JP5827058B2 - Method for producing silsesquioxane compound - Google Patents

Description

The present invention relates to a method for producing a silsesquioxane compound.

  Conventionally, photolithography technology has been widely used in the manufacture of integrated circuit devices such as semiconductor devices, and in this photolithography technology, there has been a demand for higher integration of integrated circuit devices in recent years. As the light, instead of conventionally used, for example, KrF excimer laser light and ArF excimer laser light, extreme ultraviolet (EUV: Extreme Ultra-Violet) which is light having a shorter wavelength than these excimer laser lights is used. Therefore, it has been studied to cope with the miniaturization of a circuit pattern to be formed, and research and development on a photolithography process and a resist material in the case where extreme ultraviolet rays are used as exposure light are being conducted.

In resist films where an exposure pattern corresponding to the circuit pattern to be formed by exposure light is formed, it is necessary to reduce the film thickness in order to form a fine pattern with high precision, but the patterned resist film is etched. Since the processing of the substrate performed as a mask is generally performed by dry etching, there is a problem in that sufficient etching resistance may not be obtained for a thinned etching mask.
As a technique for solving such a problem, a multilayer resist method in which a resist film has a multilayer structure has attracted attention (for example, see Non-Patent Documents 1 to 6). As this multilayer resist method, for example, in the two-layer resist method in which the resist film has a two-layer structure, the lowermost layer formed on the surface of the substrate is processed by dry etching using oxygen plasma. As a constituent resist material, a polymer compound containing a silicon atom in a molecule and having dry etching resistance against dry etching by oxygen plasma has been proposed (see, for example, Non-Patent Documents 7 to 12).

J. et al. D. Meador et al. , Proc. SPIE. , 5376, 1138 (2004). H. Sugita et al. , J Appl Polymer Sci. , 88, 636 (2003) Y. Kimura et al. , Proc. SPIE. , 3333, 347 (1998) G. W. Ray et al. , J .; Electrochem. Soc. , 9, 2152 (1982) S. P. Lyman et al. , J .; Vac. Sci. Technol. , 19, 1325 (1981) J. et al. M.M. Moran et al. , J .; Vac. Sci. Technol. 16, 1620 (1979) W. S. Han et al. , J .; Photopoly. Sci. Technol, 16, 499 (2003) A. Zampini et al. , J .; Photopoly. Sci. Technol, 17, 511 (2004) J. et al. Hatakeyama et al. , J .; Photopoly. Sci. Technol. , 17, 519 (2004) H. Ito et al. , J .; Photopoly. Sci. Technol, 18, 355 (2005) T. T. et al. Hoson et al. , J .; Photopoly. Sci. Technol, 18, 365 (2005) K. Ober et al. , Proc. SPIE. , 5039, 1204 (2003)

The present invention is based on the above situation, and based on the fact that a low molecular weight compound is useful as a resist material for photolithography that uses extreme ultraviolet light as exposure light, the inventors have conducted research on molecular molecules. introducing relative low molecular weight compounds which cage Shi Le silsesquioxane containing a silicon atom, a group derived from adamantane compound utilized has been attempted to various applications because of their unique properties in As a result of finding out that this is possible.

An object of the present invention is to provide a novel process for producing a silsesquioxane compound in which a group derived from an adamantane compound is introduced .

The process for producing a silsesquioxane compound of the present invention comprises reacting a compound represented by the following chemical formula (2) with a compound represented by the following chemical formula (3) to thereby produce a silsesquioxane represented by the following chemical formula (1). An oxane compound is obtained .

[Wherein R ¹ represents a group represented by the following chemical formula (a). ]

[Wherein R ² represents a methyl group . ]

[Wherein R ³ represents a group represented by the following chemical formula (b). ]

[Wherein R ² represents a methyl group , and X represents a halogen atom or a monovalent organic group. ]

Produced by the manufacturing method of the sheet Le silsesquioxane compound of the present invention, a compound represented by the formula (2) is to react a compound represented by the following chemical formula (4), and a 4-(tert-butoxy) styrene It is preferably obtained by deprotecting the compound to be obtained.

[Wherein R ⁴ represents a group represented by the following chemical formula (c). ]

  Since the silsesquioxane compound of the present invention has a low molecular weight containing a silicon atom in the molecule and has a group derived from an adamantane compound, it can be easily formed into a film. The thin film obtained from the silsesquioxane compound has low LER (Line Edge Roughness), that is, the degree of roughness of the film surface is small, and thus a fine pattern is highly accurate and stable. In addition, since it has dry etching resistance against dry etching by oxygen plasma, the uppermost layer in a resist film having a multilayer structure used for photolithography using extreme ultraviolet light as exposure light is formed. Therefore, it is useful as a resist material.

According to the manufacturing method of the silsesquioxane compound of the present invention, it is possible to obtain a sheet Le silsesquioxane compound of the present invention easily.

According to the resist material of the present invention, since those containing shea Le silsesquioxane compound of the present invention, a low LER (Line Edge Roughness), i.e. less degree of rough film surface, therefore a fine pattern with high precision And can be formed stably.

1 is a ¹ H-NMR spectrum of the raw material compound (1-1) obtained in Example 1. 3 is a ¹³ C-NMR spectrum of the raw material compound (1-1) obtained in Example 1. 1 is a ¹ H-NMR spectrum of an intermediate product obtained in Example 1. It is the raw material compound (1) IR spectrum obtained in Example 1. 1 is a ¹ H-NMR spectrum of the raw material compound (1) obtained in Example 1.

  Embodiments of the present invention will be described below.

  The silsesquioxane compound of the present invention is a compound represented by the above chemical formula (1) and has a group derived from an adamantane compound.

In the chemical formula (1) relating to the silsesquioxane compound of the present invention, R ¹ is a group derived from the adamantane compound represented by the chemical formula (a).

In the chemical formula (a), R ² is an alkyl group.
Examples of the alkyl group in the chemical formula (a) include C1-C4 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
In chemical formula (a), R ² is preferably a methyl group.

The silsesquioxane compound of the present invention having such a structure includes a silsesquioxane compound represented by the chemical formula (2) (hereinafter also referred to as “raw material compound (1)”) and the chemical formula (3). It can be obtained by reacting the adamantane compound represented (hereinafter also referred to as “raw material compound (2)”).
Here, in the chemical formula (2) relating to the raw material compound (1), R ³ is a group represented by the above chemical formula (b). In the chemical formula (3) relating to the raw material compound (2), R ² is an alkyl group. X is a halogen atom or a monovalent organic group. Examples of X related to the chemical formula (3) include monovalent organic groups such as halogen atoms such as bromine atom and chlorine atom, and groups derived from p-toluenesulfonic acid ester.

The raw material compound (1) includes, for example, a silsesquioxane compound represented by the chemical formula (4) (hereinafter also referred to as “raw material compound (1-1)”) and a hydroxy group protected with a tert-butyl group. The compound (hereinafter also referred to as “intermediate product”) produced by reacting 4-tert-butoxystyrene (hereinafter also referred to as “raw compound (1-2)”) having a deprotection reaction. Can be obtained.
Here, in the chemical formula (4) relating to the raw material compound (1-1), R ⁴ is a group represented by the chemical formula (c).

In the reaction step of obtaining an intermediate product by reacting the raw material compound (1-1) and the raw material compound (1-2), the amounts of the raw material compound (1-1) and the raw material compound (1-2) used Is preferably 1.1 to 5.0 mol of the raw material compound (1-2) with respect to 1 mol of the group represented by the chemical formula (c) in the raw material compound (1-1).
The reaction between the raw material compound (1-1) and the raw material compound (1-2) can be performed in an appropriate solvent in the presence of a catalyst.
Here, as the catalyst, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex or the like can be used. Moreover, it is preferable that the usage-amount of a catalyst is 0.1-100 mol% with respect to a raw material compound (1-1).
As the solvent, toluene or the like can be used.
As reaction conditions, for example, the reaction temperature is 0 to 160 ° C., and the reaction time is 0.5 to 72 hours.

  In the reaction step of deprotecting the intermediate product obtained by reacting the raw material compound (1-1) and the raw material compound (1-2), a strong acidic solution is allowed to act on the intermediate product, and then By distilling off the solvent, the starting compound (1) which is the target product can be obtained.

In the reaction system in which the silsesquioxane compound of the present invention is obtained by reacting the raw material compound (1) with the raw material compound (2), the amount of the raw material compound (1) and the raw material compound (2) used is The raw material compound (2) is preferably 1.1 to 5.0 mol with respect to 1 mol of the group represented by the chemical formula (b) in the compound (1).
The reaction between the raw material compound (1) and the raw material compound (2) can be carried out in an appropriate solvent in the presence of a catalyst.
Here, tetrabutylammonium bromide (TBAB) or the like can be used as the catalyst. Moreover, it is preferable that the usage-amount of a catalyst is 0.1-2.0 mol% with respect to a raw material compound (1-1).
As the solvent, N-methyl-2-pyrrolidone (NMP) or the like can be used.
As reaction conditions, for example, the reaction temperature is 0 to 160 ° C., and the reaction time is 1 to 72 hours.

  An example of the synthesis process of the silsesquioxane compound of the present invention is shown in the following reaction formula (1).

[Wherein, R ¹ represents a group represented by the chemical formula (a), R ² represents an alkyl group, R ³ represents a group represented by the chemical formula (b), and R ⁴ represents the chemical formula (c). R ⁵ represents a group represented by the following chemical formula (d), and X represents a halogen atom or a monovalent organic group. ]

  Since the silsesquioxane compound of the present invention as described above has a low molecular weight containing a silicon atom in the molecule and has a group derived from an adamantane compound, it can be easily formed into a film. In addition, the thin film obtained from the silsesquioxane compound is sensitive to extreme ultraviolet rays, and can form a fine pattern with a low LER with high accuracy and stability. Since it has dry etching resistance against dry etching by oxygen plasma, it is useful as a resist material for forming the uppermost layer in a resist film having a multilayer structure used for photolithography using extreme ultraviolet light as exposure light.

The resist material of the present invention contains the silsesquioxane compound of the present invention.
Specifically, for example, together with the silsesquioxane compound of the present invention, a radiation-sensitive acid generator that generates acid when irradiated with radiation such as extreme ultraviolet rays, and an acid resist generated from the radiation-sensitive generator It contains an acid diffusion controller for controlling the diffusion phenomenon in the film (resist film), an organic solvent, and optional components such as a surfactant and a sensitizer as required.
Here, the resist material of the present invention may be one in which the silsesquioxane compound of the present invention constituting the resist material is used alone or in combination of two or more.

In the resist material of the present invention, the content ratio of the silsesquioxane compound of the present invention is preferably 1 to 50% by mass.
When the content ratio of the silsesquioxane compound of the present invention is too small, there is a possibility that no film is formed. On the other hand, when the content ratio of the silsesquioxane compound of the present invention is excessive, a uniform thin film may not be obtained.

The radiation-sensitive generator is a substance that generates an acid in the resist material of the present invention when irradiated with light such as an electron beam and extreme ultraviolet rays, and the resist material of the present invention is irradiated with light. In the case, in the silsesquioxane compound body of the present invention constituting the resist material of the present invention, the group derived from the acid dissociable adamantane compound (group represented by the chemical formula (a)) is dissociated; Become.
From the viewpoint of acid generation efficiency and heat resistance, for example, onium salts, diazomethane compounds, sulfonimide compounds and other nonionic acid generators are preferably used as the radiation sensitive generator. These compounds can also be used independently and can also be used in combination of 2 or more type.

  Specific examples of the radiation sensitive generator include sulfonyloxyimide compounds represented by the following general formula (B-1).

[In the above formula, R ⁶ represents a divalent group such as an alkylene group, an arylene group, an alkoxylene group, a cycloalkylene group, a cycloalkylene group containing a cyclic skeleton having an unsaturated bond, and R ⁷ represents a halogen atom, An alkyl group which may be substituted with a cycloalkyl group, an alkyl group, a cycloalkyl group which may be substituted with a group having an ester bond, an aryl group which may be substituted with a halogen atom or an alkyl group. ]

  In this invention, a sulfonyloxyimide compound can be used individually or in mixture of 2 or more types.

  Specific examples of the sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide. N- (4-toluenesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-{(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) And sulfonyloxy} succinimide.

  The other nonionic acid generator is preferably a sulfonyldiazomethane compound. As a sulfonyl diazomethane compound, the compound represented by the following general formula (B-2) can be mentioned, for example.

[In the above formulae, each R ⁸ independently represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. ]

  Specific examples of the sulfonyldiazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). Diazomethane, bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-chlorobenzenesulfonyl) diazomethane, methylsulfonyl, 4-toluenesulfonyldiazomethane, cyclohexanesulfonyl, 4-toluenesulfonyldiazomethane, cyclohexanesulfonyl, 1,1-dimethylethane Sulfonyldiazomethane, bis (1,1-dimethylethanesulfonyl) diazomethane, bis (1-methylethanesulfonyl) dia Examples include methane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, and the like. be able to.

  As said onium salt, what generate | occur | produces the benzenesulfonic acid which may be substituted by a fluorine atom can be used.

  Specific examples of the onium salt compound include compounds represented by the following general formula (B-3) and general formula (B-4).

[In the above formula (B-3), R ⁹ and R ¹⁰ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or may be substituted. It may be a good aryl group having 6 to 18 carbon atoms, or R ⁹ and R ¹⁰ may be bonded to each other to form a cyclic structure together with an iodine atom in the formula. In said formula (B-4), R <^11> , R < ¹² > and R <^13> are mutually independently the C1-C10 linear or branched alkyl group which may be substituted, or substituted. Or an aryl group having 6 to 18 carbon atoms, or any two of R ¹¹ , R ¹² and R ¹³ are bonded to each other to form a cyclic structure together with the sulfur atom in the formula, May be a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 18 carbon atoms which may be substituted. Further, in general formula (B-3) and the general formula (B-4), X ' - is R ¹⁴ -SO ₃ ^- or R ¹⁵ -COOH ^- are shown, R ¹⁴ and R ¹⁵ are each independently a fluorine atom , A group derived from an alkyl group or an aromatic derivative which may be substituted with a hydroxyl group, an alkoxyl group and a carboxyl group. ]

Preferred R ¹⁴ —SO ₃ ^{— according to the} general formula (B-3) and the above general formula (B-4) includes trifluoromethanesulfonate, nonafluoro-n-butanesulfonate, benzenesulfonate, 10-camphorsulfonate, Fluoromethylbenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 2,4-difluorobenzenesulfonate, perfluorobenzenesulfonate, 2- (bicyclo [2.2.1] heptan-2-yl) -1,1-difluoroethanesulfonate 2- (bicyclo [2.2.1] heptan-2-yl) ethanesulfonate.

  The content ratio of the radiation sensitive generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the silsesquioxane compound of the present invention.

The acid diffusion control agent suppresses the occurrence of a chemical reaction in the non-exposed region by controlling the diffusion phenomenon in the resist film (resist coating) of the acid generated from the radiation sensitive generator constituting the resist material of the present invention. It has an action to do.
As the acid diffusion controller, a nitrogen-containing organic compound or a photosensitive basic compound is preferably used. These compounds can also be used independently and can also be used in combination of 2 or more type.

  Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (C-1) (hereinafter referred to as “nitrogen-containing compound (i)”) and the following general formula (C-2). A compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (ii)”), a polyamino compound or polymer having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound ( iii) "), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

[In the above formula, a plurality of R ¹⁶ are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or a substituted group. The aralkyl group which may be sufficient is shown. ]

[In the above formula, a plurality of R ¹⁷ are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or a substituted group. And L ′ represents a single bond or an alkylene group having 1 to 6 carbon atoms, an ether group, a carbonyl group or an alkoxycarbonyl group. ]

  Examples of the nitrogen-containing compound (i) include substituted alkylamines such as di (cyclo) alkylamines, tri (cyclo) alkylamines and trialcoholamines, and aromatic amines such as anilines.

  Examples of the nitrogen-containing compound (iii) include triazines, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  As said amide group containing compound, the compound represented by the following general formula (C-3) can be mentioned, for example.

[In the above formula, a plurality of R ¹⁸ are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or a substituted group. A plurality of R ¹⁸ may be bonded to each other to form a heterocyclic structure. R ¹⁹ represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group, or an optionally substituted aralkyl group. ]

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Examples include thiourea.

  Examples of the nitrogen-containing heterocyclic compound include imidazoles, pyridines, piperazines, piperidines, triazines, morpholines, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, 1,4-diazabicyclo [2 2.2.2] Octane and the like can be cited as preferred examples.

  The content ratio of the acid diffusion controller is preferably 15 parts by mass or less with respect to 100 parts by mass of the silsesquioxane compound of the present invention.

  As said organic solvent, what can melt | dissolve the other component which comprises the resist material of this invention is used.

  Examples of the organic solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; propylene glycol Propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl Ether, propylene glycol di-n-butyl ether Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol mono-n-butyl ether acetate; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate , Aliphatic carboxylic acid esters such as i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate, i-butyl propionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, Other esters such as ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone Keto such as cyclohexanone Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolacun;

  The content of the organic solvent is preferably such that the total solid concentration in the resist material is 5 to 70% by mass.

In the resist material of the present invention having such a structure, for example, together with the silsesquioxane compound of the present invention, a radiation-sensitive acid generator, an acid diffusion controller, and if necessary, an optional component are dissolved in an appropriate solvent. Preferably, it can be produced by filtering the obtained solution through a filter having a pore size of 0.2 μm.
Moreover, the resist material of the present invention thus obtained uses, for example, a plurality of types (for example, two types) of resist materials having different etching selectivity, and each resist material is applied by spin coating, casting coating, roll coating. A resist film (resist film) having a multilayer structure is formed by sequentially applying on a substrate such as a silicon wafer by an appropriate application method such as, and extreme ultraviolet rays are applied to the uppermost layer (resist uppermost layer) in the resist layer. The desired resist pattern is formed by exposure such as development with an appropriate developer, and the resist layer positioned below the uppermost layer is formed using the uppermost layer thus patterned as an etching mask. In the photolithographic process that performs dry etching with oxygen plasma, It is suitably used as a constituent material.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

[Example 1]
(Synthesis of raw material compound (1-1))
A 25-mL two-necked eggplant flask was purged with nitrogen, charged with 13.2 mL (120 mmol) of dimethylchlorosilane and 15 mL of hexane, and then dissolved in 11.4 g (10 mmol) of octaanion in 15 mL of methanol under ice cooling. Was slowly added, followed by reaction by stirring at room temperature for 3 hours.
After the reaction was completed, the reaction solution was diluted with hexane, washed three times with water, and the organic phase was dried using magnesium sulfate as a drying agent. The desiccant was filtered off and distilled under reduced pressure to obtain a white solid. The obtained white solid was washed with methanol and dried to obtain 4.60 g of a reaction product with a yield of 45%.
From the results of ¹ H-NMR analysis and ¹³ C-NMR analysis, the obtained reaction product was a compound represented by the chemical formula (4) (hereinafter also referred to as “raw material silsesquioxane compound (A)”). It was confirmed that.
Moreover, about the raw material silsesquioxane compound (A), when the molecular weight and molecular weight distribution were confirmed by GPC (gel permeation chromatography) method, number average molecular weight (Mn) was 896, and molecular weight distribution (Mw / Mn) Was 1.02. The theoretical molecular weight is 1017.

The results of ¹ H-NMR analysis and ¹³ C-NMR analysis of the starting silsesquioxane compound (A) are shown below, and ¹ H-NMR spectrum is shown in FIG. 1 and ¹³ C-NMR spectrum is shown in FIG.

○ ¹ H NMR (600 MHz, CDCl ₃ , TMS ) Δ (ppm):
^{0.25-0.26 (d, 6H, H a} ),
4.73-4.74 (m, 1H, ^Hb )

○ ¹³ C NMR (150 MHz, CDCl ₃ , TMS ) Δ (ppm):
0.26 (C ^a )

(Synthesis of intermediate product)
Add 0.51 g (0.5 mmol) of the raw silsesquioxane compound (A) to the eggplant flask, and replace with nitrogen gas. 4-tert-butoxystyrene (tBS) 0.35 g (5 mmol), 3 mL of toluene as a solvent added. Next, after adding 0.3 mL (2 mmol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex [Pt (dvs)] xylene solution as a catalyst, the conditions at 100 ° C. For 30 minutes. After completion of the reaction, the reaction mixture was diluted with chloroform and activated carbon was added. The activated carbon was filtered off and concentrated to obtain a brownish viscous liquid.
The obtained reaction product is a compound (hereinafter also referred to as “intermediate product (A)”) shown as an intermediate product in the above reaction formula (1) from the result of ¹ H-NMR analysis. It was confirmed.

The ¹ H-NMR spectrum of the intermediate product (A) is shown in FIG.

(Synthesis of raw material compound (1))
An eggplant flask was charged with 1.21 g (0.5 mmol) of the intermediate product (A), 4 mL of 3N hydrochloric acid was added together with 6 mL of 1,4-dioxane as a solvent, and the reaction was allowed to proceed for 12 hours at a temperature of 85 ° C. It was.
After the reaction was completed, precipitation was performed using a mixed solvent of water and methanol (mass ratio of water and methanol (water: methanol) = 8: 2). The obtained viscous liquid was dissolved in a small amount of tetrahydrofuran and dropped into n-hexane to obtain 0.58 g of a reaction product consisting of a brown solid in a yield of 59%.
The obtained reaction product was confirmed to be a compound represented by the chemical formula (2) (hereinafter also referred to as “raw material compound (A)”) from the results of IR analysis and ¹ H-NMR analysis, From the result of ¹ H-NMR analysis, it was confirmed that the deprotection rate was 99% or more.
Moreover, when the molecular weight and molecular weight distribution were confirmed by the GPC (gel permeation chromatography) method about the raw material compound (A), the number average molecular weight (Mn) was 2134, and molecular weight distribution (Mw / Mn) was 1.11. Met. The theoretical molecular weight is 198.3.

The results of IR analysis and ¹ H-NMR analysis of the raw material compound (A) are shown below, and the IR spectrum is shown in FIG. 4 and the ¹ H-NMR spectrum is shown in FIG.

○ IR (film, cm ^-1 ):
3348 (ν C—H),
2957 (ν C—H (aromatic)),
1512 (ν C = C (aromatic)),
1253 (ν Si-C),
1084 (ν Si—O)

○ ¹ H NMR (600 MHz, CDCl ₃ , TMS ) Δ (ppm):
0.07-0.12 (d, 36H, a ),
0.89-1.35 (b, 16H, b),
1.29-1.35 (b, 16H, c),
6.65-6.95 (b, 32H, d and e),
9.00-9.13 (b, 8H, OH)

(Synthesis of silsesquioxane compound having specific adamantyl group)
Raw material compound (A) 0.20 g (0.1 mmol) was charged into a 100 mL volumetric flask, tetrabutylammonium bromide (TBAB) 0.03 g (0.10 mmol) as a phase transfer catalyst, and potassium carbonate 0 as a base. After adding 1 mL of N-methyl-2-pyrrolidone (NMP) together with .14 g (1.0 mmol), the mixture was reacted at room temperature for 3 hours (salt formation reaction). After the reaction is completed and a salt is formed, 0.11 g (0.4 mmol) of a compound in which X is a bromo group and R ² is a methyl group in chemical formula (3) is added and the reaction is performed at a temperature of 60 ° C. The reaction was allowed to stir for hours.
After the reaction was completed, the reaction solution was diluted with ethyl acetate, washed 3 times with 3% by mass oxalic acid aqueous solution and 3 times with tap water, and the organic phase was dried using magnesium sulfate as a desiccant. The desiccant was filtered off and concentrated to obtain 0.28 g of reaction product in 89% yield.
The resulting reaction product was the results of ¹ H-NMR analysis, the chemical formula (1), a compound wherein R ² is a methyl group of formula (a) (hereinafter, also referred to as "sheet Le silsesquioxane compound (A)" .).
Moreover, when the molecular weight and molecular weight distribution were confirmed by the GPC (gel permeation chromatography) method about the silsesquioxane compound (A), the number average molecular weight (Mn) was 3600, and molecular weight distribution (Mw / Mn) was 1.10.

Claims (2)

A silsesquioxane compound represented by the following chemical formula (1) is obtained by reacting a compound represented by the following chemical formula (2) with a compound represented by the following chemical formula (3). A method for producing an oxane compound.
[Wherein R ³ represents a group represented by the following chemical formula (b). ]
[Wherein R ² represents a methyl group, and X represents a halogen atom or a monovalent organic group. ]
[Wherein R ¹ represents a group represented by the following chemical formula (a). ]
[Wherein R ² represents a methyl group. ] The compound represented by the chemical formula (2) is obtained by deprotecting a compound produced by reacting a compound represented by the following chemical formula (4) with 4- (tert-butoxy) styrene. The method for producing a silsesquioxane compound according to claim 1 .
[Wherein R ⁴ represents a group represented by the following chemical formula (c). ]