and unexposed areas using a pre-defined mask. Exposure can utilize KrF excimer lasers (248 nm wavelength), ArF excimer lasers (193 nm wavelength), F2 excimer lasers (157 nm wavelength), EUV (13.5 nm wavelength), electron beams, etc.

[0456] The exposure process is preferably continued until the difference in water contact angle between the exposed and unexposed areas is 10 degrees or more, particularly preferably until the difference is 20 degrees or more, and even more preferably until the difference is 30 degrees or more. This is because if the difference in water contact angle between the exposed and unexposed areas is within the above range, a layered structure that can be easily and selectively formed in specific regions is obtained. Specifically, in the exposure process, by using 20 mJ / cm... 2 The above exposure amounts expose the surface-modified precursor film, thereby easily obtaining a surface-modified film within the aforementioned contact angle range.

[0457] <Thinning process>

[0458] The thinning process involves contacting the surface-modified film after the exposure process with a thinning solution to thin the surface-modified film, thereby obtaining a surface-modified film with a thickness of less than 5 nm. It should be noted that the thinning process can also be performed on the surface-modified precursor film after the film formation process and before the exposure process to obtain a surface-modified precursor film with a thickness of less than 5 nm, after which the above-mentioned exposure process can be performed.

[0459] If a photosensitive surface modifier containing a polymer and solvent is coated and then fired, a film with crosslinked polymer is obtained. However, it is not easy to obtain a thin film (e.g., a film thickness of less than 5 nm) without film defects such as pinholes and with uneven coating by this process alone. It is necessary to fully control the coating conditions, firing conditions, etc.

[0460] Therefore, as a manufacturing method for a laminate capable of forming a thin surface-modified layer, a thinning process can be used, which involves thinning a layer by contacting it with a thinning solution after a layer with a film thickness that is thicker than the target film thickness has been formed, thereby forming a thin surface-modified layer.

[0461] It should be noted that by cross-linking the polymer during the film formation process, excessive dissolution of the surface-modified layer in the thinning solution can be prevented during the thinning process.

[0462] In the thinning process, there are no particular limitations on the method of contacting the surface-modified film with the thinning solution, but spin coating is preferred in terms of uniform thinning and easy management of the degree of thinning with high precision. That is, the thinning process is preferably a process in which the surface-modified film is thinned by spin coating the surface-modified film with the thinning solution to obtain a surface-modified film with a thickness of 5 nm or less.

[0463] There are no particular limitations on the conditions for spin coating, including, for example, coating processes in which a thinning liquid is applied to a surface-modified film on a substrate to which a surface-modified film has been formed, and spin processes in which the substrate is rotated.

[0464] For coating processes, such as when applying a thinning solution to a surface-modified film, the substrate is not rotated or rotates at a low speed (e.g., below 1000 rpm). In a coating process, the thinning solution is brought into contact with the surface-modified film, causing components in the surface-modified film to migrate into the thinning solution.

[0465] For rotational processing, for example, rotating the substrate at a high speed (e.g., more than 1,000 rpm and less than 5,000 rpm) removes the thinning liquid from the substrate on which the surface-modified film has been formed.

[0466] By doing so, the surface-modified film becomes thinner in accordance with the components that move into the thinning solution, resulting in a surface-modified film with a thickness of less than 5 nm.

[0467] Examples of coating treatment times include, for example, 10 seconds to 2 minutes.

[0468] Examples of rotation processing times include, for instance, 5 seconds to 1 minute.

[0469] It should be noted that during rotation, for example, an axis orthogonal to the surface of the substrate is used as the axis of rotation.

[0470] For the thinning process, it is preferable that the thickness of the surface-modified film is 0.5 nm or more and 10 nm thinner than the thickness of the film before the thinning process, and more preferably 1 nm or more and 5 nm thinner.

[0471] <<Thinning Solution>>

[0472] As a thinning solution, there are no particular limitations as long as it is a liquid that can make the surface-modified film thinner by contacting the surface-modified film with the thinning solution. Examples include organic solvents, water, and alkaline aqueous solutions. One of them can be used alone or two or more can be used in combination.

[0473] Examples of organic solvents include alcohols, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic esters.

[0474] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents. Specific examples of these include the aforementioned monohydric alcohol solvents and polyhydric alcohol solvents used as solvents for hydrolysis and condensation.

[0475] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0476] Examples of monoalkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, and propylene glycol monobutyl ether.

[0477] Examples of alkylene glycol dialkyl ethers include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc.

[0478] Examples of alkylene glycol monoalkyl ether carboxylic esters include, for example, alkylene glycol monoalkyl ether acetates.

[0479] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0480] 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 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, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate. Propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl 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, methyl 3-methoxybutylacetate, methyl 3-methoxypropylacetate, methyl 3-methoxybutylacetate, methyl 3-methoxybutylpropionate, methyl 3-methoxybutylbutyrate, methyl acetoacetate, methyl methylpropyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone, etc.

[0481] Examples of alkaline aqueous solutions include, for instance, the developing solution used in photolithography processes.

[0482] Examples of alkaline aqueous solutions include, for example, inorganic alkaline aqueous solutions and organic alkaline aqueous solutions. Examples of inorganic alkaline aqueous solutions include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium phosphate aqueous solution, potassium phosphate aqueous solution, etc. Examples of organic alkaline aqueous solutions include tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, monoethanolamine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, etc.

[0483] There are no particular restrictions on the concentration of alkali in an alkaline aqueous solution.

[0484] In one embodiment of the present invention, an organic underlayer film may be disposed between the substrate and the surface-modified film in the laminate.

[0485] There are no particular restrictions on the organic underlying film used here; any material that has been conventionally used in photolithography processes to date can be selected.

[0486] By employing a scheme in which an organic underlayer film is formed on a substrate, a surface-modified film is formed thereon, and a resist film (described later) is formed thereon, substrate processing can be performed even when the pattern width of the resist film is narrowed and the resist film is thinly coated to prevent pattern collapse. For example, using a fluorine-based gas with a sufficiently fast etching rate relative to the resist film as the etching gas allows for the processing of the underlayer film; using an oxygen-based gas with a sufficiently fast etching rate relative to the underlayer film allows for the processing of the organic underlayer film; and using a fluorine-based gas with a sufficiently fast etching rate relative to the organic underlayer film as the etching gas allows for the processing of the substrate.

[0487] It should be noted that the substrates and coating methods that can be used at this time are the same as those described above.

[0488] <Selective film formation process>

[0489] The method for manufacturing the laminate of the present invention may further include a selective film-forming process.

[0490] Selective film deposition is a process in which the upper layer is preferentially formed in either the exposed or unexposed area.

[0491] Examples of upper layers include, for instance, metal oxide films.

[0492] Selective film deposition processes can be performed by using any of the following methods to form the top layer: vacuum evaporation, CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition), and MLD (Molecular Layer Deposition). ALD is suitable for applications requiring excellent high-gradient coverage.

[0493] When using the ALD method as a selective film formation process, it is preferable to use at least two gases to form the upper layer. Specifically, regarding the steps of (1) introducing the first gas (precursor) into the film formation apparatus, (2) purging the apparatus, (3) introducing the second gas, and (4) purging the apparatus, these four steps can be repeated as one cycle to form the upper layer. Alternatively, a plasma treatment step can be performed after steps (2) and (4).

[0494] The first gas (precursor) can be organometallic compounds, metal halides, metal oxide halides, etc. For example, known halogens, alkyl compounds, alkoxides, alkylamides, diketonates, and other compounds can be used as precursors in the ALD process. The second gas can be a gas that decomposes the first gas or a gas that removes the ligands of the precursor of the first gas; for example, water (H₂O). The carrier gas can be helium, argon, nitrogen, etc. There are no particular restrictions on the reaction temperature for the formation of the upper layer; for example, temperatures above 100°C and below 800°C.

[0495] In the method for manufacturing the laminate of the present invention, a surface-modified film with two different regions having different surface characteristics, namely exposed and unexposed regions, is obtained through an exposure process. Therefore, for a selective film deposition process, the difference in surface characteristics between these two regions can be used to selectively form the upper layer.

[0496] For example, by modifying the surface of the exposed area with a high hydrophilicity (small water contact angle) and the unexposed area with a lower hydrophilicity (larger water contact angle) compared to the exposed area after the exposure process, a resist film is formed by ALD, thereby creating a tendency to selectively deposit a large amount of metal film on the exposed area. This makes it easier to form a metal film, etc., with the same pattern as the pattern formed on the exposed and unexposed areas of the surface-modified film, as the upper layer.

[0497] The upper layer is not particularly limited and can include metal films, oxide films, nitride films, carbide films, sulfide films, etc. As the upper layer, films containing, for example, pure elements (e.g., Si, Cu, Ta, W), oxides (e.g., SiO2, GeO2, HfO2, ZrO2, Ta2O5, TiO2, Al2O3, ZnO, SnO2, Sb2O5, B2O3, In2O3, WO3), nitrides (e.g., Si3N4, TiN, AlN, BN, GaN, NbN), carbides (e.g., SiC), sulfides (e.g., CdS, ZnS, MnS, WS2, PbS), selenides (e.g., CdSe, ZnSe), phosphides (GaP, InP), arsenides (e.g., GaAs, InAs), or mixtures thereof can be formed.

[0498] Example

[0499] The present invention is illustrated in more detail by the following synthetic examples and embodiments, but the present invention is not limited to the following embodiments.

[0500] It should be noted that, in the embodiments, the apparatus and conditions used for the analysis of the physical properties of the samples are as follows.

[0501] (1) Molecular weight determination

[0502] The molecular weight of the polysiloxane used in this invention is the molecular weight obtained by GPC analysis and converted to polystyrene.

[0503] The determination of GPC can be carried out under the following conditions, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Co., Ltd.), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate of 1.0 mL / min, and a standard sample of polystyrene (manufactured by Showa Denko Co., Ltd.).

[0504] (2) 1 H-NMR

[0505] Using JEOL nuclear magnetic resonance imaging equipment 1 The evaluation was performed using 1H-NMR (400MHz) and the solvent d6-acetone.

[0506] (3) Residual nitric acid

[0507] The amount of nitric acid remaining in the system was determined by ion chromatography.

[0508] [1] Synthesis of polymers (hydrolysis condensates)

[0509] (Synthesis example 1)

[0510] 17.76 g of (3-triethoxysilyl)propyl succinic anhydride, 16.37 g of triphenylsulfonium hydroxide, and 51.17 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 14.72 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0511] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, the ethanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0512] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0513] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1200 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 3 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.07%.

[0514]

[0515] (Synthesis example 2)

[0516] 12.89 g of 3-(trihydroxysilyl)-1-propanesulfonic acid, 20.68 g of triphenylsulfonium bicarbonate, and 50.35 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 16.08 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0517] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, water, which was a reaction byproduct, was removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0518] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0519] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1800 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 5 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.08%.

[0520]

[0521] (Synthesis example 3)

[0522] (2-(((2-hydroxy-5-(2-trimethoxysilyl)ethylcyclohexyl)oxy)carbonyl)phenylphenyliodide 37.38 g of trifluoromethanesulfonate and 56.07 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 6.54 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0523] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, methanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0524] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0525] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1500 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated atoms was 4 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.06%.

[0526]

[0527] (Synthesis Example 4)

[0528] 37.74 g of (3-((2-hydroxy-5-(2-(trimethoxysilyl)ethyl)cyclohexyl)oxy)phenyl)(4-hydroxyphenyl)(phenyl)sulfonium nonafluorobutane sulfonate and 56.60 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 5.66 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0529] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, methanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0530] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0531] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 2200 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoalkyl ether-terminated silica was 3 mol% relative to the Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.08%.

[0532]

[0533] (Synthesis Example 5)

[0534] 16.69 g of (3-triethoxysilyl)propylsuccinic anhydride and diphenyl iodide were added. 17.77 g of 2-carboxylate and 51.70 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 12.78 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0535] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, the ethanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0536] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0537] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1500 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silicon atoms was 6 mol%. Furthermore, the residual nitric acid content in the polymer solution was 0.08%.

[0538]

[0539] (Synthesis Example 6)

[0540] 12.90g of 3-(trihydroxysilyl)-1-propanesulfonic acid and diphenyl iodine 20.67 g of 2-carboxylate and 50.35 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 16.09 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0541] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, water, which was a reaction byproduct, was removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0542] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0543] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 2000 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 3 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.06%.

[0544]

[0545] (Synthesis Example 7)

[0546] 32.49 g of trifluoropropyltrimethoxysilane and 48.73 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 18.78 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0547] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, methanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0548] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0549] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1300 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 3 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.05%.

[0550]

[0551] (Synthesis Example 8)

[0552] 34.41 g of pentafluorophenyltriethoxysilane and 51.61 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 13.98 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0553] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, the ethanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0554] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0555] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is converted to 1000 for polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated atoms was 4 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.06%.

[0556]

[0557] (Synthesis Example 9)

[0558] 33.80 g of chlorophenyltriethoxysilane and 51.61 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 13.98 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0559] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, the ethanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0560] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0561] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is converted to 1000 for polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 3 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.07%.

[0562]

[0563] (Synthesis Example 10)

[0564] 33.80 g of bromophenyltriethoxysilane and 51.61 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 13.98 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0565] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, the ethanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0566] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0567] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1100 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 3 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.06%.

[0568]

[0569] (Synthesis Example 11)

[0570] 34.07 g of iodopropyltrimethoxysilane and 51.11 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 14.81 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0571] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, methanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0572] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0573] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1200 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated atoms was 4 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.06%.

[0574]

[0575] (Synthesis Example 12)

[0576] In Synthesis Example 12, iodophenylsulfonylpropyltrimethoxysilane obtained in the following synthesis example was used.

[0577] <Example of raw material synthesis>

[0578] In a 200 mL round-bottom flask, 14.4 g (0.048 mol) of 4-iodobenzene-1-sulfonyl chloride, 9.0 g (0.072 mol) of sodium sulfite, 18.0 g (0.215 mol) of sodium bicarbonate, and 45.0 g of water were added and heated to 100 °C for 1 hour. Then, 50.0 g of toluene was added, and the mixture was heated to reflux. Water was recovered using Dean-Stark solvent extraction. Next, 9.5 g (0.048 mol) of 3-chloropropyltrimethoxysilane, 1.4 g (0.010 mol) of sodium iodide, and 45.0 g of N-methyl-2-pyrrolidone were added, and the mixture was heated and stirred for 3 hours while distilling off the solvent at 150 °C. After separation of the reaction mixture with toluene and water, sodium carbonate was added to the organic phase, and the mixture was stirred / filtered. Toluene was removed using an evaporator to obtain the crude product. The following compound 1, the target substance, was obtained in 36% yield by vacuum distillation of the crude product.

[0579] 1 H-NMR (500MHz, CDCl3): 0.70ppm (t, 2H), 1.82ppm (m, 2H), 3.12ppm (t, 2H), 3.53ppm (s, 9H), 7.61ppm (d, 2H), 7.93ppm (d, 2H)

[0580] Me represents methyl.

[0581] 35.80 g of iodophenylsulfonylpropyltrimethoxysilane and 53.70 g of propylene glycol monoethyl ether obtained in the above synthesis example were added to a 300 mL flask. While stirring the resulting mixture with an electromagnetic stirrer, 10.49 g of 0.1 M nitric acid aqueous solution was added dropwise.

[0582] After the addition, the flask was transferred to an oil bath adjusted to 100°C and allowed to react for 20 hours. Then, methanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0583] Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass based on a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0584] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is 1300 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monoethyl ether-terminated silica was 4 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.05%.

[0585]

[0586] (Comparative Synthesis Example 1)

[0587] 32.20 g of tetraethoxysilane and 48.3 g of propylene glycol monoethyl ether were added to a 300 mL flask. While stirring the mixture with an electromagnetic stirrer, 19.5 g of 0.1 mol / L nitric acid aqueous solution was added dropwise.

[0588] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the ethanol and water, which were reaction byproducts, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution.

[0589] Propylene glycol monomethyl ether was further added to the solution, and the concentration was adjusted by converting the solid residue at 140°C to 20% by mass, based on a solvent ratio of 100% propylene glycol monomethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size).

[0590] The resulting polymer comprises a polysiloxane having the structure shown in the following formula, and its weight-average molecular weight obtained by GPC is Mw 5,800 when converted to polystyrene. Furthermore, according to... 1 H-NMR showed that the amount of propylene glycol monomethyl ether-terminated silica was 9 mol% relative to the number of Si atoms. Furthermore, the residual nitric acid content in the polymer solution was 0.08%.

[0591]

[0592] [2] Preparation of the composition coated on the resist pattern

[0593] By mixing the polysiloxane (polymer), acid (additive 1), photoacid generator (additive 2), and solvent obtained in the above synthesis example in the proportions shown in Table 1, and filtering the mixture through a 0.1 μm fluoropolymer filter, compositions were prepared to be coated onto the resist pattern. The amounts of each additive in Table 1 are expressed in parts by mass.

[0594] It should be noted that although the hydrolysis condensate (polymer) was prepared into a composition in the form of a solution containing the condensate obtained in the synthesis example, the polymer addition ratio in Table 1 does not represent the amount of polymer solution added, but rather the amount of polymer itself added.

[0595] The meanings of the abbreviations in Table 1 are as follows.

[0596] <Solvent>

[0597] DIW: Ultrapure Water

[0598] PGEE: Propylene Glycol Monoethyl Ether

[0599] PGME: Propylene Glycol Monomethyl Ether

[0600] <Additive 1>

[0601] MA: Maleic acid

[0602] <Additive 2>

[0603] TPSNO3: Triphenylsulfonium nitrate

[0604] TPSML: Triphenylsulfonium maleate

[0605] TPSTfAc: Triphenylsulfonium trifluoroacetate

[0606] BTEAC: Benzyltriethylammonium chloride

[0607] TPSCl: Triphenylsulfonium chloride salt

[0608] [Table 1]

[0609] [3] Substrate surface modification test

[0610] Coating solutions 1-12 and comparative coating solution 1 were each coated onto bare-Si and bare-Si with a SiON (50nm) film, respectively. Specifically, 1ml of each of coating solutions 1-12 and comparative coating solution 1 was coated onto the wafer using CLEANTRACK ACT8 (Tokyo Electron), and spin-coated at 1500rpm for 60 seconds, followed by firing at 215°C (120°C for comparative coating solution 1). Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was coated onto each surface-modified film and spin-dried to form a photosensitive surface-modified film with a thickness of 30Å (3nm). The water contact angle was then measured on the substrates with the photosensitive surface-modified films of coating solutions 1-12 and comparative coating solution 1. The water contact angle was measured in a constant temperature and humidity environment (23℃±2℃, 45%RH±5%) using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). The water volume was 3 μl, and the measurement was taken after the solution had been in contact with the solution and allowed to stand for 5 seconds. This process was repeated 5 times, and the average contact angle was calculated. The water contact angles of bare Si and SiON (50nm) were both below 20 degrees. Therefore, a water contact angle less than 30 degrees was defined as not suitable for surface modification and thus "poor," while a water contact angle greater than 30 degrees was defined as suitable for surface modification and thus "good." The measurement results are recorded in Table 2 below.

[0611] [Table 2]

[0612] As shown above, in Examples 1-12, the water contact angle of the substrate with the SiON film is greater than that of the bare Si substrate by the surface modification film, which is 30 degrees or more. Compared with the substrate before the surface modification film is formed, the substrate has a low hydrophilicity (high hydrophobicity) surface state.

[0613] [4] Formation of hydrophilic films exposed by ArF

[0614] Compositions obtained from coating solutions 1-12 and comparative coating solution 1 were spin-coated onto bare Si substrates. The substrates were heated at any temperature for 1 minute, and then each coated film was coated with a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) and spin-dried to form surface-modified films (1-3 nm) with a thickness of less than 30 Å. The entire wafer surface was further exposed using a Nikon ArF exposure apparatus (S307E).

[0615] Then, the water contact angle was measured and compared with the water contact angle before ArF exposure. Cases where surface modification of more than 20 degrees could not be performed (contact angle not reduced by more than 20 degrees) were marked as "poor", and cases where surface modification of more than 20 degrees could be performed (contact angle reduced by more than 20 degrees) were marked as "good". The measurement results are recorded in Table 3 below.

[0616] [Table 3]

[0617] [5] Formation of hydrophilic films using EUV exposure

[0618] Compositions obtained from coating solutions 2, 8, 12, and comparative coating solution 1 were spin-coated onto bare Si substrates and heated at an arbitrary temperature for 1 minute. Then, each coated film was coated with a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) and spin-dried to form surface-modified films (1–3 nm) with a thickness of less than 30 Å. The entire wafer surface was further exposed using an ASML NXE3400B.

[0619] Then, the water contact angle was measured and compared with the water contact angle before ArF exposure. Cases where surface modification of more than 20 degrees could not be performed were marked as "poor," and cases where surface modification of more than 20 degrees could be performed were marked as "good." The measurement results are recorded in Table 4 below.

[0620] [Table 4]

[0621] As shown above, for the surface-modified films with a contact angle of 30 degrees or more in Examples 1-12, if exposed by ArF and EUV in Examples 13-27, the contact angle of the exposed areas is reduced by more than 20 degrees. That is, different surface properties with varying hydrophilicity are observed in the cases where exposure by ArF and EUV is performed and in the cases where exposure by ArF and EUV is performed.

[0622] Therefore, according to various embodiments, a surface-modified film is obtained that exhibits a hydrophilic-hydrophobic contrast through exposure to ArF, EUV, etc., and has regions with different hydrophilicity depending on the presence or absence of exposure. Therefore, on the substrate surface exhibiting a hydrophilic-hydrophobic contrast, metal atoms and organic molecules can be selectively deposited only on the hydrophilized surface using atomic layer deposition or molecular layer deposition, etc., to obtain a patterned substrate.

Claims

1. A laminate having a substrate and a surface modification film formed from a photosensitive surface modifier containing a photosensitive polymer, and irradiated with light or an electron beam, the surface modification film has an exposed region irradiated with the light or the electron beam, and an unexposed region, either of the exposed region and the unexposed region is a selective upper layer formation region selectively forming an upper layer.

2. The laminate according to claim 1, wherein the photosensitive polymer is a polysiloxane.

3. The laminate according to claim 2, wherein the polysiloxane contains a polysiloxane modifier in which at least a part of silanol groups is modified with an alcohol or protected with an acetal.

4. The laminate according to claim 2, the polysiloxane containing at least one structure selected from the group consisting of a hydrocarbon group having 1 to 8 carbon atoms which can be substituted with a halogen atom, an aromatic ring having 6 to 30 carbon atoms which can be substituted with a halogen atom, an alkenyl group, an alkynyl group, a norbornene ring, a phenolic group, a protected phenolic group, an amino group, an amido group, a cyclic amido group, an imido group, a cyclic imido group, a sulfonyl group, a sulfonamide group, a nitro group, a cyano group, a thiocyanate group, an isocyanate group, a halide group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, a sulfonic acid ester group, a phosphoric acid group, a phosphoric acid ester group, an ammonium group, a sulfonium group, an epoxy group, a glycidyl group, a cyclohexene epoxy group, an opened epoxy group, an opened glycidyl group, an opened cyclohexene epoxy group, a hydroxyl group, a mercapto group, an acryloyloxy group, and a methacryloyloxy group.

5. The laminate according to claim 2, wherein the polysiloxane contains a group bonded to a silicon atom and having an ionic bond.

6. The 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 sulfonate anion, a carboxylate anion or a phosphate anion, the cation is a sulfonium cation, an iodonium cation, cation, a dihydroimidazolium cation or an ammonium cation.

7. The 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 iodonium cation cationic group, cationic group, a dihydroimidazolium cation or an ammonium cation, the anion is a sulfonate anion, a carboxylate anion or a phosphate anion.

8. The laminate according to claim 2, wherein the polysiloxane contains a Q unit.

9. The laminate according to claim 1, wherein the substrate is composed of a material containing an inorganic substance or an organic substance.

10. The laminate according to claim 1, wherein the substrate has a film composed of a material containing an inorganic substance or an organic substance.

11. The laminate according to claim 9 or 10, wherein the inorganic substance is at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxycarbide and a metal carbonitride.

12. The laminate according to claim 9 or 10, wherein the organic substance is at least one selected from the group consisting of amorphous carbon, graphite, fullerene, a carbon nanotube, diamond, diamond-like carbon, polyimide and an organic film which is doped or partially replaced with boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen.

13. A method for producing the laminate according to any one of claims 1 to 10, comprising the following steps: a film formation step of forming a surface modification precursor film on the substrate by the photosensitive surface modifier containing the photosensitive polymer and a solvent; and an exposure step of forming the surface modification film having the exposed region and the unexposed region by irradiating the surface modification precursor film with the light or the electron beam.

14. The method for producing the laminate according to claim 13, wherein the laminate further has a resist underlayer film containing silicon or a resist underlayer film containing carbon.

15. The method for producing the laminate according to claim 13, wherein the surface modification film has a film thickness of 5 nm or less.

16. The method for producing the laminate according to claim 15, further comprising a thinning step of bringing the surface modification film into contact with a thinning solution to make the film thickness of the surface modification film 5 nm or less.

17. The method for manufacturing a laminate according to claim 16, wherein the thinning solution is at least one selected from the group consisting of an organic solvent, water, and an alkaline aqueous solution.

18. The method for manufacturing a laminate according to claim 16, wherein the thinning process is a process of thinning the surface modification film by spin coating a thinning solution on the surface modification film to obtain a surface modification film having a film thickness of 5 nm or less.

19. The method for manufacturing a laminate according to claim 13, further comprising a selective film forming process of preferentially forming an upper layer in either of the exposed region and the unexposed region.

20. The method for manufacturing a laminate according to claim 19, wherein the selective film forming process is a process of forming an upper layer by any one of vacuum evaporation, chemical vapor deposition (CVD), atomic layer deposition (ALD), and molecular layer deposition (MLD).

21. A photosensitive surface modifier containing the photosensitive polymer and a solvent, which is a forming material of the surface modification film of the laminate according to any one of claims 1 to 10.

22. The photosensitive surface modifier according to claim 21, wherein the solvent contains at least one selected from the group consisting of alcohols, alkylene glycol alkyl ether, alkylene glycol monoalkyl ether carboxylate, and water.

23. The photosensitive surface modifier according to claim 21, which contains an acid.

24. The photosensitive surface modifier according to claim 21, which contains an acid generator. ​

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