JPH04211258A - Chemical amplification type resist material - Google Patents

Abstract

PURPOSE:To obtain a positive type resist material which possesses the high transmissivity for the far infrared light and KrF excimer laser beam, the superior sensitivity for light exposure, heat resistance, and the close adhesion performance with a substrate. CONSTITUTION:A chemical amplification type resist material contains the polymer shown by the formula, photosensitive compound which generates acids through light exposure, and a solvent which dissolves the above-described chemicals. In the formula, R<1> is a methyl group, isopropyl group, tert-butyl group, tetrahydropyranyl group, trimethyl silyl group or tert-butoxy carbonyl group, and each of (k) and (l) is a natural number (k/(k+l)=0.1-0.9). As the polymer, is listed p-tert-butoxystyrene-p-hydroxystyrene polymer, and as the acid generating agent, is listed bis(p-toluene sulfonyl) diazomethane. Further, as the solvent, is listed methyl cellosolve acetate.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to resist materials used in the manufacture of semiconductor devices and the like. Specifically, far ultraviolet light of 300 nm or less is used as an exposure energy source, for example, 248.4 nm.
The present invention relates to a resist material for forming a positive pattern using a KrF excimer laser beam or the like.

[Conventional technology]

[0002] In recent years, with the high density integration of semiconductor devices, the light source of exposure equipment used for microfabrication, especially photolithography, has become increasingly shorter in wavelength, and KrF excimer laser (248.4 nm) light is now being considered. It's getting to that point. However, a resist material suitable for this wavelength has not yet been found.

For example, as a resist material using KrF excimer laser light or deep ultraviolet light as a light source, a resin with high transparency to light around 248.4 nm and a compound 15

[Chemical 1
5] A dissolution-preventing resist material made of a photosensitive compound having a group represented by the following has been developed (for example, JP-A No.
80944; JP 1-154048; JP 1-155338; JP 1-155339
No. JP-A-1-188852; Y. Tani
et al., SPIE's 1989 Sympo. ,1086-
03 etc.). However, these dissolution-inhibited resist materials have low sensitivity in common and cannot be used for deep ultraviolet light or KrF excimer laser light applications that require highly sensitive resist materials. In addition, in recent years, methods for reducing the amount of exposure energy (
To increase sensitivity), a chemically amplified resist material using acid generated by exposure as a medium was proposed [H. Ito et al., P.
olym. Eng. Sci. , vol. 23, p. 1012 (1
983)], and various reports have been made regarding this (for example, H. Ito et al., U.S. Pat. No. 4,491,628).
No. (1985); J. V. Crivello, US Pat. No. 4,603,101 (1986); W. R. Brun
svold et al., SPIE's 1989 Sympo. ,1
086-40;T. Neenan et al., SPIE's 1
989 Sympo. , 1086-01; Japanese Patent Publication No. 1986-
115440, etc.). However, in these existing chemically amplified resist materials, the resin used is, for example, poly(4-tert-butoxycarbonyloxystyrene), poly(4-tert-butoxycarbonyloxy-α-methylstyrene), poly(4-tert-butoxycarbonyloxy-α-methylstyrene), (4-tert-butoxystyrene), poly(4-tert-butoxy-α-
In the case of phenol ether resins such as methylstyrene, they all have poor heat resistance and poor adhesion to the substrate, so the film easily peels off during development, making it impossible to obtain a good pattern shape. It also contains carboxylic acid ester resins, such as poly(tert-butyl-
4-vinylbenzoate), etc., the light transmittance around 248.4 nm is insufficient due to the aromatic ring,
In the case of poly(tert-butyl methacrylate), the resin has problems such as poor heat resistance and dry etch resistance.

[Problems to be solved by the invention]

Although chemically amplified resist materials have higher sensitivity than conventional resist materials, the resin has poor heat resistance, poor adhesion to the substrate, and Practical use is difficult due to insufficient light transmittance in the vicinity. Therefore, there is a current need for a practical high-sensitivity resist material that overcomes these problems.

[Purpose of the invention]

The present invention was developed in view of the above-mentioned situation, and has high transparency to far ultraviolet light, KrF excimer laser light, etc., and high resistance to exposure by these light sources, electron beams, and X-ray irradiation. It is an object of the present invention to provide a positive resist material using a polymer that has sensitivity and has extremely excellent heat resistance and adhesion to a substrate.

[Structure of the invention]

[0006] In order to achieve the above object, the present invention consists of the following configuration. ``The following 1

[Formula 1] [wherein R1 is a methyl group, an isopropyl group, t
represents an ert-butyl group, a tetrahydropyranyl group, a trimethylsilyl group, or a tert-butoxycarbonyl group, R2 represents a hydrogen atom or a methyl group, and k and l are each independently a natural number {however, k/(k+l)=0 .1～
It is 0.9. } represents. ], a photosensitive compound that generates an acid upon exposure to light, and a solvent capable of dissolving these, and the following chemical formula 2:

[Formula 2] [In the formula, R3 and R5 each independently represent a hydrogen atom or a methyl group, and R4 is a hydrogen atom, a carboxyl group, a cyano group, or a cyano group.

[Formula 3] (wherein R7 represents a hydrogen atom, a halogen atom or a lower alkyl group), R6 is a hydrogen atom,
Cyano group or -COOR8 (However, R8 has 1 to 1 carbon atoms
0 linear, branched or cyclic alkyl group. )
where k', l' and m are each independently natural numbers {provided that 0.1≦k'/(k'+l')≦0.9, and 0.
05≦m/(k'+l'+m)≦0.50}. )
represents. R1 and R2 are the same as above. ], a photosensitive compound that generates an acid upon exposure to light, and a solvent capable of dissolving these. ”

The resist material of the present invention utilizes chemical amplification in order to reduce the amount of exposure energy as much as possible. That is, the resist material of the present invention consists of a monomer unit having a functional group that undergoes a chemical change upon heating in the coexistence of an acid generated from a photosensitive compound upon exposure and becomes alkali-soluble, and a monomer unit having a phenolic hydroxyl group. In this case, a polymer composed of a third monomer unit (hereinafter abbreviated as "polymer according to the present invention"), which has high light transmittance in the vicinity of 248.4 nm, and which is resistant to acid upon exposure or irradiation. This is a novel resist material characterized by the use of a generated photosensitive compound (hereinafter abbreviated as "acid generator"). The present inventors have developed p- or m- monomers that have a functional group that becomes alkali-soluble by heating in an acid atmosphere (hereinafter abbreviated as "specific functional group"), and that have a protecting group that can be removed with an acid. Hydroxystyrene derivatives and p- or m-hydroxy-α-methylstyrene derivatives were selected. More specifically, p- or m-methoxystyrene, p- or m-isopropoxystyrene, p- or m-tert-butoxystyrene, p- or m-tetrahydropyranyloxystyrene, p- or m-
-trimethylsilyloxystyrene, p- or m-te
rt-butoxycarbonyloxystyrene and these p
This is a p- or m-hydroxy-α-methylstyrene derivative having the same protecting group as the - or m-hydroxystyrene derivative. In addition, examples of monomers having a phenolic hydroxyl group include p- or m-vinylphenol and p-
- or m-hydroxy-α-methylstyrene was selected. In addition to the above-mentioned two types of monomer units, the polymer according to the present invention has a third monomer unit such as α-methylstyrene, p-chlorostyrene, etc. for the purpose of increasing the light transmittance of the entire polymer in the vicinity of 248.4 nm. , acrylonitrile, fumaronitrile, methyl methacrylate, tert-butyl methacrylate, tert p-ethenylphenoxyacetic acid
It may also contain monomer units such as t-butyl.

In the polymer according to the present invention, the composition ratio of the monomer unit having the above-mentioned specific functional group to the monomer unit having a phenolic hydroxyl group is usually 1:9 to 9:1; The ratio of 2:8 to 7:3 is more preferable because it can be used as the resist material of the invention, but the polymer has extremely good heat resistance and adhesion to the substrate.

Specific examples of the polymer according to the present invention include p-isopropoxystyrene-p-hydroxystyrene polymer, p-tetrahydropyranyloxystyrene-
p-hydroxystyrene polymer, p-tert-butoxystyrene-p-hydroxystyrene polymer, p-trimethylsilyloxystyrene-p-hydroxystyrene polymer, p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene polymer, p-methoxy-
α-methylstyrene-p-hydroxy-α-methylstyrene polymer, p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene-methyl methacrylate polymer, p-tetrahydroxypyranyloxystyrene-p-hydroxystyrene- methacrylic acid tert-
Butyl polymer, p-tert-butoxystyrene-p-
Hydroxystyrene-fumaroniloryl polymer, p-trimethylsilyloxystyrene-p-hydroxystyrene-p-chlorostyrene polymer, p-tert-butoxystyrene-p-hydroxystyrene-methacrylic acidte
rt-butyl polymer, p-tert-butoxystyrene-p-hydroxystyrene-acrylonitrile polymer,
p-tert-butoxystyrene-p-hydroxystyrene-tert-butyl p-ethenylphenoxyacetate polymer, m-isopropoxystyrene-p- or m-hydroxystyrene polymer, m-tetrahydropyranyloxystyrene-p- or m-hydroxystyrene polymer,
m-tert-butoxystyrene-p- or m-hydroxystyrene polymer, m-trimethylsilyloxystyrene-p- or m-hydroxystyrene polymer, m-t
ert-butoxycarbonyloxystyrene-p- or m-hydroxystyrene polymer, m-methoxy-α-methylstyrene-p- or m-hydroxy-α-methylstyrene polymer, m-tert-butoxycarbonyloxystyrene-p - or m-hydroxystyrene-methyl methacrylate polymer, m-tetrahydroxypyranyloxystyrene-p- or m-hydroxystyrene-tert-butyl methacrylate polymer, m-tert-butoxystyrene-p- or m- Hydroxystyrene-fumaroniloryl polymer, m-trimethylsilyloxystyrene-p- or m-hydroxystyrene-p-chlorostyrene polymer, p-tert-butoxystyrene-p- or m-hydroxystyrene-tert-butyl methacrylate polymer , m-tert-butoxystyrene-p- or m-hydroxystyrene-acrylonitrile polymer and m-tert-butoxystyrene-p- or m-hydroxystyrene-p-ethenylphenoxyacetic acid tert
-butyl polymers, etc., but are not limited thereto.

[0010] The polymer according to the present invention has, for example, the following a) to
It can be easily obtained by the three methods shown in c). a) Method-1 The monomer having the above-mentioned specific functional group alone or this and a third monomer are mixed in an organic solvent such as benzene, toluene, tetrahydrofuran, 1,4-dioxane, etc. according to a conventional method for producing polymers. , a radical polymerization initiator [e.g.
2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'
- an azo polymerization initiator such as azobis(methyl 2-methylpropionate), a peroxide polymerization initiator such as benzoyl peroxide, lauroyl peroxide, etc.] in a nitrogen or argon stream at 50 to 110°C. The polymerization reaction is carried out for 1 to 10 hours. After the reaction, a post-treatment is performed according to a conventional method for obtaining polymers to isolate a polymer consisting of monomer units having the above-mentioned specific functional group or a copolymer containing monomer units having the above-mentioned specific functional group. . This polymer or copolymer is then treated with a suitable acid [e.g., sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, p-toluenesulfonic acid, etc.] in an organic solvent such as tetrahydrofuran, acetone, or 1,4-dioxane. Acids are preferred. ] at 30 to 100°C for 1 to 10 hours to eliminate the above-mentioned specific functional groups at an arbitrary ratio. After the reaction, the desired polymer is isolated by post-treatment according to conventional methods for obtaining polymers.

b) Method-2 Monomer having the above specific functional group and p-hydroxystyrene (or p-hydroxy-α-methylstyrene)
After copolymerizing the copolymer and, if necessary, a third monomer, by the same operation method as Method-1, post-treatment is performed according to a conventional method for obtaining polymers, and the desired polymer is isolated.

c) Method-3: Polymerizing or copolymerizing p-hydroxystyrene (or p-hydroxy-α-methylstyrene) alone or with a third monomer using the same procedure as Method-1. After that, the above-mentioned specific functional groups are chemically introduced into the obtained polymer or copolymer in an arbitrary ratio, and then post-treatment is performed according to the conventional method for obtaining polymers to obtain the desired polymer in a single form. Let go.

Although the polymer according to the present invention can be obtained by any of these three methods, the polymer obtained by method-1 has a molecular weight of 248. It is most preferable because it has extremely excellent light transmittance around 4 nm.

This will be explained in detail below, taking as an example poly(p-tert-butoxystyrene-p-hydroxystyrene), which is the most representative of the polymers according to the present invention and is shown by Chemical Formula 1. . That is, poly(p-tert-butoxystyrene-p-hydroxystyrene) obtained by method-1 and poly(p-tert-butoxystyrene-p-hydroxystyrene) obtained by the other two methods.
When p-tert-butoxystyrene-p-hydroxystyrene) (ratio of each unit of the polymer is 1:1) was formed into a film, and the light transmittance near 248.4 nm at a film thickness of 1 μm was compared, The transmittance of the polymer according to the present invention is about 70%, while the transmittance of other polymers is about 55-55%.
It was 61%. This difference in transmittance is a fatal difference for photoresist polymers that require higher resolution performance because they are used in photolithography for ultrafine processing.

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 the preferred range is the weight determined by GPC measurement using polystyrene as a standard. The average molecular weight is usually about 1,000 to 40,000, preferably about 3,000 to 20,000.

The acid generator used in the present invention may be any photosensitive compound that literally generates acid upon exposure to light, as long as it does not adversely affect photoresist pattern formation. Particularly preferable acid generators include, for example, the following compounds 6, 11, 13, or 14.
Examples include compounds represented by:・6

[Formula 6] [wherein R9 and R10 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 a haloalkyl group having 1 to 10 carbon atoms, or

[Formula 7] (wherein R11 and R12 are each independently a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a lower alkyl group having 1 to 5 carbon atoms)
represents a haloalkyl group, and n represents 0 or a natural number. ), and X represents a carbonyl group, carbonyloxy group or sulfonyl group. ]・Case 11

[Formula, R13 is a linear chain having 1 to 10 carbon atoms,
Branched or cyclic alkyl group, trifluoromethyl group or chemical formula 9

Represents a group represented by the following formula (wherein R17 represents a hydrogen atom or a methyl group), R14 and R15 each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, and R16 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, phenyl group, halogen-substituted phenyl group, alkyl-substituted phenyl group, alkoxy-substituted phenyl group or alkylthio-substituted phenyl group. ]・C13

embedded image (wherein R18, R19, R20 and R21
each independently represents a hydrogen atom, a halogen atom, a carbon number of 1 to 1
0 linear, branched or cyclic alkyl group or 1 carbon number
-10 alkoxy groups, Z- represents perchlorate ion, p-toluenesulfonate ion or trifluoromethanesulfonate ion. ) ・C14

[Formula 14] (wherein, R22 is a trichloroacetyl group, p
-toluenesulfonyl group, p-trifluoromethylbenzenesulfonyl group, methanesulfonyl group or trifluoromethanesulfonyl group, and R23 and R24 each independently represent a hydrogen atom, a halogen atom or a nitro group. )

[0017] Furthermore, the compound represented by chemical formula 6 is
Further, compounds represented by the following chemical formulas 8, 9 and 10 may be mentioned.・C8

15. The resist material according to claim 14, which is a compound represented by the following formula: (wherein R9 and R10 are the same as above).・C9

15. The resist material according to claim 14, which is a compound represented by the following formula (wherein R9 and R10 are the same as above).・C10

[Formula 10] (In the formula, R9 and R10 are the same as above.)

[
Specific examples of acid generators preferred in the present invention include bis(p-toluenesulfonyl)diazomethane, 1-p-toluenesulfonyl-1-methanesulfonyldiazomethane, bis(isopropylsulfonyl)diazomethane, and bis(cyclohexylsulfonyl). ) Diazomethane, 1-cyclohexylsulfonyl-1-tert-
Butylsulfonyldiazomethane, 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane,
2-Methyl-2-p-toluenesulfonylpropiophenone, 2-methanesulfonyl-2-methyl-(4-methylthio)propiophenone, 2,4-dimethyl-2-(
p-Toluenesulfonyl)pentan-3-one, 2-(
cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, diphenyl-p-methylphenacylsulfonium perchlorate, diphenyl-2,5-dimethoxyphenacylsulfonium p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, Examples include 2,6-dinitrobenzyl trichloroacetate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate, but needless to say, the present invention is not limited to these.

The solvent used in the present invention may be any solvent as long as it can dissolve both the polymer and the acid generator, but it is usually more preferable to use a solvent that does not have absorption in the vicinity of 230 to 300 nm. 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-methoxypropion. Ethyl acid, N-
Examples include methyl-2-pyrrolidone, cyclohexanone, methyl ethyl ketone, 1,4-dioxane, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether, but are not limited thereto.

[0020]Although the resist material of the present invention usually has the above three components (polymer, acid generator, and solvent) as its main components, dyes, surfactants, etc. may be added as necessary. .

[0021] To form a pattern using the resist material according to the present invention, the following procedure may be performed, for example. A resist material containing the compound according to the present invention is applied onto a substrate such as a silicon wafer to a thickness of approximately 0.5 to 2 μm (0.1 to 2 μm when used as the upper layer of three layers).
(approximately 0.5 μm) and heat it in an oven at 70-130°C.
, for 10-30 minutes, or on a hot plate for 70-30 minutes.
Pre-bake at 130°C for 1-2 minutes. Next, a mask for forming a desired pattern is held over the above resist film, and an exposure amount (exposure amount) of deep ultraviolet light of 300 nm or less is applied.
After irradiating at a dose of about 1 to 100 mJ/cm2, using a developer such as a 0.1 to 5% tetramethylammonium hydroxide (TMAH) aqueous solution for about 0.5 to 3 minutes, immersion method. Paddle (p
A desired pattern can be formed on the substrate by developing it by a conventional method such as the Uddle method or the spray method.

[0022] The polymer according to the present invention and the photosensitive compound,
The mixing ratio in the positive resist material is 1 polymer to 1 polymer.
The amount of the photosensitive compound relative to the weight may be 0.01 to 0.3 weight, preferably around 0.01 to 0.1 weight. In addition, the amount of solvent in the resist material of the present invention is an amount that does not cause any trouble when applying the positive resist material obtained as a result of dissolving the polymer and photosensitive compound of the present invention onto a substrate. If it is present, it may be mentioned without particular limitation, but it is usually 1 to 20 weights, preferably around 1.5 to 6 weights, per 1 weight of the polymer.

[0023] Also, depending on the solubility of the resin used in the resist material in the alkaline solution, the developer used in the various pattern forming methods as described above will hardly dissolve the unexposed areas, but will dissolve the exposed areas. It is sufficient to select an alkaline solution with an appropriate concentration to dissolve the alkaline solution, usually 0.01
-20%. In addition, examples of the alkaline solution used include organic amines such as TMAH, choline, triethanolamine, etc., such as NaOH, KO
Examples include solutions containing inorganic alkalis such as H.

[0024] The polymer according to the present invention has heat resistance, dry etching resistance, and excellent adhesion to a substrate because it contains a component having a hydroxystyrene skeleton. . In addition, the polymer according to the present invention produced by the above method-1 has a 248.4n
The light transmittance near m is extremely excellent.

The resist material of the present invention generates acid not only when exposed to KrF excimer laser light but also when exposed to electron beams or X-rays.
It has been confirmed that chemical amplification works. Therefore, the resist material of the present invention is a resist material that can be patterned using chemical amplification with a low exposure dose of far ultraviolet light, KrF excimer laser light (248.4 nm), electron beam, or X-ray irradiation. .

[Effect]

To explain the action of the present invention using a specific example, first, a region exposed to KrF excimer laser light, far ultraviolet light, etc. undergoes a photoreaction shown by, for example, the following formula 1, formula 2, formula 3, or formula 4. Acid is generated.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4] When heat treatment follows the exposure step, specific functional groups (in Formula 5, t
Illustrated as ert-butoxy group. ) undergoes a chemical change with acid and becomes a hydroxyl group, becoming alkali-soluble and eluting into the developer during development.

[Formula 5] On the other hand, since no acid is generated in the unexposed area, no chemical change occurs even after heat treatment, and instead the hydrophilic group portion of the polymer used for the purpose of strengthening adhesion to the substrate is converted into an acid generator. The protective effect against infiltration of alkaline developer is developed. In this way, when pattern formation is performed using the resist material of the present invention, a large solubility difference occurs in an alkaline developer between the exposed and unexposed areas, and moreover, the resin in the unexposed areas is attached to the substrate. Since it has strong adhesion to the surface, the film does not peel off during development, and as a result, a positive pattern with good contrast is formed. Further, as shown in the above equation 5, since the acid generated by exposure acts catalytically, exposure only needs to generate the necessary acid, making it possible to reduce the amount of exposure energy.

The present invention will be explained in more detail below with reference to Examples, Production Examples, Reference Examples, and Comparative Examples, but the present invention is not limited in any way by these.

【Example】

Production example 1. Synthesis of poly(p-tert-butoxystyrene-p-hydroxystyrene) -1
(1) A catalytic amount of 2,2'-azobisisobutyronitrile was added to 17.6 g of p-tert-butoxystyrene, and a polymerization reaction was carried out at 80° C. for 6 hours in a toluene solvent under a nitrogen stream. After cooling the reaction solution, it was poured into methanol to cause crystallization, and the precipitated crystals were filtered, washed with methanol, and dried under reduced pressure to obtain 15.5 g of poly(p-tert-butoxystyrene) as white powder crystals. Weight average molecular weight approximately 10,000 (G
PC method: polystyrene standard). (2) 15.0 g of poly(p-tert-butoxystyrene) obtained in (1) above was dissolved in 1,4-dioxane, 10 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 water to cause crystallization, and the precipitated crystals were filtered, washed with water, and dried under reduced pressure to obtain 11.8 g of poly(p-tert-butoxystyrene-p-hydroxystyrene) as white powder crystals. . The composition ratio of p-tert-butoxystyrene units and p-hydroxystyrene units in the obtained polymer was approximately 1:1 according to 1HNMR measurement. Weight average molecular weight approximately 10,000 (GPC method: polystyrene standard).

Production example 2. Synthesis of poly(p-tert-butoxystyrene-p-hydroxystyrene-tert-butyl methacrylate) (1) p-tert-butoxystyrene 28.2g (0
．． 16 mol) and tert-butyl methacrylate 5.7
g (0.04 mol), a catalytic amount of 2,2'-azobis(2
, 4-dimethylvaleronitrile) was added thereto, and a polymerization reaction was carried out at 80° C. for 8 hours in toluene. After cooling the reaction solution, it was poured into petroleum ether to cause crystallization, and the precipitated crystals were filtered, washed with petroleum ether, and dried under reduced pressure to obtain poly(p-tert-butoxystyrene-tert-butyl methacrylate) 23.8
g was obtained as a white powder crystal. (2) 23.5 g of poly(p-tert-butoxystyrene-tert-butyl methacrylate) obtained in (1) above was dissolved in 1,4-dioxane, 2 g of p-toluenesulfonic acid was added, and the mixture was stirred and refluxed. After cooling for 1.5 hours, the reaction solution was poured into water.
The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 14.1 g of p-poly(p-tert-butoxystyrene-p-hydroxystyrene-tert-butyl methacrylate) as white powder crystals. p-tert of the obtained polymer
The composition ratio of -butoxystyrene units and p-hydroxystyrene units was approximately 4:6 as determined by 1HNMR measurement. Weight average molecular weight approximately 15,000 (GPC method: polystyrene standard).

Production example 3. Synthesis of poly(p-tert-butoxystyrene-p-hydroxystyrene) -2
3.5 g (0.02 mol) p-tert-butoxystyrene and 2.7 g (0.022 mol) p-hydroxystyrene
The polymerization reaction was carried out in the same manner as in Production Example 1 except that mol) was used as the starting material, and then the reaction solution was poured into petroleum ether to crystallize it. The precipitated crystals were filtered, washed, and dried under reduced pressure to obtain polyester. 5.0 g of (p-tert-butoxystyrene-p-hydroxystyrene) was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene units and p-hydroxystyrene units in the obtained copolymer was approximately 1:1 according to 1H NMR measurement. Weight average molecular weight approximately 10,000 (GP
Method C: polystyrene standard).

Production example 4. Synthesis of poly(p-tert-butoxystyrene-p-hydroxystyrene) -3
(1) A polymerization reaction was carried out in the same manner as in Production Example 1 except that 5.0 g of p-hydroxystyrene was used as the starting material,
After cooling, the precipitated crystals were filtered, washed, and dried under reduced pressure to obtain poly(p-
4.2 g of hydroxystyrene) were obtained as white powder crystals. (2) 4.0 g of the poly(p-hydroxystyrene) obtained in (1) above in dimethoxyethane (70 ml) in a pressure-resistant container.
Add 60g of isobutylene and 0.3g of sulfuric acid to the solution.
ml was added below -60°C. Next, the mixture was stirred and reacted at 45° C. for 1 hour and then at room temperature for 22 hours. After the reaction, the reaction solution was concentrated, the residue was neutralized with sodium carbonate, poured into water, crystallized, and the precipitated crystals were filtered, washed with water, and dried under reduced pressure to obtain poly(p-tert-butoxystyrene-p-hydroxy). 4.1 g of styrene was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene units and p-hydroxystyrene units in the obtained polymer was 1.
The ratio was approximately 1:1 by HNMR measurement. Weight average molecular weight approximately 10,000 (GPC method: polystyrene standard).

Production example 5. Synthesis of poly(p-tert-butoxystyrene-p-hydroxystyrene-fumaronitrile) (1) p-tert-butoxystyrene 28
．． 2g (0.16 mol) and 3.1g (0.16 mol) of fumaronitrile (
0.04 mol) was subjected to a polymerization reaction in the presence of 2,2'-azobis(methyl 2-methylpropionate) in a toluene solvent at 90°C under a nitrogen stream for 2 hours. After the reaction, the reaction solution is poured into methanol to crystallize, and the precipitated crystals are filtered, washed,
After drying, 21.3 g of poly(p-tert-butoxystyrene-fumaronitrile) was obtained as white powder crystals. (2) Using 20.0 g of poly(p-tert-butoxystyrene-fumaronitrile) obtained in (1) above, reaction and post-treatment were carried out in the same manner as in (2) of Production Example 1.
15.4 g of tert-butoxystyrene-p-hydroxystyrene-fumaronitrile was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene units and p-hydroxystyrene units in the obtained polymer was 1HNM.
According to R measurement, the ratio was about 1:1. Weight average molecular weight approximately 12
000 (GPC method: polystyrene standard).

Production example 6. Synthesis of poly(p-tert-butoxycarbonyloxystyrene-p-hydroxystyrene) (1) U.S. Pat. No. 4,491,628 (1)
p-tert obtained by the method described in
Using 22 g (0.1 mol) of -butoxycarbonyloxystyrene in the presence of a 2,2'-azobis(2,4-dimethylvaleronitrile) catalyst in toluene under a nitrogen stream for 90 hours.
After polymerization reaction at ℃ for 5 hours, the reaction solution was converted into (1
) to obtain 15.2 g of poly(p-tert-butoxycarbonyloxystyrene) as white powder crystals. Weight average molecular weight approximately 12,000 (GPC method: polystyrene standard). (2) Using 7 g of poly(p-tert-butoxycarbonyloxystyrene) obtained in (1) above, (
The reaction and post-treatment were carried out in the same manner as in 2), and poly(p-t
4.8 g of ert-butoxycarbonyloxystyrene (p-hydroxystyrene) was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene units and p-hydroxystyrene units in the obtained polymer was approximately 1:1 according to 1HNMR measurement.

Production example 7. Synthesis of poly(p-tetrahydropyranyloxystyrene-p-hydroxystyrene) Poly(hydroxystyrene) [weight average molecular weight approx.
000: GPC method (polystyrene standard)] 9 g was dissolved in dimethoxyethane (100 ml), and then 3,4-
12.6 g of dihydro-2H-pyran and 0.5 ml of sulfuric acid
was added and stirred at 30 to 40°C for 15 hours. After the reaction, the reaction solution was concentrated under reduced pressure, the residue was neutralized with sodium carbonate, poured into water and crystallized, the precipitated crystals were filtered, washed with water, and dried under reduced pressure to obtain poly(p-tetrahydropyranyloxystyrene-p). −
11.0 g of hydroxystyrene) were obtained as white powder crystals. The composition ratio of p-tetrahydropyranyloxystyrene units and p-hydroxystyrene units in the obtained polymer was about 3:7 according to 1HNMR measurement.

Production example 8. Synthesis of poly(p-tert-butoxystyrene-p-hydroxystyrene-methyl methacrylate) (1) p-tert-butoxystyrene 15.8g (0
．． 09 mol) and methyl methacrylate 1.0 g (0.0
A catalytic amount of 2,2'-azobis(2,4-dimethylvaleronitrile) was added to 9 mol) and polymerization reaction was carried out in toluene at 80°C under a nitrogen stream for 8 hours. After cooling the reaction solution, it was poured into petroleum ether to cause crystallization, and the precipitated crystals were filtered, washed with petroleum ether, and dried under reduced pressure to obtain 10.9 g of poly(p-tert-butoxystyrene-methyl methacrylate) as white powder crystals. obtained as. (2) 10.5 g of poly(p-tert-butoxystyrene-methyl methacrylate) obtained in (1) above was added to 1,4-
It was dissolved in dioxane, 1 g of p-toluenesulfonic acid was added, and the mixture was stirred and refluxed for 1.5 hours. After cooling, the reaction solution was poured into water and crystallized. The precipitated crystals were filtered, washed with water, and dried under reduced pressure to obtain poly( 7.1 g of p-tert-butoxystyrene-p-hydroxystyrene-methyl methacrylate was obtained as white powder crystals. The composition ratio of p-tert-butoxystyrene units to p-hydroxystyrene units in the obtained polymer was about 4:6 according to 1HNMR measurement. Weight average molecular weight approximately 15,000 (GPC method: polystyrene standard).

Production Example 9. Synthesis of 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane (1) 23.9 g of metallic magnesium (shavings)
．． 98 atoms) was suspended in ethyl ether, and to this was added 160 g (0.98 mol) of bromocyclohexane under stirring and reflux.
was added dropwise, followed by stirring and refluxing for 1 hour. After cooling, the resulting Grignard reagent was mixed with 95 g of isobutyric acid chloride (
The mixture was added dropwise to an ethyl ether solution of 0.89 mol) at -5 to 0°C, stirred and reacted at the same temperature for 3 hours, and then left overnight at room temperature. The reaction solution was poured into water, and the separated ether layer was collected, washed with water, and dried over anhydrous magnesium sulfate. After filtering off the desiccant, the solvent is distilled off, and the residue is distilled under reduced pressure to obtain bp.
50 g of 1-cyclohexyl-2-methyl-1-propanone from a 95-100° C./20 mmHg fraction was obtained as a pale yellow oil. 1NMR δppm (deuterochloroform)
: 1.06 (6H, d, methyl group x 2), 1.12~
1.87 (10H, m, cyclohexane ring methylene x 5
), 2.51 (1H, m, cyclohexane ring methine),
2.76 (1H, m, methine). IR(Neat) cm-1:1710. (2) After adding 42 g (0.31 mol) of sulfuryl chloride dropwise to 47.6 g (0.31 mol) of 1-cyclohexyl-2-methyl-1-propanone obtained in (1) above at 25 to 35°C, The reaction was stirred at 50° C. for 3.5 hours. After concentrating the reaction solution, it was distilled under reduced pressure to bp. 99-105℃/18mm
30.1 g of 2-chloro-1-cyclohexyl-2-methyl-1-propanone, a Hg fraction, was obtained as a yellow oil. 1NMR δppm (deuterochloroform): 1.18
~1.87 (16H, m, methyl group x 2 and cyclohexane ring methylene x 5), 3.13 (1H, m, cyclohexane ring methine). (3) 30.0 g (0.16 g) of 2-chloro-1-cyclohexyl-2-methyl-1-propanone obtained in (2) above
molar) in dimethyl sulfoxide (DMSO) solution of p-
Sodium toluenesulfinate 30.0g (0.17
mol) was added thereto, and the mixture was stirred and reacted at 60°C for 20 hours. The reaction solution was poured into cold water and stirred at 0 to 5°C for 1 hour. The precipitated crystals were filtered, washed with water, and dried. 18 g of the crude crystals obtained were recrystallized from a mixture of n-hexane and benzene to obtain 2- 13.5 g of (cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane was obtained as white needles. mp. 123-123.5°C. 1NMR δppm (deuterochloroform): 1.19~
1.91 (16H, m, methyl group x 2 and cyclohexane ring methylene x 5), 2.45 (3H, s, methyl group derived from tosylic acid), 3.25 (1H, m, cyclohexane ring methine), 7 .33 (2H, d, J = 8 Hz, aromatic ring 3-H, 5-H), 7.65 (2H, d, J = 8
Hz, aromatic ring 2-H, 6-H). IR (KBr) cm-1: 1705, 1310.

Production example 10. Synthesis of bis(cyclohexylsulfonyl)diazomethane (1) After dissolving 22.5 g (0.35 mol) of sodium azide in a small amount of water, 130 ml of 90% aqueous ethanol
Diluted in ml. Next, an ethanol solution in which 60 g (0.32 mol) of p-toluenesulfonyl chloride was dissolved was added dropwise at 10 to 25°C, and the mixture was reacted at room temperature for 2.5 hours. The reaction solution was then concentrated under reduced pressure, and the residual oil was washed with water several times and then dried over anhydrous magnesium sulfate. The drying agent was filtered off to obtain 50.7 g of p-toluenesulfonyl azide as a colorless oil. 1NMR δppm (deuterochloroform): 2.43 (
3H, s, methyl group), 7.24 (2H, d, J=8H
z, aromatic ring 3-H, 5-H), 7.67 (2H, d
, J=8Hz, aromatic ring 2-H, 6-H). IR(Neat) cm-1:2120. (2) An ethanol solution of 12.0 g (0.21 mol) of potassium hydroxide was added dropwise to 20.2 g (0.17 mol) of cyclohexylthiol at room temperature, and the mixture was reacted with stirring at 30±5° C. for 30 minutes. Next, 18.2 g (2.14 g) of methylene chloride
mol) was injected, and the mixture was stirred and reacted at 50±5°C for 6 hours. After standing overnight at room temperature, 55 ml of ethanol was poured into the reaction solution.
After diluting and adding 400 mg of sodium tungstate, 50 g (0.44 mol) of 30% hydrogen peroxide was added to 45
The mixture was added dropwise at ~50°C, and the reaction was further stirred at the same temperature for 4 hours. After the reaction, 200 ml of water was poured and left overnight at room temperature. The precipitated crystals were filtered, washed with water, and dried. 22 g of the resulting crude crystals were recrystallized from ethanol, and 15.5 g of bis(cyclohexylsulfonyl)methane was added to a white needle. Obtained as crystals. mp. 137-139°C. 1NMR δppm (deuterochloroform): 1.13~
2.24 (20H, m, cyclohexane ring methylene x 1
0), 3.52-3.66 (2H, m, cyclohexane ring methine x 2), 4.39 (2H, s, methylene). IR(KBr) cm-1:1320, 1305. (3) Dissolve 1.7 g of sodium hydroxide in 70 ml of 60% aqueous ethanol, and add to this the bis-hydroxide obtained in (2) above.
Cyclohexylsulfonylmethane 12.1g (0.04
mol) was added. Next, an ethanol solution of 8.2 g (0.04 mol) of p-toluenesulfonyl azide obtained in the above (1) was added dropwise at 5 to 10°C, and the mixture was stirred and reacted at room temperature for 7 hours. After standing overnight at room temperature, the precipitated crystals were filtered, washed with ethanol, and dried. 11 g of the crude crystals obtained were recrystallized from acetonitrile to obtain bis(cyclohexylsulfonyl).
8.0 g of diazomethane was obtained as pale yellow prism crystals. mp. 130-131℃. 1NMR δppm (deuterochloroform): 1.13~
2.25 (20H, m, cyclohexane ring methylene x 1
0), 3.36-3.52 (2H, m, cyclohexane ring methine x 2). IR (KBr) cm-1: 2130, 1340, 13
20.

Production example 11. Synthesis of 2,6-dinitrobenzyl p-toluenesulfonate (1) 19.6 g of 2,6-dinitrobenzaldehyde (
0.1 mol) was suspended in 200 ml of methanol and 15
After gradually adding 5.8 g of sodium borohydride at ~25°C, the mixture was allowed to react at room temperature for 1 hour. After the reaction, the solvent was distilled off, 100 ml of water and 100 ml of chloroform were added to the residue, and the mixture was stirred and reacted for 1 hour, then left to stand and separated into layers, and the chloroform layer was separated, washed with water, and dried over anhydrous magnesium sulfate. The drying agent was filtered off and the solvent was distilled off to obtain a residue of 15.0 g of 2,6-dinitrobenzyl alcohol as yellow crystals. mp. 92.5-93.5°C. 1NMR δppm (deuterochloroform): 2.77 (
1H, t, J = 7Hz, hydroxyl group), 4.97 (2H, d
, J=7Hz, methylene), 7.66(1H,t,J=
8Hz, 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 An acetone solution of 15 g of dicyclohexylamine was added dropwise at 0 to 10° C., and the mixture was stirred and reacted at room temperature for 4 hours. After the reaction, the precipitate was filtered, the filtrate was concentrated, and the residue (29 g) was recrystallized from carbon tetrachloride to obtain 19.8 g of 2,6-dinitrobenzyl p-toluenesulfonate as pale yellow scale-like crystals. Obtained. mp. 98-99°C. 1NMR δppm (deuterochloroform): 2.45 (
3H, s, methyl group), 5.57 (2H, s, methylene), 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 (2
H, d, J = 8Hz, p-methylbenzene ring 2-H,
6-H), 7.72 (2H, d, J=8Hz, dinitrobenzene ring 3-H, 5-H). IR (KBr) cm-1: 1360, 1170.

Production Example 12.2-Methyl-2-(p-
Synthesis of toluenesulfonyl)propiophenone Using isobutyrophenone as a starting material, the reaction and post-treatment were carried out in the same manner as in Production Example 9 (2) and (3).
The crude crystals were recrystallized from methanol to give 2-methyl-2-(
p-Toluenesulfonyl)propiophenone was obtained as white needles. mp. 64-64.5°C. 1NMR δppm (deuterochloroform): 1.70 (
6H, s, methyl group x 2), 2.45 (3H, s, methyl group derived from tosylic acid), 7.32 (2H, d, J = 7H
z,p-methylbenzene ring 3-H,5-H), 7.4
4 (2H, t, J = 7Hz, 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 = 7
Hz, aromatic ring 2-H, 6-H). IR (KBr) cm-1: 1680, 1303, 12
90.

Production example 13.2,4-dimethyl-2-
Synthesis of (p-toluenesulfonyl)pentan-3-one Production Example 9 Using diisoproyl ketone as a starting material
The reaction and post-treatment were carried out in the same manner as in (2) and (3) above, and the crude crystals were recrystallized from an n-hexane-benzene mixture to give 2,4-dimethyl-2-(p-toluenesulfonyl)pentane-3. -one was obtained as white flaky crystals. mp. 76-79°C. 1NMR δppm (deuterochloroform): 1.15 (
6H, d, methyl group x 2), 1.55 (6H, s, methyl group x 2), 2.45 (3H, s, methyl group derived from tosylic acid), 3.54 (1H, m, J = 7Hz , methine)
, 7.34 (2H, d, J = 8Hz, aromatic ring 3-H,
5-H), 7.65 (2H, d, J = 8Hz, aromatic ring 2
-H, 6-H). IR (KBr) cm-1: 1715, 1305, 12
90.

Production example 14. Methylsulfonyl p
-Synthesis of toluenesulfonyldiazomethane (1) Methylthiomethyl p-tolylsulfone 6.0
g (0.03 mol) in 40 ml of methanol and 40 ml of water.
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 the mixture was reacted under stirring and reflux for 10 hours. After standing overnight at room temperature, the reaction solution was poured into 400 ml of water, and the precipitated crystals were filtered, washed with water, and dried. 7.2 g of the obtained crude crystals were recrystallized from ethanol to give methylsulfonyl p-toluenesulfonylmethane 6. .1 g was obtained as white needles. mp. 163.5-165°C. 1NMR δppm (deuterochloroform): 2.48 (
3H,s, methyl group derived from tosylic acid), 3.28(3H,
s, methyl group), 4.56 (2H, s, methylene), 7
．． 40 (2H, d, J = 8Hz, aromatic ring 3-H, 5-H
), 7.87 (2H, d, J = 8Hz, aromatic ring 2-H
, 6-H). (2) Using 5.0 g (0.02 mol) of methylsulfonyl p-toluenesulfonylmethane obtained in (1) above, the reaction and post-treatment were carried out in the same manner as in Production Example 10 (3). 3 g of the crude crystals were recrystallized from ethanol to obtain 2.2 g of methylsulfonyl p-toluenesulfonyldiazomethane as pale yellow flaky crystals. mp. 107.5-109°C. 1NMR δppm (deuterochloroform): 2.46 (
3H, s, methyl group derived from tosylic acid), 3.42 (3H,
s, methyl group), 7.38 (2H, d, J = 8 Hz, aromatic ring 3-H, 5-H), 7.87 (2H, d, J = 8
Hz, aromatic ring 2-H, 6-H). IR (KBr) cm-1: 2120, 1350, 13
30.

Production Example 15. Synthesis of 1-diazo-1-methylsulfonyl-4-phenylbutan-2-one
(1) 50 g (0.33 mol) of 3-phenylpropionic acid was dissolved in 220 ml of methanol, and after injecting 5 g of concentrated sulfuric acid, the mixture was reacted for 1 hour under stirring and reflux. After concentrating the reaction solution,
The residue was poured into ice water and extracted three times with 75 ml of methylene chloride. Wash the organic layer obtained by separating with water (125ml x 2)
and dried over anhydrous magnesium sulfate, and 54 g of the crude oil obtained by distilling off the solvent was distilled under reduced pressure to give bp. 94-95℃/5
Methyl 3-phenylpropionate in mmHg fraction 51.
Obtained 5 g as a colorless oil. IR(Neat) cm-1:1745. (2) DM 42g (0.45mol) of dimethylsulfone
60% sodium hydride dissolved in 225 ml of SO
7.9 g (0.45 mol) was added little by little at 18 to 20°C, stirred and reacted at 65 to 70°C for 30 minutes, and then diluted by injecting 225 ml of tetrahydrofuran. Next, a solution of 36.6 g (0.22 mol) of methyl 3-phenylpropionate obtained in the above (1) in tetrahydrofuran (110 ml) was added dropwise at 33 to 41°C, and the mixture was reacted for 1 hour under stirring and reflux. After cooling the reaction solution, it was poured into a dilute aqueous hydrochloric acid solution, extracted with chloroform (100 ml x 5), and the resulting organic layer was poured into water (2
00ml x 3), saturated aqueous sodium bicarbonate solution (20ml
0 ml) and water (200 ml), and dried over anhydrous magnesium sulfate. After filtering off the desiccant, 60.8 g of crude crystals obtained by concentration were recrystallized from ethyl acetate to obtain 1-methylsulfonyl-4.
24.7 g of -phenylbutan-2-one were obtained as white needles. mp. 97.6-98.4°C. 1NMR δppm (deuterochloroform): 2.91~
3.09 (7H, m, methylene x 2 and methyl group),
3.99 (2H, s, methylene), 7.16-7.33
(5H, m, aromatic ring hydrogen). IR (KBr) cm-1: 1730, 1320, 13
05. (3) 12 g (0.05 mol) of 1-methylsulfonyl-4-phenylbutan-2-one obtained in (2) above was dissolved in 135 ml of methylene chloride, and 11.
After dropping 5 g, the mixture was stirred and reacted for 30 minutes. Then,
11.5 g (0.06 mol) of p-toluenesulfonyl azide obtained in Production Example 10 (1) was added dropwise at 0 to 5°C, and the mixture was stirred and reacted at the same temperature for 5 hours. 26.6 g of crude solid obtained by concentrating the reaction solution was recrystallized from carbon tetrachloride to give 1-diazo-1-methylsulfonyl-4-phenylbutane-2-
7.5 g of ion was obtained as slightly yellow needle-like crystals. mp. 52.5-54°C. 1NMR δppm (deuterochloroform): 2.88~
3.07 (4H, m, methylene x 2), 3.17 (3H
, s, methyl group), 7.16-7.35 (5H, m, aromatic ring hydrogen). IR (KBr) cm-1: 2120, 1655, 13
35, 1315.

Production example 16.1-diazo-1-(p-
toluenesulfonyl)-3,3-dimethylbutane-2-
(1) 33.3 g (0.19 mol) of 1-bromo-3,3-dimethylbutan-2-one was dissolved in DMSO 3
34.9 g (0.20 mol) of sodium p-toluenesulfinate was added thereto at 30 to 40°C. Next, after reacting with stirring at 60 to 70°C for 18 hours, the reaction solution was poured into 2 liters of ice water, and the precipitated crystals were filtered.
Washed with water and dried, 1-(p-toluenesulfonyl)-3,
41.6 g of 3-dimethylbutan-2-one was obtained as white crystals. mp. 119-122°C. 1NMR δppm (deuterochloroform): 1.12 (
9H, s, methyl group x 3), 2.45 (3H, s, methyl group), 4.31 (2H, s, methylene), 7.36 (
2H, d, J=8Hz, aromatic ring 3-H, 5-H), 7.
82 (2H, d, J = 8Hz, aromatic ring 2-H, 6-H
). IR (KBr) cm-1: 1715, 1320, 12
90. (2) 20 g (0.0
The reaction and post-treatment were carried out in the same manner as in Production Example 15 (3), and 24 g of the resulting crude solid was recrystallized from ethanol to give 1-diazo-1-(p-toluenesulfonyl). -3,3-dimethylbutan-2-one 12.6
g was obtained as pale yellow short needle crystals. mp. 120.5-121.5°C. 1NMR δppm (deuterochloroform): 1.17 (
9H, s, methyl group x 3), 2.44 (3H, s, methyl group), 7.34 (2H, d, J = 8Hz, aromatic ring 3
-H, 5-H), 7.93 (2H, d, J=8Hz, aromatic ring 2-H, 6-H). IR (KBr) cm-1: 2140, 1660, 13
05.

Production Example 17. Synthesis of cyclohexyl 2-diazo-2-phenylsulfonylacetate (1) 15.6 g of cyclohexyl 2-bromoacetate (
0.07 mol) was dissolved in 120 ml of DMSO, and 15 g of sodium benzenesulfinate dihydrate (
0.075 mol) was added at 30-40°C. Then,
After reacting with stirring at 60°C for 6 hours, the reaction solution was diluted with ice water for 1.5 hours.
The precipitated crystals were filtered, washed with water, and dried to obtain 15.3 g of cyclohexyl 2-phenylsulfonylacetate as white crystals. mp. 35-38℃. 1NMR δppm (deuterochloroform): 1.11~
1.82 (10H, m, cyclohexane ring methylene x 5
), 4.11 (2H, s, methylene), 4.46-4.
84 (1H, m, cyclohexane ring methine), 7.50
~7.98 (5H, m, aromatic ring hydrogen). IR (KBr) cm-1: 1735, 1290. (2) 2-phenylsulfonylacetic acid obtained in (1) above
Reaction and post-treatment were carried out in the same manner as in Production Example 15 (3) using 10 g (0.035 mol) of cyclohexyl.
11 g of the obtained crude solid was subjected to column chromatography [filling material: Wakogel C-200 (Wako Pure Chemical Industries, Ltd.)]
(Product name), eluent; n-hexane: methylene chloride = 6:
1 → 4:1 → 1:1] to obtain 2-diazo-2-
5.8 g of cyclohexyl phenylsulfonylacetate was obtained as a pale yellow oil. 1NMR δppm (deuterochloroform): 1.15~
1.86 (10H, m, cyclohexane ring methylene x 5
), 4.73-4.89 (1H, m, cyclohexane ring methine), 7.47-8.07 (5H, m, aromatic ring hydrogen). IR (Neat) cm-1: 2160, 1730, 1
310.

Experimental example 1. Poly(p-te) obtained in Production Example 1, Production Example 3 and Production Example 4
rt-butoxystyrene-p-hydroxystyrene) were prepared into the following compositions. Poly(p-tert-butoxystyrene-p-
Hydroxystyrene) 3.0g
diethylene glycol dimethyl ether
7.0g
The above composition was spin-coated onto a substrate such as a semiconductor, and heated to 90°C.
After soft baking on a hot plate for 90 seconds, a polymer film with a thickness of 1 μm was obtained. Next, each polymer film was subjected to UV measurement. Its UV spectrum is shown in FIG. From the results shown in FIG. 2, it can be seen that the polymer obtained by Production Example 1 has significantly better light transmittance in the vicinity of 240 to 250 nm than the polymers obtained by the other two production methods.

Experimental example 2. Production Example 1 (1), Production Example 1 (2), Production Example 6 (1)
) and various polymers obtained in Production Example 6 (2) were compared in heat resistance and adhesion. The heat resistance test was conducted by performing differential thermal analysis (DTA) measurement to determine the glass transition temperature (Tg) of each polymer. Further, the substrate adhesion test was conducted by preparing a resist material having the composition shown below, forming a pattern as described below, and observing and comparing the results with the naked eye. polymer

6.0g 2,4
-dimethyl-2-(p-toluenesulfonyl)pentan-3-one (acid generator of Production Example 13)

0.3g diethylene glycol dimethyl ether
13.7g A pattern forming method using the above resist material will be explained with reference to FIG. The above-mentioned resist material 2 is spin-coated on a semiconductor substrate etc. 1, and 90
℃, after soft baking on a hot plate for 90 seconds, 1.0
A resist material film with a thickness of μm was obtained (FIG. 1(a)). Next, KrF excimer laser light 3 of 248.4 nm was selectively exposed through a mask 4 (FIG. 1(b)). and 1
After baking on a hot plate at 10° C. for 90 seconds, developing with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds dissolves and removes only the exposed areas of the resist material 2, forming a positive pattern 2a.
was obtained (Figure 1(c)). The results obtained are shown in Table 1.

[Table 1] From the results in Table 1, it was found that the polymer containing a monomer unit having a phenolic hydroxyl group as a constituent unit [Production Example 1 ((
2) and (2) of Production Example 6], the resist material consists of:
Polymers without it [(1) of Production Example 1 and Production Example 6
It can be seen that the resist material has excellent heat resistance and substrate adhesion compared to the resist material consisting of (1)].

Example 1. A resist material having the composition shown below was prepared, and a pattern was formed using this in the same manner as in Experimental Example 2. Poly(p-tert-butoxystyrene-p-
Hydroxystyrene) (Polymer of Production Example 1)
6.0g 2
-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane (acid generator of Production Example 9)
0.3g diethylene glycol dimethyl ether
13.7g The obtained positive pattern has a resolution of 0.3 μm line and space, and the exposure energy amount is approximately 18 mJ/c.
It was m2.

Examples 2 to 20 0.6 g of a specified polymer, 0.3 g of a specified acid generator, and 13.7 g of diethylene glycol dimethyl ether
A resist material containing the above was prepared, and using this, pattern formation was performed in the same manner as in Experimental Example 2, and the results shown in Table 2 were obtained.

[Table 2] From the results in Table 2, it can be seen that when pattern formation is performed using the resist material of the present invention, fine patterns with good shapes on the order of submicrons can be easily obtained. In addition, from the results of Examples 2 to 4, when pattern formation was performed using the resist material containing the polymer obtained in Production Example 1, the same type obtained by the other two production methods It can be seen that a finer pattern can be easily obtained with a smaller amount of exposure energy than the resist material containing the polymer (Production Examples 3 and 4).

【Effect of the invention】

As is clear from the above, the resist material of the present invention is used as a resist material for exposure to a light source of 300 nm or less, such as deep ultraviolet light (Deep UV), such as KrF excimer laser light (248.4 nm). In some cases, fine patterns with good shapes on the order of submicrons can be easily obtained. Therefore, the present invention has great value for the formation of ultra-fine patterns in the semiconductor industry and the like.

[0050] The resist material of the present invention is resistant to deep ultraviolet light, K
Although it is particularly effective in pattern formation using rF excimer laser light, it can also be used satisfactorily in pattern formation using i-line light, electron beams, X-rays, etc.

[Brief explanation of the drawing]

[Figure 1]

FIG. 1 is a process cross-sectional view of a positive pattern forming method using the resist material of the present invention.

[Figure 2]

FIG. 2 shows ultraviolet ray spectral curves of each resist material film obtained in Experimental Example 1.

[Explanation of symbols]

1... Substrate, 2... Resist material film containing the compound of the present invention, 3... KrF excimer laser light, 4... Mask, 2a... Resin pattern, I...
・UV spectral curve of the resist material film obtained using the polymer obtained in Production Example 1, II...UV spectral curve of the resist material film obtained using the polymer obtained in Production Example 3, I
II: Ultraviolet spectral curve of a resist material film obtained using the polymer obtained in Production Example 4.

Claims (26)

[Claims] [Claim 1] The following formula 1 [Formula 1] [wherein R1 is a methyl group, an isopropyl group, a tert-
represents a butyl group, tetrahydropyranyl group, trimethylsilyl group or tert-butoxycarbonyl group, R2
represents a hydrogen atom or a methyl group, and k and l are each independently a natural number {however, k/(k+l)=0.1 to 0.9. } represents. ], a photosensitive compound that generates an acid upon exposure to light, and a solvent capable of dissolving these. [Claim 2] R1 of the polymer represented by chemical formula 1 is ter
The resist material according to claim 1, wherein the resist material is a t-butyl group, a tetrahydropyranyl group, or a trimethylsilyl group, and R2 is a hydrogen atom. Claim 3: R1 of the polymer represented by chemical formula 1 is ter
Claim 1: It is a t-butyl group, and R2 is a hydrogen atom.
Resist materials described in . [Claim 4] The following formula 2 [Formula 2] [wherein R3 and R5 each independently represent a hydrogen atom or a methyl group, and R4 is a hydrogen atom, a carboxyl group, a cyano group, or a cyano group [Formula 3] In the formula, R7 represents a hydrogen atom, a halogen atom or a lower alkyl group. ), R6 represents a hydrogen atom, a cyano group, or -COOR8 (wherein R8 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms), and k', l' and m is an independently natural number {however, 0.
1≦k'/(k'+l')≦0.9 and 0.05≦m
/(k'+l'+m)≦0.50}. ). R1 and R2 are the same as above. ] and a polymer represented by
A resist material characterized by containing a photosensitive compound that generates acid upon exposure to light and a solvent that can dissolve these compounds. 5. R1 of the polymer represented by chemical formula 2 is ter
t-butyl group, tetrahydropyranyl group or trimethylsilyl group, R4 is a hydrogen atom or a cyano group,
Claim 4, wherein R6 is a cyano group or a tert-butoxycarbonyl group, and R2, R3 and R5 are hydrogen atoms.
Resist materials described in . 6. R1 of the polymer represented by chemical formula 2 is ter
5. The resist material according to claim 4, wherein the resist material is a t-butyl group, R4 is a hydrogen atom or a cyano group, R6 is a cyano group, and R2, R3, and R5 are hydrogen atoms. 7. R1 of the polymer represented by chemical formula 2 is ter
is a t-butyl group, R4 is a hydrogen atom, R6 is a cyano group, and R2, R3 and R5 are hydrogen atoms,
The resist material according to claim 4. 8. R1 of the polymer represented by chemical formula 2 is ter
is a t-butyl group, R4 and R6 are cyano groups,
The resist material according to claim 4, wherein R2, R3 and R5 are hydrogen atoms. 9. R1 of the polymer represented by chemical formula 2 is ter
5. The resist material according to claim 4, wherein the resist material is a t-butyl group, R6 is a tert-butoxycarbonyl group, and R2, R3, R4, and R5 are hydrogen atoms. 10. The polymer represented by the formula 1 is obtained by polymerizing the compound represented by the formula 4 (wherein R1 and R2 are the same as above), and then optionally prepared using an appropriate acid. R1 at the rate of
2. The resist material according to claim 1, which is a polymer obtained by eliminating . 11. The polymer represented by chemical formula 1 is p-te
2. The resist material according to claim 1, which is a polymer obtained by polymerizing rt-butoxystyrene and then removing R1 at an arbitrary ratio using an appropriate acid. 12. The polymer represented by Chemical Formula 2 is obtained by copolymerizing the compound represented by Chemical Formula 4 and the compound represented by Chemical Formula 5 (wherein R3 to R4 are the same as above). After that, R is added at any ratio using an appropriate acid.
5. The resist material according to claim 4, which is a polymer obtained by eliminating 1. 13. The polymer represented by chemical formula 2 is p-te
5. The resist material according to claim 4, which is a polymer obtained by copolymerizing rt-butoxystyrene and a compound represented by Chemical Formula 5, and then removing R1 at an arbitrary ratio using an appropriate acid. . 14. A photosensitive compound that generates an acid upon exposure to light, wherein R9 and R10 each independently have 1 to 10 carbon atoms;
linear, branched or cyclic alkyl group, having 1 to 1 carbon atoms
0 haloalkyl group or chemical formula 7 (wherein, R11 and R12 each independently represent a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms, and n is 0 or a natural number), and X represents a carbonyl group, carbonyloxy group or sulfonyl group. ] The resist material according to any one of claims 1 to 13, which is a compound represented by the following. [Claim 15] The compound represented by chemical formula 6 is represented by chemical formula 8 [chemical formula 8]
15. The resist material according to claim 14, which is a compound represented by the formula (wherein R9 and R10 are the same as above). 16. The compound represented by chemical formula 6 is represented by chemical formula 9 [chemical formula 9]
15. The resist material according to claim 14, which is a compound represented by the formula (wherein R9 and R10 are the same as above). 17. The resist material according to claim 14, wherein the compound represented by formula 6 is a compound represented by formula 10 (wherein R9 and R10 are the same as above). 18. R9 is a linear, branched or cyclic alkyl group, phenyl group or p-methylphenyl group having 1 to 10 carbon atoms, and R10 is a straight chain having 1 to 10 carbon atoms;
Claims 15 to 17 which are branched or cyclic alkyl groups.
The resist material described in any of the above. 19. The resist material according to claim 15, wherein R9 and R10 are each independently a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 20. A photosensitive compound that generates an acid upon exposure to light, wherein R13 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, trifluoromethyl; Group or chemical formula 12 [
represents a group represented by the following formula (wherein R17 represents a hydrogen atom or a methyl group), R14 and R15 each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms,
R16 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a phenyl group, a halogen-substituted phenyl group, an alkyl-substituted phenyl group, an alkoxy-substituted phenyl group or an alkylthio-substituted phenyl group. ] The resist material according to any one of claims 1 to 13, which is a compound represented by the following. 21. R13 and R16 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms;
The resist material according to claim 20, wherein the resist material is a phenyl group or a p-methylphenyl group, and R14 and R15 are methyl groups. 22. R13 is a straight chain having 1 to 10 carbon atoms,
A branched or cyclic alkyl group, phenyl group or p-methylphenyl group, R16 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R14 and R1
21. The resist material according to claim 20, wherein 5 is a methyl group. 23. Claim 20, wherein R13 is a phenyl group or p-methylphenyl group, R16 is a branched or cyclic alkyl group having 3 to 6 carbon atoms, and R14 and R15 are methyl groups. Resist materials listed. 24. R13 is a phenyl group or p-methylphenyl group, R16 is an isopropyl group, 2-methylbutyl group, tert-butyl group, cyclopentyl group or cyclohexyl group, and R14 and R15 are methyl groups, The resist material according to claim 20. 25. A photosensitive compound that generates an acid upon exposure to light, wherein R18, R19, R20 and R21 each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 10 carbon atoms. represents a linear, branched or cyclic alkyl group or an alkoxy group having 1 to 10 carbon atoms, Z- is a perchlorate ion, p
- represents toluenesulfonate ion or trifluoromethanesulfonate ion. ) The resist material according to any one of claims 1 to 13, which is a compound represented by: 26. A photosensitive compound that generates an acid upon exposure to light is a compound of the following formula: or a trifluoromethanesulfonyl group, and R23 and R24 each independently represent a hydrogen atom, a halogen atom, or a nitro group.