JPH09204046A - Novel resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material having high resolving power to far UV, etc., undergoing no change with the lapse of time and giving a high precision pattern by incorporating a specified polymer, a photosensitive compd. which generates an acid by exposure and a solvent capable of dissolving them. SOLUTION: This resist material contains a polymer represented by the formula, a photosensitive compd. which generates an acid by exposure and a solvent capable of dissolving them. In the formula, R<1> is H or methyl, each of R<2> and R<3> is H, 1-6C straight chain, branched or cyclic alkyl, both of R<2> and R<3> are not H, R<4> is 1-10C straight chain, branched or cyclic alkyl, etc., R<5> is H or cyano, R<6> is H or methyl, R<7> is H, cyano, etc., each of (k) and (l) is a natural number, 0.1<=k/(k+1)<=0.9, (m) is 0 or a natural number and 0.05<=m/(k+l+m)<=0.50.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist material used in the manufacture of semiconductor devices and the like. For details, far ultraviolet light of 300 nm or less, such as 248.4
The present invention relates to a resist material used when forming a positive pattern by using KrF excimer laser light of nm.

[0002]

2. Description of the Related Art In recent years, with the high integration of semiconductor devices, the light source of an exposure apparatus used for microfabrication, especially for photolithography, has become shorter and shorter in wavelength. It's getting better. However, no suitable resist material has been found yet for this wavelength.

For example, as a resist material using KrF excimer laser light or far-ultraviolet light as a light source, a dissolution-inhibiting resist material comprising a resin having a high transmittance for light around 248.4 nm and a photosensitive compound having a diazodiketo group in the molecule. Have been developed (for example, Japanese Patent Application Laid-Open Nos. 1-80944; 1-154048; 1-155338; 1-15).
5339; JP 1-188852; Y. Tani et al., SPIE's
1989 Sympo., 1086-03 etc.). However, these dissolution-inhibiting resist materials have low sensitivity in common, and cannot be used for far-ultraviolet light and KrF excimer laser light applications where high-sensitivity resist materials are required. Further, in recent years, a chemically amplified resist material using an acid generated by exposure as a medium has been proposed as a method for reducing the amount of exposure energy (higher sensitivity) [H.
Ito et al., Polym. Eng. Sci., 23, 1012 (1983)],
Various reports have been made on this (eg H.It.
o, U.S. Pat. No. 4,491,628 (1985); JVCrivello,
U.S. Pat. No. 4,603,101 (1986); WRBrunsvolt et al., SPI
E's 1989 Sympo., 1086-40; T. Neenan et al., SPIE's 1989 S
ympo., 1086-01; JP 62-115440, JP-B 2-276
No. 60 bulletin etc.). However, in these existing chemically amplified resist materials, the resin used is, for example, poly (4-
tert-butoxycarbonyloxystyrene), poly (4-t
ert-butoxycarbonyloxy-α-methylstyrene),
Heat resistance for all phenol ether resins such as poly (4-tert-butoxystyrene), poly (4-tert-butoxy-α-methylstyrene), poly (p-ethenylphenoxyacetate tert-butyl) In addition, it has a defect that the film is easily peeled off during development due to poor adhesion to the substrate, and a good pattern shape cannot be obtained, and a carboxylic acid ester resin such as poly ( In the case of (tert-butyl-4-vinylbenzoate), etc., 248.
Insufficient light transmission around 4 nm, poly (tert-
Butyl methacrylate) and the like have problems such as poor heat resistance and dry etch resistance of the resin.

In addition, a resist material using a silyl-containing polymer has been disclosed (for example, Japanese Patent Publication No. 3-44290).
However, when using a p-trimethylsilyloxystyrene polymer or a p-tert-butyldimethylsilyloxystyrene polymer, for example, there are problems such as low sensitivity and complete removal by ashing because they contain silicon. Yes Practical application is difficult.

Furthermore, a resist material using a copolymer of p-tert-butoxycarbonyloxystyrene and p-hydroxystyrene as a resist material which has recently improved the above drawbacks (Japanese Patent Laid-Open No. 2-209977). , A resist material using a copolymer of p-tetrahydropyranyloxystyrene and p-hydroxystyrene (Japanese Patent Application Laid-Open No. 2-19847; Japanese Patent Application Laid-Open No. 2-161436; Japanese Patent Application Laid-Open No. 2-25850), p
Resist material using a copolymer of -tert-butoxystyrene and p-hydroxystyrene (Japanese Patent Laid-Open No. 62544/1990)
Etc. have been reported. However, these copolymers such as p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene, p-tetrahydropyranyloxystyrene-p-hydroxystyrene and p-tert-butoxystyrene-p-hydroxystyrene are used as resist materials. When used as a resin component of, a strong acid is present in order to maintain high sensitivity and to eliminate the protective groups such as tert-butoxycarbonyl group, tetrahydropyranyl group and tert-butyl group to make them alkali-soluble. There is a need. Therefore, in a resist material containing the above-mentioned copolymer as a resin component, a triphenylsulfonium salt, a diphenyliodonium salt, tris (trichloromethyl), which generates an extremely strong acid upon exposure, is used as a photosensitizer (photosensitive compound). ) -S-triazine / triethanolamine etc. are used, but when pattern formation is performed in the presence of such a strong acid, the pattern size changes significantly with the passage of time from exposure to heat treatment. However, even if it is possible to form a pattern in an extremely short time, a good pattern cannot be formed in an actual operation that requires time from exposure to heat treatment.

Further, since the above-mentioned photosensitizers are generally unstable, the storage stability of the resist material containing them is also poor, and in any case, there is a problem that it cannot be actually used as it is. There is.

In each of the above-mentioned polymers or copolymers, tert-butoxycarbonyl group, tert-butyl group, trimethylsilyl group, tetrahydropyranyl group, tert-butoxycarbonyl group used as a protective group for hydroxyl group. Methoxy groups and the like are not completely eliminated even in the presence of a strong acid, so existing polymers or copolymers having a monomer component whose hydroxyl group is protected by these protecting groups are used as resin components. Each of the resist materials has a common problem that the difference in dissolution rate between the exposed portion and the unexposed portion in the alkali developing solution is small, and as a result, the resolution performance is insufficient.

[0008]

As described above, although the chemically amplified resist material has higher sensitivity than the conventional resist material, the heat resistance of the resin is poor and the adhesion with the substrate is poor. It is difficult to put it to practical use because it has problems such as insufficient light transmission around 248.4 nm, insufficient resolution performance, and change in pattern dimension over time. Therefore, there is a great demand for a practical high-sensitivity resist material that solves all of these problems.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation and has a high transparency to far-ultraviolet light, KrF excimer laser light, and the like.
High sensitivity to radiation, excellent heat resistance and adhesion to substrate, high resolution, and practical pattern with high accuracy without pattern dimension change over time It is intended to provide a positive resist material.

[0010]

To achieve the above object, the present invention comprises the following configurations. "(1) The following general formula [I]

[0011]

Embedded image

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom or a carbon number of 1 to 1;
6 represents a linear, branched or cyclic alkyl group (provided that R ² and R ³ are both hydrogen atoms), and
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, or a C 1 to 6 carbon atom. Represents a linear, branched or cyclic haloalkyl group or 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 or -COOY (where, Y represents a linear 1 to 6 carbon atoms, represents. a branched or cyclic alkyl group) represents, also, R ⁵ and R ^7, taken together -CO-O-CO It may be −, and k and l each independently represent a natural number (provided that 0.1 ≦ k / (k + 1))
≤ 0.9. }, M represents 0 or a natural number (however, m
Is a natural number, 0.05 ≦ m / (k + 1 + m) ≦ 0.50. ). ] The resist material containing the polymer shown by these, the photosensitive compound which generate | occur | produces an acid by exposure, and the solvent which can melt | dissolve these.

(2) General formula [I]

[0014]

Embedded image

[In the formula, 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 number of 1 to 1;
6 represents a linear, branched or cyclic alkyl group (provided that R ² and R ³ are both hydrogen atoms), and
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, or a C 1 to 6 carbon atom. Represents a linear, branched or cyclic haloalkyl group or 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 or -COOY (where, Y represents a linear 1 to 6 carbon atoms, represents. a branched or cyclic alkyl group) represents, also, R ⁵ and R ^7, taken together -CO-O-CO It may be −, and k and l each independently represent a natural number (provided that 0.1 ≦ k / (k + 1))
≤ 0.9. }, M represents 0 or a natural number (however, m
Is a natural number, 0.05 ≦ m / (k + 1 + m) ≦ 0.50. ). ] And a photosensitive compound capable of generating an acid upon exposure (excluding onium salts and a combination of a photosensitizer capable of generating hydrogen halide and a hydrogen donor).
And a solvent capable of dissolving these, a resist material.

(3) (i) a step of applying the resist material as described in (1) on a substrate, and (ii) a step of exposing with a light of 300 nm or less through a mask after the heat treatment, iii)
A pattern forming method, which comprises a step of performing a heat treatment if necessary and a step of developing with a developing solution. 』

That is, the inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, the general formula [I]

[0018]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^5
6 , R ⁷ , k, l and m are as described above. The inventors have found that a chemically amplified resist material containing a polymer represented by the formula (1) as a resin component can achieve the object, and completed the present invention.
In the general formula [I], the number of carbon atoms represented by R ² and R ³ is 1
6 alkyl group, the alkyl group of the haloalkyl group having 1 to 6 carbon atoms represented by R ^4, R a COOR ⁸ represented by R ⁵
Examples of the alkyl group having 1 to 6 carbon atoms represented by ⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group and a hexyl group (whether linear, branched or cyclic) Yes). Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁴ include methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, octyl group,
Examples thereof include nonyl group and 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 benzyl group, phenethyl group, phenylpropyl group, methylbenzyl group, methylphenethyl group, ethylbenzyl group and the like.

The polymer represented by the general formula [I] according to the present invention has a general formula [VIII] which can be eliminated by an acid.

[0021]

Embedded image

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

[0023]

Embedded image

The greatest feature is that it comprises a monomer unit represented by the formula (wherein R ¹ , R ² , R ³ and R ⁴ are the same as above). In particular, the functional group represented by the general formula [VIII] is extremely easily removed by an acid as compared with the existing functional groups such as tert-butoxycarbonyl group, tert-butyl group and similar tetrahydropyranyl group, so that the resolution performance is improved. It is greatly advantageous in improving the pattern and maintaining the pattern size.

The monomer unit represented by the general formula [IX] is specifically a p- or m-hydroxystyrene derivative having a functional group represented by the general formula [VIII], p- or m-hydroxy-α-methyl. Although derived from monomers such as styrene derivatives, specific examples of those monomers include:
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-cyclopentyloxyethoxystyrene, p- or m-1- (2-ethylhexyloxy) ethoxystyrene, p- or m-1-ethoxy-1-methylethoxystyrene, p- or m-1-n -Propoxyethoxystyrene, p- or m-1-methyl-1-n-propoxyethoxystyrene, p- or m-1-ethoxypropoxystyrene, p- or m-1-methoxybutoxystyrene, p- or m-1 -Methoxycyclohexyloxystyrene and these p- or m-hydroxystyrene With derivatives and similar protecting group p- or m-
Examples thereof include hydroxy-α-methylstyrene derivatives.
Further, among these monomer units, particularly in the general formula [IX], R ² and R ³ are both alkyl groups, p- or m-
1-methoxy-1-methylethoxystyrene, p- 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 and the like are preferable because the protecting group is very easily removed by the action of an acid and the resolution performance which is one of the objects of the present invention is improved.

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

[0027]

Embedded image

(Wherein R ¹ is the same as above) and, if necessary, the general formula [XI]

[0029]

Embedded image

(In the formula, R ⁵ , R ⁶ and R ⁷ are the same as the above.) A copolymer comprising a monomer unit. The monomer unit represented by the general formula [X] 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 is mentioned.

Examples of the monomer unit represented by the general formula [XI] which is the third component of the polymer according to the present invention include monomer units such as acrylonitrile, fumaronitrile, methyl methacrylate, tert-butyl methacrylate, maleic anhydride and the like. Is mentioned.

In the polymer of the present invention represented by the general formula [I], when m = 0, that is, when the third component is not contained, the following general formula [II] is inevitable.

[0033]

Embedded image

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom or a carbon number of 1 to 1;
6 represents a linear, branched or cyclic alkyl group (provided that R ² and R ³ are both hydrogen atoms), and
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 1 to 6 carbon atoms. Represents a linear, branched or cyclic haloalkyl group or an aralkyl group, and k and l each independently represent a natural number {provided that 0.1 ≤ k / (k +
l) ≦ 0.9. ｝. ] It becomes a polymer shown.

In the polymer of the present invention represented by the general formula [I] or [II], the monomer unit represented by the general formula [IX] and the monomer unit represented by the general formula [X] are constituted. The ratio is usually 1: 9 to 9: 1. In any case, it can be used as the resist material of the present invention, but 2: 8 to 7: which makes the heat resistance of the polymer and the adhesion to the substrate extremely good. 3 is more preferable.

Specific examples of the polymer according to the present invention include p-1-methoxy-1-methylethoxystyrene-p-hydroxystyrene polymer, p-1-benzyloxy-1-methylethoxystyrene-p-hydroxy polymer. Styrene polymer, p-1-ethoxyethoxystyrene-p-hydroxystyrene polymer, p-1-methoxyethoxystyrene-p-hydroxystyrene polymer, p-1-n-butoxyethoxystyrene-p-hydroxystyrene polymer , P-1-isobutoxyethoxystyrene-p-hydroxystyrene polymer, p-1- (1,1-dimethylethoxy) -1-methylethoxystyrene-p-hydroxystyrene polymer, m-1- (2- Chloroethoxy) ethoxystyrene-m-hydroxystyrene polymer, p-1-cyclohexyloxyethoxystyrene-p-hydroxystyrene polymer, m-1- (2-ethylhexyloxy) ethoxy Styrene-m-hydroxystyrene polymer, p-1-methoxy-1-
Methylethoxy-α-methylstyrene-p-hydroxy-α-
Methylstyrene polymer, p-1-ethoxyethoxystyrene-p-hydroxystyrene-acrylonitrile polymer, p-
1-Ethoxyethoxystyrene-p-hydroxystyrene-fumaronitrile polymer, p-1-n-butoxyethoxystyrene-p-hydroxystyrene-methyl methacrylate polymer, p-1-cyclohexyl-1-ethoxyethoxystyrene p-Hydroxystyrene-tert-butyl methacrylate polymer, p-1-methoxycyclohexyloxystyrene-p-
Hydroxystyrene polymer, p-1-ethoxy-1-methylethoxystyrene-p-hydroxystyrene polymer, p-1-cyclopentyloxyethoxystyrene-p-hydroxystyrene polymer, p-1- (2-chloroethoxy) Ethoxystyrene-p-hydroxystyrene-methacrylic acid tert-butyl polymer, m-1-cyclohexyloxyethoxystyrene-m-hydroxystyrene-maleic anhydride polymer, and the like, but of course, are not limited to these Absent.

The polymer according to the present invention includes, for example, the following a) to
It can be easily obtained by the four methods shown in d). a) Method-1 The following general formula [XII] having a functional group represented by the above general formula [VIII].

[0038]

Embedded image

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as above.) A single monomer or a third monomer thereof is mixed with, for example, benzene according to a conventional method for producing a polymer. ,
In an organic solvent such as toluene, tetrahydrofuran, 1,4-dioxane, a radical polymerization initiator [eg, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile)] , 2,2'-azobis (methyl 2-methylpropionate) and other azo polymerization initiators, benzoyl peroxide, lauroyl peroxide and other peroxide polymerization initiators, etc.] , 1 ~ 10 at 50 ~ 110 ℃
Polymerize for a period of time. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer to obtain a homopolymer consisting of a monomer unit represented by the above general formula [IX] or the above general formula [I
The copolymer containing the monomer unit represented by X] is isolated. Then, the homopolymer or copolymer is tetrahydrofuran, acetone, in an organic solvent such as 1,4-dioxane,
Suitable acids [for example, Lewis acids such as sulfuric acid, phosphoric acid, hydrochloric acid and hydrobromic acid, and organic acids such as p-toluenesulfonic acid, malonic acid and oxalic acid are preferable. ] At 30 to 100 ° C. for 1 to 10 hours to eliminate the functional group represented by the general formula [VIII] at an arbitrary ratio. After the reaction, a post-treatment is carried out according to a conventional method for obtaining a polymer to isolate a desired polymer.

B) Method-2 The monomer represented by the above general formula [XII], 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 in accordance with a conventional method for obtaining a polymer to isolate a desired polymer.

C) Method-3 Commercially available p-tert-butoxystyrene alone or in combination with the third
And a monomer obtained by polymerizing the monomer in the same manner as in Method-1 to obtain poly (p-tert-butoxystyrene) or pt
ert-copolymer containing a butoxystyrene unit tetrahydrofuran, acetone, in an organic solvent such as 1,4-dioxane,
Suitable acids [for example, Lewis acids such as sulfuric acid, phosphoric acid, hydrochloric acid and hydrobromic acid, and organic acids such as p-toluenesulfonic acid, malonic acid and oxalic acid are preferable. ] At 30 to 110 ° C. for 1 to 20 hours to completely eliminate the tert-butyl group, which is a functional group, to obtain poly (p-hydroxystyrene) or a monomer unit represented by the general formula [X]. The copolymer containing the compound and an arbitrary amount of the following general formula [XIII]

[0042]

Embedded image

A vinyl ether compound or an isopropenyl ether compound represented by the formula (wherein R ² and R ⁴ are the same as above) and 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 1 to 10 ° C. After reacting for 20 hours, the above general formula [VI
II] chemically introduce the functional group represented by [II] at an arbitrary ratio, and then perform a post-treatment according to a conventional method for obtaining a polymer,
The desired polymer is isolated.

D) Method-4 The same procedure as in Method-3 using a commercially available poly (p-hydroxystyrene) and an arbitrary amount of the vinyl ether compound or isopropenyl ether compound represented by the above general formula [XIII]. After the reaction in step 1, the polymer is subjected to post-treatment according to a conventional method for obtaining a polymer to isolate a target polymer.

The method for producing the polymer according to the present invention is the above-mentioned method.
Although it may be any of 1 to Method-4, Method-1 and Method-3, in which a polymer having a good light transmittance around 248.4 nm is obtained.
Is particularly preferred. In method-2 or method-4, during polymerization,
Oxidation or the like occurs due to the use of p- or m-hydroxystyrene, and the resulting polymer has poor light transmittance in this wavelength range and adversely affects the resolution performance.
It cannot be said that it is an advantageous method as compared with 1 and Method-3.

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, but a preferable range is a weight determined by a GPC measuring method using polystyrene as a standard. The average molecular weight is usually about 1000 to 40,000, more preferably 3000
It is about 25,000.

The photosensitive compound which generates an acid upon exposure (hereinafter abbreviated as "acid generator") used in the present invention is a photosensitive compound which literally generates an acid upon exposure, which adversely affects resist pattern formation. It may be any as long as it does not reach, especially an acid generator capable of maintaining high transparency of the resist material with good light transmittance near 248.4 nm,
Alternatively, an acid generator capable of increasing the light transmittance around 248.4 nm by exposure and maintaining the high transparency of the resist material is preferable.
In the present invention, particularly preferred acid generators include compounds represented by the following general formula [III], general formula [V], general formula [VI] or general formula [VII].

Embedded image

[In the formula, R ⁸ and R ⁹ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms or the general formula [IV]

[0049]

Embedded image

[In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms,
Alternatively, it represents a haloalkyl group having 1 to 5 carbon atoms (which may be linear or branched), and n represents 0 or a natural number. Represents｝. ]

[0051]

[Chemical 21]

[Wherein, R ¹² represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group, a trifluoromethyl group, a phenyl group or a tolyl group, and R ¹³ and R ¹⁴ Each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 5 carbon atoms, and R ¹⁵ is a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, phenyl Represents a group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group, an alkoxy-substituted phenyl group or an alkylthio-substituted phenyl group. ]

[0053]

Embedded image

[Wherein R ¹⁶ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group, a trifluoromethyl group, a phenyl group or a tolyl group, and R ¹⁷ represents a carbon number. 1 to 10 represents a linear, branched or cyclic alkyl group, aralkyl group or alkoxy group. ]

[0055]

Embedded image

[Wherein R ¹⁸ is a trichloroacetyl group, p-
It represents a toluenesulfonyl group, a p-trifluoromethylbenzenesulfonyl group, a methanesulfonyl group or a trifluoromethanesulfonyl group, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom or a nitro group. ]

Specific examples of the preferred acid generator used in the present invention include bis (p-toluenesulfonyl) diazomethane, methylsulfonyl p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-
(1,1-Dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 1-p-toluenesulfonyl-1-cyclohexyl Carbonyldiazomethane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2-methanesulfonyl-2-methyl- (4-methylthio) propiophenone, 2,4-dimethyl-2- (p-toluenesulfonyl) ) Pentan-3-one, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, 1-
Cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl- 2-butanone, 1-
Acetyl-1- (1-methylethylsulfonyl) diazomethane, 1-diazo-1- (p-toluenesulfonyl) -3,3-dimethyl-2-butanone, 1-diazo-1-benzenesulfonyl-3,3-
Dimethyl-2-butanone, 1-diazo-1- (p-toluenesulfonyl) -3-methyl-2-butanone, 2-diazo-2- (p-toluenesulfonyl) acetic acid cyclohexyl, 2-diazo-2-benzenesulfonyl Tert-butyl acetate, isopropyl 2-diazo-2-methanesulfonyl acetate, cyclohexyl 2-diazo-2-benzenesulfonyl acetate, tert-butyl 2-diazo-2- (p-toluenesulfonyl) acetate, p-toluenesulfonic acid 2 -Nitrobenzyl, p-toluenesulfonic acid 2,6-
Examples include dinitrobenzyl and 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate, but it goes without saying that they are not limited thereto.

Various acid generators other than those mentioned above, such as triphenylsulfonium salt and diphenyliodonium salt, have been known so far. When they are used as an acid generator for a chemically amplified resist material, they are exposed to light. The generated acid (Lewis acid) is a strong acid and rich in volatility, so that it volatilizes from the surface layer of the resist film after exposure and is extremely susceptible to the atmosphere such as amine, resulting in exposure. There is a problem that a film formation (T-shape) occurs in the pattern formation, the pattern formation size changes greatly, or the pattern formation cannot be performed at all, as the time from the development to the development elapses. It is not preferable. One of the major characteristics of the polymer according to the present invention is that it is not necessary to use such an acid generator that generates a strong acid.

As the solvent used in the present invention, any solvent can be used so long as it can dissolve both the polymer and the acid generator, but normally, a solvent having no absorption around 230 to 300 nm is more preferable. It is preferably used. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-methoxypropione. Ethyl acid, 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 dimethyl ether and the like can be mentioned, but they are not limited thereto. The resist composition of the present invention usually contains the above-mentioned three components (polymer, acid generator, solvent) as main constituent components. Agent or diazodiketo group (-CO-C in the molecule)
(= N ₂ ) -CO-) or diazoketo group (-CO-C (= N
₂ )-)-containing photobleaching agent and the like may be added.

Pattern formation using the resist material according to the present invention may be performed as follows, for example. A resist material containing the compound according to the present invention is applied on a substrate such as a silicon wafer to a thickness of about 0.5 to 2 μm (about 0.1 to 0.5 μm when used as an upper layer of three layers), and this is applied. 70 ~ 130 ℃ in the oven, 10 ~ 30 minutes,
Alternatively, pre-bake on a hot plate at 70-130 ℃ for 1-2 minutes. Then, a mask for forming a desired pattern is held over the resist film, and a far-ultraviolet light having a wavelength of 300 nm or less is irradiated so as to have an exposure dose of 1 to 100 mJ / cm ² , and then hot. 70-150 on the plate
Bake for 1-2 minutes at ℃. Further, using a developing solution such as a 0.1 to 5% tetramethylammonium hydroxide (TMAH) aqueous solution for about 0.5 to 3 minutes, a dipping method, a paddle method.
If a conventional method such as a (puddle) method or a spray method is used for development, a desired pattern is formed on the substrate.

The mixing ratio of the polymer according to the present invention and the acid generator in a positive resist composition is 0.01 to 0.3 weight, preferably 0.01 to 0.3 weight of the acid generator per 1 weight of the polymer.
Around 0.1 weight is mentioned. Further, as the amount of the solvent in the resist material of the present invention, an amount that does not hinder the application of a positive resist material obtained by dissolving the polymer according to the present invention and the acid generator onto a substrate There is no particular limitation as long as it is present, but it is usually 1 to 20 weights, preferably 1.5 to 6 weights per 1 weight of the polymer.

Further, as a developing solution used in the various pattern forming methods as described above, the unexposed portion is hardly dissolved depending on the solubility of the polymer used for the resist material in the alkaline developing solution, For parts, it is sufficient to select an alkaline solution of an appropriate concentration that dissolves, usually 0.01 to
It is selected from the range of 20%. Examples of the alkaline solution used 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 comprises the monomer unit represented by the general formula [IX] having the functional group represented by the general formula [VIII] as described above, and thus has the same conventional purpose. Compared with the polymer used in the above, it has the property of more easily desorbing the functional group in the presence of an acid to become alkali-soluble. Therefore, the time from exposure to heat treatment (baking) is On the other hand, it is possible to maintain stable pattern dimensions. Further, the polymer according to the present invention has heat resistance, dry etching resistance, and adhesion to a substrate due to the fact that it contains a hydroxystyrene unit represented by the general formula [X]. Is also excellent. When R ² and R ³ in the general formula [I] or the general formula [II] are both hydrogen atoms (for example, p-alkoxymethoxystyrene), the resist material acts in a negative type. It is not applicable to the invention.

General formula [III], [V], [VI] or [V]
The resist material of the present invention containing an acid generator represented by [II] is used not only for KrF excimer laser light but also for electron beam and X-ray.
It has been confirmed that an acid is generated even by irradiation with rays and that it has a chemical amplification action. Therefore, the resist material of the present invention is a resist material which can be patterned by low-exposure far-ultraviolet light, KrF excimer laser light (248.4 nm), electron beam or X-ray irradiation method using the chemical amplification method.

[0065]

[Operation] The operation of the present invention will be described in a concrete example.
First, an acid is generated at a portion exposed by KrF excimer laser light, far-ultraviolet light or the like according to the photoreaction shown by the following formula 1, formula 2, formula 3 or formula 4.

[0066]

(Equation 1)

[0067]

(Equation 2)

[0068]

(Equation 3)

[0069]

(Equation 4)

When heat treatment is performed after the exposure step, the following formula 5 is obtained.
According to the reaction formula, a specific functional group of the polymer according to the present invention (exemplified as 1-ethoxyethoxy group in Formula 5) undergoes a chemical change by acid to become a hydroxyl group, becomes alkali-soluble, and during development, It elutes in the developer.

[0071]

(Equation 5)

On the other hand, since no acid is generated in the unexposed area, no chemical change occurs even if heat treatment is performed, and instead the acid generator is added to the hydrophilic group portion of the polymer used for the purpose of enhancing adhesion to the substrate. A function of protecting from infiltration of the alkaline developer is developed. Thus, when patterning is performed using the resist material of the present invention, a large difference in solubility with respect to the alkali developing solution occurs between the exposed portion and the unexposed portion, and the polymer in the unexposed portion is not Since it has a strong adhesion to the film, it does not cause film peeling during development, and as a result, a positive pattern having good contrast is formed. Further, since the acid generated by the exposure acts as a catalyst as shown in the formula 5, the exposure need only generate the necessary acid, and the exposure energy amount can be reduced.

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 p-bromophenol 50 g (0.29 mol), ethyl Vinyl ether 41.7g (0.58mol) and p-toluenesulfonic acid
Pyridine salt (1.5 g) was dissolved in methylene chloride (300 ml), and the mixture was reacted with stirring at room temperature for 6 hours. Next, 400 ml of a 5% aqueous sodium hydrogen carbonate solution was poured, and after stirring, liquid separation was performed by standing to separate an organic layer, which was washed with water (300 ml × 3) and dried over anhydrous magnesium sulfate. After the desiccant is filtered off, the solvent is distilled off and the residue 82
g was distilled under reduced pressure to obtain 71.1 g of p-bromo- (1-ethoxyethoxy) benzene as a slightly yellow oily substance in a bp.112 to 114 ° C / 6 mmHg fraction. ¹ HNMR δppm (CDCl ₃ ): 1.20 (3H, t, J = 7Hz, -CH
_{2 C H 3), 1.49 (} 3H, d, J = 5.1Hz, -OCHC H 3), 3.4
_{7~3.83 (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) ν cm ^-1 : 2970,2930,2890,1595,1490.

(2) Synthesis of p- (1-ethoxyethoxy) styrene In a nitrogen stream, 3.7 g (0.15 atom) of magnesium metal (cutting) was suspended in 30 ml of dry tetrahydrofuran, and the suspension was obtained in (1) above. P-bromo- (1-ethoxyethoxy) benzene 35 g (0.14 mol) in dry tetrahydrofuran (15
The solution (0 ml) was added dropwise with stirring under reflux, and the mixture was further stirred under reflux for 1 hour. Then, after cooling the reaction solution to 10 ° C, dichloro {1,2-bis (diphenylphosphino) ethane} nickel
0.8 g was added, and 15.3 g of vinyl bromide (0.14 g
20-30 mol of dry tetrahydrofuran (50 ml) solution
The mixture was added dropwise at ℃, and further stirred at room temperature for 1 hour. After injecting 200 ml of ammonium chloride aqueous solution into the reaction solution, 200 ml of methylene chloride
Was injected, stirred, and allowed to stand. Separate the organic layer and wash with water (20
0 ml × 2), dried over anhydrous magnesium sulfate, filtered to remove the desiccant, and then the solvent was distilled off to obtain 30 g of the residue, which was distilled under reduced pressure by adding tert-butylcatechol (polymerization inhibitor).
21.5 g of p- (1-ethoxyethoxy) styrene of ˜96 ° C./1 mmHg fraction was obtained as a colorless oil. ¹ HNMR δppm (CDCl ₃ ): 1.20 (3H, t, J = 7Hz, CH
_{2 C H 3), 1.50 (} 3H, d, J = 5.1Hz, -OCHC H 3), 3.49
_{~3.85 (2H, m, -C H} 2 CH 3), 5.13 (1H, d, J = 10.6H
_{z, C H 2 = CH -} ), 5.35~5.41 (1H, q, J = 5.5Hz, -
OC H CH ₃ ), 5.62 (1H, d, J = 17.6Hz, C H 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 = 8.8Hz, aromatic ring 2-H, 6-H). IR (Neat) νcm ^-1 : 2970,2930,2890,1635 (C = C), 1605,
1505. Elemental analysis value (C ₁₂ H ₁₆ O ₂ ) Theoretical value: C% 74.97; H% 8.39 Actual value C% 75.08: H% 8.33

(3) Polymerization of p- (1-ethoxyethoxy) styrene p- (1-ethoxyethoxy) styrene obtained in (2) above
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 in a nitrogen stream. After cooling, the reaction solution was poured into 1000 ml of methanol with stirring, allowed to stand and decanted, and the obtained viscous oil was washed twice with 500 ml of methanol, and then concentrated under reduced pressure to remove residual poly [p- (1 -Ethoxyethoxy) styrene] 16.3 g
Was obtained as a slightly yellow viscous oil. As a result of GPC measurement (polystyrene standard), this product has a weight average molecular weight (Mw).
It was about 10,000 and the number average molecular weight (Mn) was about 5,500.

(4) Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 15.5 g of poly [p- (1-ethoxyethoxy) styrene] obtained in (3) above was added to 1,4 -Dissolved in 150 ml dioxane, oxalic acid
1.6 g was added and the mixture was stirred and refluxed for 3 hours. After cooling, the reaction solution was poured into 1000 ml of water and crystallized with stirring, and the precipitated crystal was collected by filtration, washed with water, and dried under reduced pressure to give 12.0 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] as white. Obtained as a powder crystal. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit of the obtained polymer was ¹ H.
NMR measurement (5.2-5.4ppm methine hydrogen and 6.2-6.8ppm
Calculated from the integral ratio of hydrogen of aromatic ring) of about 1: 1. Weight average molecular weight of 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 g
Polymerization reaction was carried out in the same manner as in Production Example 1 (3), and the reaction solution was poured into 1000 ml of petroleum ether for crystallization,
The precipitated crystals were collected by filtration, washed, and dried under reduced pressure to give poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 12.8g.
Was obtained as white powdery crystals. The obtained copolymer p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit were about 1: 1 by ¹ HNMR measurement. Weight average molecular weight of 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 p-tert-butoxystyrene 17.6 g with catalytic amount of 2,2 ' -Azobisisobutyronitrile was added, and a polymerization reaction was carried out in a toluene solvent at 80 ° C for 6 hours in a nitrogen stream. After cooling the reaction solution, it was poured into 1000 ml of methanol for crystallization, and the precipitated crystal was collected by filtration, washed with methanol and dried under reduced pressure to obtain 15.5 g of poly (p-tert-butoxystyrene) as a white powder crystal. Weight average molecular weight of about 10,000 (GPC method: polystyrene standard).

(2) Synthesis of poly (p-hydroxystyrene) Poly (p-tert-butoxystyrene) 15.0 obtained in the above (1)
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 crystal was collected by filtration, washed with water and dried under reduced pressure to obtain 9.7 g of poly (p-hydroxystyrene) as a white powder crystal.

(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 treated with 1,4- It was dissolved in 35 ml of a mixed solution of dioxane and pyridine, 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, 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 give 5.0 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] as white powder crystals. I got it. The compositional ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit of the obtained polymer was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight is 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
5000: Brand name Marcalinker M] 8.0 g and ethyl vinyl ether 3.0 g are dissolved in 70 ml of 1,4-dioxane, and p-
Toluenesulfonic acid / pyridine salt (0.5 g) was added, and the mixture was reacted with stirring at room temperature for 24 hours. After the reaction, the reaction solution was poured into water, and the mixture was crystallized with stirring. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to give 10.0 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] as white powder crystals. Got as. P- (1-ethoxyethoxy) styrene unit and p- of the obtained polymer
The composition ratio of the hydroxystyrene unit was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight of about 11,000 (GPC
Method: polystyrene standard).

Production Example 5. Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 4.0 g of poly (p-hydroxystyrene) obtained in (2) of the above Production Example 3 and 1.5 g of ethyl vinyl ether were dissolved in acetone. Add a catalytic amount of sulfuric acid / pyridine salt to
The mixture was reacted with stirring at room temperature for 12 hours. Next, the reaction solution is 1000 ml of water
The mixture was poured into 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. P- (1-ethoxyethoxy) styrene unit and p- of the obtained polymer
The composition ratio of the hydroxystyrene unit was about 35:65 by ¹ HNMR measurement. Weight average molecular weight about 10,000 (GPC
Method: polystyrene standard).

Production Example 6. Synthesis of poly [p- (1-methoxyethoxy) styrene-p-hydroxystyrene] [Method-1] (1) Synthesis of p-bromo- (1-methoxyethoxy) benzene p-bromophenol 17.3 g (0.1 mol) and Using 14.0 g (0.2 mol) of methyl vinyl ether (1) in Preparation Example 1
24g of the crude oil obtained was distilled under reduced pressure and b
20.8 g of p-bromo- (1-methoxyethoxy) benzene was obtained as a slightly yellow oily substance in the p.89-90 ° C / 2 mmHg fraction. ¹ HNMR δppm (CDCl ₃ ): 1.46 (3H, d, J = 5.4Hz, O
CHC 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 = 8.8Hz, 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 as in (2) of Production Example 1 Carried out in
10.7 g of the obtained crude oily substance was distilled under reduced pressure in the presence of p-tert-butylcatechol to obtain p- of a bp.86-87 ° C / 3 mmHg fraction.
8.8 g of (1-methoxyethoxy) styrene was obtained as a colorless oil. ¹ HNMR δppm (CDCl ₃ ): 1.46 (3H, d, J = 5.5Hz, O
_{CHC H 3), 3.37 (3H} , s, -C H 3), 5.12 (1H, d, J = 1
_{1Hz, C H 2 = CH -} ), 5.30 (1H, q, J = 5.1Hz and 5.5H
z, OC H CH ₃ ), 5.60 (1H, d, J = 17.6Hz, C H ₂ = C
H -), 6.64 (1H, dd, J = 11Hz and J = 17.6Hz, CH ₂ = C
H- ), 6.95 (2H, d, J = 8.8Hz, aromatic ring 3-H, 5-H), 7.32
(2H, d, J = 8.8Hz, aromatic ring 2-H, 6-H). IR (Neat) νcm ^-1 : 2980,2920,2820,1620 (C = C), 1600,
1500. Elemental analysis value (C ₁₁ H ₁₄ O ₂ ) Theoretical value: C% 74.13; H% 7.92 Actual value: C% 74.41; H% 7.88 (3) p- (1-methoxy Polymerization of ethoxy) styrene p- (1-methoxyethoxy) styrene obtained in (2) above 8.0
g was carried out in the same manner as in Production Example 1 (3), and poly [p-
(Methoxyethoxy) styrene] (7.2 g) was obtained as a slightly yellow viscous oil. Weight average molecular weight of about 10,000, number average molecular weight of about 5,000 (GPC method: polystyrene standard).

(4) Synthesis of poly [p- (1-methoxyethoxy) styrene-p-hydroxystyrene] Production was carried out using 6.2 g of poly [p- (1-methoxyethoxy) styrene] obtained in (3) above. Performed in the same manner as (4) of Example 1,
3.0 g of poly [p- (1-methoxyethoxy) styrene-p-hydroxystyrene] was obtained as white powder crystals. The composition ratio of p- (1-methoxyethoxy) styrene unit and p-hydroxystyrene unit of the obtained polymer was about 4 by ¹ HNMR measurement.
It was 5:55. Weight average molecular weight of 9000, Mw / 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) and 2-methoxy-1 obtained in the same manner as in (2) of Production Example 3 above. -Propene 4.8 g
Was dissolved in 35 ml of a mixed solution of 1,4-dioxane and pyridine, a catalytic amount of chlorosulfonic acid was added thereto, and the mixture was reacted with stirring at room temperature for 20 hours. After the reaction, the reaction solution was treated in the same manner as in Production Example 2 (3) to obtain 4.1 g of poly [p- (1-methoxy-1-methylethoxy) styrene-p-hydroxystyrene] as white powder crystals. The obtained polymer p- (1-methoxy-
The compositional ratio of ¹ -methylethoxy) styrene unit to p-hydroxystyrene unit was about 1: 1 by ¹ HNMR measurement. Weight average molecular weight of about 10,000 (GPC method: polystyrene standard).

Production Example 8. Synthesis of poly [p- (1-n-butoxyethoxy) styrene-p-hydroxystyrene] 4.8 g of poly (p-hydroxystyrene) and 3.0 g of n-butyl vinyl ether obtained in the same manner as in the above Production Example 3 (2).
Was dissolved in 50 ml of a mixed solution of 1,4-dioxane and pyridine, to which a catalytic amount of sulfuric acid was added, and the mixture was reacted with stirring 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 powder crystals. The composition ratio of p- (1-n-butoxyethoxy) styrene unit and p-hydroxystyrene unit of the obtained polymer was 4: 6 by ¹ HNMR measurement. Weight average molecular weight about 10,000 (GP
Method C: polystyrene standard).

Production Example 9. Synthesis of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-fumaronitrile] (1) Synthesis of poly (p-tert-butoxystyrene-fumaronitrile) p-tert-butoxystyrene 28.2 g (0.16 Mol) and 3.1 g (0.04 mol) of fumaronitrile were subjected to a polymerization reaction in the presence of a catalytic amount of 2,2'-azobis (methyl 2-methylpropionate) in a toluene solvent at 90 ° C for 2 hours in a nitrogen stream. 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-fumaronitrile) Using 20.0 g of poly (p-tert-butoxystyrene-fumaronitrile) obtained in (1) above, The reaction and post-treatment were carried out in the same manner as in 2) to obtain 10.6 g of poly (p-hydroxystyrene-fumaronitrile) as white powder crystals. Weight average molecular weight of 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 the above (2) and ethyl The reaction and post-treatment were carried out in the same manner as in Production Example 3 (3) using 3.0 g of vinyl ether to give 8.8 g of poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-fumaronitrile] as white powder crystals. Got as. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit of the obtained polymer was ¹ HN.
It was about 4: 6 from the MR measurement. Weight average molecular weight 110
00 (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-butylmethacrylate] p- (1-ethoxyethoxy) styrene obtained in (2) of Production Example 1 17.3 g (0.09 mol) and tert-butyl methacrylate 1.
A catalytic amount of 2,2'-azobis (methyl 2,4-dimethylpropionate) was added to 4 g (0.01 mol) to prepare a toluene solvent,
Polymerization reaction was carried out at 80 ° C. for 8 hours under nitrogen stream. After cooling the reaction solution, it was poured into petroleum ether with stirring, allowed to stand and decanted, and the resulting crude viscous oil was washed twice with 500 ml of methanol and then concentrated under reduced pressure to remove the residual poly [p- (1 -Ethoxyethoxy) styrene-tert-butylmethacrylate] 15.5 g was obtained as a slightly 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] Poly [p- (1-ethoxyethoxy) styrene-obtained in (1) above. Dissolve 12.0 g of tert-butyl methacrylate] in 1,4-dioxane, add 0.5 g of p-toluenesulfonic acid, and add 80 ° C.
And reacted for 30 minutes with stirring. After cooling, the reaction solution was poured into 1000 ml of water and crystallized with stirring, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene-tert-butyl methacrylate. ] 9.8 g was obtained as a white powder crystal. The composition ratio of p- (1-ethoxyethoxy) styrene unit and p-hydroxystyrene unit of the obtained polymer was about 35:65 as a result of ¹ HNMR measurement. Weight average molecular weight of about 11,000 (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 of about 10,000, number average molecular weight of about 5,000: Brand name Marcalinker M] 9.0 g of dimethoxyethane 100 ml
, 3,4-dihydro-2H-pyran (12.6 g) and sulfuric acid (0.5 ml) were added, and the mixture was stirred at 30-40 ° C for 15 hr. After the reaction, the reaction solution was concentrated under reduced pressure, the residue was neutralized with sodium carbonate, and
The mixture was poured into 1000 ml and crystallized, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to obtain 11.0 g of poly (p-tetrahydropyranyloxystyrene-p-hydroxystyrene) as white powder crystals. The composition ratio of p-tetrahydropyranyloxystyrene unit and p-hydroxystyrene unit of the obtained polymer was ¹ H.
It was about 3: 7 from NMR measurement. Weight average molecular weight about 1
0000 (GPC method: polystyrene standard).

Reference Example 2. Synthesis of poly (p-tert-butoxystyrene-p-hydroxystyrene) Poly (p-hydroxystyrene) [Maruzen Petrochemical Co., Ltd.,
Weight average molecular weight of about 10,000, number average molecular weight of about 5,000: brand name Marcalinker M] 4.0 g and dimethoxyethane 70 ml
Place in a pressure vessel and add 60 g of isobutylene and sulfuric acid.
After adding 0.3 g at -60 ° C or lower, the mixture was reacted with stirring at 45 ° C for 1 hour and then at room temperature for 22 hours. After the reaction, the reaction mixture was concentrated, the residue was neutralized with sodium carbonate, 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 give poly (p-tert-butoxystyrene-p -Hydroxystyrene) 4.1 g was obtained as white powder crystals. Of the obtained polymer
The composition ratio of p-tert-butoxystyrene unit and p-hydroxystyrene unit was about 1: 1 by ¹ HNMR measurement.
Weight average molecular weight of about 10,000 (GPC method: 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 US Pat. No. 4,491,628 (1985) Was used in the presence of a 2,2'-azobis (2,4-dimethylvaleronitrile) catalyst in a toluene flow in a nitrogen stream at 90 ° C for 4 hours. After cooling the reaction solution,
It was poured into methanol for crystallization, and the precipitated crystal was collected by filtration, washed with methanol and dried under reduced pressure to obtain 15.2 g of poly (p-tert-butoxycarbonyloxystyrene) as a white powder crystal.
Weight average molecular weight of about 12000 (GPC method: polystyrene standard).

(2) 7.0 g of poly (p-tert-butoxycarbonyloxystyrene) obtained in (1) above 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 for crystallization, and the precipitated crystals were collected by filtration, washed with water and dried under reduced pressure to give poly (p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene).
4.8 g was obtained as white powder crystals. P-ter of the obtained polymer
The composition ratio of t-butoxycarbonyloxystyrene unit and p-hydroxystyrene unit was about 1: 1 by ¹ HNMR measurement.
Met. Weight average molecular weight of 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 (cutting) was suspended in ethyl ether, and Under stirring and reflux, 160 g (0.98 mol) of bromocyclohexane was added dropwise, and then the mixture was stirred and refluxed for 1 hour. After cooling, the obtained Grignard reagent was added dropwise to an ethyl ether solution of 95 g (0.89 mol) of isobutyric acid chloride at -5 to 0 ° C, and the mixture was reacted with stirring at the same temperature for 3 hours, and then left overnight at room temperature. 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 desiccant, the solvent was distilled off,
The residue was distilled under reduced pressure to obtain 50 g of 1-cyclohexyl-2-methyl-1-propanone as a slightly yellow oily substance in a bp. 95-100 ° C / 20 mmHg fraction. ¹ HNMR δ ppm (CDCl ₃ ): 1.06 (6H, d, C H ₃ ×
2), 1.12 to 1.87 (10H, m, cyclohexane ring C H ₂ ×
5), 2.51 (1H, m, cyclohexane ring C H ), 2.76 (1
H, m, C H ). IR (Neat) (nu) cm < ^-1 >: 1710 (C = O).

(2) 1-cyclohexyl-2-obtained in the above (1)
Methyl-1-propanone (47.6 g, 0.31 mol) and sulfuryl chloride (42 g, 0.31 mol) were added dropwise at 25-35 ° C, then at 50 ° C.
The reaction was stirred for 3.5 hours. The reaction solution was concentrated and then distilled under reduced pressure to obtain 30.1 g of 2-chloro-1-cyclohexyl-2-methyl-1-propanone as a yellow oily substance in a bp. 99-100 ° C./18 mmHg fraction. _{^{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) p-Toluenesulfinic acid was added to a solution of 30.0 g (0.16 mol) of 2-chloro-1-cyclohexyl-2-methyl-1-propanone obtained in (2) above in dimethylsulfoxide (DMSO) (320 ml). Sodium (30.0 g, 0.17 mol) was added, and the mixture was reacted with stirring at 60 ° C for 20 hours. The reaction solution was poured into cold water and stirred at 0 to 5 ° C for 1 hour, and then precipitated crystals were collected by filtration, washed with water and dried to obtain 18 g of crude crystals, which were recrystallized from an n-hexane-benzene mixed solution to give 2-. (Cyclohexylcarbonyl) -2-
13.5 g of (p-toluenesulfonyl) propane was obtained as white needle crystals. 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 = 8Hz, aromatic ring 3-H, 5-H), 7.65 (2
H, d, J = 8Hz, aromatic ring 2-H, 6-H). IR (KBr) (nu) cm-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, the same procedure as in Reference Example 4 (2) and (3) was conducted. The reaction and post-treatment are carried out, and the crude crystals are recrystallized from methanol to give 2-methyl-2- (p
21.2 g of -toluenesulfonyl) propiophenone was obtained as white needle crystals. 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 = 7H
z, p-methylbenzene ring 3-H, 5-H), 7.44 (2H, t, J = 7H
z, aromatic ring 3-H, 5-H), 7.54 (1H, 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, (2) and (3) of Reference Example 4 were used. Reaction and post-treatment in the same manner as in ()), and recrystallizing the crude crystal from an n-hexane-benzene mixture.
2,4-Dimethyl-2- (p-toluenesulfonyl) pentane-3-
16.5 g of on was obtained as white scaly crystals. mp. 76 ~ 79
° C. ¹ HNMR δ ppm (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) (nu) cm < _-1 >: 1715 (C = O), 1305,1290.

Reference Example 7. Synthesis of bis (cyclohexylsulfonyl) diazomethane (1) 22.5 g (0.35 mol) of sodium azide was dissolved in a small amount of water and then diluted with 130 ml of 90% hydrous ethanol. Then 60 g of p-toluenesulfonyl chloride at 10-25 ℃
An ethanol (300 ml) solution in which (0.32 mol) was dissolved was added dropwise, and the mixture was reacted at room temperature for 2.5 hours. Then, the reaction solution was concentrated under reduced pressure, the residual oily matter was washed with water several times, and then dried over anhydrous magnesium sulfate. The desiccant was filtered off to obtain 50.7 g of p-toluenesulfonyl azide as a colorless oily substance. _{^{1 HNMR δppm (CDCl 3):}} 2.43 (3H, s, C H 3),
7.24 (2H, d, J = 8Hz, aromatic ring 3-H, 5-H), 7.67 (2H, d, J = 8
Hz, aromatic rings 2-H, 6-H). IR (Neat) ν cm ^-1 : 2120 (N ₃ ).

(2) Cyclohexanethiol 20.2 g (0.17
12.0 g (0.21 mol) of potassium hydroxide in ethanol (50 ml) was added dropwise thereto at room temperature, and the mixture was stirred and reacted at 30 ± 5 ° C. for 30 minutes. Then, 18.2 g (2.14 mol) of methylene chloride was injected, and the mixture was reacted with stirring at 50 ± 5 ° C. for 6 hours. After left overnight at room temperature, 55 ml of ethanol was added to the reaction mixture to dilute it, and after adding 400 mg of sodium tungstate, 50 g (0.44 mol) of 30% hydrogen peroxide solution was added dropwise at 45 to 50 ° C, and at the same temperature, 4
The mixture was stirred and reacted for hours. After the reaction, 200 ml of water was poured and the mixture was left at room temperature overnight, and the precipitated crystals were collected by filtration, washed with water and dried to obtain crude crystals.
22 g was recrystallized from ethanol to obtain 15.5 g of bis (cyclohexylsulfonyl) methane as white needle crystals.
mp. 137-139 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.13 to 2.24 (20 H, m, cyclohexane ring C H ₂ × 10), 3.52 to 3.66 (2 H, m, cyclohexane ring C H ), 4.39 (2 H, s, C H ₂ ). IR (KBr) (nu) cm < ^-1 >: 1320,1305.

(3) 1.7 g of sodium hydroxide was dissolved in 70 ml of 60% water-containing ethanol, and 12.1 g (0.04 mol) of bis (cyclohexylsulfonyl) methane obtained in (2) above was added thereto. Then, a solution of 8.2 g (0.04 mol) of p-toluenesulfonyl azide obtained in (1) above in ethanol (10 ml) was added to
The mixture was added dropwise at -10 ° C, and then reacted with stirring at room temperature for 7 hours. After standing at room temperature overnight, the precipitated crystals were collected by filtration, washed with ethanol and dried to obtain 11 g of crude crystals, which were recrystallized from acetonitrile to give bis (cyclohexylsulfonyl) diazomethane 8.0 g.
Was obtained as pale yellow prism crystals. mp. 130-131 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.13 to 2.25 (20 H, m, cyclohexane ring C H ₂ × 10), 3.36 to 3.52 (2 H, m, cyclohexane ring C H × 2). ^{IR (KBr) νcm -1: 2130} (CN 2), 1340,1320.

Reference Example 8. Synthesis of methylsulfonyl p-toluenesulfonyldiazomethane (1) Methylthiomethyl p-tolylsulfone 6.0 g (0.03
Mol) in 40 ml of methanol and 40 ml of water, and after adding 60 mg of sodium tungstate, 6.8 g (0.06 mol) of 30% hydrogen peroxide solution was added dropwise at 45 to 50 ° C, and then reacted under stirring and reflux for 10 hours. Let After standing overnight at room temperature, 400 ml of water
The reaction solution was poured into the reaction solution, 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 obtain 6.1 g of methylsulfonyl p-toluenesulfonylmethane as white needle crystals. . 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), 7.4
0 (2H, d, J = 8Hz, aromatic ring 3-H, 5-H), 7.87 (2H, d, J = 8H
z, aromatic ring 2-H, 6-H).

(2) Methylsulfonyl p-obtained in (1) above
Reaction and post-treatment were carried out in the same manner as (3) of Reference Example 7 using 5.0 g (002 mol) of toluenesulfonylmethane, and 3 g of the obtained crude crystal was recrystallized from ethanol to give methylsulfonyl p-toluenesulfonyldiazomethane. 2.2 g were obtained as pale yellow scaly 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 = 8Hz, 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 9. Synthesis of bis (1,1-dimethylethylsulfonyl) diazomethane Using 18.0 g (0.2 mol) of tert-butyl mercaptan, the reaction and post-treatment were carried out in the same manner as in (2) and (3) of Reference Example 7 to obtain The crude crystals were recrystallized from ethanol to give bis (1,1-dimethylethylsulfonyl) diazomethane.
8.5 g was obtained as pale yellow needles. mp. 121-121.5 ° C. ¹ HNMR δppm (CDCl ₃ ): 1.52 (18H, s, C H ₃ ×
6). ^{IR (KBr) νcm -1: 2120} (CN 2), 1330,1315.

Reference Example 10.1-Diazo-1-cyclohexyl
Synthesis of sulfonyl-3,3-dimethyl-2-butanone (1) Water in 23 g (0.198 mol) of cyclohexanethiol
13.7 g (0.207 mol) of potassium oxide in ethanol (80 m
l) The solution was added dropwise at 15 ° C and stirred at the same temperature for 24 hours. Next
Brush 1-Brom-3,3-dimethyl-2-butanone 35.4 g (0.198
(Mol) was added dropwise at 10 ~ 15 ℃, then stirred at 20 ℃ for 5 hours.
I let it. Add 2.5 g of sodium tungstate
After that, 220g (1.96mol) of 30% hydrogen peroxide water at 45-50 ° C
Was added dropwise at 60 to 80 ° C. for 30 hours. After cooling,
Extract with ethylene (300 ml x 1), and add organic layer to anhydrous magnesium sulfate.
Dried with sium. The desiccant is filtered off and the solvent is distilled off
1-cyclohexylsulfonyl-3,3-dimethyl-2-butano
14 g was obtained as a pale yellow oil.¹ HNMR δppm (CDCl_Three): 1.10 to 2.19 (19H, m, CH
_Three × 3 and cyclohexane ring CH _Two × 5), 3.37 to 3.53
(1H, m, cyclohexane ring CH), 4.12 (2H, s, CH
_Two ). IR (Neat) νcm^-1: 1700 (C = O), 1310.

(2) 13 g (53 mmol) of crude 1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone obtained in (1) above.
And 6.14 g (61 mmol) of triethylamine were dissolved in 40 ml of ethanol, and 11.4 g (58 mmol) of p-toluenesulfonylazide obtained in (1) of Reference Example 7 was added dropwise at 0 to 5 ° C, and at 10 to 20 ° C. The reaction was stirred for 8 hours. After standing overnight at room temperature, the reaction mixture was concentrated under reduced pressure, and the residue was diluted with 250 ml of ethyl ether.
Was injected, and the organic layer was added to a 5% aqueous potassium hydroxide solution (100 m
l) and then twice with saturated saline solution (100 ml),
It was dried over anhydrous magnesium sulfate. 15 g of crude oily substance obtained by filtering off the desiccant and distilling off the solvent was applied to column chromatography [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.), eluent: n-hexane / methylene chloride]. = 7/1 →
4/1 → 2/1] and then recrystallized from a mixed solution of n-hexane-ethyl ether to give 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone (2.5 g) as slightly yellow needle crystals. Got as. mp. 80.5-82.0 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.05~2.16 (19H, m, C H 3
× 3 and cyclohexane ring C H ₂ × 5), 3.52~3.66
(1H, m, cyclohexane ring CH ). IR (KBr) νcm ^-1 : 2105 (CN ₂ ), 1650 (C = O), 1320 (SO
₂ ).

Reference Example 11. Synthesis of 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone (1) 50 g (0.33 mol) of 3-phenylpropionic acid was dissolved in 220 ml of methanol, and 5 g of concentrated sulfuric acid was injected. Then, the mixture was reacted under stirring and reflux for 1 hour. After concentrating the reaction solution, the residue was poured into cold water and extracted three times with 75 ml of methylene chloride. The organic layer obtained by liquid separation was washed with water (125 ml × 3), dried over anhydrous magnesium sulfate, and 54 g of a crude oily substance obtained by distilling off the solvent was distilled under reduced pressure to yield bp. 94 to 95 ° C / 5 mmHg. 51.5 g of a methyl 3-phenylpropionate fraction was obtained as a colorless oil. IR (Neat) ν cm ^-1 : 1745 (CO ₂ ).

(2) 42 g (0.45 mol) of dimethyl sulfone was dissolved in 225 ml of DMSO to obtain 17.9 g of 60% sodium hydride.
(0.45 mol) is added little by little at 18 to 20 ℃, and at 65 to 70 ℃
After reacting for 30 minutes with stirring, 225 ml of tetrahydrofuran was injected and diluted. Then, a solution of 36.6 g (0.22 mol) of methyl 3-phenylpropionate obtained in (1) above in tetrahydrofuran (110 ml) was added dropwise at 33 to 41 ° C., and the mixture was reacted under stirring and reflux for 1 hour. After cooling the reaction mixture, it was poured into a dilute aqueous hydrochloric acid solution and extracted with chloroform (100 ml x 5). The obtained organic layer was washed with water (200 ml x 3), saturated aqueous sodium hydrogen carbonate solution (200 ml) and water (200 ml). , Dried over anhydrous magnesium sulfate. Crude crystals (60.8 g) obtained by filtering the desiccant and then concentrating the crystals were recrystallized from ethyl acetate to give 1-methylsulfonyl-4-phenyl-2-butanone (24.7 g) as white needle crystals. mp. 97.6-98.4 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.91~3.09 (7H, m, C H 2
× 2, and _{C H 3), 3.99 (2H} , s, C H 2), 7.16~7.33
(5H, m, aromatic ring). IR (KBr) (nu) cm < ^-1 >: 1730 (C = O), 1320,1305.

(3) 1-Methylsulfonyl-4 obtained in (2) above
-Phenyl-2-butanone 12 g (0.05 mol) in methylene chloride
It was dissolved in 135 ml, 11.5 g of triethylamine was added dropwise, and the mixture was reacted with stirring for 30 minutes. Then, 11.5 g (0.06 mol) of p-toluenesulfonyl azide obtained in (1) of Reference Example 7 was added to 0.
The mixture was added dropwise at ˜5 ° C., and the mixture was reacted with stirring at the same temperature for 5 hours. 26.6 g of a crude solid product obtained by concentrating the reaction solution was recrystallized from carbon tetrachloride to obtain 7.5 g of 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone as pale yellow needle crystals. mp. 52.5 ~
54 ° C. _{^{1 HNMR δppm (CDCl 3):}} 2.88~3.07 (4H, m, C H 2
× 2), 3.17 (3H, s, C H 3), 7.16~7.35 (5H, m,
Aromatic ring). IR (KBr) νcm ^-1 : 2120 (CN ₂ ), 1655 (C = O), 1335,131
Five .

Reference Example 12. Synthesis of 1-diazo-1- (p-toluenesulfonyl) -3,3-dimethyl-2-butanone (1) 1-Brom-3,3-dimethyl-2-butanone 33.3 g ( 0.19 mol) was dissolved in 330 ml of DMSO, and 34.9 g (0.20 mol) of sodium p-toluenesulfinate was added thereto at 30 to 40 ° C. Then, after stirring and reacting at 60 to 70 ° C. for 18 hours, the reaction solution was poured into 2000 ml of ice water, and the precipitated crystals were collected by filtration, washed with water and dried to give 1- (p-toluenesulfonyl) -3,3-dimethyl-. 4-1.6 g of 2-butanone was obtained as white crystals. mp.119-122
° C. _{^{1 HNMR δppm (CDCl 3):}} 1.12 (9H, s, C H 3 ×
3), 2.45 (3H, s , C H 3), 4.31 (2H, s, C H 2), 7.
36 (2H, d, J = 8Hz, aromatic ring 3-H, 5-H), 7.82 (2H, d, J = 8H
z, aromatic ring 2-H, 6-H). IR (KBr) (nu) cm < ^-1 >: 1715 (C = O), 1320,1290.

(2) 20 g (0.08 mol) of 1- (p-toluenesulfonyl) -3,3-dimethyl-2-butanone obtained in (1) above was used in the same manner as in (3) of Reference Example 7. After the reaction and post-treatment, 24 g of the obtained crude solid substance was recrystallized from ethanol.
1-diazo-1- (p-toluenesulfonyl) -3,3-dimethyl-2
-Butanone 12.6 g was obtained as slightly yellow short needle crystals. mp. 12
0.5-121.5 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.17 (9H, s, C H 3 ×
3), 2.44 (3H, s, C H ₃ ), 7.34 (2H, d, J = 8Hz, aromatic ring
3-H, 5-H), 7.93 (2H, d, J = 8Hz, aromatic ring 2-H, 6-H). I
R (KBr) νcm ⁻¹ : 2140 (CN ₂ ), 1660, 1305.

Reference Example 13. Synthesis of 1-acetyl-1- (1-methylethylsulfonyl) diazomethane (1) Ethanol of 11.5 g (0.174 mol) of potassium hydroxide in 12.2 g (0.16 mol) of 2-propanethiol Solution (100 ml) 15
The mixture was added dropwise at a temperature below ℃ and stirred at the same temperature for 24 hours. Then, after adding 23.1 g (0.25 mol) of chloroacetone at 10 to 15 ° C,
The mixture was reacted at 20 ° C. for 4 hours with stirring. Furthermore, after adding 0.8 g of sodium tungstate, 36 g of 30% hydrogen peroxide solution was added.
(0.32 mol) was added dropwise at 45 to 55 ° C, and the mixture was reacted with stirring at room temperature for 14 hours. The reaction solution was extracted with methylene chloride (200 ml x 1), the organic layer was separated, washed with water, and dried over anhydrous magnesium acetate. The desiccant was filtered off and the solvent was distilled off to obtain 18.9 g of crude 1- (1-methylethylsulfonyl) acetone as a tan oil. ¹ HNMR δppm (CDCl ₃ ): 1.40 (6H, d, J = 7Hz) C
H ₃ × 2), 2.40 (3H, s, C H ₃ ), 3.30 (1H, m, C
H ), 4.00 (2H, s, C H ₂ ) IR (Neat) νcm ⁻¹ : 1310, 1110.

(2) The crude 1- (1-methylethylsulfonyl) acetone 8.65 g (53 mmol) obtained in the above (1) and 6.14 g (61 mmol) of triethylamine were dissolved in 40 ml of ethanol to prepare a mixture of Reference Example 7 P-toluenesulfonyl azide obtained in (1) of
11.4 g (58 mmol) was added dropwise at 0 to 5 ° C and 5 at 10 to 20 ° C.
The reaction was stirred for a period of time. After standing overnight at room temperature, the reaction mixture was concentrated under reduced pressure, 200 ml of methylene chloride was poured into the residue, the organic layer was washed once with a 5% aqueous potassium hydroxide solution (200 ml) and three times with water (200 ml), and then the solvent was added. 12.4 g of the residue obtained by evaporation was subjected to column chromatography [filler: Waco-Gel C-200] (trade name of Wako Pure Chemical Industries, Ltd.), eluent: n-hexane / methylene chloride = 4/1 → 1 1] and then recrystallized from a mixed solution of n-hexane-ethanol to give 1-acetyl-1-
2.6 g of (1-methylethylsulfonyl) diazomethane was obtained as pale yellow short needle crystals. mp.53.0-55.0 ° C. _{^{1 HNMR δppm (CDCl 3):}} 1.44 (6H, d, J = 7Hz C H
_{3 × 2), 2.39 (3H} , m, C H 3), 3.51 (1H, m, C H). IR (KBr) νcm ⁻¹ : 2140 (CN ₂ ), 1330 (SO ₂ ), 114
0.

Reference Example 14. p-toluenesulfonic acid 2,6-
Synthesis of dinitrobenzyl (1) 2,6-dinitrobenzaldehyde 19.6 g (0.1 mol)
Is suspended in 200 ml of methanol and hydrogenated at 15-25 ° C.
After gradually adding 5.8 g of sodium arsenide, at room temperature for 1 hour
The reaction was carried out with stirring. After the reaction, the solvent was distilled off and 100% water was added to the residue.
ml and chloroform 100 ml were added, and the mixture was reacted for 1 hour with stirring.
After standing, let stand and separate, wash the chloroform layer with water, and add anhydrous sulfuric acid.
Dried over magnesium. After filtering off the desiccant, the solvent is distilled off
Then, add 15.0 g of 2,6-dinitrobenzyl alcohol to yellow.
Obtained as crystals. mp. 92.5-93.5 ° C. ¹ HNMR δppm (CDCl_Three): 2.77 (1H, t, J = 7Hz, O
H), 4.97 (2H, d, J = 7Hz, CH _Two ), 7.66 (1H, t, J = 8H
z, aromatic ring 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 (1) above and 15.7 g (0.083 mol) of p-toluenesulfonyl chloride were dissolved in 150 ml of acetone, and 15 g of dicyclohexylamine was dissolved therein. Acetone
(25 ml) solution was added dropwise at 0 to 10 ° C., and then the mixture was reacted with stirring at room temperature for 4 hours. After the reaction, the precipitate was filtered off and the filtrate was concentrated. The residue (29 g) was recrystallized from carbon tetrachloride to give 2,6-dinitrobenzyl p-toluenesulfonate (19.8 g) as slightly yellow scale crystals. Got as. 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-Diazo-2-benzenesulfonylacetic acid cyclohexyl (1) Bromoacetic acid cyclohexyl (15.6 g, 70.5 mmol) was dissolved in DMSO (120 ml), and sodium benzenesulfinate dihydrate (15 g, (75 mmol) was added little by little at 20 to 40 ° C, and the mixture was reacted at 60 ° C for 6 hours with stirring. After cooling, the reaction solution was poured into 1500 ml of ice water, and the precipitated crystals were collected by filtration, washed with water and dried to give cyclohexylbenzenesulfonylacetate.
1.53 g was obtained as white crystals. mp. 35-38 ° C. ¹ HNMR δppm (CDCl ₃ ): 1.11 to 1.82 (10H, m, cyclohexane ring C H ₂ ), 4.11 (2H, s, C H ₂ ), 4.64 to 4.8
2 (1H, m, C H ), 7.50~7.98 (5H, m, aromatic ring). ^{IR (KBr) νcm -1: 1735} (C = 0), 1325 (SO 2), 1295.

(2) 10 g (35 mmol) of cyclohexylbenzenebenzenesulfonylacetate obtained in (1) above was added to 100 ml of methylene chloride.
It was dissolved in ml, 4.2 g (41 mmol) of triethylamine was added, and the mixture was reacted with stirring for 30 minutes. Then (1) of Reference Example 7
8.3 g (39 mmol) of p-toluenesulfonyl azide obtained in
Was added dropwise at 0 to 5 ° C., and the mixture was reacted with stirring at the same temperature for 4 hours.
The reaction solution was concentrated, and 250 ml of ethyl ether was added to the residue,
After dissolution, the organic layer was washed once with a 5% aqueous potassium hydroxide solution (200 ml) and once with a saturated saline solution (100 ml), and then dried over anhydrous magnesium acetate. The desiccant was filtered off and the solvent was distilled off to obtain 11 g of the residue which was subjected to column chromatography [filler: Waco-Gel C-200, eluent: n-hexane / methylene chloride = 6.
1/1 → 4/1 → 2/1 → 1 /]] and separated by 2-diazo-2-benzenesulfonylacetic acid cyclohexyl 5.6 g
Was obtained as pale yellow crystals. mp. 42.0 to 45.0 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.11 to 1.82 (10 H , m, cyclohexane ring C H ₂ ), 4.02 to 4.90 (1 H, m, cyclohexane ring C H ), 7.47 to 8.07 (5 H, m, aromatic ring). IR (Neat) νcm ⁻¹ : 2160 (CN ₂ ), 1730 (C = 0), 1365
(SO ₂ ), 1310.

Reference Example 16. Synthesis of poly (p-ethenylphenoxyacetic acid 1-methylcyclohexyl / p-hydroxystyrene) (1) Dissolve 70.8 g (0.62 mol) of 1-methylcyclohexan-1-ol and 8.5 g of pyridine in 300 ml of methylene chloride and stir. , Chloroacetyl chloride 70g (0.62mol) 20
The mixture was added dropwise at -30 ° C, and then the mixture was reacted with stirring at the same temperature for 2 hours. After the reaction, the precipitate was filtered off and the solvent was distilled off to obtain 116 g of a residue, which was purified by column chromatography [filler: Waco-Gel C-200, eluent: n-hexane / ethyl acetate = 10 /
1 (V / V)] to obtain 53.2 g of 1-methylcyclohexyl monochloroacetate as a pale yellow oily substance. ¹ HNMR δppm (CDCl ₃ ): 1.27 to 2.18 (13H, s, C H
₃ and cyclohexane ring CH), 4.00 (2H, s , C H 2). IR (Neat) νcm ^-1 : 1760 (C = 0). (2) 4.0 g of poly (p-hydroxystyrene) obtained in (2) of Preparation Example 3 and 3.2 g of 1-methylcyclohexyl monochloroacetate obtained in (1) above were dissolved in 35 ml of acetone, and 2.4 g of potassium carbonate was added thereto. g and 0.33 g of potassium iodide were added, and the mixture was refluxed for 6 hours with stirring. After cooling, the precipitate was filtered off, the filtrate was poured into 600 ml of water for crystallization, and the precipitated crystal was collected by filtration, washed with water and dried to give poly (p-ethenylphenoxyacetic acid).
1-methylcyclohexyl / p-hydroxystyrene) 4.9
g was obtained as a white powder crystal. The compositional ratio of ¹ -methylcyclohexyl unit of p-ethenylphenoxyacetate to p-hydroxystyrene unit of the obtained polymer was about 1: 1 by ¹ HNMR measurement. The weight average molecular weight is about 10,000 (GP
Method C: polystyrene standard).

Reference Example 17: Synthesis of poly (p-ethenylphenoxyacetate tert-butyl / p-hydroxystyrene) Poly (p-hydroxystyrene) obtained in (2) of Production Example 3.
The reaction and post-treatment were carried out in the same manner as in Reference Example 16 (2) using 0 g and tert-butyl monochloroacetate (commercially available product), and poly (p-ethenylphenoxyacetate tert-butyl / p-
5.0 g of hydroxystyrene) was obtained as white powder crystals.
The composition ratio of the tert-butyl p-ethenylphenoxyacetate unit and the p-hydroxystyrene unit of the obtained polymer was ¹ HNM.
It was about 1: 1 from the R measurement. The weight average molecular weight is about
It was 10,000 (GPC method: polystyrene standard).

Example 1. The poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] obtained in Production Example 1 and Production Example 4 was prepared into the following compositions. Poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] 3.0 g Diethylene glycol dimethyl ether 7.0 g The above composition was spin-coated on a substrate (quartz wafer),
After prebaking at 90 ° C. for 90 seconds on a hot plate, a polymer film having a thickness of 1 μm was obtained. Then, UV measurement of each polymer film was performed. The UV spectrum is shown in FIG. In the figure, I shows the ultraviolet spectrum of the polymer film obtained by using the polymer obtained in Production Example 1, and II shows the ultraviolet ray of the polymer film obtained by using the polymer obtained in Production Example 4. The spectral curve is shown. From the results of FIG. 1, the polymer obtained in Production Example 1 has a KrF excimer laser light wavelength particularly as compared with the polymer obtained in Production Example 4.
It can be seen that the light transmittance in the vicinity of 240 to 250 nm is excellent (high transparency).

Example 2. A photoresist material having the following composition was prepared and patterned as described below. Poly [p- (1-ethoxyethoxy) styrene-p-hydroxystyrene] (polymer of Production Example 1) 6.0 g 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane (acid generator of Reference Example 4) ) 0.3 g diethylene glycol dimethyl ether 13.7 g A pattern forming method using the above resist material will be described with reference to FIG. The resist material 2 was spin-coated on a semiconductor substrate 1 and prebaked at 90 ° C. for 90 seconds on a hot plate to obtain a resist material film having a thickness of 1.0 μm (FIG. 2).
a). Next, 248.4 nm KrF excimer laser light 3 was selectively exposed through the mask 4 (FIG. 2b). And 100
After post-baking on a hot plate at 90 ° C for 90 seconds, the exposed portion of the resist material 2 is dissolved and removed by developing for 60 seconds with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution), and the positive pattern 2a
Was obtained (Fig. 2c). The obtained positive pattern is 0.25 μm
It has line-and-space resolution performance, and the exposure dose at this time was about 5 mJ / cm ² . Also, using this resist material, the pattern change with time from exposure to heat treatment (post-baking) was measured.
The 0.25 μm line and space was resolved without any problems.

Examples 3 to 30 Photoresist materials having the compositions shown in Tables 1 to 7 below were prepared.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

[Table 4]

[0131]

[Table 5]

[0132]

[Table 6]

[0133]

[Table 7]

Pattern formation was performed in the same manner as in Example 2 using each of the resist materials prepared above. The results are shown in Tables 8 and 9.

[0135]

[Table 8]

[0136]

[Table 9]

As is clear from Tables 8 and 9, Examples 3 to
In any of 30 examples, a positive type pattern was formed as in Example 2, and 0.22 to 0.3 μm even after 8 hours from exposure to heat treatment (post-baking) as in Example 2.
The line and space was resolved without any problems.

Comparative Examples 1 to 11 For comparison, photoresist materials having the compositions shown in Tables 10 to 12 were prepared and patterned in the same manner as in Example 2. Table 13 shows the results. In addition, the pattern result (film-tension phenomenon: T-shape) in Comparative Example 1 when heat-treated (post-baked) and developed 30 minutes after exposure is shown in FIG.
In addition, the pattern results of the heat treatment and development of Comparative Examples 2 and 3 after 30 minutes after exposure and the heat treatment and development of Comparative Examples 4 to 6 and Comparative Example 15 after 15 minutes after exposure (pattern Not formed) is shown in FIG. 4, respectively.

In Comparative Examples 7 and 8, after exposure,
When heat-treated and then developed, not only the exposed areas but also the unexposed areas were dissolved and no pattern could be formed.

[0140]

[Table 10]

[0141]

[Table 11]

[0142]

[Table 12]

[0143]

[Table 13]

As is clear from Table 13, FIG. 3 and FIG. 4, in these comparative examples, the resolution performance is inferior to the resist material using the material of the present invention. In addition, Comparative Examples 1 to
As is clear from 6, 10 and 11, from exposure to heat treatment (post bake), in most cases, it takes 15 minutes to 30 minutes (some 8 hours or more) or more, and a film-tension phenomenon (T-shape) occurs, Pattern formation becomes impossible. Further, when the polymer according to the present invention and an existing iodonium salt or sulfonium salt as an acid generator were combined to form a resist material, as apparent from the results of Comparative Examples 7 and 8, it was completely dissolved after development after exposure. A positive pattern was not formed. Further, when the polymer according to the present invention and the existing tris (trichloromethyl) -s-triazine / hydrogen donor as an acid generator are combined to form a resist material, the results of Comparative Example 9 are obvious. If it takes 15 to 30 minutes from exposure to heat treatment, it becomes impossible to form a pattern.

[0145]

As is clear from the above description, the resist material of the present invention is used as a light source having a wavelength of 300 nm or less, for example, deep UV light, for example, KrF excimer laser light (248.4).
When used as a resist material for exposure such as (nm), it has extremely high resolution performance, and it is possible to maintain a stable pattern dimension with the passage of time from exposure to heat treatment (post bake). A practical fine pattern of quarter micron order can be easily obtained. Therefore, the present invention has great value for forming ultrafine patterns in the semiconductor industry and the like. The resist material of the present invention is particularly effective for pattern formation using far-ultraviolet light and KrF excimer laser light.
It can be sufficiently used in pattern formation using electron beams, X-rays and the like.

[0146]

[Brief description of drawings]

FIG. 1 shows an ultraviolet spectrum curve diagram of each polymer film obtained in Example 2.

FIG. 2 is a process cross-sectional view of a positive pattern forming method using a resist material of the present invention.

FIG. 3 is a film-tension phenomenon (T-) observed when a positive pattern is formed using the resist material of Comparative Example 1.
It is a sectional view of shape.

FIG. 4 is a cross-sectional view of a pattern that cannot be formed, which is observed when a positive pattern is formed using the resist materials of Comparative Examples 2 to 6 and Comparative Example 9.

[Explanation of symbols]

I ... Ultraviolet spectroscopic curve of polymer film obtained by using polymer obtained in Production Example 1, II ... Ultraviolet spectroscopy of polymer film obtained by using polymer obtained in Production Example 4 Curve, 1 ... Substrate, 2 ...
..Resist material films containing the compound of the present invention, 3 ... Kr
F excimer laser light, 4 ... Mask, 2a ... Resin pattern.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keiji Ono Keiji Ohgo, Saitama Prefecture 1633 Otoba, Wako Junyaku Kogyo Co., Ltd. (72) Inventor Takaaki Negishi Takago, Saitama Prefecture 1633 Wako Junyaku Kogyo Co., Ltd. Tokyo Research Center

Claims (11)

[Claims] 1. A compound of the general formula [I] [In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ^2
3 are 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
Except when both are 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, 1 to 6 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, and R ⁷ represents a hydrogen atom. , Cyano group or —COOY (wherein Y represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms), and R ⁵ and R ⁷ are bonded to each other to —CO. −
It may be O-CO-, and k and l each independently represent a natural number (provided that 0.1≤k / (k + l) ≤0.9. }, M represents 0 or a natural number (however, when m is a natural number, 0.05 ≦ m / (k + l + m) ≦ 0.50). ]
A resist material comprising a polymer represented by, a photosensitive compound that generates an acid upon exposure, and a solvent capable of dissolving these. 2. A compound of the general formula [I] [In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ^2
3 are 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
Except when both are hydrogen atoms. ), Or 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, 1 to 6 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, and R ⁷ represents a hydrogen atom. Represents a cyano group or -COOY (wherein Y represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms), and R ⁵ and R ⁷ are bonded to each other to -CO. −
It may be O-CO-, and k and l each independently represent a natural number (provided that 0.1≤k / (k + l) ≤0.9. }, M represents 0 or a natural number (however, when m is a natural number, 0.05 ≦ m / (k + l + m) ≦ 0.50). ]
And a photosensitive compound capable of generating an acid upon exposure to light (excluding onium salts and a combination of a photosensitizer capable of generating hydrogen halide and a hydrogen donor), and a solvent capable of dissolving these. A resist material comprising: 3. A polymer represented by the general formula [I] is represented by the following general formula [II]: [In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ^2
3 are 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
Except when both are 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,
Represents a linear, branched or cyclic haloalkyl group having 1 to 6 carbon atoms or an aralkyl group, and k and l each independently represent a natural number (provided that 0.1 ≤ k / (k + l) ≤ 0.9) . ｝. ] The resist material of Claim 1 or 2 which is a polymer shown by these. 4. In the general formula [II], R ¹ is a hydrogen atom, R ² is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ³ is The resist material according to claim 3, which is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and R ⁴ is a straight-chain or branched alkyl group having 1 to 10 carbon atoms. . 5. In the general formula [II], R ¹ is a hydrogen atom, R ² is a hydrogen atom or a methyl group, R ³ is a methyl group or an ethyl group, and R ⁴ has 1 carbon atom. The resist material according to claim 3, which is a linear or branched alkyl group of 4 to 4. 6. The weight average molecular weight of the polymer is 3000 to 20000.
The resist material according to any one of claims 1 to 5, which is 7. A photosensitive compound which generates an acid upon exposure is represented by the following general formula [III]: [In the formula, R ⁸ and R ⁹ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms or the general formula [IV] ] {In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or 1 carbon atom.
5 represents a haloalkyl group (which may be linear or branched), and n represents 0 or a natural number. Represents｝. ]
The resist material according to any one of claims 1 to 6, which is a compound represented by: 8. A photosensitive compound which generates an acid upon exposure is a compound represented by the following general formula [V]: [Wherein, R ¹² is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group, a trifluoromethyl group,
Represents a phenyl group or a tolyl group, R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ¹⁵ represents a straight chain having 1 to 10 carbon atoms. It represents a chain, branched or cyclic alkyl group, phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group, alkoxy-substituted phenyl group or alkylthio-substituted phenyl group. ] The resist material in any one of Claims 1-6 which is a compound shown by these. 9. A photosensitive compound which generates an acid upon exposure is represented by the following general formula [VI]: [Wherein R ¹⁶ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group, a trifluoromethyl group,
It represents a phenyl group or a tolyl group, and R ¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aralkyl group or an alkoxy group. ] The resist material in any one of Claims 1-6 which is a compound shown by these. 10. A photosensitive compound capable of generating an acid upon exposure is represented by the following general formula [VII]: [In the formula, R ¹⁸ represents a trichloroacetyl group, a p-toluenesulfonyl group, a p-trifluoromethylbenzenesulfonyl group, a methanesulfonyl group or a trifluoromethanesulfonyl group, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, Represents a halogen atom or a nitro group. ] The resist material in any one of Claims 1-6 which is a compound shown by these. 11. (i) A step of applying the resist material according to claim 1 on a substrate, and (ii) a step of exposing with a light of 300 nm or less through a mask after the heat treatment, (iii) ) A pattern forming method, which comprises a step of performing a heat treatment if necessary and a step of developing with a developing solution. [0001]