KR100269501B1 - Chemically amplified resist large in transparency and sensitivity to exposure kight less than 248 nanometer wavelength and process of forming mask - Google Patents

Abstract

The polymer represented by Chemical Formula 1 is polymerized to obtain a polymer, and the polymer and the photoacid generator are dissolved in a solvent to form a chemically amplified resist layer having both high transparency and high sensitivity to ArF excimer laser light and improved resolution.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group having 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, and R ³ is a hydrogen atom, a methyl group Or an acetyl group.

Description

Highly transparent and sensitive chemically amplified resist and mask formation method for exposure light below wavelength 248 nanometers

The present invention relates to chemically amplified resists and, more particularly, chemically amplified resists sensitive to ultraviolet light, far ultraviolet rays, electron beams, ion beams and x-rays and methods of forming masks therefrom.

The integration density of semiconductor integrated circuit devices, such as dynamic random access memory (D-RAM) devices, is becoming higher and higher, so the lithographic method of transferring a very small pattern to a photosensitive compound layer applied on a thin layer to form a pattern is expected. Are gathering.

One way to obtain a very small pattern is to use shorter wavelengths of exposed light. The 256-megabit D-RAM device is expected in the near future and is designed to have a minimum pattern width of less than 0.25 microns. Since the wavelength of the KrF excimer laser is 248 nanometers, which is shorter than that of 365 nanometers of i-rays, KrF excimer lasers will be used rather than i-rays for pattern transfer to achieve the minimum pattern width.

Next-generation D-RAM devices, or 1 Gigabit D-RAM devices, will have a minimum pattern width of 0.2 microns or less, and these tiny patterns require shorter wavelengths. In fact, research and development efforts on lithography using an ArF excimer laser having a wavelength of 193 nanometers have been made.

Lithography for maximum integration requires high sensitivity and high resolution resist materials. High sensitivity is desired because the image is transferred to the resist layer through a small amount of exposed light. Small amounts of exposed light reduce damage to optical components such as lenses in the exposure machine. In addition, pattern transfer through a small amount of exposed light causes less degradation of the laser source gas sealed in the excimer laser light source. Laser source gases are very expensive, so pattern transfer through small amounts of exposed light reduces the production cost of large scale integration.

Chemically amplified resists achieve high sensitivity. Chemically amplified resists contain photoacid generators, such as cation generators, which provide an acid that is photochemically generated when exposed to activating light. Japanese Patent Publication No. 2-27660 discloses a chemically amplified resist consisting of triphenylsulfonium-hexafluoroarsenate and poly (t-butoxycarbonyloxy-α-methylstyrene). Chemically amplified resists are characteristic of their components. When the chemically amplified resist is exposed to light, the photochemical acid generator generates a protic acid. This protic acid acts as a thermally actuated catalyst as it moves into the resist in the solid state during the post-heating process to amplify the reaction 100 to 1000 times. If the efficiency of a photochemical reaction is defined as the ratio of chemical reactions per photon, the photochemical reaction efficiency of a conventional resist is less than one. However, chemically amplified resists significantly increase the efficiency of photochemical reactions and improve sensitivity to light irradiation. Most resist materials are chemically amplified and chemical amplification is essential for new resist materials.

Conventional photosensitive synthetic resin compounds are of little use for lithography using excimer laser light having a wavelength of 220 nanometers or less, because the resin components have low transparency and resistance to etching agents.

Conventional lithography uses exposed light with a longer wavelength than KrF excimer laser light having a wavelength of 248 nanometers, and the photosensitive synthetic resin contains a resin component such as novolak resin or poly (p-vinylphenol). Resins usable in resists contain an aromatic ring in the structural unit, which gives the resist dry etching resistance. However, conventional aromatic resins are difficult to be used in resists because aromatic rings have strong absorbance for light having a wavelength of 220 nanometers or less and the surface portion of the resist absorbs most of the exposed light. In other words, the exposure light does not reach the boundary between the resist and the substrate so that the microscopic pattern is hard to be transferred to the resist mask. This phenomenon is reported in Sasago et al., "ArF Excimer Laser Lithography (3) -Evaluation of Resist-", proceedings of Joint Lectures of 35 Meeting of Applied Physics Society, 1p-K-4, 1989. For this reason, next-generation lithography requires resins that achieve large dry etch resistance without aromatic rings.

Several high molecular weight compounds have been proposed that are dry etch resistant and have excellent transparency to light at wavelengths of 193 nanometers. The following are known conventional high molecular weight compounds.

Takechi et al., “Alicyclic Polymer for ArF and KrF Excimer Resist Based on Chemical Aplification,” Journal of Photopolymer Science and Technology, v. 5, No. 3 (1992), pp. 439-446 discloses copolymers of adamantyl methacrylate with tert-butyl methacrylate. Adamantyl methacrylate is a kind of alicyclic high molecular weight compound that forms a structural unit of the copolymer.

Japanese Patent Laid-Open (JPA) No. 5-265212 discloses a high molecular weight compound similar to that proposed by Dagechi et al.

Endo et al. Disclosed poly (norbornyl methacrylate) in "Challenges in Excimer Laser Lithography for 256 DRAM and beyond", proceedings of IEDM, CA 14-18, San Francisco, 1992.

Wallaf et al., "Single-layer chemically amplified photoresists for 193-nm lithography," Journal of Vacuum Science and Technology, B11, v. 6, pp. 2783-2788, discloses copolymers with poly (isobornyl methacrylate) units.

Japanese Patent Laid-Open No. 8-82925 describes poly (mentyl-methacrylate) units.

Alicyclic groups such as adamantyl, norbornyl, isobornyl or menthyl groups impart good dry etching resistance to the high molecular weight compounds of the prior art. However, there are no residues in these groups that will change the solubility between the exposed and unexposed portions. For this reason, the high molecular weight compounds can be used as a resin component only when a copolymer is formed together with a comonomer in which carboxyl groups of methacrylic acid units are protected, such as tertiary butyl methacrylate or tetrahydropyranyl methacrylate. Prior art resists require from 30 to 50 mole percent of the comonomer to obtain a difference in solubility between the exposed and unexposed portions. The comonomers have low dry etch resistance, so the resists of the prior art also have low dry etch resistance. This means that the resin component of the prior art is difficult to use in actual lithography.

Moreover, the cycloaliphatic groups and the polar converters are hydrophobic, and therefore the polymers having these hydrophobic groups have low adhesion to the silicon substrate. For this reason, it is difficult to reproduce the micro pattern using the resist of the prior art. Another disadvantage inherent in prior art resists is that residue or residue remains in the alkaline developer, which residue degrades the developer.

In order to overcome the above disadvantages, the present inventors have proposed an improved polymer and photosensitive resin compound in Japanese Patent Laid-Open No. 8-259626. This polymer has good transparency to exposed light with a wavelength of 220 nanometers or less, good dry etching resistance, and a large difference in solubility between exposed and unexposed areas.

Specifically, the alicyclic group imparts excellent dry etching resistance to the polymer, and the carboxyl group has a large polarity. The inventors have found that binding of the cycloaliphatic group to the carboxyl group improves the polarity and hydrophilicity of the polymer. Using the polymer, the present inventors produced a photosensitive resin compound. This photosensitive resin compound has good transparency, i.e. 70% per micron, good dry etch resistance as good as poly (vinylphenol) based chemically amplified positive resists suitable for KrF laser light, good adhesion to silicon substrates, and 2.38% by weight. Good solubility in alkaline developers such as alkaline developers containing tetramethylammonium hydroxide was shown. A representative example of the alkaline developer was NMD-3 manufactured by Tokyo Applied Chemical Industry Corporation. Maeda et al., One of the inventors, evaluated the pattern formation characteristics of the photosensitive resist compound. A 0.16 micron line-space pattern was transferred to the photosensitive resist compound layer using a Nikon Corporation circular exposure machine equipped with an ArF excimer laser source and a lens unit with a numerical aperture of 0.6. The latent image of the line-space pattern was developed and Maeda et al., "Novel Alkaline-Soluble Alicyclic Polymer Poly (TCDMACOOH) for ArF Chemically Amplified Positive Resists", proceedings of SPIE, v.2724, pp. 377-385 confirmed good resolution.

Therefore, the existing chemically amplified resists proposed by the present inventors show considerably good properties for exposed light and alkali solutions of less than 200 nanometers in wavelength. However, the chemically amplified resist has the following problems.

First, as described above, the carboxyl group gives good polarity to the resin compound so that the chemically amplified resist realizes high resolution. However, carboxyl groups dissolve faster than poly (vinylphenol) resins in alkaline solutions. This means that the unexposed portions of the chemically amplified resist are likely to be dissolved in the alkaline developer. As a result, the resist mask is reduced in thickness during the development stage, so that the reproducibility of the micro pattern is not satisfactory to the manufacturer. Therefore, small resistance to the alkaline developer of the unexposed portion is the first problem.

When a polar converter, such as tert-butyl or tetrahydropyranyl, is introduced into the chemically amplified resist, the polar converter improves the protective ratio of the protecting group so that the carboxylic acid may remain in the polymer. This improves the resistance to the alkaline developer. However, polarity converters reduce the polarity of the polymer and result in low adhesion. Low adhesion breaks the micro pattern resist mask.

Thus, in the previously proposed prior art chemically amplified resists, there is a relationship between the resistance and adhesion of unexposed resist portions to alkaline developers, such as developers containing 2.38% by weight of tetramethylammonium hydroxide, which is popular for conventional lithography. Had to balance.

It is an important object of the present invention to provide a chemically amplified resist that exhibits great resistance and high adhesion to alkaline developers.

Another important object of the present invention is to provide a method of forming a resist mask with the chemically amplified resist.

1 is a graph showing the relationship between "x" and the dissolution rate in the formula (2).

2 to 7 are cross-sectional views showing a method of forming a resist mask according to the present invention.

<Explanation of symbols for the main parts of the drawings>

1: Semiconductor wafer 2: Liquid chemically amplified resist layer

3: hot plate 4: chemically amplified resist layer

5: exposure machine 7: spray nozzle

8: mask layer

The present inventors have contemplated the problems inherent in the prior art chemically amplified resist and found that the copolymer of the new compound shows excellent resistance to alkaline developer and great adhesion.

In order to achieve the object of the present invention, the present inventors have proposed to polymerize an alicyclic hydrocarbon residue and a monomer containing a polar group having a polarity lower than that of the carboxyl group. These cycloaliphatic hydrocarbon residues give the polymer excellent transparency and large etch resistance to exposed light of wavelengths less than 220 nanometers, and examples of polar groups include hydroxyl groups, methoxy groups and acetyloxy groups.

According to one aspect of the invention,

Photoacid generators contained in an amount of 0.2 to 25 parts by weight, and

A polymer made by copolymerizing a monomer represented by Formula 1 with another polymerizable compound and contained in an amount of 50 to 99.8 parts by weight.

A chemically amplified resist is provided.

<Formula 1>

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group having 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, and R ³ is a hydrogen atom, a methyl group Or an acetyl group.

According to another aspect of the invention,

Photoacid generator contained in an amount of 0.2 to 25 parts by weight,

Crosslinker activated in the presence of an acid and contained in an amount of 1 to 40 parts by weight, and

A polymer made by copolymerizing a monomer represented by Formula 1 with another polymerizable compound and contained in an amount of 50 to 98.8 parts by weight.

A chemically amplified resist is provided.

<Formula 1>

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group having 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, and R ³ is a hydrogen atom, a methyl group Or an acetyl group.

According to another aspect of the invention,

a) preparing a solid structure,

b) applying a chemically amplified resist to the surface of the solid structure to form a chemically amplified resist layer on the surface,

c) irradiating the chemically amplified resist layer with light through a mask to form a latent image in the layer, and

d) developing the latent image to form a resist mask from the chemically amplified resist layer

The chemically amplified resist

Photoacid generators contained in an amount of 0.2 to 25 parts by weight, and

A polymer made by copolymerizing a monomer represented by Formula 1 with another polymerizable compound and contained in an amount of 50 to 99.8 parts by weight.

A resist mask forming method is provided.

<Formula 1>

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group having 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, and R ³ is a hydrogen atom, a methyl group Or an acetyl group.

According to another aspect of the invention,

a) preparing a solid structure,

b) a photoacid generator contained in an amount of 0.2 to 25 parts by weight,

Crosslinker activated in the presence of an acid and contained in an amount of 1 to 40 parts by weight, and

A polymer made by copolymerizing a monomer represented by Formula 1 with another polymerizable compound and contained in an amount of 50 to 98.8 parts by weight.

Applying a chemically amplified resist to the surface of the solid structure to form a chemically amplified resist layer on the surface,

<Formula 1>

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group of 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, R ³ is a hydrogen atom, Methyl group or acetyl group.)

c) irradiating the chemically amplified resist layer with light through a mask to form a latent image in the layer, and

d) developing the latent image to form a resist mask from the chemically amplified resist layer

A resist mask forming method is provided.

The bridged hydrocarbon group is tricyclo [5.2.1.0 ^2,6 ] decanediyl group, norbornanediyl group, methyl norbornanediyl group, isobornanediyl group, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dode Candiyl group, methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 2,7-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 2,10 -Di-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, hexahexa [ ^{6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14} ] hepta-decane-diyl, octahydro-bicyclo [8.8.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^{13, 16} .0.0 ^{3,8 12,17} ] docosandiyl or adamantanediyl. Structural formulas of bridged hydrocarbon groups of this kind are as shown in Table 1 below.

Bridged hydrocarbon groups constitutional formula Norbornandy Diary Methyl norbornanediyl group Isobornandi diary Tricyclo [5.2.1.0 ^2,6 ] decanediyl groups Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl groups Methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group

Bridged hydrocarbon groups constitutional formula 2,7-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group 2,10-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group Hexahydro cyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane-diyl ^Octacyclo [8.8.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0.0 ^3,8 .0 ^12,17 ] docosanediyl groups

The polymer copolymerized from the vinyl monomer and another polymerizable compound has a weight average molecular weight in the range of 1,000 to 50,000, and may be represented by the following Chemical Formula 2.

In the formula, R ¹ , R ⁴ and R ⁶ represent a hydrogen atom or a methyl group, R ² , R ⁵ and R ⁷ represent a bridged hydrocarbon group having 7 to 22 carbon atoms, and R ³ represents a hydrogen atom, a methyl group or acetyl R ⁸ represents a group which is decomposed by an acid, m is 0 or 1, n is 0 or 1, i is 0 or 1, k is 0 or 1, and x + y + z = 1, x is 0.05 to 0.75, y is 0 to 0.8 and z is 0 to 0.6.

The bridged hydrocarbon group is tricyclo [5.2.1.0 ^2,6 ] decanediyl, norbornanediyl, methylnorbornanediyl, isobornanediyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecanediyl group, methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 2,7-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dode Candiyl group, 2,10-di-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dode alkanediyl group, cyclo hexa ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane-diyl, octahydro-bicyclo [8.8.1 ^2,9 .1 ^4,7 .1 ^{11 , 18} .1 ^13,16 .0.0 ^3,8 .12 ^12,17 ] docosandiyl or adamantanediyl.

Examples of groups decomposed by an acid include tert-butyl group, tetrahydropyran-2-yl group, 4-methoxytetrahydropyran-4-yl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-propoxy An ethyl group and 3-oxocyclohexyl group are mentioned.

The features and advantages of the chemically amplified resist and method of the present invention will become apparent from the following description with reference to the accompanying drawings.

Synthesis of chemically amplified resist

Formula 1 represents a derivative of monomethacrylate monool or a derivative of monoacrylate monool when R ¹ is a hydrogen atom or a methyl group, which is synthesized as follows.

First, to prepare a diol compound, it can be represented by the formula (3).

HO-C _m H _2m -R ² -C _n H _2n -OH

In the formula,

R ² is a bridged hydrocarbon group having 7 to 22 carbon atoms, for example tricyclo [5.2.1.0 ^2,6 ] decanediyl group, norbornanediyl group, methylnorbornanediyl group, iso Boranediyl group, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 2,7-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 2,10-di-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecanedioic group, cyclo hexa ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane-diyl group, octanoyl bicyclo [ 8.8.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0.0 ^3,8 .0 ^12,17 ] docosandiyl or adamantanediyl, etc.,

m is 0 or 1,

n is 0 or 1;

This cyclic hydrocarbon is then ice-cooled or in equimolar amounts of methacryloyl chloride or acryloyl for 1 to 10 hours in a solvent such as anhydrous tetrahydrofuran or methylene chloride in the presence of triethylamine or pyridine below 50 ° C. React with chloride. The reaction product is then typically processed and purified.

The monomer represented by the formula (1) or the copolymer using the same are polymerized in a solvent such as tetrahydrofuran in an inert atmosphere formed by argon or nitrogen. Suitable radical initiators are added thereto, with a molar ratio of monomer / initiator in the range of 10 to 200. Stirring is continued at 50-70 ° C. for 0.5-10 hours.

The average degree of polymerization corresponding to the n value in the formula (2) is 10 to 500, preferably 10 to 200.

The inventors evaluated the transparency of the polymer as follows. A polymer thin film was formed to a thickness of 1.0 micron. An ArF excimer laser light of wavelength 193 nanometers was irradiated to this thin film and transparency was measured. Transparency for the ArF excimer laser ranged from 65 to 74%, and the polymer was practical for lithography using ArF excimer laser light.

Next, the inventors evaluated the adhesion of the polymer to the silicon substrate and confirmed that the polymer was strongly attached to the silicon substrate.

We evaluated the etch rate of the polymer. First, the present inventors have formulas in which R ¹ is a hydrogen atom, R ³ is a methyl group, R ² is a tricyclo [5.2.1.0 ^2,6 ] decanedimethyl group, m = 1, n, i, k = 0 The polymer represented by 2 was prepared. A thin film was formed from this polymer, and reactive ion etching was performed on the thin film using a CF ₄ gas phase etching agent. The etch rate was comparable to poly (vinylphenol) at 180 angstroms per minute.

As defined in the claims, the key components of chemically amplified resists are polymers, photoacid generators and solvents. The photoacid generator is preferably reactive to light having a wavelength of 300 nanometers or less, preferably 220 nanometers or less. Another requirement is to dissolve with the polymer in an organic solvent and apply it uniformly onto the solid phase structure, such as a semiconductor substrate structure. Any photoacid generator can be used in the chemically amplified resist according to the present invention so long as it meets the above requirements. The chemically amplified resist may contain two or more kinds of photoacid generators, and a sensitizer may be further mixed with the chemically amplified resist.

When chemically amplified resists are used in lithography for wavelength 220 nanometer exposed light, it is expected that not only the polymer but also the photoacid generator will be transparent to the exposed light. If the photoacid generator is a compound having an aromatic ring such as triphenylsulfonium-hexafluoroarsenate disclosed in Japanese Patent Laid-Open No. 2-27660, it is possible to strictly limit the content of the photoacid generator so as not to reduce the transparency to the exposure light. It is necessary.

In order to achieve great transparency for the exposure light having a wavelength of 220 nm or less, the inventors of the present invention already have lower absorbance than conventional photoacid generators having aromatic rings in Japanese Patent Publication Nos. 5-174528 and 5-174532, Higher photoacid generators have been proposed.

Photoacid generators proposed by the present inventors are represented by the following formula (4) or (5).

Wherein R ⁹ and R ¹⁰ are a straight alkyl group, a branched alkyl group or a cycloalkyl group, and R ¹¹ is a straight alkyl group, a branched alkyl group, a cycloalkyl group, a 2-oxocycloalkyl group, a 2-oxo straight chain alkyl group or a 2-oxo branched chain alkyl group, A- is _{^{BF 4 -, AsF 6 -,}} SbF 6 -, PF 6 -, CF 3 COO -, ClO 4 -, CF 3 SO 3 - or a counterion such as alkyl sulfonate, or aryl sulfonate.

Wherein R ¹² and R ¹³ are each a hydrogen atom, a straight chain alkyl group, a branched chain alkyl group and a cycloalkyl group, and R ¹⁴ is a straight chain alkyl group, a branched chain alkyl group or a haloalkyl group such as trifluoromethyl or perfluoroalkyl.

Another example of a photoacid generator usable in the chemically amplified resist according to the present invention is James V. Krivelo et al., Entitled "A New Preparation of Triarylsulfonium and-selenoium Salts via the Copper (II)-Catalyzed Arylation of Sulfides and Selenides with Diaryliodonium Salts", Journal of the Organic Chemistry, vol 43, No. 15, pp. 3055-3058, 1978). Photoacid generators disclosed herein are derivatives of triarylsulfonium salts. Other onium salts available for chemically amplified resists are, for example, sulfonium salts, iodonium salts, phosphonium salts, diazonium salts and ammonium salts.

tea. X. Ninan et al. (SPIE Proceedings, vol. 1086, pp. 2-10, 1989, "Chemically Amplified Resists: A Lithographic Comparsion of Acid Generating Species") suggest other photoacid generators available for the chemically amplified resists of the present invention. It was. tea. X. Ninan et al. Proposed 2,6-dinitrobenzyl esters as photoacid generators.

Takumi Ueno et al., Described in the Proceedings of PME "89, Kodansha, pp. 413-424, 1990," Chemical Amplification Positive Resist Systems Using Novel Sulfonates as Acid Generators ", 1,2,3-tri (methanesulfonyloxy Benzene has been proposed, which can be used in the chemically amplified resist of the present invention, Japanese Patent Laid-Open No. 5-134416 discloses sulfosuccinimide as a photoacid generator.

Thus, there are several photoacid generators available for the chemically amplified resists of the present invention. Nevertheless, it is suitable for lithography using exposure light of 220 nm wavelength or less since the photoacid generator represented by the formula (4) or (5) does not impair the permeability of the chemically amplified resist to the exposure light. For example, the triphenylsulfonium trifluoromethanesulfonate (abbreviated as TPS) proposed by Krivelo et al. Has an extremely high absorbance for far ultraviolet rays having a wavelength of 220 nm or less, and therefore the content of the photoacid generator is limited. Is applied. The present inventors compared TPS with photoacid generators represented by the formulas (4) and (5) below.

When the chemically amplified resist represented by Formula 2 contained 1.5 parts by weight of TPS, the chemically amplified resist layer having a thickness of 1 μm exhibited a transmittance of 40% for an ArF excimer laser having a wavelength of 193.4 nm. As the TPS increased to 5.5 parts by weight, the permeability decreased to 6%. On the other hand, when poly (methyl methacrylate) contains cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate which is an example of a derivative of the sulfonium salt represented by the formula (4), the transmittance to far ultraviolet rays is As follows. When the polymer contained the derivative at 5% by weight, the permeability was 71%. When the derivative was increased to 30 parts by weight, the permeability was 55%. Furthermore, the permeability was about 50% when the photoacid generator represented by the formula (4) was replaced by 5 parts by weight of the photoacid generator represented by the formula (5) such as N-hydroxysuccinimidotrifluoromethanesulfonate. Accordingly, the photoacid generators represented by the formulas (4) and (5) exhibit very small absorbances to far ultraviolet rays in the wavelength range of 185.5 to 220 nm, and are preferable as component compounds of chemically amplified resists for ArF excimer laser lithography.

Photoacid generators represented by the formulas (4) and (5) are, for example, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfo Acetate, triphenylsulfonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate and N-hydroxysuccinimide are also trifluoromethanesulfonates. Of course, the photoacid generators represented by the formulas (4) and (5) are not limited to the above examples.

The chemically amplified resists of the present invention may contain one or more photoacid generators. When the total amount including the photoacid generator is expressed as 100 parts, the photoacid generator or the photoacid generators is 0.2 to 25 parts by weight, preferably 1 to 15 parts by weight. If the photoacid generator is less than 0.2 part by weight, the chemically amplified resist is too photosensitive so that it is difficult to accurately form a latent image. On the other hand, when the photoacid generator exceeds 25 parts by weight, the chemically amplified resist is not uniformly applied, and residues or residues remain in the developer. The content of the polymer compound is 75 to 99.8 parts by weight based on the total amount including the polymer compound.

The chemically amplified resist of the present invention acts as either a positive type or a negative type depending on the copolymerization ratio, ie x: y: z (see Formula 2) and additives. For example, the polymer represented by the formula (2) is not all 0, x, y and z, that is, for example x = 0.4, y = 0.3, z = 0.3, R ¹ , R ³ , R ⁴ and R ⁶ Each is a hydrogen atom, m, n, i and k are 0, R ² , R ⁵ and R ⁷ are tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl groups and R ⁸ is 3% by weight of a derivative of the sulfonium salt represented by the formula (4), such as cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, adjusted to a tetrahydropyran-2-yl group If provided as a generator, the chemically amplified resist acts as a positive type. In this case, when the chemically amplified positive resist is exposed to light, an acid is generated, which decomposes R ^{8 so} that the polarity of the resist is reversed. As a result, the exposed portion of the chemically amplified resist becomes soluble in the alkaline developer. Thus, the chemically amplified resist is provided as a positive resist.

In contrast, when a crosslinker is added to a chemically amplified resist containing a photoacid generator and a polymer or resin, the photoacid causes the crosslinker to crosslink the polymer so that the chemically amplified resist acts as a negative type. For example, in the polymer represented by Formula 2, z is 0, x and y are for example 0.5 and 0.5, R ¹ , R ³ , R ⁴ and R ⁶ are each hydrogen atom, m, n, i and k is 0, R ² is a tricyclo [5.2.1.0 ^2,6 ] decanediyl group, R ⁷ is a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, and R ⁸ is If it is a tetrahydropyran-2-yl group, a crosslinking agent called hexamethoxymethylolmelamine is added to the polymer at 10% by weight based on the total amount, and cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate The sulfonium salt derivative represented by Formula 4 is added to the polymer by 2% by weight based on the total amount as a photoacid generator. The chemically amplified resist then acts as a negative resist. When the chemically amplified negative resist is exposed to light, the photoacid reacts with hexamethoxymethylolmelamine to promote crosslinking of the polymer. The crosslinker reduces the solubility of the polymer exposed to light through crosslinking, and the unexposed portion remains soluble to the developer. Thus, chemically amplified resists act as negative types.

Any crosslinking agent may be used in the chemically amplified negative resist of the present invention as long as it is well mixed with the polymers represented by Formulas 1 and / or 2, dissolved in a casting solvent, and promotes crosslinking of the polymer at a high speed. One or more crosslinkers may be incorporated into the chemically amplified negative resist. Crosslinking agents available for negative resists are, for example, melamine compounds such as hexamethoxymethylolmelamine, urea compounds such as dimethoxymethylethylene urea, isocyanurs such as tris (2-hydroxyethylisocyanurate) There is a rate compound. These compounds are not described as a limitation of the crosslinkers available for the chemically amplified negative resists of the invention.

As described above, the chemically amplified resists of the present invention are used in positive and negative types. The copolymerization ratio x / y / z and additives determine the type of chemically amplified resist. For example, when using a chemically amplified resist as the positive type, x, y and z are each not zero.

For example, in the resin represented by the formula (2), x is 0.4, y is 0.3, z is 0.3, R ¹ , R ³ , R ⁴ and R ⁶ are each hydrogen atoms, and m, n, i and k are each 0. R ² , R ⁵ and R ⁷ are each a tetra-cyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, R ⁸ is a tetrahydropyran-2-yl group, represented by the formula (4) Under the condition that the photoacid generator is a derivative of a sulfonium salt such as cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate mixed at 3% by weight relative to the total weight, the chemically amplified resist is of positive type. Works. The chemically amplified positive resist generates an acid when exposed to light, and the acid decomposes the group R ⁸ . The resin then changes in polarity so that the chemically amplified positive resist is soluble in the developer in alkaline aqueous solution.

On the other hand, when a crosslinking agent is added to the resin together with the photoacid generator, the chemically amplified resist acts as a negative type. Crosslinkers initiate crosslinking in the presence of an acid. In the resin represented by the formula (2), z is 0, x is 0.5, y is 0.5, R ¹ , R ³ , R ⁴ and R ⁶ are each hydrogen atom, m, n, i and k are each 0, R is ^{When the divalent} tricyclo [5.2.1.0 ^2,6 ] decanediyl group and R ⁷ is a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, the crosslinking compound is for example a total weight It may be 10% by weight of hexamethoxymethylolmelamine. The photoacid generator may be a derivative of the sulfonium salt represented by the formula (4) such as 2% by weight of cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate. When the chemically amplified negative resist is exposed to light, the photoacid generator supplies hexamethoxymethylolmelamine with acid to promote the crosslinker to crosslink the polymer. The chemically amplified negative resist is then less soluble in the developer so that the unexposed portions of the chemically amplified negative resist form a negative resist pattern.

Any crosslinking agent can be used in the chemically amplified negative resist as long as it is well mixed with the resin, solubilized in the casting solvent, and initiates crosslinking in the presence of an acid. One or more crosslinkers may be incorporated into the chemically amplified negative resist of the present invention. Crosslinking agents available for the chemically amplified negative resists of the present invention include hexamethoxymethylolmelamine, methylolurea, dimethylated methylolurea, diethylated methylolurea, diisobutylated methylolurea, di-β-oxo Propylated methylolurea, 1,3-bis (hydroxymethyl) ethyleneurea, 1,3-bis (hydroxymethyl) ethyleneurea, 1,3-bis (isobutoxymethyl) ethylene urea, 1,3-bis (Methoxymethyl) ethyleneurea, 1,3-bis (ethoxymethyl) ethyleneurea, 1,3-bis (β-oxopropoxymethyl) ethyleneurea, 1,3-bis (hydroxymethyl) -4, 5-bis (hydroxy) ethyleneurea, 1,3-bis (hydroxymethyl) -4,5-bis (hydroxy) ethyleneurea, 1,3-bis (methoxymethyl) -4,5-bis- (Methoxy) ethyleneurea, 1,3-bis- (ethoxymethyl) -4,5-bis (ethoxy) ethyleneurea, 1,3-bis (isopropoxymethyl) -4,5-bis (iso Propoxy) ethyleneurea, 1,3-bis (t-butock) Methyl) -4,5-bis (t-butoxy) ethyleneurea, 1,3-bis (β-oxopropoxymethyl) -4,5-bis (β-oxopropoxy) ethyleneurea, 1,3 -Bis (hydroxymethyl) -tetra-hydro-2 (1H) -pyrimidinone, dimethylated 1,3-bis (hydroxymethyl-tetrahydro-2 (1H) pyrimidinone, diethylated 1,3 Or bis (hydroxymethyl) tetrahydro-2 (1H) pyrimidinone or butylated 1,3-bis (hydroxymethyl) -tetrahydro-2 (1H) pyrimidinone. Used as binder: dimethyloluron, 1,3-bis (hydroxymethyl) -tetrahydro-5-hydroxy-2 (H) -pyrimidinone, 1,3,4,6-tetrakis (hydroxy Methyl) glycoluril (1,3,4,6-tetrakis (hydroxymethyl) acetyleneurea, same as tetramethylolated glyoxaldiene), 1,3,4,6-tetrakis (hydroxymethyl) glycol Uryl, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (ethoxymeth Glycoluril, 1,3,4,6-tetrakis (isobutoxymethyl) glycoluril and 1,3,4,6-tetrakis (β-oxopropoxymethyl) glycoluril.Tris (2-hydroxyethyl Isocyanurate compounds, such as isocyanurate), are also available as crosslinking agents in chemically amplified resists.

The compound for crosslinking in the presence of an acid optionally binds to a compound having a hydroxyl group. For this reason, when R ³ is hydrogen in the resin of the present invention, the crosslinking proceeds at a high speed. In the chemically amplified negative resist, when R ³ is a hydrogen atom, it is preferable that the value of x is large in the formula (2).

When a compound having two or more hydroxyl groups is added to the photosensitive resin compound, the chemically amplified resist has a very dense crosslinked structure after exposure to actinic light. Examples of compounds having two or more hydroxyl groups include bridged hydrocarbon compounds having hydroxyl groups or aromatic hydrocarbon compounds having hydroxyl groups. Some examples are 2,3-dihydroxy 5 (6) -hydroxymethylnorbornene, 3,4,8 (9) -trihydroxytricyclodecane, 2-hydroxy-5 (6)-( Bridged hydrocarbon compounds such as 1 ', 2'-dihydroxyethyl) norbornene and 2-hydroxy-5,6-bishydroxymethylnorbornene and catechol.

The copolymerization ratio, ie x: y: z, affects the solubility of the resulting polymer in the developer. In the polymers available for chemically amplified resists, x is 0.05 to 0.75, y and z are not zero at the same time, y is 0 to 0.8 and z is 0 to 0.6. More preferably x is 0.2 to 0.7, y is 0 to 0.5 and z is 0 to 0.45. We investigated the effect of x on the rate of decomposition to determine the preferred ranges of x, y and z. For example, when z is 0, the compound with x is tricyclodecanediol monoacrylate, that is, in Formula 2, R ¹ , R ³ , R ² , m and n each represent a hydrogen atom, a hydrogen atom, and a tricyclodecane. The diyl group, 0 and 0, and the compound with y is carboxytetracyclodecene, i.e., when R ⁴ , i, and R ⁵ in formula (2) are each hydrogen atom, 0 and tetracyclododecanediyl group, x is from 0 to 0.75 The polymer is dissolved at 0.7-4 micron / sec in alkaline developer containing 2.38% of tetramethylammonium hydroxide, even if changed to. Therefore, the dissolution rate is acceptable in the lithographic method. However, as x increased to 0.8, the dissolution rate decreased to 3 × 10 ⁻⁵ micron / second. Therefore, the preferable upper limit in the case of x was 0.75.

Any organic solvent is available for the chemically amplified resist of the present invention as long as other compounds such as high molecular compounds and alkylsulfonium salts are well dissolved and the resulting solution is uniformly applied using a spin coater. One or more organic solvents may be mixed. Organic solvents usable in the chemically amplified resists of the present invention are, for example, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, t-butyl alcohol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether Acetate, methyl lactate, ethyl lactate, 2-methoxybutyl acetate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, N-methyl- 2-pyrrolidinone, cyclohexanone, cyclopentanone, cyclohexanol, methyl ethyl ketone, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether or di Ethylene glycol dimethyl ether. The organic solvents available for chemically amplified resists are not limited to this kind of solvent.

As described above, the essential components of the chemically amplified resist of the present invention are alkylsulfonium salt compounds, high molecular compounds and solvents, and the chemically amplified negative resist further contains a crosslinking agent. Other additives may be further introduced into the chemically amplified resist of the present invention. Examples of such additives include surfactants, colorants, stabilizers, coatable modifiers and pigments.

The latent image in the chemically amplified resist of the present invention is developed in a developer selected from an organic solvent, a mixture of organic solvents, an alkaline solution of an appropriate concentration, an aqueous solution, and a mixture thereof depending on the solubility of the polymer compound.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, alcohols such as t-butyl alcohol, cyclopentanol and cyclohexanol, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, isoamyl, benzene, toluene, xylene, and phenol.

Examples of alkaline solutions include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium silicate, organic amines such as ethylamine, propylamine, diethylamine, dipropylamine, trimethylamine and triethylamine, tetramethylammonium hydroxide , Aqueous solutions of organic ammonium salts such as tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide and trimethylhydroxyethylammonium hydroxide, organic solvents and mixtures thereof. However, the alkaline solution is not limited to these examples.

<Description of a Preferred Embodiment>

Monomer

Example 1

The synthesis of norbornanediol monomethacrylate [dihydroxyheptane monomethacrylate] was carried out as follows.

Synthesis processes are indicated in Hines et al. (Chemishe Verihite, vol. 105, pp. 1019, 1972) or Lambert et al. (Journal of the American Chemical Society, vol. 100, pp. 2501). Assemble a four-necked 500 ml flask equipped with a dry tube with calcium chloride, a static dropping funnel, and a thermometer, and 12.8 g (equivalent to 100 mM) norbornean-2,3-diol, 10.1 g (at 100 mM). Anhydrous triethylamine and 200 ml anhydrous tetrahydrofuran were added to the flask and stirred to obtain a uniform solution. This solution was cooled in ice water.

10.4 g of methacryloyl chloride corresponding to 100 mM was dissolved in 50 ml of anhydrous tetrahydrofuran and the solution was poured into a dropping funnel. This solution was added dropwise to the flask via a dropping funnel while vigorously stirring the solution in the flask using a Teflon rod. Methacryloyl chloride was prepared by Tokyo Kasei. The solution was stirred in a flask and reacted in iced water for 1 hour and then at room temperature for 10 hours.

The precipitate was filtered off and the solvent was removed from the filtrate under vacuum. The residue was dissolved in 500 ml of chloroform and the solution was treated with 0.5 N hydrochloric acid, followed by saturated brine, 3% aqueous sodium bicarbonate solution, and saturated brine. Magnesium sulfate was used to dehydrate the chloroform layer and then filtered. The solvent was removed using an evaporator and the residue was separated and purified using a silica gel column. This gave the target compound, yield 25%.

IR analyzers IR-470 and ¹ H-NMR analyzer AMX-400 manufactured by Shimadzu Manufacturing Company and Bruker Instruments Co., Ltd. were prepared, respectively. 3.5 g of the target compound in 18% yield were analyzed.

Elemental analysis results (% by weight)

C: 68.30 (68.38)

H: 10.61 (10.59)

Values in parentheses are calculated by C ₁₃ H ₂₄ O ₃ (molecular weight: 228.3308).

IR (cm ^-1 ): 3350 (ν _OH ), 1725 (ν _{c = 0} ), 1630 (ν _{c = c} )

NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 1.0-2.3 (m, 11H), 3.8 (m, 1H), 4.8 (m, 1H), 5.6 (m, 1H), 6.1 (m, 1H )

Example 2

Tricyclodecane dimethanol monomethacrylate was synthesized as follows.

A four-necked 500 ml flask equipped with a dry tube with calcium chloride, a static dropping funnel and a thermometer was assembled and the following compound was stirred in the flask to obtain a uniform solution.

19.6 g of trichlorodecane-4,8-dimethanol corresponding to 100 mM (manufactured by Aldrich Chemical, USA), lot number B4, 590-9),

10.1 g of anhydrous triethylamine, corresponding to 100 mM

200 ml of anhydrous tetrahydrofuran.

This solution was cooled in ice water. 10.4 g of methacryloyl chloride corresponding to 100 mM was dissolved in 50 ml of anhydrous tetrahydrofuran and the solution was poured into a dropping funnel. The solution from the flask was added dropwise from the dropping funnel to the flask with great agitation using a Teflon rod. Methacryloyl chloride was prepared by Tokyo Kasei. The solution was stirred in a flask and reacted in iced water for 1 hour and then at room temperature for 10 hours.

The precipitate was filtered off and the solvent was removed from the filtrate under vacuum. The residue was dissolved in 500 ml of chloroform and the solution was treated with 0.5 N hydrochloric acid, followed by saturated brine, 3% aqueous sodium bicarbonate solution, and saturated brine. Magnesium sulfate was used to dehydrate the chloroform layer and then filtered. The solvent was removed using an evaporator and the residue was separated and purified using a silica gel column. This gave the target compound, yield 25%.

Elemental analysis results (% by weight)

C: 73.6 (73.43)

H: 10.2 (10.27)

Values in parentheses are calculated from C ₁₈ H ₃₀ O ₃ (molecular weight: 294.4332).

IR (cm ^-1 ): 3350 (ν _OH ), 1720 (ν _{c = 0} ), 1640 (ν _{c = c} )

NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 0.9-2.1 (m, 17H), 3.2 (s, 2H), 3.9 (s, 2H), 4.3-4.5 (s, 1H), 5.6 (m , 1H), 6.1 (m, 1H)

Example 3

Tricyclodecane dimethanol monoacrylate was synthesized as follows.

Tricyclodecanedimethanol monoacrylate was synthesized in the same manner as in Example 2 using 9.1 g (100 mmol) of acryloyl chloride instead of 10.4 g (100 mmol) of methacryloyl chloride. The yield was 5.0 g at 20%.

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane): 0.8-2.45 (m, 14H), 3.2-3.35 (w, 2H), 3.6-3.85 (w, 2H), 5.45-5.55 (w, 1H), 6-6.05 (w, 1H)

Elemental analysis results (% by weight)

C: 72.8 (72.82)

H: 10.1 (10.06)

Values in parentheses are calculated for C ₁₇ H ₂₈ O ₃ (molecular weight: 280.4064).

IR (cm ^-1 ): 3350 (ν _OH ), 1725 (ν _{c = 0} ), 1630 (ν _{c = c} )

NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 0.9-2.1 (m, 14H), 3.2 (s, 2H), 3.8 (s, 2H), 5.6-6.4 (m, 3H)

Example 4

Tricyclodecanediol monomethacrylate was synthesized as follows.

50 g of hydroxytricyclodecene is dissolved in methylene chloride in a 500 ml eggplant flask, and 42 g of 2,3H-dihydropyran and 1.6 g of toluenesulfonic acid pyridine salt are added to the solution for 5 hours. Left. The resulting material was dissolved in 300 ml of diethyl ether and then washed three times with 2.5% by weight aqueous sodium hydroxide solution and three times with water. The resulting material was dried overnight using magnesium sulfate and the solvent was removed using an evaporator. Thus, 76.36 g of tetrahydropyranyloxytricyclodecene was obtained.

500 ml four-necked flask was equipped with a dropping funnel. In a flask, 70 g of hydroxytricyclodecene corresponding to 0.3 mole was dissolved in 100 ml of anhydrous THF solution and cooled in ice water. A 1 M hexane solution of boranetetrahydrofuran complex was prepared and 150 ml of solution was added dropwise from the dropping funnel into the flask under argon atmosphere. After dropwise addition, the resulting solution was stirred in ice water for 30 minutes and at room temperature for 3 hours. Subsequently, the obtained material was cooled in ice water, and again 24 ml of water, 54 ml of 3M aqueous sodium hydroxide solution, and 36 ml of 30% aqueous H ₂ O ₂ solution were continuously added dropwise. The resulting solution was stirred for 2 h at room temperature and 300 ml of diethyl ether were added. The material obtained was washed 5 times with saturated brine. The ether layer was separated and the material obtained was dried over magnesium sulfate overnight. Solvent was removed to yield 71 g of tetrahydropyranyloxytetracyclodecanol.

Prepare a 300 ml four-necked flask equipped with a cooling tube and dissolve 0.1 g of tetrahydropyranyloxytetracyclodecanol and 20 g of anhydrous pyridine in 200 ml of anhydrous tetrahydrofuran under an argon atmosphere. And this solution was cooled in ice water. 21 ml of methacryloyl chloride was added dropwise into the solution and stirred at ice temperature for 1 hour and at room temperature for 3 hours. 300 ml of diethyl ether were added and the resulting material was washed three times with 2.5% aqueous sodium hydroxide solution, twice with 2% aqueous hydrochloric acid solution and three times with water. The ether layer was dried over magnesium sulfate overnight. The solvent was removed in vacuo and the material obtained was purified through a column. Elution solvents were hexane and methyl acetate in a 2: 1 ratio. This gave 52 g of tetrahydropyranyloxytricyclodecyl methacrylate.

A 500 ml eggplant flask was prepared with a reflux condenser. In the flask, 50 g of tetrahydropyranyloxytricyclodecyl methacrylate corresponding to 0.155 mole was dissolved in 150 ml of ethanol. 0.5 g of toluenesulfonic acid was added to this solution, and the obtained material was heated for 3 hours. The obtained material was dissolved in 300 ml of diethyl ether and then washed three times with an aqueous 2.5% sodium hydroxide solution and three times with water. The obtained material was dried over magnesium sulfate overnight and the solvent was removed. 29 g of hydroxytricyclodecanyl methacrylate was obtained. Yield 80%.

Elemental analysis results (% by weight)

C: 71.2 (71.39)

H: 9.7 (9.59)

Values in parentheses are calculated by C ₁₅ H ₂₄ O ₃ (molecular weight: 252.3528).

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane): 0.95-2.5 (m, 12H), 3.2-3.35 (s, 1H), 3.6-3.85 (m, 1H), 4.5-4.8 (m, 1H), 5.48-5.55 (w, 1H), 6-6.05 (w, 1H)

Example 5

Tricyclodecanediol monoacrylate was synthesized as follows.

Tricyclodecanediol monoacrylate was synthesized in the same manner as in Example 4 using 9.1 g (100 mmol) of acryloyl chloride instead of 10.4 g (100 mmol) of methacryloyl chloride. The yield was 5.2 g at 21%.

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane): 0.95-2.5 (m, 13H), 3.0-3.2 (s, 1H), 4.0-4.05 (m, 1H), 4.6-4.8 (m, 0.7H), 5.2-5.3 (m, 0.3H), 5.75-5.8 (m, 1H), 6.0-6.1 (m, 1H), 6.3-6.45 (m, 1H).

Elemental analysis results (% by weight)

C: 71.0 (70.6)

H: 9.10 (9.3)

Values in parentheses are calculated by C ₁₄ H ₂₂ O ₃ (molecular weight: 238.16).

IR (cm ^-1 ): 3350 (ν _OH ), 1725 (ν _{c = 0} ), 1630 (ν _{c = c} )

Example 6

Tetracyclododecanediol monomethacrylate was synthesized as follows.

50 g of 5-norbornene-2-yl acetate, product number 10774-3 manufactured by Aldrich, was reacted with 87 g of dicyclopentadiene and 0.137 g of methylhydroquinone for 15 hours at 170 to 180 ° C. The reaction product was evaporated in vacuo to afford 17.5 g of 3-tetracyclo [4.4.0.1 ^2,5 .1, ¹⁰ ] dodecen-8-yl acetate with a boiling point of 120-121 ° C. under 2 mmHg.

35 g of 3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecen-8-yl acetate was dissolved in 70 mL of anhydrous THF and the solution was cooled to 0 ° C. The reaction system was placed under argon atmosphere and 96 ml of a 1 M THF solution of borane THF complex was added dropwise to the solution. The reaction was continued at 0 ° C. for 1 hour and then at room temperature for 1 hour. The resulting material was cooled to 0 ° C. and 13.3 mL of water, 29.5 mL of a 3 M NaOH aqueous solution and 19.9 mL of 30% H ₂ O ₂ were added dropwise successively. The reaction was continued for 1.5 hours at room temperature, and sodium chloride was added to saturate the aqueous layer with sodium chloride. The aqueous layer was separated and the organic layer was dried over magnesium sulfate. The solvent was removed in vacuo. This gave 36.8 g of hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecen-8-yl acetate.

Then 36.8 g of hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecen-8-yl acetate was dissolved in 110 mL of 95% ethanol and 15.4 g of potassium hydroxide were added. The resulting material was heated and refluxed. After cooling, the solvent was removed in vacuo and 200 ml of water and 200 ml of ether were added. The aqueous layer was separated and the organic layer was washed successively with saturated brine and water. The resulting material was dried over magnesium sulfate. The solvent was removed in vacuo to give 12 g of a solid white compound, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediol.

Subsequently, 12 g of tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediol, 4.89 g of pyridine and 20 mg of phenothiazine were dissolved in 70 ml of dry THF and the solution was cooled to 0 ° C. 6.46 g of methacryloyl chloride was dissolved in 20 mL of anhydrous THF and this solution was added dropwise to the solution. The reaction was continued for 1 hour at 0 ° C. and then overnight at room temperature. Pyridine hydrochloride salt was filtered out of solution and the filtrate was evaporated in vacuo. The concentrate was diluted in 150 ml of ether and washed in the order of 0.5 N hydrochloric acid, saturated brine, 3% aqueous sodium bicarbonate solution, saturated saline and water. The resulting organic layer was dried over magnesium sulfate and the ether was evaporated. The resulting material was separated and purified using a silica gel column. Eluent was used as hexane and ethyl acetate 2: 1. Thus 6 g of the desired material were obtained in the form of a viscous liquid.

Elemental analysis result (% by weight)

C: 73.1 (73.43)

H: 10.4 (10.27)

The values in parentheses are the calculated C ₁₈ H ₃₀ O ₃ (molecular weight 294.4332).

¹ H-NMR (CDCl ₃ ) δ 0.64-1.83 (7H, m), 1.91 (3H, s), 1.95-2.6 (7H, m), 4.04-4.24 (1H, m), 4.99 (1H, br) , 5.52 (1 H, s), 6.05 (1 H, s);

^{IR (㎝ -1): 3420 (} ν OH), 2950, 2890 (ν CH), 1714 (ν C = O), 1630 (ν C = C), 1165 (ν CO).

Example 7

Tetracyclododecanediol monoacrylate was synthesized as follows.

Tetracyclododecanediol monoacrylate was synthesized in the same manner as in Example 6 using 9.1 g (100 mmol) of acryloyl chloride instead of 10.4 g (100 mmol) of methacryloyl chloride. The yield was 5.0 g at 20%.

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane): 0.65-2.6 (m, 14H), 4.04-4.24 (m, 1H), 4.99 (m, 1H), 5.75-5.8 (m, 1H) , 6.0-6.1 (m, 1 H), 6.3-6.45 (m, 1 H).

Elemental analysis results (% by weight)

C: 72.7 (72.69)

H: 8.89 (9.15)

Values in parentheses are calculated by C ₁₆ H ₂₄ O ₃ (molecular weight: 264.17).

^{IR (cm -1): 3420 (} ν OH), 1715 (ν C = O), 1634 (ν C = C), 1165 (ν CO).

Example 8

Hexacycloheptadecanediol monomethacrylate was synthesized as follows.

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 65 g of ^7,10 ] -3-dodecene, 87 g of dicyclopentadiene, and 0.14 g of methylhydroquinone were placed in a 300 ml eggplant flask and reacted at 170 to 180 ° C. for 17 hours. The reaction product is cooled down and 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^7,10 ] -3-dodecene and dicyclopentadiene were removed from the reaction product via evaporation under vacuum. Hot methanol was added to the residue and the insoluble component was filtered off. The filtrate was concentrated in vacuo. Recrystallization of the residue from methanol to give the hepta-decene 10 g 12- methoxycarbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14].

12-methoxycarbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene to 3.6 g was dissolved in 95% ethanol 30 ㎖, the 1.25 g of potassium hydroxide To the solution. The resulting material was heated and refluxed for 2 hours. The resulting material was then cooled and concentrated to boil using an evaporator. 50 ml of water and 50 ml of ether were added to separate the water components. Water was changed to acidic by adding 3% HCl. Then a white precipitate was obtained and filtered. The white precipitate was washed with water, it made neutral to give the 12-carboxy-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene 2.2 g.

12-carboxy-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene and 2.1 g 3,4-dihydro -2H- pyran 1.71 g Tetrahydrofuran 50 It was dissolved in ml and 0.03 g of p-toluenesulfonic acid was added to the solution. The reaction was continued for 2 hours at room temperature. The reaction product was diluted in 100 mL of ether and the resulting material was washed successively with 3% Na ₂ CO ₃ aqueous solution, saturated brine and water. The resulting organic layer was dried over MgSO ₄ . 3,4-Dihydro-2H-pyran, which did not react with ether, was evaporated under vacuum using an evaporator. Then, to give the 12-tetrahydropyranyl-oxy-carbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene 2 g.

Then, 12-tetrahydropyranyl-oxy-carbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene 2 g of mixture of anhydrous THF and 8 ㎖, 0 Cooled to ° C. 6 ml of 1M borane THF complex solution was added dropwise. The resulting material was stirred at 0 ° C. for 1 hour and then at room temperature for 1 hour. The resulting material was cooled to 0 ° C., and 0.5 mL of water, 1.1 mL of 3M aqueous sodium hydroxide solution and 0.7 mL of 30% H ₂ O ₂ were added dropwise to the resulting material at 20 ° C. or lower.

The resulting material was stirred at rt for 1.5 h and the aqueous layer was saturated with sodium chloride. The resulting material was dried over MgSO ₄ and ether removed. Thus hydroxy-tetrahydropyranyl-oxy-carbonyl-hexahydro to give the bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane 1.8 g.

Then, the hydroxy-tetrahydropyranyl-oxy-carbonyl-hexahydro cyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane 1.8 g pyridine and 0.48 g of anhydrous THF 4 ㎖ Dissolved in and the resulting material was cooled to 0 ° C. 0.63 g of methacryloyl chloride was dissolved in 1 mL of THF and the solution was added dropwise to the resulting material. Stirred for 1 hour and the reaction continued overnight at room temperature. Pyridine hydrochloride salt was filtered out of solution. The filtrate was diluted in 20 ml of ether and washed in the order of 0.5 N hydrochloric acid, saturated brine, 3% Na ₂ SO ₄ aqueous solution and saturated brine. The resulting organic layer was dried over magnesium sulfate and the ether was evaporated in vacuo. The residue was dissolved in 10 mL of solvent, acetic acid / tetrahydrofuran / water 4: 2: 1. The reaction was continued for 1 hour at 40 to 45 ° C. The resulting solution was poured into 50 ml of ice water. Then, a white precipitate was obtained. The white precipitate was filtered off, washed with water and dried to give 1 g of the desired material.

Elemental analysis result (% by weight)

C: 76.3 (76.62)

H: 10.2 (10.06)

Values in parentheses are calculated C ₂₃ H ₃₆ O ₃ (molecular weight 360.5356).

Example 9

Octacyclodocosandiol monomethacrylate was synthesized as follows.

Synthesis was performed in the same manner as in Example 6 except that hexacycloheptadecenyl acetate synthesized in Example 8 was used instead of 5-norbornene-2-yl acetate.

Elemental analysis result (% by weight)

C: 78.5 (78.83)

H: 9.7 (9.92)

Values in parentheses are calculated from C ₂₈ H ₄₂ O ₃ (molecular weight 426.638).

Example 10

Carboxynorbornyl methacrylate was synthesized as follows.

50 g of bicyclo [2.2.1] hept-5-ene-2-carboxylic acid tert-butylester and 133 g of methacrylic acid were mixed in a 200 ml three-necked flask with 1.35 g of concentrated sulfuric acid and 2 g of water, 60 to The reaction was continued for 5 hours at 70 ° C. The resulting material was cooled and the remaining methacrylic acid was evaporated in vacuo. The residual material was separated and purified using a silica gel column to give 2 g of the desired compound.

Elemental analysis result (% by weight)

C: 65.7 (65.60)

H: 9.7 (9.44)

The values in parentheses are calculated from C ₁₄ H ₂₄ O ₄ (molecular weight 256.3412).

IR (cm ⁻¹ ): 2400 to 3600 (ν _OH ), 2960 to 2880 (ν _CH ), 1704 (ν _{C = O} ), 1628 (ν _{C = C} ), 1168 (ν _CO )

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm:

1.25 to 2.05 (6H), 1.92 (3H), 2.3 to 2.85 (3H), 4.69 to 4.74 (1H), 5.53 (1H), 6.06 (1H)

Example 11

Carboxycicyclocyclodecanylmethyl methacrylate was synthesized as follows.

A 500 ml four-necked flask with thermometer was equipped with a dry tube with calcium chloride and a static dropping funnel. Tricyclo [5.2.1.0. Product No. B4,590-9, manufactured by Aldrich Chemicals, USA. 50 g (0.25 mol) of ^2,6 ] decane-4,8-dimethanol and 25.76 g (0.25 mol) of anhydrous pyridine were mixed with 300 ml of anhydrous tetrahydrofuran in a flask. The solution was stirred and cooled in ice water. 26.53 g (0.25 mol) of methacryloyl chloride prepared by Tokyo Kasei Co., Ltd. was dissolved in 100 mL of anhydrous tetrahydrofuran and the solution was added dropwise to the flask using a dropping funnel with vigorous stirring with Teflon bars.

After the dropwise addition, the resulting material was stirred and cooled in ice water for 1 hour and the reaction continued at room temperature for 10 hours. The precipitate was filtered off and the filtrate was evaporated in vacuo to remove solvent. The residue was dissolved in 500 ml of methylene chloride and the solution was treated in the order of 0.5 N hydrochloric acid, saturated brine, 3% aqueous sodium bicarbonate solution and saturated brine. The methylene chloride layer was dehydrated with magnesium sulfate and the resulting material was filtered off. The solvent was removed using an evaporator, the residue was separated and purified using a silica gel column. In this way, tricyclo [5.2.1.0. 29.6 g of ^2,6 ] decane-4,8-dimethanol-monomethacrylate was obtained. Yield 44%.

24.9 g (66.2 mmol) of pyridinium dichromate were then mixed with 40 mL of N, N-dimethylformamide in a 100 mL four-necked flask equipped with a calcium chloride drying tube and a static dropping funnel. After vigorous stirring to make the solution uniform, tricyclo [5.2.1.0. 5 g (18.9 mmol) of ^2,6 ] decane-4,8-dimethanol monomethacrylate were dissolved in 10 ml of N, N-dimethylformamide and the solution was added dropwise to the flask. The reaction was continued for 10 hours at room temperature. The resulting solution was diluted in 500 ml of water, and the organic compound layer was extracted three times with 150 ml of diethyl ether. The ether layer was dehydrated with magnesium sulfate and the resulting material was filtered off. The solvent was removed using an evaporator, the residue was separated and purified using a silica gel column. This gave 2.12 g of the target compound as a viscous liquid. Yield 40%.

Elemental analysis result (% by weight)

C: 70.0 (70.13)

H: 9.05 (9.15)

The values in parentheses are the calculated C ₁₈ H ₂₈ O ₄ (molecular weight 308.4168).

IR (㎝ ^-1): 2400 to _{3350 (ν OH), 2950 (} ν CH), 1696 (ν C = O), 1626 (ν C = C), 1166 (ν CO)

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm:

0.95 to 2.74 (m, 14H), 1.95 (s, 3H), 3.88 to 4.17 (m, 2H), 5.55 (d, J = 1.5 Hz, 1H), 6.5 (s, 1H), 9.58 to 10.8 (br s , 1H)

Example 12

Carboxycicyclocyclodecanylmethyl acrylate was synthesized as follows.

Carboxycicyclocyclodecanylmethyl acrylate was synthesized in the same manner as in Example 11 using 9.1 g (100 mmol) of acryloyl chloride instead of 10.4 g (100 mmol) of methacryloyl chloride. The yield was 5.0 g at 20%.

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane): 0.8-2.7 (m, 14H), 3.88-4.17 (m, 2H), 5.75-5.8 (m, 1H), 6.0-6.1 (m, 1H), 6.3-6.45 (m, 1H).

Elemental analysis results (% by weight)

C: 70.33 (68.55)

H: 8.52 (8.63)

Values in parentheses are calculated by C ₁₆ H ₂₄ O ₄ (molecular weight: 280.167).

^{IR (cm -1): 3355 (} ν OH), 1725 (ν C = O), 1635 (ν C = C).

Example 13

Carboxytetracyclododecene methacrylate was synthesized as follows.

10 g of 8-tert-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene are mixed with 25 mL of anhydrous THF in a 100 mL four-necked flask and the resulting material is 0 ° C. Cooled to. The atmosphere was changed to argon and 20 ml of THF solution of 1M borane-THF complex was added dropwise to the flask. The solution was stirred at 0 ° C. for 1 hour and at room temperature for 1 hour. The resulting material was cooled to 0 ° C. and 3 ml of water was added dropwise. In addition, 6.6 ml of 3M NaOH aqueous solution and 4.3 ml of 30% H ₂ O ₂ solution were added dropwise at 20 占 폚 or lower. The solution was stirred at rt for 1.5 h and the water was saturated with NaCl. The resulting material was diluted with 100 mL of ether. The ether layer was washed with saturated brine and water and the resulting material was dried over MgSO ₄ . The ether was evaporated and 10 g of hydroxy-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecane were obtained. Yield 94%.

7.7 g (0.0276 mol) of hydroxy-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecane and 2.19 g (0.0276 mol) of pyridine were then dried with anhydrous THF. It was dissolved in 40 ml. The solution was cooled to 0 ° C. 289 g (0.0276 mol) of methacrylic acid chloride were dissolved in 10 ml of THF and the solution was added dropwise to the solution at 0 ° C. Stirred for 1 hour and allowed to react overnight at room temperature. Pyridine hydrochloride was isolated and filtered. The filtrate was concentrated and diluted with 100 ml of methylene chloride. After washing in the order of 5% hydrochloric acid, 3% NaCO ₃ solution and saturated brine, the resulting material was dried over MgSO ₄ and methylene chloride was evaporated. The resulting material was separated through a column with hexane and ethyl acetate adjusted to 10: 1. Thus 4.5 g of t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanyl methacrylate was obtained. Yield 47%.

Subsequently, 3 g of the obtained methacrylate was dissolved in 20 ml of toluene and 10 drops of trifluoromethanesulfonic acid were added to the solution. Stir at room temperature for 5 hours. The toluene layer was washed with saturated brine and extracted using 3% NaCO ₃ solution. Hydrochloric acid was added to the aqueous layer to make it acidic, and the organic layer was extracted using ether. The resulting material was washed with saturated brine and water and dried over MgSO ₄ . Hexane and ethyl acetate were adjusted to 1: 1 and purified through a column to obtain 1.68 g of the target substance as a viscous liquid, yield 67%.

Elemental analysis result (% by weight)

C: 70.56 (70.77)

H: 9.22 (9.387)

Values in parentheses are calculated from C ₁₉ H ₃₀ O ₄ (molecular weight 324.4436).

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm:

1.1 to 1.9 (9H, m), 2.1 to 2.7 (6H, m), 4.98 (1H, s), 5.52 (1H, s), 6.05 (1H, s), 10.5 to 12.4 (1H, br s)

IR (cm ⁻¹ ): 2800 to 3400 (ν _OH ), 3048, 2960 (ν _CH ), 1710, 1700 (ν _{C = O} ), 1632 (ν _{C = C} ), 1170 (ν _CO )

Example 14

Carboxytetracyclododecene acrylate was synthesized as follows.

Carboxytetracyclododecene acrylate was synthesized in the same manner as in Example 13 using 9.1 g (100 mmol) of acryloyl chloride instead of 10.4 g (100 mmol) of methacryloyl chloride. The yield was 5.0 g at 20%.

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane): 1.1-1.95 (10H, m), 2.1-2.85 (5H, m), 5.0 (1H, s), 5.79 (1H, d), 6.07 (1H, doublet), 6.36 (1H, d), 10.5-12 (1H, br).

Elemental analysis results (% by weight)

C: 70.81 (69.84)

H: 7.92 (8.27)

Values in parentheses are calculated for C ₁₇ H ₂₄ O ₄ (molecular weight: 292.167).

^{IR (cm -1): 2800-3450 (} ν OH), 2950 (ν CH), 1700, 1714 (ν C = O), 1618, 1632 (ν C = C), 1200 (ν OO).

Example 15

Carboxyhexacycloheptadecane methacrylate was synthesized as follows.

65 g of 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 87 g of dicyclopentadiene and 0.14 g of methylhydroquinone were mixed in a 300 ml eggplant flask, The reaction was continued at 170 to 180 ° C for 17 hours. The reaction product was cooled and the remaining 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and residual dicyclopentadiene were evaporated under vacuum. Hot methanol was added to the residue and the insoluble component was filtered off. The filtrate was concentrated in vacuo and the residue was recrystallized from methanol. Thus it was obtained 10 g of a white crystal of 12-hepta-methoxycarbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] decene.

Then, 12-methoxycarbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene was dissolved 3.6 g of 95% ethanol solution of 30 ㎖, potassium 1.25 g was added to the solution. The resulting material was heated and refluxed and then cooled for 2 hours. The solution was concentrated to water using an evaporator. 50 ml of water and 50 ml of ether were added to the resulting material to separate the aqueous layer. 3% hydrochloric acid was added to the aqueous layer to change the aqueous layer to acidic. Thus a white precipitate was obtained. The white precipitate was filtered off and washed with water until neutral. Thus to give the 12-carboxy-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene 2.2 g.

Then, carboxy-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene and 2.1 g 3,4-dihydro -2H- pyran 1.71 g Tetrahydrofuran 50 It was dissolved in ml and 0.03 g of p-toluenesulfonic acid was added to the solution. The reaction was continued for 2 hours at room temperature. The resulting material was diluted in 100 mL of ether, washed in the order of 3% Na ₂ CO ₃ , saturated brine and water, and the organic layer was dried over MgSO ₄ . The ether and residual 3,4-dihydro-2H-pyran are removed using an evaporator under vacuum to give a viscous liquid 12-tetrahydropyranyloxycarbonylhexacyclo [6.6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14 ] 2 g of heptadecene was obtained.

Then, 12-tetrahydropyranyl-oxy-carbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-decene to 2 g was dissolved in anhydrous THF ㎖ 8, 0 Cooled to ° C. The atmosphere was changed to argon and 6 ml of THF solution of 1M borane-THF complex was added dropwise. The resulting material was stirred at 0 ° C. for 1 hour and at room temperature for 1 hour. The resulting material was then cooled to 0 ° C. and 0.5 ml of water was added dropwise. In addition, 1.1 ml of a 3 M NaOH aqueous solution and 0.7 ml of a 30% H ₂ O ₂ solution were added dropwise at 20 占 폚 or lower. Stir at room temperature for 1.5 hours and saturate water with NaCl. The resulting material was diluted with 100 mL of ether. The ether layer was washed with saturated brine and water and dried over MgSO ₄ . Removal of the ether to give the hepta-decane 2 g hydroxy-tetrahydropyranyl-oxy-carbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14].

Subsequently, hydroxy-tetrahydropyranyl-oxy-carbonyl-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane 2 g pyridine and 0.53 g of anhydrous THF 8 ㎖ Dissolved in. After cooling to 0 ° C., 0.7 g of methacryloyl chloride was dissolved in 1 mL of THF and the solution was added dropwise to the solution. Stir for 1 hour and continue the reaction overnight at room temperature. Pyridine hydrochloride was separated and filtered. The filtrate was diluted with 20 mL of ether and washing was repeated in the order of 0.5 N hydrochloric acid, saturated saline, 3% Na ₂ CO ₃ solution and saturated saline. The resulting material was dried over MgSO ₄ . The ether was evaporated in vacuo and column separation was performed by adjusting hexane and ethyl acetate to 5: 1. Thus it was obtained a viscous liquid carboxy-hexafluoro bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl methacrylate decane 2 g. 2 g of this methacrylate were dissolved in a mixture of acetic acid / tetrahydrofuran / water adjusted to 4: 2: 1. The mixture was 14 ml. The reaction was continued for 45 minutes at 40-45 ° C. and the solution was poured into 250 ml of ice water. The separated crystals were filtered off and washed several times with water. Washing with hexane gave 0.79 g of the target compound.

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm:

1.0-1.88 (m, 1H), 1.93-2.75 (m, 1H), 1.91 (3H, s), 4.99 (1H, s), 5.51 (1H, s), 6.04 (1H, s), 9.5-11.3 ( 1H, br).

^{IR (㎝ -1): 2800-3600 (} ν OH), 2950, 3048 (ν CH), 1712 (ν C = O), 1634 (ν C = C), 1172 (ν CO).

Elemental analysis result (% by weight)

C: 73.98 (74.19)

H: 9.11 (9.34)

The values in parentheses are calculated from C ₂₄ H ₃₆ O ₄ (molecular weight 388.5460).

Example 16

Carboxyoctacyclodocoic acid methacrylate was synthesized as follows.

Carboxyoctacyclodoco acid methacrylate was synthesized in the same manner as in Example 15. In this synthesis, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .11 ^17,10 ] -3-dodecene was converted to 12-methoxycarbonylhexacyclo [6.6.1.1, which is the intermediate product of Example 11. ^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] was replaced with hepta-decene.

IR (cm ⁻¹ ): 3050, 2940 (ν _CH ), 1710, 1715 (ν _{C = O} ), 1636 (ν _{C = C} ), 1170 (ν _CO )

Elemental analysis result (% by weight)

C: 76.3 (76.61)

H: 9.10 (9.31)

The values in parentheses are calculated from C ₂₉ H ₄₂ O ₄ (molecular weight 454.6484).

Example 17

In Formula 6, R ⁶ is a methyl group, R ⁷ is a tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl group, R ⁸ is a tert-butyl group, and k is a vinyl monomer. .

A 100 ml round bottom flask was equipped with a dry tube containing calcium chloride, 5 g (0.018 mol) of vinyl monomer synthesized in Example 11, 30 ml of methylene chloride and 3.99 g (0.054 mol) of t-butyl alcohol and 4-dimethylamino 1.76 g (0.014 mol) of pyridine was mixed in a round bottom flask. The mixture was cooled to 0 ° C. 4.08 g (0.02 mol) of dicyclohexylcarbodiimide was slowly added to the cooled mixture. Stir at 0 ° C. for 5 minutes and then at room temperature for 4 hours. Cyclohexylurea was isolated and filtered. The filtrate was washed twice with 10 ml of 0.5 M hydrochloric acid and twice with 10 ml of saturated aqueous sodium bicarbonate solution. The organic layer was dehydrated with magnesium sulfate and filtered. The solvent was removed using an evaporator and then purified through a silica gel column. This gave 5.67 g of the target compound in the form of a viscous liquid. Yield 90%.

Elemental analysis result (% by weight)

C: 71.4 (71.96)

H: 9.4 (9.78)

The values in parentheses are calculated from C ₂₁ H ₃₄ O ₄ (molecular weight 350.4972).

IR (cm ⁻¹ ): 2950, 2874 (ν _CH ), 1716 (ν _{C = O} ), 1626 (ν _{C = C} ), 1166 (ν _CO )

Example 18

In formula (6), R ⁶ is a methyl group, R ⁷ is a tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl group, R ⁸ is a tetrahydrofuran-2-yl group and k is 1 a vinyl monomer. Synthesis was as follows.

<Formula 6>

2,3-dihydrofuran was used in place of t-butyl alcohol and the desired monomer was synthesized in the same manner as in Example 17. The desired monomer was a viscous liquid and the yield was 62%.

Elemental analysis result (% by weight)

C: 68.9 (69.20)

H: 8.3 (8.85)

The values in parentheses are calculated from C ₂₁ H ₃₂ O ₅ (molecular weight 364.4808).

IR (cm ⁻¹ ): 2950, 2874 (ν _CH ), 1718 (ν _{C = O} ), 1630 (ν _{C = C} ), 1166 (ν _CO )

¹ H-NMR (CDCl ₃ , internal standard: tetramethylsilane) ppm:

1.1-2.8 (m, 18H), 3.5-3.8 (m, 2H), 3.8-4.1 (m, 2H), 5.6-6.5 (m, 4H)

Example 19

In formula (6), R ⁶ is hydrogen, R ⁷ is tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl group, R ⁸ is tetrahydropyran-2-yl group, k is 1 vinyl monomer Was synthesized as follows.

<Formula 6>

A dry tube containing calcium chloride was assembled into a 200 ml three-necked flask with a thermometer, and the vinyl monomer synthesized in Example 12 (wherein R ⁶ is hydrogen and R ⁷ is tricyclo [5.2.1.0 ^2,6 ] 6 g (0.022 mol) and 4.54 g (0.054 mol) of 3,4-dihydro-2H-pyran and 80 ml of methylene chloride were added to decan-4,8-diyl, R ⁸ is hydrogen, k is 1 Mix and cool the mixture with ice water.

20 mg of p-toluenesulfonic acid monohydrate was added and the mixture was stirred for 30 minutes. After the reaction was completed, the reaction product was diluted with 120 ml of diethyl ether and washed successively with 80 ml of saturated aqueous solution of sodium bicarbonate, 80 ml of saturated brine and 150 ml of water. The obtained organic layer was dehydrated with magnesium sulfate and filtered. 6.59 g of the desired monomer were obtained by removing the solvent and remaining 3,4-dihydro-2H-pyran using an evaporator. The desired monomer was a viscous liquid and the yield was 84%.

Elemental analysis results (% by weight)

C: 69.5 (69.2)

H: 8.64 (8.85)

The values in parentheses are calculated from C ₂₁ H ₃₂ O ₅ (molecular weight 364.23).

^{IR (㎝ -1): 2950,} 2870 (ν CH), 1716 (ν C = O), 1632 (ν C = C), 1166 (ν CO).

¹ HNMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 1.2-2.7 (m, 20H), 3.47-3.57 (m, 1H), 3.63-3.73 (m, 1H), 3.8-4.1 (m, 2H ), 5.79 (m, 1H), 5.9-6.0 (s, 1H), 6.05 (m, 1H), 6.36 (m, 1H).

Example 20

In formula (6), R ⁶ is hydrogen, R ⁷ is tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl group, R ⁸ is 1-ethoxyethyl group, k is 1, and a vinyl monomer is It was synthesized as follows.

<Formula 6>

A dry tube containing calcium chloride was assembled into a 200 ml three-necked flask with a thermometer, and the vinyl monomer synthesized in Example 12 (wherein R ⁶ is hydrogen and R ⁷ is tricyclo [5.2.1.0 ^2,6 ] and decane-4,8-diyl group, R ⁸ is hydrogen, k is 1 Im) to 6 g (0.022 mol) and vinyl ethyl ether, 1.30 g (0.022 mol) and a mixture of methylene chloride 60 ㎖, and the mixture with ice-water Cooled.

15 mg of p-toluenesulfonic acid monohydrate was added and the mixture was stirred for 1 hour. After the reaction was completed, the reaction product was diluted with 120 ml of diethyl ether and washed successively with 80 ml of saturated aqueous solution of sodium bicarbonate, 80 ml of saturated brine and 150 ml of water. The obtained organic layer was dehydrated with magnesium sulfate and filtered. The solvent was removed using an evaporator to give 5.67 g of the desired monomer. The desired monomer was a viscous liquid and the yield was 90%.

Elemental analysis results (% by weight)

C: 69.9 (68.15)

H: 9.02 (9.15)

The values in parentheses are calculated from C ₂₀ H ₃₂ O ₅ (molecular weight 352.225).

^{IR (㎝ -1): 2950,} 2872 (ν CH), 1720 (ν C = O), 1630 (ν C = C), 1166 (ν CO).

¹ HNMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 1.0-2.7 (m, 14H), 1.45 (d, 3H), 1.95 (s, 3H), 3.75 (q, 2H), 3.8-4.1 ( m, 2H), 5.75 (m, 1H), 5.9 (s, 1H), 6.05 (m, 1H), 6.36 (m, 1H).

Example 21

In formula (6), R ⁶ is a methyl group, R ⁷ is a tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl group, R ⁸ is a 1-butoxyethyl group, k is a vinyl monomer having 1 It was synthesized as follows.

<Formula 6>

A vinyl monomer was synthesized in the same manner as in Example 20 using butyl vinyl ether instead of vinyl ethyl ether. The target monomer was a viscous liquid, the yield being 70%.

Elemental analysis results (% by weight)

C: 68.05 (67.29)

H: 9. 12 (9.33)

The values in parentheses are calculated from C ₂₃ H ₃₈ O ₆ (molecular weight 410.5496).

Example 22

In formula (6), R ⁶ is hydrogen, R ⁷ is tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, R ⁸ is tert-butyl group, and k is 0. Synthesized together.

<Formula 6>

A dry tube containing calcium chloride was assembled into a 100 ml round bottom flask with a thermometer, 5 g (0.018 mol) of vinyl monomer synthesized in Example 14, 30 ml of methylene chloride, 3.99 g (0.054 mol) of t-butyl alcohol and 1.76 g (0.014 mol) of 4-dimethylaminopyridine were mixed in a flask and the mixture was cooled with ice water.

4.08 g (0.02 mol) of dicyclohexylcarbodiimide were added and the mixture was stirred at 0 ° C. for 5 minutes and then at room temperature for 4 hours. Cyclohexylurea was precipitated and filtered. The filtrate was washed twice with 10 ml of 0.5 M hydrochloric acid and twice with 10 ml of saturated aqueous sodium bicarbonate solution. The obtained organic layer was dehydrated with magnesium sulfate and filtered. The solvent was removed using an evaporator and purified through a silica gel column to give 5.67 g of the target compound. The desired monomer was a viscous liquid and the yield was 90%.

Elemental analysis results (% by weight)

C: 72.6 (72.38)

H: 9.03 (9.15)

The values in parentheses are the calculations for C ₂₁ H ₃₂ O ₄ (molecular weight 348.23).

^{IR (㎝ -1): 3460 (} ν OH), 2950 (ν CH), 1720 (ν C = O), 1634 (ν C = C), 1166 (ν CO).

Example 23

In formula (6), R ⁶ is hydrogen, R ⁷ is tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecanediyl group, R ⁸ is tetrahydrofuran-2-yl group, k is 0 vinyl monomer Was synthesized as follows.

<Formula 6>

Instead of t-butyl alcohol, the target monomer was obtained in the same manner as in Example 22 using 2,3-dihydrofuran. The desired monomer was a viscous liquid and the yield was 62%.

Elemental analysis results (% by weight)

C: 69.98 (69.59)

H: 8.28 (8.34)

The values in parentheses are calculated from C ₂₁ H ₃₀ O ₅ (molecular weight 362.209).

^{IR (㎝ -1): 2950,} 2874 (ν CH), 1718 (ν C = O), 1630 (ν C = C), 1166 (ν COC).

¹ HNMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 1.1-2.8 (m, 21H), 3.5-3.8 (m, 1H), 3.8-4.1 (m, 2H), 5.7 (m, 1H), 5.95 (s, 1 H), 6.05 (m, 1 H), 6.36 (m, 1 H).

Example 24

In the formula 6 R ⁶ is a methyl group, R ⁷ is a cyclo hexa ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane-diyl group, R ⁸ is a tetrahydropyran- A vinyl monomer having a 2-yl group and k being 0 was synthesized as follows.

<Formula 6>

A dry tube containing calcium chloride was assembled into a 200 ml three-necked flask with a thermometer, and the vinyl monomer synthesized in Example 15 (wherein R ⁶ is a methyl group and R ⁷ is hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 .0 ^2,7 .0 ^9,14] hepta-decane-diyl group and, R ⁸ is hydrogen, k is zero) 6 g (0.022 mol) and 3,4-dihydro -2H- pyran 4.54 g (0.054 mol) was mixed with 80 ml of methylene chloride and the mixture was cooled with ice water.

20 mg of p-toluenesulfonic acid monohydrate was added and the mixture was stirred for 30 minutes. After the reaction was completed, the reaction product was diluted with 120 ml of diethyl ether and washed successively with 80 ml of saturated aqueous solution of sodium bicarbonate, 80 ml of saturated brine and 150 ml of water. The obtained organic layer was dehydrated with magnesium sulfate and filtered. 6.59 g of the desired monomer were obtained by removing the solvent and the remaining 3,4-dihydro-2H-pyran using an evaporator. The desired monomer was a viscous liquid and the yield was 84%.

Elemental analysis results (% by weight)

C: 74.33 (73.65)

H: 8.98 (8.83)

Values in parentheses are calculated from C ₂₈ H ₄₀ O ₅ (molecular weight 456.6210).

^{IR (㎝ -1): 2950,} 2870 (ν CH), 1716 (ν C = O), 1632 (ν C = C), 1166 (ν CO).

¹ HNMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 1.2-2.7 (m, 20H), 1.95 (s, 3H), 3.47-3.57 (m, 1H), 3.63-3.73 (m, 1H), 3.8-4.1 (m, 2H), 5.55 (s, 1H), 5.94 (s, 1H), 6.1 (s, 1H).

Example 25

In the formula 6 R ⁶ is a methyl group, R ⁷ is a cyclo hexa ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] hepta-decane-diyl group, R ⁸ is 1-ethoxy The vinyl monomer which is an ethyl group and k is 0 was synthesize | combined as follows.

<Formula 6>

A dry tube containing calcium chloride was assembled into a 200 ml three-necked flask with a thermometer, and the vinyl monomer synthesized in Example 15 (wherein R ⁶ is a methyl group and R ⁷ is hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 .0 ^2,7 .0 ^9,14] heptadecyl and decane-diyl group, R ⁸ is hydrogen, k is zero) 6 g (0.022 mol) and vinyl ethyl ether, 1.30 g (0.022 mol) chloride Mix with 60 ml methylene and cool the mixture with ice water.

15 mg of p-toluenesulfonic acid monohydrate was added and the mixture was stirred for 1 hour. After the reaction was completed, the reaction product was diluted with 120 ml of diethyl ether and washed successively with 80 ml of saturated aqueous solution of sodium bicarbonate, 80 ml of saturated brine and 150 ml of water. The obtained organic layer was dehydrated with magnesium sulfate and filtered. The solvent was removed using an evaporator to give 5.67 g of the desired monomer. The desired monomer was a viscous liquid and the yield was 90%.

Elemental analysis results (% by weight)

C: 71.22 (72.94)

H: 8.9 (9.07)

The values in parentheses are calculated from C ₂₇ H ₄₀ O ₅ (molecular weight 444.6100).

^{IR (㎝ -1): 2950,} 2872 (ν CH), 1720 (ν C = O), 1630 (ν C = C), 1166 (ν CO).

¹ HNMR (CDCl ₃ , internal standard: tetramethylsilane) ppm: 1.0-2.7 (m, 14H), 1.2 (t, 3H), 1.45 (d, 3H), 1.95 (s, 3H), 3.75 (q, 2H), 3.8-4.1 (m, 2H), 5.55 (s, 1H), 5.9 (q, 1H), 6.1 (s, 1H).

Example 26

In formula (6), R ⁶ is a methyl group, R ⁷ is ^octacyclo [8.8.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,15 .0.0 ^2,8 .0 ^12,17 ] docosanediyl group , R ⁸ is a 1-butoxyethyl group, and k is 0. A vinyl monomer was synthesized as follows.

<Formula 6>

Instead of the vinyl monomer of Example 15, the vinyl monomer of Example 16 (wherein R ⁶ is a methyl group and R ⁷ is ^octacyclo [8.8.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^{13, 15} .0.0 ^2,8 .0 ^12,17] docosyl di diary and, R ⁸ is hydrogen, k by using the zero), and use a vinyl ether instead of the vinyl ethyl ether in like manner as example 25 purpose Monomers were synthesized. The desired monomer was a viscous liquid and the yield was 70%.

Elemental analysis results (% by weight)

C: 73.98 (75.80)

H: 9.21 (9.35)

The values in parentheses are calculated from C ₃₄ H ₅₀ O ₅ (molecular weight 538.7660).

Example 27

In Formula 7, R ² is a norbornane group, m is 0 and n is 0, a vinyl monomer was synthesized as follows.

5.9 g of norbornanediol monomethacrylate obtained in Example 1 was dissolved in 6 ml of pyridine, and the solution was cooled to 0 ° C. 3 ml of acetic anhydride was added and reaction continued for 15 hours at room temperature. The obtained material was poured into 100 ml of ice water, and the obtained organic layer was extracted using 100 ml of ether. The obtained organic compound was washed successively with 0.5 N hydrochloric acid, saturated saline, 3% aqueous solution of sodium bicarbonate, saturated saline and water. The ether layer was dried over MgSO ₄ and the ether was distilled off. 5 g of the target monomer was obtained by refine | purifying the obtained material using the solvent which adjusted hexane and ethyl acetate to 2: 1 in the silica gel column. The desired monomer was a viscous liquid.

Elemental analysis results (% by weight)

C: 66.0 (66.12)

H: 8.53 (8.72)

The values in parentheses are calculated from C ₁₄ H ₂₂ O ₄ (molecular weight 254.3254).

^{IR (㎝ -1): 2880,} 2920 (ν CH), 1718, 1738 (ν C = O), 1634 (ν C = C), 1240, 1164 (ν CO).

Example 28

In Formula 7, R ² is a tricyclo [5.2.1.0 ^2,6 ] decane-4,8-diyl group, m is 1, and n is 1, a vinyl monomer was synthesized as follows.

<Formula 7>

5.9 g of tricyclo [5.2.1.0 ^2,6 ] decane-4,8-dimethanol monomethacrylate synthesized in Example 2 was dissolved in 6 ml of pyridine and the solution was cooled to 0 ° C. 3 ml of acetic anhydride was added and reaction continued for 15 hours at room temperature. The obtained material was poured into 100 ml of ice water, and the obtained organic layer was extracted using 100 ml of ether. The obtained organic compound was washed successively with 0.5 N hydrochloric acid, saturated saline, 3% aqueous solution of sodium bicarbonate and saturated saline. The ether layer was dried over MgSO ₄ and the ether was distilled off. 5 g of the target monomer was obtained by refine | purifying the obtained material using the solvent which adjusted hexane and ethyl acetate to 2: 1 in the silica gel column. The desired monomer was a viscous liquid.

Elemental analysis results (% by weight)

C: 69.89 (70.77)

H: 8.58 (9.38)

The values in parentheses are the calculated C ₁₉ H ₃₀ O ₄ (molecular weight 322.4436).

^{IR (㎝ -1): 2880,} 2950 (ν CH), 1718, 1738 (ν C = O), 1634 (ν C = C), 1240, 1164 (ν CO).

Example 29

R 7 in the formula ² is a tetracyclo [4.4.0.1 ^2,5 .0 ^7,10] dodecanedioic group, m is 0 and n is 0, a vinyl monomer was synthesized as follows.

<Formula 7>

5.9 g of tetracyclododecanediol monomethacrylate synthesized in Example 6 was dissolved in 6 ml of pyridine, and the solution was cooled to 0 deg. 3 ml of acetic anhydride was added and reaction continued for 15 hours at room temperature. The obtained material was poured into 100 ml of ice water, and the obtained organic layer was extracted using 100 ml of ether. The obtained organic compound was washed successively with 0.5 N hydrochloric acid, saturated saline, 3% aqueous solution of sodium bicarbonate and saturated saline. The ether layer was dried over MgSO ₄ and the ether was distilled off. 5 g of the target monomer was obtained by refine | purifying the obtained material using the solvent which adjusted hexane and ethyl acetate to 2: 1 in the silica gel column. The desired monomer was a viscous liquid.

Elemental analysis results (% by weight)

C: 70.65 (71.39)

H: 9.23 (9.59)

Values in parentheses are calculated from C ₂₀ H ₃₂ O ₄ (molecular weight 336.4704).

^{IR (㎝ -1): 2880,} 2950 (ν CH), 1718, 1738 (ν C = O), 1634 (ν C = C), 1240, 1164 (ν CO).

Example 30

In Formula 7, R ² is a hexacycloheptadecane group, m is 0, and n is 0. A vinyl monomer was synthesized as follows.

<Formula 7>

5.9 g of hexacycloheptadecanediol monomethacrylate synthesized in Example 8 was dissolved in 6 ml of pyridine, and the solution was cooled to 0 ° C. 3 ml of acetic anhydride was added and reaction continued for 15 hours at room temperature. The obtained material was poured into 100 ml of ice water, and the obtained organic layer was extracted using 100 ml of ether. The obtained organic compound was washed successively with 0.5 N hydrochloric acid, saturated saline, 3% aqueous solution of sodium bicarbonate and saturated saline. The ether layer was dried over MgSO ₄ and the ether was distilled off. 5 g of the target monomer was obtained by refine | purifying the obtained material using the solvent which adjusted hexane and ethyl acetate to 2: 1 in the silica gel column. The desired monomer was a viscous liquid.

Elemental analysis results (% by weight)

C: 73.21 (74.58)

H: 8.98 (8.87)

The values in parentheses are calculated from C ₂₄ H ₃₄ O ₄ (molecular weight 386.5302).

^{IR (㎝ -1): 2880,} 2950 (ν CH), 1718, 1738 (ν C = O), 1634 (ν C = C), 1240, 1164 (ν CO).

Example 31

In Formula 7, R ² is an octacyclodocoacid group, m is 0, and n is 0. A vinyl monomer was synthesized as follows.

<Formula 7>

5.9 g of octacyclodocosandiol monomethacrylate synthesized in Example 7 was dissolved in 6 ml of pyridine, and the solution was cooled to 0 deg. 3 ml of acetic anhydride was added and reaction continued for 15 hours at room temperature. The obtained material was poured into 100 ml of ice water, and the obtained organic layer was extracted using 100 ml of ether. The obtained organic compound was washed successively with 0.5 N hydrochloric acid, saturated saline, 3% aqueous solution of sodium bicarbonate and saturated saline. The ether layer was dried over MgSO ₄ and the ether was distilled off. 5 g of the target monomer was obtained by refine | purifying the obtained material using the solvent which adjusted hexane and ethyl acetate to 2: 1 in the silica gel column. The desired monomer was a viscous liquid.

Elemental analysis results (% by weight)

C: 75.21 (76.95)

H: 8.98 (8.91)

The values in parentheses are calculated from C ₂₉ H ₄₀ O ₄ (molecular weight 452.6326).

^{IR (㎝ -1): 2880,} 2950 (ν CH), 1718, 1738 (ν C = O), 1634 (ν C = C), 1240, 1164 (ν CO).

Copolymer

Example 32

Using the vinyl monomer of Example 17, the vinyl monomer of Example 11 and the vinyl monomer of Example 3, a copolymer was synthesized as follows.

A 100 ml eggplant flask was prepared and three stoppers and a cold tube were attached to the flask. The vinyl monomer of Example 17, the vinyl monomer of Example 11 and the vinyl monomer of Example 3 were dissolved in 50 ml of dry tetrahydrofuran to 0.4 mol: 0.4 mol: 0.2 mol. 0.164 g (= 1.0 mmol) of azobisisobutyronitrile serving as a polymerization initiator was added to the solution and heated to 60 ° C. for 3 hours in an argon gas atmosphere. The reaction system was cooled to room temperature and the reaction product was poured into 0.5 L of ether. The precipitates were collected and the precipitation purification was repeated once more in tetrahydrofuran / ether. The copolymer was precipitated and filtered. The copolymer was dried at 40 ° C., 2 mmHg for 24 hours. 3.5 g of the desired copolymer were obtained in the form of a white powder, yield 70%. The copolymer was analyzed using a model LC-9A / SPD-6A analyzer manufactured by Shimadzu Corporation, GPCKF-80M manufactured by Showa Denko, and tetrahydrofuran solvent were used as the analysis column. The weight average molecular weight was 9000 in polystyrene conversion value.

Analysis

IR (cm ^-1 ): 3350 (ν _OH ), 1720 (ν _{C = O} )

disappearance band corresponding to ν _{C = C.}

Examples 33-44

In the same manner as in Example 32 described above, a copolymer as shown in Table 2 was synthesized. In Table 2, the proportion of monomers is expressed in moles.

Example Monomer Proportion of monomers x / y / z Molecular Weight 33 Example-19 Example-4 0.5 / 0 / 0.5 0.45 / 0 / 0.55 26000 34 Example-22 Example-6 0.4 / 0 / 0.6 0.41 / 0 / 0.59 32700 35 Example-23 Example-13 Example-6 0.5 / 0.3 / 0.2 0.5 / 0.3 / 0.2 27600 36 Example-24 Example-15 Example-8 0.3 / 0.4 / 0.3 0.29 / 0.39 / 0.32 43100 37 Example-26 Example-16 Example-9 0.5 / 0.3 / 0.2 0.5 / 0.31 / 0.19 29000 38 Example-22 Example-13 Example-29 0.4 / 0.2 / 0.4 0.39 / 0.18 / 0.43 28750 39 Example-25 Example-30 0.5 / 0 / 0.5 0.51 / 0 / 0.49 33000 40 Example-26 Example-16 Example-31 0.3 / 0.4 / 0.3 0.25 / 0.41 / 0.33 36200 41 Example-5 Example-12 Example-19 0.6 / 0.3 / 0.1 0.6 / 0.25 / 0.15 27000 42 Example-7 Example-14 Example-22 0.7 / 0.2 / 0.1 0.6 / 0.2 / 0.2 26000 43 Example-7 Example-14 0.7 / 0.3 / 0 0.72 / 0.28 / 0 20000 44 Example-5 Example-14 0.68 / 0.32 / 0 0.7 / 0.3 / 0 23000

Examples 45-57

2 g of each of the copolymers of Examples 33 to 44 were dissolved in 10 g of diethylene glycol dimethyl ether, and the solution was filtered using a Teflon filter. The average pore diameter of the Teflon filter was 0.2 micron. The filtrate was spin coated onto a 3 inch silicon substrate and baked on a hot plate at 90 ° C. for 60 seconds. The filtrate formed a 0.7 micron thick thin film.

The etching rate of each thin film was measured using a model DEM451 reactive ion etching apparatus manufactured by Nichiden-Anerva. The etching gas was CF ₄ at a pressure of 5 kPa and 30 sccm. The power was adjusted to 100 watts. Etch rates are summarized in Table 3 below.

For comparison, a coating film made of poly (p-vinylphenol), which is widely used as a base resin of a KrF excimer laser lithography resist, and polymethyl methacrylate, a polymer containing no cyclic hydrocarbon group bridged in molecular structure, is used. The result at the time of doing was displayed.

Example Copolymer Etch Rate (Å / min) 45 Example 32 167 46 Example 33 163 47 Example 34 160 48 Example 35 159 49 Example 36 105 50 Example 37 103 51 Example 38 161 52 Example 39 107 53 Example 40 102 54 Example 41 164 55 Example 42 163 56 Example 43 162 57 Example 44 165 Reference Example 1 Poly (p-vinylphenol) 167 Reference Example 2 Poly (methyl methacrylate) 262

As will be understood from Table 3, the copolymers of the present invention had a lower etch rate compared to poly (methyl methacrylate). Even when the copolymer was compared with poly (p-vinylphenol), the etching rate of the copolymer was not larger than that of the polyvinylphenol. Thus, it has been found that the copolymer according to the present invention has sufficient etching resistance as a resist material.

Chemically amplified resist

Example 58

A resist material consisting of the following composition was prepared. The following experiment was carried out under a yellow lamp.

(a) a polymer: Example 32. 0.950 g

(b) photoacid generator: cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate represented by the formula (4). 0.050 g

(c) solvent: propylene glycol monomethyl ether acetate; 4.000 g

The polymer and photoacid generator were dissolved in a solvent and the solution was filtered using a 0.2 micron Teflon filter to obtain a chemically amplified resist.

This chemically amplified resist was spin coated onto a 3 inch silicon wafer and baked on a hot plate at 80 ° C. for 60 seconds. The thickness of the chemically amplified resist film was 0.7 micron. The dependence of the transmittance | permeability of the obtained film | membrane on the exposure light wavelength was measured using the ultraviolet-visible-spectrophotometry detector. It was confirmed that the transmittance for light having a wavelength of 193.4 nm was 71%, showing sufficient transparency as a single layer chemically amplified resist.

Example 59

The chemically amplified resist film shown in Example 58 was placed in an ArF reduction exposure machine, and the chemically amplified resist film was exposed to form a latent image of a line-space pattern. The numerical aperture was 0.55 and sigma was 0.7. After exposure, the chemically amplified resist film was baked on a hot plate at 90 ° C. for 60 seconds and soaked in an alkaline developer at room temperature for 60 seconds to develop a latent image. The alkaline developer contained 2.3 parts by weight of tetramethyl-ammonium hydroxide. The chemically amplified resist film was then washed with pure water for 60 seconds and the exposed portion of the chemically amplified resist was dissolved in and removed from the developer to obtain a positive pattern. In this experiment, 0.20 micron line-space resolution was obtained when the exposure energy was 15 mJ / cm 2. The line-space pattern was observed using Hitachi's Model SE-4100 scanning electron microscope, and found no developer residue and no delamination of the pattern from the wafer.

Examples 60-69

A chemically amplified resist solution was prepared in the same manner as in Example 58, and the exposure experiment was conducted in the same manner as in Example 59. The results are summarized in Table 4 below.

Example polymer Sensitivity (mJ / ㎠) Resolution (μm) 60 Example 33 37 0.20 61 Example 34 45 0.20 62 Example 35 8 0.19 63 Example 36 15 0.18 64 Example 37 17 0.20 65 Example 38 23 0.25 66 Example 39 16 0.19 67 Example 40 33 0.22 68 Example 41 12 0.20 69 Example 42 35 0.20

Example 70

A resist material consisting of the following composition was prepared. The following experiment was carried out under a yellow lamp.

(a) a polymer: Example 43. 0.87 g

(b) photoacid generator: cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate represented by the formula (4). 0.03 g

(c) crosslinker: hexamethoxymethylolmelamine... 0.1 g

(d) solvent: cyclohexanone... 5.67 g

The polymer, photoacid generator and crosslinker were dissolved in the solvent and the solution was filtered using a 0.2 micron Teflon filter. The chemically amplified negative resist thus obtained was spin coated onto a 3 inch silicon wafer in the same manner as in Example 58 and baked on a hot plate at 120 ° C. for 60 seconds. The thickness of the chemically amplified negative resist film was 0.5 micron.

Subsequently, a chemically amplified negative resist film was placed in an ArF reduction exposure machine as in Example 59, and the chemically amplified resist film was exposed to form a latent image of a line-space pattern. The numerical aperture was 0.55 and sigma was 0.7. As a result of developing the latent image, the exposed portion of the resist film was insolubilized and only the unexposed portion was dissolved in and removed from the developer to obtain a negative resist pattern. In this experiment, 0.30 micron line-space resolution was obtained when the exposure energy was 6 mJ / cm 2. Observation of the line-space pattern using a scanning electron microscope confirmed that there was no developing residue and there was no delamination of the pattern from the wafer.

Example 71

A thin film of 0.5 micron thick chemically amplified resist using the polymer of Example 44, using the polymer of Example 44, and spincoating the resist onto a silicon wafer in the same manner as Example 58 and baking on a hot plate at 115 ° C. for 60 seconds. Was formed. Again, it developed and exposed using the ArF reduction exposure machine similarly to Example 59. As a result, a negative resist pattern was obtained. In this experiment, 0.20 micron line-space resolution was obtained when the exposure energy was 9.5 mJ / cm 2. Observation of the line-space pattern through a scanning electron microscope confirmed that there was no developing residue and no peeling of the pattern from the wafer.

Examples 72-83

The polymers obtained in Examples 33 to 44 were used to apply a thin film to a silicon wafer in the same manner as in Example 45. In addition, i-line novolak resist and poly (carboxytetracyclododecene methacrylate) manufactured by Sumitomo Chemical Co., Ltd., product number "PFI-15A" as reference samples (the monomers of Example 13 Similarly, it was dissolved in dry tetrahydrofuran, and azobisisobutyronitrile was added thereto and heated in an argon atmosphere to polymerize).

Thereafter, the contact angles with respect to pure water and methylene iodide of the obtained membrane were measured. For measurement, a CA-X type contact angle measuring instrument manufactured by Kyowa Kaimen Kagaku Co., Ltd. was used. Based on the values obtained, see H. Yanazawa et al., Colloids and Surfaces, vol. 9, pages 133-145, 1984, using the Young-Owens equation to evaluate the adhesion as an indicator of substrate adhesion of the polymer. The results are summarized in Table 5 below.

Example Component polymer Adhesive force (mN · cm ^-2 ) 72 Example 33 84.6 73 Example 34 84.4 74 Example 35 85.5 75 Example 36 85.7 76 Example 37 84.9 77 Example 38 84.9 78 Example 39 85.1 79 Example 40 84.7 80 Example 41 86.0 81 Example 42 84.3 82 Example 43 85.7 83 Example 44 86.2 Reference Example 3 PFI-15A 80.3 Reference Example 4 Poly (carboxytetracyclododecene methacrylate) 84.3

From Table 5, it is evident that the polymers of Examples 33-44 exhibited greater adhesion than the resist for i-ray exposure and therefore had sufficient adhesion to the substrate. In addition, neither polymer exhibits greater adhesion than poly (carboxytetracyclododecene methacrylate) (when both x and z in Formula 2 are 0), thereby introducing a substrate of the resist by introducing a monomer unit corresponding to x (Formula 1). It becomes clear that the adhesive force to is greatly increased.

Example 84

In formula (2), each of R ¹ and R ³ is hydrogen, m is 0, n is 0, R ² is a tricyclodecanediyl group, R ⁴ is hydrogen, i is 0, and R ⁵ is tetracyclodode When the candiyl group was z and 0, the dissolution rate of the resist in the alkaline developer was measured when x was changed from 0 to 1. As an alkaline developer, 2.38% of tetramethylammonium hydroxide aqueous solution was used. The measurement results are shown in FIG. When x changed from 0 to 0.75, the dissolution rate varied from 0.7 microns / second to 4 microns / second showing that it dissolves at a sufficient rate as a resist. However, as x increased to 0.8, the dissolution rate decreased to 3 × 10 ⁻⁵ microns / sec. Thus, the chemically amplified resist according to the present invention exhibits an unusual behavior of having a threshold in dissolution behavior when x takes an appropriate value (0.75 in this example). In this way, x can be set in consideration of the dissolution behavior. In addition, using these thresholds, slight changes in solubility resulting from the reaction of the acid-degradable polar converter (R ⁸ in Formula 2) or the crosslinkable compound in the chemically amplified resist of the present invention can be applied to the entire chemically amplified resist composition of the present invention. It becomes clear that the solubility is easy to change drastically. Furthermore, it becomes apparent that by using the chemically amplified resist composition of the present invention, extremely high resolution patterns are easily obtained at a small amount of active light energy.

Pattern transfer process

Using the chemically amplified resist according to the present invention, the pattern is transferred to a chemically amplified resist mask as follows. First, the chemically amplified resist is spin coated onto a solid structure such as the semiconductor wafer 1 to form a liquid chemically amplified resist layer 2 as shown in FIG.

The semiconductor wafer 1 is placed on the hot plate 3, and the chemically amplified resist layer is baked as shown in FIG. The solvent is then evaporated so that the semiconductor wafer 1 is covered with the chemically amplified resist layer 4.

The semiconductor wafer 1 is placed in the exposure machine 5 and the ArF excimer laser light is irradiated from the laser light source 5a. The excimer laser light passes through the reticle 5b, and the phase transfer light is incident on the chemically amplified resist layer 4 as shown in FIG. Thus, a latent image was formed in the chemically amplified resist layer 4.

The chemically amplified resist layer 4 is post-baked as shown in FIG. 5. At this time, a hot plate is used for post-baking. However, another heater such as an infrared oven can be used for post-baking.

The latent image is developed using an alkaline developer. At this time, the semiconductor wafer 1 is transported under the spray nozzle 7, and the alkaline solution is sprayed onto the chemically amplified resist layer 4 as shown in FIG. However, other developing devices may be used. The alkaline developer partially dissolves the chemically amplified resist layer so that the mask layer 8 remains on the semiconductor wafer 1 as shown in FIG.

Chemically amplified resists containing polymers obtained by polymerizing the novel monomers according to the present invention have high transparency for far-ultraviolet regions of 248 nm or less, and exhibit high sensitivity and resolution for far-ultraviolet exposure light. Therefore, it is most suitable for the photoresist which uses the ArF excimer laser which is far ultraviolet rays below 248 nm as exposure light. In addition, by using the chemically amplified resist of the present invention, it is possible to form a fine pattern required for manufacturing a semiconductor device.

While particular embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

Claims (10)

A chemically amplified resist consisting of a polymer, a photoacid generator, and a crosslinking agent activated in the presence of an acid, The photoacid generator and the crosslinking agent are contained in an amount of 0.2 to 25 parts by weight and 1 to 40 parts by weight, respectively, The polymer is formed by copolymerizing a monomer represented by the following formula (1) with another polymerizable compound, and contained in an amount of 50 to 98.8 parts by weight in the chemically amplified resist. Chemically amplified resist, characterized in that. <Formula 1> In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group having 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, and R ³ is a hydrogen atom, a methyl group Or an acetyl group. The chemically amplified resist according to claim 1, wherein the polymer has a weight average molecular weight of 1,000 to 50,000 and is represented by the following Chemical Formula 2. <Formula 2> In the formula, R ¹ , R ⁴ and R ⁶ represent a hydrogen atom or a methyl group, R ² , R ⁵ and R ⁷ represent a bridged hydrocarbon group having 7 to 22 carbon atoms, and R ³ represents a hydrogen atom, a methyl group or acetyl R ⁸ represents a group which is decomposed by an acid, m is 0 or 1, n is 0 or 1, i is 0 or 1, k is 0 or 1, and x + y + z = 1, x is 0.05 to 0.75, y is 0 to 0.8 and z is 0 to 0.6. The chemically amplified resist of claim 1, wherein the chemically amplified resist forms a negative resist pattern when dissolved in a developer after selective light irradiation. The chemically amplified resist according to claim 2, wherein the chemically amplified resist forms a negative resist pattern when dissolved in a developer after selective light irradiation. a) preparing a solid structure, b) a photoacid generator contained in an amount of 0.2 to 25 parts by weight, Crosslinker activated in the presence of an acid and contained in an amount of 1 to 40 parts by weight, and A polymer made by copolymerizing a monomer represented by Formula 1 with another polymerizable compound and contained in an amount of 50 to 98.8 parts by weight. Applying a chemically amplified resist to the surface of the solid structure to form a chemically amplified resist layer on the surface, <Formula 1> (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a bridged hydrocarbon group of 7 to 22 carbon atoms, m is 0 or 1, n is 0 or 1, R ³ is a hydrogen atom, Methyl group or acetyl group.) c) irradiating the chemically amplified resist layer with light through a mask to form a latent image in the layer, and d) developing the latent image to form a resist mask from the chemically amplified resist layer A resist mask forming method consisting of. The method of claim 5, wherein the polymer has a weight average molecular weight of 1,000 to 50,000 and is represented by the following formula (2). <Formula 2> In the formula, R ¹ , R ⁴ and R ⁶ represent a hydrogen atom or a methyl group, R ² , R ⁵ and R ⁷ represent a bridged hydrocarbon group having 7 to 22 carbon atoms, and R ³ represents a hydrogen atom, a methyl group or acetyl R ⁸ represents a group which is decomposed by an acid, m is 0 or 1, n is 0 or 1, i is 0 or 1, k is 0 or 1, and x + y + z = 1, x is 0.05 to 0.75, y is 0 to 0.8 and z is 0 to 0.6. 6. The method of claim 5, wherein the wavelength of light is 248 nanometers or less. 8. The method of claim 7, wherein the light is irradiated with an ArF excimer laser light source. 6. The method of claim 5 wherein an alkaline developer is used in step d). 6. The method of claim 5, wherein the step of heating the chemically amplified resist applied to the surface of the solid structure between steps b) and c) to form a chemically amplified resist layer; and d) heating the chemically amplified resist layer therebetween.