JP2002249478A - Amine compound, resist composition and method of forming pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new amine compound which has high effect of preventing decrease in a resist film and also imparts good resolution and effect of enlarging a focus margin, and also provide a resist material containing the same and a method of producing a pattern using the resist material. SOLUTION: This amine compound is represented by formulas (1), (2), (3) and (4). [wherein, R<1> represents a straight chain or branched 1-4C alkylene group; R<2> represents H or a straight chain, branched or cyclic alkyl group and may include a hydroxy, ether, carbonyl or ester group, a lactone ring, a carbonate or a cyano group; R<3> represents a straight chain or branched 2-20C alkylene group and may include a hydroxy, ether, thio-ether, carbonyl, ester or thio-ester group or a carbonate; R<4> is the same or different and a straight chain or branched 1-4C alkylene group; a represents an integer of 1-3, and a+b=3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel amine compound having high utility as a basic component in a resist material,
The present invention relates to a novel resist material suitable for fine processing technology containing the amine compound and a pattern forming method using the same.

[0002]

2. Description of the Related Art LSI
With the demand for finer pattern rules in accordance with higher integration and higher speed, far-ultraviolet lithography is regarded as promising as a next-generation fine processing technology. In the deep ultraviolet lithography, processing with a thickness of 0.2 μm or less is also possible. When a resist material having low light absorption is used, a pattern having side walls nearly perpendicular to the substrate can be formed. In recent years, a technique using a high-brightness KrF excimer laser as a light source of far ultraviolet light has attracted attention, and since it is used as a mass production technique, light absorption is low.
There is a demand for a highly sensitive resist material.

[0003] From such a viewpoint, an acid-catalyzed chemically amplified positive resist material (JP-B 2-2) has recently been developed.
No. 7660, JP-A-63-27829)
Is a resist material that has high sensitivity, resolution, dry etching resistance, and excellent characteristics, and is particularly promising for deep ultraviolet lithography.

[0004] However, a disadvantage of the chemically amplified resist material is that the exposure to PEB (Post Exposure) is not possible.
If the standing time until re bake becomes long, the line pattern becomes a T-top shape when the pattern is formed, that is, the pattern upper portion becomes thicker [PED].
(Referred to as “Post Exposure Delay”), or a so-called tailing phenomenon in which a pattern near a substrate on a basic substrate, particularly a silicon nitride or titanium nitride substrate becomes thicker. The T-top phenomenon is considered to be due to a decrease in the solubility of the resist film surface, and the tailing on the substrate surface is considered to be due to a decrease in the solubility near the substrate. In addition, a dark reaction of elimination of the acid labile group progresses from the exposure to the PEB, resulting in a problem that the remaining dimension of the line is reduced. These are major drawbacks when the chemically amplified resist material is put to practical use. Due to this drawback, the conventional chemically amplified positive resist material has a problem that dimensional control in a lithography process is difficult, and dimensional control is impaired even in processing a substrate using dry etching [Ref: Hinsb
erg, et. al. , J. et al. Photopolym. S
ci. Technol. , 6 (4), 535-546
(1993). , T .; Kumada, et. al. ,
J. Photopolym. Sci. Techno
l. , 6 (4), 571-574 (1993). ].

In a chemically amplified positive resist material, P
It is considered that the cause of the problem of ED or footing of the substrate surface largely depends on a basic compound in the air or on the substrate surface. The acid on the surface of the resist film generated by the exposure reacts and deactivates with the basic compound in the air, and the longer the standing time until PEB, the greater the amount of deactivated acid. Is less likely to occur. Therefore, a hardly-solubilized layer is formed on the surface, and the pattern has a T-top shape.

It is well known that the addition of a basic compound suppresses the influence of the basic compound in the air, which is also effective for PED (US Pat. No. 5,609,989). , WO 98/37458
JP-A-63-149640, JP-A-5-1136
Nos. 66, 5-232706, 5-249683, etc.). As the basic compound, a nitrogen-containing compound is well known, and examples thereof include an amine compound or an amide compound having a boiling point of 150 ° C. or higher. Specifically, pyridine, polyvinylpyridine, 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
Triazine compounds such as -quinoline carboxylic acid, 2-amino-4-nitrophenol, and 2- (p-chlorophenyl) -4,6-trichloromethyl-s-triazine. Among these, pyrrolidone, N-methylpyrrolidone, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and 1,2-phenylenediamine are particularly exemplified.

However, these nitrogen-containing compounds are weak bases and can alleviate the problem of T-top, but cannot control the reaction when a highly reactive acid labile group is used, that is, cannot control acid diffusion. Addition of a weak base, in particular, causes the dark reaction in the PED to proceed to the unexposed portion, causing a reduction in the line size (slimming) in the PED and a reduction in the film thickness on the line surface. In order to solve the above problem, it is preferable to add a strong base. However, the higher the basicity is, the better the effect is, and a sufficient effect cannot be obtained even by adding a quaternary amine such as DBU, DBN, proton sponge or tetramethylammonium hydroxide which is called a super strong base.

[0008]

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[0009] In order to achieve a high contrast for achieving a high resolution, it is effective to add a base which has an excellent effect of capturing the generated acid. The dissociation constant of an acid and a base in water can be explained by pKa, but there is no direct relationship between the ability of the acid to scavenge in the resist film and the pKa of the base. These are described by Hatakeyama et al. of PhotopolymerS
ci. and Technology Vol. 13,
Number 4, p519-524 (2000).

The present invention has been made in view of the above circumstances, and is intended to provide a novel amine compound having a high effect of preventing a film loss of a resist, providing excellent resolution and a focus margin expanding effect, a resist material containing the same, and a resist material containing the same. It is an object to provide a pattern forming method used.

[0011]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that amine compounds containing a cyano group, particularly the following general formulas (1) and (2) ), (3) or (4) that the amine compound has a high effect in preventing the resist from being reduced in film thickness, and has a high resolution and a focus margin expanding effect.
The present invention has been made. Claim 1: An amine compound represented by the following general formulas (1), (2), (3) and (4).

Embedded image(Where R¹May be the same or different linear C 1-4
Or a branched alkylene group, R^TwoIs a hydrogen atom, or
Same or different straight-chain, branched or branched having 1 to 20 carbon atoms
Is a cyclic alkyl group, a hydroxy group, an ether
Group, carbonyl group, ester group, lactone ring, carbon
Or a cyano group. ^ThreeIs carbon number 2
~ 20 linear or branched alkylene groups,
Hydroxy group, ether group, thioether group, carbonyl
Group, ester group, thioester group or carbonate
May contain R^FourAre the same or different and have 1 to 4 carbon atoms
Is a linear or branched alkylene group. a is 1
整数 3, and a + b = 3. Claim 2: R in the general formulas (1) and (3)^TwoBut below
Represented by the general formula (5), (6), (7) or (8)
The amine compound according to claim 1, wherein

Embedded image(Where R^Five, R⁷, R^TenIs a straight-chain or straight-chain having 1 to 4 carbon atoms
Is a branched alkylene group;⁶, R⁹Is a hydrogen atom,
Or a linear, branched or cyclic C 1-20
Alkyl group, hydroxy group, ether group, ester
Group, a lactone ring or a cyano group. R^Five
And R⁶Binds to form a ring with the oxygen atom to which they are attached.
It may be formed. R⁸Is a single bond or one having 1 to 4 carbon atoms
A linear or branched alkylene group;¹¹Is charcoal
Linear, branched or cyclic alkyl having a prime number of 1 to 20
Group, a hydroxy group, an ether group, an ester group,
It may contain a couton ring. R¹²Is a straight chain having 1 to 4 carbon atoms
A chain or branched (n + 1) -valent organic group, R¹³Is the same
A linear or branched C1-C10 which may be one or different.
A branched or cyclic alkyl group; an ether group,
Stel group, hydroxy group, lactone ring, cyano group or
It may contain a rubonyl group. Also, R¹²And R ¹³,Ah
Or two R¹³Are bonded to each other and
An elementary or oxygen atom and R¹²Form a ring with the carbon atoms of
May be. n is 2, 3 or 4. Claim 3: Addition of a basic compound containing a cyano group
Resist material. Claim 4: As the basic compound containing a cyano group,
Bases represented by general formulas (1), (2), (3) and (4)
Characterized in that it contains one or more kinds of sexual compounds
The resist material according to claim 3.

Embedded image(Where R¹May be the same or different linear C 1-4
Or a branched alkylene group, R^TwoIs a hydrogen atom, or
Same or different straight-chain, branched or branched having 1 to 20 carbon atoms
Is a cyclic alkyl group, a hydroxy group, an ether
Group, carbonyl group, ester group, lactone ring, carbon
Or a cyano group. ^ThreeIs carbon number 2
~ 20 linear or branched alkylene groups,
Hydroxy group, ether group, thioether group, carbonyl
Group, ester group, thioester group or carbonate
May contain R^FourAre the same or different and have 1 to 4 carbon atoms
Is a linear or branched alkylene group. a is 1
整数 3, and a + b = 3. Claim 5: R^TwoIs the following general formula (5), (6), (7) or
Is a group represented by the formula (8).
Fees.

Embedded image(Where R^Five, R⁷, R^TenIs a straight-chain or straight-chain having 1 to 4 carbon atoms
Is a branched alkylene group;⁶, R⁹Is a hydrogen atom,
Or a linear, branched or cyclic C 1-20
Alkyl group, hydroxy group, ether group, ester
Group, a lactone ring or a cyano group. R^Five
And R⁶Binds to form a ring with the oxygen atom to which they are attached.
It may be formed. R⁸Is a single bond or one having 1 to 4 carbon atoms
A linear or branched alkylene group;¹¹Is charcoal
Linear, branched or cyclic alkyl having a prime number of 1 to 20
Group, a hydroxy group, an ether group, an ester group,
It may contain a couton ring. R¹²Is a straight chain having 1 to 4 carbon atoms
A chain or branched (n + 1) -valent organic group, R¹³Is the same
A linear or branched C1-C10 which may be one or different.
A branched or cyclic alkyl group; an ether group,
Stel group, hydroxy group, lactone ring, cyano group or
It may contain a rubonyl group. Also, R¹²And R ¹³,Ah
Or two R¹³Are bonded to each other and
An elementary or oxygen atom and R¹²Form a ring with the carbon atoms of
May be. n is 2, 3 or 4. Claim 6: (A) The amine compound according to Claim 1 or 2, (B) Organic
Solvent, (C) having acidic functional group protected by acid labile group
Alkali-insoluble or poorly soluble resin,
Base tree that becomes alkali-soluble when the fixed group is eliminated
Fat type, containing a (D) acid generator
Resist material. In a preferred embodiment, the composition further comprises (E) a dissolution inhibitor.
7. The positive resist material according to claim 6, wherein: Claim 8: (A) the amine compound according to claim 1 or 2, and (B) an organic compound.
Solvent, (C) an alkali-soluble resin,
Base resin which becomes hardly soluble in alkali by crosslinking,
(D) an acid generator, and (F) a crosslinking agent capable of crosslinking by an acid.
A negative resist material comprising: Claim 9: (1) The resist according to any one of claims 3 to 8
Step of applying a material on a substrate, (2) heat treatment
Then, through a photomask, high energy of wavelength 300 nm or less
Exposure with energy beam or electron beam (3)
After the heat treatment, a step of developing using a developing solution is performed.
A pattern forming method comprising:

Hereinafter, the present invention will be described in more detail.
The amine compound of the present invention has the following general formula (1), (2),
(3) or (4).

[0013]

Embedded image(Where R¹May be the same or different linear C 1-4
Or a branched alkylene group, R^TwoIs a hydrogen atom, or
Same or different straight-chain, branched or branched having 1 to 20 carbon atoms
Is a cyclic alkyl group, a hydroxy group, an ether
Group, carbonyl group, ester group, lactone ring, carbon
Or a cyano group. ^ThreeIs carbon number 2
~ 20 linear or branched alkylene groups,
Hydroxy group, ether group, thioether group, carbonyl
Group, ester group, thioester group or carbonate
May contain R^FourAre the same or different and have 1 to 4 carbon atoms
Is a linear or branched alkylene group. a is 1
整数 3, and a + b = 3. )

Here, the linear or branched alkylene group having 1 to ⁴ carbon atoms for R ¹ and R ⁴ includes a methylene group,
Examples include an ethylene group, a propylene group, and a butylene group. R ² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms; -Butyl group, isobutyl group, tert
-Butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, etc., and these alkyl groups include a hydroxy group, an ether group, a carbonyl group, and an ester group. ,
It may contain a lactone ring, a carbonate, or a cyano group.

In the above formulas (1) and (3), R
² may be a group represented by the following general formula (5), (6), (7) or (8).

[0016]

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In the formula, R ⁵ , R ⁷ and R ¹⁰ are a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁶ and R ⁹ are a hydrogen atom or 1 to 20 carbon atoms, particularly It is a linear, branched or cyclic alkyl group of 1 to 10, and may contain a hydroxy group, an ether group, an ester group, a lactone ring or a cyano group. R ⁵ and R ⁶ are bonded to each other, and together with the oxygen atom to which they are bonded, have 3 to 20 carbon atoms, particularly 4 to 12 carbon atoms.
May form a ring. R ⁸ is a single bond or 1 carbon atom
4 to 4 linear or branched alkylene groups;
Reference numeral ¹¹ denotes a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may include a hydroxy group, an ether group, an ester group, and a lactone ring. R ¹² has 1 to 1 carbon atoms
4 is a linear or branched (n + 1) -valent organic group. Where n is 2, 3 or 4, and therefore R
¹² is a trivalent, tetravalent or pentavalent organic group. Specifically, the following hydrocarbon groups can be mentioned.

[0018]

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R ¹³ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be the same or different, and includes an ether group, an ester group, a hydroxy group,
It may contain a lactone ring, a cyano group or a carbonyl group. Examples of the alkyl group and the alkoxy group represented by R ¹³ include the groups described above. Note that the R ¹² and R ¹³ are,
They may be bonded to each other to form a ring having 2 to 20 carbon atoms, particularly 3 to 12 carbon atoms, together with the oxygen atom to which they are bonded;
Two R ¹³ are bonded to each other and these bonded oxygen atoms,
Further, a ring having 1 to 20, especially 2 to ¹² carbon atoms may be formed together with the carbon atom of R ¹² to which these oxygen atoms are bonded.

In this case, the above equations (5), (6),
Specific examples of (7) and (8) include the following formulas (5) -1 to (5) -1.
(5) -12, (6) -1 to (6) -12, (7) -1
To (7) -17 and (8) -1 to (8) -12.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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In the above formulas (2) and (4), the group represented by the following formula (A) is specifically represented by the following formula (A) -1:
Examples of the group represented by (A) -12 can be given.

[0027]

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Specific examples of the amine compound represented by the general formula (1) include (3-diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N -Bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-
Bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl)-
3-aminopropiononitrile, N, N-bis [2-
(Methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N-
(2-cyanoethyl) -N- (2-hydroxyethyl)
Methyl-3-aminopropionate, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl)
-N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N
-(2-cyanoethyl) -N- (2-methoxyethyl)
-3-Aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3
-Aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-
Propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-
(3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl)- 3-aminopropiononitrile, diethylaminoacetonitrile,
N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2 -Methoxyethyl) aminoacetonitrile, N, N-bis [2
-(Methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl)-
Methyl 3-aminopropionate, N-cyanomethyl-N
Methyl-(2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, N-cyanomethyl-N- (2-formyloxyethyl) aminopropion Methyl acid, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile , N-cyanomethyl-N-
(2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl]
Aminoacetonitrile, N- (cyanomethyl) -N-
(3-hydroxy-1-propyl) aminoacetonitrile, N- (3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile , N, N-bis (cyanomethyl) aminoacetonitrile.

Specific examples of the amine compound represented by the general formula (2) include 1-pyrrolidinepropiononitrile,
-Piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-aziridinepropiononitrile,
Examples thereof include 1-azetidinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, and 4-morpholineacetonitrile.

Specific examples of the amine compound represented by the general formula (3) include cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-
Cyanomethyl aminopropionate, N, N-bis (2-
(Acetoxyethyl) -3-cyanomethyl 3-aminopropionate, N, N-bis (2-formyloxyethyl) -3
-Cyanomethyl aminopropionate, N, N-bis (2
-Methoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl, 3-diethylaminopropionate (2-cyanoethyl), N, N
-Bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2 -Formyloxyethyl)-
3-aminopropionic acid (2-cyanoethyl), N, N
-Bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-
Cyanoethyl), N, N-bis (2-cyanoethyl)-
Cyanomethyl 3-aminopropionate, N, N-bis (2-cyanoethyl) -3-aminopropionic acid (2-
Cyanoethyl), N, N-bis (cyanomethyl) -3-
Examples include cyanomethyl aminopropionate and N, N-bis (cyanomethyl) -3-aminopropionate (2-cyanoethyl).

Specific examples of the amine compound represented by the general formula (4) include cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, and (2-cyanoethyl) 1-pyrrolidinepropionate. , 1-piperidinepropionate (2-cyanoethyl) and 4-morpholinepropionate (2-cyanoethyl).

The nitrile-containing amine compounds of the present invention represented by the general formulas (1), (2), (3) and (4) can be selected from the following methods, for example, by the most suitable method according to the structure of the compound. It can be selected and manufactured, but is not limited to these. The details will be described below.

First, as a first method, a primary or secondary amine compound and an α, β-unsaturated nitrile compound {in the case of general formulas (1) and (2)} or a nitrile-containing α, β-unsaturated ester Compounds {in the case of general formulas (3) and (4)} can be synthesized using a Michael addition reaction of an amine.

Examples of the α, β-unsaturated nitrile compound include acrylonitrile and methacrylonitrile. Examples of the nitrile-containing α, β-unsaturated ester compound include cyanomethyl acrylate, 2-cyanoethyl acrylate, and 2-cyanoethyl methacrylate. It can be exemplified, but not limited to these.

The amount of the α, β-unsaturated nitrile compound or the nitrile-containing α, β-unsaturated ester compound used is 1.0 to 10 mol when the amine compound is a primary amine with respect to 1 mol of the amine compound. In particular, the amount is preferably 1.6 to 2.4 mol, and when the amine compound is a secondary amine, the amount is preferably 0.5 to 5.0 mol, particularly 0.8 to 1.2 mol. . The reaction is performed without a solvent or in a solvent. As the solvent, methanol, ethanol, isopropyl alcohol, t-butyl alcohol, alcohols such as ethylene glycol, hexane, heptane, benzene, toluene, hydrocarbons such as xylene, diethyl ether, dibutyl ether, tetrahydrofuran,
Ethers such as 1,4-dioxane and diglyme; chlorinated solvents such as methylene chloride, chloroform and 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 among nitriles such as acetonitrile, amines such as pyridine and triethylamine, and water depending on the reaction conditions, and used alone or as a mixture. The reaction temperature is selected in the range from 0 ° C. to the reflux temperature of the solvent according to the reaction rate. In order to increase the reaction rate in the reaction, a catalyst such as hydrochloric acid, sulfuric acid, or an inorganic acid such as nitric acid or salts thereof, p-toluenesulfonic acid, formic acid, acetic acid,
Organic acids such as oxalic acid and trifluoroacetic acid or salts thereof may be added. A polymerization inhibitor such as hydroquinone, p-methoxyphenol, benzoquinone, or phenylenediamine may be added to prevent polymerization of the α, β-unsaturated nitrile or the nitrile-containing α, β-unsaturated ester compound. The reaction time is desirably monitored by gas chromatography (GC) or thin-layer chromatography (TLC) to complete the reaction by tracking the reaction, but it is usually about 2 to 200 hours. The reaction mixture can be used directly or in an ordinary aqueous workup.
After rk-up), the mixture is concentrated under reduced pressure to give the target nitrile-containing amine compound (1), (2), (3),
Obtain (4). The obtained nitrile-containing amine compounds (1), (2), (3) and (4) are distilled if necessary.
It can be purified by a conventional method such as chromatography and recrystallization.

Next, as a second method, a primary or secondary amine compound and a haloalkyl nitrile compound {in the case of the general formulas (1) and (2)} or a nitrile-containing halocarboxylic acid ester compound} a general formula (3) In the case of (4), it can be synthesized by utilizing an N-alkylation reaction of an amine.

As the haloalkyl nitrile compound, bromoacetonitrile, chloroacetonitrile, 2-chloropropiononitrile, 3-chloropropiononitrile,
Examples thereof include 4-bromobutyronitrile and 5-bromopentanenitrile. Examples of the nitrile-containing halocarboxylic acid ester compounds include cyanomethyl chloroacetate and 2-chloroacetic acid.
Cyanoethyl, cyanomethyl 2-chloropropionate,
Examples thereof include, but are not limited to, 2-cyanoethyl 4-bromobutyrate and cyanomethyl 5-bromovalerate.

The amount of the haloalkyl nitrile compound or the nitrile-containing halocarboxylic acid ester compound used is 1.0 to 20 mol, particularly 1.6 to 4.8, when the amine compound is a primary amine, based on 1 mol of the amine compound. It is preferable that the amount be 0.5 mol to 10 mol, particularly 0.8 to 2.4 mol when the amine compound is a secondary amine. This reaction is promoted by adding a basic compound. As the basic compound to be added, pyridine, triethylamine, diisopropylethylamine, N, N-dimethylaniline, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0]
Amines such as undec-7-ene, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate,
One selected from inorganic bases such as sodium carbonate and sodium hydrogen carbonate can be used alone or in combination of two or more. The amount of the basic compound used is 0.1 to 10 mol, particularly 0.8 to 10 mol, per mol of the haloalkyl nitrile compound or the nitrile-containing halocarboxylic acid ester compound.
Desirably, it is 2.0 mol. Further, a catalyst may be added to accelerate the reaction. Examples of the catalyst include sodium iodide and tetrabutylammonium iodide. The amount of the catalyst is 0.001 to 1 mol based on 1 mol of the haloalkylnitrile compound or the nitrile-containing halocarboxylic acid ester compound.
It is desirably 0.5 mol, preferably 0.005 to 0.1 mol. The reaction is performed without a solvent or in a solvent. As the solvent, methanol, ethanol, isopropyl alcohol, t-butyl alcohol, alcohols such as ethylene glycol, hexane, heptane, benzene, toluene, hydrocarbons such as xylene, diethyl ether,
Ethers such as dibutyl ether, tetrahydrofuran, 1,4-dioxane and diglyme; chlorinated solvents such as methylene chloride, chloroform and 1,2-dichloroethylene; N, N-dimethylformamide; N, N-dimethylacetamide; dimethyl sulfoxide Aprotic polar solvents such as 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 and triethylamine Such amines and water can be selected depending on the reaction conditions and used alone or in combination. The reaction temperature is selected in the range from 0 ° C. to the reflux temperature of the solvent according to the reaction rate. The reaction time is preferably from the viewpoint of the yield by pursuing the reaction by gas chromatography (GC) or thin layer chromatography (TLC) from the viewpoint of the yield.
It is about 200 hours. The reaction mixture is filtered or concentrated under reduced pressure after usual aqueous work-up, whereby the desired nitrile-containing amine compounds (1), (2), (3) and (4) are obtained. The obtained nitrile-containing amine compounds (1), (2),
If necessary, (3) and (4) can be purified by a conventional method such as distillation, chromatography and recrystallization.

The resist material of the present invention contains an amine compound containing a cyano group. In this case, as the amine compound containing a cyano group, a compound represented by the above general formula (1), (2), (3) or (4) is preferable.

In this case, the compounding amount of the amine compound in the resist material of the present invention is determined by the total base resin
0.001 to 2 parts, especially 0.01 to 1 part, is suitable for parts (parts by weight, hereinafter the same). If the amount is less than 0.001 part, the compounding effect is not obtained, and if the amount is more than 2 parts, the sensitivity may be excessively lowered.

The resist material of the present invention contains the above-mentioned amine compound. The resist material may be either a positive type or a negative type, and is particularly used as a chemically amplified positive type resist material or a negative type resist material.

In this case, as the positive resist material,
(A) the amine compound, (B) an organic solvent, and (C) an alkali-insoluble or poorly soluble resin having an acidic functional group protected by an acid labile group, wherein the acid labile group is eliminated. It is preferable to contain a base resin that becomes alkali-soluble, and (D) an acid generator, and if necessary, further contain (E) a dissolution inhibitor.

As the negative resist material,
(A) the amine compound, (B) an organic solvent, (C) an alkali-soluble resin, a base resin which becomes hardly soluble in alkali by crosslinking with a crosslinking agent, (D) an acid generator,
(F) Those containing a crosslinking agent capable of crosslinking by an acid are preferred.

The organic solvent (B) used in the present invention may be any organic solvent capable of dissolving an acid generator, a base resin, a dissolution inhibitor and the like. 100 to 5,000 parts per part, especially 2
00 to 3,000 parts are used. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol,
-Methyl-3-methoxybutanol, 1-methoxy-2
Alcohols such as -propanol and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethers such as ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono -T
Esters such as tert-butyl ether acetate are mentioned, and one of these can be used alone or in combination of two or more, but is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate, which is a safe solvent, And a mixed solvent thereof are preferably used.

The base resin used as the component (C) is used as a resist for a KrF excimer laser.
Polyhydroxystyrene (PHS), a copolymer of PHS with styrene, (meth) acrylate, maleimide N carboxylate, and a resist for ArF excimer laser include (meth) acrylate,
Alternating copolymer system of norbornene and maleic anhydride, alternating copolymer system of tetracyclododecene and maleic anhydride,
Polynorbornene, metathesis polymerization based on ring-opening polymerization, KrF, ArF for F ₂ excimer laser
Examples of the polymer include a fluorine-substituted polymer and a copolymer with tetrafluoroethylene, but the polymer is not limited to these polymer-based polymers. In the case of a positive resist, the dissolution rate of an unexposed portion is generally reduced by partially substituting a hydrogen atom of a phenolic hydroxyl group or a carboxyl group or a hydroxyl group of a fluorinated alkyl alcohol with an acid labile group. .

As the acid labile group of the base resin, various types are selected. It is preferable that the alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like.

[0047]

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In the formula (9), R ¹² has 4 to 2 carbon atoms.
0, preferably a tertiary alkyl group having 4 to 15 carbon atoms, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the general formula (1)
1) represents a group represented by 1), and specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group,
1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-
Examples thereof include a 2-cyclopentenyl group, a 1-ethyl-2-cyclohexenyl group, and a 2-methyl-2-adamantyl group. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and dimethyl-tert.
And the like. Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2 group.
-Oxooxolan-5-yl group and the like. a1
Is an integer of 0 to 6.

In the formula (10), R ¹³ and R ^{14 each} represent a hydrogen atom or a linear group having 1 to 18, preferably 1 to 10 carbon atoms;
A branched or cyclic alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl And an n-octyl group. R ¹⁵ has 1 to 1 carbon atoms
18, preferably a monovalent hydrocarbon group which may have 1 to 10 hetero atoms such as an oxygen atom, and is a linear, branched or cyclic alkyl group, and a part of these hydrogen atoms is a hydroxyl group , An alkoxy group, an oxo group, an amino group, an alkylamino group or the like, and specific examples thereof include the following substituted alkyl groups.

[0050]

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[0051] R ¹³ and R ^14, and R ¹³ and R ^15, R ¹⁴ and R ¹⁵ may form a ring, when they form a ring R ^13,
R ¹⁴ and R ¹⁵ each have 1 to 18 carbon atoms, preferably 1 to
And 10 linear or branched alkylene groups.

Specific examples of the acid labile group of the above formula (9) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group,
1,1-diethylpropyloxycarbonyl group, 1,1
-Diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-
2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1
-Ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

Further, substituents represented by the following formulas (9) -1 to (9) -9 can also be mentioned.

[0054]

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Here, R ⁰¹ is the same or different and is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁰² is a hydrogen atom or a carbon atom. It is a linear, branched or cyclic alkyl group of the formulas 1 to 10.

R ⁰³ represents the same or different linear or branched or cyclic alkyl group having 2 to 10 carbon atoms;
Or it is a C6-C20 aryl group.

Among the acid labile groups represented by the above formula (10), those having a linear or branched structure are represented by the following formula (10)
-1 to (10) -23.

[0058]

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[0059]

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Among the acid labile groups represented by the above formula (10), cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, -Methyltetrahydropyran-2-yl group and the like.

The general formula (10a) or (10
The base resin may be cross-linked intramolecularly or intramolecularly by the acid labile group represented by b).

[0062]

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In the formula, R ¹⁹ and R ²⁰ represent a hydrogen atom or a carbon atom
And represents a linear, branched or cyclic alkyl group of 1 to 8. Alternatively, R ¹⁹ and R ²⁰ may combine to form a ring, and when forming a ring, R ¹⁹ and R ²⁰ represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ²¹ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b and d are 0 or 1 to 10, preferably 0 or 1 to 5;
It is an integer of 7. A represents a (c + 1) -valent carbon number of 1 to 50;
Represents an aliphatic or alicyclic saturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed or a part of a hydrogen atom bonded to the carbon atom. It may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-
O-, -NHCO-O- or -NHCONH- is shown.

In this case, A is preferably a divalent, tetravalent, linear or branched alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, or a C6 to C30 These are arylene groups, and these groups may have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. C is preferably an integer of 1 to 3.

The crosslinked acetal groups represented by the general formulas (10a) and (10b) are specifically represented by the following formula (10) -2
4 to (10) -35.

[0066]

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Next, in the formula (11), R ¹⁶ , R ¹⁷ , R
¹⁸ is a monovalent hydrocarbon group, typically a straight, branched or cyclic alkyl group of 1 to 20 carbon atoms, oxygen, sulfur, nitrogen, which may contain a hetero atom such as fluorine, R ¹⁶ and R
¹⁷ , R ¹⁶ and R ¹⁸ , and R ¹⁷ and R ¹⁸ may combine with each other to form a ring having 3 to 20 carbon atoms.

The tertiary alkyl group represented by the formula (11) includes a tert-butyl group, a triethylcarbyl group,
-Ethylnorbonyl group, 1-methylcyclohexyl group,
1-ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, te
An rt-amyl group and the like can be mentioned.

Further, specific examples of the tertiary alkyl group include the following formulas (11) -1 to (11) -18.

[0070]

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In the formulas (11) -1 to (11) -18, R ²²
Represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group such as a phenyl group having 6 to 20 carbon atoms. R ²³ and R ^{25 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²⁴ represents an aryl group such as a phenyl group having 6 to 20 carbon atoms.

Further, the following formulas (11) -19 and (11) -2
As shown in 0, the polymer may be crosslinked within or between the molecules, including a divalent or higher valent alkylene group and an arylene group R ²⁶ . Equations (11) -19, (1
1) In -20, R ²² is the same as described above, and R ²⁶ is C 1-2.
0 represents a linear, branched or cyclic alkylene group or an arylene group such as a phenylene group, and may contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
b1 is an integer of 1 to 3.

[0073]

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Further, R ¹⁶ , R ¹⁷ , and R ¹⁸ in the formula (11) may have a hetero atom such as oxygen, nitrogen, sulfur, etc. Specifically, the following formulas (12) -1 to (12) 12) -7.

R ¹² in the formulas (9), (10) and (11)
R ¹⁵ and R ¹⁸ represent a phenyl group, a p-methylphenyl group, p
-Ethylphenyl group, unsubstituted or substituted aryl group such as alkoxy-substituted phenyl group such as p-methoxyphenyl group,
Examples include an aralkyl group such as a benzyl group and a phenethyl group, an alkyl group represented by the following formulas (12) -1 to (12) -5, and an oxoalkyl group represented by the formulas (12) -6 to (12) -9. be able to.

[0076]

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Examples of the trialkylsilyl group in which each alkyl group used as the acid labile group has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group,
a tert-butyldimethylsilyl group;

The weight average molecular weight of the base resin as the component (C) is preferably 5,000 to 100,000, and if it is less than 5,000, the film formability and resolution may be poor. , More than 100,000, the resolution may be poor.

The acid generator of the component (D) includes an onium salt of the following general formula (13), a diazomethane derivative of the formula (14), a glyoxime derivative of the formula (15), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like. (R ³⁰ ) _b M ⁺ K ⁻ (13) (where R ³⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 7 to 12 carbon atoms) represents an aralkyl group, M ⁺ represents iodonium, sulfonium, K ^- represents a non-nucleophilic counter ion, b is 2 or 3).

As the alkyl group for R ^30, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. As the aryl group, a phenyl group,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 2,2,2-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 2,3,4,5,6-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0081]

Embedded image (However, R ³¹ and R ³² are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or a halogenated aryl group having 6 to 12 carbon atoms, or a carbon atom having 7 to 12 carbon atoms. 12 represents an aralkyl group.)

Examples of the alkyl group of R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert.
An alkoxyphenyl group such as -butoxyphenyl group, 2-
Examples thereof include an alkylphenyl group such as a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 2,3,4,5,6-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0083]

Embedded image (Provided that R ³³ , R ³⁴ and R ³⁵ are linear having 1 to 12 carbon atoms;
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms or an aryl group, or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may be bonded to each other to form a cyclic structure. In the case of forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ³³ , R ³⁴ and R ³⁵ , the same groups as described for R ³¹ and R ³² can be mentioned. The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

More specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate Onium salts such as bis (benze) Sulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane, bis (xylene sulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (cyclopentyl sulfonyl) diazomethane, bis (n- butylsulfonyl)
Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (t
tert-butylsulfonyl) diazomethane, bis (n-
Amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1
-(Tert-butylsulfonyl) diazomethane, 1-
Diazomethane derivatives such as cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane and 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane; bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime , Bis-o-
(P-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, Bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o-
(N-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o −
(N-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2
-Methyl-3,4-pentanedione glyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α
-Dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α
-Dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-
o- (p-tert-butylbenzenesulfonyl) -α
Glyoxime derivatives such as -dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2
Β-ketosulfone derivatives such as-(p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; 2,6-dinitro p-toluenesulfonate Nitrobenzylsulfonate derivatives such as benzyl and 2,4-dinitrobenzyl p-toluenesulfonate;
Tris (methanesulfonyloxy) benzene, 1,2,2
Sulfonate derivatives such as 3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-
Tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,
Imido-yl-sulfonate derivatives such as 3-dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, etc., and triphenylsulfonium trifluoromethanesulfonate; Triphenylmethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-
Onium such as tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), and tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate Salt, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, Bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl)
Diazomethane derivatives such as diazomethane and bis (tert-butylsulfonyl) diazomethane; bis-o- (p-
Glyoxime derivatives such as toluenesulfonyl) -α-dimethylglyoxime and bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, and naphthoquinonediazidosulfonic acid ester derivatives are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect. However, the fine adjustment of the profile can be performed by combining the two.

The compounding amount of the acid generator is 100
Parts to 0.2 to 50 parts, particularly preferably 0.5 to 40 parts, and if less than 0.2 part, the amount of acid generated at the time of exposure is small, and sensitivity and resolution may be poor. If it exceeds 50 parts, the transmittance of the resist may decrease, and the resolution may be poor.

Next, as the dissolution inhibitor as the component (E), a compound having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, particularly a low molecular weight phenol of 2,500 or less, or Compounds in which part or all of the carboxylic acid derivative is substituted with an acid-labile substituent can be mentioned.

Examples of the phenol or carboxylic acid derivative having a molecular weight of 2,500 or less include bisphenol A, bisphenol H, bisphenol S, 4,4-bis (4 ′
-Hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-
Hydroxyphenyl) ethane, phenolphthalein,
Thymolphthalein and the like, as The acid labile substituents are the same as those for R ^4.

Examples of the dissolution inhibitor preferably used include bis (4- (2'-tetrahydropyranyloxy)
Phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert
-Butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-
tert-butoxycarbonylmethyloxyphenyl)
Methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1′-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″)
-Tetrahydropyranyloxy)) propane, 2,2-
Bis (4 '-(2 "-tetrahydrofuranyloxy)
Phenyl) propane, 2,2-bis (4′-tert-
Butoxyphenyl) propane, 2,2-bis (4′-t
tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′
-(1 ''-ethoxyethoxy) phenyl) propane,
2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4′-
Tert-butyl (2 ″ -tetrahydropyranyloxy) phenyl) valerate, 4,4-bis (4 ′-(2 ″
-Tetrahydrofuranyloxy) phenyl) valeric acid te
tert-butyl, 4,4-bis (4'-tert-butoxyphenyl) tert-butyl valerate, 4,4-bis (4-tert-butoxycarbonyloxyphenyl)
Tert-butyl valerate, 4,4-bis (4′-ter
tert-butyl t-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate,
Tert-Butyl 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate, tris (4-
(2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) ) Methane, Tris (4-te
rt-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4 '-
(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-
Tris (4′-tert-butoxyphenyl) ethane,
1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 '-(1'-
Ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane and the like can be mentioned.

The addition amount of the dissolution inhibitor in the resist material of the present invention is not more than 20 parts, preferably not more than 15 parts with respect to 100 parts of solids in the resist material. If the amount is more than 20 parts, the monomer component increases and the heat resistance of the resist material decreases.

Examples of the crosslinking agent as the component (F) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule. ) Melamine and the like are preferably used. For example, N, N, N ′, N′-tetramethoxymethylurea and hexamethoxymethylmelamine, tetraalkoxymethyl-substituted glycolurils such as tetrahydroxymethyl-substituted glycolurils and tetramethoxymethylglycoluril, substituted and unsubstituted Phenol compounds such as bis-hydroxymethylphenols and bisphenol A and condensates such as epichlorohydrin are exemplified. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril or 1,3,5,7-tetramethoxymethylglycoluril or 1,3,5,7-tetramethoxymethylglycoluril.
5,7-tetrahydroxymethylglycoluril,
2,6-dihydroxymethyl p-cresol, 2,6-
Dihydroxymethylphenol, 2,2 ', 6,6'-
Tetrahydroxymethylbisphenol A, and 1,4
-Bis- [2- (2-hydroxypropyl)]-benzene, N, N, N ', N'-tetramethoxymethylurea and hexamethoxymethylmelamine. The addition amount is optional, but is 1 to the total solid content in the resist material.
It is 25 parts by weight, preferably 5 to 20 parts by weight. These may be added alone or in combination of two or more.

In addition to the basic compound of the present invention, one or more bases other than the conventionally used base of the present invention can be used in combination. Conventionally used bases include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl. A nitrogen-containing compound having a group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group,
Examples include an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

As aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine,
sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. Illustrative, secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylua Tertiary aliphatic amines such as trimethylamine, triethylamine, tri-n-propyl, and the like. Amine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine,
Tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N,
N ', N'-tetramethylmethylenediamine, N, N,
N ′, N′-tetramethylethylenediamine, N, N,
N ', N'-tetramethyltetraethylenepentamine and the like are exemplified.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.). , P-toluenesulfonate and the like. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinoline. Diol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-
Diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1
-Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine,
1- (2-hydroxyethyl) -2-pyrrolidinone, 3
-Piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (B) -100 and (B) -101 can be blended.

[0097]

Embedded image (Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ , and R ⁴⁸ are each independently a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ^{50 each} represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group;
⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ , and R ⁴⁹ and R ⁵⁰ may be bonded to each other to form a ring. S, T, and U each represent an integer of 0 to 20. However, when S, T, U = 0, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ ,
R ⁵⁰ does not include a hydrogen atom. )

Here, the alkylene group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
-10, more preferably 1-8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-
Examples include a pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

The alkyl group of R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, which may be linear, branched or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

Further, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ^46
46, if R ⁴⁴ and R ⁴⁵ and R ^46, R ⁴⁹ and R ⁵⁰ form rings, the number of carbon atoms in the ring is 1 to 20, more preferably 1 to
8, more preferably 1 to 6, and in these rings, an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms may be branched.

S, T and U are each an integer of 0 to 20, more preferably 1 to 10, further preferably 1 to 8.

Specific examples of the compounds of the above formulas (B) -100 and (B) -101 include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, tris [ 2-{(2-methoxyethoxy) methoxy} ethyl] amine, tris {2- (2
-Methoxyethoxy) ethyl @ amine, tris-2-
(1-methoxyethoxy) ethyl {amine, tris} 2
-(1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16, 21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosan, 4,7,13,18-tetraoxa-1,
10-diazabicyclo [8.5.5] eicosan, 1,
4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4,1,
-Aza-15-crown-5, 1-aza-18-crown-6 and the like.

The resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving coating properties, in addition to the above components. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

The surfactant is preferably a nonionic surfactant, and examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45, S-381, S-383 (all manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "," F-1
71 "," F-172 "," F-173 "," F-17 "
7 "(all manufactured by Dainippon Ink and Chemicals, Inc.)," X-7
0-092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are exemplified. Further, in order to improve the wettability of the developer, a nonionic surfactant having various hydrocarbon chains can be added.

A pattern can be formed by using the resist material of the present invention by a known lithography technique. .1 to 1.0 μ
m on a hot plate.
~ 200 ° C, 10 seconds ~ 10 minutes, preferably 80 ~ 15
Prebake at 0 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, a high energy ray such as an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² . Preferably 10 to 100
After irradiating to about mJ / cm ^2, post exposure bake (PEB) is performed on a hot plate at 60 to 150 ° C. for 10 seconds to 5 minutes, preferably at 80 to 130 ° C. for 30 seconds to 3 minutes. Further, using a developing solution of an aqueous alkali solution such as 0.1 to 5%, preferably 2 to 3% of tetramethylammonium hydroxide (TMAH),
Dipping for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes (d
ip) method, paddle method, spray method (sp
(ray) method to form a target pattern on the substrate by performing development. In addition, the material of the present invention is preferably a deep ultraviolet ray or excimer laser having a wavelength of 254 to 120 nm, particularly an ArF having a wavelength of 193 nm, among high energy rays.
57 nm F ₂ , 146 nm Kr ₂ , 134 nm Kr
Excimer laser such as Ar, 126 nm Ar _2, etc.
It is most suitable for fine patterning by 3 nm, 11 nm, and 8 nm soft X-rays, EBs, and X-rays. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0106]

The resist material of the present invention has a high effect in preventing the resist from being reduced in film thickness, and has a high resolution and a high focus margin expanding effect.

[0107]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

[Synthesis Example] The basic compound of the present invention was synthesized according to the following formulation. [Synthesis Example 1] Synthesis of 3- (diethylamino) propiononitrile (Amine 1) 5.31 g of acrylonitrile was added to 7.31 g of diethylamine at 20 to 30 ° C, and left for 16 hours. 0.2 g (quantitative).

[Synthesis Example 2] Synthesis of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile (A
min 2) N, N-bis (2
-Hydroxyethyl) -3-aminopropiononitrile was obtained.

Synthesis Example 3 Synthesis of N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile (A
3) N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile 15.0 g, triethylamine 25.
22.3 g of acetic anhydride was added to a mixture of 0 g, 50 mg of 4-dimethylaminopyridine and 50 g of anhydrous tetrahydrofuran at 20 to 30 ° C., followed by stirring for 10 hours. After adding 10 g of water and stopping the reaction, liquid separation and water washing were performed. After concentration under reduced pressure,
Purification was performed by distillation under reduced pressure, and N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile 20.9
g was obtained (boiling point: 136 ° C./30 Pa, yield 89%). IR (thin film): ν = 2960, 2838, 2249, 1
738, 1458, 1373, 1240, 1043cm
^{-1 1 H-NMR (300MHz in} CDCl 3): δ =
2.03 (6H, s), 2.44 (2H, t, J = 6.
9 Hz), 2.81 (4H, t, J = 6.0 Hz),
2.90 (2H, t, J = 6.9 Hz), 4.10 (4
H, t, J = 6.0 Hz).

[Synthesis Example 4] Synthesis of N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile (Amine 4) N, N-bis (2-hydroxyethyl) -3-aminopropiono A mixture of 15.0 g of nitrile and 150 g of formic acid was stirred at 70 ° C. for 10 hours. After concentration under reduced pressure, the residue was diluted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, and concentrated again under reduced pressure to obtain N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile.

Synthesis Example 5 Synthesis of N, N-bis (2-methoxyethyl) -3-aminopropiononitrile (Am
ine 5) bis (2-methoxyethyl) instead of diethylamine
By the same method as in Synthesis Example 1 except that an amine was used,
N, N-bis (2-methoxyethyl) -3-aminopropiononitrile was obtained (boiling point: 87 ° C./60 Pa, yield: 91%). IR (thin film): ν = 2927, 2877, 2825, 2
247, 1458, 1363, 1196, 1149, 1
^{119,1070,1012,960cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.46 (2H, t, J = 6.9 Hz), 2.74 (4
H, t, J = 5.6 Hz), 2.94 (2H, t, J =
6.9 Hz), 3.31 (6H, s), 3.44 (4
H, t, J = 5.6 Hz).

[Synthesis Example 6] Synthesis of N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile (Amine 6) Bis [2- (methoxymethoxy) ethyl] amine instead of diethylamine N, N-bis [2- (methoxymethoxy) ethyl] in the same manner as in Synthesis Example 1 except that
-3-Aminopropiononitrile was obtained.

[Synthesis Example 7] N- (2-cyanoethyl)-
Synthesis of methyl N- (2-methoxyethyl) -3-aminopropionate (Amine 7) To 10.0 g of 2-methoxyethylamine was added 11.4 g of methyl acrylate at 20 to 30 ° C, and the mixture was allowed to stand for 2 hours.
Next, 15.0 g of acrylonitrile was added, and 20 hours, 7
Heated to 0 ° C. Concentration under reduced pressure gave methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate.

[Synthesis Example 8] N- (2-cyanoethyl)-
Synthesis of Methyl N- (2-hydroxyethyl) -3-aminopropionate (Amine 8) N- (2-hydroxyethyl) -3-aminopropionate
(2-cyanoethyl) -N- (2-hydroxyethyl)
Methyl -3-aminopropionate was synthesized.

Synthesis Example 9 Synthesis of methyl N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropionate (Amine 9) N, N-bis (2-hydroxyethyl) -3 N- (2-cyanoethyl) in place of -aminopropiononitrile
N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-amino was obtained in the same manner as in Synthesis Example 3 except that methyl-N- (2-hydroxyethyl) -3-aminopropionate was used. Methyl propionate was synthesized.

[Synthesis Example 10] N- (2-cyanoethyl)
Synthesis of -N-ethyl-3-aminopropiononitrile (Amine 10) 30 g of acrylonitrile was added to 10.0 g of ethylamine.
The mixture was added at 0 to 30 ° C, and then heated to 70 ° C and stirred for 100 hours. Purification was performed by distillation under reduced pressure to obtain N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile.

[Synthesis Example 11] N- (2-cyanoethyl)
Synthesis of -N- (2-hydroxyethyl) -3-aminopropiononitrile (Amine 11) N- (2-cyanoethyl) was prepared in the same manner as in Synthesis Example 10 except that 2-aminoethanol was used instead of ethylamine. ) -N- (2-hydroxyethyl) -3-aminopropiononitrile was synthesized.

Synthesis Example 12 Synthesis of N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile (Amine 12) N, N-bis (2-hydroxyethyl) -3 N- (2-cyanoethyl) in place of -aminopropiononitrile
N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-amino was obtained in the same manner as in Synthesis Example 3 except that -N- (2-hydroxyethyl) -3-aminopropiononitrile was used. Propiononitrile was synthesized. IR (thin film): ν = 2960, 2848, 2249, 1
736, 1466, 1423, 1373, 1240, 1
^{144,1041cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.05 (3H, s), 2.47 (4H, t, J = 6.
8Hz), 2.82 (2H, t, J = 5.6Hz),
2.92 (4H, t, J = 6.8 Hz), 4.12 (2
H, t, J = 5.6 Hz).

[Synthesis Example 13] N- (2-cyanoethyl)
Synthesis of -N- (2-formyloxyethyl) -3-aminopropiononitrile (Amine 13) N- (2-cyanoethyl was used instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile )
N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-by the same method as in Synthesis Example 4 except that -N- (2-hydroxyethyl) -3-aminopropiononitrile was used. Aminopropiononitrile was synthesized.

[Synthesis Example 14] N- (2-cyanoethyl)
Synthesis of -N- (2-methoxyethyl) -3-aminopropiononitrile (Amine 14) N- (2
-Cyanoethyl) -N- (2-methoxyethyl) -3-
Aminopropiononitrile was synthesized (boiling point: 130 ° C.
/ 19 Pa). IR (thin film): ν = 2931,287
7, 2845, 2247, 1464, 1421, 136
7,1267,1252,1198,1146,111
^{7,1076,1043,968cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.47 (4H, t, J = 6.9 Hz), 2.76 (2
H, t, J = 5.3 Hz), 2.99 (4H, t, J =
6.9 Hz), 3.32 (3H, s), 3.45 (2
H, t, J = 5.3 Hz).

[Synthesis Example 15] N- (2-cyanoethyl)
Synthesis of -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile (Amine 15) A method similar to that of Synthesis Example 10 was used except that 2- (methoxymethoxy) ethylamine was used instead of ethylamine. N- (2-Cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile was synthesized.

[Synthesis Example 16] N- (2-cyanoethyl)
Synthesis of -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile (Amine 16) A method similar to that of Synthesis Example 10 except that 3-hydroxy-1-propylamine was used instead of ethylamine. ,
N- (2-cyanoethyl) -N- (3-hydroxy-1
-Propyl) -3-aminopropiononitrile was synthesized.

[Synthesis Example 17] N- (3-acetoxy-1)
Synthesis of (-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile (Amine 17) N- (2-cyanoethyl) -3-aminopropiononitrile instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile Cyanoethyl)
N- (3-acetoxy-1-propyl) -N was prepared in the same manner as in Synthesis Example 3 except that -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile was used.
-(2-Cyanoethyl) -3-aminopropiononitrile was synthesized (boiling point: 173 ° C / 20 Pa, yield: 95).
%). IR (thin film): ν = 2960, 2839, 2247, 1
732, 1466, 1423, 1367, 1246, 1
^{138,1087,1045cm -1 1 H-NMR (270MHz} in CDCl 3): δ =
1.77 (2H, tt, J = 7.2, 6.2 Hz),
2.03 (3H, s), 2.46 (4H, t, J = 6.
9Hz), 2.62 (2H, t, J = 7.2Hz),
2.85 (4H, t, J = 6.9 Hz), 4.13 (2
H, t, J = 6.2 Hz).

[Synthesis Example 18] N- (2-cyanoethyl)
Synthesis of -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile (Amine 18) Instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N- ( 2-cyanoethyl)
N- (2-cyanoethyl) -N- (3-formyloxy-1) was obtained in the same manner as in Synthesis Example 4 except that -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile was used. -Propyl) -3-aminopropiononitrile was synthesized.

[Synthesis Example 19] N- (2-cyanoethyl)
Synthesis of —N-tetrahydrofurfuryl-3-aminopropiononitrile (Amine 19) N-tetrahydrofurfurylamine was prepared in the same manner as in Synthesis Example 10 except that tetrahydrofurfurylamine was used instead of ethylamine.
(2-cyanoethyl) -N-tetrahydrofurfuryl-
3-Aminopropiononitrile was synthesized.

[Synthesis Example 20] Synthesis of N, N-bis (2-cyanoethyl) -3-aminopropiononitrile (Am
ine 20) After adding 50 g of acrylonitrile to 10 g of a 28% aqueous ammonia solution at 0 ° C., the temperature was raised to 100 ° C., and the mixture was stirred for 100 hours. After concentration under reduced pressure, purify by vacuum distillation,
N, N-bis (2-cyanoethyl) -3-aminopropiononitrile was obtained.

[Synthesis Example 21] Synthesis of diethylaminoacetonitrile (Amine 21) 12.0 g of bromoacetonitrile was added to 14.6 g of diethylamine at 0 ° C, and the temperature was raised to 20 ° C over 10 hours. Ethyl acetate was added, and the resulting solid was filtered off and distilled to obtain diethylaminoacetonitrile (boiling point: 1
70 ° C, 90% yield). IR (thin film): ν = 2976, 2222, 1461, 1
389, 1322, 1206, 1093, 984 cm ^{-1 13} C-NMR (75 MHz in CDCl ₃ ): δ =
12.6, 40.5, 47.9, 114.8.

[Synthesis Example 22] Synthesis of N, N-bis (2-hydroxyethyl) aminoacetonitrile (Amine
22) N, N-bis (2-hydroxyethyl) aminoacetonitrile was synthesized in the same manner as in Synthesis Example 21 except that diethanolamine was used instead of diethylamine.

[Synthesis Example 23] Synthesis of N, N-bis (2-acetoxyethyl) aminoacetonitrile (Amine
23) By the same method as in Synthesis Example 3 except that N, N-bis (2-hydroxyethyl) aminoacetonitrile was used instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile was synthesized (boiling point: 1
20 ° C / 25 Pa). IR (thin film): ν = 2962, 2839, 2222, 1
740,1651,1433,1371,1234,1
^{045cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.04 (6H, s), 2.83 (4H, t, J = 5.
5 Hz), 3.68 (2H, s), 4.14 (4H,
t, J = 5.5 Hz).

[Synthesis Example 24] Synthesis of N, N-bis (2-formyloxyethyl) aminoacetonitrile (Ami
ne 24) By the same method as in Synthesis Example 4 except that N, N-bis (2-hydroxyethyl) aminoacetonitrile was used instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile. , N, N-bis (2-formyloxyethyl) aminoacetonitrile.

[Synthesis Example 25] Synthesis of N, N-bis (2-methoxyethyl) aminoacetonitrile (Amine
25) bis (2-methoxyethyl) instead of diethylamine
By the same method as in Synthesis Example 21 except that an amine was used,
N, N-bis (2-methoxyethyl) aminoacetonitrile was synthesized.

[Synthesis Example 26] Synthesis of N, N-bis [2- (methoxymethoxy) ethyl] aminoacetonitrile (Amine 26) Except that bis [2- (methoxymethoxy) ethyl] amine was used instead of diethylamine According to a method similar to that of Synthesis Example 21, N, N-bis [2- (methoxymethoxy)
[Ethyl] aminoacetonitrile was synthesized.

[Synthesis Example 27] N-cyanomethyl-N-
Synthesis of methyl (2-methoxyethyl) -3-aminopropionate (Amine 27) To 10.0 g of 2-methoxyethylamine was added 11.4 g of methyl acrylate at 20 to 30 ° C, and the mixture was allowed to stand for 2 hours.
Next, 7.92 g of bromoacetonitrile was added and added for 20 hours.
Heated to 0 ° C. After diluting with ethyl acetate and filtering off the solid, the mixture was concentrated under reduced pressure to obtain methyl N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate.

[Synthesis Example 28] N-cyanomethyl-N-
Synthesis of Methyl (2-Hydroxyethyl) -3-Aminopropionate (Amine 28) In the same manner as in Synthesis Example 27 except that 2-aminoethanol was used instead of 2-methoxyethylamine,
-Cyanomethyl-N- (2-hydroxyethyl) -3-
Methyl aminopropionate was synthesized.

[Synthesis Example 29] Synthesis of methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate (Amine 29) N, N-bis (2-hydroxyethyl) -3-aminopropiono N-cyanomethyl-N- instead of nitrile
By the same method as in Synthesis Example 3 except that methyl (2-hydroxyethyl) -3-aminopropionate was used, N-
Methyl (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate was synthesized.

[Synthesis Example 30] N-cyanomethyl-N-
Synthesis of (2-hydroxyethyl) aminoacetonitrile (Amine 30) 6.11 g of ethanolamine, 20. triethylamine.
12.0 g of bromoacetonitrile was added to 2 g of the mixture at 20 to 30 ° C, and the mixture was heated to 70 ° C for 20 hours. After diluting with ethyl acetate and filtering off the solid matter, the filtrate was concentrated under reduced pressure to obtain N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile.

[Synthesis Example 31] Synthesis of N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile (Amine 31) Replacement of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile N-cyanomethyl-N-
N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile was synthesized in the same manner as in Synthesis Example 3 except that (2-hydroxyethyl) aminoacetonitrile was used.

[Synthesis Example 32] N-cyanomethyl-N-
Synthesis of (2-formyloxyethyl) aminoacetonitrile (Amine 32) N-cyanomethyl-N- instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile
N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile was synthesized in the same manner as in Synthesis Example 4 except that (2-hydroxyethyl) aminoacetonitrile was used.

[Synthesis Example 33] N-cyanomethyl-N-
Synthesis of (2-methoxyethyl) aminoacetonitrile (Amine 33) In the same manner as in Synthesis Example 30, except that (2-methoxyethyl) amine was used instead of ethanolamine, N
-Cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile was synthesized.

[Synthesis Example 34] N-cyanomethyl-N-
Synthesis of [2- (methoxymethoxy) ethyl] aminoacetonitrile (Amine 34) N-cyanomethyl- was prepared in the same manner as in Synthesis Example 30 except that [2- (methoxymethoxy) ethyl] amine was used instead of ethanolamine. N- [2- (methoxymethoxy) ethyl] aminoacetonitrile was synthesized.

[Synthesis Example 35] N- (cyanomethyl) -N
Synthesis of-(3-hydroxy-1-propyl) aminoacetonitrile (Amine 35) In the same manner as in Synthesis Example 30, except that 3-amino-1-propanol was used instead of ethanolamine, N
-(Cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile was synthesized.

[Synthesis Example 36] N- (3-acetoxy-1)
Synthesis of -propyl) -N- (cyanomethyl) aminoacetonitrile (Amine 36) N- (cyanomethyl) -N instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile
N- was obtained in the same manner as in Synthesis Example 3 except that-(3-hydroxy-1-propyl) aminoacetonitrile was used.
(3-Acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile was synthesized.

[Synthesis Example 37] N-cyanomethyl-N-
Synthesis of (3-formyloxy-1-propyl) aminoacetonitrile (Amine 37) N- (cyanomethyl) -N instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile
N- was obtained in the same manner as in Synthesis Example 4 except that-(3-hydroxy-1-propyl) aminoacetonitrile was used.
Cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile was synthesized.

[Synthesis Example 38] Synthesis of N, N-bis (cyanomethyl) aminoacetonitrile (Amine 38) 28% ammonia aqueous solution, triethylamine 50.0 g
Was added to the mixture at 0 ° C., and the mixture was heated to 70 ° C. for 20 hours. After diluting with ethyl acetate and filtering off solids, the mixture was concentrated under reduced pressure to obtain N, N-bis (cyanomethyl) aminoacetonitrile.

[Synthesis Example 39] Synthesis of 1-pyrrolidinepropiononitrile (Amine 39) 5.31 g of acrylonitrile was added to 7.11 g of pyrrolidine at 20 to 30 ° C, followed by stirring for 2 hours. Purification was performed by distillation under reduced pressure to obtain 1-pyrrolidinepropiononitrile.

[Synthesis Example 40] Synthesis of 1-piperidinepropiononitrile (Amine 40) 1-piperidinepropiononitrile was synthesized in the same manner as in Synthesis Example 39 except that piperidine was used instead of pyrrolidine (boiling point). : 110 ° C / 210 Pa).

[Synthesis Example 41] Synthesis of 4-morpholinepropiononitrile (Amine 41) 4-morpholinepropiononitrile was synthesized in the same manner as in Synthesis Example 39 except that morpholine was used instead of pyrrolidine (boiling point). : 97 ° C / 120 Pa). IR (thin film): ν = 2956, 2856, 2818, 2
249, 1458, 1448, 1360, 1292, 1
^{275,1144,1117,1009cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.40-2.55 (6H, m), 2.65 (2H,
m), 3.68 (4H, m).

Synthesis Example 42 Synthesis of 1-pyrrolidineacetonitrile (Amine 42) 7.11 g of pyrrolidine
Was added at 20 to 30 ° C., and the mixture was stirred for 2 hours. After diluting with ethyl acetate, washing with water and concentration under reduced pressure gave 1-pyrrolidineacetonitrile.

[Synthesis Example 43] Synthesis of 1-piperidineacetonitrile (Amine 43) 1-piperidineacetonitrile was synthesized in the same manner as in Synthesis Example 42 except that piperidine was used instead of pyrrolidine.

Synthesis Example 44 Synthesis of 4-morpholineacetonitrile (Amine 44) 4-Morpholineacetonitrile was synthesized in the same manner as in Synthesis Example 42 except that morpholine was used instead of pyrrolidine. IR (thin film): ν = 2980, 2937, 2866, 2
829, 2231, 1462, 1427, 1321, 1
294,1144,1111,1072,1009,8
^{93,852cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.57 (4H, m), 3.49 (2H, s), 3.7
2 (4H, m).

[Synthesis Example 45] Synthesis of cyanomethyl 3-diethylaminopropionate (Amine 45) 22.2 g of cyanomethyl acrylate was added to 14.6 g of diethylamine at 20 to 30 ° C, followed by stirring for 10 hours.
Cyanomethyl diethylaminopropionate was obtained.

[Synthesis Example 46] Synthesis of cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate (Amine 46) A method similar to that of Synthesis Example 45 was used except that diethanolamine was used instead of diethylamine. , N, N-bis (2-hydroxyethyl) -3-aminopropionate cyanomethyl was synthesized.

[Synthesis Example 47] Synthesis of cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate (Amine 47) N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile Was replaced with N, N-bis (2-hydroxyethyl) -3-aminopropionate except that cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate was used. Cyanomethyl propionate was synthesized.

[Synthesis Example 48] Synthesis of cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate (Amine 48) N, N-bis (2-hydroxyethyl) -3-aminopropiono N, N-bis (2-formyloxyethyl) -3 was prepared in the same manner as in Synthesis Example 4 except that cyanomethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate was used instead of nitrile. -Cyanomethyl aminopropionate was synthesized.

[Synthesis Example 49] Synthesis of cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate (Amine 49) Bis (2-methoxyethyl) was used instead of diethylamine
By the same method as in Synthesis Example 45 except that an amine was used,
Cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate was synthesized.

Synthesis Example 50 Synthesis of cyanomethyl N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate (Amine 50) Bis [2- (methoxymethoxy) ethyl] amine instead of diethylamine Was used in the same manner as in Synthesis Example 45 except that N, N-bis [2- (methoxymethoxy)
Ethyl] -3-aminopropionate cyanomethyl was synthesized.

[Synthesis Example 51] Synthesis of 3-diethylaminopropionic acid (2-cyanoethyl) (Amine 5
1) In the same manner as in Synthesis Example 45 except that cyanoethyl acrylate was used instead of cyanomethyl acrylate, 3
-Diethylaminopropionic acid (2-cyanoethyl) was synthesized.

Synthesis Example 52 Synthesis of N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) (Amine 52) The procedure of Synthesis Example 51 was repeated except that diethanolamine was used instead of diethylamine. In a similar manner, N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) was synthesized.

[Synthesis Example 53] Synthesis of N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl) (Amine 53) N, N-bis (2-hydroxyethyl) -3- By the same method as in Synthesis Example 3 except that N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) was used instead of aminopropiononitrile,
N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl) was synthesized (yield 90).
%). IR (thin film): ν = 2966, 2837, 2252, 1
736, 1456, 1371, 1238, 1188, 1
^{041cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
2.04 (6H, s), 2.48 (2H, t, J = 7.
1 Hz), 2.70 (2H, t, J = 6.2 Hz),
2.75 (4H, t, J = 5.9 Hz), 2.88 (2
H, t, J = 7.1 Hz), 4.08 (4H, t, J =
5.9 Hz), 4.26 (2H, t, J = 6.2H)
z).

[Synthesis Example 54] Synthesis of N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl) (Amine 54) N, N-bis (2-hydroxyethyl) -3 In the same manner as in Synthesis Example 4 except that N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) was used instead of -aminopropiononitrile,
N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl) was synthesized.

[Synthesis Example 55] Synthesis of N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl) (Amine 55) Bis (2-methoxyethyl) was used instead of diethylamine
By the same method as in Synthesis Example 51 except that an amine was used,
N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl) was synthesized (boiling point: 13).
2 ° C / 27 Pa, yield 90%). IR (thin film): ν = 2929, 2877, 2819, 2
252,1740,1458,1332,1246,1
182,1119,1055,1012cm ^{-1 1} H-N
MR (300 MHz in CDCl ₃ ): δ = 2.5
1 (2H, t, J = 7.2 Hz), 2.69 (2H,
t, J = 6.3 Hz), 2.70 (4H, t, J = 5.
9 Hz), 2.90 (2H, t, J = 7.2 Hz),
3.31 (6H, s), 3.43 (4H, t, J = 5.
9 Hz), 4.26 (2H, t, J = 6.3 Hz).

[Synthesis Example 56] N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2
Synthesis of -cyanoethyl) (Amine 56) N, N-bis [2- (methoxymethoxy) was obtained in the same manner as in Synthesis Example 51 except that bis [2- (methoxymethoxy) ethyl] amine was used instead of diethylamine.
Ethyl] -3-aminopropionic acid (2-cyanoethyl) was synthesized.

[Synthesis Example 57] Synthesis of cyanomethyl 1-pyrrolidinepropionate (Amine 57) Cyanomethyl 1-pyrrolidinepropionate was synthesized in the same manner as in Synthesis Example 45 except that pyrrolidine was used instead of diethylamine.

Synthesis Example 58 Synthesis of Cyanomethyl 1-Piperidine Propionate (Amine 58) Cyanomethyl 1-piperidinepropionate was synthesized in the same manner as in Synthesis Example 45 except that piperidine was used instead of diethylamine.

[Synthesis Example 59] Synthesis of cyanomethyl 4-morpholinepropionate (Amine 59) Cyanomethyl 4-morpholinepropionate was synthesized in the same manner as in Synthesis Example 45 except that morpholine was used instead of diethylamine.

[Synthesis Example 60] Synthesis of (2-cyanoethyl) 1-pyrrolidinepropionate (Amine 60) In the same manner as in Synthesis Example 51 except that pyrrolidine was used instead of diethylamine, 1-pyrrolidinepropionic acid (2 -Cyanoethyl) was synthesized.

[Synthesis Example 61] Synthesis of 1-piperidinepropionic acid (2-cyanoethyl) (Amine 61) A method similar to that of Synthesis Example 51 was repeated, except that piperidine was used instead of diethylamine. -Cyanoethyl) was synthesized.

[Synthesis Example 62] Synthesis of 4-morpholinepropionic acid (2-cyanoethyl) (Amine 62) A method similar to that of Synthesis Example 51 except that morpholine was used instead of diethylamine, to prepare 1-piperidinepropionic acid (2 -Cyanoethyl) was synthesized.

[Synthesis Example 63] N- (2-cyanoethyl)
Synthesis of -N- (2-hydroxypropyl) -3-aminopropiononitrile (Amine 63) N- (2) was prepared in the same manner as in Synthesis Example 10 except that 2-amino-1-propanol was used instead of ethylamine. -Cyanoethyl) -N- (2-hydroxypropyl) -3-
Aminopropiononitrile was synthesized.

[Synthesis Example 64] Synthesis of N- (2-acetoxypropyl) -N- (2-cyanoethyl) -3-aminopropiononitrile (Amine 64) N, N-bis (2-hydroxyethyl) -3 N- (2-cyanoethyl) in place of -aminopropiononitrile
N- (2-acetoxypropyl) -N- (2-cyanoethyl) -3-aminopropionate was prepared in the same manner as in Synthesis Example 3 except that -N- (2-hydroxypropyl) -3-aminopropiononitrile was used. Ononitrile was synthesized (boiling point: 160 ° C./20 Pa, yield: 86%). IR (thin film): ν = 2980, 2937, 2846, 2
249, 1732, 1464, 1423, 1373, 1
247, 1130, 1092, 1063, 1020, 9
^{60cm -1 1 H-NMR (270MHz} in CDCl 3): δ =
1.22 (3H, d, J = 6.2 Hz), 2.05 (3
H, s), 2.47 (4H, m), 2.57 (1H, d
d, J = 13.9, 4.9 Hz), 2.65 (1H, d
d, J = 13.9, 7.0 Hz), 2.90 (4H,
m), 4.97 (1H, ddq, J = 6.2, 7.0,
4.9 Hz).

[Synthesis Example 65] N- (2-cyanoethyl)
-N- [2- (2-hydroxyethoxy) ethyl] -3
Synthesis of aminopropiononitrile (Amine 6
5) N- (2-cyanoethyl) -N- [2- (2-hydroxyethoxy) ethyl]-in the same manner as in Synthesis Example 10 except that 2- (2-aminoethoxy) ethanol was used instead of ethylamine. 3-Aminopropiononitrile was synthesized.

[Synthesis Example 66] N- [2- (2-acetoxyethoxy) ethyl] -N- (2-cyanoethyl) -3
Synthesis of aminopropiononitrile (Amine 6
6) N- (2-cyanoethyl) -N- [2- (2-hydroxyethoxy) ethyl] instead of N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile
N- [2- (2-acetoxyethoxy) ethyl] -N- (2-cyanoethyl) -3-aminopropiononitrile was synthesized in the same manner as in Synthesis Example 3 except that -3-aminopropiononitrile was used. (Boiling point: 194 ° C / 2
0 Pa, 91% yield). IR (thin film): ν = 2952, 2865, 2247, 1
736, 1456, 1423, 1373, 1248, 1
^{128,1053cm -1 1 H-NMR (270MHz} in CDCl 3): δ =
2.07 (3H, s), 2.49 (4H, t, J = 6.
8 Hz), 2.80 (2H, t, J = 5.1 Hz),
2.95 (4H, t, J = 6.8 Hz), 3.56 (2
H, t, J = 5.1 Hz), 3.63 (2H, m),
4.20 (2H, m).

[Synthesis Example 67] Synthesis of 4-morpholinobutyronitrile (Amine 67) A mixture of 10.0 g of 4-bromobutyronitrile, 14.7 g of morpholine and 40 g of tetrahydrofuran was heated under reflux for 10 hours. cooling,
After diluting with diethyl ether, filtering and concentrating under reduced pressure, purification was performed by distillation under reduced pressure to give 4-morpholinobtyronitrile 9.4.
g was obtained (boiling point: 85 ° C./50 Pa, yield: 91%). IR (thin film): ν = 2954, 2854, 2812, 2
247, 1458, 1360, 1304, 1277, 1
269, 1142, 1119, 1072, 1036, 1
^{024,1011,966,918,866cm -1 1 H-NMR (300MHz} in CDCl 3): δ =
1.79 (2H, tt, J = 6.9, 6.9 Hz),
2.35-2.50 (8H, m), 3.67 (4H,
m).

[Synthesis Example 68] N- (2-cyanoethyl)
Synthesis of -N-tetrahydrofurfuryl-3-aminopropiononitrile (Amine 68) N- (2-cyanoethyl) -N-tetrahydro is obtained in the same manner as in Synthesis Example 10 except that tetrahydrofurfurylamine is used instead of ethylamine. Furfuryl-3-aminopropiononitrile was synthesized (boiling point: 143 ° C / 1
5 Pa, yield 90%). IR (thin film): ν = 2953, 2866, 2247, 1
464,1421,1367,1277,1142,1
^{065,1034,985,920cm -1 1 H-NMR (270MHz} in CDCl 3): δ =
1.50 (1H, m), 1.75-2.05 (3H,
m), 2.49 (4H, t, J = 6.8 Hz), 2.6
3 (1H, dd, J = 14.3, 6.8 Hz), 2.7
1 (1H, dd, J = 14.3, 4.6 Hz), 2.9
7 (4H, t, J = 6.8 Hz), 3.65-4.00
(3H, m).

[Synthesis Example 69] N- (2-cyanoethyl)
Synthesis of -N- (2,2-dimethoxyethyl) -3-aminopropiononitrile (Amine 69) A method similar to that of Synthesis Example 10 except that 2,2-dimethoxyethylamine was used instead of ethylamine, N- ( 2-
Cyanoethyl) -N- (2,2-dimethoxyethyl)-
3-Aminopropiononitrile was synthesized (boiling point: 13
5 ° C./13 Pa, yield 86%). IR (thin film): ν = 2939, 2835, 2247, 1
466,1446,1423,1367,1340,1
^{192,1126,1076,972cm -1 1 H-NMR (270MHz} in CDCl 3): δ =
2.48 (4H, t, J = 6.9 Hz), 2.71 (2
H, d, J = 5.0 Hz), 2.96 (4H, t, J =
6.9 Hz), 3.39 (6H, s), 4.36 (1
H. t, J = 5.0 Hz).

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[0180]

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[Examples and Comparative Examples] The following polymers (Polymers 1 to 10) and acid generators (PAG 1
5), basic compounds (Amine 1-62 and other basic compounds), dissolution inhibitors (DRI), crosslinking agents (Cr
osslinker) with propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (E
L) in a 70:30 ratio mixed solvent;
A resist solution was prepared by filtering through an m-size Teflon (registered trademark) filter.

Next, the obtained resist solution was formed into a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) on a silicon wafer to a thickness of 55 nm, and a KrF excimer laser beam (248 nm) was used.
Was spin-coated on a substrate having a reflectance of 1% or less, and baked at 100 ° C. for 90 seconds using a hot plate to reduce the thickness of the resist to 550 nm.

This was treated with a KrF excimer laser stepper (Nikon Corporation, NSR-S202A, NA-0.6, σ
(0.75, 2/3 annular illumination) while changing the exposure amount and focus, and immediately after exposure, the exposure was performed at 110 ° C. for 9 hours.
The pattern was obtained by baking for 0 second and developing with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds. The obtained resist pattern was evaluated as follows.

Evaluation method: The exposure amount for resolving a 0.16 μm line and space at a ratio of 1: 1 was determined as the optimum exposure amount (Eo).
The focus margin at this time was determined as p). The definition of the focus margin was that the film of the pattern did not decrease and the size was within a range of 0.16 μm ± 10%. The results are shown in Tables 1 to 4 (Examples) and Table 5 (Comparative Examples).

Next, the phenol-free polymer was evaluated by exposure to ArF excimer laser light (193 nm). The resist solution prepared in the same manner as above was applied to a silicon wafer by applying DUV-30 (manufactured by Nissan Chemical) to 42 nm.
And a film thickness of ArF excimer laser light (193)
The substrate was spin-coated on a substrate having a reflectance of 1% or less at 100 nm and baked at 100 ° C. for 90 seconds using a hot plate to make the thickness of the resist 350 nm.

This was exposed to light using an excimer laser microstepper (Nikon Corporation, NA-0.55, σ0.8, ／ annular illumination) while changing the exposure amount and focus. 1. bake for 90 seconds;
The pattern was obtained by developing with a 38% aqueous solution of tetramethylammonium hydroxide for 60 seconds. The obtained resist pattern was evaluated as follows.

The exposure margin for resolving a 0.14 μm line and space at a ratio of 1: 1 was defined as the optimal exposure (Eop), and the focus margin at this time was determined. The definition of the focus margin was that the film of the pattern was not reduced, and the size was within a range of 0.14 μm ± 10%. The results are shown in Table 6 (Example) and Table 7 (Comparative Example).

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

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[Table 6]

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[Table 7]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 7/038 601 7/038 601 7/039 601 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Takeshi Watanabe 28-1 Nishifukushima, Nishigusuku-mura, Nakakubijo-gun, Niigata Shin-Etsu Chemical Co., Ltd. New Functional Materials Technology Research Institute F-term (reference) 2H025 AA02 AA04 AB16 AC04 AC06 AC08 AD01 AD03 CB41 CC17 CC20 FA17 4H006 AA01 AA03 AB92

Claims (9)

[Claims] 1. The following general formulas (1), (2), (3) and
An amine compound represented by (4). Embedded image(Where R¹May be the same or different linear C 1-4
Or a branched alkylene group, R^TwoIs a hydrogen atom, or
Same or different straight-chain, branched or branched having 1 to 20 carbon atoms
Is a cyclic alkyl group, a hydroxy group, an ether
Group, carbonyl group, ester group, lactone ring, carbon
Or a cyano group. ^ThreeIs carbon number 2
~ 20 linear or branched alkylene groups,
Hydroxy group, ether group, thioether group, carbonyl
Group, ester group, thioester group or carbonate
May contain R^FourAre the same or different and have 1 to 4 carbon atoms
Is a linear or branched alkylene group. a is 1
整数 3, and a + b = 3. ) 2. R in the general formulas (1) and (3)
^TwoIs represented by the following general formula (5), (6), (7) or (8)
The amine compound according to claim 1, which is represented. Embedded image(Where R^Five, R⁷, R^TenIs a straight-chain or straight-chain having 1 to 4 carbon atoms
Is a branched alkylene group;⁶, R⁹Is a hydrogen atom,
Or a linear, branched or cyclic C 1-20
Alkyl group, hydroxy group, ether group, ester
Group, a lactone ring or a cyano group. R^Five
And R⁶Binds to form a ring with the oxygen atom to which they are attached.
It may be formed. R⁸Is a single bond or one having 1 to 4 carbon atoms
A linear or branched alkylene group;¹¹Is charcoal
Linear, branched or cyclic alkyl having a prime number of 1 to 20
Group, a hydroxy group, an ether group, an ester group,
It may contain a couton ring. R¹²Is a straight chain having 1 to 4 carbon atoms
A chain or branched (n + 1) -valent organic group, R¹³Is the same
A linear or branched C1-C10 which may be one or different.
A branched or cyclic alkyl group; an ether group,
Stel group, hydroxy group, lactone ring, cyano group or
It may contain a rubonyl group. Also, R¹²And R ¹³,Ah
Or two R¹³Are bonded to each other and
An elementary or oxygen atom and R¹²Form a ring with the carbon atoms of
May be. n is 2, 3 or 4. ) 3. A resist material obtained by adding a basic compound containing a cyano group. 4. A basic compound containing a cyano group,
Represented by the general formulas (1), (2), (3) and (4)
It is characterized by containing one or more basic compounds
The resist material according to claim 3, wherein Embedded image(Where R¹May be the same or different linear C 1-4
Or a branched alkylene group, R^TwoIs a hydrogen atom, or
Same or different straight-chain, branched or branched having 1 to 20 carbon atoms
Is a cyclic alkyl group, a hydroxy group, an ether
Group, carbonyl group, ester group, lactone ring, carbon
Or a cyano group. ^ThreeIs carbon number 2
~ 20 linear or branched alkylene groups,
Hydroxy group, ether group, thioether group, carbonyl
Group, ester group, thioester group or carbonate
May contain R^FourAre the same or different and have 1 to 4 carbon atoms
Is a linear or branched alkylene group. a is 1
整数 3, and a + b = 3. ) 5. R^TwoIs the following general formula (5), (6),
The compound according to claim 4, which is a group represented by (7) or (8).
Zyst material. Embedded image(Where R^Five, R⁷, R^TenIs a straight-chain or straight-chain having 1 to 4 carbon atoms
Is a branched alkylene group;⁶, R⁹Is a hydrogen atom,
Or a linear, branched or cyclic C 1-20
Alkyl group, hydroxy group, ether group, ester
Group, a lactone ring or a cyano group. R^Five
And R⁶Binds to form a ring with the oxygen atom to which they are attached.
It may be formed. R⁸Is a single bond or one having 1 to 4 carbon atoms
A linear or branched alkylene group;¹¹Is charcoal
Linear, branched or cyclic alkyl having a prime number of 1 to 20
Group, a hydroxy group, an ether group, an ester group,
It may contain a couton ring. R¹²Is a straight chain having 1 to 4 carbon atoms
A chain or branched (n + 1) -valent organic group, R¹³Is the same
A linear or branched C1-C10 which may be one or different.
A branched or cyclic alkyl group; an ether group,
Stel group, hydroxy group, lactone ring, cyano group or
It may contain a rubonyl group. Also, R¹²And R ¹³,Ah
Or two R¹³Are bonded to each other and
An elementary or oxygen atom and R¹²Form a ring with the carbon atoms of
May be. n is 2, 3 or 4. ) 6. An alkali-insoluble or sparingly soluble resin having (A) the amine compound according to claim 1 or (2), (B) an organic solvent, and (C) an acidic functional group protected by an acid labile group. And a base resin which becomes alkali-soluble when the acid labile group is eliminated, and (D) an acid generator. 7. The positive resist material according to claim 6, further comprising (E) a dissolution inhibitor. 8. (A) The amine compound according to claim 1 or 2, (B) an organic solvent, (C) an alkali-soluble resin, which is a base resin which becomes hardly alkali-soluble by crosslinking with a crosslinking agent, (D) A negative resist material comprising: an acid generator; and (F) a crosslinking agent that is crosslinked by an acid. 9. A step of applying (1) a step of applying the resist material according to claim 3 on a substrate; and (2) a step of applying heat through a photomask after the heat treatment to a wavelength of 300 nm.
The following high-energy or electron beam exposure step,
(3) A pattern forming method comprising a step of performing a heat treatment as needed and then developing with a developer.