JP2013028744A - Cyclodextrin derivative and method for producing the same and resist material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a new cyclodextrin derivative into which a group derived from an adamantane compound having high heat resistance is introduced; and a production method thereof; and a resist material that can form fine patterns stably in high accuracy.SOLUTION: This cyclodextrin derivative comprises 6 to 8 glucose units, in which at least one hydroxy group of a glucose unit is ether-linked with a group represented by formula (a), in formula, Rrepresents an alkyl group.

Description

  The present invention relates to a cyclodextrin derivative, a method for producing the same, and a resist material.

  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 miniaturization of circuit patterns to be formed.

  Thus, when using extreme ultraviolet rays as exposure light in the photolithography process, it has amorphous properties, film-forming properties, heat resistance, rigidity, sensitivity to extreme ultraviolet rays, and low LER (Line Edge Roughness), that is, Development of a resist material that can form a fine pattern with high accuracy and stability with little roughness of the film surface is required.

Mitsuru Ueda et al. Macromolecules, 43, 2832 (2010) Huining Xiao et al. Tetrahedron Letters. , 51, 235 (2010) Khan, A .; R; Forgo, P .; Stine, K .; J. et al. D'Souza, V .; T.A. Chem. Rev. , 98, 1977, (1998)

  The present invention has been studied by the inventors 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. It is possible to introduce a group derived from an adamantane compound that has been tried to be used in various applications because of its unique properties with respect to cyclodextrin having a molecular weight and many hydroxyl groups in the molecule. It was made as a result of finding out.

An object of the present invention is to provide a novel cyclodextrin derivative in which a group derived from an adamantane compound is introduced and a method for producing the same.
Another object of the present invention is to provide a cyclodextrin derivative having high heat resistance and capable of forming a film easily, and a method for producing the cyclodextrin derivative.
Still another object of the present invention is to provide a resist material that has a low LER and can therefore form a fine pattern with high accuracy and stability.

  The cyclodextrin derivative of the present invention is represented by the following chemical formula (1).

[Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom or a group represented by the following chemical formula (a). n is an integer of 6-8. Further, at least one of the plurality of R ^{1 to} R ³ is a group represented by the following formula (a). ]

[Wherein, R ⁴ represents an alkyl group. ]

  In the cyclodextrin derivative of the present invention, the content of the group represented by the chemical formula (a) is preferably 7% or more.

  The method for producing a cyclodextrin derivative of the present invention comprises a compound represented by the following chemical formula (2) and a compound represented by the following chemical formula (3) in the presence of sodium hydroxide in the compound represented by the chemical formula (2). The cyclodextrin derivative according to claim 1 or 2 is obtained by reacting the compound represented by the chemical formula (3) with respect to 1 mol of all hydroxyl groups under a condition of 0.1 mol or more.

[In formula, n is an integer of 6-8. ]

[Wherein R ⁴ represents an alkyl group, and X represents a halogen atom. ]

  The resist material of the present invention comprises the above cyclodextrin derivative.

The cyclodextrin derivative of the present invention has a low molecular weight having a cyclodextrin skeleton and a group derived from an adamantane compound, so that excellent heat resistance is obtained and the content of the group derived from the adamantane compound is high. When the content is 7% or more, the film can be easily formed because it has solubility in an organic solvent.
The cyclodextrin derivative of the present invention is sensitive to extreme ultraviolet rays, and the thin film obtained from the cyclodextrin derivative has a low LER and forms a fine pattern with high accuracy and stability. Therefore, it is useful as a resist material using extreme ultraviolet light as exposure light.

According to the method for producing a cyclodextrin derivative of the present invention, the cyclodextrin derivative of the present invention can be easily obtained.
Moreover, in the manufacturing method of the cyclodextrin derivative of this invention, it is possible to control the content rate of the group derived from adamantane in the cyclodextrin derivative obtained by the usage-amount of sodium hydroxide.

  According to the resist material of the present invention, since it contains the cyclodextrin derivative of the present invention, the low LER (Line Edge Roughness), that is, the degree of film surface roughness is small, and thus a fine pattern is highly accurate. And it can form stably.

2 is an IR spectrum of the cyclodextrin derivative obtained in Example 1. 2 is an NMR spectrum of the cyclodextrin derivative obtained in Example 1. 2 is TGA data of a cyclodextrin derivative obtained in Example 1. 2 is an NMR spectrum of the cyclodextrin derivative obtained in Example 2. 3 is an NMR spectrum of the cyclodextrin derivative obtained in Example 3. 2 is an NMR spectrum of the cyclodextrin derivative obtained in Example 4. 3 is an IR spectrum of a cyclodextrin derivative obtained in Reference Example 1. 2 is an NMR spectrum of the cyclodextrin derivative obtained in Reference Example 1. 3 is TGA data of a cyclodextrin derivative obtained in Reference Example 1.

  Embodiments of the present invention will be described below.

The cyclodextrin derivative of the present invention is a compound represented by the chemical formula (1) and has a group derived from an adamantane compound.
The cyclodextrin derivative of the present invention is not limited to those in which all of the repeating units constituting the cyclodextrin derivative have the same configuration, and R ^{1 to} R ³ and R ⁴ in each repeating unit are part or all of them. May be different.

In the chemical formula (1) relating to the cyclodextrin derivative of the present invention, R ^{1 to} R ³ are each independently a hydrogen atom or a group derived from an adamantane compound represented by the chemical formula (a) (hereinafter referred to as “specific adamantyl group”). And at least one of the plurality of R ^{1 to} R ³ is a specific adamantyl group.
Here, in the cyclodextrin derivative of the present invention, at least one of R ^{1 to} R ³ related to at least one repeating unit among the plurality of repeating units constituting the cyclodextrin derivative may be a specific adamantyl group. .

In the chemical formula (a) relating to the specific adamantyl group, R ⁴ 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 the chemical formula (a), R ⁴ is preferably a methyl group.

  Moreover, in Chemical formula (1), n is an integer of 6-8, Preferably it is 7.

In the cyclodextrin derivative of the present invention, the content of the specific adamantyl group indicated by the etherification rate with respect to all hydroxyl groups in the cyclodextrin is preferably 7% or more, and more preferably 10% or more.
Here, the content rate of a specific adamantyl group can be calculated | required based on a < ¹ > H-NMR spectrum.

The cyclodextrin derivative of the present invention having such a structure can be obtained by reacting a cyclodextrin compound as a raw material compound with a compound having a specific adamantyl group.
Here, specific examples of the cyclodextrin compound as the raw material compound include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

Specifically, the cyclodextrin derivative of the present invention includes a cyclodextrin compound represented by the chemical formula (2) (hereinafter also referred to as “raw material compound (1)”) and a specific adamantyl represented by the chemical formula (3). It can be obtained by reacting a compound having a group (hereinafter also referred to as “raw compound (2)”) in the presence of sodium hydroxide.
Here, in the chemical formula (3) relating to the raw material compound (2), X is a halogen atom. Examples of X according to the chemical formula (3) include a bromine atom, a chlorine atom, and an iodine atom.

  The amount of the raw material compound (1) and the raw material compound (2) used is such that the raw material compound (2) is 0.1 mol or more with respect to 1 mol of the hydroxyl group in the raw material compound (1), preferably 0.1 to 5 0.0 mol, more preferably 0.5 to 1.0 mol.

It is preferable that the usage-amount of sodium hydroxide is 0.1-2.0 mol with respect to 1 mol of hydroxyl groups in a raw material compound (1), More preferably, it is 0.3-1.0 mol.
When the amount of sodium hydroxide used is too small or too large, there is a possibility that the content of the specific adamantyl group cannot be controlled in the obtained cyclodextrin derivative in any case.

  The reaction of the raw material compound (1) and the raw material compound (2) in the presence of sodium hydroxide can be performed by using an appropriate catalyst in an appropriate solvent.

  As the solvent, for example, N-methyl-2-pyrrolidone (NMP), dimethyl sulfide (DMS), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like can be used.

Examples of the catalyst that can be used include tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetraphenylammonium bromide, and tetrabutylphosphonium bromide.
The amount of the catalyst used is preferably 0.5 to 1.0 mol%.

  Moreover, as reaction conditions, reaction temperature is 0-100 degreeC, for example, and reaction time is 1 to 72 hours.

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

[Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom or a group represented by the following chemical formula (a), and n is an integer of 6 to 8. Further, at least one of the plurality of R ^{1 to} R ³ is a group represented by the following formula (a). R ⁴ represents an alkyl group, and X represents a halogen atom. ]

The cyclodextrin derivative of the present invention as described above has a low molecular weight having a cyclodextrin skeleton and a group derived from an adamantane compound, so that excellent heat resistance is obtained and the content ratio of a specific adamantane group Is 7% or more, the film can be easily formed because it has solubility in an organic solvent.
The cyclodextrin derivative of the present invention is sensitive to extreme ultraviolet rays, and the thin film obtained from the cyclodextrin derivative has a low LER and forms a fine pattern with high accuracy and stability. Therefore, it is useful as a resist material using extreme ultraviolet light as exposure light.

The resist material of the present invention contains the cyclodextrin derivative of the present invention.
Specifically, for example, together with the cyclodextrin derivative of the present invention, a radiation-sensitive acid generator that generates an acid when irradiated with radiation such as extreme ultraviolet rays, and an acid resist film generated from the radiation-sensitive generator ( It contains an acid diffusion control agent for controlling the diffusion phenomenon in the 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 a single or a combination of two or more of the cyclodextrin derivatives of the present invention constituting the resist material.

In the resist material of the present invention, the content of the cyclodextrin derivative of the present invention is preferably 1 to 30% by mass.
If the content of the cyclodextrin derivative of the present invention is too small, there is a possibility that a thin film cannot be formed. On the other hand, when the content ratio of the cyclodextrin derivative of the present invention is excessive, there is a possibility that a uniform thin film cannot be formed.

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 this case, the specific adamantyl group having acid dissociation property in the cyclodextrin derivative of the present invention constituting the resist material of the present invention is dissociated.
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 ⁵ represents an alkylene group, an arylene group, an alkoxylene group, a cycloalkylene group, a divalent group such as a cycloalkylene group containing a cyclic skeleton having an unsaturated bond, and R ⁶ 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 ⁷ 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 ⁸ and R ⁹ 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 ⁸ and R ⁹ 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 < ¹⁰ >, R < ¹¹ > and R <^12> 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 ¹⁰ , R ¹¹ and R ¹² are bonded to each other to form a cyclic structure together with the sulfur atom in the formula, and the rest 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 ¹³ -SO ₃ ^- or R ¹⁴ -COOH ^- are shown, R ¹³ and R ¹⁴ each independently represent 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 ¹³ —SO ₃ ^{— according to the} general formula (B-3) and the 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 cyclodextrin derivative 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 the effect | action which carries out.
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 ¹⁵ 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 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. 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 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. A plurality of R ¹⁷ may be bonded to each other to form a heterocyclic structure. R ¹⁸ 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 cyclodextrin derivative 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 monoalkyl ether acetates such as propylene glycol mono-n-propyl ether acetate, 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.

The resist material of the present invention having such a structure is preferably prepared by dissolving, for example, a radiation-sensitive acid generator, an acid diffusion controller, and, if necessary, an optional component together with the cyclodextrin derivative of the present invention in an appropriate solvent. Can be produced by filtering the obtained solution through a filter having a pore size of 0.2 μm.
In addition, the resist material of the present invention thus obtained can be obtained by, for example, applying the resist material on a substrate such as a silicon wafer by an appropriate application method such as spin coating, cast coating, or roll coating. A resist film (resist film) is formed, a desired resist pattern is formed on the resist film by exposure to extreme ultraviolet rays, and the resist film is suitably used in a photolithography process in which development is performed with an appropriate developer.

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

[Example 1]
(Synthesis example of cyclodextrin derivative)
In a eggplant flask having a volume of 50 mL, 0.23 g (0.2 mmol) of β-cyclodextrin (hereinafter also referred to as “β-CD”), which is a compound having n of 7 in the chemical formula (2), and N-methyl-2 -10 mL of pyrrolidone (hereinafter also referred to as “NMP”) was charged, and β-CD was dissolved in NMP. To this solution, 0.1 g of sodium hydroxide (equivalent to 4.2 mmol of hydroxyl group in β-CD) and 0.058 g of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”) (hydroxyl group of β-CD) Adamantyl bromoacetate (hereinafter also referred to as “BMA”), which is a compound in which X is a bromine atom and R ⁴ is a methyl group in the chemical formula (3), 1.2 g (β-CD The reaction was carried out by stirring at a temperature of 40 ° C. for 20 hours.
After the reaction was completed, the reaction solution was diluted with chloroform, washed once with 0.1N hydrochloric acid and twice with tap water, and the organic phase was recovered. Thereafter, the recovered organic phase was dried using anhydrous magnesium sulfate as a drying agent. The desiccant was filtered off, distilled off under reduced pressure, and then precipitated using ether as a poor solvent. The precipitate was collected and dried under reduced pressure at room temperature for 24 hours to obtain 0.0822 g of a reaction product. In addition, the mass of the obtained reaction product contains NMP.
The obtained reaction product is a compound represented by the following chemical formula (1-1) (hereinafter also referred to as “cyclodextrin derivative (1)”) from the results of IR analysis and ¹ H-NMR analysis. Was confirmed.
In this cyclodextrin derivative (1), it was confirmed that the content of the specific adamantane group (the etherification rate with respect to all hydroxyl groups in β-CD) was 39%.
Further, when the molecular weight and molecular weight distribution of the cyclodextrin derivative (1) were confirmed by GPC (gel permeation chromatography) method, the number average molecular weight (Mn) was 1200 and the molecular weight distribution (Mw / Mn) was 1. 06.

The results of IR analysis and ¹ H-NMR analysis of the cyclodextrin derivative (1) are shown below, and the IR spectrum is shown in FIG. 1 and the NMR spectrum is shown in FIG.

○ IR (KrS, cm ^-1 ):
3465 (νO-H)
2914 (νC-H)
1741 (νC = O)
1145, 1092, 1031 (νC—O—C)

○ ¹ H NMR (500 MHz, DMSO-d ₆ , TMS) δ (ppm):
1.50-2.18 (m, 195.33, H _h -H _z )
_{4.80 (s, 7, H a} )

(Characteristics of cyclodextrin derivatives)
About the obtained cyclodextrin derivative (1), the thermal stability, the solubility with respect to an organic solvent, and film-forming property were confirmed with the following method.

(1) Thermal stability (heat resistance)
When thermal stability (heat resistance) was confirmed by thermogravimetric analysis (TGA), Td ⁱ was 107.4 ° C, Td ^5.2% 188.2 ° C, and Td ^10.2% was 191.4 ° C. Was confirmed. TGA data is shown in FIG.
Here, “Td ⁱ ” is a thermal decomposition start temperature, “Td ^5.2% ” is a 5% weight pyrolysis loss temperature, and “Td ^10.2% ” is a 10% weight pyrolysis loss temperature. It is.

(2) Solubility in organic solvent The solubility of cyclodextrin derivative (1) in organic solvent was confirmed by adding 50 mg of cyclodextrin derivative (1) to 1 mL of organic solvent. Propylene glycol monomethyl ether (PGME), diglyme It was confirmed that it was dissolved in (diethylene glycol dimethyl ether) and ethyl lactate under room temperature (25 ° C.) conditions, and was dissolved in propylene glycol monomethyl ether acetate (PGMEA) under heating conditions. On the other hand, it was confirmed that the tetramethylammonium (TMAH) aqueous solution having a concentration of 2.38% by mass has no solubility.

(3) Film-forming property A solution in which 50 mg of cyclodextrin derivative (1) is dissolved in 1 mL of propylene glycol monomethyl ether (PGME), a solution in which 50 mg of cyclodextrin derivative (1) is dissolved in 1 mL of diglyme, and a cyclodextrin derivative (1) A solution in which 50 mg was dissolved in 1 mL of ethyl lactate was prepared, and a film was formed by the following method using each of the obtained solutions. It was confirmed that it can be formed.
Here, the film was formed by a technique of spin-coating a solution on a silicon wafer.

[Example 2]
In the synthesis example of the cyclodextrin derivative of Example 1, the amount of β-CD used was 2 mmol, the amount of sodium hydroxide used was 42 mmol, and the amount of BMA used was 14 mmol (1/3 equivalent to the hydroxyl group in β-CD) And the cyclodextrin of Example 1 except that the amount of TBAB was changed to 5 mol% with respect to the hydroxyl group of β-CD in accordance with the change in the amount of β-CD used. A reaction product was obtained in the same manner as in the synthesis example of the derivative.
The obtained reaction product is represented by the above chemical formula (1-1) from the results of IR analysis and ¹ H-NMR analysis, and the content of the specific adamantane group (the etherification rate with respect to all hydroxyl groups in β-CD) is It was confirmed that the compound was 76.9% (hereinafter also referred to as “cyclodextrin derivative (2)”).
Further, when the molecular weight and molecular weight distribution of the cyclodextrin derivative (2) were confirmed by GPC (gel permeation chromatography) method, the number average molecular weight (Mn) was 1404 and the molecular weight distribution (Mw / Mn) was 1. 06.
The NMR spectrum of the cyclodextrin derivative (2) is shown in FIG.

  About the obtained cyclodextrin derivative (2), the solubility with respect to the organic solvent was confirmed by the method similar to Example 1. FIG.

As for the solubility of the cyclodextrin derivative (2) in the organic solvent, the solubility of the cyclodextrin derivative (2) in the organic solvent was confirmed by adding 50 mg of the cyclodextrin derivative (2) to 1 mL of the organic solvent. (DMSO), tetrahydrofuran (THF), ethyl acetate, ethyl lactate, chloroform, diglyme (diethylene glycol dimethyl ether) and propylene glycol monomethyl ether (PGME) are dissolved at room temperature (25 ° C), and methanol and propylene glycol. It was confirmed that a part of monomethyl ether acetate (PGMEA) was dissolved at room temperature (25 ° C.). On the other hand, it was confirmed that ethyl ether and a tetramethylammonium (TMAH) aqueous solution having a concentration of 2.38% by mass have no solubility.
Moreover, it was confirmed that cyclodextrin derivative (2) has no solubility in water by adding 50 mg of cyclodextrin derivative (2) to 1 mL of water.

Example 3
In the synthesis example of the cyclodextrin derivative of Example 1, the amount of β-CD used was 4 mmol, the amount of sodium hydroxide used was 42 mmol (1/3 equivalent to the hydroxyl group in β-CD), and the amount of BMA used was 42 mmol (equivalent to the hydroxyl group in β-CD) and the amount of TBAB used is 5 mol% with respect to the hydroxyl group of β-CD according to the change in the amount of β-CD used. A reaction product was obtained in the same manner as in the synthesis example of the cyclodextrin derivative of Example 1 except that the change was made.
The obtained reaction product is represented by the above chemical formula (1-1) from the results of IR analysis and ¹ H-NMR analysis, and the content of the specific adamantane group (the etherification rate with respect to all hydroxyl groups in β-CD) is It was confirmed that the compound was 39.0% (hereinafter also referred to as “cyclodextrin derivative (3)”).
Moreover, when the molecular weight and molecular weight distribution of the cyclodextrin derivative (3) were confirmed by GPC (gel permeation chromatography) method, the number average molecular weight (Mn) was 1206, and the molecular weight distribution (Mw / Mn) was 1. 06.
The NMR spectrum of the cyclodextrin derivative (3) is shown in FIG.

  About the obtained cyclodextrin derivative (3), the solubility with respect to the organic solvent was confirmed by the same method as Example 1.

Regarding the solubility of the cyclodextrin derivative (3) in the organic solvent, the solubility of the cyclodextrin derivative (3) in the organic solvent was confirmed by adding 50 mg to 1 mL of the organic solvent. As a result, dimethyl sulfoxide (DMSO), methanol, It dissolves in tetrahydrofuran (THF), ethyl lactate, chloroform and propylene glycol monomethyl ether (PGME) at room temperature (25 ° C.) conditions, and also acetone, ethyl acetate, propylene glycol monomethyl ether acetate (PGMEA) and diglyme (diethylene glycol) (Dimethyl ether) was confirmed to partially dissolve under room temperature (25 ° C.) conditions. On the other hand, it was confirmed that ethyl ether, n-hexane and a tetramethylammonium (TMAH) aqueous solution having a concentration of 2.38% by mass have no solubility.
Moreover, it was confirmed that cyclodextrin derivative (3) has no solubility in water by adding 50 mg of cyclodextrin derivative (3) to 1 mL of water.

Example 4
In the synthesis example of the cyclodextrin derivative of Example 1, the amount of β-CD used was 6 mmol, the amount of sodium hydroxide used was 42 mmol, the amount of BMA used was 42 mmol, and the amount of TBAB used was β-CD. A reaction product was obtained in the same manner as in the synthesis example of the cyclodextrin derivative of Example 1 except that the amount used was changed to 5 mol% with respect to the hydroxyl group of β-CD according to the change in the amount used.
The obtained reaction product is represented by the above chemical formula (1-1) from the results of IR analysis and ¹ H-NMR analysis, and the content of the specific adamantane group (the etherification rate with respect to all hydroxyl groups in β-CD) is It was confirmed that the compound was 36.9% (hereinafter also referred to as “cyclodextrin derivative (4)”).
Moreover, when the molecular weight and molecular weight distribution of the cyclodextrin derivative (4) were confirmed by GPC (gel permeation chromatography) method, the number average molecular weight (Mn) was 1176, and the molecular weight distribution (Mw / Mn) was 1. 06.
The NMR spectrum of the cyclodextrin derivative (4) is shown in FIG.

[Reference Example 1]
In the synthesis example of the cyclodextrin derivative of Example 1, the amount of β-CD used was 5 mmol, the amount of sodium hydroxide used was 21 mmol, the amount of BMA used was 21 mmol, and the amount of TBAB used was β-CD. In the same manner as in the synthesis example of the cyclodextrin derivative of Example 1, except that the amount was changed to 5 mol% with respect to the hydroxyl group of β-CD according to the change in the amount used, 4.633 g of the reaction product was added. Obtained. In addition, the mass of the obtained reaction product contains NMP.
The obtained reaction product is represented by the above chemical formula (1-1) from the results of IR analysis and ¹ H-NMR analysis, and the content of the specific adamantane group (the etherification rate with respect to all hydroxyl groups in β-CD) is It was confirmed that the compound was 6% (hereinafter also referred to as “cyclodextrin derivative (5)”).
In addition, when the molecular weight and molecular weight distribution of the cyclodextrin derivative (5) were confirmed by GPC (gel permeation chromatography) method, the number average molecular weight (Mn) was 866 and the molecular weight distribution (Mw / Mn) was 1. 29.
The results of IR analysis and ¹ H-NMR analysis of the cyclodextrin derivative (5) are shown below, and the IR spectrum is shown in FIG. 7 and the NMR spectrum is shown in FIG.

○ IR (KrS, cm ^-1 ):
3355 (νO-H)
2925 (νC-H)
1734 (νC = O)
1155, 1080, 1028 (νC—O—C)

○ ¹ H NMR (500 MHz, DMSO-d ₆ , TMS) δ (ppm):
1.50-2.18 (m, 195.33, H _h -H _z )
_{4.80 (s, 7, H a} )

  About the obtained cyclodextrin derivative (5), the heat stability and the solubility with respect to the organic solvent were confirmed by the same method as Example 1.

The thermal stability of the cyclodextrin derivative (5) (heat resistance), thermal gravimetric analysis (TGA) around confirming thermal stability (heat resistance) by a Td ⁱ is 107 ° C., ^5.2% Td is 188 ° C. And it was confirmed that Td ^10.2% was 191 ° C. The TGA data is shown in FIG.

Regarding the solubility of the cyclodextrin derivative (5) in the organic solvent, the solubility of the cyclodextrin derivative (5) in the organic solvent was confirmed by adding 50 mg of the cyclodextrin derivative (5) to 1 mL of the organic solvent. , Methanol, tetrahydrofuran, ethyl acetate, ethyl lactate, ethyl ether, chloroform, propylene glycol monomethyl ether acetate, n-hexane, diglyme, propylene glycol monomethyl ether, soluble in tetramethylammonium hydroxide with a concentration of 2.38% by mass It was confirmed that it does not have.
Further, it was confirmed that a part of the cyclodextrin derivative (5) was dissolved in water at room temperature (25 ° C.) by adding 50 mg of the cyclodextrin derivative (5) to 1 mL of water.

  According to Examples 1 to 4, the content of the specific adamantane group of the cyclodextrin derivative obtained by adjusting the amount of sodium hydroxide used (the etherification rate relative to all hydroxyl groups in the cyclodextrin) can be controlled. It was confirmed that it was possible. It was confirmed that the content of the specific adamantane group of the cyclodextrin derivative obtained (the etherification ratio of all hydroxyl groups in the cyclodextrin) could not be controlled depending on the amount of BMA used.

Claims (4)

A cyclodextrin derivative represented by the following chemical formula (1):

[Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom or a group represented by the following chemical formula (a). n is an integer of 6-8. Further, at least one of the plurality of R ^{1 to} R ³ is a group represented by the following formula (a). ]

[Wherein, R ⁴ represents an alkyl group. ]   The cyclodextrin derivative according to claim 1, wherein the content of the group represented by the chemical formula (a) is 7% or more. In the presence of sodium hydroxide, a compound represented by the following chemical formula (2) and a compound represented by the following chemical formula (3) are represented by the chemical formula (3) with respect to 1 mol of all hydroxyl groups in the compound represented by the chemical formula (2). A process for producing a cyclodextrin derivative according to claim 1 or 2, wherein the cyclodextrin derivative according to claim 1 or 2 is obtained by reacting under a condition that the compound represented is 0.1 mol or more.

[In formula, n is an integer of 6-8. ]

[Wherein R ⁴ represents an alkyl group, and X represents a halogen atom. ]   A resist material comprising the cyclodextrin derivative according to claim 1.