Silicon-containing resist underlayer film-forming composition

Abstract

The present invention provides a resist underlayer film and a composition for forming the same, which form an excellent resist pattern shape when an upper layer resist is exposed and developed using an alkaline developer, an organic solvent. The solution to the present invention is a lithography resist underlayer film forming composition containing an aliphatic polycyclic structure, which includes a hydrolyzable silane, a hydrolyzate thereof, a hydrolysis condensate thereof, or a combination thereof as a silane, and the aliphatic polycyclic structure is a hydrolyzable silane having a structure represented by Formula (1) (in Formula (1), R 1 is an organic group containing an aliphatic polycyclic structure and bonded to a Si atom through a Si-C bond. R 3 represents an ethoxy group. a represents 1, b represents an integer from 0 to 2, and a+b represents an integer from 1 to 3.) or a structure contained in a compound added in the form of an aliphatic polycyclic compound, an aliphatic polycyclic dicarboxylic acid, or an aliphatic polycyclic dicarboxylic anhydride, which can have a double bond, a hydroxyl group, or an epoxy group.

Description

[0001] This application is a divisional application of the patent application filed on July 10, 2015, with application number 201580038119.0 and entitled "Composition for forming a silicon-containing photoresist underlayer film having an organic group containing an aliphatic polycyclic structure". Technical Field

[0002] This invention relates to a composition for forming a lower layer film between a substrate and a resist (e.g., photoresist, electron beam resist) used in the manufacture of semiconductor devices. More specifically, it relates to a photolithography resist lower layer film forming composition for forming a lower layer film used beneath a photoresist during the photolithography process of manufacturing semiconductor devices. Furthermore, it relates to a method for forming a resist pattern using the lower layer film forming composition. Background Technology

[0003] Traditionally, semiconductor device manufacturing has relied on photolithography, which uses photoresist, for microfabrication. This microfabrication involves forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet light through a mask pattern depicting a semiconductor device, developing the photoresist pattern, and then etching the substrate using the resulting photoresist pattern as a protective film. This process creates micro-unfolds corresponding to the aforementioned pattern on the substrate surface. However, in recent years, with the increasing integration of semiconductor devices, the active light used has tended towards shorter wavelengths, such as KrF excimer lasers (wavelength 248 nm) and ArF excimer lasers (wavelength 193 nm). Consequently, the reflection of this active light from the semiconductor substrate has become a significant problem.

[0004] Furthermore, as the lower layer film between the semiconductor substrate and the photoresist, films known as hard masks containing metallic elements such as silicon and titanium are currently being used. In this case, the composition of the photoresist and the hard mask differs significantly, therefore the rate at which they are removed by dry etching largely depends on the type of gas used in the dry etching process. Moreover, by appropriately selecting the type of gas, the hard mask can be removed by dry etching without a substantial reduction in the thickness of the photoresist film. Thus, in recent years, in the manufacture of semiconductor devices, photoresist lower layers have been placed between the semiconductor substrate and the photoresist to achieve various effects, such as anti-reflection effects. Furthermore, while research on compositions for photoresist lower layers has been ongoing, the diverse range of required properties necessitates the development of new materials for photoresist lower layers.

[0005] An invention is described as a composition for forming a lower layer film of a silicon-containing photoresist, comprising a polysiloxane having an organic group having a hydroxyl or carboxylic acid group, the organic group having an aliphatic polycyclic structure such as norbornene (see Patent Document 1).

[0006] An invention is described as a composition for forming a silicon-containing photoresist underlayer film, comprising a polysiloxane having an organic group having a hydroxyl or carboxylic acid group substituted with an acid-instable group, the organic group having an aliphatic polycyclic structure such as norbornene (see Patent Document 2).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2013-166812

[0010] Patent Document 2: Japanese Patent Application Publication No. 2013-167669 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] The object of the present invention is to provide a composition for forming a photoresist underlayer film for photolithography, which can be used in the manufacture of semiconductor devices. More specifically, the object of the present invention is to provide a composition for forming a photoresist underlayer film for photolithography that can be used as a hard mask. Furthermore, the object of the present invention is to provide a composition for forming a photoresist underlayer film for photolithography that can be used as an anti-reflective film. Additionally, the object of the present invention is to provide a photoresist underlayer film for photolithography that does not cause mixing with the photoresist, has a dry etching rate higher than that of the photoresist, and a composition for forming the photoresist underlayer film for forming such an underlayer film.

[0013] In particular, the present invention aims to provide a composition for forming a photoresist underlayer film, wherein the photoresist underlayer film can form an excellent photoresist pattern shape when an upper photoresist layer is exposed and developed using an alkaline developer or an organic solvent, and a rectangular photoresist pattern can be transferred to the underlayer by subsequent dry etching.

[0014] Methods for solving problems

[0015] Regarding the present invention, as a first point of view, there is a composition for forming a photoresist underlayer film, which contains an aliphatic polycyclic structure. The composition comprises a hydrolyzable silane as a silane, its hydrolysate, its hydrolysate condensate, or a combination thereof. The aliphatic polycyclic structure is a structure possessed by the hydrolyzable silane of formula (1), or a structure contained in a compound added in the form of an aliphatic polycyclic compound that may have double bonds, hydroxyl groups, or epoxy groups, an aliphatic polycyclic dicarboxylic acid, or an aliphatic polycyclic dicarboxylic anhydride.

[0016] (In equation (1), R) 1 It is an organic group containing an aliphatic polycyclic structure and bonded to Si atoms through Si-C bonds; R 2 It is an alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, or an organic group having an epoxy, acryloyl, methacryloyl, mercapto, amino, or cyano group, and is bonded to a silicon atom via a Si-C bond; R 3 It represents ethoxy; a represents 1, b represents an integer from 0 to 2, and a+b represents an integer from 1 to 3. As a second point of view, it is the composition for forming a resist underlayer film according to the first point of view, wherein R in formula (1) 1 It is a substituted norbornene, a substituted norbornane, a cyclic aliphatic group containing heteroatoms, or an organic group containing them. As a third point of view, it is the composition for forming a resist underlayer film according to the second point of view, R of formula (1) 1 The substituents are carboxyl, carboxylic anhydride, carboxylic ester, hydroxyl, alkoxy, or oxygen atoms. As a fourth point of view, the composition for forming the lower layer film of the resist according to the first or second point of view is wherein the hydrolyzable silane is a combination of the hydrolyzable silane represented by formula (1) and other hydrolyzable silanes, wherein the other hydrolyzable silanes are at least one hydrolyzable silane selected from formulas (2) and (3).

[0017] (In equation (2), R) 4 It is an alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, or organic group having an epoxy, acryloyl, methacryloyl, mercapto, or cyano group, and is bonded to a silicon atom via a Si-C bond. 5 (This indicates an alkoxy, acyloxy, or halogen group, with c representing an integer from 0 to 3.)

[0018] (In equation (3), R) 6 It is an alkyl group and is bonded to silicon atoms via Si-C bonds, R7 (This indicates an alkoxy, acyloxy, or halogen group; Y indicates an alkylene or arylene group; d indicates 0 or 1; e indicates 0 or 1.) As a fifth point of view, there is a composition for forming a resist underlayer film, which contains, in polymer form, a hydrolytic condensate of a hydrolyzable silane, wherein the hydrolyzable silane comprises a combination of the hydrolyzable silane represented by formula (1) described in the first point of view and the hydrolyzable silane represented by formula (2) described in the fourth point of view. As a sixth point of view, it is a composition for forming a resist underlayer film according to any one of the first to fifth points of view, which further comprises an acid as a hydrolysis catalyst. As the seventh point of view, it is a composition for forming a resist underlayer film according to any one of the first to sixth points of view, further comprising water. As the eighth point of view, there is a photoresist underlayer film, which is obtained by coating a photoresist underlayer film forming composition according to any one of the first to seventh points onto a semiconductor substrate and then firing it. As a ninth perspective, there is a method for manufacturing a semiconductor device, comprising the following steps: coating a resist underlayer film forming composition as described in any one of the first to seventh perspectives onto a semiconductor substrate and firing it to form a resist underlayer film; coating the resist composition onto the underlayer film to form a resist film; exposing the resist film; developing the resist film after exposure to obtain a resist pattern; etching the resist underlayer film using the resist pattern; and processing the semiconductor substrate using the patterned resist and the resist underlayer film. As a tenth perspective, there is a method for manufacturing a semiconductor device, comprising the following steps: forming an organic underlayer film on a semiconductor substrate; coating a resist underlayer film forming composition as described in any one of the first to seventh perspectives onto the substrate and firing it to form a resist underlayer film; coating a resist composition onto the resist underlayer film to form a resist film; exposing the resist film; developing the resist film after exposure to obtain a resist pattern; etching the resist underlayer film using the resist pattern; etching an organic underlayer film using the patterned resist underlayer film; and processing a semiconductor substrate using the patterned organic underlayer film.

[0019] Invention Effects

[0020] The resist underlayer film forming composition of the present invention, by having the configuration shown above, results in less variation in film thickness after coating, and the resulting resist underlayer film exhibits high stability.

[0021] In this invention, a photoresist underlayer film is formed on a substrate by coating, or a photoresist underlayer film is formed on an organic underlayer film on the substrate by coating, and a photoresist film (e.g., photoresist, electron beam photoresist) is formed on the photoresist underlayer film. Then, a photoresist pattern is formed by exposure and development, and the photoresist pattern is used to dry etch the photoresist underlayer film to transfer the pattern, and the pattern is used to process the substrate; or the pattern is transferred by etching the organic underlayer film, and the organic underlayer film is used to process the substrate.

[0022] To prevent pattern collapse, the resist film thickness tends to decrease as fine patterns are formed. Due to the thinning of the resist, the dry etching used to transfer the pattern to the underlying film must be faster than the etching rate of the upper film to achieve pattern transfer. In this invention, the process involves coating a substrate with a resist underlayer film (containing an inorganic silicon-based compound) using the composition of this invention (either via an organic underlayer film or without an organic underlayer film), followed by coating a resist film (organic resist film) on top of the resist underlayer film. The dry etching rates of organic and inorganic films differ significantly depending on the choice of etching gas; organic films using oxygen-based gases exhibit higher dry etching rates, while inorganic films using halogen-containing gases exhibit higher dry etching rates.

[0023] For example, a resist underlayer film formed using the composition of the present invention, on which a resist pattern is formed and located beneath the resist layer, is dry-etched using a halogen-containing gas to transfer the pattern onto the resist underlayer film. The substrate is then processed using the pattern transferred onto the resist underlayer film and a halogen-containing gas. Alternatively, using a patterned resist underlayer film, an organic underlayer film beneath it is dry-etched using an oxygen-based gas to transfer the pattern onto the organic underlayer film. The substrate is then processed using the patterned organic underlayer film and a halogen-containing gas.

[0024] In this invention, the photoresist underlayer film functions as a hard mask. In any photolithography process or development process, the acidity of the underlayer film needs to be adjusted to control the shape of the photoresist.

[0025] In particular, the silicon-containing photoresist underlayer film containing organic groups with norbornene or norbornene skeletons can form ultra-fine patterns and exhibit good adhesion at various exposure wavelengths of ArF, EUV, and EB. Detailed Implementation

[0026] The present invention is a composition for forming a photoresist underlayer containing an aliphatic polycyclic structure, comprising a hydrolyzable silane as a silane, its hydrolysate, its hydrolysate condensate, or a combination thereof. Regarding the aliphatic polycyclic structure, the hydrolyzable silane shown in formula (1) has an aliphatic polycyclic structure, or is added in the form of an aliphatic polycyclic compound having a double bond, hydroxyl group, or epoxy group, an aliphatic polycyclic dicarboxylic acid, or an aliphatic polycyclic dicarboxylic anhydride.

[0027] In equation (1), R 1 It is an organic group containing an aliphatic polycyclic structure and bonded to Si atoms through Si-C bonds. R 2 It is an alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, or an organic group having an epoxy, acryloyl, methacryloyl, mercapto, amino, or cyano group, and is bonded to a silicon atom via a Si-C bond. 3 It represents ethoxy. a represents 1, b represents an integer from 0 to 2, and a+b represents an integer from 1 to 3.

[0028] As R 1 Among organic groups containing aliphatic polycyclic structures and bonded to Si atoms through Si-C bonds, examples of aliphatic polycyclic structures include adamantane rings and norbornene rings.

[0029] R in equation (1) 1 Preferably, it is a substituted norbornene, a substituted norbornane, an aliphatic polycyclic group containing a heteroatom, or an organic group containing them. Regarding these organic groups containing norbornene or norbornane, the norbornene ring or norbornane ring can be directly bonded to the Si atom or bonded to the Si atom via an alkylene group or the like. Examples of alkylene groups include those derived from the alkyl groups exemplified below.

[0030] R in equation (1) 1 The substituents can be, for example, carboxyl, carboxylic anhydride, carboxylic ester, hydroxyl, alkoxy, or oxygen atoms.

[0031] Of all silanes, the silane represented by formula (1) may be used in the range of less than 50 mol%, or 0.05 to 50 mol%, 0.1 to 50 mol%, or 0.1 to 40 mol%.

[0032] The resist underlayer film forming composition of the present invention comprises a hydrolyzable silane represented by formula (1), or a hydrolyzable silane represented by formula (1) and other hydrolyzable silanes (e.g., a hydrolyzable silane represented by formula (2)), its hydrolysate, or its hydrolyzed condensate, and a solvent. Furthermore, as optional components, it may contain acids, water, alcohols, curing catalysts, acid-generating agents, other organic polymers, light-absorbing compounds, and surfactants.

[0033] The solid component in the resist underlayer film forming composition of the present invention is, for example, 0.1 to 50% by mass, or 0.1 to 30% by mass, or 0.1 to 25% by mass. Here, the solid component refers to the component remaining after removing the solvent component from all components of the resist underlayer film forming composition.

[0034] In the solid component, the proportion of hydrolyzable silane, its hydrolysate, and its hydrolyzable condensate is more than 20% by mass, for example, 50-100% by mass, 60-99% by mass, and 70-99% by mass.

[0035] Furthermore, the aforementioned hydrolyzable silanes, their hydrolysates, and their hydrolysis condensates can also be used in the form of mixtures thereof. They can also be used as condensates obtained by hydrolyzing the hydrolyzable silane and condensing the resulting hydrolysates. They can also be used as mixtures obtained by partially hydrolyzing hydrolysates that were not completely hydrolyzed during the process of obtaining the hydrolysis condensate, or by mixing silane compounds into the hydrolysis condensate. The condensate is a polymer having a polysiloxane structure. The polysiloxane contains the hydrolyzable silane represented by formula (1), or a hydrolysis condensate of the hydrolyzable silane represented by formula (1) with other hydrolyzable silanes (e.g., the hydrolyzable silane represented by formula (2)). In addition, a hydrolytic condensate of a hydrolytic silane containing a combination of a hydrolytic silane containing ...

[0036] The aforementioned alkyl groups are straight-chain or branched alkyl groups with 1 to 10 carbon atoms, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-propyl, etc. 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.

[0037] In addition, cyclic alkyl groups can also be used, for example, cyclic alkyl groups with 1 to 10 carbon atoms, such as 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 The compounds include 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-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, etc.

[0038] Alkenyl groups are alkenyl groups with 2 to 10 carbon atoms, and examples 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, 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, etc.

[0039] Aryl groups include those with 6 to 20 carbon atoms, such as phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl.

[0040] Examples of organic groups containing epoxy groups include epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, and epoxycyclohexyl.

[0041] Examples of organic groups containing an acryloyl group include acryloylmethyl, acryloylethyl, and acryloylpropyl.

[0042] Examples of organic groups containing a methacryloyl group include methacryloylmethyl, methacryloylethyl, and methacryloylpropyl.

[0043] Examples of organic groups containing a thiol group include ethyl thiol, butyl thiol, hexyl thiol, and octyl thiol.

[0044] Examples of organic groups containing a cyano group include cyanoethyl and cyanopropyl.

[0045] Examples of alkoxy groups having 1 to 20 carbon atoms include those having a straight-chain, branched, or cyclic alkyl moiety with 1 to 20 carbon atoms, such as 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, and 2-methyl-n-pentoxy. Oxide groups include 3-methyl-n-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. Furthermore, cyclopropoxy groups can be cited as cyclic alkoxy groups. 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, 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.

[0046] Examples of acyloxy groups with 2 to 20 carbon atoms include 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-pentyl Carbonyloxy, 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 p-toluenesulfonylcarbonyloxy, etc.

[0047] Examples of halogen groups include fluorine, chlorine, bromine, and iodine.

[0048] The hydrolyzable silane represented by formula (1) can be exemplified as follows.

[0049]

[0050] In the above formula, T represents ethyl.

[0051]

[0052] The T in the above refers to an alkyl group having 1 to 10 carbon atoms. For example, it represents methyl, ethyl, etc.

[0053] In this invention, the hydrolyzable silane is a combination of the hydrolyzable silane represented by formula (1) and other hydrolyzable silanes, and the other hydrolyzable silanes may be at least one hydrolyzable silane selected from formulas (2) and (3).

[0054] In equation (2), R 4 It is an alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, or organic group having an epoxy, acryloyl, methacryloyl, mercapto, or cyano group, and is bonded to a silicon atom via a Si-C bond. 5 It represents an alkoxy, acyloxy, or halogen group, and c represents an integer from 0 to 3.

[0055] In equation (3), R 6 It is an alkyl group and is bonded to silicon atoms via Si-C bonds, R 7 The symbol represents an alkoxy, acyloxy, or halogen group; Y represents an alkylene or arylene group; d represents 0 or 1; and e represents 0 or 1.

[0056] The above-mentioned alkyl, aryl, haloalkyl, haloaryl, alkenyl, or organic groups having epoxy, acryloyl, methacryloyl, mercapto, or cyano groups, alkoxy, acyloxy, or halogen groups may be used in the examples described above.

[0057] Examples of silicon-containing compounds represented by formula (2) include, for instance, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethoxysilane, epoxypropoxymethyltrimethoxysilane, epoxypropoxymethyltriethoxysilane, α-epoxypropoxyethyltrimethoxysilane, α-epoxypropoxyethyltriethoxysilane, β-epoxypropoxyethyltrimethoxysilane, etc. oxysilanes, β-glycidoxypropyltriethoxysilane, 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-glycidoxypropyltriethoxysilane β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, δ-epoxypropoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, 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, epoxypropoxymethylmethyldimethoxysilane, epoxypropoxymethylmethyldiethoxysilane, α-epoxypropoxyethylmethyldimethoxysilane, α-epoxypropoxyethylmethyldiethoxysilane, β-epoxypropoxyethylmethyldimethoxysilane, β-epoxypropoxyethylethyldimethoxysilane, α-epoxypropoxypropylmethyldimethoxysilane, α-epoxypropoxypropylmethyldiethoxysilane, β-epoxypropoxypropylmethyldimethoxysilane, β-epoxypropoxypropylethyldimethoxysilane, γ-epoxypropoxypropylmethyldimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, γ-epoxypropoxypropylmethyldipropoxysilaneγ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane , Methoxybenzyltriacetoxysilane, Methoxybenzyltrichlorosilane, Methoxyphenylethyltrimethoxysilane, Methoxyphenylethyltriethoxysilane, Methoxyphenylethyltriacetoxysilane, Methoxyphenylethyltrichlorosilane, Ethoxyphenyltrimethoxysilane, Ethoxyphenyltriethoxysilane, Ethoxyphenyltriacetoxysilane, Ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, Isopropoxyphenyltrimethoxysilane, Isopropoxyphenyltriethoxysilane, Isopropoxyphenyltriacetoxysilane, Isopropoxyphenyltrichlorosilane, Isopropoxybenzyltrimethoxysilane, Isopropoxybenzyltriethoxysilane, Isopropoxybenzyltriethoxysilane, Isopropoxybenzyltrimethoxysilane, Isopropoxybenzyltriethoxysilane, Isopropoxy γ-chloropropyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane Acyloxysilanes, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane,Methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc.

[0058] In addition, the following hydrolyzable silanes can also be used.

[0059]

[0060] Examples of silicon-containing compounds represented by formula (3) include, for example, methylene bis(trimethoxysilane), methylene bis(trichlorosilane), methylene bis(triacetoxysilane), ethyl bis(triethoxysilane), ethyl bis(trichlorosilane), ethyl bis(triacetoxysilane), propyl bis(triethoxysilane), butyl bis(trimethoxysilane), phenyl bis(trimethoxysilane), phenyl bis(triethoxysilane), phenyl bis(methyl)ethoxysilane, phenyl bis(methyl)methoxysilane, naphthyl bis(trimethoxysilane), bis(trimethoxy)silane, bis(triethoxy)silane, bis(ethyl)ethoxysilane, and bis(methyl)methoxysilane.

[0061] As a specific example of the hydrolytic condensate (polysiloxane) used in this invention, the following examples can be cited.

[0062]

[0063] The hydrolytic condensates (polyorganosiloxanes) of the aforementioned hydrolyzable silanes can yield condensates with a weight-average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000. These molecular weights were obtained by conversion from polystyrene using GPC analysis.

[0064] The determination conditions for GPC were as follows: a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Corporation), a GPC column (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko), a column temperature of 40°C, a tetrahydrofuran eluent, a flow rate of 1.0 ml / min, and polystyrene (manufactured by Showa Denko Corporation) as the standard sample.

[0065] The hydrolysis of alkoxysilyl, acylsilyl, or halosilyl groups uses 0.5 to 100 moles of water, preferably 1 to 10 moles, relative to 1 mole of the hydrolyzable group.

[0066] In addition, a hydrolysis catalyst can be used in an amount of 0.001 to 10 moles, preferably 0.001 to 1 mole, relative to 1 mole of the hydrolyzable group.

[0067] The reaction temperature for hydrolysis and condensation is usually 20~80℃.

[0068] Hydrolysis can occur completely or partially. That is, hydrolysates and monomers may remain in the hydrolysate condensate.

[0069] A catalyst can be used when hydrolyzing and condensing it.

[0070] Examples of hydrolysis catalysts include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0071] Examples of metal chelate compounds that can serve as hydrolysis catalysts include triethoxy compounds. Mono(acetylacetone)titanium, tri-n-propoxy Mono(acetylacetone)titanium, triisopropoxy Mono(acetylacetone)titanium, tri-n-butoxy Mono(acetylacetone)titanium, trisec-butoxy Mono(acetylacetone)titanium, tritert-butoxy Mono(acetylacetone)titanium, diethoxy bis(acetylacetone)titanium, di-n-propoxy bis(acetylacetone)titanium, diisopropoxy bis(acetylacetone)titanium, di-n-butoxy bis(acetylacetone)titanium, disec-butoxy bis(acetylacetone)titanium, di-tert-butoxy bis(acetylacetone)titanium, monoethoxy Tri(acetylacetone)titanium, mono-n-propoxy Tri(acetylacetone)titanium, monoisopropoxy Tri(acetylacetone)titanium, mono-n-butoxy Tri(acetylacetone)titanium, monosec-butoxy Tri(acetylacetone)titanium, monotert-butoxy Tri(acetylacetone)titanium, Tetra(acetylacetone)titanium, Triethoxy Mono(ethyl acetoacetate)titanium, tri-n-propoxy Mono(ethyl acetoacetate)titanium, triisopropoxy Mono(ethyl acetoacetate)titanium, tri-n-butoxy Mono(ethyl acetoacetate)titanium, trisec-butoxy Mono(ethyl acetoacetate)titanium, tritert-butoxy Mono(ethyl acetoacetate)titanium, diethoxy bis(ethyl acetoacetate)titanium, di-n-propoxy bis(ethyl acetoacetate)titanium, diisopropoxy bis(ethyl acetoacetate)titanium, di-n-butoxy bis(ethyl acetoacetate)titanium, disec-butoxy bis(ethyl acetoacetate)titanium, di-tert-butoxy bis(ethyl acetoacetate)titanium, monoethoxy Tri(ethyl acetoacetate)titanium, mono-n-propoxy Tri(ethyl acetoacetate)titanium, monoisopropoxy Tri(ethyl acetoacetate)titanium, mono-n-butoxy Tri(ethyl acetoacetate)titanium, monosec-butoxy Tri(ethyl acetoacetate)titanium, monotert-butoxy Titanium chelate compounds 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)mono(ethyl acetoacetate)titanium; triethoxy Mono(acetylacetone)zirconium, tri-n-propoxy Mono(acetylacetone)zirconium, triisopropoxy Mono(acetylacetone)zirconium, tri-n-butoxy Mono(acetylacetone)zirconium, trisec-butoxy Mono(acetylacetone)zirconium, tritert-butoxy Mono(acetylacetone)zirconium, diethoxy bis(acetylacetone)zirconium, di-n-propoxy bis(acetylacetone)zirconium, diisopropoxy bis(acetylacetone)zirconium, di-n-butoxy bis(acetylacetone)zirconium, disec-butoxy bis(acetylacetone)zirconium, di-tert-butoxy bis(acetylacetone)zirconium, monoethoxy Tri(acetylacetone)zirconium, mono-n-propoxy Tri(acetylacetone)zirconium, monoisopropoxy Tri(acetylacetone)zirconium, mono-n-butoxy Tri(acetylacetone)zirconium, monosec-butoxy Tri(acetylacetone)zirconium, monotert-butoxy Tri-(acetylacetone)zirconium, Tetra-(acetylacetone)zirconium, Triethoxy Mono(ethyl acetoacetate) zirconium, tri-n-propoxy Mono(ethyl acetoacetate)zirconium, triisopropoxy Mono(ethyl acetoacetate) zirconium, tri-n-butoxy Mono(ethyl acetoacetate) zirconium, trisec-butoxy Mono(ethyl acetoacetate)zirconium, tritert-butoxy Mono(ethyl acetoacetate)zirconium, diethoxy bis(ethyl acetoacetate)zirconium, di-n-propoxy bis(ethyl acetoacetate)zirconium, diisopropoxy bis(ethyl acetoacetate)zirconium, di-n-butoxy bis(ethyl acetoacetate)zirconium, disec-butoxy bis(ethyl acetoacetate)zirconium, di-tert-butoxy bis(ethyl acetoacetate)zirconium, monoethoxy Tri(ethyl acetoacetate)zirconium, mono-n-propoxy Tri(ethyl acetoacetate)zirconium, monoisopropoxy Tri(ethyl acetoacetate)zirconium, mono-n-butoxy Tri(ethyl acetoacetate)zirconium, monosec-butoxy Tri(ethyl acetoacetate)zirconium, monotert-butoxy Zirconium chelate compounds 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 chelate compounds such as tri(acetylacetone)aluminum, tri(ethyl acetoacetate)aluminum, etc.

[0072] Examples of organic acids that can act as hydrolysis catalysts 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, arachidic 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.

[0073] Inorganic acids that can act as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0074] Examples of organic bases that can serve as hydrolysis catalysts include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. Examples of inorganic bases include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and one or more of these can be used simultaneously.

[0075] Examples of organic solvents used for hydrolysis 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 hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, and trimethylbenzene; methyl... Alcohols, 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, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol Monool solvents such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, and cresol; polyol 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, and 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, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone-based acetone, diacetone alcohol, acetophenone, fentanyl ketone, etc.; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, 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, triethylene glycol monoethyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether Ether solvents such as acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, 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, and acetic acid. Methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, triethylene glycol methoxyacetate, ethyl propionate, n-butyl propionate, isopropionate Ester solvents such as pentyl ester, 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-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonic acid lactone. These solvents can be used alone or in combination of two or more.

[0076] From the perspective of solution preservation stability, ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, and fentanyl ketone are particularly preferred.

[0077] In addition, bisphenol S or bisphenol S derivatives may be added as additives. The amount of bisphenol S or bisphenol S derivatives relative to 100 parts by weight of polyorganosiloxane is 0.01 to 20 parts by weight, or 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight.

[0078] Preferred bisphenol S or bisphenol S derivatives are shown below.

[0079]

[0080] Furthermore, in this invention, aliphatic polycyclic compounds, aliphatic polycyclic dicarboxylic acids, or aliphatic polycyclic dicarboxylic anhydrides that may have double bonds, hydroxyl groups, or epoxy groups may be added. Aliphatic polycyclic dicarboxylic anhydrides are preferred.

[0081] These additives can be exemplified as follows.

[0082]

[0083] The resist underlayer film forming composition of the present invention may contain a curing catalyst. The curing catalyst acts as a curing catalyst when a coating film containing a polyorganosiloxane comprising a hydrolysis condensate is heated and cured.

[0084] As a curing catalyst, ammonium salts, phosphine compounds, etc. can be used. Salt, sulfite.

[0085] Examples of ammonium salts include quaternary ammonium salts having the structures shown in formulas (D-1) to (D-5) and tertiary ammonium salts having the structure shown in formula (D-6).

[0086] (Where, m represents an integer from 2 to 11, n represents an integer from 2 to 3, and R...) 21 (Indicates alkyl or aryl; Y- indicates anion.)

[0087] (where R) 22 R 23 R 24 and R 25Indicates alkyl or aryl, N represents nitrogen atom, Y - Represents anion, and R 22 R 23 R 24 and R 25 (Both are bonded to nitrogen atoms via CN bonds)

[0088] (where R) 26 and R 27 Y represents alkyl or aryl. - (representing anion)

[0089] (where R) 28 Y represents alkyl or aryl. - (representing anion)

[0090] (where R) 29 and R 30 Y represents alkyl or aryl. - (representing anion)

[0091] (Where, m represents an integer from 2 to 11, n represents an integer from 2 to 3, H represents a hydrogen atom, Y...) - (Indicates anion).

[0092] In addition, as Salt, as exemplified by the quaternary salts shown in formula (D-7), can be considered. Salt,

[0093] (where R) 31 R 32 R 33 and R 34 Indicates alkyl or aryl, P represents phosphorus atom, Y - Represents anion, and R 31 R 32 R 33 and R 34 (They are bonded to phosphorus atoms via CP bonds respectively).

[0094] Furthermore, as a matte salt, the tertiary matte salt shown in formula (D-8) can be cited as an example.

[0095] (where R) 35 R 36 and R 37Indicates alkyl or aryl, S represents sulfur atom, Y - Represents anion, and R 35 R 36 and R 37 (They are bonded to sulfur atoms via CS bonds).

[0096] The compound of formula (D-1) above is an amine-derived quaternary ammonium salt, where m represents an integer from 2 to 11, and n represents an integer from 2 to 3. The R of this quaternary ammonium salt... 21 The carbon number is 1 to 18, preferably 2 to 10, and examples include straight-chain 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 such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - (e.g., acid radicals).

[0097] The compound of formula (D-2) above 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 These are alkyl or aryl compounds with 1 to 18 carbon atoms, or silane compounds bonded to silicon atoms via Si-C bonds. Anion (Y - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - (e.g., quaternary ammonium salts). These quaternary ammonium salts are available in commercially available forms, and examples include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0098] The compound of formula (D-3) above is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms ranges from 1 to 18, R26 and R 27 The total number of carbon atoms is preferably 7 or more. For example, R 26 Examples include methyl, ethyl, propyl, phenyl, benzyl, R 27 Examples include benzyl, octyl, and octadecyl. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - The compound is available in commercially available form, but it can also be prepared by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with haloalkyl or haloaryl groups such as benzyl bromide or methyl bromide.

[0099] The compound of formula (D-4) above is a quaternary ammonium salt derived from pyridine, R 28 It is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms; examples include butyl, octyl, benzyl, and lauryl. Anion (Y - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - This compound is available commercially, but can also be prepared by reacting pyridine with halogenated alkyl or halogenated aryl groups 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.

[0100] The compounds of formula (D-5) described above are quaternary ammonium salts derived from substituted pyridines, such as methylpyridine, R 29 It is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18, and examples include methyl, octyl, lauryl, benzyl, etc. R 30 It is an alkyl or aryl group having 1 to 18 carbon atoms, such as in the case of quaternary ammonium derived from methylpyridine. 30 It is a methyl group. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I)- Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - This compound is available in commercially available form, but can also be prepared by reacting substituted pyridines, such as methylpyridine, with haloalkyl or haloaryl groups, such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include, for example, N-benzylmethylpyridinium chloride, N-benzylmethylpyridinium bromide, and N-laurylmethylpyridinium chloride.

[0101] The compounds of formula (D-6) above are amine-derived tertiary ammonium salts, where m represents an integer from 2 to 11, and n represents an integer from 2 to 3. Furthermore, the anion (Y...) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - Anions such as γ-amino acids (γ-amino acids) 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 (γ-amino acid)... - ) is (HCOO) - In the case of using acetic acid, the anion (Y) - (CH3COO) - Furthermore, when using phenol, the anion (Y) - (C6H5O) - ).

[0102] The compound of formula (D-7) above is one having 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 It is an alkyl or aryl compound having 1 to 18 carbon atoms, or a silane compound bonded to silicon atoms via Si-C bonds, but preferably in the R... 31 ~R 34Of these four substituents, three are phenyl or substituted phenyl groups, such as phenyl and tolyl. The remaining substituent is an alkyl, aryl, or silane compound with 1 to 18 carbon atoms, or a silane compound bonded to silicon atoms via a Si-C bond. Furthermore, the anion (Y... - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - Anions such as ) and ) are present. This compound is available in commercially available forms, for example, tetra-n-butyl halotri. Halogenated tetra-n-propyl Isohalotetraalkyl , halotriethylbenzyl isohalogenated trialkylbenzyl halogenated triphenylmethyl halogenated triphenylethyl Isohyetalized triphenylmonoalkyl , halotriphenylbenzyl Halotetraphenyl Halogenated trimethylyl monoaryl or halogenated trimethylyl monoalkyl (The halogen atom is a chlorine or bromine atom). A particularly preferred option is triphenylmethyl halogen. halogenated triphenylethyl Isohyetalized triphenylmonoalkyl , halotriphenylbenzyl isohalogenated triphenyl monoaryl halogenated trimethylyl monophenyl Isohyetalized trimethylolyl monoaryl , halotrimethylyl monomethyl Isohyetalized trimethylyl monoalkyl (The halogen atom is a chlorine atom or a bromine atom).

[0103] 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.

[0104] The compound of formula (D-8) above is one having R 35 R 36 R 37 S + Y -Tertiary sulfonium salts with a structure of R. 35 R 36 and R 37 It is an alkyl or aryl compound having 1 to 18 carbon atoms, or a silane compound bonded to silicon atoms via Si-C bonds, but R is preferred. 35 ~R 37 Of these four substituents, three are phenyl or substituted phenyl groups, such as phenyl and tolyl. The remaining substituent is an alkyl or aryl group having 1 to 18 carbon atoms. Furthermore, the anion (Y... - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions such as α-halogen ions and carboxylate ions (-COO-) - ), sulfonate ions (-SO3) - ), alkoxy ions (-O) - This compound contains anions such as maleic acid anions and nitrate anions. It is available commercially in the form of halogenated tri-n-butylsulfonium, halogenated tri-n-propylsulfonium, halogenated trialkylbenzylsulfonium, halogenated diethylbenzylsulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylethylsulfonium, halogenated triphenylsulfonium (with chlorine or bromine atoms), tri-n-butylsulfonium carboxylate, tri-n-propylsulfonium carboxylate, and other tetraalkyl groups. Trialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmethylsulfonium carboxylate, diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylates are used. Furthermore, halogenated triphenylsulfonium and triphenylsulfonium carboxylates are preferred.

[0105] Furthermore, in this invention, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of nitrogen-containing silane compounds include silane compounds containing an imidazole ring, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0106] The curing catalyst is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass relative to 100 parts by mass of polyorganosiloxane.

[0107] Hydrolyzable silanes are hydrolyzed and condensed in a solvent using a catalyst. The resulting hydrolyzed condensate (polymer) can be purified by removing byproducts such as alcohol, the hydrolysis catalyst used, and water simultaneously through vacuum distillation. Furthermore, acidic or basic catalysts used for hydrolysis can be removed by neutralization or ion exchange. Moreover, in the photoresist underlayer film forming composition of the present invention, for stabilization, an organic acid, water, alcohol, or a combination thereof can be added to the photoresist underlayer film forming composition containing the hydrolyzed condensate.

[0108] Examples of the aforementioned 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. The amount of the added organic acid is 0.1 to 5.0 parts by weight relative to 100 parts by weight of the condensate (polyorganosiloxane). Furthermore, the added water can be pure water, ultrapure water, or ion-exchanged water, and its amount can be 1 to 20 parts by weight relative to 100 parts by weight of the composition for forming the lower layer of the resist film.

[0109] Furthermore, the added alcohol is preferably an alcohol that is easily volatilized by heating after coating, such as methanol, ethanol, propanol, isopropanol, butanol, etc. The added alcohol can be 1 to 20 parts by weight relative to 100 parts by weight of the composition for forming the underlayer film of the resist.

[0110] In addition to the above-mentioned components, the composition for forming a lower layer film for photolithography of the present invention may include organic polymer compounds, photoacid generators, and surfactants as needed.

[0111] By using organic polymer compounds, the dry etching rate (the amount of reduction in film thickness per unit time), attenuation coefficient, and refractive index of the resist underlayer film formed by the photolithography underlayer film formation composition of the present invention can be adjusted.

[0112] There are no particular limitations on the organic polymer compound used; various organic polymers can be used. Condensation polymers and addition polymers can be used. Polyesters, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenolic varnish, naphthol varnish, polyether, polyamide, polycarbonate, and other addition and condensation polymers can be used. Organic polymers with aromatic ring structures such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings, which function as light-absorbing sites, are preferred.

[0113] Examples of such organic polymer compounds 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 varnish and naphtholic varnish.

[0114] When using addition polymers as organic polymer compounds, the polymer compound can be a homopolymer or a copolymer. Addition polymers use addition monomers in their manufacture. Examples of such addition polymers include acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0115] Examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantane acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, and glycidyl acrylate.

[0116] Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantane methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate.

[0117] Examples of acrylamide compounds include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0118] Examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthraylacrylamide.

[0119] 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, and vinylanthracene.

[0120] Examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0121] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0122] When using condensation polymers as the polymer, examples of such polymers include condensation polymers of glycol compounds and dicarboxylic acid compounds. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, 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, for example, polypyrrolidone tetramethylimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0123] In the case of an organic polymer compound containing a hydroxyl group, the hydroxyl group can form a crosslinking reaction with the polyorganosiloxane.

[0124] As organic polymer compounds, polymer compounds with a weight average molecular weight of, for example, 1,000 to 1,000,000, or 3,000 to 300,000, or 5,000 to 200,000, or 10,000 to 100,000 can be used.

[0125] Organic polymer compounds can be used in isolation or in combination of two or more.

[0126] When using organic polymer compounds, the proportions are 1 to 200 parts by mass, or 5 to 100 parts by mass, or 10 to 50 parts by mass, or 20 to 30 parts by mass relative to 100 parts by mass of the condensate (polyorganosiloxane).

[0127] The composition for forming the lower layer of the resist film according to the present invention may contain an acid-generating agent.

[0128] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents.

[0129] Photoacid-generating agents produce acid when the resist is exposed. Therefore, the acidity of the lower film can be adjusted. This is a method to match the acidity of the lower film with that of the upper resist. Furthermore, by adjusting the acidity of the lower film, the pattern shape of the resist formed on the upper layer can be adjusted.

[0130] Examples of photoacid generators included in the resist lower layer film forming composition of the present invention include: Salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds, etc.

[0131] As Salt compounds, such as diphenyliodine, can be cited as an example. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate and bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Salt compounds, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butane sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethane sulfonate.

[0132] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0133] Examples of disulfonyl diazonium compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium.

[0134] Photo-acid generators can be used in single-use or in combination of two or more.

[0135] When using a photoacid-generating agent, the proportion is 0.01 to 15 parts by mass, or 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the condensate (polyorganosiloxane).

[0136] When the photoresist lower film forming composition of the present invention is coated on a substrate, the surfactant is effective in suppressing the occurrence of pinholes and streaks.

[0137] Examples of surfactants included in the resist lower film forming composition of the present invention include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol monostearate. Nonionic surfactants such as polyoxyethylene dehydrated sorbitol tristearate and other polyoxyethylene dehydrated sorbitol fatty acid esters, trade names: Eftofo EF301, EF303, EF352 (manufactured by Tokem Prodact), and Megafak F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation). Fluorinated surfactants such as Rad FC430, FC431 (manufactured by Sumitomo Silem Co., Ltd.), trade names Asahigard AG710, Servolon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) are used. These surfactants can be used alone or in combination of two or more. When using surfactants, the proportion is 0.0001 to 5 parts by weight, or 0.001 to 1 part by weight, or 0.01 to 1 part by weight relative to 100 parts by weight of the condensate (polyorganosiloxane).

[0138] Furthermore, rheology modifiers and adhesion promoters can be added to the resist underlayer film forming composition of the present invention. Rheology modifiers are effective in improving the flowability of the underlayer film forming composition. Adhesion promoters are effective in improving the adhesion between the semiconductor substrate or the resist and the underlayer film.

[0139] As a solvent used in the resist lower film forming composition of the present invention, any solvent capable of dissolving the aforementioned solid components can be used without particular limitation. Examples of such solvents include, for instance, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl methanol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate. Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, 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, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, lactic acid Isobutyl ester, 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 hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more.

[0140] The following describes the use of the resist underlayer film forming composition of the present invention.

[0141] The resist underlayer film forming composition of the present invention is applied to a substrate used for manufacturing semiconductor devices (e.g., silicon wafer substrate, silicon / silicon dioxide coated substrate, silicon nitride substrate, glass substrate, ITO substrate, polyimide substrate, and low-k material coated substrate, etc.) using a suitable coating method such as a spinner or coater, and then formed by firing. The firing conditions are appropriately selected from a firing temperature of 80°C to 250°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 250°C and the firing time is 0.5 to 2 minutes. Here, the film thickness of the formed underlayer film is, for example, 10 to 1000 nm, 20 to 500 nm, 50 to 300 nm, or 100 to 200 nm.

[0142] Next, a layer of, for example, photoresist is formed on the lower resist film. The photoresist layer can be formed by a known method, namely, coating and firing a photoresist composition solution onto the lower film. The thickness of the photoresist film is, for example, 50-10000 nm, 100-2000 nm, or 200-1000 nm.

[0143] In this invention, after forming an organic lower layer film on a substrate, a photoresist lower layer film of the present invention can be formed on the organic lower layer film, and a photoresist can be further coated on the photoresist lower layer film. This narrows the pattern width of the photoresist, allowing for the selection of a suitable etching gas for substrate processing even when the photoresist is thinly coated to prevent pattern collapse. For example, a fluorine-based gas with a sufficiently fast etching rate for the photoresist can be used as the etching gas to process the photoresist lower layer film of the present invention. Furthermore, an oxygen-based gas with a sufficiently fast etching rate for the photoresist lower layer film of the present invention can be used as the etching gas to process the organic lower layer film, and a fluorine-based gas with a sufficiently fast etching rate for the organic lower layer film can be used as the etching gas to process the substrate.

[0144] As the photoresist formed on the lower layer film of the photoresist of the present invention, there is no particular limitation as long as it is a photosensitive photoresist used for exposure. Either negative or positive photoresists can be used. Positive photoresists composed of phenolic varnish resin and 1,2-diazonaphthoquinone sulfonate are available; chemically amplified photoresists are composed of a binder having groups that increase the alkali dissolution rate through acid decomposition and a photoacid-generating agent; chemically amplified photoresists are composed of a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition, an alkali-soluble binder, and a photoacid-generating agent; and chemically amplified photoresists are composed of a binder having groups that increase the alkali dissolution rate of the photoresist through acid decomposition, a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition, and a photoacid-generating agent. Examples include APEX-E manufactured by Sifure Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, examples include fluorinated atom polymer-based photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0145] Next, exposure is performed through a specified mask. Exposure can be performed using a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F2 excimer laser (wavelength 157 nm), among others. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 to 10 minutes.

[0146] Furthermore, in this invention, an electron beam lithography resist or an EUV lithography resist can be used instead of a photoresist. As an electron beam resist, either a negative or positive type can be used. There are chemically amplified resists composed of an acid-generating agent and a binder having groups that decompose through acid, thereby changing the rate of alkali dissolution; chemically amplified resists composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that decomposes through acid, thereby changing the rate of alkali dissolution of the resist; chemically amplified resists composed of an acid-generating agent, a binder having groups that decompose through acid, thereby changing the rate of alkali dissolution of the resist, and a low-molecular-weight compound that decomposes through acid, thereby changing the rate of alkali dissolution of the resist; non-chemically amplified resists composed of a binder having groups that decompose through electron beams, thereby changing the rate of alkali dissolution; and non-chemically amplified resists composed of a binder having a portion that is cut by electron beams, thereby changing the rate of alkali dissolution. The use of these electron beam resists can form resist patterns in the same way as when electron beams are used as the irradiation source and photoresist is used.

[0147] Furthermore, methacrylate resin-based resists, methacrylate-polyhydroxystyrene mixed resin-based resists, and polyhydroxystyrene resin-based resists can be used as EUV resists. Negative and positive types can be used as EUV resists. There are chemically amplified resists composed of an acid-generating agent and a binder having groups that decompose through acid, thereby changing the rate of alkali dissolution; chemically amplified resists composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that decomposes through acid, thereby changing the rate of alkali dissolution of the resist; chemically amplified resists composed of an acid-generating agent, a binder having groups that decompose through acid, thereby changing the rate of alkali dissolution of the resist, and a low-molecular-weight compound that decomposes through acid, thereby changing the rate of alkali dissolution of the resist; non-chemically amplified resists composed of a binder having groups that decompose through EUV light, thereby changing the rate of alkali dissolution; and non-chemically amplified resists composed of a binder having a portion that is cut off by EUV light, thereby changing the rate of alkali dissolution.

[0148] Next, development is performed using a developer (e.g., an alkaline developer). Thus, for example, when using a positive photoresist, the exposed portions of the photoresist are removed, forming a photoresist pattern.

[0149] Examples of developing solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developing solutions. The developing conditions can be appropriately selected from a temperature of 5–50°C and a time of 10–600 seconds.

[0150] Furthermore, in this invention, an organic solvent can also be used as the developer. After exposure, development is performed using the developer (solvent). Thus, for example, when using a positive photoresist, the unexposed portions of the photoresist are removed, forming a photoresist pattern.

[0151] For example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate 4-Propoxybutylacetic acid ester, 2-Methoxypentylacetic acid ester, 3-Methoxypentylacetic acid ester, 4-Methoxypentylacetic acid ester, 2-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-4-Methoxypentylacetic acid ester, 4-Methyl-4-Methoxypentylacetic acid ester, propylene glycol diacetate, methyl formate, ethyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate Examples include propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, surfactants can be added to these developers. The developing conditions can be appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0152] Then, the patterned photoresist (upper layer) formed therefrom is used as a protective film to remove the lower resist film (intermediate layer) of the present invention. Next, the film containing the patterned photoresist and the lower resist film (intermediate layer) of the present invention is used as a protective film to remove the organic lower film (lower layer). Finally, the patterned lower resist film (intermediate layer) and organic lower film (lower layer) of the present invention are used as protective films to process the semiconductor substrate.

[0153] First, the photoresist lower layer film (intermediate layer) of the present invention, with the photoresist portion removed, is removed by dry etching to expose the semiconductor substrate. Dry etching of the photoresist lower layer film of the present invention can be performed using gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, boron trichloride, and boron dichloride. Halogen gases are preferably used for dry etching of the photoresist lower layer film. Dry etching using halogen gases is generally difficult to remove photoresist containing organic matter. In contrast, the photoresist lower layer film of the present invention, containing many silicon atoms, is rapidly removed by halogen gases. Therefore, the reduction in photoresist film thickness caused by dry etching of the photoresist lower layer film can be suppressed. Moreover, as a result, the photoresist can be used in thin film form. Dry etching of the resist underlayer is preferably performed using a fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0154] Then, the organic underlayer film is removed using a film containing the patterned photoresist and the photoresist underlayer film of the present invention as a protective film. The organic underlayer film (underlayer) is preferably removed by dry etching using an oxygen-based gas. This is because the photoresist underlayer film of the present invention, which contains many silicon atoms, is difficult to remove by dry etching using an oxygen-based gas.

[0155] Finally, the semiconductor substrate is processed. The semiconductor substrate is preferably processed by dry etching using fluorine-based gases.

[0156] Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0157] Furthermore, an organic antireflective film can be formed on top of the photoresist lower layer of the present invention before the photoresist is formed. Therefore, there are no particular limitations on the antireflective film composition used, and any material commonly used in photolithography processes can be selected. In addition, the antireflective film can be formed by common methods, such as coating and firing using a spin coater or a coating machine.

[0158] Furthermore, regarding a substrate coated with the resist underlayer film forming composition of the present invention, its surface may have an organic or inorganic antireflective film formed by CVD or the like, and the underlayer film of the present invention may also be formed thereon.

[0159] Furthermore, the photoresist lower layer film formed by the photoresist lower layer film formation composition of the present invention sometimes absorbs light depending on the wavelength of the light used in the photolithography process. In such cases, it can function as an anti-reflective film that prevents light reflected from the substrate. Moreover, the lower layer film of the present invention can also be used as a layer to prevent interaction between the substrate and the photoresist, a layer to prevent adverse effects on the substrate from materials used in the photoresist or substances generated during exposure to the photoresist, a layer to prevent the diffusion of substances generated from the substrate during heating and firing onto the upper photoresist, and a barrier layer to reduce the toxic effects of the photoresist layer caused by the dielectric layer of the semiconductor substrate.

[0160] Furthermore, the resist underlayer film formed from the resist underlayer film formation composition is suitable for substrates with via holes formed in dual damascene processes, and can be used as an embedding material capable of filling the gaps without gaps. Additionally, it can also be used as a planarization material for planarizing the surface of uneven semiconductor substrates.

[0161] In addition to its function as a hard mask, the lower layer film of the EUV resist can also be used for the following purposes. As a lower antireflective film for the EUV resist, which can prevent the reflection of undesirable exposure light during EUV exposure (wavelength 13.5nm), such as the aforementioned UV and DUV (ArF light, KrF light), from the substrate or interface without mixing with the EUV resist, the above-mentioned resist lower layer film forming composition can be used. Reflection can be effectively prevented in the lower layer of the EUV resist. When used as an EUV resist lower layer film, the process can be performed in the same way as for a photoresist lower layer film.

[0162] Example

[0163] Synthesis example 1

[0164] 25.37 g (70 mol%) of tetraethoxysilane, 4.46 g (10 mol%) of 5-(dicycloheptenyl)triethoxysilane, 6.20 g (20 mol%) of methyltriethoxysilane, and 54.06 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.60 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was placed in an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (2-1), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0165] Synthesis example 2

[0166] 24.95 g (70 mol%) of tetraethoxysilane, 8.77 g (20 mol%) of 5-(dicycloheptenyl)triethoxysilane, 3.05 g (10 mol%) of methyltriethoxysilane, and 55.16 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.41 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was placed in an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (2-1), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0167] Synthesis example 3

[0168] 23.39 g (70 mol%) of tetraethoxysilane, 12.33 g (30 mol%) of 5-(dicycloheptenyl)triethoxysilane, and 53.58 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.69 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was placed in an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution. The methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (2-2), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0169] Synthesis example 4

[0170] 23.91 g (70 mol%) of tetraethoxysilane, 5.88 g (10 mol%) of tert-butyl-5-(triethoxysilyl)bicyclo[2,2,1]heptane-2-carboxylate, 5.85 g (20 mol%) of methyltriethoxysilane, and 53.44 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.93 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was placed in an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. The methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (2-3), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0171] Synthesis example 5

[0172] 23.98 g (70 mol%) of tetraethoxysilane, 1.63 g (5 mol%) of phenyltrimethoxysilane, 2.93 g (10 mol%) of methyltriethoxysilane, 4.22 g (10 mol%) of 5-(dicycloheptenyl)triethoxysilane, 2.85 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.42 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.97 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-4), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0173] Synthesis example 6

[0174] 23.29 g (70 mol%) of tetraethoxysilane, 1.58 g (5 mol%) of phenyltrimethoxysilane, 2.85 g (10 mol%) of methyltriethoxysilane, 5.25 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methanoisobenzofuran-1,3-dione, 2.77 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.65 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-5), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0175] Synthesis Example 7

[0176] 24.90 g (70 mol%) of tetraethoxysilane, 1.69 g (5 mol%) of phenyltrimethoxysilane, 1.52 g (5 mol%) of methyltriethoxysilane, 4.38 g (10 mol%) of 5-(dicycloheptenyl)triethoxysilane, 2.07 g (5 mol%) of methoxybenzyltrimethoxysilane, 2.95 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.17 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.39 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-6), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0177] Synthesis example 8

[0178] 24.15 g (70 mol%) of tetraethoxysilane, 1.64 g (5 mol%) of phenyltrimethoxysilane, 1.48 g (5 mol%) of methyltriethoxysilane, 5.44 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione, 2.01 g (5 mol%) of methoxybenzyltrimethoxysilane, 2.87 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.37 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.04 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-7), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0179] Synthesis example 9

[0180] 23.05 g (70 mol%) of tetraethoxysilane, 1.57 g (5 mol%) of phenyltrimethoxysilane, 4.37 g (10 mol%) of 4-(2-(triethoxysilyl)ethyl)dihydrofuran-2(3H)-one, 4.05 g (10 mol%) of 5-(dicycloheptenyl)triethoxysilane, 2.74 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.68 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.54 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-8), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0181] Synthesis example 10

[0182] 22.42 g (70 mol%) of tetraethoxysilane, 1.52 g (5 mol%) of phenyltrimethoxysilane, 4.25 g (10 mol%) of 4-(2-(triethoxysilyl)ethyl)dihydrofuran-2(3H)-one, 5.05 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione, 2.66 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.85 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.25 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue at 140°C equivalent to 20% by weight. The resulting polymer corresponds to formula (2-9), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0183] Synthesis example 11

[0184] 23.37 g (70 mol%) of tetraethoxysilane, 0.95 g (3 mol%) of phenyltrimethoxysilane, 1.14 g (4 mol%) of methyltriethoxysilane, 2.22 g (5 mol%) of 4-(2-(triethoxysilyl)ethyl)dihydrofuran-2(3H)-one, 5.26 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione, 2.78 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, 1.88 g (3 mol%) of methoxyphenylsulfonylpropyltriethoxysilane, and 53.59 g of acetone were placed in a 300 ml flask. While stirring the mixture with a magnetic stirrer, 10.69 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was placed in an oil bath adjusted to 85°C and reacted under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue at 140°C equivalent to 20% by weight. The resulting polymer corresponds to formula (2-10), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0185] Synthesis example 12

[0186] 23.24 g (70 mol%) of tetraethoxysilane, 0.95 g (3 mol%) of phenyltrimethoxysilane, 1.14 g (4 mol%) of methyltriethoxysilane, 2.43 g (5 mol%) of 3-(3-(triethoxysilyl)propyl)dihydrofuran-2,5-dione, 5.24 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione, 2.76 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, 1.87 g (3 mol%) of methoxyphenylsulfonylpropyltriethoxysilane, and 53.62 g of acetone were placed in a 300 ml flask. While stirring the mixture with a magnetic stirrer, 10.63 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was placed in an oil bath adjusted to 85°C and reacted under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue at 140°C equivalent to 20% by weight. The resulting polymer corresponds to formula (2-11), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0187] Synthesis example 13

[0188] 23.28 g (70 mol%) of tetraethoxysilane, 1.58 g (5 mol%) of phenyltrimethoxysilane, 5.27 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-epoxyisobenzofuran-1,3-dione, 2.85 g (10 mol%) of methyltriethoxysilane, 2.77 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.64 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-12), and its weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0189] Synthesis Example 14

[0190] 23.41 g (70 mol%) of tetraethoxysilane, 1.59 g (5 mol%) of phenyltrimethoxysilane, 5.08 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-epoxyisobenzofuran-1(3H)-one, 2.86 g (10 mol%) of methyltriethoxysilane, 2.78 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.60 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.70 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-13), and its weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0191] Synthesis Example 15

[0192] 23.16 g (70 mol%) of tetraethoxysilane, 1.57 g (5 mol%) of phenyltrimethoxysilane, 5.45 g (10 mol%) of 2-hydroxy-5-(triethoxysilyl)hexahydro-1H-4,7-methyleneisoindole-1,3(2H)-dione, 2.83 g (10 mol%) of methyltriethoxysilane, 2.75 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.65 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.59 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-14), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0193] Synthesis Example 16

[0194] 23.29 g (70 mol%) of tetraethoxysilane, 1.58 g (5 mol%) of phenyltrimethoxysilane, 5.25 g (10 mol%) of 5-(triethoxysilyl)dihydro-2'H-spiro[bicyclo[2.2.1]heptane-2,3'-furan]-2'-one, 2.85 g (10 mol%) of methyltriethoxysilane, 2.77 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.65 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-15), and its weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0195] Synthesis Example 17

[0196] 23.92 g (70 mol%) of tetraethoxysilane, 1.63 g (5 mol%) of phenyltrimethoxysilane, 4.30 g (10 mol%) of 4-((triethoxysilyl)methyl)dihydrofuran-2(3H)-one, 2.93 g (10 mol%) of methyltriethoxysilane, 2.84 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.44 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.94 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-16), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0197] Synthesis example 18

[0198] 23.79 g (70 mol%) of tetraethoxysilane, 1.62 g (5 mol%) of phenyltrimethoxysilane, 4.51 g (10 mol%) of 3-((triethoxysilyl)methyl)dihydrofuran-2,5-dione, 2.83 g (10 mol%) of methyltriethoxysilane, 2.83 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.47 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.88 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-17), and the weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0199] Synthesis example 19

[0200] 23.29 g (70 mol%) of tetraethoxysilane, 1.58 g (5 mol%) of phenyltrimethoxysilane, 5.25 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione (exomeric isomer), 2.85 g (10 mol%) of methyltriethoxysilane, 2.77 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.65 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-18), and its weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0201] Synthesis example 20

[0202] 23.29 g (70 mol%) of tetraethoxysilane, 1.58 g (5 mol%) of phenyltrimethoxysilane, 5.25 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione (endomeric isomer), 2.85 g (10 mol%) of methyltriethoxysilane, 2.77 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.65 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-19), and its weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0203] Synthesis Example 21

[0204] 23.29 g (70 mol%) of tetraethoxysilane, 1.58 g (5 mol%) of phenyltrimethoxysilane, 5.25 g (10 mol%) of 5-(triethoxysilyl)hexahydro-4,7-methyleneisobenzofuran-1,3-dione (endo and exo isomers), 2.85 g (10 mol%) of methyltriethoxysilane, 2.77 g (5 mol%) of phenylsulfonylpropyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.65 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was transferred to an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether at 20 / 80, with a solids residue of 20% by weight at 140°C. The resulting polymer corresponds to formula (2-20), and its weight-average molecular weight, measured by GPC, is Mw1500 (converted to polystyrene).

[0205] Synthesis example 22

[0206] 25.70 g (70 mol%) of tetraethoxysilane, 1.75 g (5 mol%) of phenyltrimethoxysilane, 7.86 g (25 mol%) of methyltriethoxysilane, and 53.61 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.75 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was placed in an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (22-1), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0207]

[0208] Synthesis example 23

[0209] 25.70 g (70 mol%) of tetraethoxysilane, 4.64 g (10 mol%) of 5-(triethoxysilyl)-2-azabicyclo[2.2.1]heptane-3-one, 6.06 g (20 mol%) of methyltriethoxysilane, and 53.20 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.33 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was placed in an oil bath adjusted to 85 °C and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution. The methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (2-21), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0210] Synthesis example 24

[0211] 22.93 g (70 mol%) of tetraethoxysilane, 12.88 g (30 mol%) of 5-(triethoxysilyl)-2-azabicyclo[2.2.1]heptane-3-one, and 53.71 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 10.48 g of 0.01 mol / L hydrochloric acid was added dropwise to the mixture. After addition, the flask was placed in an oil bath adjusted to 85 °C and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution. The methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was then concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (2-22), and the weight-average molecular weight, as measured by GPC, is Mw1500 (converted to polystyrene).

[0212] Comparative Synthesis Example 1

[0213] 25.81 g (70 mol%) of tetraethoxysilane, 9.47 g (30 mol%) of methyltriethoxysilane, and 52.92 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.80 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was placed in an oil bath adjusted to 85 °C and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) solution of propylene glycol monomethyl ether acetate. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), and the solid residue at 140 °C was converted to 20% by weight. The resulting polymer is equivalent to formula (3-1), and the weight-average molecular weight measured by GPC is Mw1500 when converted to polystyrene.

[0214]

[0215] Comparative Synthesis Example 2

[0216] 25.41 g (70 mol%) of tetraethoxysilane, 6.21 g (20 mol%) of methyltriethoxysilane, 3.73 g (10 mol%) of 5-(dicycloheptenyl)trimethoxysilane, and 53.03 g of acetone were placed in a 300 mL flask. While stirring the mixture with a magnetic stirrer, 11.62 g of 0.01 mol / L hydrochloric acid was added dropwise. After addition, the flask was placed in an oil bath adjusted to 85 °C, and the reaction was carried out under reflux for 240 minutes. Then, the reaction solution was cooled to room temperature, and 70.00 g of propylene glycol monomethyl ether acetate was added. Methanol, ethanol, acetone, water, and hydrochloric acid, which were reaction byproducts, were removed by vacuum distillation. The solution was concentrated to obtain a hydrolyzed condensate (polymer) propylene glycol monomethyl ether acetate solution. Propylene glycol monoethyl ether was added to adjust the solvent ratio to 20 / 80 (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether), with a solids residue of 20% by weight at 140°C. The resulting polymer is equivalent to formula (3-2), and the weight-average molecular weight, as measured by GPC, is Mw1700 (converted to polystyrene).

[0217]

[0218] (Adjustment of the lower layer film of the photoresist containing Si)

[0219] The silicon-containing polymer, acid, curing catalyst, additive, solvent, and water obtained from Synthesis Example 1 were mixed in the proportions shown in Table 1, and filtered using a 0.1 μm fluororesin filter to prepare solutions of the composition for forming the lower layer of the photoresist film. The polymer addition proportions in Tables 1 and 2 show the amount of polymer itself added, not the amount of polymer solution added.

[0220] In Tables 1 and 2, maleic acid is abbreviated as MA, benzyltriethylammonium chloride as BTEAC, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole as IMIDTEOS, triphenylsulfonium nitrate as TPSNO3, monotriphenylsulfonium maleate as TPSMA, triphenylsulfonium trifluoroacetate as TPSTFA, triphenylsulfonium chloride as TPSCl, triphenylsulfonium camphor sulfonate as TPSCS, triphenylsulfonium trifluoromethane sulfonate as TPSTf, triphenylsulfonium nonafluorobutane sulfonate as TPSNf, and triphenylsulfonium adamantium as... Alkylcarboxy-1,1,2-trifluorobutane sulfonate is abbreviated as TPSAdTF, dihydroxyphenylphenylsulfonium p-toluenesulfonate is abbreviated as DHTPPSpTS, diphenyl sulfone is abbreviated as BPS, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, propylene glycol monoethyl ether is abbreviated as PGEE, propylene glycol monomethyl ether is abbreviated as PGME, 5-norbornene-2,3-dicarboxylic anhydride is abbreviated as NorAn, cis-4-cyclohexene-1,2-dicarboxylic anhydride is abbreviated as HexAn, and 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride is abbreviated as EpoPhAn. Ultrapure water is used. All amounts added are expressed in parts by mass.

[0221] [Table 1]

[0222] [Table 2]

[0223] [Table 3]

[0224] (Adjustment of the organic resist underlayer film)

[0225] Under nitrogen atmosphere, add carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) to a 100 mL four-necked flask, and then add 1,4-dioxane. Alkane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred, and heated to 100°C to dissolve it and initiate polymerization. After 24 hours, the mixture was cooled to 60°C, and then diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and then precipitated again in methanol (168 g, manufactured by Kanto Chemical Co., Ltd.). The resulting precipitate was filtered and dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer (Formula (4-1), hereinafter abbreviated as PCzFL).

[0226]

[0227] PCzFL 1 The results of the H-NMR measurements are as follows.

[0228] 1 H-NMR (400MHz, DMSO-d6): δ7.03-7.55(br,12H), δ7.61-8.10(br,4H), δ11.18(br,1H)

[0229] The weight-average molecular weight (Mw) of PCzFL, converted to polystyrene using GPC, is 2800, and the polydispersity (Mw / Mn) is 1.77.

[0230] 3.0 g of tetramethoxymethyl urea (manufactured by Mitsui Cytec Co., Ltd., trade name Powderlink 1174) as a crosslinking agent and pyridine as a catalyst were mixed into 20 g of the obtained resin. A solution was prepared by dissolving 0.30 g of p-toluenesulfonate and 0.06 g of megafalk R-30 (manufactured by Dai Nippon Inki Chemical Co., Ltd., trade name) as a surfactant in 88 g of propylene glycol monomethyl ether acetate. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm, and subsequently filtered again using a polyethylene microfilter with a pore size of 0.05 μm, thereby preparing a solution of a composition for forming the lower layer (A layer) of an organic resist used in photolithography processes utilizing multilayer films.

[0231] (Optical constant measurement)

[0232] Using a spin coater, the Si-containing resist underlayer film formation compositions prepared in Examples 1-10 and Comparative Example 1 were coated onto a silicon wafer. The wafer was heated at 200°C for 1 minute on a hot plate to form a Si-containing resist underlayer film (film thickness 0.05 μm). Then, using a spectroscopic ellipsometry (JAWoollam, VUV-VASE VU-302), the refractive index (n value) and optical absorption coefficient (k value, also known as attenuation coefficient) of these resist underlayer films at a wavelength of 193 nm were measured.

[0233] (Determination of dry etching rate)

[0234] The etching machine and etching gas used for measuring the dry etching rate are as follows.

[0235] ES401 (manufactured by Japan's Sasuke Technology Co., Ltd.): CF4

[0236] RIE-10NR (manufactured by SAMU): O2

[0237] A solution of the Si-containing photoresist underlayer film formation composition prepared by Examples 1-10 and Comparative Example 1 was coated onto a silicon wafer using a spin coater. The wafer was heated at 240°C for 1 minute on a hot plate to form Si-containing photoresist underlayer films (film thickness 0.08 μm (for etching rate measurement using CF4 gas) and 0.05 μm (for etching rate measurement using O2 gas), respectively. Similarly, an organic underlayer film formation composition was coated onto a silicon wafer using a spin coater (film thickness 0.20 μm). The dry etching rate was measured using O2 gas as the etching gas, and the dry etching rates of the Si-containing photoresist underlayer films of Examples 1-10 and Comparative Example 1 were compared. The dry etching rates of fluorine-based gases were recorded in nm / min. Furthermore, the rate ratio of oxygen-based gases was calculated as (dry etching rate of the Si-containing photoresist underlayer film) / (dry etching rate of the organic underlayer film).

[0238] (Evaluation of resist pattern formation)

[0239] The organic lower layer film (layer A) forming composition comprising formula (4-1) was coated onto a silicon wafer and baked on a hot plate at 400°C for 60 seconds to obtain an organic lower layer film (layer A) with a thickness of 200 nm. The Si-containing resist lower layer film (layer B) forming composition obtained in Examples 1-10 and Comparative Example 1 was coated onto this organic lower layer film and baked on a hot plate at 400°C for 60 seconds to obtain a Si-containing resist lower layer film (layer B). The Si-containing resist lower layer film (layer B) had a thickness of 45 nm.

[0240] A commercially available photoresist solution (manufactured by JSR Corporation, trade name AR2772) was applied to the lower layer of the photoresist film using a spin coater. The film was then baked on a heated plate at 110°C for 60 seconds to form a 120 nm thick photoresist film (C layer). The photoresist pattern was formed using a NIKON ArF exposure machine S-307E (wavelength 193 nm, NA, σ: 0.85, 0.93 / 0.85 (Dipole) immersion solution: water). The target object was exposed through a mask set to create so-called dense lines and gaps (line spacing) of 0.062 μm after development.

[0241] Then, it is baked on a hot plate at 110°C for 60 seconds. After cooling, it is developed in a 60-second single-paddle process using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (developer). In the shape of the resist pattern after photolithography, the shape with rectangular lines is denoted as straight, and the shape with thicker lines at the bottom is denoted as footing.

[0242] Table 3 shows the results for the refractive index at 193 nm, optical absorption coefficient, fluorine etching rate, oxygen gas resistance, and resist underside shape based on photolithography evaluation.

[0243] [Table 4]

[0244] (Evaluation of resist pattern formation: Evaluation via NTD process involving development in organic solvents)

[0245] The organic lower layer film (layer A) formation composition obtained above was coated onto a silicon wafer and baked on a hot plate at 240°C for 60 seconds to obtain an organic lower layer film (layer A) with a thickness of 200 nm. The Si-containing resist lower layer film (layer B) formation composition obtained in Examples 11-18 and Comparative Examples 1 and 2 was coated onto this organic lower layer film and baked on a hot plate at 240°C for 60 seconds to obtain a Si-containing resist lower layer film (layer B). The Si-containing resist lower layer film (layer B) had a thickness of 30 nm.

[0246] A commercially available photoresist solution (manufactured by Fuji Film Co., Ltd., trade name FAiRS-9521NT05) was applied to layer B using a spin coater. The layer was then heated at 100°C for 1 minute on a hot plate to form a photoresist film (layer C) with a thickness of 85 nm.

[0247] Using an NSR-S307E scanner (193nm wavelength, NA, σ: 0.85, 0.93 / 0.85) manufactured by Niconico Ltd., exposure was performed using masks set to a line width and inter-line width of 0.060μm after development (i.e., forming dense lines with a line width and inter-line gap (L / S) of 0.060μm) and masks set to a line width and inter-line width of 0.058μm after development (i.e., forming dense lines with an inter-line gap (L / S) of 0.058μm) of 1 / 1. The images were then baked at 100°C for 60 seconds on a heated plate, cooled, and developed for 60 seconds using butyl acetate (solvent developer) to form a negative pattern on the lower resist film (layer B). Regarding the resulting photoresist pattern, a good result is characterized by the absence of significant pattern peeling, edge biting, and thickening (skirting) at the bottom of the lines.

[0248] Table 4 shows the results of refractive index at 193 nm, optical absorption coefficient, fluorine etching rate, oxygen gas resistance, and the shape of the resist underside after photolithography evaluation.

[0249] [Table 5]

[0250] [Table 6]

[0251] [Using EUV exposure to form resist patterns: positive alkaline development]

[0252] The above-described organic lower layer film (layer A) formation composition was coated onto a silicon wafer and baked at 215°C for 60 seconds on a hot plate to obtain an organic lower layer film (layer A) with a thickness of 90 nm. A solution of the resist lower layer film formation composition prepared according to Examples 1, 6, 8, 10, and Comparative Example 1 of the present invention was spin-coated onto this organic lower layer film and heated at 215°C for 1 minute to form a resist lower layer film (layer B) (20 nm). An EUV resist solution (methacrylate resin-based resist) was spin-coated onto this hard mask and heated to form an EUV resist layer (layer C). Exposure was performed using an EUV exposure apparatus (MicroExposure Tool, MET) under the conditions of NA=0.30, σ=0.36 / 0.93, and a quadrupole. After exposure, PEB is performed, and the plate is cooled to room temperature on a clean plate. Development is then carried out for 60 seconds using an alkaline developer (2.38% TMAH aqueous solution), followed by rinsing to form the resist pattern. The formation of 24nm lines and gaps is evaluated, as is the pattern shape observed based on cross-sectional views.

[0253] In Table 5, “good” means there is no shape between the skirt and the bite edge and no obvious residue in the blank area; “collapse” means the resist pattern is peeled off and broken, which is an undesirable condition; and “bridge” means the upper or lower part of the resist pattern is in contact with each other, which is an undesirable condition.

[0254] [Table 7]

[0255] [Using EUV exposure to form resist patterns: negative solvent development]

[0256] The above-described organic lower layer film (layer A) formation composition was coated onto a silicon wafer and baked at 215°C for 60 seconds on a hot plate to obtain an organic lower layer film (layer A) with a thickness of 90 nm. A resist lower layer film formation composition solution prepared according to Examples 1, 6, 8, 10, and Comparative Example 1 of the present invention was spin-coated onto this organic lower layer film and heated at 215°C for 1 minute to form a resist lower layer film (layer B) (20 nm). An EUV resist solution (methacrylate resin-based resist) was spin-coated onto this hard mask and heated to form an EUV resist layer (layer C). Exposure was performed using an EUV exposure apparatus (MicroExposure Tool, MET) under the conditions of NA=0.30, σ=0.36 / 0.93, and quadrupole. After exposure, PEB was performed, and the surface was cooled to room temperature on a clean plate. Development was then performed for 60 seconds using butyl acetate (solvent developer) to form a resist pattern. The evaluation assesses whether 24nm lines and gaps can be formed, and evaluates the pattern shape based on cross-sectional observations.

[0257] In Table 6, “good” means there is no shape between the skirt and the bite edge and no obvious residue in the blank area; “collapse” means the resist pattern is peeled off and broken, which is an undesirable condition; and “bridge” means the upper or lower part of the resist pattern is in contact with each other, which is an undesirable condition.

[0258] [Table 8]

[0259] [Evaluation of film thickness changes after storage at 35°C for 1 month]

[0260] Spin coating was performed on the resist underlayer film forming composition solution prepared according to Examples 1, 6, 8, 10 and Comparative Example 2 of the present invention, and the solution was heated at 215°C for 1 minute to obtain a resist underlayer film, and the film thickness was measured. Alternatively, the resist underlayer film forming composition solution prepared according to Examples 1, 6, 8, 10 and Comparative Example 2 of the present invention was stored at 35°C for 1 month, and then spin coated on, heated at 215°C for 1 minute to obtain a resist underlayer film, and the film thickness was measured.

[0261] In Table 7, "good" indicates that the film thickness after one month of storage at 35°C changes by less than 1 nm compared to the initial film thickness, while "bad" indicates that the film thickness after one month of storage at 35°C changes by more than 1 nm compared to the initial film thickness.

[0262] [Table 9]

[0263] Industrial availability

[0264] The present invention can be used in compositions for forming a lower layer of resist film such as ArF and KrF photoresist, compositions for forming a lower layer of resist film such as EUV resist, compositions for forming an upper layer of resist such as EUV resist, compositions for forming a lower layer of resist film such as electron beam resist, compositions for forming an upper layer of resist such as electron beam resist, and compositions for forming a reverse (reverse) material.

Claims

1. A composition for forming a lower layer film of a resist used in EUV photolithography containing an aliphatic polycyclic structure, wherein, As silanes, they include hydrolyzable silanes, their hydrolysates, their hydrolysate condensates, or combinations thereof. The composition comprises the hydrolytic condensate having structural units from a hydrolyzable silane having an aliphatic polycyclic structure as shown in formula (1), and structural units from a silane compound having a sulfonyl structure as shown in formula (1-1) below. In equation (1), R 1 It is an organic group containing an aliphatic polycyclic structure and bonded to Si atoms through Si-C bonds; R 2 It is an alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, or an organic group having an epoxy, acryloyl, methacryloyl, mercapto, amino, or cyano group, and is bonded to a silicon atom via a Si-C bond; R 3 It represents ethoxy; a represents the integer 1, b represents the integer from 0 to 2, and a+b represents the integer from 1 to 3. 。 2. The composition for forming the lower layer of resist for EUV photolithography according to claim 1, wherein R in formula (1) 1 It is a substituted norbornene, a substituted norbornane, an aliphatic polycyclic group containing heteroatoms, or an organic group containing a substituted norbornene, a substituted norbornane, or an aliphatic polycyclic group containing heteroatoms.

3. The composition for forming the lower layer of resist for EUV photolithography according to claim 2, wherein R in formula (1) 1 The substituents are carboxyl, carboxylic anhydride, carboxylic ester, hydroxyl, alkoxy, or oxygen atoms.

4. The composition for forming the lower layer of resist for EUV exposure lithography according to claim 1, wherein the hydrolyzable silane is a combination of the hydrolyzable silane of formula (1) and other hydrolyzable silanes. Other hydrolyzable silanes are selected from at least one hydrolyzable silane from formulas (2) and (3). In equation (2), R 4 It is an alkyl, aryl, haloalkyl, haloaryl, alkoxyaryl, alkenyl, or organic group having an epoxy, acryloyl, methacryloyl, mercapto, or cyano group, and is bonded to a silicon atom via a Si-C bond. 5 It represents an alkoxy, acyloxy, or halogen group, and c represents an integer from 0 to 3; In equation (3), R 6 It is an alkyl group and is bonded to silicon atoms via Si-C bonds, R 7 Y represents an alkoxy, acyloxy, or halogen group; d represents an alkylene or arylene group; and e represents an integer of 0 or 1.

5. A composition for forming a resist underlayer film for EUV exposure lithography, comprising, in polymer form, a hydrolytic condensate of a hydrolytic silane formed by a combination of a hydrolytic silane of formula (1) as described in claim 1 and a hydrolytic silane of formula (2) as described in claim 4.

6. The composition for forming a resist underlayer film for EUV exposure lithography according to any one of claims 1 to 5, further comprising an acid as a hydrolysis catalyst.

7. The composition for forming a resist underlayer film for EUV exposure lithography according to any one of claims 1 to 5, further comprising water.

8. A resist underlayer film for EUV exposure lithography is obtained by coating a resist underlayer film forming composition for EUV exposure lithography as described in any one of claims 1 to 7 onto a semiconductor substrate and then firing it.

9. A method for manufacturing a semiconductor device, comprising the steps of: coating a composition for forming a resist underlayer film for EUV exposure lithography as described in any one of claims 1 to 7 onto a semiconductor substrate and firing it to form a resist underlayer film for EUV exposure lithography; and coating a resist composition onto the underlayer film to form a resist film. The process of exposing the resist film; The process includes: developing the resist film after exposure to obtain a resist pattern; etching the resist underlayer using the resist pattern; and processing a semiconductor substrate using the patterned resist and resist underlayer.

10. A method for manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a semiconductor substrate; coating the substrate with a composition for forming an EUV photoresist underlayer film according to any one of claims 1 to 7, and firing it to form an EUV photoresist underlayer film; and coating the photoresist underlayer film with a photoresist composition to form a photoresist film. The process of exposing the resist film; The process includes: developing the resist film after exposure to obtain a resist pattern; etching a resist underlayer using the resist pattern; etching an organic underlayer using the patterned resist underlayer; and processing a semiconductor substrate using the patterned organic underlayer.

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