WO2005108343A1

WO2005108343A1 - Adamantane derivative, method for producing same and photosensitive material for photoresist

Info

Publication number: WO2005108343A1
Application number: PCT/JP2005/008354
Authority: WO
Inventors: Katsuki Ito; Shinji Tanaka; Hidetoshi Ono; Naoyoshi Hatakeyama
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2004-05-10
Filing date: 2005-05-06
Publication date: 2005-11-17
Also published as: TW200600489A; JPWO2005108343A1

Abstract

Disclosed is an adamantane derivative useful as a monomer for a functional resin such as a photoresist resin which is used as a photosensitive material for photoresists that is suitably used in fine processing, particularly in one using excimer laser light or electron beam. Also disclosed are a method for efficiently producing such an adamantane derivative and a photosensitive material for photoresists containing such an adamantane derivative and having the above-mentioned characteristics. Specifically disclosed is an adamantane derivative which is characterized by having a structure represented by the following general formula (I) (wherein R represents a hydrogen atom, a methyl group or a trifluoromethyl group; Y represents an alkyl group having 1-10 carbon atoms, a halogen atom or a hydroxyl group, or alternatively two Ys may combine together to form =O, and a plurality of Ys may be the same as or different from one another; k represents an integer of 0-15; m represents 0 or 1; and n represents an integer of 1-3). Also specifically disclosed are a method for producing an adamantane derivative represented by the above general formula (I) by reacting a haloalkyl adamantyl carboxylate with a (meth)acrylic acid or an acid anhydride thereof, and a photosensitive material for photoresists containing a polymer obtained from such an adamantane derivative.

Description

FIELD OF THE INVENTION

The present invention relates to a novel adamantane derivative, a method for producing the same, and a photosensitive material for a photoresist obtained by using the adamantane derivative, and more particularly, to fine processing using excimer laser light or an electron beam. Novel adamantyloxycarboxyalkyl (meth) atalylates useful as monomers for functional resins such as resin for photoresist used in suitable photoresist photosensitive materials, and to efficiently produce these The present invention also relates to a method and a photosensitive material for a photoresist having the above-mentioned properties, including a polymer obtained from the (meth) acrylate.

Background art

[0002] Adamantane is a stable compound with a high symmetry having a structure in which four cyclohexane rings are condensed in a cage, and its derivative shows a unique function. It is known to be useful as a raw material for highly functional industrial materials. For example, because of its optical characteristics and heat resistance, it has been attempted to use it for optical disk substrates, optical fibers, lenses, and the like (for example, see Patent Documents 1 and 2).

Also, attempts have been made to use adamantane esters as a resin raw material for photoresists by utilizing their acid sensitivity, dry etching resistance, and ultraviolet transmittance (for example, see Patent Document 3). reference).

In recent years, in the field of microfabrication in the manufacturing technology of liquid crystal display devices, there has been rapid progress in miniaturization due to advances in lithography technology. As a method of miniaturization, a shorter wavelength of an exposure light source is generally used, and specifically, the ultraviolet rays typified by the conventional g-line and i-line have been changed to DUV (Deep UV).

At present, KrF excimer laser (248 nm) lithography technology has been introduced into the field, and ArF excimer laser (193 nm) lithography technology with a shorter wavelength is being introduced. Excimer laser (157nm) litho

2

The photographic technology has been studied. [0003] In addition, when the wavelength of the light source is shortened, the resin used for the resist must undergo a structural change, and in KrF excimer laser lithography technology, polyhydroxystyrene or the like having high transparency to 248 nm is used. Those whose hydroxyl groups are protected with acid-dissociable, dissolution controlling groups are used.In the ArF excimer laser lithography technology, the above resin is insufficiently transparent at 193 nm and is almost unusable. For some acrylic resins (for example, see Patent Document 3), a cycloolefin resin (for example, see Patent Document 4) has attracted attention. As an alternative to these techniques, attempts have been made to use (meth) atalylates having a ratatone skeleton instead of a cycloolefin ring to improve the adhesion to the substrate and the dry etching resistance (eg, , Patent Document 5). However, even when these resins are used, their performance is still insufficient, and in this field, in addition to higher dry etching resistance, adhesion to substrates, resolution, and coating However, the required characteristics such as heat resistance required in this case are increasing.

Patent Document 1: Japanese Patent Application Laid-Open No. Hei 6-305044

Patent Document 2: Japanese Patent Application Laid-Open No. 9-302077

Patent Document 3: JP-A-4-39665

Patent Document 4: JP-A-10-153864

Patent Document 5: Japanese Patent Application Laid-Open No. 2001-22073

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention has been made under such circumstances, and in particular, a functional material such as resin for photoresist used in a photosensitive material for photoresist suitable for fine processing using excimer laser light or electron beam. It is an object of the present invention to provide an adamantane derivative useful as a resin monomer, a method for efficiently producing the same, and a photosensitive material for photoresist having the above-mentioned properties including the adamantane derivative.

Means for solving the problem

[0006] The present inventors have conducted intensive studies to achieve the above object, and as a result, adamantyloxycarbonylalkyl (meth) atalylates having a specific structure are new and unpublished in the literature. Compounds that are well suited for that purpose, and these compounds are: It has been found that the reaction can be efficiently carried out by reacting the corresponding haloalkylcarboxylate adamantyls with (meth) acrylic acids or anhydrides thereof. The present invention has been completed based on such findings.

[0007] That is, the present invention provides:

(1) General formula (I)

[0008] [Formula 1]

(Wherein, R is a hydrogen atom, a methyl group or a trifluoromethyl group, Y is an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group or formed by combining two Y = Represents 0. Further, a plurality of Ys may be the same or different, k represents an integer of 0 to 15, m represents 0 or 1, and n represents an integer of 1 to 3.)

An adamantane derivative, having a structure represented by

(2) The adamantane derivative represented by the general formula (I) has a chemical formula (II)

[0010] [Formula 2]

(In the formula, R represents a hydrogen atom, a methyl group or a trifluoromethyl group.)

An adamantane derivative according to the above (1), which is a compound represented by the formula:

(3) —General formula (III) [0012] [Formula 3]

(Wherein, X represents a halogen atom. Y represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, or = 0 formed by joining together two Y's. Y may be the same or different, k represents an integer of 0 to 15, m represents 0 or 1, and n represents an integer of 1 to 3.)

A haloalkylcarboxylic acid adamantyl represented by the formula (IV):

[0014] [Formula 4]

CH ₂ = C——COOH •••• (IV)

Reacting a (meth) acrylic acid or an acid anhydride thereof represented by the general formula (I)

[0016] [Formula 1]

(Wherein, R, Y, k, m and n are the same as described above.)

A method for producing an adamantane derivative represented by

(4) a method for producing the adamantane derivative of the above (3), wherein the adamantyl haloalkylcarboxylate represented by the general formula (ΠΙ) is a 2 alkyl 2-adamantyl α-haloacetate; (5) The method for producing an adamantane derivative according to the above (3), wherein the adamantyl haloalkylcarboxylate represented by the general formula (ΠΙ) is purified!

(6) The method for producing an adamantane derivative according to the above (5), wherein the purification is performed by recrystallization or crystallization.

(7) The method for producing an adamantane derivative according to any one of (3) to (6), wherein the adamantane derivative represented by the general formula (I) is further purified by silica gel treatment.

(8) The method for producing an adamantane derivative according to (7), wherein the adamantane derivative represented by the general formula (I) is a compound represented by the chemical formula (Π),

(9) a photoresist photosensitive material containing a polymer having the adamantane derivative represented by the general formula (I) as a constituent,

Is to provide.

The invention's effect

The adamantane derivative of the present invention is a novel adamantyl oxycarbyl alkyl (meth) atalylate, and is particularly suitable as a photosensitive material for a photoresist suitable for fine processing using an excimer laser beam or an electron beam. It is useful as a monomer for functional resins such as photoresist resin used in photoresists.When used in photoresist materials, it has particularly good dry etching resistance and surface roughness after exposure (LER: side surface of resist). It can be expected to improve the surface roughness, LWR: undulation when the wiring is viewed from directly above, and the temperature dependency of PEB (heat treatment for diffusing the acid generated by exposure).

BEST MODE FOR CARRYING OUT THE INVENTION

The adamantane derivative of the present invention is a novel compound represented by the general formula (I), and the compounds and their production methods will be described below.

First, the compound of the present invention has the general formula (I) [0020] [Formula 1]

Adamantyloxycarboxyalkyl (meth) atalylates having a structure represented by the following formula:

In the general formula (I), R is a hydrogen atom, a methyl group or a trifluoromethyl group, Y is an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, or two Ys are formed together. Indicates = 0. Here, a plurality of Y may be the same or different. k represents an integer of 0 to 15, m represents 0 or 1, and n represents an integer of 1 to 3.

In the above, the alkyl group of 1 to L0 carbon atoms in Y may be any of linear, branched or cyclic, for example, methyl group, ethyl group, various propyl groups, various butyl groups, various pentyls Groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, and the like. These alkyl groups may be substituted by a halogen atom, a hydroxyl group or the like. m is preferably 0, and n is preferably 1. Further, examples of the halogen atom for Y include fluorine, chlorine, bromine and iodine.

Particularly preferred compounds represented by the above general formula (I) include, for example, (1-adamantyloxy) carbolmethyl methacrylate, (2-adamantyloxy) carbolmethyl methacrylate, [(2 —Methyl-2-adamantyl) oxy] carbolmethyl methacrylate, [(2-ethyl-2-adamantyl) oxy] carbomethylmethacrylate, [(4oxo1-adamantyl) oxy] carbomethylmethacrylate , [(4-oxo-2-adamantyl) oxy] carboxymethyl methacrylate, (1- adamantyl methoxy) carboxymethyl methacrylate, (perfluoro-1-adamantyl oxy) Methyl methacrylate, (perfluoro-2-adamantyloxy) carbol Methyl methacrylate, (perfluoro-1-adamantyl) Butoxy) carboxamide - Rumechirume methacrylate, 2- [(1 over § Dammann chill O carboxymethyl) carbo - le] E chill meth Tari rate, 2- [ (2-adamantyloxy) carbol] ethyl methacrylate, 2-[[(2-methyl-2-adamantyl) oxy] carbol] ethyl methacrylate, 2-[[(2-ethylethyl 2- [adamantyl) oxy] carbol] ethyl methacrylate, 2-[[(4 oxo 1-damantyl) oxy] carbol] ethyl methacrylate, 2-[[(4 oxo 2 ada Mantyl) oxy] carbol] ethyl methacrylate, 2-[(1-adamantylmethoxy) carbol] ethyl methacrylate, 2-[(perfluoro-1-adamantyloxy) carbo- Le] ethyl methacrylate, 2-[(perfluoro-2-adamantyloxy) force, reporter] ethyl methacrylate, 2-[[((perfluoro-1-adamantyl) methoxy] carbol] ethyl meta Tallylate, 3— [(1 adamantholoxy [Carbole] propyl methacrylate, 3-[(2-adamantyloxy) carbol] propyl methacrylate, 3-[[[(2-methyl-2 adamantyl) oxy] carbol] propyl Methacrylate, 3-[[(2-ethyl-2-adamantyl) oxy] carbol] propyl methacrylate, 3-[[((4-oxo1-adamantyl) oxy] carbol] propyl methacrylate, 3- [[(4-oxo-2 adamantyl) oxy] carbol] propyl methacrylate, 3-[(1- adamantyl methoxy) carbol] propyl methacrylate, 3- [(perfulol 1 adamantyl 3) [(Perfluorool 2-adamantyloxy) carbol] propyl methacrylate, 3 [[(Perfluorool 1-adamantyl) methoxy] carbol The Metatarireto propyl meth Tali rates and their reduction compounds, and the like Atari rate or α triflate Ruo Russia methyl Atari rate every conversion example compounds. Among them, [(2-methyl-2-adamantyl) oxy] carbomethylmethacrylate represented by the chemical formula (Π) is preferred! /.

Next, a preferred method for producing the adamantane derivative of the present invention will be described.

The adamantane derivative of the present invention can be obtained by reacting an adamantyl haloalkylcarbonate represented by the general formula (III) with a (meth) acrylic acid represented by the general formula (IV) or an acid anhydride thereof. can get.

In this reaction, the haloalkyl carboxylic acid adamantyl represented by the general formula (ΠΙ) can be obtained, for example, by reacting a noroalkyl carboxylic acid halide with an adamantane (see Open 2004—026798). Improving the quality of the adamantane derivative of the present invention For this purpose, it is preferable to use purified adamantyl haloalkylcarboxylates. Without purification, the adamantane derivative represented by the general formula (I)

When obtained by the reaction, a serious problem arises in production, such as the hue of the resulting product being polymerized by (meth) acrylic acids.

As a purification method, a general method such as activated carbon treatment, silica gel treatment, recrystallization, crystallization, or distillation can be selected. Above all, a method of combining activated carbon treatment with which recrystallization or crystallization is preferred and any of recrystallization or crystallization is more preferable. Here, there is no particular limitation before and after performing the activated carbon treatment and recrystallization or crystallization before or after the activated carbon treatment and recrystallization or crystallization. Alternatively, crystallization may be performed, or activated carbon treatment may be performed after recrystallization or crystallization.

In addition, as a specific means of the activated carbon treatment, a method in which the activated carbon is added to a liquid obtained by mixing and reacting the above-described raw materials, stirring is performed for a predetermined time, and then the activated carbon is removed by filtration or the like, or the above-described method is applied to a column filled with activated carbon. A method in which raw materials are mixed and allowed to pass through a reacted liquid may be used.

Examples of the adamantyl haloalkylcarboxylates represented by the general formula (ΠΙ) include 1-adamantyl chloroacetate, 2-adamantyl chloroacetate, 2-methyl-2- adamantyl chloroacetate, and 2-ethyl acetic acid 2-adamantyl acetate. Acetic acid 4-oxo 1-adamantyl, Acetic acid 4-oxo 2 adamantyl, Acetic acid 1-adamantinolemethinole, Acetic acid perfluoro-1,4-adamantyl, Acetic acid perfluoro-2, -adamantyl, Acetic acid (perfluoro- 1-adamantyl) methyl, 1-adamantyl chloropropionate, 2-propanate chloropropionate, 2-methyl-2-propanate chloropropionate, 2-ethyl-2-propylate clopropionate 2-adamantyl, clopropionate 4 —Oxo 1—Adamantil, Prop 4-oxo-2-adamantyl acid, 1-adamantyl methyl cyclopropionate, nofluoro-1-adamantyl cyclopropionate, perfluoro-2-adamantyl cyclopropionate, methyl propionate (perfluoro-1-adamantyl) methyl 1-adamantyl clobutyrate, 2-adamantyl clobutyrate, 2-methyl 2-butamate, chlorobutyrate 2-ethyl 2-adamantyl, clobutyrate 4-oxo 1-adamantyl Cyl, butyric acid 4-oxo-2 adamantyl, chlorobutyrate 1-adamantylmethyl, perfluoro-1-butamate, adamantyl chlorobutyrate, perfluoro-2-butyrate 2-adamantyl, chlorobutyrate (perfluoro-1-adamantyl) methyl 1-adamantyl bromoacetate, 2-adamantyl bromoacetate, 2-methyl-2-adamantyl bromoacetate, 2-ethyl-2-adamantyl bromoacetate, 4-oxo-1-adamantyl bromoacetate, 4-oxo-2-adamantyl bromoacetate, 1-adamantyl bromoacetate Butyl, perfluoro-1-adamantyl bromoacetate, perfluoro-2-adamantyl bromoacetate, methyl bromoacetate (perfluoro-1-adamantyl), β —1-adamantyl bromopropionate, 2-adamantyl 13 bromopropionate, β — 2-Methyl-2-adamantyl lomopropionate, 2-ethyl 2-adamantyl 13-bromopropionate, 4-oxo1-adamantyl 13-bromopropionate, 4-oxo2-adamantyl bromopropionate, 1-adamantyl-methyl bromopropionate, j8-bromo Perfluoro-1-adamantyl propionate, j8-Perfluoro-2-adamantyl bromopropionate, j8-Bromopropionic acid (perfluoro-1-adamantyl) methyl, _γ -bromobutyrate 1-adamantyl, _γ -bromobutyrate 2-adamantyl, γ-bromobutyrate 2-methyl-2- Adamantyl, γ-bromobutyric acid 2-ethyl-2 adamantyl, γ-bromobutyric acid 4-oxo-1-adamantyl, Ίbromobutyric acid 4-oxo-2 adamantyl, γ-bromobutyric acid 1-adamantyl methyl, y-bromobutyric acid Furuoro 1 Adamanchiru, gamma-bromobutyrate Per Furuoro 2 Adamanchiru, such as gamma-bromobutyrate (perfluoro-1 Adamanchiru) methylation can be exemplified. The amount of the (meth) acrylic acid or acid anhydride to be reacted therewith is usually 1 to 1.5 in molar ratio with respect to the adamantyl haloalkylcarboxylate.

In this reaction, a reaction accelerator is used as necessary, and a solvent is used as necessary. Examples of the reaction accelerator include trimethylamine, triethylamine, triptylamine, trioctylamine, pyridine, lithium carbonate, potassium carbonate, sodium carbonate, and the like. Can be. These reaction accelerators may be used alone or in combination of two or more. May be.

[0026] The solvent is preferably 0.5% by mass or more, more preferably 5% by mass or more at the reaction temperature, which is stable to the reaction accelerator and has a solubility in adamantyl haloalkylcarboxylate as a raw material. Use something. The amount of the solvent is such that the concentration of the adamantyl haloalkylcarbonate in the reaction mixture is preferably at least 0.5% by mass, more preferably at least 5% by mass. At this time, the adamantyl haloalkylcarboxylate may be in a suspended state, but is preferably dissolved. Specifically, N-methylpyrrolidone (NMP), hexamethylphosphoric triamide (HMPA), N, N-dimethylformamide (DMF), and trimethylamine, triethylamine, and triptylamine used as reaction accelerators , Trioctylamine, pyridine and the like. These solvents may be used alone or as a mixture of two or more.

[0027] The reaction temperature is usually in the range of -200 to 200 ° C. In this range, the reaction rate does not decrease and the reaction time does not become too long. Also, there is no increase in by-products of the polymer. Preferably, it is in the range of room temperature to 50 ° C.

The reaction pressure is usually in the range of 0.01 to: LOMPa in absolute pressure. In this range, a special pressure-resistant device is not necessary and is economical. Preferably, it is in the range of normal pressure to IMPa.

The reaction time is generally in the range of 1 minute to 24 hours, preferably 30 minutes to 6 hours.

[0028] After completion of the reaction, the salt is removed by washing with water, and then a by-product polymer is precipitated with a poor solvent such as methanol or ether, and the polymer is removed by filtration or the like to purify the target compound. For purification and separation of the target compound, distillation, crystallization, silica gel treatment, column separation, etc. are possible, and can be selected according to the properties of the product and the type of impurities. Among them, silica gel treatment is preferred because the effect of improving the hue of the obtained product and removing impurities that affect the polymerizability of the (meth) acrylates represented by the general formula (I) is extremely high. . As a specific means of silica gel treatment, silica gel is put into the liquid after the reaction, stirred for a predetermined time, and then the silica gel is removed by filtration, etc., or the liquid after the reaction is passed through a column filled with silica gel. And the like. Thus, the general formula An adamantane derivative represented by (I) is obtained.

The identification of the obtained compound was performed by gas chromatography (GC), liquid chromatography (LC), gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy ( IR) and a melting point measuring device.

The copolymer of the adamantane derivative of the present invention and another monomer such as 2-methyl-2-adamantyl methacrylate can be used as a photosensitive material for a photoresist.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1]

Structural formula

[0031] [Formula 5]

[0032] Synthesis of [(2-methyl-2 adamantyl) oxy] carbomethylmethacrylate

Attach a stirrer and a dropping funnel to a 1-liter three-necked flask. 2-bromoacetic acid 2-methyl-2-adamantyl 100 g (348.2 mmol), potassium carbonate 105.87 g (766.0 mmol), polymerization prohibited 100 mg (l, 000 mass ppm) of the agent methoquinone was added and dissolved in 500 ml of N-methylpyrrolidone (NMP). At this time, since potassium carbonate was a solid, stirring was carried out to mix well. Then, at room temperature, 59.95 g (696.4 mmol) of methacrylic acid was slowly added dropwise over 1 hour so that the liquid temperature was 30 ° C or lower. After reacting for 1 hour, 100 ml of water was added to the reactor to stop the reaction. At this point, the transfer ratio measured by gas chromatography was 100%, and the selectivity was 98.0%. At this time, the NMP The occurrence of fever was observed. Subsequently, extraction was performed with 500 ml of getyl ether, washed twice with 500 ml (1 time) of water, dried over magnesium sulfate, and the solvent was distilled off with an evaporator. (Yield 98.69 g). When the crude product was stirred in 500 milliliters of methanol while stirring, a white precipitate was formed. The precipitate was filtered under reduced pressure using a 3 m membrane filter. From the filtrate, methanol was distilled off by an evaporator. 500 ml of getyl ether was added to the obtained crude product, and 4.5 g of activated carbon was added to perform decolorization treatment. After evaporating the solvent again using an evaporator, the residue was dried under vacuum to obtain the desired product (liquid) (yield: 71.98 g, isolation yield: 71.0%, GC purity: 98.98%).

The data of ^ Η-Η ^ ^13C- NMR and GC-MS are shown below.

[0033] Nuclear magnetic resonance spectroscopy (NMR): CDC1

Three

iH—NMR ^ OOMHz): 1.64 (s, 3H, g) ゝ

1.71〜: L 89 (m, 8H), 1.98 (d, J = l.6Hz, 3H, a),

2.01 to 2.04 (m, 1H), 2.29 (s, 1H, i or 1 or m),

4.63 (d, J = l.6Hz, 2H, e), 5.64 (q, J = l.5Hz, b 1),

6.21 (s, 1H, b ² )

¹³ C-NMR (127 MHz): 18.10 (a), 22.18 (h),

26.47 (1 or m), 27.16 (m or 1),

32.79 (j or k), 34.39 (k or j), 36.15 (i),

37.97 (n), 61.19 (e), 88.99 (e), 126.38 (b),

135.47 (c), 166.37 (d or f), 166.56 (f or d)

• Gas chromatography mass spectrometry (GC-MS): EI

292 (M ⁺ , 0.99%), 148 (100%), 133 (18.0%),

106 (68.5%), 93 (16.3%), 91 (14.2%), 79 (16.4%),

69 (22.6%)

[Examples 2 to 4]

In Example 1, 2-bromoacetic acid 2-methyl-2-adamantyl was used as a starting material, 1.5 mmol, methacrylic acid was used as a methacrylic anhydride, 3.0 mmol, and the reaction temperature was set at 25 ° C. In the same manner as in Example 1 except that the reaction time was 30 minutes, the reaction accelerator was 3.3 mmol as shown in Table 1, and the solvent was 5.0 mL as shown in Table 1. [(2-Methyl 2-adamantyl) oxy] carbolmethyl methacrylate was synthesized. Table 1 shows the reaction results obtained by gas chromatography.

(Production Example 1)

Structural formula

[0036]

Synthesis of methyl ethyl acetate 2 amadantyl represented by the formula

In a four-necked flask equipped with a three-way cock, attach a Dimroth and a dropping funnel, and add 27.5 g (165 mmol) of 2-methyl-2-adamantanol and 30.Og (248 mmol) of dimethyla-phosphorus, and add 55 g of dry tetrahydrofuran to the flask. Dissolved. The solution was heated to 40 ° C, and acetic chloride 29.lg (258 mmol) was added dropwise over 2 hours.The mixture was stirred at 40 ° C for 4 hours, allowed to react, cooled, and further cooled with ice water. And quenched. Then, the mixture was transferred to a separating funnel, n-heptane was added thereto, and the organic layer was separated. The organic layer was neutralized with a cooled aqueous solution of 10% carbon dioxide and further washed with pure water, and the obtained organic layer was separated. The organic layer was filtered using a filter covered with 5% by mass of activated carbon based on the total amount of the organic layer, and the activated carbon was washed with n-heptane. The combined filtrate and rinse were subjected to simple distillation to remove the solvent. An aqueous methanol solution (90% by mass of methanol, 10% by mass of water) is added to the concentrated solution, the temperature is raised to 45 ° C to make a homogeneous solution, and the solution is cooled to 0 ° C. —Methyl-2-adamantyl 32. Og was obtained (isolation yield 79.9%, GC purity 99.5%) o

Example 5

Synthesis of [(2-Methyl-2-adamantyl) oxy] carbomethylmethacrylate 17.32 g (71 mmol) of chloroacetic acid-2-methyl-2-adamantyl obtained in Production Example 1 in a 500 ml eggplant-shaped flask equipped with a stirrer, 63 g of N, N dimethylformamide, potassium carbonate 14. 79 g (107 mmol), 4.44 g (27 mmol) of potassium, and methoquinone (100 wt ppm) were added as a polymerization inhibitor. To this, 9.21 g (107 mmol) of methacrylic acid was added dropwise at room temperature over 1 hour, and the mixture was stirred and reacted at room temperature for 4 hours, followed by solid-liquid separation. To the solution after separation, n-heptane and water were added, and the mixture was stirred and allowed to stand. Then, the aqueous layer was removed. Then, after washing with water three times, the organic layer was separated. 1.73 g of silica gel was added to the organic layer, and the mixture was stirred at room temperature for 1 hour. The silica gel was filtered and the silica was rinsed with heptane. After the filtrate and the rinsing solution were combined, metoquinone was added, and the solvent was removed by distillation under reduced pressure to obtain the desired product, [(2-methyl-2-adamantyl) oxy] carbolmethyl methacrylate (yield: 20). 8g, isolation yield: 93.6%, GC purity: 99.2%).

[Production Example 2]

Synthesis of 2-Ethyl-2-aminodantyl acetate

In a four-necked flask equipped with a three-way cock, attach a Dimroth and a dropping funnel, and add 27.5 g (165 mmol) of 2-methyl-2-adamantanol and 30.Og (248 mmol) of dimethyla-phosphorus, and add 55 g of dry tetrahydrofuran to the flask. Dissolved. The temperature of the solution was raised to 40 ° C, and acetic chloride 29.lg (258 mmol) was added dropwise over 2 hours.The mixture was stirred at 40 ° C for 4 hours to react, then ice water was added and quenched. did. Then, the mixture was transferred to a separating funnel, n-heptane was added, and the organic layer was separated. The organic layer was neutralized with a cooled aqueous solution of 10% calcium carbonate and further washed with pure water, and the obtained organic layer was separated. The solvent was removed by simple distillation to obtain 38.3 g of the desired 1,2-methyl-2-adamantyl acetate. (Isolation yield: 95.7%, GC purity: 94.0%).

[Comparative Example 1]

[(2-Methyl-2-adamantyl) oxy] carbomethylmethyl methacrylate was synthesized in the same manner as in Example 5 except that the 2-mouthyl-2-amadantyl acetate obtained in Production Example 2 was used.

[Comparative Example 2]

In a 500 ml eggplant-shaped flask equipped with a stirrer, the black mouth vinegar obtained in Production Example 1 was Acid-2-methyl-2 adamantyl 17.32 g (71 mmol), N, N dimethylformamide 63 g, potassium carbonate 14.79 g (107 mmol), potassium iyo-dani 4.44 g (27 mmol) and polymerization inhibitor Was added as methquinone (100 wtppm). To this, methacrylic acid (9.21 g, 107 mmol) was added dropwise at room temperature over 1 hour, and the mixture was stirred and reacted at room temperature for 4 hours. After the reaction, solid-liquid separation was performed. To the solution after separation, n-heptane and water were added, and the mixture was stirred and allowed to stand, and then the aqueous layer was removed. Then, after water washing was performed three times, the organic layer was separated, metoquinone was added to the organic layer, and the solvent was removed by distillation under reduced pressure.

Examples 1 to 5 showed good reaction results. On the other hand, in Comparative Example 1 in which purification was not performed when synthesizing 2-ethyl acetate-2 amadantyl, and Comparative Example 2 in which purification was not performed when synthesizing the target product, the solvent was distilled under reduced pressure. In the removal step, polymerization of the target substance, 2-methyl-2-adamantyl acetate, was carried out.

[Table 1] Table 1

HMPA: Hexamethylphosphoric triamide

NMP: N-methylpyrrolidone Industrial applicability

The adamantane derivative of the present invention is a novel adamantyl oxycarbyl alkyl (meth) atalylate, and is particularly suitable as a photosensitive material for a photoresist suitable for fine processing using excimer laser light or electron beam. It is useful as a monomer for functional resins such as photoresist resin used in photoresists.When used in photoresist materials, it has particularly good dry etching resistance and surface roughness after exposure (LER: side surface of resist). It can be expected to improve the surface roughness, LWR: undulation when the wiring is viewed from directly above, and the temperature dependency of PEB (heat treatment for diffusing the acid generated by exposure).

Claims

Claims [1] General formula (I)

[Chemical 1]

(Wherein, R represents a hydrogen atom, a methyl group or a trifluoromethyl group, Y represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, or formed by combining two Y = 0. A plurality of Ys may be the same or different, k represents an integer of 0 to 15, m represents 0 or 1, and n represents an integer of 1 to 3.)

An adamantane derivative having a structure represented by the following formula:

[2] The adamantane derivative represented by the general formula (I) has the chemical formula (II)

[Formula 2]

2. The adamantane derivative according to claim 1, which is a compound represented by the formula:

[3] General formula (III)

[Formula 3]

• (III)

(In the formula, X represents a halogen atom. Y represents an alkyl group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, or = 0 formed by joining together two Ys. K represents an integer of 0 to 15, m represents 0 or 1, and n represents an integer of 1 to 3.)

A haloalkylcarboxylic acid adamantyl represented by the formula (IV):

[Formula 4]

[Chemical 1]

(Wherein, R, Y, k, m and n are the same as above.)

A method for producing an adamantane derivative represented by the formula:

[4] The adamantyl haloalkylcarboxylate represented by the general formula (ΠΙ) is an _α -haloacetic acid

4. The method for producing an adamantane derivative according to claim 3, which is 2 alkyl-2-adamantyl.

[5] The method for producing an adamantane derivative according to claim 3, wherein the adamantyl haloalkylcarboxylate represented by the general formula (III) is purified.

6. The method for producing an adamantane derivative according to claim 5, wherein the purification is performed by recrystallization or crystallization.

[7] Further, the adamantane derivative represented by the general formula (I) is obtained by purification by silica gel treatment. A method for producing an adamantane derivative according to any one of claims 3 to 6.

[8] The method for producing an adamantane derivative according to claim 7, wherein the adamantane derivative represented by the general formula (I) is a compound represented by the chemical formula (II).

[9] A photosensitive material for photoresists containing a polymer containing the adamantane derivative represented by the general formula (I) as a constituent.