JP2009030006A - Silicon-containing film-forming composition, silicon-containing film, silicon-containing film-forming substrate and patterning method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-curable silicon-containing film-forming composition that forms an excellent pattern by using a formed silicon-containing intermediate film and ensures effective transfer of a photoresist pattern and accurate processing of a substrate. <P>SOLUTION: The heat-curable silicon-containing film-forming composition comprises (A) a silicon-containing compound obtained through hydrolytic condensation of a hydrolyzable silicon compound in the presence of an acid catalyst, (B) a compound represented by the formula (1): L<SB>a</SB>H<SB>b</SB>X (wherein L is Li, Na, K, Rb or Ce; X is a hydroxy group or an organic acid group; a is ≥1; and b is 0 or ≥1) or (2) a compound represented by the formula (2): M<SB>a</SB>H<SB>b</SB>A (wherein M is sulfonium, iodonium or ammonium; and A is the X or a nonnucleophilic counter ion), (C) an organic acid, (D) an alcohol containing a cyclic ether as a substituent group and (E) an organic solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a silicon-containing film used as an intermediate layer of a multilayer resist method used for microfabrication in a manufacturing process of a semiconductor element or the like, particularly a silicon-containing film forming composition suitable for forming an intermediate layer by spin coating. The present invention relates to a silicon-containing film formed using the same, a silicon-containing film-formed substrate, and a pattern forming method using the same.

  With the high integration and high speed of LSI, the pattern size is rapidly miniaturized. In accordance with the miniaturization, the lithography technique has achieved the formation of a fine pattern by shortening the wavelength of the light source and appropriately selecting the resist composition corresponding thereto. At the center of this is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a resist structure in which a resist resin has a skeleton having etching resistance to dry etching by chlorine-based or fluorine-based gas plasma, and an exposed portion is dissolved. Thus, the exposed portion is dissolved to form a pattern, and the substrate to be processed to which the resist composition is applied is dry-etched using the remaining resist pattern as an etching mask.

  However, when the film thickness of the photoresist film to be used is miniaturized as it is, that is, when the pattern width is made smaller, the resolution performance of the photoresist film is lowered, and when trying to pattern develop the photoresist film with a developer, The so-called aspect ratio becomes too large, resulting in pattern collapse. For this reason, the photoresist film thickness has been reduced with the miniaturization.

On the other hand, a method of processing a substrate by dry etching using a patterned photoresist film as an etching mask is usually used for processing a substrate to be processed. However, in reality, the substrate is processed between the photoresist film and the substrate to be processed. Since there is no dry etching method that can achieve complete etching selectivity, the resist film is damaged during the processing of the substrate, the resist film collapses during the processing of the substrate, and the resist pattern can be accurately transferred to the substrate to be processed. Disappear. Therefore, with the miniaturization of patterns, high dry etching resistance has been demanded from resist compositions.
Further, since the resin used for the photoresist composition by shortening the exposure wavelength is required to be a resin having low light absorption at the exposure wavelength, novolak resin, polyhydroxystyrene is used against changes to i-line, KrF, and ArF. However, in reality, the etching rate under the above-mentioned dry etching conditions has become faster, and the recent photoresist composition with high resolution has been changed to a resin having an aliphatic polycyclic skeleton. Things tend to be less etch resistant.
For this reason, the substrate to be processed must be dry-etched with a thinner and less resistant photoresist film, and securing materials and processes in this processing step has become an urgent task.

  One method for solving such problems is a multilayer resist method. In this method, a photoresist film, that is, an intermediate film having etching selectivity different from that of the resist upper layer film is interposed between the resist upper layer film and the substrate to be processed to obtain a pattern on the resist upper layer film, and then the upper resist pattern is dry etched. In this method, the pattern is transferred to the intermediate film by dry etching as a mask, and further the pattern is transferred to the substrate to be processed by dry etching using the intermediate film as a dry etching mask.

  In the two-layer resist method, which is one of the multilayer resist methods, for example, there is a method in which a silicon-containing resin is used for the upper layer resist composition and a novolak resin is used as an intermediate film (for example, Patent Document 1: Japanese Patent Laid-Open No. Hei 5- (1997)). 6-95385). Silicon resin exhibits good etching resistance against reactive dry etching by oxygen plasma, but is easily removed by etching using fluorine-based gas plasma. On the other hand, novolak resin is easily removed by reactive dry etching using oxygen gas plasma, but exhibits good etching resistance against dry etching using fluorine-based gas plasma or chlorine-based gas plasma. Therefore, a novolac resin film is formed as a resist intermediate film on the substrate to be processed, and a resist upper film using a silicon-containing resin is formed thereon. Subsequently, pattern formation is performed on the silicon-containing resist film by post-treatment such as irradiation with energy rays and development, and the novolak resin in the portion where the resist pattern is removed by reactive dry etching using oxygen plasma is used as a dry etching mask. The pattern is transferred to the novolac film by removing it by dry etching, and the pattern transferred to the substrate to be processed is etched using fluorine gas plasma or chlorine gas plasma with the pattern transferred to the novolak film as a dry etching mask. be able to.

  In such pattern transfer by dry etching, when the etching resistance of the etching mask is sufficient, a transfer pattern with a relatively good shape can be obtained. Such a problem hardly occurs, and a pattern with a relatively high aspect ratio can be obtained. Therefore, for example, when a resist film using a novolac resin is made to have a thickness corresponding to the film thickness of the intermediate film, the fine pattern that cannot be directly formed due to a pattern collapse at the time of development or the like due to an aspect ratio problem. However, according to the above two-layer resist method, a novolak resin pattern having a sufficient thickness as a dry etching mask for a substrate to be processed can be obtained.

  Further, as a multilayer resist method, there is a three-layer resist method that can be performed using a general resist composition used in a single layer resist method. For example, an organic film made of novolak or the like is formed as a resist underlayer film on a substrate to be processed, a silicon-containing film is formed thereon as a resist intermediate film, and a normal organic photoresist film is formed thereon as a resist upper layer film Form as. For dry etching with fluorine-based gas plasma, the organic resist upper layer film has good etching selectivity with respect to the silicon-containing resist intermediate film, so the resist pattern should be dry-etched with fluorine-based gas plasma. Is transferred to the silicon-containing resist intermediate film. According to this method, it is difficult to form a pattern having a sufficient film thickness for directly processing a substrate to be processed, or a resist composition having insufficient dry etching resistance for processing a substrate. However, if the pattern can be transferred to the silicon-containing film, a novolac film pattern having sufficient dry etching resistance for processing can be obtained as in the two-layer resist method.

Examples of the silicon-containing resist intermediate film used in the three-layer resist method as described above include silicon-containing inorganic films obtained by CVD, such as SiO ₂ films (for example, Patent Document 2: JP-A-7-183194) and SiON films. (For example, Patent Document 3: JP-A-7-181688, etc.) As a film obtained by spin coating, SOG (spin-on glass) film (for example, Patent Document 4: JP-A-5-291208, etc.) Non-Patent Document 1: J. Appl.Polym.Sci., Vol.88, 636-640 (2003)), a crosslinkable silsesquioxane film (for example, Patent Document 5: JP 2005-520354 A), etc. And a polysilane film (for example, Patent Document 6: Japanese Patent Laid-Open No. 11-60735) may be used. Among these, the SiO ₂ film and the SiON film have high performance as a dry etching mask when dry etching the lower organic film, but require a special apparatus for film formation. On the other hand, SOG films, crosslinkable silsesquioxane films, and polysilane films can be formed only by spin coating and heating, and are considered to have high process efficiency.

  The application range of the multilayer resist method is not limited to an attempt to increase the resolution limit of the resist film. Like the via-first method, which is one of the substrate processing methods, if the processed intermediate substrate has a large level difference, there is a large difference in resist film thickness when trying to form a pattern with a single resist film. There arises a problem that the focus cannot be accurately adjusted during exposure. In such a case, the step is filled with a sacrificial film and planarized, and then a resist film is formed thereon to form a resist pattern. In this case, however, the above-described multilayer resist method is inevitably required. (For example, Patent Document 7: Japanese Patent Application Laid-Open No. 2004-349572, etc.).

  There are several problems with silicon-containing films that have been used in such a multilayer resist method. For example, it is well known that when a resist pattern is formed by photolithography, exposure light is reflected by a substrate and interferes with incident light, causing a so-called standing wave problem. In order to obtain a fine pattern with no reflection, it is necessary to insert an antireflection film as an intermediate film. In particular, reflection control is an essential condition under the most advanced high NA exposure conditions.

  Therefore, in order to control reflection, it is necessary to insert an organic antireflection film between the resist upper layer film and the silicon-containing intermediate film in the multilayer resist method, particularly in the process of forming a silicon-containing film as an intermediate layer by CVD. It will be. However, when the organic antireflection film is inserted, it is necessary to pattern the organic antireflection film using the resist upper layer film as a dry etching mask, and after dry etching the antireflection film using the resist upper layer film as a mask during dry etching, The process moves to the processing of the silicon-containing intermediate layer. For this reason, a load of dry etching is applied to the upper-layer photoresist as much as the antireflection film is processed. In particular, the state-of-the-art photoresist film is becoming thinner, and this dry etching load cannot be overlooked. Therefore, a three-layer resist method in which a light-absorbing silicon-containing film that does not cause an etching load as described above is applied as an intermediate film has attracted attention.

  As such a light-absorbing silicon-containing intermediate film, a spin coating type light-absorbing silicon-containing intermediate film is known. For example, a method of giving an aromatic structure as a light absorption structure is disclosed (Patent Document 8: Japanese Patent Application Laid-Open No. 2005-15779). However, the aromatic ring structure that efficiently absorbs light has a function of reducing the dry etching rate in the dry etching process using fluorine-based gas plasma, so that the intermediate film is dry etched without applying a load to the photoresist film. This is a disadvantageous direction. Therefore, it is not preferable to add a large amount of such a light-absorbing substituent, so it is necessary to suppress the introduction amount to a minimum.

  Furthermore, the dry etching rate with respect to reactive dry etching by oxygen gas plasma generally used when processing a resist underlayer film using the intermediate film as a dry etching mask increases the etching selectivity of the intermediate film and the underlayer film. For this purpose, an interlayer film having a silicon content high in reactivity with a fluorine-based etching gas is desired. Thus, it can be said that an intermediate film having a high content of silicon and a component having high reactivity to fluorine gas is preferable as a requirement from processing conditions for both the upper photoresist film and the lower organic film.

  However, the actual composition for forming a spin-coated silicon-containing intermediate film contains an organic substituent so that the silicon-containing compound can be dissolved in an organic solvent. Among the conventionally known silicon-containing intermediate films, a composition for forming an SOG film is not disclosed in Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-) in lithography using KrF excimer laser light. 640 (2003)). However, since there is no description regarding the light absorbing group in this composition, it is expected that the silicon-containing film obtained from this composition has no antireflection function. For this reason, lithography using a state-of-the-art high NA exposure machine cannot suppress reflection during exposure, and thus may not be able to obtain a high-definition pattern shape.

  In addition to the requirements for the dry etching characteristics and the antireflection effect as described above, the storage stability of the composition is particularly problematic in the composition for forming an intermediate film having a high silicon content. The storage stability in this case may be that the silanol group in the silicon-containing compound contained in the composition is condensed and the molecular weight of the composition changes. Then, film thickness fluctuations and lithography performance fluctuations are observed. In particular, since fluctuations in lithography performance are sensitive, even if silanol groups in the molecule are condensed and cannot be observed as an increase in film thickness or a change in molecular weight, they are observed as a change in high-definition pattern shape.

Conventionally, if such highly reactive silanol groups can be kept relatively stable in an acidic state, Non-Patent Document 2 (CJ Brinker and GW Scherer, “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing ", Academic Press, San Diego (1990)) and the like. Furthermore, Non-Patent Document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)), Patent Document 9 (JP 2004-157469 A), and Patent Document 10 (JP 2004-191386). No.) and the like disclose that water is added to improve storage stability. However, in the case of silicon-containing compounds produced by the method disclosed in the patent document, the silanol group condensation reaction cannot actually be completely stopped even if such measures are taken. The silicon-containing compound changes slowly, and the properties of the silicon-containing film obtained from the changed composition also change. Therefore, it must be stored refrigerated or frozen until just before use, returned to the use temperature (usually 23 ° C.) and used up quickly.
JP-A-6-95385 JP-A-7-183194 JP-A-7-181688 Japanese Patent Laid-Open No. 5-291208 JP 2005-520354 A Japanese Patent Laid-Open No. 11-60735 JP 2004-349572 A JP-A-2005-15779 JP 2004-157469 A JP 2004-191386 A J. et al. Appl. Polym. Sci. , Vol. 88, 636-640 (2003) C. J. et al. Brinker and G.M. W. Scherer, “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing”, Academic Press, San Diego (1990).

  The problems of the present invention are as follows: (1) When a photoresist film is formed on a silicon-containing film formed on an organic film, and then a resist pattern is formed, the silicon-containing film has a light absorption performance, so that a high NA A good pattern can be formed even under exposure conditions, and (2) a good silicon-containing film for a dry etching mask can be formed between a photoresist film that is an upper layer of a silicon-containing film and an organic film that is a lower layer. 3) To provide a silicon-containing film-forming composition having good storage stability, a silicon-containing film obtained from the composition, a substrate on which the silicon-containing film is formed, and a pattern forming method.

The present inventors diligently studied the lithography characteristics and stability of the silicon-containing intermediate film forming composition. As a result, the silicon-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound using an acid as a catalyst. By adding the following component (B), component (C), component (D) and component (E),
(1) By introducing a light-absorbing substituent described later, it is possible to obtain a silicon-containing film that can suppress reflection under high NA exposure conditions of either dry or immersion.
(2) A silicon-containing film is obtained that has a sufficient etching selectivity as a dry etching mask.
(3) The present inventors have found that a composition for forming a silicon-containing film that does not change in performance while maintaining lithography performance for a long period of time can be obtained, and the present invention has been completed.

That is, the present invention provides (A) a silicon-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound using an acid as a catalyst,
(B) One or more compounds represented by the following general formula (1) or (2),
L _a H _b X (1)
(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, and b is 0. Or an integer of 1 or more, and a + b is a valence of a hydroxyl group or an organic acid group.)
M _a H _{b A} (2)
(In the formula, M is sulfonium, iodonium or ammonium, A is the above X or non-nucleophilic counter ion, a and b are the same as above, and a + b is a hydroxyl group, an organic acid group or a non-nucleophilic counter ion. The valence of
(C) a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms,
(D) a monovalent or divalent alcohol having a cyclic ether as a substituent,
(E) A thermosetting silicon-containing film-forming composition comprising an organic solvent is provided (claim 1).

  Generally, when water is allowed to act on a hydrolyzable silicon compound (hereinafter referred to as a monomer) in the presence of an acid catalyst, the hydrolyzable substituent bonded to the silicon atom is hydrolyzed to form a silanol group. This silanol group further undergoes a condensation reaction with another silanol group or an unreacted hydrolyzable group to form a siloxane bond. This reaction repeatedly occurs one after another, forming so-called oligomers and polymers, and in some cases, silicon-containing compounds called sols. At this time, the condensation reaction proceeds in order from the most reactive among the silanol groups derived from the monomers, oligomers, polymers, etc. produced by the hydrolysis reaction in the system and belongs to the monomers, oligomers, polymers, etc. Silanol groups are consumed and silicon-containing compounds are formed. This condensation reaction proceeds indefinitely, and may proceed until the silicon-containing compound solution is finally gelled.

  However, the fact that this condensation reaction is suppressed at a specific pH is described in Non-Patent Document 2 (CJ Brinker and GW Scherer, “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing”, Academic Press, San Diego (1990), etc., and in particular, in non-patent document 1 (J. Appl. Polym. Sci., Vol. 88, 636-640 (2003)), the pH is about 1.5 ( Hereinafter, it is described as being stabilized at a stable pH.

  In the present invention, it has been found that when the pH is controlled to a stable pH using the component (C), the storage stability is improved.

  Furthermore, when intensive studies were made to suppress the condensation of the remaining silanol groups contained in the silicon-containing compound near room temperature, a monovalent or divalent alcohol having a cyclic ether as a substituent was added as a stabilizer. It has been found that condensation near room temperature is suppressed and the storage stability of the composition is dramatically improved.

  Conventionally, silicon-containing compounds have been cured by an acid catalyst using a high temperature of 300 ° C. or higher or a thermal acid generator. In the present invention, when the composition is applied and heat-cured, the pH around the silanol group is lowered from the stable pH by the action of the added component (B) (around pH 3, non-patent document 2). : CJ Brinker and GW Scherer, “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing”, described in Academic Press, San Diego (1990). It became possible to cure the film. That is, when heat-cured under the same conditions as the conventional temperature conditions, it is possible to provide a film that has undergone much more crosslinking than conventional cured films. Therefore, the movement of the active ingredient in the resist film to the silicon-containing film is suppressed, and lithographic properties comparable to those of a normal organic antireflection film can be obtained.

  Thus, a combination of techniques of pH control, addition of a stabilizer and addition of a crosslinking catalyst has been found to provide a composition that is stable at room temperature and can be cured efficiently at the time of curing, thereby achieving the same stability as a conventional organic antireflection coating. A silicon-containing antireflection film composition can be obtained.

  In the present invention, as the silicon-containing compound, the acid catalyst is obtained from a reaction mixture obtained by hydrolytic condensation of a hydrolyzable silicon compound using one or more compounds selected from inorganic acids and sulfonic acid derivatives as an acid catalyst. 2. The thermosetting silicon-containing film-forming composition according to claim 1, comprising a silicon-containing compound that can be obtained through a substantially removing step (claim 2).

  The silicon-containing compound produced by the prior art has been used in a composition for forming a coating film without substantially removing the acid catalyst used during hydrolysis condensation. Therefore, since the condensation reaction catalyst remains in the composition, even a composition controlled to a stable pH cannot suppress silanol condensation, and only a composition having poor storage stability can be obtained.

  In addition, in the composition for forming a coating film obtained by using an acidic substance having a stable pH of silanol as a hydrolysis condensation catalyst from the beginning, the silanol group condensation reaction does not sufficiently proceed. Will increase. Therefore, even if the composition is kept at a stable pH, the amount of silanol groups is too large, so that only a composition having low storage stability can be obtained.

  In the present invention, after substantially removing the acid catalyst from the silicon-containing compound obtained using the acid catalyst optimal for hydrolysis condensation, the storage stability is improved by using the components (C) and (D). It became possible to make it.

  In the present invention, there is provided the thermosetting silicon-containing film forming composition according to claim 1 or 2, wherein M in the general formula (2) is tertiary sulfonium, secondary iodonium or quaternary ammonium. 3).

  When a cured film is formed using a composition using the compound represented by formula (2) as the component (B), a crosslinked film can be provided. Therefore, the movement of the active ingredient in the resist film to the silicon-containing film is suppressed, and lithographic properties comparable to those of a normal organic antireflection film can be obtained.

  In this invention, M of General formula (2) is photodegradable, The composition for thermosetting silicon containing film formation of Claims 1-3 characterized by the above-mentioned is provided (Claim 4).

  When the component (B) does not volatilize at the time of heat curing, the component (B) may remain in the silicon-containing film. This component may deteriorate the resist pattern shape. On the other hand, when a compound in which the cation portion of the component (B) is decomposed during exposure is used, it is possible to prevent the resist pattern shape from being deteriorated during exposure. Therefore, it has been found that the curing performance of the silicon-containing compound is dramatically improved and a silicon-containing cured film having a good lithography shape can be provided.

  The present invention provides the composition for forming a thermosetting silicon-containing film according to any one of claims 1 to 4, which contains water (claim 5).

  By adding water, silanol groups in the silicon-containing compound are activated, and a denser film can be obtained by a thermosetting reaction. When such a dense film is used, the lithography performance of the upper photoresist layer can be made to be equal to or higher than that of a general organic antireflection film.

  The present invention further provides a composition for forming a thermosetting silicon-containing film according to any one of claims 1 to 5, further comprising a photoacid generator (claim 6).

  When the component (B) does not volatilize at the time of heat curing or exposure, the component (B) remaining in the silicon-containing film may affect the pattern shape. In order to prevent this, it is possible to prevent deterioration of the resist pattern shape by generating an acid in the silicon-containing film when forming the resist pattern.

The present invention further provides the following silicon-containing film, substrate and pattern forming method.
An organic film is formed on a substrate to be processed, a silicon-containing film is formed thereon, and a resist film is further formed thereon using a chemically amplified resist composition not containing silicon, and this resist film is patterned. After that, the silicon-containing film is patterned using the resist film pattern, the lower organic film is patterned using the processed silicon-containing film pattern as an etching mask, and further processed using the processed organic film as an etching mask. A silicon-containing film used in a multilayer resist method for etching a substrate, wherein the silicon-containing film is formed from the composition according to any one of claims 1 to 6 (claim 7).

In the step of the multilayer resist method according to claim 7, a silicon-containing film used in a multilayer resist method in which an organic antireflection film is interposed between a resist film obtained from a chemically amplified resist composition and a silicon-containing film, A silicon-containing film formed from the composition according to any one of claims 1 to 6 (claim 8).
An organic film, a silicon-containing film formed from the composition according to any one of claims 1 to 6 on the organic film, and a photoresist film are sequentially formed thereon. A substrate characterized by the above (claim 9).

An organic film, a silicon-containing film formed from the composition according to any one of claims 1 to 6, an organic antireflection film, and a photoresist film are sequentially formed on the organic film. A substrate characterized in that it is made (claim 10).
11. The substrate according to claim 9 or 10, wherein the organic film is a film having an aromatic skeleton.

  A method for forming a pattern on a substrate, comprising preparing the substrate according to claim 9, exposing a pattern circuit region of the photoresist film on the substrate, and then developing with a developer to form a resist pattern on the photoresist film The silicon-containing film is dry-etched using the photoresist film on which the resist pattern is formed as an etching mask, and the organic film is etched using the silicon-containing film on which the pattern is formed as an etching mask. A pattern forming method comprising: forming a pattern on a substrate by etching the substrate using the film as a mask (claim 12).

  A method of forming a pattern on a substrate, comprising preparing the substrate according to claim 10, exposing a pattern circuit region of the photoresist film on the substrate, and then developing with a developer to form a resist pattern on the photoresist film The organic antireflection film and the silicon-containing film are dry-etched using the photoresist film on which the resist pattern is formed as an etching mask, and the organic film is etched using the silicon-containing film on which the pattern is formed as an etching mask. A pattern forming method characterized in that a pattern is formed on a substrate by etching the substrate using the organic film formed with a mask as a mask (claim 13).

  14. The pattern forming method according to claim 12 or 13, wherein the organic film is a film having an aromatic skeleton.

  15. The pattern forming method according to claim 12, 13 or 14, wherein the resist pattern is formed by using a photolithography method using light having a wavelength of 300 nm or less.

If a pattern is formed on a substrate by lithography using the intermediate film or substrate of the present invention, a fine pattern can be formed on the substrate with high accuracy.
In this case, when an organic film having an aromatic skeleton is used, not only has an antireflection effect in the lithography process, but also an organic film having sufficient etching resistance when the substrate is etched, and etching is possible.
In the present invention, when a pattern is formed by lithography using light having a wavelength of 300 nm or less, particularly an ArF excimer laser, a fine pattern can be formed with high accuracy.

  By using the silicon-containing intermediate film formed using the thermosetting silicon-containing film-forming composition of the present invention, it is possible to form a favorable pattern on the photoresist film formed thereon. Moreover, since high etching selectivity is obtained with respect to the organic material, the formed photoresist pattern can be transferred using the dry etching process in order of the silicon-containing intermediate film and the organic underlayer film. Finally, the substrate can be processed with high accuracy using the organic underlayer film as an etching mask. In addition, the generation of pattern defects after lithography can be suppressed, and a material excellent in storage stability can be provided.

  In the thermosetting silicon-containing film forming composition of the present invention, the silicon-containing compound used in the present invention is obtained by hydrolytic condensation of a monomer (hydrolyzable silicon compound) with an acid catalyst. Although the following method can be illustrated as a manufacturing method of a preferable silicon-containing compound, it is not restricted to this method.

The monomer used as a starting material can be represented by the following general formula (3).
R ¹ _m1 R ² _m2 R ³ _m3 Si (OR) _(4-m1-m2-m3) (3)
(R is an alkyl group having 1 to 3 carbon atoms, and R ¹ , R ² and R ³ may be the same or different from each other, and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. , M1, m2, and m3 are 0 or 1. m1 + m2 + m3 is preferably 0 to 3, particularly preferably 0 or 1.)
One obtained by hydrolyzing and condensing one or more mixtures selected from the monomers represented by the general formula (3).

Here, the organic group means a group containing carbon, further contains hydrogen, and may contain nitrogen, oxygen, sulfur, silicon and the like. Examples of the organic group for R ¹ , R ² , and R ³ include linear, branched, and cyclic alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, and other unsubstituted monovalent hydrocarbon groups, and these A group in which one or more of the hydrogen atoms of the group is substituted with an epoxy group, an alkoxy group, a hydroxy group, or the like, or -O-, -CO-, -OCO-, -COO-, -OCOO- are interposed And a group represented by the general formula (4) to be described later, an organic group containing a silicon-silicon bond, and the like.

Preferred as R ¹ , R ² , R ³ of the monomer represented by the general formula (3) are hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl. Group, sec-butyl group, t-butyl group, n-pentyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-diethylpropyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and other alkyl groups, Examples thereof include alkenyl groups such as a vinyl group and an allyl group, alkynyl groups such as an ethynyl group, and aryl groups such as a phenyl group and a tolyl group, and aralkyl groups such as a benzyl group and a phenethyl group as light absorbing groups.

  For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxysilane can be exemplified as monomers as the tetraalkoxysilane in which m1 = 0, m2 = 0, and m3 = 0. Tetramethoxysilane and tetraethoxysilane are preferable.

  For example, as trialkoxysilane in which m1 = 1, m2 = 0, m3 = 0, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-iso-propoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltri-n-propoxysilane, vinyltri-iso-propoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-i o-propoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, n-butyltrimethoxysilane, n-butyltri Ethoxysilane, n-butyltri-npropoxysilane, n-butyltri-iso-propoxysilane, sec-butyltrimethoxysilane, sec-butyl-triethoxysilane, sec-butyl-tri-n-propoxysilane, sec-butyl- Tri-iso-propoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltri-npropoxysilane, t-butyltri-iso-propoxysilane, cyclopropyltrimethoxysilane, cyclopropyltrieth Sisilane, cyclopropyl-tri-n-propoxysilane, cyclopropyl-tri-iso-propoxysilane, cyclobutyltrimethoxysilane, cyclobutyltriethoxysilane, cyclobutyl-tri-n-propoxysilane, cyclobutyl-tri-iso-propoxy Silane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclopentyl-tri-n-propoxysilane, cyclopentyl-tri-iso-propoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyl-tri-n-propoxysilane, cyclohexyl -Tri-iso-propoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyl-to Ri-n-propoxysilane, cyclohexenyl-tri-iso-propoxysilane, cyclohexenylethyltrimethoxysilane, cyclohexenylethyltriethoxysilane, cyclohexenylethyl-tri-n-propoxysilane, cyclohexenylethyltri-iso-propoxy Silane, cyclooctanyltrimethoxysilane, cyclooctanyltriethoxysilane, cyclooctanyl-tri-n-propoxysilane, cyclooctanyl-tri-iso-propoxysilane, cyclopentadienylpropyltrimethoxysilane, cyclopentadi Enylpropyltriethoxysilane, cyclopentadienylpropyl-tri-n-propoxysilane, cyclopentadienylpropyl-tri-iso-propoxysilane, bicyclohepteni Trimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenyl-tri-n-propoxysilane, bicycloheptenyl-tri-iso-propoxysilane, bicycloheptyltrimethoxysilane, bicycloheptyltriethoxysilane, bicycloheptyl-tri- Examples thereof include n-propoxysilane, bicycloheptyl-tri-iso-propoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, adamantyl-tri-n-propoxysilane, adamantyl-tri-iso-propoxysilane and the like. Further, as a light-absorbing monomer, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, benzyltri-n-propoxysilane Benzyltri-iso-propoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltri-n-propoxysilane, tolyltri-iso-propoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltri-n-propoxysilane, Phenethyl tri-iso-propoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltri-n-propoxysilane, naphthyltri-i It can be exemplified o- propoxy silane.

  Preferably, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyl Trimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltrimethoxysilane, iso-butyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyl Trimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohex Cycloalkenyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, benzyl trimethoxysilane, benzyl triethoxysilane, phenethyl trimethoxysilane, phenethyl triethoxysilane.

  For example, as dialkoxysilane in which m1 = 1, m2 = 1, m3 = 0, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl -Di-iso-propoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxy Silane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, diiso-propyl- Di-n-propoxysilane, -Iso-propyl-di-iso-propoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyl-di-iso- Propoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di-t- Butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butyl-di-n-propoxysilane, di-t-butyl-di-iso-propoxysilane, di-cyclopropyldimethoxysilane, di-cyclopropyldi Ethoxysilane, di-cyclopropyl-di-n-propoxysilane, di-cyclopropyl-di-is -Propoxysilane, di-cyclobutyldimethoxysilane, di-cyclobutyldiethoxysilane, di-cyclobutyl-di-n-propoxysilane, di-cyclobutyl-di-iso-propoxysilane, di-cyclopentyldimethoxysilane, di-cyclopentyl Diethoxysilane, di-cyclopentyl-di-n-propoxysilane, di-cyclopentyl-di-iso-propoxysilane, di-cyclohexyldimethoxysilane, di-cyclohexyldiethoxysilane, di-cyclohexyl-di-n-propoxysilane, Di-cyclohexyl-di-iso-propoxysilane, di-cyclohexenyldimethoxysilane, di-cyclohexenyldiethoxysilane, dicyclohexenyl-di-n-propoxysilane, di-cyclohexenyl-di-i so-propoxysilane, di-cyclohexenylethyldimethoxysilane, di-cyclohexenylethyldiethoxysilane, di-cyclohexenylethyl-di-n-propoxysilane, di-cyclohexenylethyl-di-iso-propoxysilane, di- Cyclooctanyldimethoxysilane, di-cyclooctanyldiethoxysilane, dicyclooctanyl-di-n-propoxysilane, di-cyclooctanyl-di-iso-propoxysilane, di-cyclopentadienylpropyldimethoxysilane, Di-cyclopentadienylpropyldiethoxysilane, di-cyclopentadienylpropyl-di-n-propoxysilane, di-cyclopentadienylpropyl-di-iso-propoxysilane, bis-bicycloheptenyldimethoxysilane, bi -Bicycloheptenyldiethoxysilane, bis-bicycloheptenyl-di-n-propoxysilane, bis-bicycloheptenyl-di-iso-propoxysilane, bis-bicycloheptyldimethoxysilane, bis-bicycloheptyldiethoxysilane, bis -Bicycloheptyl-di-n-propoxysilane, bis-bicycloheptyl-di-iso-propoxysilane, bis-adamantyldimethoxysilane, bis-adamantyldiethoxysilane, bis-adamantyl-di-n-propoxysilane, bis-adamantyl -Di-iso-propoxysilane etc. can be illustrated. Examples of the light absorbing monomer include diphenyldimethoxysilane, diphenyl-di-ethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyl-di-npropoxysilane, diphenyl-di-iso-propoxysilane, and the like. .

  Preferably, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, di-n-propyl-di-methoxysilane, di-n-butyldi-methoxy Examples include silane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane.

  For example, examples of the monoalkoxysilane in which m1 = 1, m2 = 1, and m3 = 1 include trimethylmethoxysilane, trimethylethoxysilane, dimethylethylmethoxysilane, and dimethylethylethoxysilane. Examples of the light absorbing monomer include dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethylbenzylmethoxysilane, dimethylbenzylethoxysilane, dimethylphenethylmethoxysilane, dimethylphenethylethoxysilane, and the like.

  Preferable examples include trimethylmethoxysilane, dimethylethylmethoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane and the like.

Another example of the organic group represented by R ¹ , R ² , or R ³ is an organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds. Specifically, it is an organic group having one or more groups selected from the group consisting of an epoxy group, an ester group, an alkoxy group, and a hydroxy group. Examples of the organic group having at least one carbon-oxygen single bond and carbon-oxygen double bond in the general formula (3) include those represented by the following general formula (4).

炭素数１〜４のアルコキシ基、炭素数１〜６のアルキルカルボニルオキシ基、又は炭素数１〜６のアルキルカルボニル基であり、Ｑ₁とＱ₂とＱ₃とＱ₄は各々独立して−Ｃ_qＨ_(2q-p)Ｐ_p−（式中、Ｐは上記と同様であり、ｐは０〜３の整数であり、ｑは０〜１０の整数（但し、ｑ＝０は単結合であることを示す。）である。）、ｕは０〜３の整数であり、Ｓ₁とＳ₂は各々独立して−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−又は−ＯＣＯＯ−を表す。ｖ１、ｖ２、ｖ３は、各々独立して０又は１を表す。これらとともに、Ｔはヘテロ原子を含んでもよい脂環又は芳香環からなる２価の基であり、Ｔの酸素原子等のヘテロ原子を含んでもよい脂環又は芳香環の例を以下に示す。ＴにおいてＱ₂とＱ₃と結合する位置は、特に限定されないが、立体的な要因による反応性や反応に用いる市販試薬の入手性等を考慮して適宜選択できる。） _{(P-Q 1 - (S} 1) v1 -Q 2 -) u - (T) v2 -Q 3 - (S 2) v3 -Q 4 - (4)
(In the above formula, P is a hydrogen atom, a hydroxyl group,

An alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or an alkylcarbonyl group having 1 to 6 carbon atoms, and Q ₁ , Q ₂ , Q _3, and Q ₄ are each independently- C _q H _(2q-p) P _p — (wherein P is the same as above, p is an integer of 0 to 3, q is an integer of 0 to 10 (provided that q = 0 is a single bond) And u is an integer of 0 to 3, and S ₁ and S ₂ are each independently —O—, —CO—, —OCO—, —COO— or —OCOO—. Represents. v1, v2, and v3 each independently represent 0 or 1. Together with these, T is a divalent group composed of an alicyclic ring or an aromatic ring which may contain a hetero atom, and examples of the alicyclic ring or aromatic ring which may contain a hetero atom such as an oxygen atom of T are shown below. The position where Q ₂ and Q ₃ are bonded to each other in T is not particularly limited, but can be appropriately selected in consideration of reactivity due to steric factors, availability of commercially available reagents used in the reaction, and the like. )

  Preferable examples of the organic group having one or more carbon-oxygen single bonds or carbon-oxygen double bonds in the general formula (3) include the following. In the following formula, (Si) is shown to indicate the bonding site with Si.

Moreover, as an example of the organic groups of R ¹ , R ² , and R ³ , an organic group containing a silicon-silicon bond can be used. Specifically, the following can be mentioned.

  One or more of these monomers can be selected and used as a reaction raw material to form a silicon-containing compound by mixing before or during the reaction.

The silicon-containing compound can be produced by performing hydrolysis condensation using a monomer, preferably using one or more compounds selected from inorganic acids, aliphatic sulfonic acids and aromatic sulfonic acids as an acid catalyst.
Examples of the acid catalyst used at this time include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. The catalyst is used in an amount of 10 ⁻⁶ to 10 mol, preferably 10 ^{−5 to} 5 mol, more preferably 10 ⁻⁴ to 1 mol, relative to 1 mol of silicon monomer.

  The amount of water when obtaining a silicon-containing compound from these monomers by hydrolysis condensation is 0.01 to 100 mol, more preferably 0.05 to 50 mol, per mol of hydrolyzable substituent bonded to the monomer. More preferably, 0.1 to 30 mol is added. Addition in excess of 100 moles is uneconomical because only the apparatus used for the reaction becomes excessive.

  As an operation method, a monomer is added to an aqueous catalyst solution to start a hydrolysis condensation reaction. At this time, an organic solvent may be added to the catalyst aqueous solution, the monomer may be diluted with the organic solvent, or both may be performed. The reaction temperature is 0 to 100 ° C, preferably 5 to 80 ° C. A method in which the temperature is maintained at 5 to 80 ° C. when the monomer is dropped and then ripened at 20 to 80 ° C. is preferable.

  Examples of organic solvents that can be added to the catalyst aqueous solution or that can dilute the monomer include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and acetone. , Acetonitrile, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene Glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, γ-Butyllactone and mixtures thereof are preferred.

Among these solvents, preferred are water-soluble ones. For example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, Examples thereof include polyhydric alcohol condensate derivatives such as propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran and the like.
Among these, those having a boiling point of 100 ° C. or less are particularly preferable.

  In addition, the usage-amount of an organic solvent is 0-1,000 ml with respect to 1 mol of monomers, Especially 0-500 ml is preferable. If the amount of organic solvent used is large, the reaction vessel becomes excessive and uneconomical.

  Thereafter, if necessary, a neutralization reaction of the catalyst is performed, and the alcohol produced by the hydrolysis condensation reaction is removed under reduced pressure to obtain an aqueous reaction mixture solution. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. The alkaline substance may be any substance as long as it shows alkalinity in water.

  Subsequently, the alcohol produced by the hydrolytic condensation reaction must be removed from the reaction mixture. The temperature at which the reaction mixture is heated at this time is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and even more preferably 15 to 80 ° C., although it depends on the added organic solvent and the type of alcohol generated by the reaction. The degree of reduced pressure at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably atmospheric pressure or lower, more preferably absolute pressure of 80 kPa or lower, and still more preferably absolute pressure. Is 50 kPa or less. Although it is difficult to accurately know the amount of alcohol removed at this time, it is desirable to remove approximately 80% by mass or more of the produced alcohol.

  Next, the acid catalyst used for the hydrolysis condensation may be removed from the reaction mixture. As a method for removing the acid catalyst, water and a silicon-containing compound are mixed, and the silicon-containing compound is extracted with an organic solvent. The organic solvent used at this time is preferably one that can dissolve the silicon-containing compound and separates into two layers when mixed with water. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl-2-n-amyl ketone, Butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether , Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Recall monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether Examples include acetate, γ-butyl lactone, methyl isobutyl ketone, cyclopentyl methyl ether, and the like, and mixtures thereof.

  It is also possible to use a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent. For example, methanol + ethyl acetate, ethanol + ethyl acetate, 1-propanol + ethyl acetate, 2-propanol + ethyl acetate, butanediol monomethyl ether + ethyl acetate, propylene glycol monomethyl ether + ethyl acetate, ethylene glycol monomethyl ether, butanediol monoethyl Ether + ethyl acetate, propylene glycol monoethyl ether + ethyl acetate, ethylene glycol monoethyl ether + ethyl acetate, butanediol monopropyl ether + ethyl acetate, propylene glycol monopropyl ether + ethyl acetate, ethylene glycol monopropyl ether + ethyl acetate, Methanol + methyl isobutyl ketone, ethanol + methyl isobutyl ketone, 1-propanol + methyl isobutyl ketone, -Propanol + methyl isobutyl ketone, propylene glycol monomethyl ether + methyl isobutyl ketone, ethylene glycol monomethyl ether, propylene glycol monoethyl ether + methyl isobutyl ketone, ethylene glycol monoethyl ether + methyl isobutyl ketone, propylene glycol monopropyl ether + methyl isobutyl ketone , Ethylene glycol monopropyl ether + methyl isobutyl ketone, methanol + cyclopentyl methyl ether, ethanol + cyclopentyl methyl ether, 1-propanol + cyclopentyl methyl ether, 2-propanol + cyclopentyl methyl ether, propylene glycol monomethyl ether + cyclopentyl methyl ether, ethylene glycol Monomethyl ether + cyclopentyl methyl ether, propylene glycol monoethyl ether + cyclopentyl methyl ether, ethylene glycol monoethyl ether + cyclopentyl methyl ether, propylene glycol monopropyl ether + cyclopentyl methyl ether, ethylene glycol monopropyl ether + cyclopentyl methyl ether, methanol + propylene Glycol methyl ether acetate, ethanol + propylene glycol methyl ether acetate, 1-propanol + propylene glycol methyl ether acetate, 2-propanol + propylene glycol methyl ether acetate, propylene glycol monomethyl ether + propylene glycol methyl ether acetate, ethyl Glycol monomethyl ether + propylene glycol methyl ether acetate, propylene glycol monoethyl ether + propylene glycol methyl ether acetate, ethylene glycol monoethyl ether + propylene glycol methyl ether acetate, propylene glycol monopropyl ether + propylene glycol methyl ether acetate, ethylene glycol mono A combination such as propyl ether + propylene glycol methyl ether acetate is preferable, but the combination is not limited thereto.

  In addition, the mixing ratio of the water-soluble organic solvent and the poorly water-soluble organic solvent is appropriately selected, but the water-soluble organic solvent is 0.1 to 1,000 parts by weight, preferably 100 parts by weight of the poorly water-soluble organic solvent, preferably 1 to 500 parts by mass, more preferably 2 to 100 parts by mass.

Subsequently, it is washed with neutral water. As this water, what is usually called deionized water or ultrapure water may be used. The amount of this water is 0.01 to 100 L, preferably 0.05 to 50 L, more preferably 0.1 to 5 L with respect to 1 L of the silicon-containing compound solution. In this washing method, both may be placed in the same container, stirred, and allowed to stand to separate the aqueous layer. The number of times of washing may be one or more, but it is preferably about 1 to 5 times because the effect of washing only is not obtained even after washing 10 times or more.
Other methods for removing the acid catalyst include a method using an ion exchange resin and a method of removing the acid catalyst after neutralization with an epoxy compound such as ethylene oxide or propylene oxide. These methods can be appropriately selected according to the acid catalyst used in the reaction.
In the above catalyst removal operation, the acid catalyst is substantially removed means that the acid catalyst used in the reaction is 10% by mass or less, preferably 5% by mass with respect to the amount added at the start of the reaction in the silicon-containing compound. % Remaining below is implied.

  The washing operation at this time may cause a part of the silicon-containing compound to escape to the aqueous layer and may have substantially the same effect as the fractionation operation. In view of the fractionation effect, it may be selected as appropriate.

  In either case of the silicon-containing compound in which the acid catalyst remains or the solution of the silicon-containing compound from which the acid catalyst has been removed, a silicon-containing compound solution is obtained by adding the final solvent and exchanging the solvent under reduced pressure. The temperature of solvent exchange at this time depends on the type of reaction solvent and extraction solvent to be removed, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 15 to 80 ° C. The degree of reduced pressure at this time varies depending on the type of the extraction solvent to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less, more preferably 50 kPa or less. It is as follows.

  At this time, the silicon-containing compound may become unstable due to the change of the solvent. Although this occurs due to the compatibility between the final solvent and the silicon-containing compound, in order to prevent this, a component (C) described later may be added as a stabilizer. The amount to be added is 0 to 25 parts by weight, preferably 0 to 15 parts by weight, more preferably 0 to 5 parts by weight, based on 100 parts by weight of the silicon-containing compound in the solution before the solvent exchange. 0.5 parts by mass or more is preferable. If necessary for the solution before the solvent exchange, the component (C) may be added to perform the solvent exchange operation.

  When a silicon-containing compound is concentrated to a certain concentration or more, a condensation reaction proceeds, and the silicon-containing compound changes to a state in which it cannot be redissolved in an organic solvent. Therefore, it is preferable to keep the solution in an appropriate concentration. As a density | concentration at this time, it is 50 mass% or less, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less.

  Preferred as the final solvent to be added to the silicon-containing compound solution is an alcohol solvent, and particularly preferred are monoalkyl ethers such as ethylene glycol, diethylene glycol and triethylene glycol, and monoalkyl ethers such as propylene glycol and dipropylene glycol. is there. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, Ethylene glycol monopropyl ether and the like are preferable.

  Moreover, as another reaction operation, water or a water-containing organic solvent is added to a monomer or an organic solution of the monomer to start a hydrolysis reaction. At this time, the catalyst may be added to the monomer or the organic solution of the monomer, or may be added to water or a water-containing organic solvent. The reaction temperature is 0 to 100 ° C, preferably 10 to 80 ° C. A method of heating to 10 to 50 ° C. at the time of dropping the water and then raising the temperature to 20 to 80 ° C. for aging is preferable.

  When an organic solvent is used, water-soluble ones are preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, tetrahydrofuran, acetonitrile, butane Diol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, Propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl Chromatography ether acetate, propylene glycol monoethyl ether acetate, a polyhydric alcohol condensate derivatives such as propylene glycol monopropyl ether and the like can be given a mixture thereof.

  The amount of the organic solvent used may be the same as the above amount. The obtained reaction mixture is post-treated in the same manner as described above to obtain a silicon-containing compound.

  The molecular weight of the resulting silicon-containing compound can be adjusted not only by monomer selection but also by controlling reaction conditions during polymerization. And coating spots may occur, and it is preferable to use 100,000 or less, more preferably 200 to 50,000, still more preferably 300 to 30,000. In addition, the data regarding the said weight average molecular weight represent molecular weight in polystyrene conversion, using polystyrene as a standard substance by gel permeation chromatography (GPC) using RI as a detector.

  As long as the composition for forming a silicon-containing film of the present invention is produced under acidic conditions, it may contain two or more kinds of silicon-containing compounds having different compositions and / or reaction conditions.

  A silicon-containing film-forming composition can be prepared by further blending the silicon-containing compound with a thermal crosslinking accelerator (B), an acid (C), a stabilizer (D), and an organic solvent (E).

In the present invention, in order to further promote the crosslinking reaction during the formation of the silicon-containing film, a thermal crosslinking accelerator must be contained as the component (B). As such a thing, the compound shown by General formula (1) or (2) can be mentioned.
L _a H _b X (1)
(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, and b is 0. Or an integer of 1 or more, and a + b is a valence of a hydroxyl group or an organic acid group.)
M _a H _{b A} (2)
(In the formula, M represents sulfonium, iodonium or ammonium, preferably tertiary sulfonium, secondary iodonium or quaternary ammonium, particularly photodegradable compounds, that is, triphenylsulfonium compounds and diphenyliodonium compounds are preferred. Is the above X or non-nucleophilic counterion, a and b are the same as above, and a + b is the valence of the hydroxyl group, organic acid group or non-nucleophilic counterion.)

  Examples of the compound represented by the general formula (1) include alkali metal organic acid salts. For example, lithium, sodium, potassium, rubidium, cesium hydrochloride, formate, acetate, propionate, butanoate, pentanoate, hexanoate, heptanoate, octanoate, nonanoate, Decanoate, oleate, stearate, linoleate, linolenate, benzoate, phthalate, isophthalate, terephthalate, salicylate, trifluoroacetate, monochloroacetate, dichloroacetate Salt, monovalent salt such as trichloroacetate, monovalent or divalent oxalate, malonate, methylmalonate, ethylmalonate, propylmalonate, butylmalonate, dimethylmalonate , Diethyl malonate, succinate, methyl succinate, glutarate, adipate, itaconate, maleate, fumarate, citracone Salt, citric acid, and carbonic acid.

  Specifically, lithium formate, lithium acetate, lithium propionate, lithium butanoate, lithium pentanoate, lithium hexanoate, lithium heptanoate, lithium octanoate, lithium nonanoate, lithium decanoate, lithium oleate, lithium stearate , Lithium linoleate, lithium linolenate, lithium benzoate, lithium phthalate, lithium isophthalate, lithium terephthalate, lithium salicylate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium monochloroacetate, lithium dichloroacetate, lithium trichloroacetate , Lithium hydroxide, lithium hydrogen oxalate, lithium hydrogen malonate, lithium methyl malonate, lithium hydrogen ethylmalonate, lithium hydrogen propylmalonate, Lithium hydrogen phosphate, lithium dimethyl malonate, lithium diethyl malonate, lithium hydrogen succinate, lithium hydrogen methyl succinate, lithium hydrogen glutarate, lithium hydrogen adipate, lithium hydrogen itaconate, lithium hydrogen maleate, hydrogen fumarate Lithium, lithium hydrogen citrate, lithium hydrogen citrate, lithium hydrogen carbonate, lithium oxalate, lithium malonate, lithium methylmalonate, lithium ethylmalonate, lithium propylmalonate, lithium butylmalonate, lithium dimethylmalonate, diethyl Lithium malonate, lithium succinate, lithium methyl succinate, lithium glutarate, lithium adipate, lithium itaconate, lithium maleate, lithium fumarate, lithium citraconic acid, que Lithium acid, lithium carbonate, sodium formate, sodium acetate, sodium propionate, sodium butanoate, sodium pentanoate, sodium hexanoate, sodium heptanoate, sodium octanoate, sodium nonanoate, sodium decanoate, sodium oleate, stearic acid Sodium, sodium linoleate, sodium linolenate, sodium benzoate, sodium phthalate, sodium isophthalate, sodium terephthalate, sodium salicylate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium monochloroacetate, sodium dichloroacetate, trichloroacetic acid Sodium, sodium hydroxide, sodium hydrogen oxalate, sodium hydrogen malonate, sodium hydrogen malonate Sodium hydrogen ethylmalonate, sodium propylmalonate, sodium butylmalonate, sodium dimethylmalonate, sodium diethylmalonate, sodium succinate, sodium methylsuccinate, sodium hydrogenglutarate, hydrogen adipate Sodium, sodium hydrogen itaconate, sodium hydrogen maleate, sodium hydrogen fumarate, sodium citraconic acid, sodium hydrogen citrate, sodium bicarbonate, sodium oxalate, sodium malonate, sodium methylmalonate, sodium ethylmalonate, propyl Sodium malonate, sodium butylmalonate, sodium dimethylmalonate, sodium diethylmalonate, sodium succinate, sodium methylsuccinate, Sodium oxalate, sodium adipate, sodium itaconate, sodium maleate, sodium fumarate, sodium citraconic acid, sodium citrate, sodium carbonate, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, hexane Potassium acetate, potassium heptanoate, potassium octanoate, potassium nonanoate, potassium decanoate, potassium oleate, potassium stearate, potassium linoleate, potassium linolenate, potassium benzoate, potassium phthalate, potassium isophthalate, potassium terephthalate , Potassium salicylate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium monochloroacetate, potassium dichloroacetate, potassium trichloroacetate, water Potassium hydrogen oxalate, potassium hydrogen oxalate, potassium hydrogen malonate, potassium hydrogen methyl malonate, potassium hydrogen ethyl malonate, potassium hydrogen propylmalonate, potassium hydrogen butylmalonate, potassium hydrogen dimethylmalonate, potassium hydrogen diethylmalonate, succinic acid Potassium hydrogen hydrogen, potassium hydrogen succinate, potassium hydrogen glutarate, hydrogen hydrogen adipate, potassium hydrogen itaconate, potassium hydrogen maleate, potassium hydrogen fumarate, potassium hydrogen citrate, potassium hydrogen citrate, potassium hydrogen carbonate, oxalic acid Potassium, potassium malonate, potassium methylmalonate, potassium ethylmalonate, potassium propylmalonate, potassium butylmalonate, potassium dimethylmalonate, potassium diethylmalonate, potassium succinate Examples thereof include potassium methyl succinate, potassium glutarate, potassium adipate, potassium itaconate, potassium maleate, potassium fumarate, potassium citraconic acid, potassium citrate, potassium carbonate and the like.

（式中、Ｒ²⁰⁴、Ｒ²⁰⁵、Ｒ²⁰⁶はそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０の置換あるいは非置換のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ²⁰⁵とＲ²⁰⁶とは環を形成してもよく、環を形成する場合には、Ｒ²⁰⁵、Ｒ²⁰⁶はそれぞれ炭素数１〜６のアルキレン基を示す。Ａ^-は非求核性対向イオンを表す。Ｒ²⁰⁷、Ｒ²⁰⁸、Ｒ²⁰⁹、Ｒ²¹⁰は、Ｒ²⁰⁴、Ｒ²⁰⁵、Ｒ²⁰⁶と同様であるが、水素原子であってもよい。Ｒ²⁰⁷とＲ²⁰⁸、Ｒ²⁰⁷とＲ²⁰⁸とＲ²⁰⁹とは環を形成してもよく、環を形成する場合には、Ｒ²⁰⁷とＲ²⁰⁸及びＲ²⁰⁷とＲ²⁰⁸とＲ²⁰⁹は炭素数３〜１０のアルキレン基を示す。） Examples of the compound represented by the general formula (2) include sulfonium compounds, iodonium compounds, and ammonium compounds represented by (Q-1), (Q-2), and (Q-3).

(Wherein R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ are each a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, and substitution having 6 to 20 carbon atoms. Alternatively, it represents an unsubstituted aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and part or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. ²⁰⁵ and R ²⁰⁶ may form a ring, and in the case of forming a ring, R ²⁰⁵ and R ²⁰⁶ each represent an alkylene group having 1 to 6 carbon atoms, A ⁻ represents a non-nucleophilic counter ion. R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ , and R ²¹⁰ are the same as R ²⁰⁴ , R ²⁰⁵ , and R ²⁰⁶ , but may be a hydrogen atom, R ²⁰⁷ and R ²⁰⁸ , R ²⁰⁷ and R ^208, and R ²⁰⁹ may form a ring, and in the case of forming a ring, R ²⁰⁷ and R ^208, R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ each represent an alkylene group having 3 to 10 carbon atoms.)

R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ , and R ²¹⁰ may be the same as or different from each other. Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , Isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl Group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like.

As A ⁻ , hydroxide ion, formate ion, acetate ion, propionate ion, butanoic acid ion, pentanoic acid ion, hexanoic acid ion, heptanoic acid ion, octanoic acid ion, nonanoic acid ion, decanoic acid ion, oleic acid ion , Stearate ion, linoleate ion, linolenate ion, benzoate ion, p-methylbenzoate ion, pt-butylbenzoate ion, phthalate ion, isophthalate ion, terephthalate ion, salicylate ion, trifluoro Acetate ion, monochloroacetate ion, dichloroacetate ion, trichloroacetate ion, fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion, chlorate ion, perchlorate ion, bromate ion, iodate ion Oxalate ion, malonate ion, Tilmalonate ion, ethylmalonate ion, propylmalonate ion, butylmalonate ion, dimethylmalonate ion, diethylmalonate ion, succinate ion, methylsuccinate ion, glutarate ion, adipate ion, itaconic acid ion, malein Acid ions, fumarate ions, citraconic acid ions, citrate ions, carbonate ions and the like can be mentioned.

  Specifically, as the sulfonium compound, triphenylsulfonium formate, triphenylsulfonium acetate, triphenylsulfonium propionate, triphenylsulfonium butanoate, triphenylsulfonium pentanoate, triphenylsulfonium hexanoate, triphenylsulfonium heptanoate, octane Triphenylsulfonium acid, triphenylsulfonium nonanoate, triphenylsulfonium decanoate, triphenylsulfonium oleate, triphenylsulfonium stearate, triphenylsulfonium linoleate, triphenylsulfonium linolenate, triphenylsulfonium benzoate, p-methyl Triphenylsulfonium benzoate, triphenylsulfonium pt-butylbenzoate, triphthalic phthalate Phenylsulfonium, triphenylsulfonium isophthalate, triphenylsulfonium terephthalate, triphenylsulfonium salicylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium monochloroacetate, triphenylsulfonium dichloroacetate, triphenylsulfonium trichloroacetate Phenylsulfonium, triphenylsulfonium hydroxide, triphenylsulfonium oxalate, triphenylsulfonium malonate, triphenylsulfonium methylmalonate, triphenylsulfonium ethylmalonate, triphenylsulfonium propylmalonate, triphenylsulfonium butylmalonate, dimethyl Triphenylsulfonium malonate, diethylmalon Triphenylsulfonium, triphenylsulfonium succinate, triphenylsulfonium methylsuccinate, triphenylsulfonium glutarate, triphenylsulfonium adipate, triphenylsulfonium itaconate, triphenylsulfonium maleate, triphenylsulfonium fumarate, triphenylcitraconic acid Sulfonium, triphenylsulfonium citrate, triphenylsulfonium carbonate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide, triphenylsulfonium nitrate, triphenylsulfonium chlorate, triphenylsulfonium perchlorate, bromic acid Triphenylsulfonium, triphenylsulfonium iodate, bistriphenylsulfonium oxalate Bistriphenylsulfonium methylmalate, bistriphenylsulfonium dimethylmalonate, bistriphenylsulfonium dimethylmalonate, bistriphenylsulfonium dimethylmalonate, bistriphenylsulfonium dimethylmalonate, Bistriphenylsulfonium succinate, bistriphenylsulfonium methyl succinate, bistriphenylsulfonium glutarate, bistriphenylsulfonium adipate, bistriphenylsulfonium itaconate, bistriphenylsulfonium maleate, bistriphenylsulfonium fumarate, bistriphenylsulfonium citraconic acid, citric acid Bistriphenylsulfo Um, and the like carbonate, bis triphenylsulfonium.

  Specific examples of the iodonium compound include diphenyliodonium formate, diphenyliodonium acetate, diphenyliodonium propionate, diphenyliodonium butanoate, diphenyliodonium pentanoate, diphenyliodonium hexanoate, diphenyliodonium heptanoate, diphenyliodonium octoate, and nonanoic acid. Diphenyliodonium, diphenyliodonium decanoate, diphenyliodonium oleate, diphenyliodonium stearate, diphenyliodonium linoleate, diphenyliodonium linolenate, diphenyliodonium benzoate, diphenyliodonium p-methylbenzoate, diphenyliodonium pt-butylbenzoate , Diphenyliodonium phthalate, isophthalate Diphenyliodonium, diphenyliodonium terephthalate, diphenyliodonium salicylate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium monochloroacetate, diphenyliodonium dichloroacetate, diphenyliodonium trichloroacetate, diphenyliodonium hydroxide, diphenyliodonium oxalate, Diphenyliodonium malonate, diphenyliodonium methylmalonate, diphenyliodonium ethylmalonate, diphenyliodonium propylmalonate, diphenyliodonium butylmalonate, diphenyliodonium dimethylmalonate, diphenyliodonium diethylmalonate, diphenyliodonium succinate, methyl Diphenyliodonium succinate, diphenyliodonium glutarate, diphenyliodonium adipate, diphenyliodonium itaconate, diphenyliodonium maleate, diphenyliodonium fumarate, diphenyliodonium citrate, diphenyliodonium citrate, diphenyliodonium carbonate, diphenyliodonium chloride, bromide Diphenyliodonium, diphenyliodonium iodide, diphenyliodonium nitrate, diphenyliodonium chlorate, diphenyliodonium perchlorate, diphenyliodonium bromate, diphenyliodonium iodate, bisdiphenyliodonium oxalate, bisdiphenyliodonium malonate, bisdiphenyl methylmalonate Iodonium, bisdiethylmalonate Phenyliodonium, Bisdiphenyliodonium propylmalonate, Bisdiphenyliodonium butylmalonate, Bisdiphenyliodonium dimethylmalonate, Bisdiphenyliodonium diethylmalonate, Bisdiphenyliodonium succinate, Bisdiphenyliodonium methylsuccinate, Bisdiphenyliodonium glutarate, Adipine Examples thereof include bisdiphenyliodonium acid, bisdiphenyliodonium itaconate, bisdiphenyliodonium maleate, bisdiphenyliodonium fumarate, bisdiphenyliodonium citraconic acid, bisdiphenyliodonium citrate, and bisdiphenyliodonium carbonate.

  On the other hand, specific examples of ammonium compounds include tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butanoate, tetramethylammonium pentanoate, tetramethylammonium hexanoate, tetramethylammonium heptanoate, Tetramethylammonium octoate, tetramethylammonium nonanoate, tetramethylammonium decanoate, tetramethylammonium oleate, tetramethylammonium stearate, tetramethylammonium linoleate, tetramethylammonium linolenate, tetramethylammonium benzoate, p- Tetramethylammonium methylbenzoate, tetramethylammonium pt-butylbenzoate, phthalic acid Tramethylammonium, tetramethylammonium isophthalate, tetramethylammonium terephthalate, tetramethylammonium salicylate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetate, tetramethylammonium monochloroacetate, tetramethylammonium dichloroacetate, trichloroacetic acid Tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium oxalate, tetramethylammonium malonate, tetramethylammonium methylmalonate, tetramethylammonium ethylmalonate, tetramethylammonium propylmalonate, tetramethylammonium butylmalonate, Tetramethylammonium dimethylmalonate Tetramethylammonium acid, tetramethylammonium succinate, tetramethylammonium methylsuccinate, tetramethylammonium glutarate, tetramethylammonium adipate, tetramethylammonium itaconate, tetramethylammonium maleate, tetramethylammonium fumarate, citraconic acid Tetramethylammonium, tetramethylammonium citrate, tetramethylammonium carbonate, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium chlorate, tetramethylammonium perchlorate, Tetramethylammonium bromate, tetramethylammonium iodate, bistetramethylan oxalate Monium, bistetramethylammonium malonate, bistetramethylammonium methylmalonate, bistetramethylammonium ethylmalonate, bistetramethylammonium propylmalonate, bistetramethylammonium butylmalonate, bistetramethylammonium dimethylmalonate, diethyl Bistetramethylammonium malonate, bistetramethylammonium succinate, bistetramethylammonium methylsuccinate, bistetramethylammonium glutarate, bistetramethylammonium adipate, bistetramethylammonium itaconate, bistetramethylammonium maleate, fumarate Bistetramethylammonium acid, Bistetramethylammonium citraconic acid, Bistetramethylammonium citrate Monium, Bistetramethylammonium carbonate, Tetrapropylammonium formate, Tetrapropylammonium acetate, Tetrapropylammonium propionate, Tetrapropylammonium butanoate, Tetrapropylammonium pentanoate, Tetrapropylammonium hexanoate, Tetrapropylammonium heptanoate, Octanoic acid Tetrapropylammonium, tetrapropylammonium nonanoate, tetrapropylammonium decanoate, tetrapropylammonium oleate, tetrapropylammonium stearate, tetrapropylammonium linoleate, tetrapropylammonium linolenate, tetrapropylammonium benzoate, p-methylbenzoic acid Acid tetrapropylammonium, pt-butylbenzoate Tetrapropylammonium, tetrapropylammonium phthalate, tetrapropylammonium isophthalate, tetrapropylammonium terephthalate, tetrapropylammonium salicylate, tetrapropylammonium trifluoromethanesulfonate, tetrapropylammonium trifluoroacetate, tetrapropylammonium monochloroacetate, dichloroacetic acid Tetrapropylammonium, trichloroacetate tetrapropylammonium hydroxide, tetrapropylammonium oxalate, tetrapropylammonium oxalate, tetrapropylammonium malonate, tetrapropylammonium methylmalonate, tetrapropylammonium ethylmalonate, tetrapropylammonium propylmalonate, butyl Malonic acid tetrapropy Ruammonium, tetrapropylammonium dimethylmalonate, tetrapropylammonium diethylmalonate, tetrapropylammonium succinate, tetrapropylammonium methylsuccinate, tetrapropylammonium glutarate, tetrapropylammonium adipate, tetrapropylammonium itaconate, tetramaleic acid tetra Propyl ammonium, tetrapropyl ammonium fumarate, tetrapropyl ammonium citrate, tetrapropyl ammonium citrate, tetrapropyl ammonium carbonate, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrapropyl ammonium iodide, tetrapropyl ammonium nitrate, chloric acid Tetrapropylammonium, tetrapropylaperchlorate Monium, tetrapropylammonium bromate, tetrapropylammonium iodate, bistetrapropylammonium oxalate, bistetrapropylammonium malonate, bistetrapropylammonium methylmalonate, bistetrapropylammonium ethylmalonate, bistetrapropyl propylmalonate Ammonium, bistetrapropylammonium butylmalonate, bistetrapropylammonium dimethylmalonate, bistetrapropylammonium diethylmalonate, bistetrapropylammonium succinate, bistetrapropylammonium methylsuccinate, bistetrapropylammonium glutarate, bisadipate Tetrapropylammonium, bistetrapropylammonium itaconate, maleic acid Stetrapropylammonium, bistetrapropylammonium fumarate, bistetrapropylammonium citraconic acid, bistetrapropylammonium citrate, bistetrapropylammonium carbonate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, butanoic acid Tetrabutylammonium, tetrabutylammonium pentanoate, tetrabutylammonium hexanoate, tetrabutylammonium heptanoate, tetrabutylammonium octanoate, tetrabutylammonium nonanoate, tetrabutylammonium decanoate, tetrabutylammonium oleate, tetrabutyl stearate Ammonium, tetrabutylammonium linoleate, tetrabutyl linolenate Ammonium, tetrabutylammonium benzoate, tetrabutylammonium p-methylbenzoate, tetrabutylammonium benzoate, tetrabutylammonium phthalate, tetrabutylammonium isophthalate, tetrabutylammonium terephthalate, tetrabutylammonium salicylate , Tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluoroacetate, tetrabutylammonium monochloroacetate, tetrabutylammonium dichloroacetate, tetrabutylammonium trichloroacetate, tetrabutylammonium hydroxide, tetrabutylammonium oxalate, tetrabutyl malonate Ammonium, tetrabutylammonium methylmalonate, tetrabutylethylmalonate Nmmonium, tetrabutylammonium propylmalonate, tetrabutylammonium butylmalonate, tetrabutylammonium dimethylmalonate, tetrabutylammonium diethylmalonate, tetrabutylammonium succinate, tetrabutylammonium methylsuccinate, tetrabutylammonium glutarate, adipic acid Tetrabutylammonium, tetrabutylammonium itaconate, tetrabutylammonium maleate, tetrabutylammonium fumarate, tetrabutylammonium citraconic acid, tetrabutylammonium citrate, tetrabutylammonium carbonate, tetrabutylammonium chloride, tetrabutylammonium bromide, Tetrabutylammonium iodide, tetrabutylammonium nitrate, chlorate Butylammonium, tetrabutylammonium perchlorate, tetrabutylammonium bromate, tetrabutylammonium iodate, bistetrabutylammonium oxalate, bistetrabutylammonium malonate, bistetrabutylammonium methylmalonate, bistetrabutyl ethylmalonate Ammonium, bistetrabutylammonium propylmalonate, bistetrabutylammonium butylmalonate, bistetrabutylammonium dimethylmalonate, bistetrabutylammonium diethylmalonate, bistetrabutylammonium succinate, bistetrabutylammonium methylsuccinate, glutaric acid Bistetrabutylammonium, bistetrabutylammonium adipate, bistetrabutylammonium itaconate Examples thereof include bistetrabutylammonium maleate, bistetrabutylammonium fumarate, bistetrabutylammonium citraconic acid, bistetrabutylammonium citrate, and bistetrabutylammonium carbonate.

  In addition, the said thermal crosslinking accelerator can be used individually by 1 type or in combination of 2 or more types. The amount of the thermal crosslinking accelerator added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained by the above method). is there.

In order to ensure the stability of the composition for forming a thermosetting silicon-containing film of the present invention, a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms must be added as the component (C). Acids added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid , Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid , Diethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid and the like. In particular, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are preferable. In order to maintain stability, two or more kinds of acids may be mixed and used. The addition amount is 0.001 to 25 parts by mass, preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the silicon-containing compound contained in the composition.
Alternatively, the organic acid is preferably converted into the pH of the composition so that 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5, and even more preferably 0.5 ≦ pH ≦ 6. It is good to mix.

  Furthermore, when a monovalent or divalent or higher alcohol having a cyclic ether as a substituent as a stabilizer (D), particularly an ether compound represented by the following structure, is added, the stability of the silicon-containing film-forming composition is improved. Can do. As such a thing, the compound shown below can be mentioned.

Here, R ^90a is a hydrogen atom, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁹¹ O— (CH ₂ CH ₂ O) _n1 — (CH ₂ ) _n2 — (Where 0 ≦ n1 ≦ 5, 0 ≦ n2 ≦ 3, R ⁹¹ is a hydrogen atom or a methyl group), or R ⁹² O— [CH (CH ₃ ) CH ₂ O] _n3 — (CH ₂ ) _n4 — ( Here, 0 ≦ n3 ≦ 5, 0 ≦ n4 ≦ 3, R ⁹² is a hydrogen atom or a methyl group), and R ^90b is a straight chain having 1 to 10 carbon atoms having a hydroxyl group, one or more hydroxyl groups. Chain, branched or cyclic monovalent hydrocarbon group, HO— (CH ₂ CH ₂ O) _n5 — (CH ₂ ) _n6 — (where 1 ≦ n5 ≦ 5, 1 ≦ n6 ≦ 3), or HO - it is (wherein, 1 ≦ n7 ≦ 5,1 ≦ n8 ≦ 3) - [CH (CH ₃₎ CH ₂ O] _n7 - (CH _{2) n8.}

In addition, the said stabilizer can be used individually by 1 type or in combination of 2 or more types. The addition amount of the stabilizer is preferably 0.001 to 50 parts by mass, more preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained by the above method). Moreover, these stabilizers can be used individually by 1 type or in mixture of 2 or more types. Among these, a preferred structure is a compound having a crown ether derivative and a bicyclo ring having a bridge head position as an oxygen atom as a substituent.
When such a stabilizer is added, the charge of the acid is further stabilized and contributes to the stabilization of the silicon-containing compound in the composition.

  In the composition containing the silicon-containing compound of the present invention, the same organic solvent as that used in the production of the silicon-containing compound as component (E), preferably a water-soluble organic solvent, particularly ethylene glycol, diethylene glycol, triethylene Monoalkyl ethers such as glycol, and monoalkyl ethers such as propylene glycol, dipropylene glycol, butanediol, and pentanediol are used. Specifically, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, An organic solvent selected from ethylene glycol monopropyl ether and the like is used.

In the present invention, water may be added to the composition. When water is added, the silicon-containing compound is hydrated, so that the lithography performance is improved. The content of water in the solvent component of the composition is more than 0% by mass and less than 50% by mass, particularly preferably 0.3 to 30% by mass, and further preferably 0.5 to 20% by mass. If each component is added in an excessive amount, the uniformity of the coating film is deteriorated, and in the worst case, repelling occurs. On the other hand, if the addition amount is small, the lithography performance deteriorates, which is not preferable.
The use amount of all the solvents including water is preferably 500 to 100,000 parts by mass, particularly 400 to 50,000 parts by mass with respect to 100 parts by mass of the base polymer.

In the present invention, a photoacid generator may be used. As the photoacid generator used in the present invention,
(AI) Onium salt of the following general formula (P1a-1), (P1a-2) or (P1b),
(A-II) a diazomethane derivative represented by the following general formula (P2):
(A-III) a glyoxime derivative of the following general formula (P3),
(A-IV) A bissulfone derivative of the following general formula (P4),
(AV) a sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),
(A-VI) β-ketosulfonic acid derivative,
(A-VII) disulfone derivative,
(A-VIII) nitrobenzyl sulfonate derivative,
(A-IX) sulfonic acid ester derivatives and the like.

（式中、Ｒ^101a、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０の置換あるいは非置換のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基にある水素原子の一部又は全部がアルコキシ基等によって置換されていてもよい。また、Ｒ^101bとＲ^101cとは環を形成してもよく、環を形成する場合には、Ｒ^101b、Ｒ^101cはそれぞれ炭素数１〜６のアルキレン基を示す。Ｋ^-は非求核性対向イオンを表す。）

Wherein R ^101a , R ^101b and R ^101c are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, and a substitution having 6 to 20 carbon atoms. Alternatively, it represents an unsubstituted aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxoalkyl group, and part or all of hydrogen atoms in these groups may be substituted with an alkoxy group or the like. R ^101b and R ^101c may form a ring, and in the case of forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms, and K ⁻ is a non-nucleophilic counter ion. Represents.)

R ^101a , R ^101b and R ^101c may be the same as or different from each other. Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl Group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group, etc. Is mentioned. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- (4 -Methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl groups, 2-methylphenyl groups, 3-methylphenyl groups, 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, dimethylphenyl groups, etc. Alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dialkyl naphthyl groups such as dimethyl naphthyl group and diethyl naphthyl group, dimethoxy naphthyl group and diethoxy naphthyl group Dialkoxynaphthyl group And the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like Groups and the like. Non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ion and bromide ion, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethane sulfonate, and nonafluorobutane sulfonate, tosylate, and benzene sulfonate. And aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

（式中、Ｒ^102a、Ｒ^102bはそれぞれ炭素数１〜８の直鎖状、分岐状又は環状のアルキル基を示す。Ｒ¹⁰³は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基を示す。Ｒ^104a、Ｒ^104bはそれぞれ炭素数３〜７の２−オキソアルキル基を示す。Ｋ^-は非求核性対向イオンを表す。）

(In the formula, R ^102a and R ^102b each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R ¹⁰³ is a linear, branched or cyclic alkylene having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms, and K ⁻ represents a non-nucleophilic counter ion.)

Specific examples of R ^102a and R ^102b include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ is methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene. Group, 1,3-cyclopentylene group, 1,4-cyclooctylene group, 1,4-cyclohexanedimethylene group and the like. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is the formula (P1a-1), can be exemplified the same ones as described in (P1a-2) and (P1a-3).

（式中、Ｒ¹⁰⁵、Ｒ¹⁰⁶は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０の置換あるいは非置換のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。）

Wherein R ¹⁰⁵ and R ¹⁰⁶ are linear, branched or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups or aryl halides having 6 to 20 carbon atoms. Group, or an aralkyl group having 7 to 12 carbon atoms.)

^Examples of the alkyl group of R ¹⁰⁵ and R ¹⁰⁶ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, amyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group. As the aryl group, an alkoxyphenyl group such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert-butoxyphenyl group, Examples thereof include alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

（式中、Ｒ¹⁰⁷、Ｒ¹⁰⁸、Ｒ¹⁰⁹は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基又はハロゲン化アルキル基、炭素数６〜２０のアリール基又はハロゲン化アリール基、又は炭素数７〜１２のアラルキル基を示す。Ｒ¹⁰⁸、Ｒ¹⁰⁹は互いに結合して環状構造を形成してもよく、環状構造を形成する場合、Ｒ¹⁰⁸、Ｒ¹⁰⁹はそれぞれ炭素数１〜６の直鎖状又は分岐状のアルキレン基を示す。）

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are each a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms, R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each have 1 to 6 carbon atoms. Represents a linear or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ include the same groups as those described for R ¹⁰⁵ and R ¹⁰⁶ . ^Examples of the alkylene group for R ¹⁰⁸ and R ¹⁰⁹ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

（式中、Ｒ^101a、Ｒ^101bは上記と同様である。）

(In the formula, R ^101a and R ^101b are the same as above.)

（式中、Ｒ¹¹⁰は炭素数６〜１０のアリーレン基、炭素数１〜６のアルキレン基又は炭素数２〜６のアルケニレン基を示し、これらの基に含まれる水素原子の一部又は全部は更に炭素数１〜４の直鎖状又は分岐状のアルキル基又はアルコキシ基、ニトロ基、アセチル基、又はフェニル基で置換されていてもよい。Ｒ¹¹¹は炭素数１〜８の直鎖状、分岐状又は置換のアルキル基、アルケニル基又はアルコキシアルキル基、フェニル基、又はナフチル基を示し、これらの基の水素原子の一部又は全部は更に炭素数１〜４のアルキル基又はアルコキシ基；炭素数１〜４のアルキル基、アルコキシ基、ニトロ基又はアセチル基で置換されていてもよいフェニル基；炭素数３〜５のヘテロ芳香族基；又は塩素原子、フッ素原子で置換されていてもよい。）

(In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, and part or all of the hydrogen atoms contained in these groups are Further, it may be substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group, or a phenyl group, and R ¹¹¹ is a straight chain having 1 to 8 carbon atoms, A branched or substituted alkyl group, an alkenyl group or an alkoxyalkyl group, a phenyl group, or a naphthyl group, wherein some or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; carbon A phenyl group which may be substituted with an alkyl group, alkoxy group, nitro group or acetyl group having 1 to 4 carbon atoms; a heteroaromatic group with 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom which may be substituted. .)

Here, as the arylene group of R ¹¹⁰ , 1,2-phenylene group, 1,8-naphthylene group, etc., and as the alkylene group, methylene group, ethylene group, trimethylene group, tetramethylene group, phenylethylene group, norbornane Examples of the alkenylene group such as -2,3-diyl group include 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5-norbornene-2,3-diyl group and the like. The alkyl group for R ¹¹¹ is the same as R ^{101a to} R ^101c, and the alkenyl group is a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isoprenyl group, 1- Pentenyl group, 3-pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl Groups such as alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, methoxyethyl, ethoxyethyl, Propoxyethyl, butoxyethyl, pentyloxyethyl, hexyloxyethyl, methoxypro Group, ethoxypropyl group, propoxypropyl group, butoxy propyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, a methoxy pentyl group, an ethoxy pentyl group, a methoxy hexyl group, a methoxy heptyl group.

  In addition, examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. As the alkoxy group of ˜4, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group and the like are an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a nitro group. As the phenyl group which may be substituted with an acetyl group, a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc. are heterocycles having 3 to 5 carbon atoms. Examples of the aromatic group include a pyridyl group and a furyl group.

  Specific examples include the following photoacid generators. Diphenyliodonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid Triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-Toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyv Nyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, butanesulfonic acid Triphenylsulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, trifluoromethane Dimethylphenylsulfonium sulfonate, dimethylphenylsulfonium p-toluenesulfonate Dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl trifluoromethanesulfonate ( Onium salts such as 2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate.

  Bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) ) Diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, B hexylsulfonyl-1-(tert-butylsulfonyl) diazomethane, 1-cyclohexyl sulfonyl-1-(tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1-(tert-butylsulfonyl) diazomethane derivatives such as diazomethane.

  Bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime Bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- ( n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O— (N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -2- Til-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (1,1 , 1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis -O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O -(P-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, Scan -O- (xylene sulfonyl)-.alpha.-dimethylglyoxime, bis -O- (camphorsulfonyl)-.alpha.-glyoxime derivatives such as dimethylglyoxime.

Bissulfone derivatives such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane.
Β-ketosulfonic acid derivatives such as 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone.
Nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.
Sulfonic acid ester derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene .

  N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinimide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2 -Chloroethane sulfonic acid ester, N-hydroxysuccinimide benzene sulfonic acid ester, N- Droxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimide ethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonic acid ester, N-hydroxyglutarimide methanesulfonic acid ester, N-hydroxyglutarimide benzenesulfonic acid Esters, N-hydroxyphthalimide methane sulfonate, N-hydroxy phthalimide benzene sulfonate, N-hydroxy phthalate Imidotrifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, N-hydroxy-5-norbornene-2,3- Dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonate Sulfonic acid ester derivatives of N-hydroxyimide compounds such as

  Among these, in particular, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid tri Phenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethylsulfonic acid cyclohexylmethyl ( 2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) Onium salts such as sulfonium, 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) ) Diazomethane derivatives such as diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis- Glyoxime derivatives such as O- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime Bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimide benzenesulfonic acid ester, etc. Acid ester derivatives are preferably used.

  In addition, the said photo-acid generator can be used individually by 1 type or in combination of 2 or more types. The addition amount of the acid generator is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 40 parts by mass with respect to 100 parts by mass of the base polymer (silicon-containing compound obtained by the above method). .

Furthermore, in this invention, it is possible to mix | blend surfactant as needed. Here, the surfactant is preferably nonionic, and perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkylethylene oxide adduct, and fluorine-containing organosiloxane compound are used. Can be mentioned. For example, Florard “FC-430”, “FC-431”, “FC-4430” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145”, “KH-10”, “ KH-20 "," KH-30 "," KH-40 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS-403 "," DS-451 "(all Daikin Industries ( ), MegaFuck “F-8151” (Dainippon Ink Industries, Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned. Preferably, Florard “FC-4430”, “KH-20”, “KH-30”, and “X-70-093” are mentioned.
In addition, the addition amount of surfactant can be made into a normal amount in the range which does not prevent the effect of this invention, and shall be 0-10 mass parts with respect to 100 mass parts of base polymers, especially 0-5 mass parts. Is preferred.

  The silicon-containing film effective for the etching mask of the present invention can be produced on the substrate from the silicon-containing film-forming composition by a spin coat method or the like in the same manner as the photoresist film. After spin coating, it is desirable to evaporate the solvent and perform baking to promote the crosslinking reaction in order to prevent mixing with the upper resist film. The baking temperature is preferably in the range of 50 to 500 ° C. and in the range of 10 to 300 seconds. Although a particularly preferable temperature range depends on the structure of the device to be manufactured, it is preferably 400 ° C. or lower in order to reduce thermal damage to the device.

Here, in the present invention, the silicon-containing film can be formed on the processed portion of the substrate to be processed via the lower layer film, and the photoresist film can be formed on the silicon-containing film, whereby pattern formation can be performed.
In this case, the processed portion of the substrate to be processed includes a low dielectric constant insulating film having a k value of 3 or less, a primary processed low dielectric constant insulating film, a nitrogen and / or oxygen-containing inorganic film, a metal film, and the like. Can do.

More specifically, the substrate to be processed can be a substrate in which a layer to be processed (processed portion) is formed on a base substrate. The base substrate is not particularly limited, and may be made of a material different from the layer to be processed, such as Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. May be used. The layer to be _{processed, Si, SiO 2, SiN,} SiON, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si , etc. and various low dielectric films and etching stopper film is used In general, it can be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

In the present invention, a commercially available organic antireflection film may be formed between the silicon-containing film and the upper resist film. At this time, the structure of the antireflection film is a compound having an aromatic substituent. This antireflection film must not cause an etching load on the upper resist film when the pattern of the upper resist film is transferred by dry etching. For example, if the thickness is 80% or less, preferably 50% or less of the upper resist film, the load during dry etching becomes very small.
In this case, the antireflection film is preferably adjusted so that the minimum reflection is 2% or less, preferably 1% or less, more preferably 0.5% or less.

  When the silicon-containing film of the present invention is used in an exposure process using ArF excimer laser light, any of the usual resist compositions for ArF excimer laser light can be used as the upper resist film. Many candidates for ArF excimer laser light resist compositions are already known. If the resist composition is positive, a resin, a photoacid generator, and an acid that are soluble in an alkaline aqueous solution by decomposition of an acid labile group by the action of an acid. If the basic substance for controlling the diffusion of the resin is a negative type, it controls the diffusion of the resin, photoacid generator, crosslinking agent and acid that reacts with the crosslinking agent by the action of an acid and becomes insoluble in an alkaline aqueous solution. However, there are differences in characteristics depending on what kind of resin is used. Already known resins are roughly classified into poly (meth) acrylic, COMA (Cyclo Olefin Male Anhydride), COMA- (meth) acrylic hybrid, ROMP (Ring Opening Polymerization), and polynorbornene. Of these, resist compositions using poly (meth) acrylic resins ensure etching resistance by introducing an alicyclic skeleton into the side chain, so the resolution performance is comparable to other resin systems. Excellent compared.

  Many resist compositions for ArF excimer lasers using poly (meth) acrylic resins are known. For positive type resist compositions, a unit for ensuring etching resistance as a main function, an acid, The polymer is composed of a combination of a unit that decomposes by alkalinity to change to alkali-soluble, a unit for ensuring adhesion, or a combination in which one unit also has two or more of the above functions. . Among these, as the unit whose alkali solubility is changed by acid, (meth) acrylic acid ester having an acid labile group having an adamantane skeleton (Japanese Patent Laid-Open No. 9-73173), norbornane or tetracyclododecane skeleton is used. A (meth) acrylic acid ester having an acid labile group (Japanese Patent Laid-Open No. 2003-84438) gives high resolution and etching resistance, and is particularly preferably used. Moreover, as a unit for ensuring adhesiveness, (meth) acrylic acid ester having a norbornane side chain having a lactone ring (WO 00/01684 pamphlet), (meth) acrylic acid having an oxanorbornane side chain An ester (Japanese Patent Laid-Open No. 2000-159758) and a (meth) acrylic acid ester having a hydroxyadamantyl side chain (Japanese Patent Laid-Open No. 8-12626) are particularly preferred because they provide good etching resistance and high resolution. it can. Further, a polymer containing a unit (for example, Polym. Mater. Sci. Eng. 1997. 77. pp449) having an alcohol that exhibits acidity by substitution with fluorine at the adjacent position as a functional group swells in the polymer. In particular, it has been attracting attention as a resist polymer corresponding to the immersion method, which has been attracting attention in recent years, because it has high resolving properties. Decreasing is a problem. The silicon-containing film for an etching mask of the present invention can be particularly effectively used for such an organic resist composition that is difficult to ensure etching resistance.

  The ArF excimer laser resist composition containing the above polymer contains an acid generator, a basic compound, etc., which can be added to the silicon-containing film-forming composition of the present invention. Almost the same ones can be used, and onium salts are particularly advantageous in terms of sensitivity and resolution. A large number of basic substances are also known and exemplified in Japanese Patent Application Laid-Open No. 2005-146252 recently published, and can be advantageously selected from them.

  After producing a silicon-containing film layer for an etching mask, a photoresist layer is produced thereon using a photoresist composition solution, and a spin coating method is preferably used in the same manner as the silicon-containing film layer for an etching mask. Pre-baking is performed after spin-coating the resist composition, but a range of 10 to 300 seconds at 80 to 180 ° C. is preferable. Thereafter, exposure is performed, post-exposure baking (PEB), and development is performed to obtain a resist pattern.

  Etching of the silicon-containing film for the etching mask is performed using a chlorofluorocarbon gas, nitrogen gas, carbon dioxide gas, or the like. The silicon-containing film for an etching mask of the present invention is characterized in that the etching rate with respect to the gas is high and the film loss of the upper resist film is small.

  In the multilayer resist method using the silicon-containing film of the present invention, a lower layer film is provided between the silicon-containing film of the present invention and the substrate to be processed. When the lower layer film is used as an etching mask for the substrate to be processed, the lower layer film is preferably an organic film having an aromatic skeleton. A silicon-containing material may be used as long as the content is 15% by mass or less.

  In addition, many organic films having an aromatic skeleton are known as a lower layer film, and 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin described in JP-A-2005-128509 ( In addition to a molecular weight of 11,000), a number of resins including novolac resins are known as resist underlayer film materials for the two-layer resist method and the three-layer resist method, and any of them can be used. In addition, if you want to increase the heat resistance than ordinary novolac, you can also add a polycyclic skeleton such as 4 '-(9H-fluorene-9-ylidene) bisphenol novolac resin, and select a polyimide resin (For example, JP, 2004-153125, A).

  In the case of a multilayer resist method using an organic film that serves as an etching mask for the substrate to be processed, the organic film is a film that transfers the patterned resist pattern to the silicon-containing film and then transfers the pattern again. In addition, the silicon-containing film has a characteristic that it can be etched under an etching condition exhibiting high etching resistance, and a characteristic that the silicon-containing film has a high etching resistance is required for the condition for etching the substrate to be processed.

  Many organic films as such lower layer films are already known as lower layer films for a three-layer resist method or a two-layer resist method using a silicon resist composition, and disclosed in JP-A-2005-128509. In addition to 4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin (molecular weight 11,000), many resins including novolak resin are used as resist underlayer film materials for two-layer resist method and three-layer resist method. Any of them can be used. In addition, when it is desired to increase the heat resistance as compared with normal novolac, a polycyclic skeleton such as 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin can be added, and further a polyimide resin. Can also be selected (for example, JP-A-2004-153125).

  The organic film can be formed on a substrate by spin coating or the like, similar to a photoresist composition, using a composition solution. After forming the resist underlayer film by spin coating or the like, it is desirable to bake to evaporate the organic solvent. The baking temperature is preferably in the range of 80 to 300 ° C. and in the range of 10 to 300 seconds.

  Although not particularly limited, the thickness of the lower layer film is 10 nm or more, particularly 50 nm or more, preferably 50,000 nm or less, although it varies depending on the etching processing conditions. The thickness is preferably 1 nm to 200 nm, and the thickness of the photoresist film is preferably 1 nm to 300 nm.

The three-layer resist method using the silicon-containing film for an etching mask of the present invention is as follows. In this process, an organic film is first formed on a substrate to be processed by a spin coating method or the like. Since this organic film acts as a mask when etching the substrate to be processed, it is desirable that the etching resistance is high, and it is required not to mix with the silicon-containing film for the upper etching mask. It is desirable to crosslink with an acid. A silicon-containing film for an etching mask and a photoresist film obtained from the composition of the present invention are formed thereon by the above method. The resist film is subjected to pattern exposure using a light source corresponding to the resist film, for example, KrF excimer laser light, ArF excimer laser light, or F ₂ laser light, according to a conventional method, and heat treatment is performed according to conditions suitable for each resist film. Thereafter, a resist pattern can be obtained by performing a developing operation with a developer. Next, using this resist pattern as an etching mask, the organic film is etched by dry etching conditions in which the etching rate of the silicon-containing film is significantly high, for example, by dry etching using fluorine-based gas plasma. When the antireflection film and the silicon-containing film are etched, a silicon-containing film pattern can be obtained with almost no influence of a pattern change caused by side etching of the resist film. Next, with respect to the substrate having the silicon-containing film pattern to which the resist pattern obtained above is transferred, dry etching conditions in which the etching rate of the lower organic film is predominantly high, for example, reactive dry etching with gas plasma containing oxygen, Then, reactive dry etching with gas plasma containing hydrogen-nitrogen is performed to etch the lower organic film. Although this etching process gives a pattern of the lower organic film, the uppermost resist layer is usually lost at the same time. Furthermore, by using the lower organic film obtained here as an etching mask, the substrate to be processed can be precisely etched by using dry etching of the substrate to be processed, for example, fluorine-based dry etching or chlorine-based dry etching. it can.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description.

[Synthesis Example 1]
200 g of methanol, 200 g of ion-exchanged water and 1 g of 35% hydrochloric acid were charged into a 1,000 ml glass flask, and a mixture of 50 g of tetraethoxysilane, 100 g of methyltrimethoxysilane and 10 g of phenyltrimethoxysilane was added at room temperature. The mixture was hydrolyzed and condensed for 8 hours at room temperature, and then 300 ml of propylene glycol monoethyl ether was added and concentrated under reduced pressure to obtain 300 g of a propylene glycol monoethyl ether solution of silicon-containing compound 1 (polymer concentration 21%). When the molecular weight of this in terms of polystyrene was measured, it was Mw = 2,000.

[Synthesis Example 2]
Propylene glycol of silicon-containing compound 2 in the same manner except that 50 g of tetraethoxysilane, 100 g of methyltrimethoxysilane and 10 g of phenyltrimethoxysilane in Synthesis Example 1 were replaced with 100 g of methyltrimethoxysilane and 20 g of phenyltrimethoxysilane. 300 g of monoethyl ether solution (polymer concentration 19%) was obtained. When the molecular weight of this in terms of polystyrene was measured, it was Mw = 3,000.

[Synthesis Example 3]
60 g of methanol of Synthesis Example 1, 200 g of ion-exchanged water, 1 g of 35% hydrochloric acid, 50 g of tetraethoxysilane, 100 g of methyltrimethoxysilane, 10 g of phenyltrimethoxysilane, and 260 g of ion-exchanged water, 5 g of 65% nitric acid, 300 g of butanediol monomethyl ether solution of silicon-containing compound 3 (polymer concentration 20%) was obtained in the same manner except that 70 g of tetramethoxysilane, 70 g of methyltrimethoxysilane, 10 g of phenyltrimethoxysilane and butanediol monomethyl ether were used. . When the molecular weight of this in terms of polystyrene was measured, it was Mw = 2,500.

[Synthesis Example 4]
Charge ion exchange water 260g, 35% hydrochloric acid 1g into a 1,000ml glass flask, add tetramethoxysilane 70g, methyltrimethoxysilane 25g, silane compound 25g of the following formula [i] and phenyltrimethoxysilane 10g at room temperature. It was. The product was subjected to hydrolysis and condensation for 8 hours at room temperature, and then by-product methanol was distilled off under reduced pressure. Thereto, 800 ml of ethyl acetate and 300 ml of propylene glycol monopropyl ether were added, and the aqueous layer was separated. To the remaining organic layer, 100 ml of ion exchange water was added, stirred, allowed to stand, and separated. This was repeated three times. 200 ml of propylene glycol monopropyl ether was added to the remaining organic layer and concentrated under reduced pressure to obtain 300 g of a propylene glycol monopropyl ether solution of silicon-containing compound 4 (polymer concentration 20%). The resulting solution was analyzed for chloro ions by ion chromatography, but was not detected. When the molecular weight of this in terms of polystyrene was measured, it was Mw = 1,800.

[Synthesis Example 5]
200 g of ethanol, 100 g of ion-exchanged water, and 3 g of methanesulfonic acid are charged in a 1,000 ml glass flask, and a mixture of 40 g of tetramethoxysilane, 10 g of methyltrimethoxysilane, 50 g of a silane compound of the following formula [ii] and 10 g of phenyltrimethoxysilane is prepared. Added at room temperature. The product was subjected to hydrolysis and condensation for 8 hours at room temperature, and then by-product methanol was distilled off under reduced pressure. Thereto, 800 ml of ethyl acetate and 300 ml of ethylene glycol monopropyl ether were added, and the aqueous layer was separated. To the remaining organic layer, 100 ml of ion exchange water was added, stirred, allowed to stand, and separated. This was repeated three times. 200 ml of ethylene glycol monopropyl ether was added to the remaining organic layer and concentrated under reduced pressure to obtain 300 g of an ethylene glycol monopropyl ether solution of silicon-containing compound 5 (polymer concentration 20%). When the resulting solution was analyzed for methanesulfonic acid ions by ion chromatography, it was found that 99% of those used in the reaction had been removed. It was Mw = 2,100 when the molecular weight of polystyrene conversion of this thing was measured.

[Examples and comparative examples]
By mixing the silicon-containing compounds 1 to 5 obtained in the above synthesis example, acid, thermal crosslinking accelerator, solvent and additive in the ratio shown in Table 1, and filtering with a filter made of 0.1 μm fluororesin, Each of the silicon-containing film-forming composition solutions was prepared. 1-10.

TPSOAc: Triphenylsulfonium acetate (photodegradable thermal crosslinking accelerator)
TPSOH: Triphenylsulfonium hydroxide (photodegradable thermal crosslinking accelerator)
TPSCl: Triphenylsulfonium chloride (photodegradable thermal crosslinking accelerator)
TPSMA: Mono (triphenylsulfonium) maleate (photodegradable thermal crosslinking accelerator)
TPSN: Triphenylsulfonium nitrate (photodegradable thermal crosslinking accelerator)
TMAOAc: Tetramethylammonium acetate (non-photodegradable thermal crosslinking accelerator)
TPSNf: Triphenylsulfonium nonafluorobutanesulfonate (photoacid generator)

  First, as a lower layer film material, a composition containing 4,4 ′-(9H-fluorene-9-ylidene) bisphenol novolac resin (molecular weight 11,000) (Japanese Patent Laid-Open No. 2005-128509) (resin 28 mass) on a Si wafer. Part, 100 parts by mass of solvent) was spin-coated and heated to 200 ° C. for 1 minute to form a lower organic film having a thickness of 300 nm. As the lower layer organic film material, in addition to the above, a number of resins including novolak resins are known as lower layer film materials for the multilayer resist method, and any of them can be used.

  Next, Sol. 1 to 10 were spin-coated and heated to 200 ° C. for 1 minute to form a silicon-containing film having a thickness of 100 nm.

  Furthermore, in order to form an upper resist film, PGMEA (propylene glycol) containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Limited) as the resist composition for ArF excimer laser light exposure (Resist 1) It was prepared by dissolving in a monomethyl ether acetate solution and filtering through a 0.1 μm fluororesin filter.

１０質量部
光酸発生剤 ：トリフェニルスルホニウムノナフルオロブタンスルホネート
０．２質量部
塩基性化合物：トリエタノールアミン ０．０２質量部

10 parts by mass Photoacid generator: Triphenylsulfonium nonafluorobutanesulfonate
0.2 parts by mass Basic compound: Triethanolamine 0.02 parts by mass

This composition was applied onto a silicon-containing intermediate layer and baked at 130 ° C. for 60 seconds to form a 200 nm-thick photoresist layer.
Next, exposure was performed with an ArF exposure apparatus (manufactured by Nikon Corporation; S305B, NA 0.68, σ 0.85, 2/3 ring illumination, Cr mask), baked at 110 ° C. for 90 seconds (PEB), and 2.38. Development was performed with a mass% tetramethylammonium hydroxide (TMAH) aqueous solution to obtain a positive pattern. Table 2 shows the result of observation of the 90 nm L / S pattern shape of the obtained pattern.

  In any of the examples, a pattern having no skirting, undercut, or intermixing phenomenon was obtained near the substrate.

Next, a dry etching resistance test was performed. The composition Sol. 1 to 10 were spin-coated and heated to 200 ° C. for 1 minute to form a silicon-containing film Film 1 to 10 having a thickness of 100 nm. These films, the lower layer film and the photoresist film were subjected to an etching test under the following etching conditions (1). The results are shown in Table 3.
(1) Etching test apparatus using CHF ₃ / CF ₄ gas: Tokyo Electron Co., Ltd. dry etching apparatus TE-8500P
Etching conditions (1):
Chamber pressure 40.0Pa
RF power 1,300W
Gap 9mm
CHF ₃ gas flow rate 30ml / min
CF ₄ gas flow rate 30ml / min
Ar gas flow rate 100ml / min
Processing time 10 sec

Subsequently, as shown in Table 4, the dry etching rate of the O ₂ gas was examined under the etching condition (2) shown below. Compared to the lower layer film and the upper layer resist film, it is sufficiently slow, and it is possible to transfer the pattern to the lower layer using the silicon-containing intermediate layer as an etching mask.

Etching conditions (2):
Chamber pressure 60.0Pa
RF power 600W
Ar gas flow rate 40ml / min
O ₂ gas flow rate 60ml / min
Gap 9mm
Processing time 20 sec

  Further, a storage stability test was conducted. The silicon-containing film-forming composition (Sol. 1 to 10) obtained above is stored at 30 ° C. for 3 months, and then coated again by the above method to test whether the film formability changes. It was. The results are shown in Table 5.

  From the results in Table 5, it was confirmed that the compositions of any of the examples had storage stability of 3 months or more at 30 ° C. and 6 months or more when converted to room temperature.

  From the above, it was confirmed that the composition of the present invention and the silicon-containing film were excellent in stability and lithography characteristics. By using such a composition, it becomes possible to form a pattern using a state-of-the-art high NA exposure machine and to process the substrate by etching.

Claims (15)

(A) a silicon-containing compound obtained by hydrolytic condensation of a hydrolyzable silicon compound using an acid as a catalyst,
(B) One or more compounds represented by the following general formula (1) or (2),
L _a H _b X (1)
(Wherein L is lithium, sodium, potassium, rubidium or cesium, X is a hydroxyl group, or a monovalent or divalent or higher organic acid group having 1 to 30 carbon atoms, a is an integer of 1 or more, and b is 0. Or an integer of 1 or more, and a + b is a valence of a hydroxyl group or an organic acid group.)
M _a H _{b A} (2)
(In the formula, M is sulfonium, iodonium or ammonium, A is the above X or non-nucleophilic counter ion, a and b are the same as above, and a + b is a hydroxyl group, an organic acid group or a non-nucleophilic counter ion. The valence of
(C) a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms,
(D) a monovalent or divalent alcohol having a cyclic ether as a substituent,
(E) A thermosetting silicon-containing film-forming composition comprising an organic solvent.   As the silicon-containing compound, the acid catalyst is substantially converted from a reaction mixture obtained by hydrolytic condensation of a hydrolyzable silicon compound using one or more compounds selected from inorganic acids and sulfonic acid derivatives as an acid catalyst. The composition for forming a thermosetting silicon-containing film according to claim 1, comprising a silicon-containing compound that can be obtained through the removing step.   The composition for forming a thermosetting silicon-containing film according to claim 1 or 2, wherein M in the general formula (2) is tertiary sulfonium, secondary iodonium, or quaternary ammonium.   The composition for forming a thermosetting silicon-containing film according to any one of claims 1 to 3, wherein M in the general formula (2) is photodegradable.   Furthermore, water is included, The composition for thermosetting silicon containing film formation of any one of Claims 1-4 characterized by the above-mentioned.   Furthermore, a photo-acid generator is included, The composition for thermosetting silicon containing film formation of any one of Claims 1-5 characterized by the above-mentioned.   An organic film is formed on a substrate to be processed, a silicon-containing film is formed thereon, and a resist film is formed thereon using a chemically amplified resist composition not containing silicon, and this resist film is patterned. After that, the silicon-containing film is patterned using the resist film pattern, the lower organic film is patterned using the processed silicon-containing film pattern as an etching mask, and further processed using the processed organic film as an etching mask. A silicon-containing film used in a multilayer resist method for etching a substrate, wherein the silicon-containing film is formed from the composition according to claim 1.   A silicon-containing film used in a multilayer resist method in which an organic antireflection film is interposed between a resist film obtained from a chemically amplified resist composition and a silicon-containing film in the step of the multilayer resist method according to claim 7. A silicon-containing film formed from the composition according to any one of claims 1 to 6.   An organic film, a silicon-containing film formed from the composition according to any one of claims 1 to 6 on the organic film, and a photoresist film formed on the organic film. A substrate characterized by.   An organic film, a silicon-containing film formed from the composition according to any one of claims 1 to 6, an organic antireflection film, and a photoresist film are sequentially formed on the organic film. A substrate characterized by being made.   The substrate according to claim 9 or 10, wherein the organic film is a film having an aromatic skeleton.   A method for forming a pattern on a substrate, comprising preparing the substrate according to claim 9, exposing a pattern circuit region of the photoresist film on the substrate, and then developing with a developer to form a resist pattern on the photoresist film. The silicon-containing film was dry-etched using the photoresist film on which the resist pattern was formed as an etching mask, and the organic film was etched using the silicon-containing film on which the pattern was formed as an etching mask to form a pattern. A pattern forming method comprising: forming a pattern on a substrate by etching the substrate using an organic film as a mask.   A method of forming a pattern on a substrate, comprising preparing the substrate according to claim 10, exposing a pattern circuit region of the photoresist film on the substrate, and then developing with a developer to form a resist pattern on the photoresist film. Forming, dry etching the organic antireflection film and the silicon-containing film using the photoresist film on which the resist pattern is formed as an etching mask, etching the organic film using the silicon-containing film on which the pattern is formed as an etching mask, A pattern forming method, wherein a pattern is formed on a substrate by etching the substrate using an organic film on which the pattern is formed as a mask.   The pattern forming method according to claim 12, wherein the organic film is a film having an aromatic skeleton.   15. The pattern forming method according to claim 12, 13 or 14, wherein a photolithography method using light having a wavelength of 300 nm or less is used in forming the resist pattern.