JP3342124B2 - Fine pattern forming material and pattern forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist material used for forming a semiconductor element or an integrated circuit by patterning using an electron beam lithography technique and a method for forming a fine pattern using the same.

[0002]

2. Description of the Related Art Conventionally, in the manufacture of ICs and LSIs, patterns are formed by photolithography using ultraviolet rays, but electron beam lithography has been used with the miniaturization of elements and the manufacture of ASICs. It is becoming possible. An electron beam resist is indispensable for forming a fine pattern by electron beam lithography. Conventionally, a positive-type electron beam resist is made of polymethyl methacrylate (PM
MA) was the mainstream. But PM
Since MA has low sensitivity, the main chain is broken by introducing an electron-withdrawing group into the side chain, such as poly (hexafluorobutyl methacrylate) or poly (2,2,2-trichloroethyl methacrylate). Higher sensitivity has been achieved in a way that makes it easier. However, none of these resists having a high sensitivity to PMMA sufficiently satisfy both the sensitivity and the resolution.
In addition, increasing the sensitivity in this way sacrifices dry etch resistance and heat resistance, and is difficult to use as a mask for dry etching, and its use is limited. Further, in order to develop a positive resist using such a one-component polymer based on PMMA, an organic solvent is required, and the resist film may swell in an organic solvent developer during development. The resolution of the pattern is reduced, and in some cases the pattern is distorted and unusable. Furthermore, organic solvent developers are harmful to the environment and health, and
It is not desirable in terms of flammability.

In recent years, developments have been made to increase the sensitivity of a positive electron beam resist by introducing the concept of chemical amplification.
There are several reports (for example, H. Ito et al., SPIE Vol. 1086
Advances in Resist Technology and Processing VI (1
989) p.11; H.Shiraishi et al., J.Vac.Sci.Technol.B9 (6),
p.3343 (1991); JP-A-3-192361; JP-A-4-155344
No.). These resists are composed of a compound capable of generating an acid when irradiated with an electron beam (hereinafter abbreviated as an acid generator) and a multi-component substance including a compound capable of causing an acid-catalyzed reaction by the acid, using a positive electron beam. It is used as a resist. Acid generators that can generate an acid when irradiated with an electron beam include triphenylsulfonium salts,
Examples include diphenyliodonium salts, tris (trichloromethyl) -s-triazine / triethanolamine, and sulfonic acid esters. These acids generate strong acids and highly volatile Lewis acids or sulfonic acids when irradiated with an electron beam. Examples of the polymer that reacts with such an acid include poly (p-tert-butoxycarbonyloxystyrene), poly (p-tetrahydropyranyloxystyrene), and poly (p-trimethylsilyloxystyrene). These polymers cause a decomposition reaction as shown in the following [Formula 1] by the generated acid, for example.

[0004]

(Equation 1)

[0005] The above reaction proceeds, and the decomposition reaction of the protecting group of the polymer proceeds. That is, by performing electron beam lithography, an acid is generated from the acid generator, and the acid makes the alkali-insoluble polymer alkali-soluble, so that a positive pattern can be formed. A multi-component material containing such a matrix polymer and an acid generator is provided on a semiconductor substrate,
Alternatively, a method has been developed in which a resist is applied on an organic flattening film and an inorganic intermediate film, and a pattern is formed by electron beam irradiation, heat treatment, and development with an organic alkali aqueous solution. However, in these polymers, the removal of the protecting group does not proceed easily. Positive resists with a resolution of 0.2 μm rule or less, which will be required in the future, and have sufficient sensitivity, require such chemical amplification. Not developed in the system. In addition, since the generated acid is a strong acid and a highly volatile acid in common with these electron beam resists, the resist is easily affected by an atmosphere such as an amine, and as a result, during electron beam writing or from writing to heat treatment. There is a problem that the pattern dimension changes in between. In addition, a vertical resist pattern is required to etch the substrate without dimensional shift by using it as an etching mask, but a good resist pattern cannot be obtained from the above-described polymer and acid generator. . Further, as described above, PMMA-based resists have problems such as swelling during development and insufficient dry etching resistance, and are not suitable for fine processing with a rule of 0.2 μm or less.

[0006]

As described above, it is effective to incorporate chemical amplification into a resist to increase sensitivity, eliminate swelling by an organic developing solution, and to have no effect on the human body and the environment. A positive resist satisfying both sensitivity and resolution has not yet been developed. In electron beam lithography, an improvement in sensitivity leads to an improvement in throughput, and therefore, improvement in resist sensitivity is a major issue. In addition, in order to use it as a mask for dry etching, it is necessary to satisfy sufficient dry etching resistance at the same time. Further, there is a large problem that the pattern dimension changes during electron beam writing. Therefore, there is a demand for a practical positive-type electron beam resist that solves these problems.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a high sensitivity, a high resolution, a high dry etch resistance and a chemically amplified positive type which can maintain a stable pattern size. An object of the present invention is to provide an electron beam resist and a method for forming a fine pattern using the same.

[0008]

In order to achieve the above object, the present invention comprises the following constitutions. "(1) The following general formula [I]

[0009]

Embedded image

[Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or a carbon atom.
6 represents a linear, branched or cyclic alkyl group (provided that R ² and R ³ are not both hydrogen atoms);
R ² and R ³ may form a methylene chain having 2 to 5 carbon atoms, and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and a C 1 to C 6 alkyl group. Represents a linear, branched or cyclic haloalkyl group or an aralkyl group, R ⁵ represents a hydrogen atom or a cyano group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom, a cyano group, —COOY (where Y represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms) or the following general formula [II]:

[0011]

Embedded image

(Where Z is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, 1 carbon atom)
Represents up to 10 linear, branched or cyclic alkoxy groups. ) Represents, also, R ⁵ and R ^7, taken together -CO-
May be made with O-CO-, k, l and m are tables to {However natural numbers each independently, 0.1 ≦ k / (k + l) ≦ 0.
9, 0.05 ≦ m / (k + 1 + m) ≦ 0.50. ｝ And a polymer represented by the following general formula [VI]

Embedded image [Wherein R ¹² represents a hydrogen atom, a halogen atom, an alkyl group or
Represents an alkoxy group, R ¹³ is a linear group having 1 to 6 carbon atoms,
Branched or cyclic alkyl group, phenyl group, alkyl group
Substituted phenyl group, halogen-substituted phenyl group or alkoxy
Represents a substituted phenyl group. ], General formula [X]

Embedded image Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom
Atom, halogen atom, C1-C10 linear, branched or
Cyclic alkyl group, haloalkyl group having 1 to 10 carbon atoms, charcoal
An alkoxyalkyl group having a prime number of 2 to 10, an aralkyl group,
Phenyl group, substituted phenyl group (substituents are halogen atoms,
A linear, branched or cyclic alkyl group having a prime number of 1 to 10,
Represents a lucoxy group, a nitro group, or a cyano group. )
R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ are each independently
Alicyclic, heteroalicyclic, aromatic ring or
It may form a heteroaromatic ring. ] Or the general formula [XI]

Embedded image [Wherein R ²⁶ is a hydrogen atom, a halogen atom, a carbon number of 1 to 10
Linear, branched or cyclic alkyl group and alkoxy group
Wherein R ²⁷ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
The stands, R ²⁸ represents an alkyl group having 1 to 3 carbon atoms, R ²⁹
Is a linear, branched or cyclic alkyl having 1 to 10 carbon atoms
Group, aralkyl group, phenyl group, substituted phenyl group (substituted
The group is a halogen atom, a straight-chain, branched or 1 to 10 carbon atoms.
Represents a cyclic alkyl group or an alkoxy group. )
You. A resist material comprising an acid generator capable of generating an acid upon irradiation with an electron beam, and a solvent capable of dissolving the acid generator. (2) The following general formula [I ']

Embedded image [In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R
³ is each independently a hydrogen atom or a straight-chain having 1 to 6 carbon atoms,
Represents a branched or cyclic alkyl group (provided that R ² and R ³
Excludes when both are hydrogen atoms. ), And R ² and R ³ are carbon
The methylene chain of several to 5 may be formed, and R ⁴ is a carbon
A linear, branched or cyclic alkyl group of 1 to 10 primes, carbon
Linear, branched or cyclic haloalkyl having a prime number of 1 to 6
R ⁵ represents a hydrogen atom or a aralkyl group;
R ⁶ represents a hydrogen atom or a methyl group ^;
Is the following general formula [II]

Embedded image (However, Z is a hydrogen atom, a halogen atom, a C1-6
Linear or branched alkyl group, linear chain having 1 to 10 carbon atoms
Represents a branched, branched or cyclic alkoxy group. ),
k, l, and m each independently represent a natural number.
≦ k / (k + 1) ≦ 0.9, 0.05 ≦ m / (k + 1 + m) ≦
0.50. ｝. A polymer represented by the following general formula:
[V]

Embedded image [Wherein, R ⁸ represents an alkyl group, an aralkyl group, a trifluoro group.
Romethyl group, phenyl group, alkyl-substituted phenyl group,
Shows alkoxy-substituted phenyl group and halogen-substituted phenyl group
And R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl
R ¹¹ represents an alkyl group, a phenyl group, an alkyl group
Substituted phenyl group, alkoxy substituted phenyl group, halogen substitution
Represents a substituted phenyl group or an alkylthio-substituted phenyl group.
You. ], General formula [VII]

Embedded image Wherein R ¹⁴ is a trichloroacetyl group, p-toluenesulfur
Phonyl group, p-trifluoromethylbenzenesulfonyl
Group, methanesulfonyl group or trifluoromethanesulfo
And R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom,
Represents a halogen atom or a nitro group. ] Or the general formula [VI
II]

Embedded image [Wherein, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogeno
Atom, or a linear or branched alkyl having 1 to 6 carbon atoms
R ¹⁹ represents a straight-chain, branched or
A cyclic alkyl group, or the following general formula [IX]

Embedded image (However, R ²⁰ and R ²¹ are each independently a hydrogen atom, a halogeno
Atom, or a linear or branched alkyl having 1 to 6 carbon atoms
Represents a hydroxyl group. ). ] Of the electron beam
An acid generator capable of generating an acid upon irradiation and
Characterized by comprising a solvent capable of dissolving etc.
Material.

(3) (i) a step of applying a resist material according to (1) or (2) on a semiconductor substrate and heating to form a resist film; and (ii) irradiating an electron beam. A fine pattern forming method comprising: a step of performing a heat treatment as necessary after drawing a pattern; and (iii) a step of forming a positive pattern by performing development using an alkaline aqueous solution.

(4) (i) a step of applying an organic polymer solution on a semiconductor substrate and heat-treating to form a lower layer film;
i) a step of forming an inorganic intermediate film on the lower film;
i) a step of applying the resist material according to (1) or (2) on the intermediate film and heating to form a resist film; and (iv) irradiating an electron beam to draw a pattern. Heat treating if necessary, (v) forming a positive pattern by performing development using an alkaline aqueous solution, and (vi) etching the intermediate film using the resist pattern as a mask. Process and
(Vii) Using the resulting pattern as a mask,
Forming a pattern by etching the lower layer film. 』

That is, the present inventors have conducted intensive studies to achieve the above object, and as a result, the general formula [I] or the general formula
[I ']

[0016]

Embedded image

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ^{7 ′} , k, l and m are as described above. The present inventors have found that a chemically amplified resist containing a polymer represented by the formula (1) as a resin component can achieve the above object, and have completed the present invention.

In the general formula [I] or [I '] , an alkyl group having 1 to 6 carbon atoms represented by R ² and R ³ , and an alkyl group represented by haloalkyl having 1 to 6 carbon atoms represented by R ⁴ , R ⁷
<br/> general formula represented by in Y and R ⁷ or R ⁷ of -COOY represented ^'[II]

[0019]

Embedded image

Examples of the alkyl group having 1 to 6 carbon atoms represented by Z include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group and a hexyl group (linear, branched or cyclic). Any possible). Carbon number 1 represented by R ⁴
10 alkyl group, following general formula R ⁷ or R ^{7 '[II]}

[0021]

Embedded image

Examples of the alkyl group of the alkoxy group having 1 to 10 carbon atoms represented by Z include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group,
Examples thereof include an octyl group, a nonyl group, and a decyl group (which may be linear, branched, or cyclic). Examples of the halogen of the haloalkyl group having 1 to 6 carbon atoms represented by R ⁴ include chlorine, bromine, fluorine and iodine. Examples of the aralkyl group represented by R ⁴ include a benzyl group, a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group.

The polymer represented by the general formula [I] or [I '] according to the present invention is a compound represented by the general formula [IV] which can be eliminated with an acid.

[0024]

Embedded image

(Wherein R ² , R ³ and R ⁴ are the same as above), that is, an alkoxyalkyl group,
A monomer unit having a haloalkoxyalkyl group or an aralkyloxyalkyl group, that is, a general formula [III]

[0026]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same as described above). In particular, the functional group represented by the general formula [IV] is an existing tert-butoxycarbonyl group, tert-butyl group,
Compared to functional groups such as trimethylsilyl and similar tetrahydropyranyl groups, the electron density of the functional group is higher due to the electron donating property of the alkoxy group, so the decomposition reaction is extremely easy with a small amount of acid. Progresses. Therefore,
Since the chemical amplification proceeds with a small dose, the sensitivity is higher than that of the conventional positive resist, and the productivity can be greatly improved. Further, it is significantly advantageous in terms of improving resolution and maintaining pattern dimensions.

Specific examples of the monomer unit represented by the general formula [III] include a p- or m-hydroxystyrene derivative having a functional group represented by the general formula [IV], a p- or m-hydroxy-α-methylstyrene derivative, and the like. Is caused by the monomer of, specific examples of such a monomer,
For example p- or m-1-methoxy-1-methylethoxystyrene, p- or m-1-benzyloxy-1-methylethoxystyrene, p- or m-1-ethoxyethoxystyrene, p- or m-
1-methoxyethoxystyrene, p- or m-1-n-butoxyethoxystyrene, p- or m-1-isobutoxyethoxystyrene, p- or m-1- (1,1-dimethylethoxy) -1-methyl Ethoxystyrene, p- or m-1- (1,1-dimethylethoxy) ethoxystyrene, p- or m-1- (2-chloroethoxy) ethoxystyrene, p- or m-1-cyclohexyloxyethoxystyrene, p -Or m-1- (2-ethylhexyloxy) ethoxystyrene, p- or m-1-ethoxy-1-methylethoxystyrene, p- or m-1-n-propoxyethoxystyrene, p- or m-1- Ethoxypropoxystyrene, p-
Or m-1-methoxybutoxystyrene, p- or m-1-methoxycyclohexyloxystyrene and a p- or m-hydroxystyrene derivative having the same protective group as the p- or m-hydroxystyrene derivative
m-hydroxy-α-methylstyrene derivatives. These monomers may be used alone or in an appropriate combination of two or more. Among these monomer units, p- or m-1-methoxy-1-methylethoxystyrene, p- or m-1-methoxy-1-methylethoxystyrene in which R ² and R ³ are both alkyl groups, particularly in the general formula [III] Or m-1-benzyloxy-1-methylethoxystyrene, p- or m-1- (1,1-dimethylethoxy)-
1-methylethoxystyrene, p- or m-1-ethoxy-1-methylethoxystyrene, p- or m-1-methyl-1-n-propoxyethoxystyrene, etc., are very easily deprotected by the action of an acid. It is more preferable to improve the resolution performance, which is one of the objects of the present invention.

The polymer according to the present invention has the above general formula [III]
In addition to the monomer unit represented by the general formula [XII]

[0030]

Embedded image

(Wherein R ¹ is the same as defined above) and a general formula [XIII] or [XIII ′]

[0032]

Embedded image

Embedded image

(Wherein R ⁵ , R ⁶ , R ⁷ and R ^{7 ′} are the same as those described above). The monomer unit represented by the general formula [XII] is derived from a monomer having a phenolic hydroxyl group, and specific examples of such a monomer include p- or m-vinylphenol, p- or m-hydroxy-α. -Methylstyrene and the like. These monomers may be used alone or in an appropriate combination of two or more.

The monomer unit represented by the general formula [XIII], which is the third component of the polymer according to the present invention, includes, for example, acrylonitrile, fumaronitrile, methyl methacrylate, tert-butyl methacrylate, maleic anhydride, p-te
and monomer units such as rt-butoxystyrene, p-methylstyrene, p-chlorostyrene, and styrene. These monomers may be used alone or in an appropriate combination of two or more.

In the polymer according to the present invention represented by the general formula [I] or [I '] , the monomer unit represented by the general formula [III] and the monomer unit represented by the general formula [XII] The composition ratio is usually from 1: 9 to 9: 1, and in any case, the composition can be used as the resist material of the present invention. 7: 3 is more preferred.

Specific examples of the polymer according to the present invention include, for example , poly (p-1-ethoxyethoxystyrene-p-hydroxy).
Styrene-acrylonitrile), poly (p-1-ethoxy)
Ethoxystyrene-p-hydroxystyrene-fumaronito
Ryl), poly (p-1-n-butoxyethoxystyrene-p-phenyl)
Droxystyrene-methyl methacrylate), poly (p-1-
Cyclohexyl-1-ethoxyethoxystyrene-p-hydrido
Roxystyrene-tert-butyl methacrylate), poly
(P-1-ethoxyethoxystyrene-p-hydroxystyrene
-P-tert-butoxystyrene), poly (p-1-methoxy)
Ethoxystyrene-p-hydroxystyrene-p-methyls
Tylene), poly (p-1-ethoxyethoxystyrene-p-phenyl)
Droxystyrene-p-chlorostyrene), poly [p-1-
(2-chloroethoxy) ethoxystyrene-p-hydroxy
Styrene-tert-butyl methacrylate], poly (m-1-si
Clohexyloxyethoxystyrene-m-hydroxys
Styrene - although maleic acid) anhydride, etc. can be mentioned, but not limited to course this like. The polymer according to the present invention,
For example, it can be easily obtained by the following four methods shown in a) to d).

A) Method-1 The following general formula [XIV] having a functional group represented by the above general formula [IV]

[0038]

Embedded image

(R ¹ , R ² , R ³ and R ⁴ are the same as described above.)
In a single unit or a monomer and a third monomer, a radical polymerization initiator [e.g., in an organic solvent such as benzene, toluene, tetrahydrofuran, and 1,4-dioxane, according to a conventional method for producing a polymer. Azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (methyl 2-methylpropionate) And benzoyl peroxide,
Polymerization initiator such as lauroyl peroxide] in a nitrogen or argon stream at 50 to 110 ° C for 1 to 10 hours. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer, and a homopolymer comprising the monomer unit represented by the above general formula [III] or a copolymer containing a monomer unit represented by the above general formula [III] is obtained. Is isolated. Then, the homopolymer or copolymer is dissolved in an organic solvent such as tetrahydrofuran, acetone, and 1,4-dioxane with a suitable acid [for example, Lewis acid such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid and the like.
organic acid such as p-toluenesulfonic acid, malonic acid, oxalic acid, etc.] at 30 to 100 ° C. for 1 to 10 hours to obtain the above-mentioned general formula [I
V] is eliminated at an optional ratio. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer, and a desired polymer is isolated.

B) Method-2: a monomer represented by the above general formula [XIV], p- or m-hydroxystyrene, p- or m-hydroxy-α-methylstyrene and, if necessary, a third monomer, After copolymerization by the same operation method as in method-1, post-treatment is carried out according to a conventional method for obtaining a polymer, and a target polymer is isolated.

C) Method-3 Commercial p-tert-butoxystyrene alone or
(P-tert-butoxystyrene) or poly (p-tert-butoxystyrene) obtained by a polymerization reaction of
In an organic solvent such as tetrahydrofuran, acetone or 1,4-dioxane, a copolymer containing tert-butoxystyrene unit is dissolved in a suitable acid [for example, Lewis acid such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid or p- Organic acid such as toluenesulfonic acid, malonic acid, oxalic acid, etc.] at 30 to 110 ° C. for 1 to 20 hours to completely or completely remove a tert-butyl group as a functional group at an arbitrary ratio. Poly (p-hydroxystyrene),
Poly (p-tert-butoxystyrene-p-hydroxystyrene) or a copolymer containing a monomer unit represented by the general formula [XII], and an arbitrary amount of the following general formula [XV]

[0042]

Embedded image

(Wherein R ² and R ⁴ are the same as defined above) with an organic solvent such as tetrahydrofuran, acetone, 1,4-dioxane, methylene chloride, dimethoxyethane and the like. In the presence of a suitable acid [eg, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, chlorosulfonic acid / pyridine salt, sulfuric acid / pyridine salt, p-toluenesulfonic acid / pyridine salt, etc.] at 10 to 100 ° C. Reaction for about 20 hours, and the above-mentioned general formula [I
V] is chemically introduced at an arbitrary ratio, followed by post-treatment according to a conventional method for obtaining a polymer.
Isolate the desired polymer.

D) Method-4 Commercially available poly (p-hydroxystyrene) or the general formula [XI
Method using a copolymer containing a monomer unit represented by the formula [I] and an arbitrary amount of a vinyl ether compound or an isopropenyl ether compound represented by the above general formula [XV]
After reacting by the same operation method as in 3, the post-treatment is carried out according to a conventional method for obtaining a polymer, and the desired polymer is isolated.

The average molecular weight of the polymer according to the present invention is not particularly limited as long as it can be used as a resist material. The preferred range is the weight determined by a GPC measurement method using polystyrene as a standard. Average molecular weight is usually about 1000 to 50,000, more preferably 3000
It is about 40,000.

The acid generator used in the present invention, which generates an acid by irradiation with an electron beam, may be any as long as it does not adversely affect the formation of a resist pattern. Needless to say, an acid generator that can generate an acid well is more preferable. Particularly preferred acid generators in the present invention include:
For example, the following general formula [V], general formula [VI], and general formula [VI
I], general formula [VIII], general formula [X] or general formula [X
I].

[0047]

Embedded image

[In the formula, R ⁸ represents an alkyl group, an aralkyl group, a trifluoromethyl group, a phenyl group, an alkyl-substituted phenyl group, an alkoxy-substituted phenyl group, or a halogen-substituted phenyl group, and R ⁹ and R ¹⁰ each independently represent Represents a hydrogen atom or an alkyl group, and R ¹¹ represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, an alkoxy-substituted phenyl group, a halogen-substituted phenyl group or an alkylthio-substituted phenyl group. ]

[0049]

Embedded image

[Wherein R ¹² is a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group, and R ¹³ has 1 to 1 carbon atoms.
6 represents a linear, branched or cyclic alkyl group, phenyl group, alkyl-substituted phenyl group, halogen-substituted phenyl group or alkoxy-substituted phenyl group. ]

[0051]

Embedded image

[Wherein R ¹⁴ is a trichloroacetyl group, p-
It represents a toluenesulfonyl group, a p-trifluoromethylbenzenesulfonyl group, a methanesulfonyl group or a trifluoromethanesulfonyl group, and R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom or a nitro group. ]

[0053]

Embedded image

[In the formula, R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁹ represents a 1 to 1 carbon atom. 10 linear, branched or cyclic alkyl groups, or the general formula [IX]

[0055]

Embedded image

(Provided that R ²⁰ and R ²¹ each independently represent a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms). ]

[0057]

Embedded image

[Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, A haloalkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an aralkyl group, a phenyl group, a substituted phenyl group (the substituent is a halogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms) , An alkoxy group, a nitro group or a cyano group), and R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R
²⁵ is each independently bonded to each other to form an alicyclic, heteroalicyclic,
It may form an aromatic ring or a heteroaromatic ring. ]

[0059]

Embedded image

[Wherein R ²⁶ is a hydrogen atom, a halogen atom,
A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R ²⁷ represents a hydrogen atom or a carbon number of 1 to 3;
R ²⁸ represents an alkyl group having 1 to 3 carbon atoms, and R ²⁹ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group, a phenyl group, or a substituted phenyl group. Group (substituent is a halogen atom, a straight chain having 1 to 10 carbon atoms,
Represents a branched or cyclic alkyl group or an alkoxy group. ). ]

Specific examples of preferred acid generators used in the present invention include, for example, 2-methanesulfonyl-2-methyl- (4-methylthio) propiophenone, 2-methyl-
2- (p-toluenesulfonyl) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, diphenyl Disulfone, di (p-
Tolyl) disulfone, p-tolyl phenyldisulfone,
Bis (p-toluenesulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, bis (p-chlorobenzenesulfonyl) diazomethane, bis (p-tert-butylbenzenesulfonyl) diazomethane ,
Bis-benzenesulfonyldiazomethane, 2-nitrobenzyl p-toluenesulfonic acid, p-toluenesulfonic acid
2,6-dinitrobenzyl, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate, 4,6-dimethyl-1,
2-oxathiin-2,2-dioxide, 4,6-diphenyl-1,
2-oxathiin-2,2-dioxide, 4-methyl-6-phenyl-1,2-oxathiin-2,2-dioxide, 3-bromo-4,
6-dimethyl-1,2-oxathiin-2,2-dioxide, 6-
(4-bromophenyl) -1,2-oxathiin-2,2-dioxide, 6-phenyl-1,2-oxathiin-2,2-dioxide, 6- (4-tolyl) -1,2-oxathiin-2 , 2-dioxide, 3-phenyl-5,6,7,8-tetrahydro-2,1-benzoxatiin-1,1-dioxide, 2,2-bis-benzenesulfonylpropane, 2,2-bis (p -Toluenesulfonyl) propane, 2- (p-toluenesulfonyl) -2-methylsulfonylpropane, 2- (p-toluenesulfonyl) -2-cyclohexylsulfonylpropane, 2-benzenesulfonyl-
2- (1,1-dimethylethylsulfonyl) propane, 2-
[(1,1-dimethylethyl) phenylsulfonyl] -2-
(1-methylethylsulfonyl) propane, 2,2-bis (p-
Examples thereof include, but are not limited to, toluenesulfonyl) butane.

As the acid generators other than those described above, various triphenylsulfonium salts, diphenyliodonium salts, pyrogallol tris (methanesulfonate), tris (trichloromethyl) -s-triazine / triethanolamine and the like have been known. However, when these are used as an acid generator of a chemically amplified resist material,
The acid (Lewis acid) generated by the irradiation of the electron beam is a strong acid and is highly volatile, so that the acid volatilizes from the surface of the resist film during or after the electron beam drawing or is exposed to an atmosphere such as an amine. It is extremely susceptible to the effect, and as a result, the film formation (T-shape) occurs during pattern formation or as time elapses from drawing to development, the pattern formation size changes greatly, or the pattern It is not preferable because there is a problem that it cannot be formed.

The solvent used in the present invention may be any solvent as long as it can dissolve both the polymer and the acid generator. Usually, a solvent having good film-forming properties is more preferably used. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, acetic acid
2-ethoxyethyl, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidone, cyclohexanone, methyl ethyl ketone, 1,4-dioxane, ethylene glycol monoisopropyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, and the like, but are not limited to these. The resist composition of the present invention usually comprises the above three components (polymer, acid generator, solvent) as main components, but if necessary, dyes such as fluorenone derivatives, anthracene derivatives, acridine compounds, pyrene derivatives, etc. Alternatively, a conductive compound such as polypyrrole or TCNQ complex, or a surfactant may be added.

To form a pattern using the resist material according to the present invention, for example, the following may be performed. A resist material containing the compound according to the present invention is spin-coated on a substrate such as a silicon wafer so as to have a thickness of about 0.5 to 2 μm, and this is heated in an oven at 70 to 130 ° C. for 10 to 30 minutes, or hot. Pre-bake on a plate at 70-130 ° C for 1-2 minutes. Then accelerating voltage 20～50KeV, after drawing a desired pattern with an electron beam dose 0.1~100μC / cm ^2, 70~150 ℃ on a hot plate 1-2
Bake for a minute. This is further immersed (dip) for about 0.5 to 3 minutes using a developing solution such as a 0.1 to 5% aqueous solution of tetramethylammonium hydroxide (TMAH) and a paddle (pud).
If development is performed by a conventional method such as a ddle) method or a spray method, a target pattern is formed on the substrate.

Further, an organic underlayer film is first formed on a substrate, an inorganic intermediate film is formed thereon, and a resist pattern is formed on the intermediate film. Can be avoided. At this time, a pattern having strong etching resistance to the semiconductor substrate can be obtained by using, for example, a material mainly composed of novolak resin as the organic underlayer film, which is generally used as a resist material for i-line and g-line. I can do it. Further, by using a silicon oxide film or spin-on-glass as the inorganic intermediate film, the film can be easily formed, a dimensional shift during lower layer etching is small, and a pattern can be accurately transferred. The mixing ratio of the polymer according to the present invention and the acid generator in the positive resist material is such that the acid generator is 0.01 weight per 1 weight of the polymer.
0.30.3 weight, preferably around 0.01-0.1 weight. Further, as the amount of the solvent in the resist material of the present invention,
The amount of the positive resist material obtained by dissolving the polymer and the acid generator according to the present invention is not particularly limited as long as it does not hinder the application on a substrate. The weight is 1 to 20 weights, preferably about 1.5 to 6 weights, per 1 weight of the combined material.

The developing solution used in the above-mentioned various pattern forming methods is such that the unexposed portion hardly dissolves and the exposed portion depends on the solubility of the polymer used for the resist material in the alkali developing solution. The part may be selected from an alkaline solution having an appropriate concentration to dissolve, usually 0.01 part.
It is selected from the range of ~ 20%. Examples of the alkaline solution include solutions containing organic amines such as TMAH, choline, and triethanolamine, and inorganic alkalis such as NaOH and KOH.

The polymer according to the present invention contains the monomer unit represented by the general formula [III] having the functional group represented by the general formula [IV] as described above, and therefore, the polymer of the same kind as the conventional one has In the presence of an acid, compared to the polymer used in
It has the property of easily desorbing a functional group and becoming easily alkali-soluble, so that it is possible to maintain a stable pattern size during the electron beam irradiation or with the lapse of time from irradiation to heat treatment (baking). is there. In addition, the polymer according to the present invention has heat resistance, dry etch resistance, and adhesion to a substrate due to containing a hydroxystyrene unit represented by the general formula [XII]. Is also excellent. When both R ² and R ³ in the general formula [I] are hydrogen atoms (for example, p-alkoxymethoxystyrene), the resist material acts negatively and cannot be applied to the present invention. is there.

The general formulas [V], [VI], [VII], [VI
II], [X] or [XI], the resist composition of the present invention comprising an acid generator represented by the following formula:
It has been confirmed that an acid is generated even by exposure to rF excimer laser light (248.4 nm) or X-ray irradiation, and a chemical amplification action is performed. Accordingly, the resist material of the present invention is a resist material that can be patterned by low dose electron beam irradiation, deep ultraviolet light exposure such as KrF excimer laser light, or X-ray irradiation using a chemical amplification method.

[0069]

The operation of the present invention will be described with reference to specific examples. First, the site irradiated with an electron beam generates an acid according to the reaction represented by the following formula 2, 3, 4, 5, 6, or 7, for example. I do.

[0070]

(Equation 2)

[0071]

(Equation 3)

[0072]

(Equation 4)

[0073]

(Equation 5)

[0074]

(Equation 6)

[0075]

Equation 7

When a heat treatment is performed after the irradiation step, the following formula 8 is obtained.
According to the reaction formula, a specific functional group of the polymer according to the present invention (in Formula 8, exemplified as 1-ethoxyethoxy group) undergoes a chemical change by an acid to become a hydroxyl group, becomes alkali-soluble, and It elutes in the developer.

[0077]

(Equation 8)

On the other hand, since no acid is generated in the non-irradiated portion, no chemical change occurs even by heat treatment. Instead, the acid generator forms the hydrophilic group site of the polymer used for the purpose of enhancing the adhesion to the substrate. An effect of protecting from infiltration of the alkali developing solution is exhibited. Thus, when a pattern is formed using the resist material of the present invention, a large solubility difference in an alkali developing solution occurs between an irradiated part and an unirradiated part, and the polymer of the unirradiated part is formed on the substrate. Because of its strong adhesion to, it does not cause film peeling during development, and as a result,
A positive pattern having good contrast is formed. In addition, since the acid generated by electron beam irradiation acts as a catalyst as shown in the above formula 8, the electron beam irradiation only needs to generate the necessary acid, and the irradiation energy amount can be reduced. In addition, since an organic alkali aqueous solution can be used as a developing solution, there is no swelling of the developing solution and no harm to the environment and the human body. Hereinafter, the present invention will be described in more detail with reference to Examples, Production Examples, Reference Examples, and Comparative Examples, but the present invention is not limited by these.

Production Example 1 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] [Method-1] (1) Synthesis of p-bromo (1-ethoxyethoxy) benzene 50 g (0.29 mol) of p-bromophenol, ethyl 41.7 g (0.58 mol) of vinyl ether and p-toluenesulfonic acid
1.5 g of the pyridine salt was dissolved in 300 ml of methylene chloride, and the mixture was stirred and reacted at room temperature for 6 hours. Next, 400 ml of a 5% aqueous sodium hydrogen carbonate solution was injected, and after stirring, the mixture was allowed to stand still to separate the organic layer, which was washed with water (300 ml × 3) and dried over anhydrous magnesium sulfate. After filtering off the desiccant, the solvent was distilled off and the residue 82
g was distilled under reduced pressure to obtain 71.1 g of p-bromo (1-ethoxyethoxy) benzene of a bp. 112 to 114 ° C./6 mmHg fraction as a slightly yellow oily substance. ¹ H NMR δ ppm (CDCl ₃ ): 1.20 (3H, t, J = 7 Hz, -CH ₂ C H ₃ ), 1.
49 (3H, d, J = 5.1Hz, -OCHC H ₃ ), 3.47-3.83 (2H, m, -C H ₂ CH
3), 5.31~5.37 (1H, q , J = 5.5Hz, -OC H CH 3), 6.95 (2H, d, J =
8.8Hz, aromatic ring 2-H, 6-H), 7.32 (2H, d, J = 8.8Hz, aromatic ring
3-H, 5-H). IR (Neat) νcm ^-1 : 2970,2930,2890,1595,1490.

(2) Synthesis of p- (1-ethoxyethoxy) styrene In a nitrogen stream, 3.7 g (0.15 atom) of metallic magnesium (sharpened) was suspended in 30 ml of dry tetrahydrofuran, and the suspension was obtained in the above (1). 35 g (0.14 mol) of p-bromo (1-ethoxyethoxy) benzene in dry tetrahydrofuran (15
0 ml) The solution was added dropwise under reflux with stirring, and further refluxed with stirring for 1 hour. Next, the reaction solution was cooled to 10 ° C., and then dichloro {1,2-bis (diphenylphosphino) ethane} nickel was added.
0.8 g, and 15.3 g (0.14 g) of vinyl bromide under a nitrogen stream.
Mol) in dry tetrahydrofuran (50 ml)
C. and the mixture was further stirred at room temperature for 1 hour. After injecting 200 ml of aqueous ammonium chloride solution into the reaction solution, 200 ml of methylene chloride was added.
Was injected, stirred and allowed to stand. Separate the organic layer and wash with water (20
0 ml × 2), dried over anhydrous magnesium sulfate, and the desiccant was filtered off. The solvent was distilled off, and 30 g of the residue was distilled under reduced pressure by addition of tert-butyl catechol (polymerization inhibitor).
21.5 g of p- (1-ethoxyethoxy) styrene of -96 ° C / 1 mmHg fraction was obtained as a colorless oil. ¹ H NMR δ ppm (CDCl ₃ ): 1.20 (3H, t, J = 7 Hz, CH ₂ C H ₃ ), 1.
50 (3H, d, J = 5.1Hz, -OCHC H ₃ ), 3.49-3.85 (2H, m, -C H ₂ C
_{H 3), 5.13 (1H,} d, J = 10.6Hz, C H 2 = CH -), 5.35~5.41 (1H,
q, J = 5.5Hz, -OC H CH ₃ ), 5.62 (1H, d, J = 17.6Hz, CH ₂ = CH
-), 6.66 (1H, dd , J = 10.6Hz and _{17.6Hz, CH 2 = C H -} ), 6.95
(2H, d, J = 8.8Hz, aromatic ring 3-H, 5-H), 7.33 (2H, d, J = 8.8H
z, aromatic ring 2-H, 6-H). IR (Neat) νcm ^-1 : 2970,2930,2890,1635 (C = C), 1605,150
Five. Elemental analysis (C ₁₂ H ₁₆ O ₂ ) Theory: C% 74.97; H% 8.39 Observed: C% 75.08: H% 8.33

(3) Polymerization of p- (1-ethoxyethoxy) styrene p- (1-ethoxyethoxy) styrene obtained in the above (2)
A catalytic amount of 2,2′-azobisisobutyronitrile was added to 19.2 g, and a polymerization reaction was carried out in a toluene solvent at 80 ° C. for 6 hours under a nitrogen stream. After cooling, the reaction solution was poured into 1000 ml of methanol with stirring, allowed to stand, decanted, and the viscous oil obtained was further washed twice with 500 ml of methanol, and then concentrated under reduced pressure to obtain a poly (p- (1 -Ethoxyethoxy) styrene] 16.3g
Was obtained as a slightly yellow viscous oil. This product was measured by GPC (polystyrene standard) and found to have a weight average molecular weight (Mw) of about 10
000, the number average molecular weight (Mn) was about 5500.

(4) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 15.5 g of poly [p- (1-ethoxyethoxy) styrene] obtained in the above (3) was added to 1,4 g -Dissolve in 150 ml of dioxane, oxalic acid
1.6 g was added thereto, and the mixture was stirred and refluxed for 3 hours. After cooling, the reaction solution was poured into 1000 ml of water, crystallized with stirring, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to obtain poly [p- (1-ethoxyethoxy). 1) Styrene-p-hydroxystyrene] as white powdery crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer is ¹ HNM
The R measurement (calculated from the integral ratio of methine hydrogen at 5.2 to 5.4 ppm and aromatic ring hydrogen at 6.2 to 6.8 ppm) showed about 1: 1. Weight average molecular weight: about 8500, Mw / Mn ≒ 1.8 (GPC method: polystyrene standard).

Production Example 2 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] [Method-2] 9.6 g of p- (1-ethoxyethoxy) styrene obtained in (2) of Production Example 1 and 6.0 of p-hydroxystyrene After performing a polymerization reaction in the same manner as in Production Example 1 (3) using g, the reaction solution was poured into 1,000 ml of petroleum ether and crystallized.
The precipitated crystals were collected by filtration, washed, and dried under reduced pressure to obtain 12.8 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene].
Was obtained as white powdery crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained copolymer was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight: about 9000, Mw / Mn ≒ 2.0 (GPC method: polystyrene standard).

Production Example 3 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] [Method-3] (1) Polymerization of p-tert-butoxystyrene A catalytic amount of 2,2 ′ was added to 17.6 g of p-tert-butoxystyrene. -Azobisisobutyronitrile was added, and a polymerization reaction was carried out in a toluene solvent at 80 ° C for 6 hours under a nitrogen stream. After cooling, the reaction solution was poured into 1000 ml of methanol for crystallization, and the precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 15.5 g of poly (p-tert-butoxystyrene) as white powder crystals. Weight average molecular weight: about 10,000 (GPC method: polystyrene standard).

(2) Synthesis of poly (p-hydroxystyrene) 15.0 of poly (p-tert-butoxystyrene) obtained in (1) above
g was dissolved in 1,4-dioxane, 10 ml of concentrated hydrochloric acid was added, and the mixture was stirred and refluxed for 4 hours. After cooling, the reaction solution was poured into 1000 ml of water for crystallization, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9.7 g of poly (p-hydroxystyrene) as white powder crystals.

(3) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 4.0 g of poly (p-hydroxystyrene) obtained in the above (2) and 1.5 g of ethyl vinyl ether were mixed with 1,4- 35 ml of a mixture of dioxane and pyridine
, And a catalytic amount of p-toluenesulfonic acid was added thereto, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction, 1000 ml of water
The reaction solution was poured into the mixture, and the mixture was crystallized. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly [p- (1-ethoxyethoxy) styrene].
p-Hydroxystyrene] was obtained as white powdery crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight about 10,000
(GPC method: polystyrene standard).

Production Example 4 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] [Method-4] Poly (p-hydroxystyrene) [Maruzen Petrochemical Co., Ltd., weight average molecular weight about 10,000, number average molecular weight about 500]
0: trade name: Marcalinker M] 8.0 g and ethyl vinyl ether 3.0 g were dissolved in 1,4-dioxane 70 ml, p-toluenesulfonic acid / pyridine salt 0.5 g was added, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction, the reaction solution was poured into water and crystallized by stirring. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 10.0 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] as white powder. As obtained. P- (1-Ethoxyethoxy) styrene unit of the obtained polymer and p-
The composition ratio of the hydroxystyrene unit was about 1: 1 based on ¹ HNMR measurement. Weight average molecular weight about 11000 (GPC method:
Polystyrene standard).

Production Example 5 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 4.0 g of poly (p-hydroxystyrene) and 1.5 g of ethyl vinyl ether obtained in (2) of Production Example 3 were dissolved in acetone. Was added with a catalytic amount of sulfuric acid / pyridine salt, and the mixture was stirred and reacted at room temperature for 12 hours. Next, the reaction solution was poured into 1000 ml of water and crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 3.9 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] as white powder crystals. Was. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer was about 35: 6 by ¹ HNMR measurement.
It was five. Weight average molecular weight about 10,000 (GPC method: poly
Styrene standard).

Production Example 6 Synthesis of poly [p- (1-methoxyethoxy) styrene-p-hydroxystyrene] [Method-1] (1) Synthesis of p-bromo (1-methoxyethoxy) benzene 17.3 g (0.1 mol) of p-bromophenol and methyl Preparation Example 1 (1) using 14.0 g (0.2 mol) of vinyl ether
The reaction and post-treatment were carried out in the same manner as in
The residue was distilled under reduced pressure at 24 g to obtain 20.8 g of p-bromo (1-methoxyethoxy) benzene as a slightly yellow oily substance at a bp of 89 to 90 ° C./2 mmHg fraction. ¹ HNMR δ ppm (CDCl ₃ ): 1.46 (3H, d, J = 5.4 Hz, OCHC H ₃ ),
3.37 (3H, s, -OC H 3), 5.29 (1H, q, J = 5.5Hz, OC H CH 3), 6.86
(2H, d, J = 8.8Hz, aromatic ring 2-H, 6-H), 7.36 (2H, d, J = 8.8H
z, aromatic ring 3-H, 5-H). IR (Neat) νcm ^-1 : 3000,2940,2850,1590,1580,1490.

(2) Synthesis of p- (1-methoxyethoxy) styrene Using 11.6 g of p-bromo (1-methoxyethoxy) benzene obtained in (1) above, the same procedure as in (2) of Production Example 1 was carried out. And 10.7 g of the obtained crude oil was p-tert-
Distillation under reduced pressure in the presence of butyl catechol, bp.
8.8 g of p- (1-methoxyethoxy) styrene from the mmHg fraction was obtained as a colorless oil. ¹ HNMR δ ppm (CDCl ₃ ): 1.46 (3H, d, J = 5.5 Hz, OCHC H ₃ ),
3.37 (3H, s, -C H 3), 5.12 (1H, d, J = 11Hz, C H 2 = CH -), 5.30
(1H, q, J = 5.1Hz and 5.5Hz, OC H CH ₃ ), 5.60 (1H, d, J = 17.6
_{Hz, C H 2 = CH -} ), 6.64 (1H, dd, J = 11Hz and J = 17.6Hz, CH ₂
= C H -), 6.95 ( 2H, d, J = 8.8Hz, aromatic 3-H, 5-H) , 7.32 (2
H, d, J = 8.8Hz, aromatic ring 2-H, 6-H). IR (Neat) νcm ^-1 : 2980,2920,2820,1620 (C = C), 1600,150
0. Elemental analysis (C ₁₁ H ₁₄ O ₂ ) Theory: C% 74.13; H% 7.92 Observed: C% 74.41; H% 7.88

(3) Polymerization of p- (1-methoxyethoxy) styrene The p- (1-methoxyethoxy) styrene obtained in the above (2) 8.0
Using g, the reaction and post-treatment were carried out in the same manner as in Production Example 1 (3) to obtain poly [p- (methoxyethoxy) styrene] 7.
2 g were obtained as a slightly yellow viscous oil. Weight average molecular weight approx.
10,000, number average molecular weight about 5000 (GPC method: polystyrene standard).

(4) Synthesis of poly [p- (1-methoxyethoxy) styrene-p-hydroxystyrene] Manufactured using 6.2 g of poly [p- (1-methoxyethoxy) styrene] obtained in (3) above. The reaction and post-treatment were carried out in the same manner as in Example 1, (4) to obtain 3.0 g of poly [p- (1-methoxyethoxy) styrene-p-hydroxystyrene] as white powdery crystals. P- (1-Methoxyethoxy) of the obtained polymer
Constituent ratio of styrene unit to p-hydroxystyrene unit is ¹ H
It was about 45:55 from NMR measurement. Weight average molecular weight 9000, M
w / Mn ≒ 1.8 (GPC method: polystyrene standard).

Production Example 7 Synthesis of poly [p- (1-methoxy-1-methylethoxy) styrene-p-hydroxystyrene] 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Production Example 3 and 4.8 g of 2-methoxy-1-propene Was dissolved in 35 ml of a mixture of 1,4-dioxane and pyridine, a catalytic amount of chlorosulfonic acid was added thereto, and the mixture was stirred and reacted at room temperature for 20 hours. After the reaction, the reaction solution was treated in the same manner as in (2) of Production Example 2 to obtain 4.1 g of poly [p- (1-methoxy-1-methylethoxy) styrene-p-hydroxystyrene] as white powdery crystals. The composition ratio of p- (1-methoxy-1-methylethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

Production Example 8 Synthesis of poly [p- (1-n-butoxyethoxy) styrene-p-hydroxystyrene] 4.8 g of the poly (p-hydroxystyrene) obtained in (2) of Production Example 3 and 3.0 g of n-butyl vinyl ether were mixed with 1, The mixture was dissolved in 50 ml of a mixture of 4-dioxane and pyridine, a catalytic amount of sulfuric acid was added thereto, and the mixture was stirred and reacted at room temperature for 16 hours. After the reaction, the reaction solution was treated in the same manner as in Production Example 2 (3) to obtain 4.2 g of poly [p- (1-n-butoxyethoxy) styrene-p-hydroxystyrene] as white powdery crystals. The composition ratio of p- (1-n-butoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer was 4: 6 by ¹ HNMR measurement.
Met. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

Production Example 9 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-fumaronitrile] (1) Synthesis of poly (p-tert-butoxystyrene-fumaronitrile) 28.2 g (0.16 g) of p-tert-butoxystyrene Mol) and 3.1 g (0.04 mol) of fumaronitrile were subjected to a polymerization reaction in a toluene solvent at 90 ° C. for 2 hours under a nitrogen stream in the presence of a catalytic amount of 2,2′-azobis (methyl 2-methylpropionate). After the reaction, the reaction solution was poured into methanol for crystallization, and the precipitated crystals were collected by filtration, washed and dried to obtain 21.3 g of poly (p-tert-butoxystyrene-fumaronitrile) as white powder crystals.

(2) Synthesis of poly (p-hydroxystyrene-fumalonitrile) Using 20.0 g of poly (p-tert-butoxystyrene-fumalonitrile) obtained in (1) above, instead of concentrated hydrochloric acid. The reaction and post-treatment were carried out in the same manner as in Production Example 3 (2) except that p-toluenesulfonic acid was used, to obtain 10.6 g of poly (p-hydroxystyrene-fumaronitrile) as white powdery crystals. Weight average molecular weight about 10,000 (GPC method: polystyrene standard).

(3) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-fumaronitrile] 9.0 g of poly (p-hydroxystyrene-fumaronitrile) obtained in (2) above and ethyl Using 3.0 g of vinyl ether, the reaction and post-treatment were carried out in the same manner as in (3) of Production Example 3 to obtain 8.8 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-fumaronitrile] as white powder. Obtained as crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer was about 4: 6 by ¹ HNMR measurement. Weight average molecular weight approx.
11000 (GPC method: polystyrene standard).

Production Example 10 Poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-methacrylic acid t
Synthesis of ert-butyl] (1) Synthesis of poly [p- (1-ethoxyethoxy) styrene-tert-butyl methacrylate] 17.3 g of p- (1-ethoxyethoxy) styrene obtained in (2) of Production Example 1 (0.09 mol) and tert-butyl methacrylate
A catalytic amount of 2,2′-azobis (methyl 2-methylpropionate) was added to 1.4 g (0.01 mol), and a polymerization reaction was carried out in a toluene solvent at 80 ° C. for 8 hours in a nitrogen stream. After cooling, the reaction solution was poured into petroleum ether with stirring, allowed to stand, decanted, and the crude viscous oil obtained was washed twice with 500 ml of methanol and then concentrated under reduced pressure to obtain poly [p- (1-ethoxy). [Ethoxy) styrene-tert-butyl methacrylate] 15.5 g was obtained as a pale yellow viscous oil. Weight average molecular weight about 12000 (GPC
Method: polystyrene standard).

(2) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-tert-butyl methacrylate] The poly [p- (1-ethoxyethoxy) styrene obtained in the above (1) was used. 12.0 g of tert-butyl methacrylate] was dissolved in 1,4-dioxane, 0.5 g of p-toluenesulfonic acid was added, and the mixture was added at 80 ° C.
For 30 minutes with stirring. After cooling, the reaction solution was poured into 1000 ml of water, crystallized with stirring, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-tert-methacrylic acid. Butyl] as white powdery crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer was about 35:65 by ¹ HNMR measurement. Weight average molecular weight about 11000 (GPC method: polystyrene standard).

Production Example 11. Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] (1) Synthesis of poly [p- (1-ethoxyethoxy) styrene] p- (1) obtained in Production Example 1 (2) A catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) was added to 19.2 g of (-ethoxyethoxy) styrene, and the mixture was added to 1,4-dioxane under a nitrogen stream at 80 ° C for 3 hours and then at 90 ° C for 4 hours. The polymerization reaction was carried out for an hour.
After cooling, the reaction solution was poured into 1,000 ml of an aqueous methanol solution,
The viscous oil obtained by standing and decanting was further treated with methanol 5
After washing twice with 00 ml, the mixture was concentrated under reduced pressure and the residue poly [p-
(1-ethoxyethoxy) styrene] was obtained as a slightly yellow viscous oil. Weight average molecular weight about 25000 (GPC
Method: polystyrene standard).

(2) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] Manufactured using 16.5 g of poly [p- (1-ethoxyethoxy) styrene] obtained in (1) above. The reaction and post-treatment were carried out in the same manner as (4) of Example 1 to obtain 13.5 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] as white powdery crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit in the obtained polymer is ¹ HNM
It was about 35:65 from the R measurement. Weight average molecular weight about 2200
0 (GPC method: polystyrene standard).

Production Example 12 Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-tert-butoxystyrene-p-hydroxystyrene] (1) Synthesis of poly (p-tert-butoxystyrene-p-hydroxystyrene) 20 g of the poly (p-tert-butoxystyrene) obtained in (1) was dissolved in 1,4-dioxane, 4 ml of concentrated hydrochloric acid was added, and the mixture was stirred and refluxed for 2 hours. After cooling, the mixture was treated in the same manner as in Production Example 3 (2) to obtain poly (p-tert-butoxystyrene).
12.0 g of (p-hydroxystyrene) was obtained as white powdery crystals. P-tert-butoxystyrene unit of the obtained polymer and
The composition ratio of the p-hydroxystyrene unit was about 1: 9 by ¹ HNMR measurement.

(2) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-tert-butoxystyrene-p-hydroxystyrene] The poly (p-tert-butoxystyrene-p- obtained in (1) above) 6.3 g of hydroxystyrene) and 1.0 of ethyl vinyl ether
The reaction and post-treatment were carried out in the same manner as in Production Example 3 (3) using g, to obtain poly [p- (1-ethoxyethoxy) styrene-p-
tert-butoxystyrene-p-hydroxystyrene] 4.6
g were obtained as white powder crystals. The composition ratio of p- (1-ethoxyethoxy) styrene unit, p-tert-butoxystyrene unit and p-hydroxystyrene unit in the obtained polymer is ¹ HNMR.
It was about 25:10:65 from the measurement. Weight average molecular weight about 1
0000 (GPC method: polystyrene standard).

Reference Example 1 Synthesis of poly (p-tetrahydropyranyloxystyrene-p-hydroxystyrene) Poly (p-hydroxystyrene) [Maruzen Petrochemical Co., Ltd., weight average molecular weight about 10,000, number average molecular weight about 5000: trade name
9.0 g of Marcalinker M] in 100 ml of dimethoxyethane, then 12.6 g of 3,4-dihydro-2H-pyran and 0.1 g of sulfuric acid.
5 ml was added and the mixture was stirred at 30 to 40 ° C for 15 hours. After the reaction, the reaction solution was concentrated under reduced pressure, the residue was neutralized with sodium carbonate, and water 1000
The reaction mixture was poured into a ml, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-tetrahydropyranyloxystyrene-p-
11.0 g of hydroxystyrene) was obtained as white powdery crystals.
The composition ratio of p-tetrahydropyranyloxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 3: 7 by ¹ HNMR measurement. Weight average molecular weight about 10,000 (G
PC method: polystyrene standard).

Reference Example 2 Poly (p-tert-butoxystyrene-p-hydroxystyrene) synthesis
Hydroxystyrene) [Maruzen Petrochemical Co., Ltd., weight-average molecular weight: about 10,000, number-average molecular weight: about 5,000: trade name: Marcalinker M] 4.0 g and dimethoxyethane 70 ml were added, and 60 g of isobutylene and 0.3 g of sulfuric acid were added at -60 ° C After the addition, the reaction was stirred at 45 ° C. for 1 hour and then at room temperature for 22 hours. After the reaction, the reaction solution was concentrated, the residue was neutralized with sodium carbonate, poured into 1000 ml of water, crystallized, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-tert-butoxystyrene-p). -Hydroxystyrene) was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene unit and p-hydroxystyrene unit in the obtained polymer was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight about 10,000 (GP
Method C: polystyrene standard).

Reference Example 3 Synthesis of poly (p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene) (1) 22 g (0.1 mol) of p-tert-butoxycarbonyloxystyrene obtained according to the method described in U.S. Pat. No. 4,491,628 (1985) ) In the presence of a 2,2'-azobis (2,4-dimethylvaleronitrile) catalyst under a nitrogen stream in toluene at 90 ° C for 4 hours. After cooling the reaction solution,
The mixture was poured into methanol for crystallization, and the precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 15.2 g of poly (p-tert-butoxycarbonyloxystyrene) as white powder crystals. Weight average molecular weight: about 12000 (GPC method: polystyrene standard).

(2) 7.0 g of the poly (p-tert-butoxycarbonyloxystyrene) obtained in the above (1) was dissolved in 1,4-dioxane, 5 ml of concentrated hydrochloric acid was added, and the mixture was stirred and refluxed for 1.5 hours. After cooling, the reaction solution was poured into 1000 ml of water and allowed to crystallize, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain poly (p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene).
4.8 g were obtained as white powder crystals. P-ter of the obtained polymer
The composition ratio of the t-butoxycarbonyloxystyrene unit and the p-hydroxystyrene unit was about 1: based on ¹ HNMR measurement.
It was one. Weight average molecular weight: about 9500 (GPC method: polystyrene standard).

Reference Example 4. Synthesis of 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane (1) 23.9 g (0.98 atom) of metallic magnesium (cut off) was suspended in ethyl ether, and suspended in ethyl ether. Under stirring and reflux, 160 g (0.98 mol) of bromocyclohexane was added dropwise, and the mixture was refluxed with stirring for 1 hour. After cooling, the resulting Grignard reagent was added dropwise to a solution of 95 g (0.89 mol) of isobutyric acid chloride in ethyl ether at -5 to 0 ° C, and the mixture was stirred and reacted at the same temperature for 3 hours, and then left at room temperature overnight. The reaction solution was poured into water, the separated ether layer was separated, washed with water, and dried over anhydrous magnesium sulfate. After filtering off the drying agent, the solvent is distilled off,
The residue was distilled under reduced pressure to obtain 50 g of 1-cyclohexyl-2-methyl-1-propanone of a bp. 95 to 100 ° C./20 mmHg fraction as a pale yellow oil. ¹ H NMR δ ppm (CDCl ₃ ): 1.06 (6H, d, CH ₃ × 2), 1.12 to 1.8
7 (10H, m, cyclohexane ring C H ₂ × 5), 2.51 (1 H, m, cyclohexane ring CH), 2.76 (1 H, m, C H ). IR (Neat) νcm ^-1 : 1710 (C = O).

(2) 1-cyclohexyl-2- obtained in the above (1)
42 g (0.31 mol) of sulfuryl chloride was added dropwise to 47.6 g (0.31 mol) of methyl-1-propanone at 25 to 35 ° C.
The reaction was stirred for 3.5 hours. After concentration of the reaction solution, distillation under reduced pressure
p. 99-100 ° C./18 mmHg fraction, 30.1 g of 2-chloro-1-cyclohexyl-2-methyl-1-propanone was obtained as a yellow oil. _{^{1 HNMR δppm (CDCl 3):}} 1.18~1.87 (16H, m, C H 3 × 2 and cyclohexane ring _{C H 2 × 5), 3.13} (1H, m, cyclohexane ring C
H ).

(3) To a solution of 30.0 g (0.16 mol) of 2-chloro-1-cyclohexyl-2-methyl-1-propanone obtained in (2) above in dimethyl sulfoxide (DMSO) was added 30.0 g of sodium p-toluenesulfinate. (0.17 mol), 60 ℃
For 20 hours. The reaction solution was poured into cold water,
After stirring at ５5 ° C. for 1 hour, the precipitated crystals were collected by filtration, washed with water and dried to obtain 18 g of crude crystals. This was recrystallized from an n-hexane-benzene mixture to give 2- (cyclohexylcarbonyl) -2-
13.5 g of (p-toluenesulfonyl) propane was obtained as white needles. mp. 123-123.5 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.19~1.91 (16H, m, C H 3 × 2 and cyclohexane ring _{C H 2 × 5), 2.45} (3H, s, Ph-C H 3), 3.25 (1H,
m, cyclohexane ring C H ), 7.33 (2H, d, J = 8 Hz, aromatic ring 3-
H, 5-H), 7.65 (2H, d, J = 8Hz, aromatic ring 2-H, 6-H). IR (KBr) νcm ^-1 : 1705 (C = O), 1310.

Reference Example 5. Synthesis of 2-methyl-2- (p-toluenesulfonyl) propiophenone Using 29.6 g (0.2 mol) of isobutyrophenone in the same manner as in (2) and (3) of Production Example 4 After performing the reaction and post-treatment, the crude crystals were recrystallized from methanol to give 2-methyl-2-
21.2 g of (p-toluenesulfonyl) propiophenone were obtained as white needles. mp. 64-64.5 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.70 (6H, s, C H 3 × 2), 2.45 (3H,
s, Ph-C H ₃ ), 7.32 (2H, d, J = 7Hz, p-methylbenzene ring 3-
H, 5-H), 7.44 (2H, t, J = 7Hz, aromatic ring 3-H, 5-H), 7.54 (1
H, t, J = 7Hz, aromatic ring 4-H), 7.67 (2H, d, J = 7Hz, p-methylbenzene ring 2-H, 6-H), 7.95 (2H, d, J = 7Hz, aromatic Ring 2-H, 6
-H). IR (KBr) νcm ^-1 : 1680,1303,1290.

Reference Example 6. Synthesis of 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one Using 22.8 g (0.2 mol) of diisopropyl ketone, the procedure of (2) and (3) of Production Example 4 was repeated. The reaction and post-treatment were performed in the same manner, and the crude crystals were recrystallized from a mixed solution of n-hexane and benzene.
16.5 g of 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one was obtained as white flaky crystals. mp. 76-79 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.15 (6H, d, C H 3 × 2), 1.55 (6H,
s, C H ₃ × 2), 2.45 (3H, s, Ph-C H ₃ ), 3.54 (1H, m, J = 7Hz, C
H ), 7.34 (2H, d, J = 8 Hz, aromatic ring 3-H, 5-H), 7.65 (2H, d, J =
8Hz, aromatic ring 2-H, 6-H). IR (KBr) νcm ^-1 : 1715 (C = O), 1305, 1290.

Reference Example 7 Synthesis of methylsulfonyl p-toluenesulfonyldiazomethane (1) 22.5 g (0.35 mol) of sodium azide was dissolved in a small amount of water and diluted with 130 ml of 90% aqueous ethanol.
Then, at 10 to 25 ° C, 60 g of p-toluenesulfonyl chloride
(0.32 mol) in which an ethanol solution was added dropwise, and the mixture was stirred and reacted at room temperature for 2.5 hours. Then, the reaction solution was concentrated under reduced pressure, and the residual oily product was washed several times with water and dried over anhydrous magnesium sulfate. The drying agent was filtered off to obtain 50.7 g of p-toluenesulfonyl azide as a colorless oil. _{^{1 HNMR δppm (CDCl 3):}} 2.43 (3H, s, C H 3), 7.24 (2H, d, J = 8
Hz, aromatic ring 3-H, 5-H), 7.67 (2H, d, J = 8Hz, aromatic ring 2-H, 6
-H). IR (Neat) νcm ⁻¹ : 2120 (N ₃ ).

(2) Methylthiomethyl p-tolylsulfone
6.0 g (0.03 mol) was dissolved in methanol (40 ml) and water (40 ml), and sodium tungstate (60 mg) was added.
6.8 g (0.06 mol) of a hydrogen peroxide solution was added dropwise at 45 to 50 ° C., and the mixture was reacted for 10 hours under reflux with stirring. After standing overnight at room temperature, the reaction solution was poured into 400 ml of water, and the precipitated crystals were collected by filtration, washed with water and dried, and 7.2 g of the obtained crude crystals were recrystallized from ethanol to give methylsulfonyl p-toluenesulfonylmethane.
6.1 g were obtained as white needles. mp. 163.5-165 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.48 (3H, s, Ph-C H 3), 3.28 (3H, s,
_{C H 3), 4.56 (2H} , s, C H 2), 7.40 (2H, d, J = 8Hz, aromatic 3-H,
5-H), 7.87 (2H, d, J = 8Hz, aromatic ring 2-H, 6-H).

(3) 0.84 g of sodium hydroxide was dissolved in 50 ml of 60% aqueous ethanol, and 5.0 g (0.02 mol) of methylsulfonyl p-toluenesulfonylmethane obtained in the above (2) was added thereto. Next, 4.0 g (0.02 mol) of p-toluenesulfonyl azide obtained in the above (1) in ethanol (5 ml)
The solution was added dropwise at 0 to 5 ° C., and then reacted at the same temperature for 4 hours with stirring. After the reaction, the precipitated crystals were collected by filtration, washed with cold methanol and dried, and 3 g of crude crystals obtained were recrystallized from ethanol to obtain 2.2 g of methylsulfonyl p-toluenesulfonyldiazomethane.
Was obtained as slightly yellow flaky crystals. mp. 107.5-109 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.46 (3H, s, Ph-C H 3), 3.42 (3H, s,
C H ₃ ), 7.38 (2H, d, J = 8 Hz, aromatic ring 3-H, 5-H), 7.87 (2H, d,
J = 8Hz, aromatic ring 2-H, 6-H). IR (KBr) νcm ^-1 : 2120 (CN ₂ ), 1350,1330.

Reference Example 8 Bis (p-toluenesulfonyl)
Synthesis of diazomethane (1) To 20 g (0.16 mol) of p-thiocresol was added 10.7 g (0.16 mol) of potassium hydroxide to ethanol (60 ml) and water (15 ml).
ml) was added dropwise at room temperature, and the mixture was stirred and reacted at room temperature for 15 minutes. Then 13.7 g (0.16 mol) of methylene chloride
Was injected, and the mixture was stirred and reacted at 50 ± 5 ° C. for 4 hours. After leaving overnight at room temperature, 30 ml of ethanol and 30 ml of water were poured into the reaction solution,
After diluting and adding 600 mg of sodium tungstate, 75 g of a 30% hydrogen peroxide solution is added dropwise at 45 to 60 ° C.
The reaction was stirred at 60 ° C. for 9 hours. After the reaction, 1200 ml of cold water was injected, and the precipitated crystals were collected by filtration, washed with water and dried, and 26 g of the crude crystals were recrystallized from ethanol to obtain 19.8 g of bis (p-toluenesulfonyl) methane as white crystals. mp. 126 ~
128 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.47 (6H, s, C H 3 × 2), 4.69 (2H, s,
C H ₂ ), 7.37 (4H, d, J = 8 Hz, aromatic ring 3-H, 5-H), 7.83 (4H, d, J
= 8Hz, aromatic ring 2-H, 6-H). IR (KBr) νcm ^-1 : 1310 (SO ₂ ).

(2) 10.0 g (0.03 mol) of bis (p-toluenesulfonyl) methane obtained in the above (1) and 7.3 g (0.037 mol) of p-toluenesulfonyl azide obtained in (1) of Reference Example 7
The reaction and after-treatment were carried out in the same manner as in (3) of Reference Example 7, and 5 g of the obtained crude crystals were recrystallized from ethanol to obtain 3.5 g of bis (p-toluenesulfonyl) diazomethane as pale yellow flaky crystals. As obtained. mp. 121.5-123 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.46 (6H, s, C H 3 × 2), 7.36 (4H, d,
J = 8Hz, aromatic ring 3-H, 5-H), 7.87 (4H, d, J = 8Hz, aromatic ring 2-
H, 6-H). IR (KBr) νcm ^-1 : 2110 (CN ₂ ), 1345.

Reference Example 9 Synthesis of bis (2,4-dimethylbenzenesulfonyl) diazomethane (1) Reaction and post-treatment were carried out in the same manner as in (1) of Reference Example 8 using 10 g (0.07 mol) of 2,4-dimethylthiophenol. 11 g of the obtained crude crystals were recrystallized from a mixed solution of ethanol / ethyl acetate to obtain 6.1 g of bis (2,4-dimethylbenzenesulfonyl) methane as white crystals. ¹ HNMR δ ppm (CDCl ₃ ): 2.39 (6H, s, p-Ph-C H ₃ × 2), 2.60
(6H, s, o-Ph-C H ₃ × 2), 4.73 (2H, s, C H ₂ ), 7.11 to 7.17 (4H,
m, (aromatic ring 3-H, 5-H) × 2), 7.77 (2H, d, J = 8Hz, (aromatic ring 6-
H) x 2).

(2) 5 g (0.014 mol) of bis (2,4-dimethylbenzenesulfonyl) methane obtained in (1) and 2.8 g (0.014 mol) of p-toluenesulfonyl azide obtained in (1) of Reference Example 7
The reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 7 using 5.2 g of the obtained crude crystals, and 5.2 g of the obtained crude crystals were recrystallized from ethanol to obtain bis (2,4-dimethylbenzenesulfonyl) diazomethane 3.3 g. g were obtained as pale yellow flaky crystals. mp. 1
35-136 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 2.39 (6H, s, p-Ph-CH ₃ × 2), 2.56
(6H, s, o-Ph-C H ₃ × 2), 7.09 to 7.15 (4H, m, (aromatic ring 3-H, 5
-H) × 2), 7.79 (2H, d, J = 8 Hz, (aromatic ring 6-H) × 2). IR (KBr) νcm ^-1 : 2140 (CN ₂ ), 1340 (SO ₂ ).

Reference Example 10 Synthesis of diphenyldisulfone In 260 ml of 5% diluted hydrochloric acid, 100 g (0.50 mol) of sodium benzenesulfinate dihydrate was added little by little at room temperature, and the mixture was stirred at room temperature for 30 minutes, and the precipitate was separated by filtration. A mixture of 42.6 g (0.42 mol) of triethylamine and 85 ml of water was added dropwise to the filtrate at 5 ° C. or lower, and then 88.3 g (0.42 mol) of benzenesulfonyl chloride was added dropwise at 0 to 5 ° C.
The mixture was stirred and reacted for minutes. After the reaction, the precipitated crystals were collected by filtration and washed with water to obtain 38 g of crude crystals (Wet). The crude crystals (Wet) were recrystallized from benzene to obtain 7.2 g of diphenyldisulfone as white prism crystals. mp. 188.5-190.0C. ¹ HNMR δ ppm (CDCl ₃ ): 7.65 to 8.05 (10H, m, aromatic ring). IR (KBr) νcm ^-1 : 1580,1440,1340,1330,1300.

Reference Example 11 Synthesis of p-tolyl phenyldisulfone Instead of sodium benzenesulfinate dihydrate
Reference Example 10 using sodium p-toluenesulfinate
Reaction and post-treatment were carried out in the same manner as described above, and the obtained crude crystals were recrystallized from benzene to give p-tolylphenyldisulfone.
9.5 g were obtained as white prism crystals. mp.153.5〜154.5
° C. _{^{1 HNMR δppm (CDCl 3):}} 2.51 (3H, s, C H 3), 7.43 (2H, d, J = 8
Hz, tolyl ring 2-H, 6-H), 7.55-7.98 (7H, m, tolyl ring 3-
H, 5-H and phenyl ring). IR (KBr) νcm ^-1 : 1595,1450,1348.

Reference Example 12 Synthesis of 3-phenyl-5,6,7,8-tetrahydro-2,1-benzoxatiin-1,1-dioxide (1) Synthesis of 2- (cyclohexen-1-yl) -1-phenylethenone Sodium ethoxy 41 g of ethanol was dissolved in 1000 ml of ethanol, added to a mixed solution of 72 g (0.6 mol) of acetophenone and 59 g (0.6 mol) of cyclohexanone at 0 to 5 ° C., and reacted by stirring at the same temperature for 8 hours and then at 15 to 20 ° C. for 9 hours. . After the reaction solution was concentrated under reduced pressure, the residue was poured into a solution consisting of 60 ml of concentrated hydrochloric acid and 3500 ml of cold water, and extracted twice with 1000 ml of ethyl acetate. The organic layer was washed with water, dried over anhydrous MgSO ₄ , and 98 g of the residue obtained by distilling off the solvent was distilled under reduced pressure to give a 2- (cyclohexen-1-yl) -1-phenylether fraction of bp 130-140 ° C./4 mmHg. Non
15.6 g was obtained as a yellow viscous oil. ¹ H NMR δ ppm (CDCl ₃ ): 1.36 to 2.54 (8H, m, cyclohexene ring C H ₂ × 4), 3.13 (2H, s, -C H _2- ), 5.57 (1H, s, cyclohexene ring -C H = ), 7.38-7.62 (3H, m, aromatic ring 3-H, 4-H, 5-
H), 7.90-8.05 (2H, m, aromatic ring 2-H, 6-H). IR (Neat) νcm ⁻¹ : 1685 (C = 0).

(2) 3-phenyl-5,6,7,8-tetrahydro-2,
Synthesis of 1-benzoxatiin-1,1-dioxide 7.8 g (39 mmol) of 2- (cyclohexen-1-yl) -1-phenylethenone obtained in the above (1) was added to 9.3 g (92 mmol) of acetic anhydride. Then, 3.8 g (39 mmol) of sulfuric acid was added dropwise at -10 ° C, and the mixture was stirred and reacted at 0 to 5 ° C for 7 hours.
8 ml of cold water was poured into the reaction solution, and the precipitated crystals were collected by filtration, washed with water, petroleum ether and then with cold methanol to obtain 3.9 g of crude crystals. The crude crystal was recrystallized from methanol to give 3-phenyl-5,6,
1.5 g of 7,8-tetrahydro-2,1-benzoxatiin-1,1-dioxide was obtained as pale yellow crystals. 132-136 ° C. ¹ HNMR δppm (CDCl ₃ ): 1.41 to 2.67 (8H, m, 2,1-benzoxathine ring C H ₂ × 4), 6.30 (1H, s, 2.1-benzoxathine ring) -C H =), 7.31~7.47 (3H , m, aromatic ring 3H, 4-H, 5- H),
7.53 to 7.72 (2H, m, aromatic ring 2-H, 6-H). IR (KBr) νcm ⁻¹ : 1365 (SO ₂ ), 1180 (SO ₂ ).

Reference Example 13 Synthesis of 4,6-dimethyl-1,2-oxathiin-2,2-dioxide 4-methyl-3-penten-2-one 22.6 g (0.23 mol) was dissolved in acetic anhydride 55.4 g (0.54 mol). 23.8 g (0.24 mol) of sulfuric acid was added dropwise at -10 to -5 ° C, and the mixture was stirred and reacted at 0 to 5 ° C for 6 hours. 250 ml of cold water was poured into the reaction solution, and the precipitated crystals were collected by filtration, washed with water and dried to obtain 17.1 g of crude crystals. The crude crystal was recrystallized from a benzene / n-hexane mixture to give 4,6-dimethyl-1,2
10.8 g of -oxathiin-2,2-dioxide was obtained as red-purple prism crystals. mp. 68-70 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.04 (3H, s, C H 3), 2.15 (3H, s, C
_{H 3), 5.61 (1H,} s, -C H =), 6.26 (1H, s, -C H =). IR (KBr) νcm ⁻¹ : 1340 (SO ₂ ), 1165 (SO ₂ ).

Reference Example 14 p-Toluenesulfonic acid 2,6-
Synthesis of dinitrobenzyl (1) 2,6-dinitrobenzaldehyde 19.6 g (0.1 mol)
Was suspended in 200 ml of methanol, 5.8 g of sodium borohydride was gradually added at 15 to 25 ° C., and the mixture was stirred and reacted at room temperature for 1 hour. After the reaction, the solvent was distilled off.
l, and 100 ml of chloroform were added, and the mixture was stirred and reacted for 1 hour. The mixture was allowed to stand, separated, and separated into chloroform layers.
It was dried over anhydrous magnesium sulfate. After the desiccant was removed by filtration, the solvent was distilled off, and the remaining 2,6-dinitrobenzyl alcohol 15.0
g were obtained as yellow crystals. mp. 92.5-93.5 ° C. ¹ H NMR δ ppm (CDCl ₃ ): 2.77 (1 H, t, J = 7 Hz, O H ), 4.97 (2
H, d, J = 7Hz, C H 2), 7.66 (1H, t, J = 8Hz, aromatic 4-H), 8.08
(2H, t, J = 8Hz, aromatic ring 3-H, 5-H).

(2) 14.9 g (0.075 mol) of 2,6-dinitrobenzyl alcohol obtained in the above (1) and 15.7 g (0.083 mol) of p-toluenesulfonyl chloride were dissolved in 150 ml of acetone, and 15 g of dicyclohexylamine was added thereto. Was added dropwise at 0 to 10 ° C., and the mixture was stirred and reacted at room temperature for 4 hours. After the reaction, the precipitate was separated by filtration, and the residue obtained by concentrating the filtrate (29 g) was recrystallized from carbon tetrachloride to give 19.8 g of 2,6-dinitrobenzyl p-toluenesulfonate as pale yellow flaky crystals. Obtained. mp. 98-99 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.45 (3H, s, C H 3), 5.57 (2H, s, C
H ₂ ), 7.34 (2H, d, J = 8Hz, p-methylbenzene ring 3-H, 5-
H), 7.68 (1H, t, J = 8Hz, dinitrobenzene ring 4-H), 7.72
(2H, d, J = 8Hz, p-methylbenzene ring 2-H, 6-H), 7.72 (2H,
d, J = 8Hz, dinitrobenzene ring 3-H, 5-H). IR (KBr) νcm ^-1 : 1680,1303,1290.

Reference Example 15. Synthesis of 2,2-bis (p-toluenesulfonyl) propane 20 g (0.16 mol) of p-thiocresol and 4.7 g of acetone
(0.08 mol) in 50 ml of ethyl ether,
Introduced hydrogen chloride for 1.5 hours. After the reaction, the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate, 120 ml of acetone and 10 ml of water were poured into the residue obtained by evaporating the solvent, and 500 mg of sodium tungstate was added. 85 g was added dropwise at 40 to 50 ° C., and the mixture was stirred and refluxed for 3.5 hours. After the reaction, 4000 ml of cold water was poured into the reaction solution, and the precipitated crystals were collected by filtration, washed with water and dried, and 4.8 g of crude crystals obtained were recrystallized from ethanol to give 2.5 g of 2,2-bis (p-toluenesulfonyl) propane. Was obtained as white crystals. mp. 156-158.
5 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.70 (6H, s, C H 3 × 2), 2.47 (6H, s,
Ph-C H ₃ × 2), 7.38 (4H, d, J = 8Hz, (aromatic ring 3-H, 5-H) ×
2), 7.89 (4H, d, J = 8 Hz (aromatic ring 2-H, 6-H) x 2). IR (KBr) νcm ⁻¹ : 1325 (SO ₂ ), 1305 (SO ₂ ).

Reference Example 16 Synthesis of di-p-tolylsulfone The reaction and post-treatment were carried out in the same manner as in Reference Example 10 using 22.3 g (0.125 mol) of sodium p-toluenesulfinate and 23.8 g (0.12 mol) of p-toluenesulfonyl chloride. The crude crystals recrystallized from toluene
9.3 g of tolyldisulfone was obtained as white prism crystals.
mp. 204.5-205.0 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.51 (6H, s, C H 3), 7.43 (4H, d, J = 8.4
Hz, aromatic ring (2-H, 6-H) x 2), 7.84 (4H, d, J = 8.4 Hz, aromatic ring (3
-H, 5-H) x 2). IR (KBr) νcm ^-1 : 1345 (SO ₂ ).

Reference Example 17 p-tolyl n-butyl disul
Synthesis of hon (1) p-Toluenesulfonyl chloride (40g) tetra
27 ml of 85% hydrazine hydrate in a solution of hydrofuran (70 ml)
After dropwise addition at 10 to 15 ° C and stirring at the same temperature for 30 minutes,
The crystals were collected by filtration, and the crude crystals were recrystallized from methanol to give p-toluene
15.8 g of ruphonyl hydrazide was obtained as white crystals. m
p. 109-112 ° C.¹ HNMR δppm (CDCl_Three): 2.35 (3H, s, CH ₃ ), 4.26 (2H, bs, NH
_Two  ), 7.38 (2H, d, J = 8 Hz, aromatic ring 3-H, 5-H), 7.67 (2H, d, J = 8H
z, aromatic ring 2-H, 6-H), 8.28 (1H, bs,NH). IR (KBr) νcm^-1: 3388,3262,1315.

(2) To a solution of 4.66 g (0.025 mol) of p-toluenesulfonyl hydrazide obtained in the above (1) in pyridine (5 ml), 3.92 g (0.025 mol) of n-butylsulfonyl chloride was added dropwise at 3 to 8 ° C. Then, the mixture was stirred at 10 to 15 ° C for 30 minutes and left at 15 to 20 ° C overnight. Dilute hydrochloric acid (1000m
The precipitate was collected by filtration and recrystallized from toluene to give 4.84 g of Np-toluenesulfonyl-N'-n-butylsulfonylhydrazine as white crystals. mp.124-126.5
° C. _{^{1 HNMR δppm (CDCl 3):}} 0.86 (3H, t, J = 7.3Hz, C H 3 CH 2 -), 1.
_{28~1.44 (2H, m, CH 3} C H 2 CH 2), 1.54~1.68 (2H, m, CH 3 CH 2
C H ₂ CH _2- ), 2.39 (3H, s, C H ₃ ), 3.00 (2H, t, J = 7.6Hz, SO ₂
C H ₂ CH _2- ), 7.42 (2 h, D, J = 8 Hz, aromatic ring 3-H, 5-H), 7.69 (2
H, d, J = 8Hz, aromatic ring 2-H, 6-H), 9.21 (1H, bs, NH SO ₂ CH ₂
-), 9.92 (1H, bs , NH NHSO 2 CH 2 -). IR (KBr) νcm ^-1 : 3236,3192,1330.

(3) 1 g (3.26 mol) of Np-toluenesulfonyl-N'-n-butylsulfonylhydrazine obtained in the above (2)
1.9 g (19.5 mol) of 65% nitric acid was added dropwise at 10 ° C or less to
Stirred at 1010 ° C. for 1 hour. Then, the reaction solution was poured into ice water, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure. The obtained crude crystals (0.3 g) were recrystallized from n-hexane / ethyl acetate to give p-
0.2 g of tolyl n-butyldisulfone was obtained as white needles. mp. 67.5-70.0C. _{^{1 HNMR δppm (DMSO-d 6}} ): 0.8
7 (3H, t, J = 7.3Hz, C H 3 CH 2 -), 1.33~1.49 (2H, m, CH 3 C H 2
CH ₂ ), 1.67 to 1.82 (2H, m, CH ₃ CH ₂ CH ₂ CH _2- ), 2.49 (3H, s,
_{C H 3), 3.69 (2H} , t, J = 7.6Hz, -SO 2 C H 2 CH 2 -), 7.63 (2H,
d, J = 8Hz, aromatic ring 3-H, 5-H), 7.92 (2H, d, J = 8Hz, aromatic ring 2-
H, 6-H). IR (KBr) νcm ^-1 : 1348 (SO ₂ ).

Reference Example 18 Synthesis of p-tolyl p-chlorophenyldisulfone (1) Using 5.04 g (27 mmol) of p-toluenesulfonylhydrazide obtained in (1) of Reference Example 17 and 5.68 g (27 mmol) of p-chlorobenzenesulfonyl chloride The reaction and post-treatment were carried out in the same manner as in (2) of Reference Example 17, and the obtained crude crystals were recrystallized from methanol to give Np-toluenesulfonyl-N'-p-chlorophenylsulfonylhydrazine 4.52
g were obtained as white crystals. _{^{1 HNMR δppm (DMSO-D 6}} ): 2.40 (3H, s, C H 3), 7.37~7.77 (8H,
m, aromatic ring), 9.66 (1H, bs, NH ), 9.77 (1H, bs, NH ).

(2) 2.00 g of Np-toluenesulfonyl-N'-p-chlorophenylsulfonylhydrazine obtained in the above (1)
(5.54 mmol), and the reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 17, and the obtained crude crystals were recrystallized from toluene to give p-tolyl p-chlorophenyldisulfone 1.1.
5 g were obtained as white prism crystals. mp.161.0-161.5 ℃
(Disassembly). _{^{1 HNMR δppm (CDCl 3):}} 2.52 (3H, s, C H 3), 7.44~7.92 (8H, m,
Aromatic ring). IR (KBr) νcm ^-1 : 1349 (SO ₂ ).

Reference Example 19 Synthesis of p-tolyl isopropyl disulfone (1) Using 4.66 g (0.025 mol) of p-toluenesulfonyl hydrazide obtained in (1) of Reference Example 17 and 3.57 g (0.025 mol) of isopropyl sulfonyl chloride,
The reaction and post-treatment were carried out in the same manner as in (2) above, and 5.7 g of the obtained crude crystals were separated by column chromatography [filler: Wakogel
C-200 (manufactured by Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / ethyl acetate (8/1 → 5/1 → 1/1)] to give Np-toluenesulfonyl-N′-isopropylsulfonylhydrazine 1.3
g were obtained as white crystals. mp 187-190 ° C. ¹ HNMR δ ppm (CDCl ₃ / DMSO-d ₆ ): 1.26 (6H, d, J = 7 Hz, (C H ₃ )
_{2 CH -), 2.36 (3H} , s, C H 3), 3.28~3.47 (1H, m, C H), 7.25 (2H,
d, J = 8Hz, aromatic ring 3-H, 5-H), 7.70 (2H, d, J = 8Hz, aromatic ring 2-
H, 6-H), 8.49 (1H, d, J = 2Hz, NH ), 9.49 (1H, d, J = 2Hz, NH ). IR (KBr) νcm ^-1 : 3207 (NH), 1335 (SO ₂ ).

(2) 1.20 g (0.04 g) of Np-toluenesulfonyl-N'-isopropylsulfonylhydrazine obtained in the above (1)
1 mol), and the reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 17, and the obtained crude crystals were recrystallized from n-hexane / ethyl acetate to give p-tolylisopropyldisulfone.
0.35 g was obtained as white crystals. mp. 150-152 ° C (decomposition). ¹ H NMR δ ppm (DMSO-d ₆ ): 1.39 (6 H, d, J = 7 Hz, (C H ₃ ) ₂ CH-),
2.45 (3H, s, C H 3), 3.92~4.07 (1H, m, CH), 7.59 (2H, d, J = 8H
z, aromatic ring 3-H, 5-H), 7.87 (2H, d, J = 8 Hz, aromatic ring 2-H, 6-
H). IR (KBr) νcm ^-1 : 1341 (SO ₂ ).

Reference Example 20 Synthesis of p-tolyl benzyldisulfone (1) Using 5.03 g (0.027 mol) of p-toluenesulfonyl hydrazide obtained in (1) of Reference Example 17 and 5.15 g (0.027 mol) of benzylsulfonyl chloride, (2) of Reference Example 17 )
The reaction and post-treatment were carried out in the same manner as described above.
0.81 g of benzylsulfonylhydrazine was obtained as white crystals. mp. 183-185 ° C. _{^{1 HNMR δppm (DMSO-d 6}} ): 2.40 (3H, s, C H 3), 4.34 (2H, s, SO 2
C H _2- ), 7.35 to 7.44 (7H, m, p-tolyl ring 3-H, 5-H and phenyl ring), 7.73 (2H, d, J = 8.4 Hz, p-tolyl ring 2-H, 6 -H), 9.38
(1H, s, NH ), 10.08 (1H, s, NH ). IR (KBr) νcm ^-1 : 3456 (NH), 3250 (NH), 1342 (SO ₂ ), 1329 (S
O ₂ ).

(2) Using 2.0 g (5.8 mmol) of Np-toluenesulfonyl-N'-benzylsulfonylhydrazine obtained in (1) above, the reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 17. The resulting crude crystals were recrystallized from methanol to obtain 0.81 g of p-tolyl benzyldisulfone as white crystals. mp.149-150.5 ° C. _{^{1 HNMR δppm (DMSO-d 6}} ): 2.47 (3H, s, C H 3), 5.13 (2H, s, SO 2
C H _2- ), 7.33 to 7.49 (5H, m, phenyl ring), 7.58 (2H, d, J = 8.4H
z, p-tolyl ring 3-H, 5-H), 7.85 (2H, d, J = 8.4Hz, p-tolyl ring
2-H, 6-H). IR (KBr) νcm ^-1 : 1350 (SO ₂ ).

Reference Example 21 Synthesis of p-tolyl p-methoxyphenyldisulfone (1) Using 4.66 g (0.025 mol) of p-toluenesulfonylhydrazide obtained in (1) of Reference Example 17 and 5.17 g (0.025 mol) of p-methoxyphenylsulfonyl chloride The reaction and post-treatment were carried out in the same manner as in (2) of Reference Example 17, and the obtained crude crystals were recrystallized from acetone to give Np-toluenesulfonyl-N'-p-methoxyphenylsulfonylhydrazine 2.75
g were obtained as white needles. mp. 209-210.5 ° C. _{^{1 HNMR δppm (DMSO-d 6}} ): 2.39 (3H, s, C H 3), 3.84 (3H, s, C H 3
O), 7.10 (2H, d, J = 8.4Hz, p-methoxyphenyl ring 3-H, 5-
H), 7.38 (2H, d, J = 8.4 Hz, p-tolyl ring 3-H, 5-H), 7.64 (2H,
d, J = 8.4Hz, p-tolyl ring 2-H, 6-H), 7.68 (2H, d, J = 8.8Hz, p-
Methoxyphenyl ring 2-H, 6-H), 9.48 (1H, bs, NH ), 9.56 (1H,
bs, NH ). IR (KBr) νcm ^-1 : 3206 (NH), 1341 (SO ₂ ).

(2) Np-toluenesulfonyl-N'-p-methoxyphenylsulfonylhydrazine 2.00 obtained in (1) above
(5.61 mol), and the reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 17, and the obtained crude crystals were recrystallized from acetone to give p-tolyl p-methoxyphenyldisulfone 1.10.
g were obtained as white crystals. mp.174-176 ° C. _{^{1 HNMR δppm (DMSO-d 6}} ): 2.47 (3H, s, C H 3), 3.93 (3H, s, C H 3
O), 7.26 (2H, d, J = 8.8Hz, p-methoxyphenyl ring 3-H, 5-
H), 7.56 (2H, d, J = 8.4 Hz, p-tolyl ring 3-H, 5-H), 7.69 (2H,
d, J = 8.4Hz, p-tolyl ring 2-H, 6-H), 7.73 (2H, d, J = 8.8Hz, p
-Methoxyphenyl ring 2-H, 6-H). IR (KBr) νcm ^-1 : 1342 (SO ₂ ).

Reference Example 22 Synthesis of p-tolyl octyl disulfone (1) Using 4.66 g (0.025 mol) of p-toluenesulfonyl hydrazide obtained in (1) of Reference Example 17 and 5.32 g (0.025 mol) of octanesulfonyl chloride in Reference Example 17, (2) )
The reaction and post-treatment were carried out in the same manner as described above.
Recrystallization from n-hexane / methylene chloride gave 3.65 g of Np-toluenesulfonyl-N'-octanesulfonylhydrazine as white crystals. mp. 95-98 ° C. ¹ HNMR δppm (DMSO-d ₆ ): 0.89 (3H, t, J = 6.7Hz,-(CH ₂ ) ₇ C
_{H 3), 1.12~1.43 (10H,} m, -CH 2 (C H 2) 5 CH 3), 1.53~1.72
_{(2H, m, SO 2 CH} 2 C H 2 CH 2 -), 2.40 (3H, s, C H 3 -Ph), 3.01 (2
H, t, J = 7.6Hz, SO ₂ C H ₂ CH _2- ), 7.42 (2H, d, J = 8.1Hz, aromatic ring 3-H, 5-H), 7.64 (2H, d, J = 8.1 Hz, aromatic ring 2-H, 6-H), 9.20
(1H, d, J = 2.4Hz, NH ), 9.91 (1H, d, J = 2.4Hz, NH ). IR (KBr) ν
^{cm -1: 3236 (NH),} 1346 (SO 2), 1325 (SO 2).

(2) Using 2.00 g (5.4 mmol) of Np-toluenesulfonyl-N'-octanesulfonylhydrazine obtained in (1) above, the reaction and post-treatment were carried out in the same manner as in (3) of Reference Example 17. The resulting crude crystals were recrystallized from n-hexane / methylene chloride to give 1.05 g of p-tolyloctyldisulfone.
Was obtained as white needles. mp. 56.5-57.5 ° C. _{^{1 HNMR δppm (DMSO-d 6}} ): 0.86 (3H, t, J = 6.6Hz, - (CH 2) 7 C H 3
), 1.15~1.47 (10H, m, -CH 2 (C H 2) 5 CH 3), 1.74 (2H, m, J =
_{5.9Hz, SO 2 CH 2 C H} 2 CH 2 -), 2.50 (3H, s, C H 3 -Ph), 3.69 (2
H, t, J = 5.1Hz, SO ₂ C H ₂ CH _2- ), 7.63 (2H, d, J = 8.1Hz, aromatic ring 3-H, 5-H), 7.92 (2H, d, J = 8.1 Hz, aromatic ring 2-H, 6-H). IR (KBr) νcm ^-1 : 1346 (SO ₂ ).

Experimental Example 1 Hereinafter, a resist material and a fine pattern forming method according to the present experimental example will be described with reference to the drawings. A resist material having the following composition was prepared, and a pattern was formed as described below. Poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] (Polymer of Production Example 1) 20.0 g Diphenyldisulfone (Acid generator of Reference Example 10) 0.1
g Diethylene glycol dimethyl ether 80.0 g FIG. 1 is a process sectional view in the fine pattern forming method according to the present invention. A resist material having the above composition is spin-coated (2000 rpm, 60 seconds) on a semiconductor substrate 11 or the like,
After prebaking on a hot plate for 2 seconds, a resist film 12 having a thickness of 1.0 μm was obtained. Next, electron beam lithography is performed at an acceleration voltage of 50 KeV and a dose of 0.1 to 300 μC / cm ² ,
After baking on a hot plate at 90 ° C. for 90 seconds, development was performed for 60 seconds with an alkali developing solution (2.38% TMAH aqueous solution) to obtain a positive pattern. FIG. 2 shows a sensitivity curve showing the relationship between the residual film ratio of the resist and the irradiation dose in this pattern formation. The sensitivity curve shows that the sensitivity of this resist film is about 0.5 μC / cm ² . or,
An acceleration voltage of 50 KeV and a dose of 1 μC /
Electron beam lithography was performed in cm ² (FIG. 1a), baking was performed at 100 ° C. for 90 seconds, and development was performed for 60 seconds, thereby obtaining an accurate and fine positive type resist pattern 12p (FIG. 1b). The minimum pattern obtained at this time is a vertical shape
It was a 0.2 μm line and space pattern, indicating that a high-resolution fine resist pattern was obtained. As described above, by using the above resist material, a fine positive resist pattern can be formed with high sensitivity and high resolution.

Experimental Example 2 A resist material having the following composition was prepared. Poly [p- (1-methoxy-1-methylethoxy) styrene-
p- hydroxystyrene] and polymer) 20.0 g p- toluenesulfonic acid 2,6-di-nitrobenzyl (acid generator of Reference Example 14) 0.4 g of diethylene glycol dimethyl ether 80.0g Example 1 using the resist material of Preparation 7 Obtained in the same way 1.
Acceleration voltage 50 KeV, dose 0.1 on 0 μm resist film
Electron beam lithography was performed at ~ 300 µC / cm ² , baking was performed at 100 ° C for 90 seconds, and development was performed with a normal organic alkali developer for 60 seconds to obtain a positive resist pattern. FIG. 3 shows a sensitivity curve showing the relationship between the resist remaining film ratio and the irradiation dose in this pattern formation. From this sensitivity curve, it can be seen that the sensitivity of this resist film is about 0.8 μC / cm ² . An acceleration voltage of 50 Ke is applied to this resist film.
V, electron beam writing at a dose of 1 μC / cm ²
After baking at 90 ° C. for 90 seconds and development for 60 seconds, an accurate and fine positive resist pattern was obtained. The minimum pattern obtained at this time was a vertical 0.2 μm line and space pattern, and a fine resist pattern with high resolution was obtained.

Experimental Example 3 FIG. 4 shows a method of forming a resist pattern for the following experimental example .
This will be described with reference to FIG. An organic polymer film-forming material containing a novolak resin as a main component was applied on the semiconductor substrate 41, and heated at 200 ° C. for 20 minutes to form an organic lower layer film 42 having a thickness of 2 μm (FIG. 4A). SOG on the lower film
(Spin on glass) was applied, and heat treatment was performed at 200 ° C. to form an intermediate layer 43 having a thickness of 0.2 μm. Next, the resist material described in Experimental Example 1 was spin-coated (4000 rpm, 60 seconds) on the intermediate layer, and heat-treated at 90 ° C. for 90 seconds to form a resist.
An upper resist film 44 having a thickness of μm was formed. A pattern was drawn on the resist film with an electron beam having an acceleration voltage of 20 KeV and a dose of 1.5 μC / cm ² (FIG. 4B). This substrate was heat-treated at 100 ° C. for 90 seconds, and then developed with a normal organic alkali developing solution for 60 seconds to form an upper resist pattern 44p.
(FIG. 4c). Next, the intermediate layer was etched using the obtained resist pattern as a mask. The selectivity of the upper resist to the intermediate layer was about 3, and the pattern was transferred accurately, and an intermediate layer pattern was obtained. Further, using the obtained intermediate layer pattern as a mask, the organic lower layer film was etched to obtain a 0.2 μm vertical, fine pattern (FIG. 4D). As described above, by using the resist material according to Experimental Example 1 as the upper layer resist of the three-layer resist process, a fine pattern with high sensitivity, high resolution, and high stability can be formed.

Experimental Example 4 After forming an organic underlayer film and an inorganic intermediate film on a semiconductor substrate in the same manner as in Experimental Example 3 , the resist material described in Experimental Example 2 was spin-coated (4000 rpm, 60 seconds) on the intermediate film, and then heated at 90 ° C. and 90 ° C. Heat treatment was performed for 2 seconds to form an upper resist film having a thickness of 0.5 μm. An acceleration voltage of 20 KeV and a dose of 1.5 are applied to the resist film.
A pattern was drawn with an electron beam of μC / cm ² . After heat-treating this substrate at 100 ° C. for 90 seconds, it was developed with a normal organic alkali developing solution for 60 seconds to obtain an upper resist pattern.
Next, the intermediate layer was etched using the obtained resist pattern as a mask. The selectivity of the upper resist to the intermediate layer was about 3, and the pattern was accurately transferred to obtain an intermediate layer pattern. Further, using the intermediate layer pattern as a mask, the organic lower layer film was etched to obtain a vertical and fine pattern of 0.2 μm.

Examples 1 to 5 Resist materials having the compositions shown in Tables 1 and 2 below were prepared.

[0147]

[Table 1]

[0148]

Using each resist material prepared with the above composition, a pattern was formed in the same manner as in Experimental Example 1 .
Table 2 shows the results.

[0150]

[Table 2]

[0151] Also in the one embodiment of the obvious as in Examples 1-5 from Table 2, to obtain a fine positive pattern was a good shape.

Comparative Example 1 A resist material having the following composition was prepared. Poly (p-tert-butoxycarbonyloxystyrene-p-
(Hydroxystyrene) (Polymer of Reference Example 3) 20.0 g Triphenylphosphonium hexafluorophosphate 0.1 g Diethylene glycol dimethyl ether 80.0 g Obtained in the same manner as in Experimental Example 1 using the above resist material.
Acceleration voltage 50 KeV, dose 1 on 1.0 μm resist film
A pattern was drawn with an electron beam of μC / cm ² and processed in the same manner as in Experimental Example 1 to form a positive pattern. However, as shown in FIG. 5, good results were not obtained with an inverted trapezoidal shape. .

Comparative Example 2 A resist material having the following composition was prepared. Poly (p-tetrahydropyranyloxystyrene-p-hydroxystyrene) (Polymer of Reference Example 1) 20.0 g Diphenyliodonium hexafluorophosphate 0.1 g Diethylene glycol dimethyl ether 80.0 g Obtained in the same manner as in Experimental Example 1 using the above resist material. Was
Acceleration voltage 30 KeV, dose 1 on 1.0 μm resist film
A pattern was drawn with an electron beam of μC / cm ² and processed in the same manner as in Experimental Example 1 to form a positive pattern.
No good results were obtained with the inverted trapezoidal shape as in the case of.

[0154]

As is apparent from the above description, by using the resist material of the present invention as an electron beam resist, it is possible to form a positive resist pattern having high sensitivity, high resolution and stable pattern dimensions. Can be formed. Particularly, the polymer according to the present invention is characterized in that it has a protecting group that can be easily removed in the presence of an acid, and extremely high sensitivity can be achieved by combining this with an appropriate acid generator. And the throughput is improved. In addition, since an alkaline aqueous solution can be used as a developing solution, there is no swelling during development, there is no problem on the environment and on the human body, a fine pattern can be easily formed, and production of an ultra-high-density integrated circuit can be achieved. Is of great value. The material for forming a fine pattern of the present invention is most effective for forming a pattern using an electron beam. However, far ultraviolet light such as KrF excimer laser light,
It can be sufficiently used in pattern formation using X-rays or the like.

[0155]

[Brief description of the drawings]

FIG. 1 is a process sectional view of a fine pattern forming method in Experimental Example 1 of the present invention.

FIG. 2 is a sensitivity curve showing a relationship between a dose amount of a resist material and a residual film ratio in Experimental Example 1 of the present invention.

FIG. 3 is a sensitivity curve showing a relationship between a dose of a resist material and a residual film ratio in Experimental Example 2 of the present invention.

FIG. 4 is a process sectional view of a fine pattern forming method in Experimental Example 3 of the present invention.

FIG. 5 is an inverted trapezoidal shape defect pattern in Comparative Example 1 of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masataka Endo 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Akiko Katsuyama 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-2-19847 (JP, A) JP-A-3-223860 (JP, A) JP-A Heisei JP-A-3-223865 (JP, A) JP-A-3-223865 (JP, A) JP-A-3-222866 (JP, A) JP-A-4-219757 (JP, A) JP-A-4-211258 (JP, A A) JP-A-62-61047 (JP, A) JP-A-3-282550 (JP, A) JP-A-2-161436 (JP, A) JP-A-3-137649 (JP, A) JP-A-2 −249226 (JP, A) JP-A-3-14511 8 (JP, A) JP-A-3-66119 (JP, A) JP-A-6-51517 (JP, A) JP-A-5-281745 (JP, A) JP-A-5-249682 (JP, A) JP-A-6-214395 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (8)

(57) [Claims] 1. A compound of the general formula [I] [In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R
³ is each independently a hydrogen atom or a straight-chain having 1 to 6 carbon atoms,
Represents a branched or cyclic alkyl group (provided that R ² and R ³
Excludes when both are hydrogen atoms. ), Also may form a methylene chain having 2 to 5 carbon atoms in R ² and R ^3, R ⁴ is a straight-chain having 1 to 10 carbon atoms, branched or cyclic alkyl group, the carbon number Represents a linear, branched or cyclic haloalkyl group or an aralkyl group of 1 to 6, R ⁵ represents a hydrogen atom or a cyano group, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a hydrogen atom , A cyano group, -COOY (where Y represents 1 carbon atom)
Represents a linear, branched or cyclic alkyl group of 1 to 6; )
Or the following general formula [II]: (However, Z represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms.) Represents
Further, R ⁵ and R ⁷ may be made combines with -CO-O-CO- each other, k, l and m are each independently <br/> table to {However natural numbers and, 0.1 ≦ k /(K+1)≦0.9, 0.05 ≦ m /
(K + 1 + m) ≦ 0.50. ｝ And a polymer represented by the following general formula [VI] : [Wherein R ¹² represents a hydrogen atom, a halogen atom, an alkyl group or
Represents an alkoxy group, R ¹³ is a linear group having 1 to 6 carbon atoms,
Branched or cyclic alkyl group, phenyl group, alkyl group
Substituted phenyl group, halogen-substituted phenyl group or alkoxy
Represents a substituted phenyl group. ], The general formula [X] [of 4] Wherein R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom
Atom, halogen atom, C1-C10 linear, branched or
Cyclic alkyl group, haloalkyl group having 1 to 10 carbon atoms, charcoal
An alkoxyalkyl group having a prime number of 2 to 10, an aralkyl group,
Phenyl group, substituted phenyl group (substituents are halogen atoms,
A linear, branched or cyclic alkyl group having a prime number of 1 to 10,
Represents a lucoxy group, a nitro group, or a cyano group. )
R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ are each independently
Alicyclic, heteroalicyclic, aromatic ring or
It may form a heteroaromatic ring. ] Or the general formula [XI] [of 5] [Wherein R ²⁶ is a hydrogen atom, a halogen atom, a carbon number of 1 to 10
Linear, branched or cyclic alkyl group and alkoxy group
Wherein R ²⁷ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
The stands, R ²⁸ represents an alkyl group having 1 to 3 carbon atoms, R ²⁹
Is a linear, branched or cyclic alkyl having 1 to 10 carbon atoms
Group, aralkyl group, phenyl group, substituted phenyl group (substituted
The group is a halogen atom, a straight-chain, branched or 1 to 10 carbon atoms.
Represents a cyclic alkyl group or an alkoxy group. )
You. A resist material comprising an acid generator capable of generating an acid upon irradiation with an electron beam, and a solvent capable of dissolving the acid generator. 2. A general formula [I '] embedded image [In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² and R
³ is each independently a hydrogen atom or a straight-chain having 1 to 6 carbon atoms,
Represents a branched or cyclic alkyl group (provided that R ² and R ³
Excludes when both are hydrogen atoms. ), And R ² and R ³ are carbon
The methylene chain of several to 5 may be formed, and R ⁴ is a carbon
A linear, branched or cyclic alkyl group of 1 to 10 primes, carbon
Linear, branched or cyclic haloalkyl having a prime number of 1 to 6
R ⁵ represents a hydrogen atom or a aralkyl group;
R ⁶ represents a hydrogen atom or a methyl group ^;
Is represented by the following general formula [II] : (However, Z is a hydrogen atom, a halogen atom, a C1-6
Linear or branched alkyl group, linear chain having 1 to 10 carbon atoms
Represents a branched, branched or cyclic alkoxy group. ),
k, l, and m each independently represent a natural number.
≦ k / (k + 1) ≦ 0.9, 0.05 ≦ m / (k + 1 + m) ≦
0.50. ｝. A polymer represented by the following general formula:
[V] embedded image [Wherein, R ⁸ represents an alkyl group, an aralkyl group, a trifluoro group.
Romethyl group, phenyl group, alkyl-substituted phenyl group,
Shows alkoxy-substituted phenyl group and halogen-substituted phenyl group
And R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl
Represents a group, R ¹¹ is an alkyl group, a phenyl group, an alkyl location
Substituted phenyl group, alkoxy substituted phenyl group, halogen substitution
Represents a substituted phenyl group or an alkylthio-substituted phenyl group.
You. ], The general formula [VII] [Image Omitted] Wherein R ¹⁴ is a trichloroacetyl group, p-toluenesulfur
Phonyl group, p-trifluoromethylbenzenesulfonyl
Group, methanesulfonyl group or trifluoromethanesulfo
And R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom,
Represents a halogen atom or a nitro group. ] Or the general formula [VI
II] [of 10] [Wherein, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogeno
Atom, or a linear or branched alkyl having 1 to 6 carbon atoms
R ¹⁹ represents a straight-chain, branched or
Cyclic alkyl group, or the following general formula [IX] embedded image (However, R ²⁰ and R ²¹ are each independently a hydrogen atom, a halogeno
Atom, or a linear or branched alkyl having 1 to 6 carbon atoms
Represents a hydroxyl group. ). ] Of the electron beam
An acid generator capable of generating an acid upon irradiation and
Characterized by comprising a solvent capable of dissolving etc.
Material. 3. A polymer represented by the general formula [I] or [I '], which is represented by the following general formula [III] : Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above. A monomer unit represented by the following general formula [IV] : Wherein R ² , R ³ and R ⁴ are the same as above. P- and m-hydroxystyrene derivatives having a functional group represented by the formula:
3. The resist material according to claim 1, wherein the resist material is derived from at least one monomer selected from the group consisting of m-hydroxy-α-methylstyrene derivative. 4. The method according to claim 1, wherein the monomers are p- and m-1-methoxy-1-methylethoxystyrene, p- and m-1-benzyloxy-1-methylethoxystyrene, p- and m-1-ethoxyethoxystyrene, p- and m-1-methoxyethoxystyrene. -And m-1-methoxyethoxystyrene, p- and m-
1-n-butoxyethoxystyrene, p- and m-1-isobutoxyethoxystyrene, p- and m-1- (1,1-dimethylethoxy) -1-methylethoxystyrene, p- and m-1- ( 1,1-dimethylethoxy) ethoxystyrene, p- and m-1- (2-chloroethoxy) ethoxystyrene, p- and m-1-cyclohexyloxyethoxystyrene, p- and m-1- (2-ethylhexyloxy ) Ethoxystyrene, p- and m-1-ethoxy-1-methylethoxystyrene, p- and m-1-n-propoxyethoxystyrene, p- and m-1-ethoxypropoxystyrene, p- and m-1- Methoxybutoxystyrene, p- and
The resist material according to claim 3, which is one or more monomers selected from the group consisting of m-1-methoxycyclohexyloxystyrene. 5. A process for forming a resist film by applying (i) applying the resist material according to claim 1 or 2 on a semiconductor substrate and subjecting it to a heat treatment, and (ii) drawing a pattern by irradiating an electron beam. After that, if necessary, a heat treatment step,
(Iii) forming a positive pattern by performing development using an alkaline aqueous solution. 6. A process for forming an underlayer film by applying and heating an organic polymer solution on a semiconductor substrate, (ii) forming an inorganic intermediate film on the underlayer film, and (iii) 3. ) a step of applying the resist material according to claim 1 or 2 on the intermediate film and heat-treating to form a resist film;
After drawing the pattern by irradiating the electron beam,
A step of performing heat treatment as necessary; (v) a step of forming a positive pattern by performing development using an alkaline aqueous solution; and (vi) a step of etching the intermediate film using the resist pattern as a mask. And (vii) a step of forming a pattern by etching the lower layer film using the pattern obtained as a mask as a mask. 7. The method according to claim 6 , wherein the organic polymer solution is a solution containing a novolak resin as a main component. 8. The method according to claim 6 , wherein the inorganic intermediate film is a silicon oxide film or spin-on-glass.