JP2003012621A - New tertiary amine compound having ester structure and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new useful ester-containing tertiary amine compound giving a photoresist excellent in resolution and focus margin in chemical amplification-type photolithography by adding the compound. SOLUTION: This ester-containing tertiary amine compound is represented by the general formula (1). The method for producing the amine is one comprising performing Michael addition reaction of a primary or secondary amine compound represented by the general formula (5) with an acrylic ester compound represented by the general formula (6), one comprising performing Michael addition reaction of a monoethanol amine or a diethanol amine represented by the general formula (7) with an acrylic ester compound represented by the general formula (6) to obtain an ester-containing amine compound represented by the general formula (8) and introducing R<1> group and one comprising performing ester exchange reaction of an ester-containing tertiary amine represented by the general formula (9) with R<2> OH.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ester group-containing tertiary amine compound useful as an additive for a novel chemically amplified resist material suitable for microfabrication technology.

[0002]

2. Description of the Related Art With the higher integration and higher speed of LSIs, finer pattern rules are required, and far-ultraviolet lithography is considered promising as a next-generation fine processing technology. Far-ultraviolet lithography is capable of processing to 0.2 μm or less, and when a resist material having low light absorption is used, it is possible to form a pattern having a side wall that is nearly vertical to the substrate. Further, in recent years, a technique using a high-intensity KrF excimer laser as a light source for far-ultraviolet rays has been attracting attention, and since this is used as a mass production technique, a resist material having low light absorption and high sensitivity is demanded. ing. From such a viewpoint, a chemically amplified positive resist material using an acid catalyst which has been developed in recent years (Japanese Patent Publication No. 2-2766).
No. 0 and JP-A-63-27829) have excellent characteristics such as high sensitivity, resolution and dry etching resistance, and are particularly promising resist materials for deep ultraviolet lithography.

As a drawback of the chemically amplified resist, when the exposure time from exposure to PEB (Post Exposure Bake) becomes long, the line pattern becomes T-top shape when the pattern is formed, that is, the pattern upper part becomes thick. [PED (Post Expos
ure Delay)], or a basic substrate, in particular, a so-called hemming phenomenon in which a pattern in the vicinity of the substrate on a silicon nitride or titanium nitride substrate becomes thick. T-
It is considered that the top phenomenon is because the solubility of the resist film surface is lowered, and the tailing on the substrate surface is because the solubility is lowered near the substrate. Further, there is a problem that a dark reaction of elimination of an acid labile group progresses from exposure to PEB, and a residual dimension of a line becomes small.

These are major drawbacks when the chemically amplified resist is put to practical use. Due to this drawback, the conventional chemically amplified positive resist material has a problem that it is difficult to control the dimensions in the lithography process and the dimension control is impaired even when the substrate is processed using dry etching [Reference: W. Hinsberg, et. al. ，
J. Photopolym. Sci. Techno
l. , 6 (4), 535-546 (1993). , T.
Kumada, et. al. J. Photopoly
m. Sci. Technol. , 6 (4), 571-5
74 (1993). ].

In the chemically amplified positive resist material, P
It is considered that the cause of the ED or the footing problem of the substrate surface is largely related to the basic compound in the air or the substrate surface. The acid generated on the resist film surface by exposure reacts with a basic compound in the air to deactivate it, and the longer the standing time to PEB, the more the amount of deactivating acid increases, so the acid labile group is decomposed. Is less likely to occur. Therefore, an insoluble layer is formed on the surface, and the pattern has a T-top shape.

[0006] Here, it is well known that the addition of a basic compound can suppress the influence of the basic compound in the air, so that it is also effective for PED (USP5609989, WO98 / 37458). No. 63-149640, No. 5-113666, No. 5-232706, No. 5-249662
issue).

As the basic compound, nitrogen-containing compounds are well known, and examples thereof include amine compounds or amide compounds having a boiling point of 150 ° C. or higher. Specifically, polyvinyl pyridine, aniline, N-methylaniline, N, N
-Dimethylaniline, o-toluidine, m-toluidine, p-toluidine, 2,4-lutidine, quinoline, isoquinoline, formamide, N-methylformamide,
N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2
-Pyrrolidone, N-methylpyrrolidone, imidazole,
α-picoline, β-picoline, γ-picoline, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine , 2-quinolinecarboxylic acid, 2-amino-4-nitrophenol, 2-
(P-Chlorophenyl) -4,6-trichloromethyl-
Examples include triazine compounds such as s-triazine.
Among these, pyrrolidone, N-methylpyrrolidone, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and 1,2-phenylenediamine are particularly preferable.

However, although these nitrogen-containing compounds are weak bases and can alleviate the T-Top problem, they control the reaction when a highly reactive acid labile group such as an acetal group such as 1-ethoxyethyl is used. That is, the acid diffusion cannot be controlled. The addition of the weak base caused a dark reaction particularly in PED to proceed in the unexposed portion, resulting in a reduction in the line dimension (slimming) in the acetal-based acid leaving group and a reduction in the film on the line surface. It was effective to add a strong base to solve the above problems. However, it is not so good that the degree of basicity is high, and it is said that DBU (1,8-
Diazabicyclo [5,4,0] -7-undecene) or DBN (1,5-diazabicyclo [4,3,0]-
(5-Nonene), proton sponge, or addition of a quaternary amine such as tetramethylammonium hydroxide could not obtain a sufficient effect.

The effect of adding the base compound to the resist composition is not only improvement of environmental stability but also improvement of resolution. The addition of a base lowers the sensitivity but improves the contrast of acid generation. In the exposed area where the number of moles of the generated acid is less than the number of moles of the added base, the acid is deactivated by neutralizing with the base, and the catalytic reaction cannot occur, but when the neutralization point is exceeded, the acid rapidly increases. Acid is generated and causes a catalytic reaction.

The rapid acid generation phenomenon near the neutralization point due to the addition of a base was reported by Hatakeyama et al. In SPIE symp. Proc., 3333, 62,
(1998) called the proton jump. Furthermore, Hatakeyama et al. Conducted a detailed study on the mechanism of the proton jump, and J. Potopolymer. Sci. Technol., Vol13, (4), p51
9 (2000) proposed a theory of competitive reaction in which a neutralization reaction between an acid and a base generated by exposure and an acid-catalyzed reaction occur simultaneously. Here, the neutralization reaction between the photo-generated acid and the added base was solved kinetically, and it was shown that the higher the reaction rate constant of the neutralization reaction, the higher the contrast.

[0011]

As a result of experiments conducted by adding various bases, it was found that the reaction rate constant with an acid and pKa are not particularly closely related to each other. For example, DBU (1,8-diazabicyclo [5,
4,0] -7-undecene) or DBN (1,5-
Diazabicyclo [4,3,0] -5-nonene) or proton sponge, quaternary amine such as tetramethylammonium hydroxide, or sodium hydroxide,
The reaction rate constant of triethanolamine, which is inferior in basicity, was higher than that of potassium hydroxide. Furthermore, tris {2- (methoxymethoxy) is better than triethanolamine.
Ethyl} amine and tris [2-{(2-methoxyethoxy) methoxy} ethyl] amine had higher reaction rate constants, and higher contrast could be obtained. By the way, the pKa of these bases is estimated to be around 7,
Much weaker base than DBU or DBN, or quaternary ammonium hydroxide or proton sponge.

From the above, it has been clarified that the base added to the resist does not have to be a super strong base, and an amine having a polar functional group such as a hydroxy group or an ether group is effective. However, even with these bases, the effect of preventing film slippage, the effect of improving contrast, and the effect of expanding the focus margin are not sufficient, and the development of an optimal base has been required.

The present invention has been made in view of the above circumstances, and is a useful novel ester group-containing tertiary amine which is added in chemical amplification photolithography to give a photoresist excellent in resolution and focus margin. It is an object to provide a compound and a method for producing the same.

[0014]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a specific structure including an ester structure represented by the following general formula (1) is obtained. Tertiary amine can be easily obtained in a high yield by the method described below, further, these ester group-containing tertiary amine compounds are highly effective in preventing resist film loss,
It was found that the effect of improving the resolution and expanding the focus margin is very excellent.

That is, the present invention is represented by the general formula (1).
An ester group-containing tertiary amine compound is provided. Well
Also, an ester group-containing tertiary amine represented by the general formula (1)
The compound represented by the following general formula (5)
A primary or secondary amine compound having the following general formula (6)
Michael addition to the indicated acrylic ester compound
Manufacturing method according to the following general formula (7)
Ruamine or diethanolamine is represented by the general formula (6).
Michael addition to the acrylic ester compound
Ester group-containing amine compound represented by the general formula (8)
After obtaining ¹Manufacturing method of introducing a group, the following general formula
Ester group-containing tertiary amine represented by (9) and R²O
A method for producing a transesterification reaction with H is provided.

[Chemical 5] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, and X represents a leaving group such as a halogen atom, an alkylsulfonyloxy group, an acyloxy group, a hydroxyl group, or an aryloxy group.)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The general formula (1) of the present invention is preferably R
¹ of carbon number 1 to 10, a number of carbon atoms in R ² is 2 to 10, an ester group-containing tertiary amine compound represented by the following general formula (2).

[Chemical 6] (In the above formula, n = 1 or 2. R ^{1 ′} is independently an alkyl group having 1 to 10 carbon atoms which may include an ether, carbonyl, or carbonyloxy group, and R ^{2 ′} is ether, carbonyl, It represents a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms which may contain a carbonyloxy group.)

In the general formula (1) of the present invention, R ¹ is preferably a formyl group or an acetyl group, R ² has 2 to 10 carbon atoms, and is represented by the following general formula (3). It is an ester group-containing tertiary amine compound.

[Chemical 7] (In the above formula, n = 1 or 2. R ^{2 ′} may have an ether, carbonyl, or carbonyloxy group and has 2 to 2 carbon atoms.
10 represents a linear, branched or cyclic alkyl group. R
¹ represents a formyl group or an acetyl group. )

Further, in the general formula (1) of the present invention, preferably, R ¹ is a methyl group, R ² has 2 to 10 carbon atoms, and an ester group represented by the following general formula (4) is contained. It is a tertiary amine compound.

[Chemical 8] (In the above formula, n = 1 or 2. R ^{2 ′} may have an ether, carbonyl, or carbonyloxy group and has 2 to 2 carbon atoms.
10 represents a linear, branched or cyclic alkyl group. )

In the ester group-containing tertiary amine compound represented by the above general formulas (1) to (4) according to the present invention,
R ¹ is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl,
Decyl, methoxymethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, (2-methoxyethoxy) methyl, 2-tetrahydrofuranyl, 2-tetrahydropyranyl, tetrahydrofurfuryl, formyl, acetyl, propionyl, butyryl. , Isobutyryl, pivaloyl, valeryl, methoxyacetyl, ethoxyacetyl, acetoxyacetyl, 2-formyloxyethyl, 2-acetoxyethyl, 2-oxopropyl,
Examples thereof include 2-oxobutyl, 2-oxocyclopentyl, 2-oxo-3-tetrahydrofuranyl, 2-oxo-3-tetrahydropyranyl, methoxycarbonyl, ethoxycarbonyl, and t-butoxycarbonyl, but are not limited thereto.

In the ester group-containing tertiary amine compound represented by the above general formulas (1) to (4) according to the present invention,
R ² is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, isobutyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, stearyl, 2-methoxyethyl, 2-ethoxyethyl. , 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2-cyclohexyloxyethyl, 2-methoxy-1-methylethyl, 3-ethoxypropyl, 3
-Butoxypropyl, 2- (2-methoxyethoxy) ethyl, 2- (2-ethoxyethoxy) ethyl, 2- [2
-(2-Methoxyethoxy) ethoxy] ethyl, 2- [2
-(2-Ethoxyethoxy) ethoxy] ethyl, 3-tetrahydrofuranyl, tetrahydrofurfuryl, 3-tetrahydrofuranylmethyl, 2-tetrahydropyranylmethyl, tetrahydro-4H-pyran-4-yl, 1,
3-dioxan-5-yl, 1,3-dioxolane-4
-Ylmethyl, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl, 2-formyloxyethyl, 2-
Acetoxyethyl, 2-propionyloxyethyl, 2
-(Methoxyacetoxy) ethyl, 2- (acetoxyacetoxy) ethyl, 2- (methoxycarbonyloxy)
Ethyl, 2- (ethoxycarbonyloxy) ethyl, 2
-(Butoxycarbonyloxy) ethyl, 2- (isobutoxycarbonyloxy) ethyl, 2- (t-butoxycarbonyloxy) ethyl, 2- (pentyloxycarbonyloxy) ethyl, 2- (hexyloxycarbonyloxy) ethyl, 2 -(Heptyloxycarbonyloxy) ethyl, 2- (octyloxycarbonyloxy) ethyl, 2- (2-nonyloxycarbonyloxy) ethyl, 2- (decyloxycarbonyloxy) ethyl, 2- (2-methoxyethoxycarbonyloxy) )
Ethyl, 2- (methoxycarbonylmethoxy) ethyl,
2- (ethoxycarbonylmethoxy) ethyl, 4-formyloxybutyl, 4-acetoxybutyl, 4-propionyloxybutyl, 4- (methoxyacetoxy) butyl, 4- (acetoxyacetoxy) butyl, 4- (methoxycarbonyloxy) butyl , 2- (ethoxycarbonyloxy) butyl, 4- (butoxycarbonyloxy) butyl, 4- (isobutoxycarbonyloxy) butyl, 4- (t-butoxycarbonyloxy) butyl,
4- (pentyloxycarbonyloxy) butyl, 4-
(Hexyloxycarbonyloxy) butyl, 4- (heptyloxycarbonyloxy) butyl, 4- (octyloxycarbonyloxy) butyl, 4- (2-nonyloxycarbonyloxy) butyl, 4- (decyloxycarbonyloxy) butyl, 4- (2-methoxyethoxycarbonyloxy) butyl, formyloxypropyl, acetoxypropyl, 2-oxo-1-propyl,
2-oxo-1-butyl, 2-oxocyclopentyl,
2-oxocyclohexyl, 2-oxo-3-tetrahydrofuranyl, 2-oxo-3-tetrahydropyranyl can be exemplified, but not limited thereto.

Specific examples of the ester group-containing tertiary amine compound of the present invention include, but are not limited to, the following compounds.

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

According to the present invention, in these ester group-containing tertiary amine compounds, an ester group having a high affinity for an acid and other oxygen functional groups can be present at appropriate positions near the amine nitrogen. It is considered that the high reaction rate with an acid can be realized, and high resolution and a wide focus margin can be achieved in the photoresist containing these tertiary amines. In addition, the general formula (1)
By selecting the optimum one from the possible combinations of R ¹ and R ² in, the basicity, reaction rate with acid,
The diffusion rate in the resist can be adjusted appropriately,
It is believed possible to provide amine additives compatible with a wide range of resist polymers and acid generators.

The ester group-containing tertiary amine compound of the present invention represented by the general formula (1) can be produced, for example, by selecting an optimum method from the following methods according to the structure of the compound. It is not limited. The details will be described below.

First, as a first method, it can be synthesized in one step from a primary or secondary amine compound and an acrylic acid ester compound by utilizing the Michael addition reaction of amine.

[Chemical 12] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. Indicates a group.)

The amount of the acrylate compound (6) used is 1.0 to 10 when n = 1, that is, when the amine compound is a primary amine, relative to 1 mol of the amine compound (5).
It is desirable that the amount is, particularly, 1.6 to 2.4 mol, and n
= 2, that is, when the amine compound is a secondary amine, the amount is preferably 0.5 to 5.0 mol, and particularly preferably 0.8 to 1.2 mol. The reaction is carried out without solvent or in a solvent.

As the solvent, methanol, ethanol,
Alcohols such as isopropyl alcohol, t-butyl alcohol and ethylene glycol, hydrocarbons such as hexane, heptane, benzene, toluene and xylene,
Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane and diglyme, chlorine-based solvents such as methylene chloride, chloroform and 1,2-dichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide Aprotic polar solvents such as dimethylsulfoxide and N-methylpyrrolidone, carboxylic acids such as formic acid and acetic acid, esters such as ethyl acetate and butyl acetate, ketones such as acetone and 2-butanone, nitriles such as acetonitrile, Pyridine, amines such as triethylamine, and water can be selected depending on the reaction conditions and used alone or in combination.

The reaction temperature is selected in the range of 0 ° C. to the reflux temperature of the solvent according to the reaction rate. In the reaction, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid or salts thereof as catalysts, organic acids such as p-toluenesulfonic acid, formic acid, acetic acid, oxalic acid and trifluoroacetic acid or salts thereof in order to improve the reaction rate. May be added. Further, in order to prevent the polymerization of acrylic acid esters, a polymerization inhibitor such as hydroquinone, p-methoxyphenol, benzoquinone, or phenylenediamine may be added. The reaction time is gas chromatography (GC) or thin layer chromatography (TL).
It is desirable from the viewpoint of yield to follow the reaction by C) to complete the reaction, but it is usually about 2 to 200 hours. The reaction mixture may be treated directly or with an ordinary aqueous aftertreatment (queeze).
The desired ester group-containing tertiary amine compound (1) is obtained by concentrating under reduced pressure after "use work-up". The obtained ester group-containing tertiary amine compound (1) can be purified by a conventional method such as distillation, chromatography and recrystallization, if necessary.

Next, as a second method, 2-aminoethanol or diethanolamine and an acrylic acid ester compound are used in two steps, in which the amine addition reaction is the first step and the hydroxyl group acylation or alkylation is the second step. It can be synthesized by the reaction of.

[Chemical 13] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. X represents a leaving group such as a halogen atom, an alkylsulfonyloxy group, an acyloxy group, a hydroxyl group and an aryloxy group.)

In the first-step reaction, the amount of the acrylic ester compound (6) used is 1.0 to 1 mol of the amine compound (7) based on 1 mol of n = 1, that is, when the amine compound is 2-ethanolamine. 10 mol, especially 1.6-2.
It is preferably 4 mol, and when n = 2, that is, when the amine compound is diethanolamine, it is 0.5 to 5.0.
It is desirable that the amount is, especially 0.8 to 1.2 mol. The reaction is carried out without solvent or in a solvent.

As the solvent, methanol, ethanol,
Alcohols such as isopropyl alcohol, t-butyl alcohol and ethylene glycol, hydrocarbons such as hexane, heptane, benzene, toluene and xylene,
Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane and diglyme, chlorine-based solvents such as methylene chloride, chloroform and 1,2-dichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide Aprotic polar solvents such as dimethylsulfoxide and N-methylpyrrolidone, carboxylic acids such as formic acid and acetic acid, esters such as ethyl acetate and butyl acetate, ketones such as acetone and 2-butanone, nitriles such as acetonitrile, Pyridine, amines such as triethylamine, and water can be selected depending on the reaction conditions and used alone or as a mixture, but it is preferable to use the same solvent as in the reaction of the next step because it does not require solvent substitution and is efficient. is there.

The reaction temperature is selected in the range of 0 ° C. to the reflux temperature of the solvent according to the reaction rate. In the reaction, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid or salts thereof as catalysts, organic acids such as p-toluenesulfonic acid, formic acid, acetic acid, oxalic acid and trifluoroacetic acid or salts thereof in order to improve the reaction rate. May be added. Further, in order to prevent the polymerization of acrylic acid esters, a polymerization inhibitor such as hydroquinone, p-methoxyphenol, benzoquinone, or phenylenediamine may be added. The reaction time is gas chromatography (GC) or thin layer chromatography (TL).
It is desirable from the viewpoint of yield to follow the reaction by C) to complete the reaction, but it is usually about 2 to 200 hours. When the reaction is carried out without a solvent or using the same solvent as the next step, the reaction in the next step can be carried out continuously in the same reaction vessel, but the reaction mixture is directly or after usual aqueous system work-up (aqueous work-up). ) Followed by concentration under reduced pressure to give an intermediate amino alcohol compound (8)
You can also get The obtained aminoalcohol compound (8) can be purified by a conventional method such as distillation, chromatography and recrystallization if necessary, but if it has a sufficient purity, it is a crude product in the second step. It is possible to carry out the reaction of.

In the second step reaction, when R ¹ is an alkyl group, specifically R ¹ X is methyl iodide, butyl bromide, dimethyl sulfate, ethyl iodide, diethyl sulfate, methoxymethyl chloride, ( 2-methoxyethoxy) methyl chloride, methyl chloroacetate and chloroacetone can be exemplified, and when R ¹ is an acyl group, specifically R ¹ X
As formic acid, formic acid-acetic acid mixed anhydride, acetic anhydride, acetic acid chloride, propionic acid anhydride, propionic acid chloride, butyric acid chloride, isobutyric acid chloride, valeric acid chloride, pivalic acid chloride, methoxyacetic acid chloride, acetoxyacetic acid chloride, pyrocarboxylic acid dit -Butyl, phenyl acetate,
Examples thereof include p-nitrophenyl acetate and 2,4,6-trichlorophenyl acetate, but are not limited thereto. R ¹
The amount of X to be used is 0.5 to 5.0 mol, particularly 1. 5 mol per 1 mol of the amino alcohol compound (8) when n = 1.
The amount is preferably 0 to 2.5 mol, and when n = 2, the amount is preferably 1.0 to 10 mol, and particularly preferably 2.0 to 5.0 mol. The reaction is carried out without solvent or in a solvent.

As the solvent, hydrocarbons such as hexane, heptane, benzene, toluene and xylene, diethyl ether, dibutyl ether, tetrahydrofuran,
Ethers such as 1,4-dioxane and diglyme, methylene chloride, chloroform, chlorinated solvents such as 1,2-dichloroethylene, N, N-dimethylformamide,
Aprotic polar solvents such as N, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone, carboxylic acids such as formic acid and acetic acid, esters such as ethyl acetate and butyl acetate, ketones such as acetone and 2-butanone, It can be selected from nitriles such as acetonitrile and amines such as pyridine and triethylamine depending on the reaction conditions and used alone or in combination.

A base compound may be added to accelerate the reaction, and specifically, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride, calcium hydride, potassium t-butoxide. ,
Alkali or alkaline earth metal salts such as lithium t-butoxide, n-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide, organometallics such as bromomagnesium diisopropylamide, pyridine, triethylamine, diisopropylethylamine, N, Examples thereof include organic amines such as N-dimethylaniline and 4-dimethylaminopyridine, but are not limited thereto. The base compounds may be used alone or in combination of two or more, and the amount used is preferably 0.8 to 10 mol, and particularly preferably 0.9 to 3.0 mol, based on 1 mol of R ¹ X.

The reaction temperature can be selected in the range of -70 ° C to the reflux temperature of the solvent, but it is particularly preferably in the range of 0 ° C to 50 ° C. The reaction time is preferably 0.2 to 20 hours, although it is desirable to follow the reaction by gas chromatography (GC) or thin layer chromatography (TLC) to complete the reaction, in terms of yield. From the reaction mixture, a conventional aqueous work-up is performed.
The target ester group-containing tertiary amine compound (1) is obtained from p). If necessary, the compound (1) can be purified by a conventional method such as distillation, chromatography and recrystallization.

Finally, as a third method, it can be synthesized from another ester group-containing tertiary amine compound of the present invention and an alcohol by a transesterification reaction using a catalyst.

[Chemical 14] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. R ⁴ is methyl, ethyl, propyl,
A lower alkyl group such as butyl is shown. )

In this reaction, the above-mentioned first or second method is used.
Ester group-containing tertiary amine compound (9) produced by
Alcohol (R²OH) and catalyst
Conducting a transesterification reaction in situ to lead to the target product (1)
become. The reaction can be carried out without solvent or in a solvent, depending on the reaction.
Newly generated alcohol (R^FourOH) while distilling off
Is preferable to improve yield and shorten reaction time.
Good Alcohol (R ²The amount of OH) used is
0.5 to 1 mol of the tertiary amine compound (9).
It is desirable to use 5.0 mol, especially 1.0 to 1.5 mol.
Yes.

As the transesterification catalyst used, triethylamine, 1,8-diazabicyclo [5.4.0]-
Organic amines such as 7-undecene and 4-dimethylaminopyridine, inorganic bases such as sodium hydroxide, potassium carbonate and sodium carbonate, sodium methoxide, potassium t-butoxide, magnesium ethoxide, titanium (IV) methoxide and the like. Examples thereof include, but are not limited to, metal alkoxides, iron (III) sulfate, salts such as calcium chloride, and inorganic or organic acids such as hydrogen chloride, sulfuric acid, p-toluenesulfonic acid. The amount of the transesterification catalyst used is the ester group-containing tertiary amine compound (9).
0.001 to 5.0 mol, especially 0.00
The use of 1 to 0.1 mol is desirable.

Tetrahydrofuran as solvent, di-n-
Ethers such as butyl ether and 1,4-dioxane,
Hydrocarbons such as n-hexane, n-heptane, benzene, toluene, xylene and cumene, and chlorinated solvents such as chloroform and dichloroethylene may be selected and used alone or in combination.

The reaction temperature varies depending on the reaction conditions, but it is 50-
200 ° C. is preferred, especially the alcohol (R ⁴ O
It is preferable to carry out the reaction at a temperature around the boiling point of the reaction solvent while distilling off H). It is desirable that the reaction time is completed by following the reaction by gas chromatography (GC) or thin layer chromatography (TLC) from the viewpoint of yield, but it is usually about 1 to 20 hours. The target ester group-containing tertiary amine compound (1) is obtained from the reaction mixture by an ordinary aqueous work-up. If necessary, the compound (1) can be purified by a conventional method such as distillation, chromatography, recrystallization and the like.
Alternatively, the target product (1) can be obtained by directly distilling the reaction mixture.

The ester group-containing tertiary amine compound of the present invention produced as described above is excellent irrespective of the exposure wavelength by adding it to the chemically amplified resist alone or in combination of two or more kinds. Preventing film loss, improving resolution,
It gives the effect of expanding the focus margin. In particular, it can be preferably used for KrF resist, ArF resist, F ₂ resist and EB resist.

The resist material containing the ester group-containing tertiary amine compound of the present invention is prepared by blending the resist base polymer, the photoacid generator, the organic solvent and the ester group-containing tertiary amine compound of the present invention. The method is common. Further, if necessary, different kinds of basic compounds, crosslinking agents, dissolution inhibitors and the like can be added. Preparation of these resist materials can be carried out by a conventional method.

The compounding amount of the ester group-containing tertiary amine compound of the present invention is preferably 0.001 to 2.0 parts by weight, and particularly preferably 0.001 to 100 parts by weight of the total base resin.
It is from 01 to 1.0 part by weight. If the blending amount is less than 0.001 part by weight, the blending effect may not be obtained, and if it exceeds 2 parts by weight, the resist sensitivity may be excessively lowered.

[0047]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Reference Examples and Comparative Reference Examples, but the present invention is not limited to the following Examples. [Synthesis Example] Of the ester group-containing tertiary amine compounds of the present invention, the above amines 1 to 81 were synthesized by the following formulations. [Synthesis Example 1] Synthesis of amine 1 To 10.5 g of diethanolamine, 10.5 g of ethyl acrylate was added at 20 to 30 ° C, and the mixture was left for 20 hours. After adding 25.6 g of triethylamine, 100 mg of 4-dimethylaminopyridine and 100 g of THF, 20 to 30 ° C.
Then, 22.4 g of acetic anhydride was added and stirred for 10 hours. After stopping the reaction by adding water, the mixture was extracted with ethyl acetate, the organic phase was washed with water and dried over anhydrous sodium sulfate. Amine 1 was obtained by concentration under reduced pressure (27.5 g, yield 95%).

Synthesis Example 2 Synthesis of Amine 2 Amine 2 was synthesized in the same manner as in Synthesis Example 1 except that propyl acrylate was used instead of ethyl acrylate (yield 96%).

[Synthesis Example 3] Synthesis of Amine 3 Amine 3 was synthesized by the same method as in Synthesis Example 1 except that isopropyl acrylate was used instead of ethyl acrylate (yield 94%).

Synthesis Example 4 Synthesis of Amine 4 Amine 4 was synthesized in the same manner as in Synthesis Example 1 except that butyl acrylate was used instead of ethyl acrylate (yield 94%).

[Synthesis Example 5] Synthesis of Amine 5 Amine 5 was synthesized in the same manner as in Synthesis Example 1 except that pentyl acrylate was used instead of ethyl acrylate (yield 93%).

Synthesis Example 6 Synthesis of Amine 6 Amine 6 was synthesized in the same manner as in Synthesis Example 1 except that hexyl acrylate was used instead of ethyl acrylate (yield 95%).

Synthesis Example 7 Synthesis of Amine 7 Amine 7 was synthesized in the same manner as in Synthesis Example 1 except that cyclohexyl acrylate was used instead of ethyl acrylate (yield 92%).

Synthesis Example 8 Synthesis of Amine 8 Amine 8 was synthesized in the same manner as in Synthesis Example 1 except that decyl acrylate was used instead of ethyl acrylate (yield 90%).

[Synthesis Example 9] Synthesis of Amine 9 Amine 9 was synthesized in the same manner as in Synthesis Example 1 except that pentadecyl acrylate was used instead of ethyl acrylate (yield 88%).

[Synthesis Example 10] Synthesis of Amine 10 Amine 10 was synthesized in the same manner as in Synthesis Example 1 except that dodecyl acrylate was used instead of ethyl acrylate (yield 85%).

[Synthesis Example 11] Synthesis of amine 11 To 10.5 g of diethanolamine, 11.6 g of 2-hydroxyethyl acrylate was added at 20 to 30 ° C, and the mixture was allowed to stand for 20 hours. After adding 38.4 g of triethylamine, 150 mg of 4-dimethylaminopyridine and 100 g of THF, 33.6 g of acetic anhydride was added at 20 to 30 ° C., and the mixture was stirred for 10 hours. After adding water to stop the reaction, extraction with ethyl acetate,
The organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by distillation under reduced pressure to obtain amine 11 (31.
3 g, yield 90%, boiling point 164-166 ° C / 27P
a). IR (thin film): ν = 2960, 2837, 1740, 1
443, 1375, 1236, 1190, 1043cm
^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
=. 2.02 (6H, s), 2.05 (3H, s),
2.45 (2H, t, J = 6.9Hz), 2.75 (4
H, t, J = 6.1 Hz), 2.88 (2H, t, J =
6.9 Hz), 4.08 (4H, t, J = 6.1H
z), 4.25 (4H, s).

[Synthesis Example 12] Synthesis of amine 12 Amine 12 was prepared in the same manner as in Synthesis Example 1 except that 2-methoxyethyl acrylate was used instead of ethyl acrylate.
Was synthesized (yield 86%, boiling point 146-148 ° C./9.
3 Pa). IR (thin film): ν = 2954, 2893, 2825, 1
738, 1456, 1371, 1238, 1198, 1
130,1039 cm ^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 2.02 (6H, s), 2.46 (2H, t, J =
7.1 Hz), 2.74 (4H, t, J = 6.0H
z), 2.88 (2H, t, J = 7.1Hz), 3.3.
6 (3H, s), 3.56 (2H, m), 4.08 (4
H, t, J = 6.0 Hz), 4.20 (2H, m).

[Synthesis Example 13] Synthesis of amine 13 Synthesis Example 1 except that acrylic acid (2-oxotetrahydrofuran-3-yl) was used in place of ethyl acrylate.
Amine 13 was synthesized in the same manner as in (yield 70%). IR (thin film): ν = 2962, 2837, 1792, 1
743, 1668, 1456, 1437, 1373, 1
240, 1196, 1095, 1043 cm ^-1 .

Synthesis Example 14 Synthesis of Amine 14 Amine 14 was synthesized in the same manner as in Synthesis Example 1 except that (methoxycarbonyl) methyl acrylate was used in place of ethyl acrylate (yield 60%, boiling point 154-15
7 ° C / 17Pa). IR (thin film): ν = 2956, 2837, 1740, 1
439, 1377, 1236, 1180, 1041 cm
^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 2.02 (6H, s), 2.54 (2H, t, J =
7.1 Hz), 2.76 (4H, t, J = 5.9H)
z), 2.92 (2H, t, J = 7.1 Hz), 3.7
4 (3H, s), 4.09 (4H, t, J = 5.9H
z), 4.59 (2H, s).

[Synthesis Example 15] Synthesis of amine 15 Amine 15 was prepared in the same manner as in Synthesis Example 1 except that 2-oxopropyl acrylate was used instead of ethyl acrylate.
Was synthesized (yield 85%, boiling point 165 ° C./27 Pa). IR (thin film): ν = 2960, 2837, 1736, 1
421, 1373, 1238, 1174, 1041 cm
^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 2.02 (6H, s), 2.13 (3H, s), 2.
55 (2H, t, J = 7.1Hz), 2.76 (4H,
t, J = 5.9 Hz), 2.92 (2H, t, J = 7.
1Hz), 4.08 (4H, t, J = 5.9Hz),
4.63 (2H, s).

[Synthesis Example 16] Synthesis of amine 16 Amine 16 was synthesized in the same manner as in Synthesis Example 1 except that tetrahydrofurfuryl acrylate was used instead of ethyl acrylate (yield 76%, boiling point 165 ° C). / 20P
a). IR (thin film): ν = 2958, 2873, 1740, 1
450, 1371, 1238, 1193, 1039cm
^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 0.56 (1H, m), 1.80-2.10 {2.0
2 (6H, s) including 10H, m}, 2.47 (2H,
t, J = 7.1 Hz), 2.74 (4H, t, J = 6.
0Hz), 2.88 (2H, t, J = 7.1Hz),
3.70-4.20 {4.06 (4H, t, J = 6.0
Hz) 9H, m}.

[Synthesis Example 17] Synthesis of amine 17 Amine 17 was synthesized in the same manner as in Synthesis Example 1 except that 2- (2-methoxyethoxy) ethyl acrylate was used instead of ethyl acrylate (yield. 88%).

[Synthesis Example 18] Synthesis of amine 18 Amine 18 was prepared in the same manner as in Synthesis Example 1 except that 2-ethoxyethyl acrylate was used instead of ethyl acrylate.
Was synthesized (yield 90%).

Synthesis Example 19 Synthesis of Amine 19 Amine 19 was synthesized in the same manner as in Synthesis Example 11 except that 4-hydroxybutyl acrylate was used instead of 2-hydroxyethyl acrylate (yield 87%. ).

[Synthesis Example 20] Synthesis of Amine 20 Amine 20 was synthesized in the same manner as in Synthesis Example 1 except that methyl acrylate was used in place of ethyl acrylate and acetoxyacetyl chloride was used in place of acetic anhydride ( Yield 80%).

[Synthesis Example 21] Synthesis of Amine 21 Amine 21 was synthesized in the same manner as in Synthesis Example 1 except that acetoxyacetic acid chloride was used instead of acetic anhydride (yield 78%).

[Synthesis Example 22] Synthesis of Amine 22 Amine 22 was synthesized in the same manner as in Synthesis Example 1 except that methyl acrylate was used in place of ethyl acrylate and methoxyacetic acid chloride was used in place of acetic anhydride. Yield 82
%).

[Synthesis Example 23] Synthesis of amine 23 Amine 23 was synthesized in the same manner as in Synthesis Example 1 except that methoxyacetic acid chloride was used instead of acetic anhydride (yield 80%).

[Synthesis Example 24] Synthesis of amine 24 Amine 24 was prepared in the same manner as in Synthesis Example 1 except that methyl acrylate was used instead of ethyl acrylate and di-t-butyl pyrocarboxylate was used instead of acetic anhydride. Synthesized (yield 85%).

[Synthesis Example 25] Synthesis of Amine 25 Amine 25 was synthesized in the same manner as in Synthesis Example 1 except that t-butyl pyrocarboxylate was used instead of acetic anhydride (yield 80%).

[Synthesis Example 26] Synthesis of Amine 26 Amine 26 was synthesized in the same manner as in Synthesis Example 1 except that methyl acrylate was used instead of ethyl acrylate and propionyl chloride was used instead of acetic anhydride. Yield 82
%).

[Synthesis Example 27] Synthesis of Amine 27 Amine 27 was synthesized in the same manner as in Synthesis Example 1 except that propionic acid chloride was used instead of acetic anhydride (yield 81%).

[Synthesis Example 28] Synthesis of amine 28 To 10.5 g of diethanolamine, 8.6 g of methyl acrylate was added at 20 to 30 ° C., and the mixture was left for 20 hours. Next, 100 g of formic acid was added and stirred at 80 ° C. for 20 hours. After diluting with ethyl acetate, 5% aqueous sodium hydrogen carbonate was added for neutralization, washing with water, and drying with anhydrous sodium sulfate. Amine 28 was obtained by concentration under reduced pressure (19.8 g, yield 80%).

[Synthesis Example 29] Synthesis of Amine 29 Amine 29 was synthesized in the same manner as in Synthesis Example 28 except that ethyl acrylate was used instead of methyl acrylate (yield 81%).

[Synthesis Example 30] Synthesis of amine 30 Amine 30 was synthesized in the same manner as in Synthesis Example 28 except that 2-hydroxyethyl acrylate was used instead of methyl acrylate (yield 40%). IR (thin film): ν = 2956, 2839, 1722, 1
456, 1275, 1254, 1173, 1061cm
^-1 . ¹ H-NMR (270 MHz in CDCl ₃ ): δ
= 2.47 (2H, t, J = 7.0Hz), 2.80
(4H, t, J = 5.9Hz), 2.90 (2H, t,
J = 7.0 Hz), 4.19 (4H, t, J = 5.9H)
z), 4.25-4.40 (4H, m), 8.03 (2
H, s), 8.06 (1H, s).

[Synthesis Example 31] Synthesis of amine 31 Amine 31 was synthesized in the same manner as in Synthesis Example 28 except that 4-hydroxybutyl acrylate was used instead of methyl acrylate (yield 70%). IR (thin film): ν = 2960, 2839, 1722, 1
466, 1363, 1254, 1176, 1065cm
^-1 . ¹ H-NMR (270 MHz in CDCl ₃ ): δ
= 1.65-1.80 (4H, m), 2.44 (2H,
t, J = 7.2 Hz), 2.80 (4H, t, J = 5.
8), 2.89 (2H, t, J = 7.2Hz), 4.0
5-4.25 (8H, m), 8.03 (2H, s),
8.04 (1H, s).

[Synthesis Example 32] Synthesis of Amine 32 Amine 32 was synthesized in the same manner as in Synthesis Example 1 except that methyl acrylate was used instead of ethyl acrylate and pivalic acid chloride was used instead of acetic anhydride. Yield 81
%).

[Synthesis Example 33] Synthesis of amine 33 Amine 33 was synthesized in the same manner as in Synthesis Example 1 except that pivalic chloride was used instead of acetic anhydride (yield 80
%).

[Synthesis Example 34] Synthesis of amine 34 A mixture of 10.0 g of methyl acrylate and 10.0 g of methanol contained 13.3 g of bis (2-methoxyethyl) amine.
Was added at 20 to 30 ° C. and left for 200 hours. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain amine 34 (215 g, yield 98%, boiling point 71-75 ° C / 27P.
a). IR (thin film): ν = 2951,927,2877,2
818, 1740, 1437, 1254, 1198, 1
119 cm ^-1 . ¹ H-NMR (270 MHz in CDCl ₃ ): δ
= 2.46 (2H, t, J = 7.3 Hz), 2.69
(4H, t, J = 6.0 Hz), 2.89 (2H, t,
J = 7.3 Hz), 3.31 (6H, s), 3.43
(4H, t, J = 6.0Hz), 3.64 (3H,
s).

[Synthesis Example 35] Synthesis of Amine 35 Amine 35 was synthesized in the same manner as in Synthesis Example 34 except that ethyl acrylate was used instead of methyl acrylate (yield 90%, boiling point 74 ° C / 16 Pa). ). IR (thin film):
ν = 2980,2929,2875,2816,17
34, 1458, 1369, 1302, 1252, 11
88,1120,1049 cm ^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 1.21 (3H, t, J = 7.2Hz), 2.42
(2H, t, J = 6.0 Hz), 2.67 (4H, t,
J = 6.2 Hz), 2.86 (2H, t, J = 6.0H
z), 3.29 (6H, s), 3.41 (4H, t, J
= 6.2 Hz), 4.08 (2H, q, J = 7.2H
z).

[Synthesis Example 36] Synthesis of Amine 36 Amine 36 was synthesized in the same manner as in Synthesis Example 34 except that propyl acrylate was used instead of methyl acrylate (yield 89%).

Synthesis Example 37 Synthesis of Amine 37 Amine 37 was synthesized in the same manner as in Synthesis Example 34 except that butyl acrylate was used instead of methyl acrylate (yield 90%).

[Synthesis Example 38] Synthesis of Amine 38 Amine 38 was synthesized in the same manner as in Synthesis Example 34 except that pentyl acrylate was used instead of methyl acrylate (yield 88%).

[Synthesis Example 39] Synthesis of amine 39 Amine 39 was synthesized in the same manner as in Synthesis Example 34 except that hexyl acrylate was used instead of methyl acrylate (yield 87%, boiling point 121 ° C / 16 Pa. ). IR (thin film): ν = 2956, 2929, 2873, 2816,
1736, 1460, 1248, 1184, 1120,
1068,1012 cm ^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 0.87 (3H, m), 1.20-1.40 (6H,
m), 1.59 (2H, m), 2.45 (2H, t, J
= 7.2 Hz), 2.70 (4H, t, J = 5.9H)
z), 2.89 (2H, t, J = 7.2Hz), 3.3.
1 (6H, s), 3.44 (4H, t, J = 5.9H
z), 4.04 (2H, t, J = 6.8Hz).

[Synthesis Example 40] Synthesis of Amine 40 Amine 40 was synthesized in the same manner as in Synthesis Example 34 except that cyclohexyl acrylate was used instead of methyl acrylate (yield 85%).

[Synthesis Example 41] Synthesis of amine 41 Amine 4 was prepared in the same manner as in Synthesis Example 34 except that 2-ethylhexyl acrylate was used instead of methyl acrylate.
1 was synthesized (yield 89%).

[Synthesis Example 42] Synthesis of amine 42 Amine 4 was prepared in the same manner as in Synthesis Example 34 except that 2-methoxyethyl acrylate was used instead of methyl acrylate.
2 was synthesized (yield 90%).

[Synthesis Example 43] Synthesis of amine 43 Amine 4 was prepared in the same manner as in Synthesis Example 34 except that 2-ethoxyethyl acrylate was used instead of methyl acrylate.
3 was synthesized (yield 89%).

[Synthesis Example 44] Synthesis of Amine 44 Amine 44 was synthesized in the same manner as in Synthesis Example 34 except that 2-propoxyethyl acrylate was used instead of methyl acrylate (yield 88%).

[Synthesis Example 45] Synthesis of amine 45 Amine 45 was synthesized in the same manner as in Synthesis Example 34 except that 2-isopropoxyethyl acrylate was used instead of methyl acrylate (yield 87%).

[Synthesis Example 46] Synthesis of amine 46 Amine 4 was prepared in the same manner as in Synthesis Example 34 except that 2-butoxyethyl acrylate was used instead of methyl acrylate.
6 was synthesized (yield 89%).

[Synthesis Example 47] Synthesis of amine 47 Amine 47 was synthesized in the same manner as in Synthesis Example 34 except that 2- (2-methoxyethoxy) ethyl acrylate was used instead of methyl acrylate (yield. 91%).

[Synthesis Example 48] Synthesis of Amine 48 Amine 48 was synthesized in the same manner as in Synthesis Example 34 except that tetrahydrofurfuryl acrylate was used instead of methyl acrylate (yield 70%, 130 ° C / 14P
a). IR (thin film): ν = 2976, 2947, 2929, 2
875, 1736, 1458, 1389, 1363, 1
250, 1184, 1119, 1078, 1024 c
m ^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 1.56 (1H, m), 1.75-2.05 (3H,
m), 2.50 (2H, t, J = 7.2Hz), 2.6
9 (4H, t, J = 6.0Hz), 3.70-4.20
(5H, m).

[Synthesis Example 49] Synthesis of amine 49 Amine 4 was prepared in the same manner as in Synthesis Example 34 except that 2-oxopropyl acrylate was used instead of methyl acrylate.
9 was synthesized (yield 88%).

[Synthesis Example 50] Synthesis of Amine 50 Amine 50 was synthesized in the same manner as in Synthesis Example 34 except that 2-acetoxyethyl acrylate was used instead of methyl acrylate (yield 90%).

[Synthesis Example 51] Synthesis of amine 51 4-acetoxy acrylate instead of methyl acrylate
Amine was prepared in the same manner as in Synthesis Example 34 except that butyl was used.
51 was synthesized (yield 84%, boiling point 137 ° C./19P
a). IR (thin film): ν = 2954, 2929, 2875, 2
815, 1738, 1458, 1389, 1365, 1
240, 1184, 1119, 1047 cm ^-1 .¹ H-NMR (300 MHz in CDCl₃): Δ
= 1.68 (4H, m), 2.03 (3H, s), 2.
46 (2H, br.t, J = 7.3 Hz), 2.70
(4H, br.t, J = 5.9Hz), 2.89 (2
H, br. t, J = 7.3 Hz), 3.31 (6H,
s), 3.43 (4H, br.t, J = 5.9Hz),
4.07 (4H, m).

[Synthesis Example 52] Synthesis of amine 52 Amine 52 was synthesized in the same manner as in Synthesis Example 34 except that 2- (acetoxyacetoxy) ethyl acrylate was used instead of methyl acrylate (yield 80%. ).

[Synthesis Example 53] Synthesis of amine 53 Synthesis Example 3 except that 2- (t-butoxycarbonyloxy) ethyl acrylate was used instead of methyl acrylate.
Amine 53 was synthesized in the same manner as in 4 (yield 83
%).

[Synthesis Example 54] Synthesis of amine 54 Synthesis Example 34 except that 2- (methoxycarbonylmethoxy) ethyl acrylate was used in place of methyl acrylate.
Amine 54 was synthesized in the same manner as in (yield 79%).

[Synthesis Example 55] Synthesis of amine 55 To 6.11 g of 2-aminoethanol was added 17.5 g of methyl acrylate at 20 to 30 ° C, and the mixture was left for 20 hours. After adding 12.1 g of triethylamine, 50 mg of 4-dimethylaminopyridine and 50 g of THF, 11.2 g of acetic anhydride was added at 20 to 30 ° C, and the mixture was stirred for 5 hours. After stopping the reaction by adding water, the mixture was extracted with ethyl acetate, the organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain amine 55 (26.2 g, yield 9
5%, boiling point 120 ° C./15 Pa). IR (thin film): ν = 2954, 2839, 1740, 1
439, 1373, 1238, 1200, 1176, 1
039 cm ^-1 . ¹ H-NMR (300 MHz in CDCl ₃ ): δ
= 2.01 (3H, s), 2.41 (4H, t, J =
6.9 Hz), 2.67 (2H, t, J = 6.0H
z), 2.79 (4H, t, J = 6.9Hz), 3.6
3 (6H, s), 4.06 (2H, t, J = 6.0H
z).

[Synthesis Example 56] Synthesis of Amine 56 Amine 56 was synthesized in the same manner as in Synthesis Example 55 except that ethyl acrylate was used instead of methyl acrylate (yield 93%).

[Synthesis Example 57] Synthesis of amine 57 Amine 57 was synthesized in the same manner as in Synthesis Example 55 except that propyl acrylate was used instead of methyl acrylate (yield 91%).

Synthesis Example 58 Synthesis of Amine 58 Amine 5 was prepared in the same manner as in Synthesis Example 55 except that 2-methoxyethyl acrylate was used instead of methyl acrylate.
8 was synthesized (yield 90%).

[Synthesis Example 59] Synthesis of amine 59 Amine 59 was synthesized in the same manner as in Synthesis Example 55 except that 2-acetoxyethyl acrylate was used instead of methyl acrylate (yield 88%).

[Synthesis Example 60] Synthesis of amine 60 Amine 60 was synthesized in the same manner as in Synthesis Example 55 except that acetoxyacetic acid chloride was used instead of acetic anhydride (yield 83%).

[Synthesis Example 61] Synthesis of amine 61 Amine 61 was synthesized in the same manner as in Synthesis Example 55 except that ethyl acrylate was used instead of methyl acrylate and acetoxyacetic acid chloride was used instead of acetic anhydride. Yield 82%).

[Synthesis Example 62] Synthesis of amine 62 Amine 62 was synthesized in the same manner as in Synthesis Example 55 except that methoxyacetic acid chloride was used instead of acetic anhydride (yield 85%).

[Synthesis Example 63] Synthesis of Amine 63 Amine 63 was synthesized in the same manner as in Synthesis Example 55 except that ethyl acrylate was used instead of methyl acrylate and methoxyacetic acid chloride was used instead of acetic anhydride. Yield 8
4%).

[Synthesis Example 64] Synthesis of amine 64 Amine 64 was synthesized in the same manner as in Synthesis Example 55 except that di-t-butyl pyrocarboxylate was used instead of acetic anhydride (yield 87%).

[Synthesis Example 65] Synthesis of amine 65 Amine 65 was prepared in the same manner as in Synthesis Example 55 except that ethyl acrylate was used instead of methyl acrylate and di-t-butyl pyrocarboxylate was used instead of acetic anhydride. It was synthesized (yield 86%).

[Synthesis Example 66] Synthesis of amine 66 Amine 66 was synthesized by the same method as in Synthesis Example 55 except that propionic acid chloride was used instead of acetic anhydride (yield 85%).

[Synthesis Example 67] Synthesis of Amine 67 Amine 67 was synthesized in the same manner as in Synthesis Example 55 except that ethyl acrylate was used in place of methyl acrylate and propionyl chloride was used in place of acetic anhydride. Yield 8
3%).

[Synthesis Example 68] Synthesis of amine 68 To 6.11 g of 2-aminoethanol was added 17.5 g of methyl acrylate at 20 to 30 ° C, and the mixture was allowed to stand for 20 hours. Subsequently, 100 g of formic acid was added, and the mixture was stirred at 80 ° C. for 20 hours.
The mixture was diluted with ethyl acetate, neutralized with 5% aqueous sodium hydrogen carbonate, washed with water, and dried over anhydrous sodium sulfate. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain amine 68 (yield 75%).

[Synthesis Example 69] Synthesis of amine 69 Amine 69 was synthesized in the same manner as in Synthesis Example 68 except that ethyl acrylate was used instead of methyl acrylate (yield 76%).

[Synthesis Example 70] Synthesis of Amine 70 Amine 70 was synthesized in the same manner as in Synthesis Example 55 except that pivalic acid chloride was used instead of acetic anhydride (yield 8
3%).

[Synthesis Example 71] Synthesis of amine 71 Amine 71 was synthesized in the same manner as in Synthesis Example 55 except that ethyl acrylate was used in place of methyl acrylate and pivalic acid chloride was used in place of acetic anhydride. Yield 82
%).

[Synthesis Example 72] Synthesis of amine 72 2-methoxyethylamine was added to a mixture of 20.0 g of methyl acrylate and 10.0 g of methanol at 20 to 30 ° C.
5 g was added and left for 200 hours. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain amine 72 (23.5 g, yield 95%, boiling point 81-85 ° C / 27 Pa). IR (thin film): ν = 2953, 2839, 1740, 1
437,1255,1200,1176,1119cm
^-1 . ¹ H-NMR (270 MHz in CDCl ₃ ): δ
= 2.44 (4H, t, J = 7.2Hz), 2.63
(2H, t, J = 6.1 Hz), 2.81 (4H, t,
J = 7.2 Hz), 3.31 (3H, s), 3.41
(2H, t, J = 6.1Hz), 3.64 (6H,
s).

[Synthesis Example 73] Synthesis of amine 73 Ethyl acrylate was used instead of methyl acrylate
Amine 73 was synthesized in the same manner as in Synthesis Example 72 except that
(Yield 93%, boiling point 120 ° C./80 Pa). IR (thin film): ν = 2981,2933,2875,2
825, 1734, 1464, 1371, 1302, 1
254, 1182, 1119, 1045 cm ^-1.¹ H-NMR (300 MHz in CDCl₃): Δ
= 1.23 (6H, t, J = 7.1Hz), 2.42
(4H, t, J = 7.2 Hz), 2.63 (2H, t,
J = 6.2 Hz), 2.81 (4H, t, J = 7.2H
z), 3.31 (3H, s), 3.41 (2H, t, J
= 6.2 Hz), 4.09 (4H, q, J = 7.1H
z).

[Synthesis Example 74] Synthesis of amine 74 Amine 74 was synthesized in the same manner as in Synthesis Example 72 except that propyl acrylate was used instead of methyl acrylate (yield 91%).

[Synthesis Example 75] Synthesis of amine 75 Amine 7 was prepared in the same manner as in Synthesis Example 72 except that 2-methoxyethyl acrylate was used instead of methyl acrylate.
5 was synthesized (yield 91%).

[Synthesis Example 76] Synthesis of amine 76 Amine 76 was synthesized in the same manner as in Synthesis Example 72 except that 2-acetoxyethyl acrylate was used instead of methyl acrylate (yield 85%).

[Synthesis Example 77] Synthesis of amine 77 To 7.5 g of 2-methoxyethylamine was added 8.6 g of methyl acrylate at 20 to 30 ° C, and the mixture was stirred for 10 hours. Subsequently, 15.0 g of ethyl acrylate was added and stirred for 200 hours. The reaction solution was concentrated under reduced pressure to obtain amine 77 (yield 97%).

[Synthesis Example 78] Synthesis of amine 78 Amine 78 was synthesized in the same manner as in Synthesis Example 55 except that 2- (2-aminoethoxy) ethanol was used instead of 2-aminoethanol (yield 90 %).

[Synthesis Example 79] Synthesis of amine 79 Amine 79 was synthesized in the same manner as in Synthesis Example 68 except that 2- (2-aminoethoxy) ethanol was used instead of 2-aminoethanol (yield 74). %).

Synthesis Example 80 Synthesis of Amine 80 21.9 g of amine 34, (1,3-dioxolane-4)
-Yl) A mixture of 10.4 g of methanol, 100 mg of sodium methoxide and 60 g of benzene was heated under reflux for 5 hours while distilling off methanol produced by the reaction. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain amine 80 (yield 90%).

[Synthesis Example 81] Synthesis of amine 81 Amine 81 was synthesized by the same method as in Synthesis Example 80 except that tetrahydropyran-4-ol was used in place of (1,3-dioxolan-4-yl) methanol. (Yield 81%).

[Reference Example and Comparative Reference Example] The effect of compounding the ester group-containing tertiary amine compound of the present invention in a photoresist was evaluated by the methods described below. The structure of the polymer used, the weight average molecular weight (Mw) and its ratio to the number average molecular weight (Mn) will be described later. The average molecular weight was measured using gel permeation chromatography (GPC) in terms of polystyrene. A polymer, an acid generator, a base, a dissolution inhibitor, and a cross-linking agent are dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) in a ratio of 70:30 by weight, and 0.1 μm-sized Teflon (registered) is registered. A resist solution was prepared by filtering with a Trademark) filter. Next, DUV-30 (manufactured by Nissan Chemical Co., Ltd.) is applied to the silicon wafer.
Was formed into a film having a thickness of 55 nm, and the obtained resist solution was spin-coated on a substrate whose reflectance was suppressed to 1% or less by KrF light (248 nm).
Bake at 00 ° C for 90 seconds to reduce the resist thickness to 550n.
The thickness is m. Excimer laser stepper (Nikon Corporation, NSR-S202A, NA = 0.5, σ =
0.75, 2/3 annular illumination) while changing the exposure amount and focus, and immediately after exposure,
After baking for 0 seconds, development was performed for 60 seconds with an aqueous solution of 2.38% tetramethylammonium hydroxide to obtain a pattern. The obtained resist pattern was evaluated as follows. The results are shown in the reference example table and the comparative reference example table.

Evaluation method: The exposure dose for resolving a 0.16 μm line and space at a ratio of 1: 1 was determined as the optimum exposure dose (Eo).
The resist sensitivity was used as p), and the focus margin at this time was determined. The definition of the focus margin is that there is no pattern film reduction and that the pattern dimension is 0.16 μm ±
It was decided to be within 10%.

From the above results, it was confirmed that the photoresist containing the ester group-containing tertiary amine compound of the present invention has a significantly wider focus margin as compared with the conventional product.

[0131]

The resist material prepared by blending the ester group-containing tertiary amine compound of the present invention is excellent in resolution and focus margin, and is useful for fine processing using electron beams or deep ultraviolet rays. KrF resist, ArF resist,
It gives a high compounding effect in F ₂ resist and EB resist, and is suitable as a fine pattern forming material for VLSI manufacturing.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Chemical 15]

[0136]

[Chemical 16]

[0137]

[Chemical 17]

[0138]

[Chemical 18]

[0139]

[Chemical 19]

Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Sachishi Hasegawa 28, Nishifukushima, Nakakubiki, Niigata prefecture No. 1 Shin-Etsu Chemical Co., Ltd., Synthetic Technology Laboratory (72) Inventor Takeshi Kinsei 28, Nishifukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture No. 1 Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (72) Inventor Jun Hatakeyama No. 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture 1 F-term in Synthetic Technology Laboratory, Shin-Etsu Chemical Co., Ltd. (reference) 4C062 AA19 4H006 AA01 AA02 AB80 AC48 AC52 BJ20 BN10 BP10 BT12 BU32 4H039 CA66 CD10 CD40

Claims (7)

[Claims] 1. An ester group-containing tertiary amine compound represented by the following general formula (1). [Chemical 1] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. Indicates a group.) 2. In the general formula (1), R ¹ has 1 carbon atom.
Is 10, claim 1 the number of carbon atoms in R ² is 2 to 10
The ester group-containing tertiary amine compound described in 1. 3. In the general formula (1), R ¹ is a formyl group or an acetyl group, and R ² has 2 to 10 carbon atoms, and the ester group-containing third group according to claim 1 or 2. Class amine. 4. The ester group-containing tertiary amine according to claim 1 or 2, wherein in the general formula (1), R ¹ is a methyl group, and R ² has 2 to 10 carbon atoms. 5. A general formula (1) characterized in that a primary or secondary amine compound represented by the following general formula (5) is Michael-added to an acrylic ester compound represented by the following general formula (6). The manufacturing method of the ester group containing tertiary amine compound shown by these. (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. A group is shown.) 6. A monoethanolamine or a diethanolamine represented by the following general formula (7) is added to the following general formula (6).
Michael addition to the acrylic acid ester compound represented by the following formula to obtain an ester group-containing ethanolamine compound represented by the following general formula (8), and then the following R ¹ group is introduced. A method for producing an ester group-containing tertiary amine compound represented by: [Chemical 3] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. Indicates a group.) 7. An ester group-containing tertiary amine represented by the following general formula (9) and R ² OH (wherein R ² is an ether,
It represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may contain a carbonyl or carbonyloxy group. ) A method for producing an ester group-containing tertiary amine compound represented by the following general formula (1), which comprises subjecting an alcohol represented by [Chemical 4] (In the above formula, n = 1 or 2. R ¹ and R ² are each independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may contain an ether, carbonyl or carbonyloxy group. R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms.)