JP2009073738A - Polycarboxylic acid ester compound, photoresist base material and photoresist composition - Google Patents

Abstract

以下、上記式に倣って、t-ブチロキシ基、アダマンチルオキシオキシ基、トリメチルシリル基などを、酸解離性溶解抑止基として導入する。
【選択図】なしDisclosed are a compound and a composition suitable for a photoresist substrate having features such as excellent heat resistance, high sensitivity, high resolution, and high fine workability.
A polycarboxylic acid ester compound represented by the following formula PCE-10.

Hereinafter, following the above formula, a t-butyroxy group, an adamantyloxyoxy group, a trimethylsilyl group, and the like are introduced as acid dissociable, dissolution inhibiting groups.
[Selection figure] None

Description

  The present invention relates to a polycarboxylic acid ester compound, a photoresist base material, and a photoresist composition. More specifically, the present invention relates to a photoresist base material used in the electrical / electronic field such as a semiconductor, an optical field, etc., in particular, a photoresist base material for ultrafine processing.

  Extreme ultraviolet light (hereinafter sometimes referred to as EUVL) or electron beam lithography is useful as a high-productivity, high-resolution microfabrication method in the production of semiconductors and the like. There is a need to develop high sensitivity, high resolution photoresists. It is indispensable to improve the sensitivity of the photoresist from the viewpoint of the productivity and resolution of the desired fine pattern.

  Examples of the photoresist used in the ultrafine processing by EUVL include a chemically amplified polyhydroxystyrene-based photoresist used in the ultrafine processing by a known KrF laser. It is known that this resist can be finely processed up to about 50 nm. However, when ultrafine processing with extreme ultraviolet light is performed with this resist and a pattern of 50 nm or less, which is the greatest advantage of processing with extreme ultraviolet light, is produced, the sensitivity and resist outgas have practicality, but the most important Line edge roughness could not be reduced. It cannot be said that the intrinsic performance of extreme ultraviolet light has been sufficiently brought out, and it has been demanded to develop a higher performance photoresist.

  For example, a method using a chemically amplified positive photoresist having a higher concentration of a photoacid generator than other resist compounds has been proposed (for example, see Patent Document 1). However, an example is a substrate comprising a terpolymer consisting of hydroxystyrene / styrene / t-butyl acrylate, at least about 5% by weight of di (t-butylphenyl) iodonium ortho-trifluoromethylsulfur in the total solids. From the viewpoint of line edge roughness, processing up to 100 nm exemplified in the case of using an electron beam is the limit for a photoacid generator composed of phonate, a tetrabutylammonium hydroxide lactate and a photoresist composed of ethyl lactate. it is conceivable that. It is presumed that the main cause of this is that the aggregate of the polymer compounds used as the base material or the three-dimensional shape of each polymer compound molecule is large and affects the production line width and the surface roughness.

  Patent Document 2 discloses a resist material containing a compound having a plurality of bisphenol groups. However, the above compound has a problem in solubility in a coating solvent and solubility in a developer after exposure, and does not have sufficient performance to meet fine processing.

  Patent Document 3 discloses calix resorcinarene compounds, but these compounds are considered to have insufficient solubility and do not describe use as a photoresist base material.

There is also a need for novel low-molecular organic compounds that are amorphous at room temperature. At this time, improvement in various performances such as improvement in etching resistance, which is a problem in the semiconductor manufacturing process, is required at the same time. Moreover, since the photoresist base material is dissolved in a solvent in the current semiconductor manufacturing process and proceeds to a film forming process, high solubility in a coating solvent is required.
JP 2002-055557 A JP 2006-285075 A US Patent No. 6,093,517

  An object of the present invention is to provide a compound and a composition suitable for a photoresist substrate having features such as excellent heat resistance, high sensitivity, high resolution, and high fine workability.

  The present inventors have found that the above problem is caused by reactivity based on the three-dimensional molecular shape and molecular structure of a photoresist base material made of a polymer compound, or the structure of a protecting group in the molecular structure. The present inventors have found that a polycarboxylic acid ester having a predetermined structure is useful as a photoresist substrate, and completed the present invention.

［式中、Ａは、２〜２０個の芳香族環を含む分子量が２５０以上５０００以下である２〜２０価の炭化水素基であり、Ａに含まれる前記芳香族環は、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシル基、炭素数１〜４のハロアルコキシル基、ヒドロキシル基、ハロゲン原子、又はこれら２以上の置換基によって置換されていてもよく、
Ａと結合している酸素原子は、Ａに含まれる前記芳香族環と結合し、
Ｒ^１は、それぞれ独立に水素原子又は酸解離性溶解抑止基であり（但し、Ｒ^１が全て水素原子の場合は無い。）、
Ｒ^１１は、それぞれ独立にヒドロキシル基、ハロゲン原子、炭素数１〜４の低級アルキル基、炭素数１〜４の低級アルコキシル基又は炭素数１〜４の低級ハロアルコキシル基であり、
Ｘは２〜２０の整数であり、
ｎは０〜３の整数であり、及び
複数のＲ^１及びＲ^１１は、それぞれ同じであっても異なってもよい。］
２．前記酸解離性溶解抑止基が、下記式（２）〜（５）で表される置換基のいずれかである１に記載のポリカルボン酸エステル化合物。

［式中、Ｒ^２〜Ｒ^１０は、それぞれ独立に炭素数１〜１２の直鎖アルキル基、炭素数３〜１２の分岐を有するアルキル基、炭素数３〜１２の環状アルキル基、又は、炭素数１〜４のアルキル基、アルコキシ基、炭素数６〜１０の芳香族基若しくはハロゲン原子で置換されてもよい炭素数６〜１４の芳香族基であり（但し、Ｒ^５及びＲ^６は、水素原子であってもよく、Ｒ^７は、酸素原子又は硫黄原子を含有する炭素数１〜１２の直鎖アルキル基、炭素数３〜１２の分岐を有するアルキル基、炭素数３〜２０の単環若しくは複素環状の脂環式アルキル基、又は、炭素数１〜４のアルキル基、アルコキシ基若しくはハロゲン原子で置換されてもよいベンジル基であってもよい。）、
Ｒ^２〜Ｒ^１０は、互いに結合して炭素数３〜２０の単環又は複素環状の脂環式アルキル基を形成してもよい。］
３．前記酸解離性溶解抑止基が、ｔｅｒｔ−ブチル基、ｔｅｒｔ−アミル基、ベンジルオキシメチレン基、トリメチルシリル基、トリエチルシリル基、ジメチル−ｔｅｒｔ−ブチルシリル基、又は下記式（６）で表される置換基のいずれかである１又は２に記載のポリカルボン酸エステル化合物。

４．前記式（１−Ａ）〜（１−Ｊ）中のＡが、下記式（７−Ａ）〜（７−Ｐ）で表される炭化水素基のいずれかである１〜３のいずれかに記載のポリカルボン酸エステル化合物。

［式中Ｒ^１２は、それぞれ独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシル基、炭素数１〜４のハロアルコキシル基、ヒドロキシル基又はハロゲン原子であり、
複数のＲ^１２は、それぞれ同じであっても異なってもよい。］
５．１〜４のいずれかに記載のポリカルボン酸エステル化合物を含有するフォトレジスト基材。
６．５に記載のフォトレジスト基材、及び溶剤を含有するフォトレジスト組成物。
７．さらに光酸発生剤を含有する６に記載のフォトレジスト組成物。
８．さらに塩基性有機化合物をクエンチャーとして含有する６又は７に記載のフォトレジスト組成物。
９．６〜８のいずれかに記載のフォトレジスト組成物を用いた微細加工方法。
１０．９に記載の微細加工方法により作製した半導体装置。 According to the present invention, the following polycarboxylic acid ester compounds and the like are provided.
1. Polycarboxylic acid ester compounds represented by the following formulas (1-A) to (1-J).

[In the formula, A is a divalent to 20-valent hydrocarbon group having a molecular weight of 2 to 20 and including 2 to 20 aromatic rings, and the aromatic ring contained in A has 1 to 1 carbon atoms. 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, haloalkoxyl groups having 1 to 4 carbon atoms, hydroxyl groups, halogen atoms, or two or more substituents,
An oxygen atom bonded to A is bonded to the aromatic ring contained in A;
Each R ¹ is independently a hydrogen atom or an acid dissociable, dissolution inhibiting group (provided that R ¹ is not a hydrogen atom);
R ¹¹ is independently a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a lower haloalkoxyl group having 1 to 4 carbon atoms,
X is an integer from 2 to 20,
n is an integer of 0 to 3, and the plurality of R ¹ and R ¹¹ may be the same or different. ]
2. 2. The polycarboxylic acid ester compound according to 1, wherein the acid dissociable, dissolution inhibiting group is any one of substituents represented by the following formulas (2) to (5).

[Wherein, R ^{2 to} R ¹⁰ are each independently a linear alkyl group having 1 to 12 carbon atoms, an alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or carbon. An alkyl group having 1 to 4 carbon atoms, an alkoxy group, an aromatic group having 6 to 10 carbon atoms or an aromatic group having 6 to 14 carbon atoms which may be substituted with a halogen atom (provided that R ⁵ and R ⁶ are It may be a hydrogen atom, and R ⁷ is a C 1-12 linear alkyl group containing an oxygen atom or a sulfur atom, a C 3-12 branched alkyl group, a C 3-20 single atom. A benzyl group which may be substituted with a ring or heterocyclic alicyclic alkyl group, or an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom).
R ^{2 to} R ¹⁰ may be bonded to each other to form a monocyclic or heterocyclic alicyclic alkyl group having 3 to 20 carbon atoms. ]
3. The acid dissociable, dissolution inhibiting group is a tert-butyl group, a tert-amyl group, a benzyloxymethylene group, a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, or a substituent represented by the following formula (6). The polycarboxylic acid ester compound according to 1 or 2, which is either

4). Any one of 1 to 3 in which A in the formulas (1-A) to (1-J) is any of hydrocarbon groups represented by the following formulas (7-A) to (7-P) The polycarboxylic acid ester compound described.

[Wherein R ¹² is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a haloalkoxyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom,
The plurality of R ¹² may be the same or different. ]
Photoresist base material containing the polycarboxylic acid ester compound in any one of 5.1-4.
6.5. A photoresist composition comprising the photoresist substrate according to 6.5 and a solvent.
7). Furthermore, the photoresist composition of 6 containing a photo-acid generator.
8). Furthermore, the photoresist composition of 6 or 7 which contains a basic organic compound as a quencher.
A fine processing method using the photoresist composition according to any one of 9.6 to 8.
A semiconductor device manufactured by the microfabrication method described in 10.9.

  ADVANTAGE OF THE INVENTION According to this invention, the compound and composition suitable for the photoresist base material which comprises the characteristics, such as outstanding heat resistance, high sensitivity, high resolution, and high fine workability, can be provided.

The polycarboxylic acid ester compound of the present invention has a structure represented by the following formulas (1-A) to (1-J).

In formulas (1-A) to (1-J), each R ¹¹ independently represents a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms, or 1 carbon atom. -4 lower haloalkoxyl groups.

X is an integer of 2 to 20, preferably an integer of 2 to 8.
n is an integer of 0 to 3, preferably an integer of 0 or 1.

R ¹ is independently a hydrogen atom or an acid dissociable, dissolution inhibiting group. However, there is no case where R ¹ is all hydrogen atoms.
The acid dissociable, dissolution inhibiting group is a substituent having high reactivity with EUVL and electron beam, and is preferably a substituent represented by the following formulas (2) to (5).

In formulas (2) to (5), R ^{2 to} R ¹⁰ are each a linear alkyl group having 1 to 12 carbon atoms, an alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, Or it is a C1-C4 alkyl group, an alkoxy group, a C6-C10 aromatic group, or a C6-C14 aromatic group which may be substituted by a halogen atom.
R ^{2 to} R ¹⁰ may be bonded to each other to form a monocyclic or heterocyclic alicyclic alkyl group having 3 to 20 carbon atoms.

The linear alkyl group having 1 to 12 carbon atoms is preferably a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group or the like.
The alkyl group having 3 to 12 carbon atoms is preferably a t-butyl group, an iso-propyl group, an iso-butyl group, a 2-ethylhexyl group or the like.
The cyclic alkyl group having 3 to 12 carbon atoms is preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or the like.
The aromatic group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.

However, among R ^{2 to} R ¹⁰ , R ⁵ and R ⁶ may be a hydrogen atom, and R ⁷ is a linear alkyl group having 1 to 12 carbon atoms containing an oxygen atom or a sulfur atom, carbon It may be substituted with an alkyl group having 3 to 12 branches, a monocyclic or heterocyclic alicyclic alkyl group having 3 to 20 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen atom. It may be a good benzyl group.

炭素数１〜４のアルキル基、アルコキシ基若しくはハロゲン原子で置換されてもよいベンジル基としては、好ましくはベンジル基、４−メトキシベンジル基、４−メチルベンジル基、３，５−ジメトキシベンジル基等である。 The linear alkyl group having 1 to 12 carbon atoms containing an oxygen atom or a sulfur atom is preferably a methoxyethyl group, an ethoxyethyl group, a methylthioethyl group, an ethylthioethyl group or the like.
The alkyl group having 3 to 12 carbon atoms containing an oxygen atom or a sulfur atom is preferably an isopropoxyethyl group, an isopropylthioethyl group or the like.
The monocyclic or heterocyclic alicyclic alkyl group having 3 to 20 carbon atoms containing an oxygen atom or a sulfur atom is preferably a tetrahydrofuranyl group, a tetrahydropyranyl group, or a substituent represented by the following formula: It is.

The benzyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom is preferably a benzyl group, a 4-methoxybenzyl group, a 4-methylbenzyl group, a 3,5-dimethoxybenzyl group, etc. It is.

The acid dissociable, dissolution inhibiting group is more preferably represented by tert-butyl group, tert-amyl group, benzyloxymethylene group, trimethylsilyl group, triethylsilyl group, dimethyl-tert-butylsilyl group, or the following formula (6). Any of the substituents.

Among the acid dissociable, dissolution inhibiting groups, a tert-butyl group, a tert-amyl group, a benzyloxymethylene group, a dimethyl-tert-butylsilyl group, and a substituent represented by the following formula are particularly preferable.

A is a 2 to 20-valent hydrocarbon group having a molecular weight of 2 to 20 and containing 2 to 20 aromatic rings.
The aromatic ring contained in A is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a haloalkoxyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, or substitution of two or more thereof. It may be substituted by a group.
The oxygen atom bonded to A is bonded to the aromatic ring contained in A.

A is preferably any one of hydrocarbon groups represented by the following formulas (7-A) to (7-P).

In formulas (7-A) to (7-P), R ¹² each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a haloalkoxyl group having 1 to 4 carbon atoms, hydroxyl group A group or a halogen atom.

Incidentally, ^{R 1} and ^{R 11} of formula (1-A) ~ (1 -J), and ^{R 12} of formula (7-A) ~ (7 -P) is there are a plurality, even in respectively the same or different May be.

  Although the structure of the polycarboxylic acid ester compound of the present invention has been described above, the polycarboxylic acid ester compound of the present invention is preferably represented by (1-A), (1-B) or (1-G). It has a structure, and A is any of the substituents represented by (7-A) to (7-G).

  As a method for producing the polycarboxylic acid ester compound of the present invention, a known production method can be used, and specifically described in Examples described later.

The polycarboxylic acid ester compound of the present invention can be suitably used as a photoresist substrate, particularly as an extreme ultraviolet light and / or electron beam photoresist substrate.
The photoresist base material comprising the polycarboxylic acid ester compound of the present invention (hereinafter sometimes referred to as the photoresist base material of the present invention) is in an amorphous state under the conditions (usually at room temperature) used as a photoresist base material. It becomes. For this reason, when the polycarboxylic acid ester compound of this invention is used as a photoresist base material, it is preferable at the point of the applicability | paintability as a photoresist composition, and the intensity | strength as a photoresist film.

  Since the polycarboxylic acid ester compound of the present invention has an aromatic compound as a basic skeleton like the structures represented by (1-A) to (1-J), it has excellent heat resistance. When the polycarboxylic acid ester compound of the present invention is used as a photoresist base material, the photoresist composition containing the photoresist base material has high sensitivity, and in the baking process at the time of development, for example, a temperature range of 100 ° C. to 200 ° C. Can be adopted.

  Since the photoresist base material of the present invention can be baked at such a high temperature, the acid generated from the photoacid generator can be further diffused. Therefore, the content of the photoacid generator can be made smaller, and the sensitivity of the photoresist base material can be improved. In addition, since the photoresist base material of the present invention can be baked at such a high temperature, pattern collapse does not occur and strict temperature control is not required. Therefore, it is possible to set a wide process window by using the photoresist base material of the present invention.

  Since the main structure of the polycarboxylic acid ester compound of the present invention is a cyclic structure, the photoresist base material comprising the polycarboxylic acid ester compound of the present invention is less likely to release low molecular weight compounds that are constituent molecules of range-out gas, Range out gas can be reduced.

  Since the acid dissociable, dissolution inhibiting group in the polycarboxylic acid ester compound structure of the present invention has high reactivity directly or indirectly to EUV and electron beam, a photoresist group comprising the polycarboxylic acid ester compound of the present invention The material has high sensitivity and excellent etching resistance and can contribute to low line edge roughness in resolution.

  The average diameter of the molecules of the polycarboxylic acid ester compound of the present invention is smaller than the line edge roughness value (5 nm or less) required for a desired pattern size, specifically 100 nm or less, particularly 50 nm or less. Therefore, the photoresist base material comprising the polycarboxylic acid ester compound of the present invention has a line edge roughness of 2 nm or less, preferably 1 nm when used for ultrafine processing (processing of 20 to 50 nm) by extreme ultraviolet light or electron beam. It can be suppressed to (3σ) below.

In addition, the polycarboxylic acid ester compound of this invention used as a photoresist base material may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, the photoresist base material which consists of the polycarboxylic acid ester compound of this invention may consist only of the polycarboxylic acid ester compound of this invention. In that case, the following impurities may be included.

  When the polycarboxylic acid ester compound of the present invention is used as a photoresist substrate, it is refined and basic impurities (for example, alkali metal ions such as ammonia, Li, Na and K, alkaline earth metal ions such as Ca and Ba, etc.) ) Etc. are preferably removed. At this time, it is preferable to reduce to 1/10 or less of the amount of impurities contained before refining the substrate. Specifically, the content of basic impurities is preferably 10 ppm or less, more preferably 2 ppm or less. By setting the content of basic impurities to 10 ppm or less, the sensitivity of the photoresist base material comprising this compound to extreme ultraviolet light and electron beams is dramatically improved. As a result, the fine processing of the photoresist composition by lithography is possible. A pattern can be suitably produced.

Examples of the purification method include acidic aqueous solution washing, ion exchange resin, ultrapure water, or reprecipitation treatment combining these purification methods. Specifically, after washing the photoresist substrate using an acetic acid aqueous solution as an acidic aqueous solution, an ion exchange resin treatment or a reprecipitation treatment using ultrapure water is performed.
The acidic aqueous solution and ion exchange resin used for purification can be appropriately selected according to the amount and type of basic impurities to be removed, the type of substrate to be treated, and the like.

  The photoresist composition of the present invention contains the above-described photoresist base material of the present invention and a solvent for dissolving the same to form a liquid composition. The photoresist composition needs to be made into a liquid composition in order to be uniformly applied to a substrate or the like to be subjected to ultrafine processing by a technique such as spin coating, dip coating, or painting.

  The solvent to be used may be appropriately selected according to the solubility of the photoresist base material, film formation characteristics, etc., and preferably 2-methoxyethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, etc. Glycols, lactates such as ethyl lactate and methyl lactate, propionates such as methyl propionate and ethyl propionate, cellosolve esters such as methyl cellosolve acetate, aromatic hydrocarbons such as toluene and xylene, Examples thereof include ketones such as methyl amyl ketone, methyl ethyl ketone, cyclohexanone and 2-heptanone, a single solvent such as butyl acetate, and a mixed solvent composed of two or more of these solvents.

  The blending amount of the solvent can be appropriately set according to the desired film thickness of the photoresist layer. For example, the solvent is blended so that the weight of components (solid content) other than the solvent of the photoresist composition is 0.1 to 50% by weight of the total weight of the photoresist composition.

  When the compound constituting the photoresist substrate contains a chromophore active against EUVL and / or an electron beam, and the photoresist substrate alone exhibits sufficient capability as a photoresist, the photoresist composition of the present invention comprises: No additives are required. However, when the photoresist substrate needs to enhance the performance (sensitivity) as a photoresist, the photoresist composition of the present invention preferably further contains a photoacid generator (PAG) as a chromophore.

［式中、Ａｒ、Ａｒ^１、Ａｒ^２は、置換又は非置換の炭素数６〜２０の芳香族基であり、
Ｒ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ_Ａは、置換又は非置換の炭素数６〜２０の芳香族基、置換又は非置換の炭素数１〜２０の脂肪族基であり、
Ｘ、Ｘ_Ａ、Ｙ、Ｚは、脂肪族スルホニウム基、フッ素を有する脂肪族スルホニウム基、テトラフルオロボレート基、ヘキサフルオロホスホニウム基である。Ｍｅはメチル基、Ｐｈはフェニル基である。］ It does not specifically limit as a photo-acid generator to be used, For example, the well-known photo-acid generator which has the following structures can be used. In addition, the photo-acid generator to be used can be suitably selected according to the photoresist base material, the shape, size, etc. of a desired fine pattern which the photoresist composition of this invention contains.

[Wherein, Ar, Ar ¹ and Ar ² are substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms,
R, R ¹ , R ² , R ³ and R _A are a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, a substituted or unsubstituted aliphatic group having 1 to 20 carbon atoms,
X, X _A , Y, and Z are an aliphatic sulfonium group, an aliphatic sulfonium group having fluorine, a tetrafluoroborate group, and a hexafluorophosphonium group. Me is a methyl group and Ph is a phenyl group. ]

  In addition, the compounding quantity of a photo-acid generator is used in 0.1-20 weight% normally with respect to a photoresist base material.

  The photoresist composition of the present invention preferably further contains a basic organic compound as a quencher. The quencher can suppress, for example, an excessive reaction of the photoacid generator, and can improve sensitivity to extreme ultraviolet light and sensitivity to electron beam of the photoresist composition of the present invention.

The basic organic compound used as a quencher is preferably a pyridine such as quinoline, indole, pyridine, bipyridine, pyrimidines, from the viewpoint of solubility in a photoresist composition and dispersibility and stability in the photoresist layer. Examples include pyrazines, piperidine, piperazine, pyrrolidine, aliphatic amines such as 1,4-diazabicyclo [2.2.2] octane, triethylamine, trioctylamine, and tetrabutylammonium hydroxide.
In addition, the quencher used for the photoresist composition of this invention is not limited to the said basic organic compound, A well-known compound can also be used as a quencher.

The amount of quencher used is usually in the range of 10 to 1 × 10 ⁻³ wt% relative to the photoresist base material or 0.01 to 50 wt% relative to the photoacid generator.

  In addition to the photoacid generator and quencher described above, the photoresist composition of the present invention is a photosensitizer, plasticizer, speed accelerator, photosensitizer, sensitizer, acid proliferation, as long as the effects of the present invention are not impaired. Functional materials, etching resistance enhancers, and the like can be added. These may be a mixture of components having the same function, a mixture of components having different functions, or a mixture of these precursors.

An example of a fine processing method using the photoresist composition of the present invention will be described below.
The photoresist composition of the present invention is applied to a substrate as a liquid coating composition by a method such as spin coating, dip coating, painting, etc., and the solvent is removed. It is common to dry by heating to ℃ to 160 ℃. Further, for the purpose of improving the adhesion to the substrate, for example, hexamethyldisilazane (HMDS) can be used as the intermediate layer. These conditions can be defined according to the type of base material and solvent to be used, or the desired film thickness of the photoresist layer.

  After drying by heating, the substrate on which the photoresist coating layer has become non-adhesive is exposed using a photomask with EUVL, or irradiated with an electron beam by any method to remove the protective groups contained in the substrate. Causing a difference in solubility between the exposed and unexposed areas of the photoresist coating layer. Further, post-exposure baking is performed to increase the difference in solubility. Thereafter, development with an alkali developer or the like is performed to form a relief image. By such an operation, an ultrafinely processed pattern is formed on the substrate. Said conditions can be prescribed | regulated according to the kind of base material and solvent to be used, or the film thickness of a desired photoresist layer.

  If the ultrafine processing by lithography of extreme ultraviolet light or electron beam is performed using the photoresist composition of the present invention, an isolated line of 100 nm or less, particularly 50 nm or less, line / space (L / S) = 1/1. Patterns such as holes can be formed with high sensitivity, high contrast, and low line edge roughness.

  By the microfabrication method of the present invention, for example, semiconductor devices such as ULSIs, large-capacity memory devices, and ultrahigh-speed logic devices can be manufactured.

Production Example 1
[Step 1]
To a 200 ml three-necked flask equipped with a magnetic stirrer, Jim Roth condenser and thermometer, 1,1′-bi-2-naphthol (structural formula (8): R, S isomer mixture: Tokyo Chemical Industry Co., Ltd.) )) 2.86 g (10 mmol), anhydrous potassium carbonate 2.76 g (20 mmol), and 4-nitrophthalonitrile (structural formula (9): Wako Pure Chemical Industries, Ltd.) 3.46 g (20 mmol) are charged. Then, nitrogen was introduced to form a nitrogen atmosphere, and 30 ml of dimethyl sulfoxide (DMSO) was added and stirred. The flask was immersed in an oil bath, the oil temperature was raised to 60 ° C., the reaction was started, and the reaction was allowed to proceed for 3 hours. After completion of the reaction, the reaction mixture was cooled to about room temperature by allowing to cool, and the reaction mixture in the flask was diluted by pouring into about 200 ml of deionized water, and further stirred for 1 hour. The produced solid was filtered out, washed with deionized water, and dried under reduced pressure to obtain 5.33 g of intermediate (10) represented by formula (10) (99% yield).

The structure of the intermediate (10) was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 7.003 (2H, dd), 7.040 (2H, d), 7.204 (2H, d), 7.282 (2H , D), 7.366 (2H, dt), 7.452 (2H, d), 7.516 (2H, dt), 7.932 (2H, d), 8.026 (2H, d)

[Step 2]
A 200 ml eggplant flask equipped with a magnetic stirrer, Jim Roth condenser and thermometer was charged with 9.24 g (85%, 0.14 M) of potassium hydroxide, 43 ml of deionized water, and 43 ml of ethylene glycol (EG). Was added and stirred to dissolve. Further, 5.3 g (9.9 mmol) of the intermediate (10) produced in Step 1 was added, the flask was immersed in an oil bath, the oil temperature was increased to 140 ° C., and the reaction was performed for 6 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and then the reaction mixture was diluted by pouring into about 200 ml of deionized water. After stirring for another 30 minutes, 10% hydrochloric acid was added to the solution to adjust the pH to 1, and the resulting solid was collected by filtration and washed with deionized water. By drying under reduced pressure, 5.53 g (yield 90%: 2 steps) of compound PRE-1 which is a precursor of the polycarboxylic acid ester compound of the present invention was obtained.

The structure of compound PRE-1 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 6.977 (2H, dd), 7.035 (2H, d), 7.177 (2H, d), 7.351 (2H, t), 7.362 (2H, d), 7.490 (2H, t), 7.632 (2H, d), 8.036 (2H, d), 8.127 (2H, d)

Production Example 2
The polycarboxylic acid of the present invention was reacted in the same manner as in Production Example 1 except that 3-nitrophthalonitrile (Structural Formula (11): Wako Pure Chemical Industries, Ltd.) was used instead of 4-nitrophthalonitrile. 5.88 g (yield 96%: 2 steps) of compound PRE-2 which is a precursor of the ester compound was obtained.

The structure of compound PRE-2 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 7.144 (2H, d), 7.152 (2H, d), 7.190 (2H, d), 7.354-7. 406 (4H, m), 7.450 (2H, t), 7.597 (2H, d), 7.976 (2H, d), 8.039 (2H, d)

Production Example 3
The reaction was carried out in the same manner as in Production Example 1 except that 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,1′-bi-2-naphthol as the starting material. This gave compound PRE-3 (yield 87%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of the present invention.

The structure of compound PRE-3 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 7.014 (4H, d), 7.076 (2H, dd), 7.191 (4H, d), 7.230 (2H, d), 7.345 (2H, t), 7.417 (2H, t), 7.492 (2H, d), 7.837 (2H, bs), 7.940 (2H, d)

Production Example 4
The reaction was conducted in the same manner as in Production Example 1 except that 2,2-bis (4-hydroxyphenyl) adamantane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,1′-bi-2-naphthol as a starting material. This gave compound PRE-4 (yield 91%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of the present invention.

The structure of compound PRE-4 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.673 (2H, bs), 1.696 (2H, bs), 1.726 (2H, bs), 1.787 (2H, bs), 1.898 (2H, bs), 1.931 (2H, bs), 2.07 (2H, bs), 6.968 (4H, d), 7.053 (2H, dd), 7. 354 (2H, bs), 7.523 (4H, d), 7.939 (2H, d)

Production Example 5
The same reaction as in Production Example 1 except that 1,3-bis (4-hydroxyphenyl) adamantane (synthesized according to Tetrahedron Lett (1972) p 3191) was used instead of 1,1′-bi-2-naphthol as a starting material. The compound PRE-5 (yield 89%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of this invention was obtained.

The structure of Compound PRE-5 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.716-1.993 (12H, m), 2.259 (2H, bs), 7.040-7.090 (6H, m ), 7.175 (2H, bs), 7.502 (4H, d), 7.892 (2H, d)

Production Example 6
The same as in Production Example 1 except that 1,1,1-tris- (4-hydroxyphenyl) ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a starting material instead of 1,1′-bi-2-naphthol. The compound PRE-6 (yield 88%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of the present invention was obtained.

The structure of Compound PRE-6 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 2.184 (3H, bs), 7.055 (6H, d), 7.124 (3H, dd), 7.141 (6H, d), 7.405 (3H, bs), 7.966 (3H, d)

Production Example 7
Α, α, α′-tris- (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 1,1′-bi-2-naphthol as a starting material Otherwise, the reaction was carried out in the same manner as in Production Example 1 to obtain compound PRE-7 (yield 81%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of the present invention.

The structure of Compound PRE-7 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.463 (6H, bs), 2.131 (3H, bs), 6.955-7.207 (16H, m), 7. 275-7.410 (6H, m), 7.948 (3H, d)

Production Example 8
[Step 1]
Sodium hydroxide, 6.25 g (96%, 150 mmol) was charged in a three-necked flask with a capacity of 1 liter, equipped with a mechanical stirrer, Dean Stark condenser, Jim Roth condenser and thermometer, under a nitrogen stream, and removed. 6 ml of ionic water and 100 ml of dimethyl sulfoxide (DMSO) were added and dissolved. Subsequently, 15.3 g (50 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane as starting materials and 200 ml of toluene were charged. While stirring with a mechanical stirrer, the flask was immersed in an oil bath, the oil temperature was raised to 130 ° C., heating and refluxing was started, and the reaction was performed for 2 hours while removing generated water with a Dean-Stark condenser. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and the toluene was removed from the reaction mixture using a rotary evaporator under reduced pressure. To the remaining reaction mixture, 22.2 g (150 mmol) of o-nitrobenzonitrile was added, the flask was immersed again in an oil bath, and the oil temperature was raised to 85 ° C. to react for 6 hours. After completion of the reaction, the reaction mixture was allowed to cool to cool to about room temperature, and the reaction mixture was diluted by pouring into 1 liter of deionized water. The produced solid was filtered out, washed with deionized water, and dried under reduced pressure to obtain 26.5 g (yield 87%) of intermediate (13) represented by formula (13).

The structure of the intermediate (13) was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 2.217 (3H, s), 6.956 (3H, d), 7.013 (6H, d), 7.127-7 .167 (9H, m), 7.476-7.521 (3H, m), 7.662 (3H, dd)

[Step 2]
A 200 ml eggplant flask equipped with a magnetic stirrer, Jim Roth condenser and thermometer was charged with 9.24 g (85%, 0.14 M) of potassium hydroxide, 43 ml of deionized water, and 43 ml of ethylene glycol (EG). Was added and stirred to dissolve. Further, 6.10 g (10 mmol) of the intermediate (13) prepared in Step 1 was added, the flask was immersed in an oil bath, the oil temperature was increased to 140 ° C., and the reaction was performed for 6 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and then the reaction mixture was diluted by pouring into about 200 ml of deionized water. After stirring for another 30 minutes, 10% hydrochloric acid was added to the solution to adjust the pH to 1, and the resulting solid was collected by filtration and washed with deionized water. By drying under reduced pressure, 5.68 g of compound PRE-8 which is a precursor of the polycarboxylic acid ester compound of the present invention was obtained. (Yield 85%)

The structure of Compound PRE-8 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 2.147 (3H, s), 6.960 (3H, dt), 6.973 (3H, d), 7.095 (6H, d), 7.435 (3H, dt), 7.645 (6H, d), 7.965 (3H, dd), 11.845 (3H, bs)

Production Example 9
Instead of 1,1,1-tris (4-hydroxyphenyl) ethane, α, α, α'-tris- (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (Tokyo Chemical Industry Co., Ltd.) The reaction was carried out in the same manner as in Production Example 8 except that the compound PRE-9 (yield 95%: 2 steps), which is a precursor of the polycarboxylic acid ester compound of the present invention, was used.

The structure of Compound PRE-9 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.65 (6H, s), 2.10 (3H, s), 6.93 (2H, d), 6.96 (4H, d), 7.01 (2H, d), 7.07 (4H, d), 7.18 (2H, d), 7.25 (2H, d), 7.42 (3H, dt), 7. 61 (3H, t), 7.62 (3H, d), 7.95 (3H, d), 11.832 (2H, bs), 11.867 (1H, bs)

Production Example 10
4,4 ′, 4 ″, 4 ′ ″-(4,4 ′-(propane-2,2-diyl) bis instead of 1,1,1-tris (4-hydroxyphenyl) ethane as starting material (Cyclohexane-4,1,1-triyl)) Except for using tetraphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), the reaction was conducted in the same manner as in Production Example 8, and the precursor of the polycarboxylic acid ester compound of the present invention was used. A certain compound PRE-10 (yield 92%: 2 steps) was obtained.

The structure of Compound PRE-10 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 0.493 (6H, s), 1.135 (4H, dd), 1.429 (2H, t), 1.627 (4H, d), 1.805 (4H, t), 2.826 (4H, d), 6.924 to 6.982 (8H, m), 7.215 (4H, d), 7.395 to 7.453 (8H, m), 7.530 (4H, d), 7.656 (4H, d), 7.947 (4H, dt), 11.8037 (2H, bs), 11.863 (2H, bs)

Production Example 11
Production Example 8 except that 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,1,1-tris (4-hydroxyphenyl) ethane as a starting material. Reaction was similarly performed to obtain Compound PRE-11 (yield 72%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of the present invention.

The structure of the compound (PRE-11) was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 6.948 (2H, t), 6.958 (2H, d), 7.131 (4H, d), 7.344 (2H, dt), 7.411 (2H, d), 7.422 (2H, t), 7.485 (2H, d), 7.593 (4H, d), 7.898 to 7.953 (4H, m ), 11.790 (2H, bs)

Production Example 12
Production Example 8 except that 1,3-bis (4-hydroxyphenyl) adamantane (synthesized according to Tetrahedron Lett (1972) p3191) was used instead of 1,1,1-tris (4-hydroxyphenyl) ethane as a starting material The compound PRE-12 (yield 91%: 2 steps) which is a precursor of the polycarboxylic acid ester compound of the present invention was obtained.

The structure of Compound PRE-12 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.764 (2H, bs), 1.880-1.977 (10H, m), 2.272 (2H, bs), 6. 945-6.983 (4H, m), 7.420-7.460 (6H, m), 7.643 (4H, d), 7.982 (2H, dd), 11.911 (2H, bs)

Production Example 13
Production Example 8 except that 2,2-bis (4-hydroxyphenyl) adamantane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,1,1-tris (4-hydroxyphenyl) ethane as a starting material. Reaction was similarly performed to obtain a precursor compound PRE-13 (yield 86%: 2 steps) of the polycarboxylic acid ester compound of the present invention.

The structure of Compound PRE-13 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.687 (2H, bs), 1.714 (2H, bs), 1.745 (2H, bs), 1.784 (2H, bs), 1.928 (2H, bs), 1.957 (2H, bs), 3.221 (2H, bs), 6.917-6.957 (4H, m), 7.415 (2H, dt) ), 7.466 (4H, d), 7.549 (4H, d), 7.917 (2H, dd), 11.837 (2H, bs)

Example 1
In a four-necked flask (capacity 500 ml) equipped with a Jim Roth condenser, thermometer and dropping funnel, under a nitrogen stream, 6.146 g (10 mmol) of compound PRE-1 prepared in Production Example 1 and 200 ml of toluene were added. While stirring with a stirrer, the flask was heated in an oil bath and raised to 85 ° C. Subsequently, 32.6 g (0.16M: manufactured by Aldrich) of N, N-dimethylformamide-di-tert-butylacetal was added into the flask from the dropping funnel. After completion of the dropping, the oil bath temperature was 125 ° C., the reaction was allowed to proceed for 8 hours, and the reaction was allowed to cool after completion of the reaction. Toluene was removed from the reaction mixture under reduced pressure using a rotary evaporator. The residue was purified with an oily substance and a silica gel column (developing solvent: N-hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 2.77 g (3.3 mmol, 33% yield) of compound PCE-1.

The structure of Compound PCE-1 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.504 (18H, s), 1.536 (18H, s), 6.805 (2H, dd), 7.012 (2H , D), 7.201 (2H, d), 7.276-7.321 (4H, m), 7.426 (2H, dt), 7.472 (2H, d), 7.903 (4H, t)

Example 2
In a four-necked flask (capacity 200 ml) equipped with a Jim Roth condenser, thermometer and dropping funnel, 0.50 g (0.81 mmol) of the compound PRE-1 prepared in Production Example 1 under a nitrogen stream, Then, 4.24 g (13 mmol) of anhydrous cesium carbonate was charged, and 10 ml of N, N-dimethylformamide (DMF) was added and stirred. The flask is cooled in an ice / water bath to an internal temperature of 5 ° C., followed by bromoacetic acid 2-methyl-adamantanol ester (Structural Formula (21): synthesized according to the method described in European Patent Publication No. 1516867) 1 0.03 g (3.6 mmol) was dissolved in 5 ml of DMF and slowly added so that the temperature did not exceed 10 ° C. After completion of the dropwise addition, cooling was stopped, stirring was continued to raise the internal temperature to about room temperature, and the reaction was continued for 16 hours at room temperature, followed by heating to 65 ° C. in an oil bath for 4 hours. After completion of the reaction, after cooling to about room temperature, the reaction solution in the flask is diluted by pouring into about 100 ml of deionized water, followed by extraction by adding about 200 ml of ethyl acetate and separating the ethyl acetate layer. And washed with deionized water and saturated brine. After further drying with anhydrous magnesium sulfate, ethyl acetate was removed from the reaction mixture under reduced pressure using a rotary evaporator. The residual oil was purified by a silica gel column (developing solvent: N-hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 1.06 g (0.74 mmol, yield 90%) of compound PCE-2.

The structure of Compound PCE-2 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 1.481-1.518 (16H, m), 1.563 (6H, s), 1.573 (6H, s), 1. 666-1.829 (32H, m), 1.951 (4H, d), 2.203 (4H, d), 4.698 (4H, s), 4.755 (4H, s), 6.998 (2H, d), 7.096 (2H, dd), 7.154 (2H, d), 7.354 (2H, t), 7.422 (2H, d), 7.511 (2H, t) , 7.716 (2H, d), 8.061 (2H, d), 8.161 (2H, d)

Example 3
A 4-neck flask (capacity: 200 ml) equipped with a Jim Roth condenser, thermometer and dropping funnel was charged with 1.0 g (1.63 mmol) of the compound PRE-1 prepared in Production Example 1 under a nitrogen stream. , 10 ml of N, N-dimethylformamide (DMF) and 0.82 g (8.14 mmol) of triethylamine were added and stirred. The flask is cooled in an ice / water bath to an internal temperature of 5 ° C., and 2-chloromethoxyadamantane (synthesized according to the method described in Structural Formula (23): SYNTHESIS, 11 (1982), p942-944) 1.65 g 8.22 mmol) was dissolved in 5 ml of DMF and slowly added so that the temperature did not exceed 10 ° C. After completion of the dropwise addition, cooling was stopped, stirring was continued to raise the internal temperature to about room temperature, and the reaction was allowed to proceed at room temperature for 16 hours. After completion of the reaction, the reaction solution in the flask is diluted by pouring into about 100 ml of deionized water, followed by extraction with about 200 ml of ethyl acetate, separating the ethyl acetate layer, deionized water, saturated Washed with brine. After further drying with anhydrous magnesium sulfate, ethyl acetate was removed from the reaction mixture under reduced pressure using a rotary evaporator. The residual oil was purified by a silica gel column (developing solvent: N-hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 1.10 g (0.865 mmol, 53% yield) of compound PCE-3.

The structure of Compound PCE-3 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.297 (2H, bs), 1.328 (2H, bs), 1.463 (2H, bs), 1.490 (4H , Bs), 1.520 (2H, bs), 1.595 (4H, bs), 1.647-1.703 (16H, m), 1.777-2.052 (24H, m), 3. 696 (2H, s), 3.781 (2H, s), 5.485-5.544 (8H, m), 6.887 (2H, dd), 7.019 (2H, d), 7.239 (2H, d), 7.266 (2H, d), 7.309 (2H, t), 7.439 (2H, t), 7.600 (2H, d), 7.899 (2H, d) , 7.943 (2H, d)

Example 4
The reaction was conducted in the same manner as in Example 3 except that the compound PRE-2 prepared in Production Example 2 was used instead of the compound PRE-1, to obtain a compound PCE-4 (yield 58%).

The structure of Compound PCE-4 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.345 (2H, bs), 1.375 (2H, bs), 1.428-1.507 (8H, m), 1 .631-1.706 (20H, m), 1.773-1.980 (16H, m), 2.027-2.058 (8H, m), 3.585 (2H, s), 3.786 (2H, s), 4.777 (2H, d), 5.319 (2H, d), 5.507 (2H, d), 5.618 (2H, d), 6.906 (2H, d) 7.056 (2H, t), 7.218 (2H, d), 7.256 (2H, d), 7.310 (2H, t), 7.433 (2H, t), 7.542 ( 2H, d), 7.889 (2H, d), 7.908 (2H, d)

Example 5
A reaction was carried out in the same manner as in Example 1 except that the compound PRE-3 prepared in Production Example 3 was used instead of the compound PRE-1, to obtain a compound PCE-5 (yield 23%).

The structure of Compound PCE-5 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.551 (18H, s), 1.563 (18H, s), 6.885 (4H, d), 6.957 (2H , Dd), 7.154 (2H, d), 7.203 (4H, d), 7.303 (2H, dt), 7.386 (2H, dt), 7.411 (2H, d), 7 .627 (2H, d), 7.785 (2H, d)

Example 6
The reaction was conducted in the same manner as in Example 3 except that the compound PRE-3 prepared in Production Example 3 was used instead of the compound PRE-1, to obtain a compound PCE-6 (yield 50%).

The structure of Compound PCE-6 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.442-1.507 (8H, m), 1.624-1.708 (16H, m), 1.755-1. 855 (16H, m), 1.964-2.062 (16H, m), 3.796 (4H, s), 5.567 (8H, d), 6.921 (4H, d), 7.040. (2H, dd), 7.174 (2H, d), 7.231 (4H, d), 7.315 (2H, t), 7.397 (2H, t), 7.422 (2H, d) , 7.772 (2H, d), 7.794 (2H, d)

Example 7
The reaction was conducted in the same manner as in Example 1 except that the compound PRE-6 prepared in Production Example 6 was used instead of the compound PRE-1, to obtain a compound PCE-7 (yield 46%).

The structure of Compound PCE-7 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.561 (27H, s), 1.574 (27H, s), 2.200 (3H, s), 6.950 (6H , D), 7.010 (3H, dd), 7.110 (6H, d), 7.193 (3H, d), 7.662 (3H, d)

Example 8
The reaction was carried out in the same manner as in Example 3 except that the compound PRE-6 prepared in Production Example 6 was used instead of the compound PRE-1, to obtain a compound PCE-8 (yield 32%).

The structure of Compound PCE-8 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.454-1.512 (12H, m), 1.642-1.707 (24H, m), 1.762-1. 862 (24H, m), 1.980-2.088 (24H, m), 2.223 (3H, s), 3.812 (6H, s), 5.581 (12H, d), 6.995 (6H, d), 7.098 (3H, dd), 7.139 (6H, d), 7.207 (3H, d), 7.818 (3H, d)

Example 9
The reaction was performed in the same manner as in Example 3 except that the compound PRE-7 prepared in Production Example 7 was used instead of the compound PRE-1, to obtain a compound PCE-9 (yield 22%).

The structure of Compound PCE-9 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.452-1.511 (12H, m), 1.651-1.706 (30H, m), 1.755-1. 877 (24H, m), 1.980-2.077 (24H, m), 2.190 (3H, s), 3.809 (6H, s), 5.572 (6H, s), 5.586 (6H, s), 6.961 (2H, d), 6.968 (4H, d), 7.009 (2H, d), 7.087-7.196 (12H, m), 7.266 ( 2H, d), 7.809 (3H, dd)

Example 10
In a four-necked flask (capacity 200 ml) equipped with a Jim Roth condenser, thermometer and dropping funnel, 0.61 g (1 mmol) of the compound PRE-1 prepared in Production Example 1 was charged under a nitrogen stream. , N-dimethylformamide (DMF) 10 ml and 0.48 g (4.75 mmol) of triethylamine were added and stirred. The flask was cooled with an ice / water bath to an internal temperature of 5 ° C., 0.76 g (4.9 mmol) of benzyl chloromethyl ether (structural formula (28): manufactured by Tokyo Chemical Industry Co., Ltd.), and a temperature of 10 ° C. Slowly added to not exceed. After completion of the dropwise addition, cooling was stopped, stirring was continued to raise the internal temperature to about room temperature, and the reaction was allowed to proceed at room temperature for 16 hours. After completion of the reaction, the reaction solution in the flask is diluted by pouring into about 100 ml of deionized water, followed by extraction with about 200 ml of ethyl acetate, separating the ethyl acetate layer, deionized water, saturated Washed with brine. After further drying with anhydrous magnesium sulfate, ethyl acetate was removed from the reaction mixture under reduced pressure using a rotary evaporator. The residual oil was purified by a silica gel column (developing solvent: N-hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 0.656 g (0.60 mmol, yield 60%) of compound PCE-10.

The structure of Compound PCE-10 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 4.604 (4H, s), 4.667 (4H, s), 5.447 (8H, dd), 6.969 (2H, d), 7.011 (2H, dd), 7.163-7229 (12H, m), 7.251-7.331 (10H, m), 7.371 (2H, t), 7.440. (2H, d), 7.505 (2H, t), 7.602 (2H, d), 8.062 (2H, d), 8.172 (2H, d)

Example 11
The reaction was carried out in the same manner as in Example 1 except that the compound PRE-11 prepared in Production Example 11 was used instead of the compound PRE-1, to obtain a compound PCE-11 (yield 71%).

The structure of Compound PCE-11 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.450 (18H, s), 7.128 (2H, dd), 7.163-7.220 (8H, m), 7 279 (2H, t), 7.363 (2H, t), 7.400-7.438 (4H, m), 7.554 (4H, d), 8.176 (2H, dd)

Example 12
The reaction was carried out in the same manner as in Example 1 except that the compound PRE-12 prepared in Production Example 12 was used instead of the compound PRE-1, to obtain a compound PCE-12 (yield 63%).

The structure of Compound PCE-12 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.474 (18H, s), 1.798 (2H, bs), 1.963 (8H, d), 2.044 (2H , D), 2.327 (2H, bs), 7.147 (2H, dd), 7.221 (2H, dt), 7.397 (4H, d), 7.416 (2H, dt), 7 .665 (4H, d), 8.201 (2H, dd)

Example 13
The reaction was conducted in the same manner as in Example 1 except that the compound PRE-5 prepared in Production Example 5 was used instead of the compound PRE-1, to obtain a compound PCE-13 (yield 37%).

The structure of Compound PCE-13 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.562 (36H, s), 1.805 (2H, bs), 1.967 (8H, d), 2.029 (2H , Bs), 2.346 (2H, bs), 6.964 (2H, dd), 6.990 (4H, d), 7.168 (2H, d), 7.395 (4H, d), 7 .642 (2H, dd)

Example 14
A reaction was carried out in the same manner as in Example 10 except that the compound PRE-12 prepared in Production Example 12 was used instead of the compound PRE-1, to obtain a compound PCE-14 (yield 96%).

The structure of Compound PCE-14 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.811 (2H, bs), 1.976 (8H, d), 2.049 (2H, d), 2.340 (2H , Bs), 4.794 (4H, s), 5.507 (4H, s), 7.185 (2H, dt), 7.282 (2H, dd), 7.304-7.365 (10H, m), 7.401 (4H, d), 7.470 (2H, dt), 7.611 (4H, d), 8.271 (2H, dd)

Example 15
The reaction was conducted in the same manner as in Example 1 except that the compound PRE-4 prepared in Production Example 4 was used instead of the compound PRE-1, to obtain a compound PCE-15 (yield 48%).

The structure of Compound PCE-15 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.542 (18H, s), 1.564 (18H, s), 1.730 (2H, bs), 1.747 (2H , Bs), 1.780 (2H, bs), 1.845 (2H, bs), 2.027 (2H, bs), 2.057 (2H, bs), 3.207 (2H, bs), 6 .902 (4H, d), 6.944 (2H, dd), 7.121 (2H, d), 7.384 (4H, d), 7.626 (2H, d)

Example 16
The reaction was carried out in the same manner as in Example 3 except that the compound PRE-4 prepared in Production Example 4 was used instead of the compound PRE-1, to obtain a compound PCE-16 (yield 50%).

The structure of compound PCE-16 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.426-1.534 (10H, m), 1.633-1.719 (20H, m), 1.683-1. 858 (20H, m), 1.983-2.095 (20H, m), 3.812 (4H, bs), 5.568 (4H, s), 5.580 (4H, s), 6.932 (4H, d), 7.021 (2H, dd), 7.179 (2H, d), 7.405 (4H, d), 7.788 (2H, d)

Example 17
The reaction was conducted in the same manner as in Example 10 except that the compound PRE-13 prepared in Production Example 13 was used instead of the compound PRE-1, to obtain a compound PCE-17 (yield 97%).

The structure of Compound PCE-17 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.729 (2H, bs), 1.755 (2H, bs), 1.788 (2H, bs), 1.836 (2H , Bs), 2.074 (2H, bs), 2.105 (2H, bs), 3.263 (2H, bs), 4.738 (4H, s), 5.456 (4H, s), 7 154 (2H, t), 7.233-7.276 (12H, m), 7.417 (4H, d), 7.442 (2H, dt), 7.510 (4H, d), 8. 218 (2H, dd)

Example 18
The reaction was carried out in the same manner as in Example 1 except that the compound PRE-10 prepared in Production Example 10 was used instead of the compound PRE-1, to obtain a compound PCE-18 (yield 33%).

The structure of Compound PCE-18 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 0.539 (6H, s), 1.220-1.286 (4H, m), 1.40-1.47 (2H, m), 1.443 (18H, s), 1.485 (18H, s), 1.602-1.655 (4H, m), 1.861-1.923 (4H, m), 2.710 (2H, bs), 2.740 (2H, bs), 7.110-7.259 (12H, m), 7.347-7.428 (8H, m), 7.534 (4H, d), 7.653 (4H, d), 8.174 (2H, dd), 8.208 (2H, dd)

Example 19
The reaction was conducted in the same manner as in Example 10 except that the compound PRE-10 prepared in Production Example 10 was used instead of the compound PRE-1, to obtain a compound PCE-19 (yield 84%).

The structure of Compound PCE-19 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent DMSOd6: ppm): 0.489 (6H, s), 1.145 (4H, dd), 1.428 (2H, t), 1.613 (4H, d), 1.795 (4H, t), 2.820 (4H, d), 4.696 (4H, s), 4.717 (4H, s), 5.409 (4H, s), 5. 428 (4H, s), 7.113 (4H, dd), 7.182 (4H, d), 7.22-7.33 (24H, m), 7.369 (4H, d), 7.436 -7.489 (4H, m), 7.558-7.599 (8H, m), 7.692 (4H, d)

Example 20
The reaction was performed in the same manner as in Example 1 except that the compound PRE-8 prepared in Production Example 8 was used instead of the compound PRE-1, to obtain a compound PCE-20 (yield 45%).

The structure of Compound PCE-20 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.484 (27H, s), 2.182 (3H, s), 7.138 (6H, d), 7.147 (3H , D), 7.212 (3H, dt), 7.415 (3H, dt), 7.610 (6H, d), 8.201 (3H, dd)

Example 21
The reaction was conducted in the same manner as in Example 10 except that the compound PRE-8 prepared in Production Example 8 was used instead of the compound PRE-1, to obtain a compound PCE-21 (yield 82%).

The structure of Compound PCE-21 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 2.197 (3H, s), 4.787 (6H, s), 5.502 (6H, s), 7.153 (6H , D), 7.192 (3H, d), 7.267-7.317 (18H, m), 7.468 (3H, dt), 7.564 (6H, d), 8.263 (3H, dd)

Example 22
The reaction was conducted in the same manner as in Example 2 except that the compound PRE-8 prepared in Production Example 8 was used instead of the compound PRE-1, to obtain a compound PCE-22 (yield 80%).

The structure of Compound PCE-22 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.581 (3H, bs), 1.613 (3H, bs), 1.690 (6H, bs), 1.703 (9H , S), 1.744 (3H, bs), 1.778 (6H, bs), 1.803 (3H, bs), 1.879 (3H, bs), 1.911 (3H, bs), 1 .939 (3H, bs), 1.969 (3H, bs), 2.199 (3H, s), 2.351 (6H, bs), 4.739 (6H, s), 6.917 (3H, d), 7.153 (3H, dt), 7.167 (6H, d), 7.453 (3H, dt), 7.838 (6H, d), 8.320 (3H, dd)

Example 23
The reaction was conducted in the same manner as in Example 3 except that Compound PRE-8 prepared in Production Example 8 was used instead of Compound PRE-1, to obtain Compound PCE-23 (yield 55%).

The structure of Compound PCE-23 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.467 (3H, bs), 1.498 (3H, bs), 1.628 (3H, bs), 1.658 (3H , Bs), 1.692 (6H, bs), 1.773 (3H, bs), 1.813 (6H, bs), 1.846 (3H, bs), 1.989 (3H, bs), 2 .019 (6H, bs), 2.077 (3H, s), 2.184 (3H, s), 3.891 (3H, bs), 5.532 (6H, s), 7.144 (6H, d), 7.166 (3H, d), 7.334 (3H, d), 7.473 (3H, dt), 7.557 (6H, d), 8.251 (3H, dd)

Example 24
The reaction was conducted in the same manner as in Example 1 except that the compound PRE-9 prepared in Production Example 9 was used instead of the compound PRE-1, to obtain a compound PCE-24 (yield 32%).

The structure of Compound PCE-24 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.479 (27H, s), 1.679 (6H, s), 2.159 (3H, s), 7.016 (2H , D), 7.114 (3H, d), 7.142 (6H, d), 7.209 (3H, dt), 7.250 (2H, d), 7.410 (3H, dt), 7 .598 (4H, d), 7.607 (2H, d), 8.197 (3H, dd)

Example 25
The reaction was conducted in the same manner as in Example 10 except that the compound PRE-9 prepared in Production Example 9 was used instead of the compound PRE-1, to obtain a compound PCE-25 (yield 96%).

The structure of Compound PCE-25 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.682 (6H, s), 2.169 (3H, s), 4.774 (6H, s), 5.493 (6H , S), 7.034 (2H, d), 7.124 (6H, d), 7.176 (3H, t), 7.24-7.292 (20H, m), 7.463 (3H, dt), 7.548 (4H, d), 7.553 (2H, d), 8.258 (3H, dd)

Example 26
In a three-necked flask (capacity 200 ml) equipped with a Jim Roth condenser, thermometer and dropping funnel, under a nitrogen stream, 4.71 g (6 mmol) of the compound PRE-9 prepared in Production Example 9 and tert- 4.50 g (30 mmol) of butyldimethylchlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged, and 20 ml of N, N-dimethylformamide (DMF) was added and stirred. The flask was cooled with an ice / water bath to an internal temperature of 5 ° C., and 2.72 g (40 mmol) of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added to such an extent that the temperature did not exceed 10 ° C. After completion of the dropping, cooling was stopped, stirring was continued to raise the internal temperature to about room temperature, and then the reaction mixture was heated to 70 ° C. in an oil bath and reacted for 8 hours. After completion of the reaction, the reaction solution in the flask is diluted by pouring into about 200 ml of deionized water, followed by extraction by adding about 200 ml of ethyl acetate, separating the ethyl acetate layer, deionized water, saturated Washing was carried out using an aqueous sodium hydrogen carbonate solution and saturated brine in this order. After further drying with anhydrous magnesium sulfate, ethyl acetate was removed from the reaction mixture under reduced pressure using a rotary evaporator. The residual oil was purified by a silica gel column (developing solvent: N-hexane: ethyl acetate = 3: 1 mixed solvent) to obtain 4.00 g (3.55 mmol, yield 59%) of compound PCE-26.

The structure of Compound PCE-26 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 0.340 (18H, s), 1.008 (27H, s), 1.679 (6H, s), 2.155 (3H , S), 6.923 (3H, d), 7.005 (2H, d), 7.095 (4H, d), 7.096 (3H, dt), 7.133 (2H, d), 7 .246 (2H, d), 7.364 (3H, dt), 7.548 (4H, d), 7.556 (2H, d), 8.157 (3H, dd)

Example 27
The reaction was performed in the same manner as in Example 2 except that the compound PRE-9 prepared in Production Example 9 was used instead of the compound PRE-1, to obtain a compound PCE-27 (yield 87%).

The structure of compound PCE-27 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.568 (3H, bs), 1.606 (3H, bs), 1.687 (6H, bs), 1.695 (9H , S), 1.705 (6H, s), 1.737 (3H, bs), 1.772 (6H, bs), 1.800 (3H, bs), 1.874 (3H, bs), 1 907 (3H, bs), 1.931 (3H, bs), 1.963 (3H, bs), 2.162 (3H, s), 2.340 (6H, bs), 4.734 (6H, s), 6.912 (3H, d), 7.039 (2H, d), 7.129-7.163 (9H, m), 7.271 (2H, d), 7.448 (3H, dt) ), 7.803 (2H, d), 7.808 (4H, d), 8.302 (3H, dd)

Example 28
In a three-necked flask (capacity: 500 ml) equipped with a Jim Roth condenser, thermometer and dropping funnel, under a nitrogen stream, 1.00 g (1.27 mmol) of the compound PRE-9 prepared in Production Example 9, and 1.49 g (4.59 mmol) of anhydrous cesium carbonate was charged, and 15 ml of N, N-dimethylformamide (DMF) was added and stirred. The flask is cooled in an ice / water bath to an internal temperature of 5 ° C., followed by bromoacetic acid 2,2-dimethylphenethyl alcohol ester (Structural Formula (25): synthesized according to the method described in European Patent Publication No. 1516867) 1 .24 g (4.59 mmol) was dissolved in 10 ml of DMF and slowly added so that the temperature did not exceed 10 ° C. After completion of the dropwise addition, cooling was stopped, stirring was continued to raise the internal temperature to about room temperature, and the reaction was allowed to stir at room temperature for 16 hours. After completion of the reaction, the reaction solution in the flask is diluted by pouring into about 150 ml of deionized water, followed by extraction by adding about 150 ml of ethyl acetate, separating the ethyl acetate layer, deionized water, saturated Washed with brine. After further drying with anhydrous magnesium sulfate, ethyl acetate was removed from the reaction mixture under reduced pressure using a rotary evaporator. The residual oil was purified with a silica gel column (developing solvent: N-hexane: ethyl acetate = 1: 1 mixed solvent) to obtain 0.53 g (0.39 mmol, yield 39%) of compound PCE-28.

The structure of Compound PCE-28 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.515 (18H, s), 1.678 (6H, s), 2.156 (3H, s), 3.097 (6H , S), 4.646 (6H, s), 6.869 (3H, d), 7.028 (2H, d), 7.118-7.278 (26H, m), 7.448 (3H, dt), 7.799 (6H, d), 8.307 (3H, dd)

Example 29
The reaction was conducted in the same manner as in Example 3 except that the compound PRE-9 prepared in Production Example 9 was used instead of the compound PRE-1, to obtain a compound PCE-29 (yield 61%).

The structure of Compound PCE-29 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 1.457 (3H, bs), 1.589 (3H, bs), 1.618 (3H, bs), 1.648 (3H , Bs), 1.681 (6H, s), 1.703 (6H, bs), 1.769 (3H, bs), 1.801 (6H, bs), 1.833 (3H, bs), 1 .984 (3H, bs), 2.012 (6H, bs), 2.044 (3H, bs), 2.155 (3H, s), 3.885 (3H, bs), 5.525 (6H, s), 7.013 (2H, d), 7.120 (4H, d), 7.129 (2H, d), 7.151 (3H, t), 7.252 (2H, d), 7. 330 (3H, d), 7.467 (3H, dt), 7.544 (4H, d), 7.554 (2H, ), 8.244 (3H, dd)

Example 30
The reaction was performed in the same manner as in Example 2 except that the compound PRE-10 prepared in Production Example 10 was used instead of the compound PRE-1, to obtain a compound PCE-30 (yield 75%).

The structure of Compound PCE-30 was confirmed by ¹ H-NMR. The spectrum data of ¹ H-NMR is shown below.
¹ H-NMR (internal standard tetramethylsilane: solvent CDCl ₃ : ppm): 0.539 (6H, s), 1.262 (4H, dd), 1.437 (2H, t), 1.551-1 .668 (20H, m), 1.694 (6H, s), 1.713 (6H, s), 1.751-1.784 (20H, m), 1.886 (4H, bs), 1. 919 (4H, bs), 1.949 (4H, bs), 1.975 (4H, bs), 2.338 (4H, bs), 2.362 (4H, bs), 2.737 (4H, d) ), 4.709 (4H, s), 4.743 (4H, s), 6.905 (4H, t), 7.143 (4H, q), 7.190 (4H, d), 7.376 (4H, d), 7.441 (4H, q), 7.738 (4H, d), 7.891 (4H, d), 8 287 (2H, dd), 8.318 (2H, dd)

Example 31
100 parts by weight of the compound PCE-1 prepared in Example 1, which is a polycarboxylic acid ester compound of the present invention, as a base material, and 2 using di (t-butylphenyl) iodonium ortho-trifluoromethylsulfonate as a photoacid generator. A solid content composed of parts by weight and 0.2 parts by weight of tetrabutylammonium hydroxide lactate was dissolved in ethyl lactate as a solvent to prepare a photoresist solution having a solid content of 5% by weight. This photoresist solution was spin-coated on a silicon wafer and dried under heating and reduced pressure to form a film having a thickness of 110 nm. Subsequently, a line / space having a ½ pitch width of 100 nm was drawn on the substrate having this film using an electron beam lithography apparatus. Thereafter, it was baked at 130 ° C. and treated with a 0.25N aqueous tetrabutylammonium hydroxide solution to develop the imaged resist layer.

The obtained resist pattern was observed using an electron microscope (SEM) to evaluate line edge roughness and the like. The exposure amount for resolving a 100 nm half pitch line / space at 1: 1 was defined as the resist sensitivity. As a result, when a line / space having a ½ pitch width of 100 nm was produced, pattern collapse or the like was not observed, and a good pattern with substantially zero line edge roughness was obtained. The sensitivity at that time was 10 mJ / cm ² .

Comparative Example 1
According to the description in JP-A-2006-285075, 10 g of the compound (30) represented by the following structural formula (30) is dissolved in 100 ml of tetrahydrofuran, 1 g of methanesulfonic acid and 5 g of ethyl vinyl ether are added, and the mixture is reacted at room temperature for 1 hour. Then, 0.25 g of aqueous ammonia (30%) was added to stop the reaction, the reaction solution was crystallized and precipitated with 200 ml of acetic acid water, washed twice with water, and the resulting solid was filtered at 40 ° C. Then, 13.5 g of a compound in which two of the four hydroxy groups of the compound (30) were substituted with ethoxyethoxy groups was obtained. The structure of the compound was confirmed using ¹³ C and ¹ H-NMR.

  The resist layer was developed in the same manner as in Example 31 except that instead of compound PCE-1, a compound in which two of the four hydroxy groups of compound (30) were substituted with ethoxyethoxy groups was used as a substrate. However, at a baking temperature of 130 ° C., a desired line / space pattern could not be obtained due to excessive reaction and melting of the resist layer.

  The photoresist base material comprising the polycarboxylic acid ester compound of the present invention and the composition thereof are suitably used in the electrical / electronic field, the optical field, and the like such as semiconductor devices. It is particularly suitable for extreme ultraviolet light and / or electronic photoresists. Thereby, the performance of a semiconductor device such as ULSI can be dramatically improved.

Claims (10)

Polycarboxylic acid ester compounds represented by the following formulas (1-A) to (1-J).

[In the formula, A is a divalent to 20-valent hydrocarbon group having a molecular weight of 2 to 20 and including 2 to 20 aromatic rings, and the aromatic ring contained in A has 1 to 1 carbon atoms. 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, haloalkoxyl groups having 1 to 4 carbon atoms, hydroxyl groups, halogen atoms, or two or more substituents,
An oxygen atom bonded to A is bonded to the aromatic ring contained in A;
Each R ¹ is independently a hydrogen atom or an acid dissociable, dissolution inhibiting group (provided that R ¹ is not a hydrogen atom);
R ¹¹ is independently a hydroxyl group, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxyl group having 1 to 4 carbon atoms or a lower haloalkoxyl group having 1 to 4 carbon atoms,
X is an integer from 2 to 20,
n is an integer of 0 to 3, and the plurality of R ¹ and R ¹¹ may be the same or different. ] The polycarboxylic acid ester compound according to claim 1, wherein the acid dissociable, dissolution inhibiting group is any one of substituents represented by the following formulas (2) to (5).

[Wherein, R ^{2 to} R ¹⁰ are each independently a linear alkyl group having 1 to 12 carbon atoms, an alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or carbon. An alkyl group having 1 to 4 carbon atoms, an alkoxy group, an aromatic group having 6 to 10 carbon atoms or an aromatic group having 6 to 14 carbon atoms which may be substituted with a halogen atom (provided that R ⁵ and R ⁶ are It may be a hydrogen atom, and R ⁷ is a C 1-12 linear alkyl group containing an oxygen atom or a sulfur atom, a C 3-12 branched alkyl group, a C 3-20 single atom. A benzyl group which may be substituted with a ring or heterocyclic alicyclic alkyl group, or an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom).
R ^{2 to} R ¹⁰ may be bonded to each other to form a monocyclic or heterocyclic alicyclic alkyl group having 3 to 20 carbon atoms. ] The acid dissociable, dissolution inhibiting group is a tert-butyl group, a tert-amyl group, a benzyloxymethylene group, a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, or a substituent represented by the following formula (6). The polycarboxylic acid ester compound according to claim 1 or 2.

The A in the formulas (1-A) to (1-J) is any one of hydrocarbon groups represented by the following formulas (7-A) to (7-P). A polycarboxylic acid ester compound according to claim 1.

[Wherein R ¹² is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a haloalkoxyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom,
The plurality of R ¹² may be the same or different. ]   The photoresist base material containing the polycarboxylic acid ester compound in any one of Claims 1-4.   A photoresist composition comprising the photoresist substrate according to claim 5 and a solvent.   Furthermore, the photoresist composition of Claim 6 containing a photo-acid generator.   The photoresist composition according to claim 6 or 7, further comprising a basic organic compound as a quencher.   The fine processing method using the photoresist composition in any one of Claims 6-8.   A semiconductor device manufactured by the microfabrication method according to claim 9.