JP5097380B2 - Adamantane derivative and method for producing the same - Google Patents

Description

  The present invention relates to a novel adamantane derivative useful as a photosensitive material for photoresist and a method for producing the same, and more particularly, an alicyclic structure particularly useful as a monomer for a functional resin such as a photosensitive resin in the field of photoresist lithography. And an adamantane derivative, which is a novel polymerizable monomer having an acid-decomposable site, and a method for efficiently producing the same.

  Adamantane has a structure in which four cyclohexane rings are condensed into a cage shape, is a highly symmetric and stable compound, and its derivatives have unique functions. It is known to be useful as a raw material for the above. For example, since it has excellent optical properties and heat resistance, attempts have been made to use it for optical disk substrates, optical fibers or lenses (see Patent Documents 1 and 2). In addition, an attempt has been made to use adamantane esters as a resin material for a photoresist by utilizing its acid sensitivity, dry etching resistance, ultraviolet light transmittance, and the like (see Patent Document 3).

Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography (photo etching) using a photoresist composition has been performed. This is obtained by forming a thin film of a photoresist composition on a substrate such as a silicon wafer, irradiating it with actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing it. In this method, the substrate is etched using the resist pattern as a protective film.
However, in recent years, the degree of integration of semiconductor devices has been rapidly increasing, and in the manufacture of VLSI and the like, processing accuracy of ultrafine patterns in the submicron region and the quarter micron region has been required. As a result, the ultraviolet light conventionally used as an exposure light source is limited by the wavelength, so the exposure wavelength tends to be shortened, and currently g-line to i-line, deep-UV, excimer laser light, etc. As a result of exposure using far-ultraviolet light, a method of forming a fine pattern using a photoresist material corresponding to irradiation light of a short wavelength such as KrF, ArF or F ₂ excimer laser light has been developed. Various studies have been made.

On the other hand, in recent years, chemically amplified photoresists have become mainstream as photoresists corresponding to deep ultraviolet light such as deep-UV and excimer laser light, and high resolution and high sensitivity. This chemically amplified photoresist is a photoresist that utilizes the catalytic action of an acid generated by irradiation of radiation, has high sensitivity and resolution, and requires a small amount of a compound that generates acid by irradiation of radiation. Has the advantage.
In Patent Document 4, an alicyclic monomer having a hydroxyl group as a polar group is introduced into the resin for radiation-sensitive materials, and when there is no polar group such as a hydroxyl group, diffusion of the proton acid catalyst generated by exposure is hindered. It is described that the chemical amplification rate decreases.
On the other hand, Patent Document 5 proposes a resin having a repeating unit derived from a hydroxyl group-containing compound. However, problems such as pattern collapse, sliding, scum, and development defect are pointed out (see Patent Document 6).

JP-A-6-305044 Japanese Patent Laid-Open No. 9-302077 Japanese Patent Laid-Open No. 4-39665 2002-194029 No. 2000-258915 No. 2003-122007

  The present invention has been made under such circumstances, and is a novel polymerizable monomer having an alicyclic structure and an acid-decomposable site useful as a monomer for a functional resin such as a photosensitive resin in the field of photoresist lithography. It is an object of the present invention to provide an adamantane derivative and a method for efficiently producing the adamantane derivative.

（式中、Ｒ¹は水素、メチル基又はトリフルオロメチル基、Ｒ²は炭素数４〜１５の３級炭化水素基、ｎは１〜３の整数を示す。）で表されることを特徴とするアダマンタン誘導体、
（２） 下記一般式(II)で表される化合物と一般式(III)で表される化合物を反応させることを特徴とする上記（１）のアダマンタン誘導体の製造方法、及び

（式(II)中、Ｒ¹は水素、メチル基又はトリフルオロメチル基を、式(III)中、Ｒ²は炭素数４〜１５の３級炭化水素基、ｎは１〜３の整数を示す。）
（３） 比誘電率εｒが７．５未満の溶媒を用いる上記（２）のアダマンタン誘導体の製造方法、
を提供するものである。 As a result of intensive studies to develop a novel adamantane derivative particularly useful for a chemically amplified photoresist, the present inventors have protected the hydroxyl group of adamantane esters having a specific structure with an acid-decomposable functional group. Thus, chemical amplification is suppressed when there is no hydroxyl group, but in the resist exposure process, the protonic acid generated by the photoacid generator decomposes the protecting group of the hydroxyl group. It was found that acid diffusion is not suppressed. The present invention has been completed based on such findings.
That is, the present invention provides (1) the following general formula (I)

Wherein R ¹ is hydrogen, a methyl group or a trifluoromethyl group, R ² is a tertiary hydrocarbon group having 4 to 15 carbon atoms, and n is an integer of 1 to 3. An adamantane derivative,
(2) A method for producing an adamantane derivative according to the above (1), comprising reacting a compound represented by the following general formula (II) with a compound represented by the general formula (III);

(In the formula (II), R ¹ represents hydrogen, a methyl group or a trifluoromethyl group. In the formula (III), R ² represents a tertiary hydrocarbon group having 4 to 15 carbon atoms, and n represents an integer of 1 to 3. Show.)
(3) The method for producing an adamantane derivative of (2) above using a solvent having a relative dielectric constant εr of less than 7.5,
Is to provide.

  According to the present invention, an adamantane derivative, which is a novel polymerizable monomer having an alicyclic structure and an acid-decomposable site, which is useful as a monomer for a functional resin such as a photosensitive resin in the field of photoresist lithography, can be efficiently used. A method of manufacturing can be provided.

The adamantane derivative of the present invention is a compound represented by the general formula (I) and is a novel compound. Hereinafter, the compounds and methods for producing them will be described.
First, the adamantane derivative of the present invention has the general formula (I)

It is a compound which has a structure represented by these.
The general formula (I) R ¹ represents hydrogen, a methyl group or a trifluoromethyl group. R ² represents a tertiary hydrocarbon group having 4 to 15 carbon atoms. n shows the integer of 1-3. Specifically, tert-butyl group, tert-pentyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 2-methyl-2-adamantyl group, 2- Mention may be made of saturated hydrocarbons such as an ethyl-2-adamantyl group.

  Particularly preferred compounds represented by the general formula (I) include 3-tert-butoxycarbonyloxy-1-adamantyl methacrylate, 3-tert-pentyloxycarbonyloxy-1-adamantyl methacrylate, and 3,5-bis-tert-butoxycarbonyl. Oxy-1-adamantyl methacrylate, 3,5-bis-tert-pentyloxycarbonyloxy-1-adamantyl methacrylate, 3,5,7-tris-tert-butoxycarbonyloxy-1-adamantyl methacrylate, 3,5,7- Examples include tris-tert-pentyloxycarbonyloxy-1-adamantyl methacrylate and compounds obtained by replacing the methacrylate portion of these compounds with acrylate or α-trifluoromethyl acrylate.

Next, the method for producing the adamantane derivative of the present invention may be any method as long as the compound having the structure represented by the general formula (I) can be obtained. However, according to the method of the present invention shown below, Thus, the desired adamantane derivative can be produced efficiently.
In the present invention, an adamantane derivative represented by the following general formula (I) is produced by reacting a compound represented by the following general formula (II) with a compound represented by the following general formula (III).

（式(II)中、Ｒ¹は水素、メチル基又はトリフルオロメチル基を、式(III)中、Ｒ²は炭素数４〜１５の３級炭化水素基を示す。）
尚、一般式(III)に表されるＲ²の詳細については前記一般式（Ｉ）において説明したＲ²と同じである
一般式（II）で表されるアダマンタン化合物のアルコール体として、例えば、３−ヒドロキシ−１−アダマンチル メタクリレート、３−ヒドロキシ−１−アダマンチル アクリレート、３−ヒドロキシ−１−アダマンチルα−トリフルオロメチルアクリレート、３，５−ジヒドロキシ−１−アダマンチルメタクリレート、３，５−ジヒドロキシ−１−アダマンチルアクリレート、３，５−ジヒドロキシ−１−アダマンチルα−トリフルオロメチルアクリレート、３，５，７−トリヒドロキシ−１−アダマンチルメタクリレート、３，５，７−トリヒドロキシ−１−アダマンチルアクリレート、３，５，７−トリヒドロキシ−１−アダマンチルα−トリフルオロメチルアクリレート等が挙げられ、一般式(III)で表されるジアルキルジカルボネートとしてはジ−tert−ブチルジカルボネート、ジ−tert−ペンチルジカルボネート、ジ（１−メチルシクロペンチル）ジカルボネート、ジ（１−メチルシクロヘキシル）ジカルボネート等が挙げられる。

(In formula (II), R ¹ represents hydrogen, a methyl group or a trifluoromethyl group, and in formula (III), R ² represents a tertiary hydrocarbon group having 4 to 15 carbon atoms.)
As the alcohol of general formula adamantane compound for details of R ² is represented in (III) represented by the general formula (II) is the same as R ² described in the general formula (I), for example, 3-hydroxy-1-adamantyl methacrylate, 3-hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl α-trifluoromethyl acrylate, 3,5-dihydroxy-1-adamantyl methacrylate, 3,5-dihydroxy-1 -Adamantyl acrylate, 3,5-dihydroxy-1-adamantyl α-trifluoromethyl acrylate, 3,5,7-trihydroxy-1-adamantyl methacrylate, 3,5,7-trihydroxy-1-adamantyl acrylate, 3, 5,7-trihydroxy-1-adamantyl α Examples of the dialkyl dicarbonate represented by the general formula (III) include di-tert-butyl dicarbonate, di-tert-pentyl dicarbonate, di (1-methylcyclopentyl) dicarbonate, di ( 1-methylcyclohexyl) dicarbonate and the like.

Next, preferable reaction conditions will be described [solvent].
As the solvent, it is desirable to use a solvent having a dielectric constant εr of less than 7.5. The specific value of εr is described in pages 323 to 324 of “Chemical Handbook Revised 4th Edition, Basic II” edited by The Chemical Society of Japan and “Solvent Pocket Book” edited by the Society of Synthetic Organic Chemistry.
When a solvent having a dielectric constant εr of 7.5 or more is used, the reaction rate is remarkably lowered, and the productivity is lowered. Specifically, saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, and ethylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, and dichlorobenzene, ethyl acetate, and ethyl propionate And oxygen-containing hydrocarbon solvents such as diethyl ether and diisopropyl ether, halogen-containing hydrogen halides such as chloroform, carbon tetrachloride, and trichloroethane, and carbon disulfide.

[Reaction pressure]
Although there is no restriction | limiting in particular about reaction pressure, Usually, the range of 0.01-10 Mpa is employ | adopted by an absolute pressure. If it is this range, the apparatus of special withstand pressure | voltage is unnecessary and it is economical. Preferably, it is in the range of normal pressure to 1 MPa. More preferably, it is desirable to carry out at normal pressure from the simplicity of the apparatus.
[Reaction temperature]
The reaction temperature is not particularly limited, but it is preferably −100 to 300 ° C., more preferably 0 to 150 ° C. By setting the reaction temperature range to the above range, there is no decrease in productivity due to a slow reaction rate, and polymerization of adamantyl acrylates can be suppressed.
In addition, about reaction time, it is the range of 1 to 48 hours normally.

[Reaction accelerator]
In the present invention, a reaction accelerator can be used as desired. Examples of the reaction accelerator include trimethylamine, triethylamine, tributylamine, trioctylamine, pyridine, lithium carbonate, potassium carbonate, sodium carbonate, sodium phosphate, monosodium dihydrogen phosphate, disodium monohydrogen phosphate, and the like.
(Polymerization inhibitor)
A polymerization inhibitor can be used as necessary to prevent adamantyl acrylates from polymerizing. As the polymerization inhibitor, those generally known can be used. Specific examples include hydroquinone, nitrosamine, phenothiazine, and 2,2,6,6-tetramethylpiperidinooxyl polymerization inhibitors.

[Post-processing]
A general-purpose post-processing method that has been conventionally performed can be implemented. For example, when there is coloring, a decoloring process using an adsorbent such as activated carbon or silica gel may be performed as necessary.
[Purification]
The purification method can be selected from general purification methods such as distillation, crystallization, and column chromatography in consideration of the production scale and the required purity. Among them, a purification method by crystallization or recrystallization that can be handled at a relatively low temperature and can process a large amount of sample at one time is preferable. As a crystallization (recrystallization) solvent, a mixed solvent of water-soluble solvent such as methyl alcohol, acetonitrile, and acetone and water, a saturated hydrocarbon solvent such as hexane, heptane, and cyclohexane, an aromatic hydrocarbon solvent such as benzene and toluene, Examples thereof include ether solvents such as diethyl ether and tetrahydrofuran, and halogen solvents such as chloroform and dichloroethane.
The obtained compound was identified by gas chromatography (GC), liquid chromatography (LC), gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), It can be performed using a melting point measuring device or the like.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
Synthesis of 3-tert-butoxycarbonyloxy-1-adamantyl methacrylate A four-necked flask equipped with a three-way cock was fitted with a Dimroth and a dropping funnel, and 3-hydroxy-1-adamantyl methacrylate (manufactured by Idemitsu Kosan Co., Ltd.) [FW: 236.31 , 30 g, 127 mmol], dimethylaminopyridine [FW: 122.17, 1.55 g, 12.7 mmol], and methoquinone [6 mg] were added and dissolved in 225 ml of dry hexane (relative permittivity εr1.890). The solution was heated to 70 ° C., and di-tert-butyl dicarbonate [FW: 218.25, 33.25 g, 152 mmol] was added dropwise. After dripping, it was made to react at 70 degreeC for 4 hours, and it was confirmed by GC analysis that 3-hydroxy-1-adamantyl methacrylate disappeared. After 250 ml of water was added to the reaction solution and stirred, it was transferred to a 1 L separatory funnel, and the organic layer was separated. Further, the organic layer was washed three times with 250 ml of water and then with 250 ml of saturated saline. 3 g of silica gel was added to the organic layer, and after stirring for 1 hour, the silica gel was filtered off and the solution was distilled off to obtain a solid. After hexane was added and dissolved therein, the solution was cooled to 0 ° C., and white crystals were precipitated. This was filtered off and dried to obtain the desired 3-tert-butoxycarbonyloxy-1-adamantyl methacrylate [FW: 226.42, 26, 1 g, yield 61, 1%].
Hereinafter, each data of ¹ H-NMR, ¹³ C-NMR and GC-MS is shown.

* Nuclear magnetic resonance spectroscopy (NMR): CDCl ₃
¹ H-NMR: 1.24 to 1.36 (3H), 1.40 (9H, o), 1.42 to 1.73 (10H), 1.93 (3H, b), 2.04 (1H ^{), 5.58 (1H, a 2} ), 6.15 (1H, a 1)
* ¹³ C-NMR: 18.0 (b), 21.3 (g or h), 23.3 (gorh), 28.5 (o), 38.1 (i), 42.4 (f or k ), 43.1 (f or k), 46.0 (j), 62.3 (l), 70.9 (m), 75.4 (e), 86.2 (n), 125.0 ( a) 136.1 (c), 167.2 (d)
* Gas chromatograph-mass spectrometry (GC-MS): EI
336 (0.30%), 280 (11.08%), 219 (20.5%), 218 (28.52%), 194 (18.60%), 69 (51.31%), 57 ( 100%)

Example 2
Synthesis of 3-tert-butoxycarbonyloxy-1-adamantyl methacrylate The same procedure as in Example 1 was performed, except that chloroform (relative permittivity εr4.9) was used as a solvent. After 4 hours, the reaction solution was sampled, and it was confirmed by GC analysis that the conversion of 3-hydroxy-1-adamantyl methacrylate was 99% and the selectivity was 95%.

Synthesis of 3-tert-butoxycarbonyloxy-1-adamantyl acrylate The reaction was performed in the same manner as in Example 1 except that 3-hydroxy-1-adamantyl acrylate (manufactured by Idemitsu Kosan Co., Ltd.) was used. The target product was white crystals, and the target product 3-tert-butoxycarbonyloxy-1-adamantyl acrylate was obtained in a yield of 40.1%.
Hereinafter, each data of ¹ H-NMR, ¹³ C-NMR and GC-MS is shown.

* Nuclear magnetic resonance spectroscopy (NMR): CDCl ₃
¹ H-NMR: 1.24 to 1.30 (2H), 1.36 (1H), 1.40 (9H, o), 1.42 to 1.73 (10H), 2.04 (1H), ^{5.58 (1H, a 2),} 6.05 (1Hc), 6.15 (1H, a 1)
* ^13C -NMR: 21.2 (g or h), 23.2 (g or h), 28.5 (o), 37.2 (i), 41.7 (f or k), 42.1 (F or k), 44.6 (j), 70.5 (e), 79.0 (l), 86.2 (n), 128.3 (c), 130.0 (a), 155. 5 (m), 166.5 (d)
* Gas chromatograph-mass spectrometry (GC-MS): EI
322 (0.02%), 266 (4.25%), 204 (36.56%), 194 (22.66%), 150 (38.26%), 133 (15.73%), 108 ( 34.36%), 92 (29.23%), 57 (100%), 55 (59.10%)

Reference Example 3 Synthesis of tert-butoxycarbonyloxy-1-adamantyl methacrylate The reaction was performed in the same manner as in Example 1 except that tetrahydrofuran (relative dielectric constant εr7.58) was used as a solvent. After 4 hours, the reaction solution was sampled, and by GC analysis, the conversion rate of 3-hydroxy-1-adamantyl methacrylate was 60%, and the reaction rate was slower than in Example 1, and the effect due to the difference in the dielectric constant of the solvent. confirmed.

The adamantane derivative of the present invention is a novel polymerizable monomer having an alicyclic structure and an acid-decomposable site, and can be suitably used as a monomer for a functional resin such as a photosensitive resin in the field of photoresist lithography.
In addition, a method for efficiently producing the adamantane derivative of the present invention can be provided.

Claims (2)

A method for producing an adamantane derivative represented by the following general formula (I), wherein a compound represented by the following general formula (II) and a general formula (III) are used using a solvent having a relative dielectric constant εr of less than 7.5: A method for producing an adamantane derivative, wherein the compound represented by formula (1) is reacted.

(In the formula, R ¹ represents hydrogen, a methyl group or a trifluoromethyl group, R ² represents a tertiary hydrocarbon group having 4 to 15 carbon atoms, and n represents an integer of 1 to 3)

(In the formula (II), R ¹ represents hydrogen, a methyl group or a trifluoromethyl group. In the formula (III), R ² represents a tertiary hydrocarbon group having 4 to 15 carbon atoms, and n represents an integer of 1 to 3. Show.)   The solvent is hexane, heptane, octane, nonane, decane, undecane, ethylcyclohexane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, ethyl acetate, ethyl propionate, diethyl ether, diisopropyl ether, chloroform, carbon tetrachloride and disulfide. The method for producing an adamantane derivative according to claim 1, which is selected from carbon.