JP2002265530A - Compound for photoresist and resin composition for photoresist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin for photoresist which is excellent in homogeneity and can give a fine pattern with a high resolution. SOLUTION: A compound represented by formula (1) (wherein R<a> is H or methyl; and R<1> is a 1-10C hydrocarbon group) is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer compound for a photoresist used for performing fine processing of a semiconductor, and the like.
And a polymerizable compound for producing the polymer compound, a photoresist resin composition containing the polymer compound, and a method for producing a semiconductor.

[0002]

2. Description of the Related Art A photoresist resin used in a semiconductor manufacturing process has a function of exhibiting substrate adhesion and a function of being desorbed by an acid generated from a photoacid generator upon exposure to become soluble in an alkali developing solution. (May be abbreviated as an acid-eliminating function). Also, the resin for photoresist is
It must also have dry etching resistance. In particular, the excimer laser
Expectations for giga-order semiconductors using ArF are increasing. However, since ArF has a wavelength of 193 nm in deep ultraviolet, the resist material is also required to have transparency in the ultraviolet region, and a novel monomer, particularly a polymerizable compound having a polycyclic alicyclic skeleton has been proposed.

As a polymerizable compound having a polycyclic alicyclic skeleton, Japanese Patent Application Laid-Open Nos. 9-73173 and 2000-98
No. 612 and the like having an adamantane skeleton and Japanese Unexamined Patent Publication No. 7-252324 have reported a skeleton having a tricyclodecane or the like. However, in order to introduce a polymerizable acrylic group into adamantane or tricyclodecane, a method having poor selectivity must be adopted, and none of them can be said to be economical compounds. Therefore,
There is a strong demand for the development of resist materials compatible with Arf excimer lasers.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel photoresist compound and a high molecular compound which have an etching resistance and an acid desorbing function and are industrially economical. It is in.

It is still another object of the present invention to provide a photoresist resin composition capable of forming a fine pattern with high precision, and a method of manufacturing a semiconductor.

[0006]

As a result of intensive studies, the present inventors have succeeded in synthesizing a monomer having a polycyclic alicyclic skeleton having a specific structure by economic means, and have succeeded in synthesizing a monomer as a resist composition. They also found that the function was excellent, and completed the present invention.

That is, the present invention provides the following formula (1)

[0008]

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(Wherein, R ^a represents a hydrogen atom or a methyl group, and R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms).

Further, the present invention provides a compound represented by the following formula (I):

[0011]

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(Wherein, R ^a represents a hydrogen atom or a methyl group, and R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms). Provide a molecular compound.

Further, the polymer according to the present invention has the above formula (I)
At least one monomer unit selected from the monomer units represented by the following formulas (IIa) to (IIj):

[0014]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and represent a hydrogen atom, a hydroxyl group or a carboxyl group, and R ⁴ represents a hydroxyl group or an oxo group. Or a carboxyl group.
X ¹ to X ³ are the same or different and each represents —CH ₂ — or —CO—
O- is shown. R ⁵ to R ⁷ are the same or different and each represent a hydrogen atom or a methyl group. R ⁸ and R ⁹ are the same or different,
It represents a hydrogen atom or a methyl group. R ¹⁰ to R ¹⁴ are the same or different and each represent a hydrogen atom or a methyl group. R ¹⁵ represents a hydrogen atom or a linear, branched, cyclic or bridged cyclic hydrocarbon having 1 to 20 carbon atoms which may have a polar substituent. R ¹⁶ ~
¹⁹ is the same or different and represents a hydrogen atom or a methyl group. R ²⁰ represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or a carboxyl group. R ²¹ to ³⁸ each represent a hydrogen atom, a methyl group or an ethyl group. o, p, q and r each represent 0 or 1. The present invention provides the polymer compound for a photoresist described above, which comprises at least one monomer unit selected from the group consisting of:

Further, the present invention relates to at least one monomer unit selected from the monomer units represented by the above formula (I) and the following formulas (IIIa) to (IIIg):

[0017]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, R ³⁹ and R ⁴⁰ are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ⁴¹ to ⁴³ are the same. or different, a hydrogen atom, a hydroxyl group or a methyl group, R ⁴⁴ and R ⁴⁵ are the same or different, a hydrogen atom, a hydroxyl group or -COOR ^46, R ⁴⁶ is t- butyl, 2-tetrahydrofuranyl R ⁴⁷ represents a methyl group or an ethyl group; R ⁴⁸ and R ⁴⁹ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group; , R ⁵⁰ represents a hydrocarbon group which may tertiary that have a substituent, R ⁵¹ ~ ⁵⁵ are the same or different and each represents a hydrogen atom or a methyl group, R ⁵⁶ also have a substituent Good tertiary hydrocarbon group, 2-tetrahydrido Represents a lofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group, where m is 1 to 3
And n represents 0 or 1. The present invention provides the polymer compound for a photoresist described above, which comprises at least one monomer unit selected from the monomer units represented by (1).

Further, the present invention provides at least one monomer unit selected from the monomer units represented by the above formula (I) and at least one monomer unit selected from the above formulas (IIa) to (IIj) And a unit represented by the formula (II)
The present invention provides the polymer compound for a photoresist described above, comprising at least one monomer unit selected from the monomer units represented by Ia) to (IIIg).

Further, the present invention provides a photoresist resin composition comprising at least the above-mentioned polymer compound for photoresist and a photoacid generator.

Further, according to the present invention, there is provided a method for producing a semiconductor, comprising the steps of applying the above-described resin composition for a photoresist onto a substrate or substrate to form a resist coating film, and exposing and developing to form a pattern. Provide a way.

The present invention also provides a method for producing the compound represented by the formula (1).

In this specification, “acryl” and “methacryl” may be collectively referred to as “(meth) acryl”, and “acryloyl” and “methacryloyl” may be collectively referred to as “(meth) acryloyl”.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The novel compounds of the present invention represented by the above formula (1) can be roughly classified into two types, and the production method is represented by the following formula as a production route.

[0025]

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As a novel compound, 2- (meth) acryloyloxy-tricyclo is used as an example of the above formula (1a).
[7.4.0.0 ^3,8 ] tridecane, which is a corresponding alcohol reduced from fluorenone as a starting material in a hydrogen atmosphere in the presence of a hydrogenation catalyst or the like.
-Hydroxytricyclo [7.4.0.0 ^3,8 ] tridecane is synthesized and further reacted with a (meth) acrylic acid-reactive derivative to obtain the compound of the formula (1a).

The catalyst used in the hydrogenation reaction is not particularly limited, but may be any one of groups 8 and 9 of the periodic table.
Group 0 or 11 metals, activated ones of these metals (Raney type or the like), or those having these metals supported on a carrier are effective. The metals may be used in combination of two or more.

Examples of Group 8, 9, 10, or 11 metals include Fe, Ru, Co, Ni, Pd, Pt, and Cu.
And the like. Examples of activated metals (Raney type or the like) include Raney Co, Raney Ni, and Raney Cu. As a catalyst in which a metal is supported on a carrier, the carrier includes activated carbon (carbon), alumina, silica, silica-alumina, and the like.
u, Co, Ni, Pd, Pt, Cu and the like. It is not specified about the amount of metal carried, but 0.1 to
20%, preferably 1 to 10%. It is also possible to use these types of different catalysts in combination or in combination.

The preferred reaction temperature in the hydrogenation reaction varies depending on the catalyst used.
~ 250 ° C, preferably -20 to 230 ° C
It is. The hydrogen pressure in the hydrogenation reaction is from normal pressure to 30
0 Pa, preferably normal pressure to 200 Pa. The preferred conditions differ depending on the catalyst used even at the hydrogen pressure, but in general, the higher the pressure, the higher the speed, but the pressure resistance of the equipment is required, and the conditions appropriate to the economics are taken respectively. .

The reaction is often carried out by dispersing a particulate catalyst in the reaction system. However, it is also effective to pack the catalyst in a column or the like and allow the reaction material and hydrogen to flow therethrough.

In the reaction, a solvent may be used, the product may be used as a solvent, or no solvent may be used. Generally, it is preferable to use a solvent because the dispersibility of the catalyst and the like is improved. Examples of the solvent used include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and s.
Examples include ec-butyl alcohol, tert-butyl alcohol, amyl alcohol and its isomers, pentyl alcohol and its isomers, hexyl alcohol and its isomers, and 2-ethylhexanol. As polyhydric alcohol solvents, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether and the like. As ester solvents, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol Monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc. A.
Examples of ethers (aliphatic and alicyclic) include diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, tetrahydrofuran, dioxane, and the like. As hydrocarbons (aliphatic and alicyclic), heptane, hexane, heptane, hexane, heptane,
Octane, cyclopentane, cyclohexane and the like.
It is also useful to use a mixture of two or more of these solvents, and it is also possible to use a mixture of the solvent and water.

2-Hydroxytricyclo [7.4.0.
[ ^3,8 ] tridecane and (meth) acrylic acid; (meth) acrylic acid-reactive derivative, in which (meth) acrylic acid-reactive derivative can react with alcohol to produce the corresponding ester Derivatives, for example, (meth) acrylic halides such as (meth) acrylic chloride; acid anhydrides such as (meth) acrylic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate,
(Meth) acrylic acid esters such as (meth) vinyl acrylate and 2-propenyl (meth) acrylate (for example,
Alkyl ester, alkenyl ester, etc.).

2-hydroxytricyclo [7.4.0.
[0 ^3,8 ] Tridecane and (meth) acrylic acid are usually reacted (esterification) in a solvent inert to the reaction.
Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; hexane,
Aliphatic hydrocarbons such as heptane, octane and decane; alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene and trifluoromethylbenzene; ethyl acetate, butyl acetate Esters such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, and tetrahydrofuran;
And a mixed solvent thereof. As the solvent, a solvent azeotropic with the by-produced water and capable of being separated from water (a solvent capable of azeotropic dehydration), such as toluene, is preferable.

The catalyst used for the esterification reaction includes, for example, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and heteropoly acids (for example, silicotungstic acid, silicomolybdic acid, phosphotungstic acid, phosphomolybdic acid, etc.); benzene sulfone Sulfonic acids such as acids, p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, and sulfonic acid-based strongly acidic ion exchange resins. These can be used alone or in combination of two or more.

In order to prevent polymerization during the reaction, it is preferable to add a polymerization inhibitor such as methoquinone or hydroquinone to the system or supply oxygen to the system. Oxygen can be used after being diluted with an inert gas such as nitrogen.

The esterification reaction between the alcohol having a cyclic skeleton and (meth) acrylic acid is carried out at normal pressure or reduced pressure, for example, at a temperature of about 50 to 150 ° C. The amount of the (meth) acrylic acid used may be 1 mol or more with respect to 1 mol of the alcohol having a cyclic skeleton, but is 1.5 mol or more (for example, 1.5 to 10 mol, particularly 2.5 to 6 mol) Mol).

2-hydroxytricyclo [7.4.0.
[0 ^3,8 ] Tridecane and a reactive derivative of (meth) acrylic acid can be reacted in the presence of a base or a transesterification catalyst depending on the type of the reactive derivative. For example,
When (meth) acrylic acid halide or acid anhydride is used as a reactive derivative of (meth) acrylic acid, in the presence of a base (acid scavenger) such as triethylamine and pyridine,
For example, the reaction is carried out in the solvent at a temperature of about 0 to 100 ° C. When (meth) acrylic acid ester is used as the reactive derivative of (meth) acrylic acid, a conventional transesterification catalyst, or when alkenyl (meth) acrylate is used as the reactive derivative, Group 3 element compound catalyst of the periodic table (for example, samarium acetate,
The reaction is performed in the presence of, for example, a samarium compound such as samarium trifluoromethanesulfonate or a samarium complex), for example, in the above-mentioned solvent at a temperature of about 0 to 150 ° C.

On the other hand, as the latter half of the above-mentioned reaction route, the compound (1b) can be obtained by reacting fluorenone with a Grignard reagent, and the alcohol compound (1c) can be obtained by catalytic hydrogenation reaction. Reaction of the alcohol compound with a (meth) acrylic acid-reactive derivative gives another target compound, compound formula (1d).

In the reaction between fluorenone and an organometallic compound, the organometallic used is represented by the following formula (A) R ¹ -M (A) (wherein R ¹ is a hydrocarbon group having 1 to 10 carbon atoms) Show, M
Is represented by a metal atom which may have a ligand, or the following formula (B) -MgY (B) (wherein, Y represents halogen).

In the organic metal represented by the formula (A), examples of the metal atom M include alkali metals such as lithium and sodium, and transition metal atoms such as cerium, titanium and copper. The metal may have a ligand. Examples of the ligand include a halogen atom such as a chlorine atom, an alkoxy group such as an isopropoxy group, a dialkylamino group such as a diethylamino group, a cyano group, an alkyl group, and an alkali metal such as a lithium atom.

Representative examples of the organometallic compound represented by the formula (A) include organometallic titanium compounds such as dimethyldiisopropoxytitanium and organomagnesium compounds such as methylmagnesium bromide, ethylmagnesium bromide and butylmagnesium bromide. (Grignard reagent, etc.), and organic lithium compounds such as methyllithium and butyllithium. The organomagnesium compound can be used in combination with a copper halide.

The amount of the organometallic compound represented by the formula (A) is, for example, 1 to 2 with respect to 1 mol of fluorenone.
It is about.

The reaction is usually performed in an organic solvent. The organic solvent may be any solvent that is inert to the reaction, and examples thereof include ethers such as diethyl ether, 1,2-dimethoxyethane, and tetrahydrofuran, and aliphatic hydrocarbons such as heptane, hexane, and octane.

The reaction temperature varies depending on the type of the organometallic compound, but can be selected, for example, in the range of about -100 to 150 ° C. For example, in the organometallic compound represented by the formula (A), when M is a metal atom (for example, lithium), the reaction temperature is, for example, -100 to 3
It is about 0 ° C. When a compound in which M represents a group represented by the formula (B) is used as the compound of the formula (A),
The reaction temperature is, for example, about 0 to 150 ° C., preferably about 20 ° C.
~ 100 ° C.

The hydrogenation reaction of the compound of the formula (1b) synthesized from fluorenone and the above-mentioned organometallic compound is carried out in the same manner as the above-mentioned hydrogenation reaction of fluorenone.

The reaction between the compound of formula (1b) and a reactive derivative of (meth) acrylic acid is carried out by the above-mentioned 2-hydroxy-tricyclo [7.4.0.0 ^3,8 ] tridecane and (meth) acrylic acid. The reaction is carried out by the same operation as the reaction with the reactive derivative of the compound of formula (1d)
Has the property of being desorbed by an acid, and as a reactive derivative of (meth) acrylic acid, (meth) acrylic acid such as (meth) acrylic acid chloride in the presence of an acid scavenger such as triethylamine is used. Acid halide; acid anhydride such as (meth) acrylic anhydride; (meth) acryl such as methyl (meth) acrylate, ethyl (meth) acrylate, vinyl (meth) acrylate, 2-propenyl (meth) acrylate Acid esters (eg, alkyl esters,
Alkenyl esters) are preferred. In particular, use of (meth) acrylic halide such as (meth) acrylic chloride is preferred.

The selectivity can also be increased by reacting the above-mentioned organometallic compound formula (A) with the above-mentioned compound formula (1c) and further reacting (meth) acrylic halide such as (meth) acrylic chloride. Is preferred for

On the other hand, Japanese Patent Application Laid-Open No. 10-57814 discloses that fluorenone as a starting material can synthesize fluorenone from fluorene with high selectivity by using an oxidation catalyst mainly containing a hydroxylimide compound.

The polymer compound for a photoresist of the present invention comprises, as a structural unit constituting a polymer molecule, at least one monomer unit (repeating unit) selected from the formula (I) (hereinafter referred to as “monomer unit 1”). ). The monomer unit 1 has a polycyclic alicyclic skeleton in the molecule, is expected to have etching resistance, and has a compound having an acid elimination function, and has a useful function as a polymer compound for photoresist. Material. [Monomer unit of the formula (I)] A monomer corresponding to the monomer unit of the formula (I) is represented by the following formula (1). In addition,
If stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0050]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, and R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms.) Typical examples include the following compounds, but are not limited thereto. Not something. [1-1] 2- (meth) acryloyloxytricyclo [7.4.0.0 ^3,8 ] tridecane (R ^a = H or CH ₃ , R ¹ = H) [1-2] 2- (meta) ) Acryloyloxy-2-methyltricyclo [7.4.0.0 ^3,8 ] tridecane (R ^a = H or CH ₃ , R ¹ = CH ₃ ) [1-3] 2- (meth) acryloyloxy- 2-ethyltricyclo [7.4.0.0 ^3,8 ] tridecane (R ^a = H or CH ₃ , R ¹ = CH ₂ CH ₃ ) [Monomer unit of formula (IIa)] The monomer corresponding to the monomer unit is represented by the following formula (2a). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0052]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and represent a hydrogen atom, a hydroxyl group or a carboxyl group, and R ⁴ represents a hydroxyl group or an oxo group. Or a carboxyl group.) Typical examples include the following compounds, but are not limited thereto. [2-1] 1-hydroxy-3- (meth) acryloyloxy adamantane (R ^a = H or ^{_{CH 3, R 2 = OH,}} R 3
^{= R 4 = H) [2-2} ] 1,3- dihydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH ^_3, R ² = R ₃
^{= OH, R 4 = H)} [2-3] 1- carboxy-3- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ² = COO
^{H, R 3 = R 4 =} H) [2-4] 1,3- dicarboxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH ^_3, R ² = R ₃
= COOH, R ⁴ = H) [2-5] 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane (R ^a = H or C
^{_{H 3, R 2 = COOH,}} R 3 = OH, R 4 = H) [2-6] 1- ( meth) acryloyloxy-4-oxo-adamantane (R ^a = H or _{^{CH 3, R 2 = R 3}} = H, R ⁴
= 4-oxo group) [2-7] 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ^a = H or CH ₃ , R
^{2 = 3-OH, R 3} = H, R 4 = 4- oxo group) [2-8] 7-hydroxy-1- (meth) acryloyloxy-4-oxo-adamantane (R ^a = H or CH _3, R
^{2 = 7-OH, R 3} = H, R 4 = 4- oxo group) monomer corresponding to the monomer unit of the formula (IIb) [monomer units of formula (IIb)] is represented by the following formula (2b) . When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0054]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, and X ¹ to X ³ are the same or different and each represents —CH ₂ —
Or -CO-O-. R ⁵ to R ⁷ are the same or different and each represent a hydrogen atom or a methyl group. Representative examples include, but are not limited to, the following compounds. [2-9] 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one (R ^a = H or CH ₃ , R ⁵ = R ⁶ = R ⁷ = H, X ¹ = X ³
= —CH ₂ —, X ² = —CO—O— (the left side is the carbon atom side to which R ⁶ is bonded)) [2-10] 1- (meth) acryloyloxy-4,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-
5,8-dione (R ^a = H or CH ₃ , R ⁵ = R ⁶ = R ⁷ =
H, X ¹ = —CO—O— (left side is a carbon atom side to which R ⁵ is bonded), X ² = —CO—O— (left side is a carbon atom side to which R ⁶ is bonded), X ³ = —CH ₂ —) [2-11] 1- (meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-
5,7-dione (R ^a = H or CH ₃ , R ⁵ = R ⁶ = R ⁷ =
H, X ¹ = —O—CO— (the carbon atom side to which R ⁵ is bonded on the left), X ² = —CO—O— (the carbon atom side to which R ⁶ is bonded), X ³ = —CH ₂ —) [2-12] 1- (meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^3,9 ] dodecane-
4,8-dione (R ^a = H or CH ₃ , R ⁵ = R ⁶ = R ⁷ =
H, X ¹ = —CO—O— (the left side is the carbon atom side to which R ⁵ is bonded), X ² = —O—CO— (the left side is the carbon atom side to which R ⁶ is bonded), X ³ = -CH _2- ) [Monomer unit of the formula (IIc)] The monomer corresponding to the monomer unit of the formula (IIc) is represented by the following formula (2c). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0056]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, and R ⁸ and R ⁹ are the same or different and represent a hydrogen atom or a methyl group. Representative examples include the following compounds. [2-13] 5- (meth) acryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (R ^a = H Or CH ₃ , R ⁸ ＲR ⁹ ＨH) [2-14] 5- (meth) acryloyloxy-5-methyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonane-2- ON (R ^a = H or CH ₃ , R ⁸ = CH ₃ , R ⁹ =
H) [Monomer unit of formula (IId)] The monomer corresponding to the monomer unit of formula (IId) is represented by the following formula (2d). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0058]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, and R ¹⁰ to R ¹⁴ are the same or different and represent a hydrogen atom or a methyl group.) Typical examples include the following compounds. However, the present invention is not limited to these. [2-15] α- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ¹⁰ = R ¹¹ = R ¹² = R ¹³
= R ¹⁴ = H) [2-16] α- (meth) acryloyloxy-α-methyl-γ-butyrolactone (R ^a = H or CH ₃ , R ¹⁰ = CH
₃ , R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = H) [2-17] α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ¹¹
= R ¹² = CH ₃ , R ¹⁰ = R ¹³ = R ¹⁴ = H) [2-18] α- (meth) acryloyloxy-α, β, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 10 = R 11}} = R 12 = CH 3, R 13 = R 14 = H) [2-19] α- ( meth) acryloyloxy-gamma, .gamma.-dimethyl -γ- butyrolactone (R ^a = H Or CH ₃ , R ^{13
_{= R 14 = CH 3, R}} 10 = R 11 = R 12 = H) [2-20] α- ( meth) acryloyloxy -α, γ, γ
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 10 = R 13}} = R 14 = CH 3, R 11 = R 12 = H) [2-21] α- ( meth) acryloyloxy-beta, beta,
γ, γ-tetramethyl-γ-butyrolactone (R ^a = H
Or CH ₃ , R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = CH ₃ , R ¹⁰ =
H) [2-22] α- (meth) acryloyloxy-α, β,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ¹⁰ = R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = C
H ₃ ) [Monomer unit of the formula (IIe)] A monomer corresponding to the monomer unit of the formula (IIe) is represented by the following formula (2e). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0060]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, and R ¹⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a polar substituent.) Typical examples include, but are not limited to, the following compounds. [2-23] (meth) acrylic acid (R ^a = H or CH ₃ , R ³³
= H) [2-24] Methyl (meth) acrylate (R ^a = H or C
H ₃ , R ¹⁵ = methyl group) [2-25] Ethyl (meth) acrylate (R ^a = H or C
H ₃ , R ¹⁵ = ethyl group) [2-26] Isopropyl (meth) acrylate (R ^a = H or CH ₃ , R ¹⁵ = isopropyl group) [2-27] n-butyl (meth) acrylate (R ^a = H or CH ₃ , R ¹⁵ = n-butyl group) [2-28] Cyclohexyl (meth) acrylate (R ^a = H
Or CH ₃ , R ¹⁵ = cyclohexyl group) [2-29] Decahydronaphthyl (meth) acrylate (R ^a
= H or CH ₃ , R ¹⁵ = decahydronaphthyl group) [2-29] norbornyl (meth) acrylate (R ^a = H or CH ₃ , R ¹⁵ = norbornyl group) [2-30] (meth) acrylic acid Isobornyl (R ^a = H or CH ₃ , R ¹⁵ = isobornyl group) [2-31] Adamantyl (meth) acrylate (R ^a = H or CH ₃ , R ¹⁵ = adamantyl group) [2-32] (Meth) Dimethyl adamantyl acrylate (R
^a = H or CH ₃ , R ¹⁵ = dimethyladamantyl group) [2-33] Tricyclo (meth) acrylate [5.2.1.
0 ^2,6 ] decyl (R ^a = H or CH ₃ , R ¹⁵ = tricyclo [5.2.1.0 ^2,6 ] decyl group) [2-34] Tetracyclo [meth] acrylate [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodecyl (R ^a = H or CH ₃ , R
¹⁵ = tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] The substituent of the dodecyl group) R ^15, hydroxyl group, a hydroxymethyl group, a carboxyl group, and an oxo group, but is not limited thereto. [Monomer unit of the formula (IIf)] The monomer corresponding to the monomer unit of the formula (IIf) is represented by the following formula (2f).

[0062]

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[2-35] Maleic anhydride [Monomer unit of the formula (IIg)] The monomer corresponding to the monomer unit of the formula (IIg) is represented by the following formula (2g). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0064]

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(In the above formula, R ¹⁶ to R ¹⁹ are the same or different and each represent a hydrogen atom or a methyl group. O, p and q each represent 0 or 1.) The following compounds are mentioned as typical examples. However, the present invention is not limited to these. [2-36] 4-oxatricyclo [5.2.1.0 ^2,6 ]
Decane-8-en-5-one ^{(R 18 = R 19 = H} , o = p
= 0, q = 1) [2-37] 3-oxatricyclo [5.2.1.0 ^2,6 ]
Decane-8-en-4-one (R ¹⁶ = R ¹⁷ = H, o = q
= 0, p = 1) [2-38] 5-oxatricyclo [6.2.1.0 ^2,7 ]
Undecane-9-en-6-one (R ¹⁸ = R ¹⁹ = H, o
= P = 0, q = 2) [2-39] 4-oxatricyclo [6.2.1.0 ^2,7 ]
Undecane-9-en-5-one ^{(R 16 = R 17 = R} 18 =
^{R 19 = H, o = 0} , p = q = 1) [2-40] 3- oxatricyclo [6.2.1.0 ^{2, 7]}
Undecane-9-en-4-one ^{(R 16 = R 17 = H} , o
= Q = 0, p = 2) [2-41] 11-oxapentacyclo [6.5.1.1]
^3,6 . 0 ^9,13 ] pentadecane-4-en-10-one (R ¹⁸ = R ¹⁹ = H, o = 1, p = 0, q = 1) [2-42] 10-oxapentacyclo [6.5. 1.1
^3,6 . 0 ^9,13 ] pentadecane-4-en-11-one (R ¹⁶ = R ¹⁷ = H, o = 1, p = 1, q = 0) [Monomer unit of the formula (IIh)] The monomer corresponding to the monomer unit is represented by the following formula (2h). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0066]

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(In the above formula, R ²⁰ represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or a carboxyl group; r represents 0 or 1.) Typical examples include the following compounds. It is not limited. [2-43] Norbornene ^{(R 20 = H, r =} 0) [2-44] 5- hydroxy-2-norbornene (R ²⁰ = O
H, r = 0) [2-45 ] 5- carboxy-2-norbornene (R ²⁰ = C
OOH, r = 0) [Monomer unit of the formula (IIi)] A monomer corresponding to the monomer unit of the formula (IIi) is represented by the following formula (2i). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0068]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, and R ²¹ to ²⁹ each represent a hydrogen atom, a methyl group or an ethyl group.) As typical examples, the following compounds may be mentioned. It is not limited. [2-46] 6- (meth) acryloyloxy-2-oxabicyclo [2.2.2] octan-3-one (R ^a = H
Or CH ₃ , R ²¹ = R ²² = R ²³ = R ²⁴ = R ²⁵ = R ²⁶ = R
²⁷ = R ²⁸ = R ²⁹ = H) [2-47] 6- (meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octan-3-one ( ^Ra = H or CH ₃ , R ²¹ = R ²² = R ²⁴ = R ²⁵ = R ^{26
= R 27 = R 28 = R} 29 = H, R 23 = CH 3) [2-48] 6- ( meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octan-3 on (R ^a = H or _{^{CH 3, R 21 = R 22}} = R 23 = R 25 = R 26
^{= R 27 = R 28 = R} 29 = H, R 24 = CH 3) [2-49] 6- ( meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane -
3-one (R ^a = H or CH ₃ , R ²¹ = R ²² = R ²⁵ = R ²⁶
= R ²⁷ = R ²⁸ = R ²⁹ = H, R ²³ = R ²⁴ = CH ₃ ) [Monomer unit of the formula (IIj)] The monomer corresponding to the monomer unit of the formula (IIj) is represented by the following formula (2j). Is done. When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0070]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, and R ³⁰ to R ³⁸ each represent a hydrogen atom, a methyl group or an ethyl group.) Representative examples include the following compounds. It is not limited. [2-50] 4- (meth) acryloyloxy-6-oxabicyclo [3.2.1] octan-7-one (R ^a = H
Or CH ₃ , R ³⁰ = R ³¹ = R ³² = R ³³ = R ³⁴ = R ³⁵ = R
³⁶ = R ³⁷ = R ³⁸ = H) [2-51] 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one ( ^Ra = H or CH ₃ , R ³⁰ = R ³¹ = R ³³ = R ³⁴ = R ^{35
= R 36 = R 37 = R} 38 = H, R 32 = CH 3) [2-52] 4- ( meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octane-7 on (R ^a = H or _{^{CH 3, R 30 = R 31}} = R 32 = R 34 = R 35
^{= R 36 = R 37 = R} 38 = H, R 34 = CH 3) [2-53] 4- ( meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane -
7-one (R ^a = H or CH ₃ , R ³⁰ = R ³¹ = R ³⁴ = R ³⁵
= R ³⁶ = R ³⁷ = R ³⁸ = H, R ³² = R ³³ = CH ₃ ) The monomers (IIi) and (IIj) are obtained by starting from a hydrocarbon having a conjugated double bond such as isoprene and acrylic acid as starting materials. Manufactured. The aforementioned monomers [2-47] and [2-51]
Will be described as an example. These two monomers are isomers having different substitution positions and are synthesized simultaneously. Using isoprene and acrylic acid as raw materials, cyclohexene having a substituent of a methyl group and a carboxyl group (hereinafter referred to as methylcyclohexene carboxylic acid) is synthesized by a Diels-Alder reaction. The reaction temperature at this time is not particularly limited, but is preferably about 50 to 150 ° C. Methylcyclohexene carboxylic acid synthesized by the Diels-Alder reaction has a double bond of the cyclohexene ring epoxidized by a peroxide such as hydrogen peroxide or peracetic acid, and a carboxyl group bonded to the cyclohexene ring is further converted to an epoxy group. And a hydroxyl group is formed while forming a lactone ring. This compound is 6-hydroxy-6
-Methyl-2-oxabicyclo [2.2.2] octan-3-one and 4-hydroxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one. In this reaction, a metal compound such as tungstic acid can be used as a catalyst.When an acid catalyst such as sulfuric acid or hydrogen peroxide is used as a peroxide, an organic acid such as acetic acid is used in the reaction system. And the reaction via an organic peracid is also effective. By reacting the synthesized mixture with a (meth) acrylic acid derivative, a mixture of the aforementioned monomers is obtained. The reaction with the (meth) acrylic acid derivative is a normal esterification reaction.
When (meth) acrylic acid is used as the (meth) acrylic acid derivative, it is a dehydration reaction using an acid catalyst, and when an ester such as methyl (meth) acrylate is used, the ester is also used as an acid catalyst. It is an exchange reaction.
Also, when using (meth) acrylic acid chloride,
A desired (meth) acrylate is obtained by a dehydrochlorination reaction with an alkyl metal compound such as butyllithium or an organic base such as triethylamine. These two esters may be used as a mixture, or may be used after being separated by column chromatography or the like. [Monomer unit of the formula (IIIa)] A monomer corresponding to the monomer unit of the formula (IIIa) is represented by the following formula (3a). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0072]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, R ³⁹ and R ⁴⁰ are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ⁴¹ to ⁴³ are the same. Or, differently, it represents a hydrogen atom, a hydroxyl group or a methyl group.) Representative examples include, but are not limited to, the following compounds. [3-1] 1- (1- (meth) acryloyloxy-1-
Methylethyl) adamantane (R ^a = H or CH _3, R ^{39
_{= R 40 = CH 3, R}} 41 = R 42 = R 43 = H) [3-2] 1- hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ^a =
H or _{^{CH 3, R 39 = R 40}} = CH 3, R 41 = OH, R 42 =
R ⁴³ = H) [3-3] 1- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane (R ^a = H or CH ₃ , R
_{^{39 = R 40 = CH 2 CH}} 3, R 41 = R 42 = R 43 = H) [3-4] 1- hydroxy-3- (1-ethyl-1- (meth) acryloyloxy propyl) adamantane (R ^a
ＨH or CH ₃ , R ³⁹ ＲR ⁴⁰ CH ₂ CH ₃ , R ⁴¹ ＯO
H, ^R42 = ^R43 = H) [3-5] 1- (1- (meth) acryloyloxy-1-)
Methylpropyl) adamantane (R ^a = H or CH ₃ , R
_{^{39 = CH 3, R 40 =}} CH 2 CH 3, R 41 = R 42 = R 4 3 =
H) [3-6] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R ^a
ＨH or CH ₃ , R ³⁹ ＣＨCH ₃ , R ⁴⁰ ＣＨCH ₂ CH ₃ , R ⁴¹
= OH, R ⁴² = R ⁴³ = H) [3-7] 1- (1- (meth) acryloyloxy-1,
2-dimethylpropyl) adamantane ( ^Ra = H or C
H ₃ , R ³⁹ = CH ₃ , R ⁴⁰ = CH (CH ₃ ) ₂ , R ⁴¹ = R ^{42
= R 43 = H) [3-8} ] 1- hydroxy-3- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ^a = H or _{^{CH 3, R 39 = CH 3}} , R ⁴⁰ = CH (C
^{_{H 3) 2, R 41 =}} OH, R 42 = R 43 = H) [3-9] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ^a = H or CH ₃ , R ³⁹ = R ⁴⁰ = CH ₃ , R ⁴¹ = R ⁴²
= OH, R ⁴³ = H) [3-10] 1,3-dihydroxy-5- (1-ethyl-1)
- (meth) acryloyloxy propyl) adamantane (R ^a = H or _{^{CH 3, R 39 = R 40}} = CH 2 CH 3, R 41 =
R ⁴² = OH, R ⁴² = H) [3-11] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R ^a = H or CH ₃ , R ³⁹ = CH ₃ , R ⁴⁰ = CH ₂ C
_{^{H 3, R 41 = R 42}} = OH, R 43 = H) [3-12] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ^a = H or CH ₃ , R ³⁹ = CH ₃ , R ⁴⁰ = CH
(CH ₃ ) ₂ , R ⁴¹ = R ⁴² = OH, R ⁴³ = H [Monomer unit of the formula (IIIb)] A monomer corresponding to the monomer unit of the formula (IIIb) is represented by the following formula (3b). . When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0074]

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(In the above formula, R ^a represents a hydrogen atom or a methyl group, R ⁴⁴ and R ⁴⁵ are the same or different and represent a hydrogen atom, a hydroxyl group or —COOR ⁴⁶ , and R ⁴⁶ is a t-butyl group. , 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group or 2-oxepanyl group.) Representative examples include the following compounds, but are not limited thereto. [3-13] 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane (R ^a = H or CH ₃ , R
⁴⁴ = R ⁴⁵ = H, R ⁴⁶ = t-butyl group) [3-14] 1,3-bis (t-butoxycarbonyl) -5
-(Meth) acryloyloxyadamantane ( ^Ra = H
Or ^{_{CH 3, R 44 = CO-}} O-C (CH 3) 3, R 45 =
H, R ⁴⁶ = t-butyl group) [3-15] 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane ( ^Ra
= H or CH ₃ , R ⁴⁴ = OH, R ⁴⁵ = H, R ⁴⁶ = t-butyl group) [3-16] 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane ( R ^a = H or CH ₃ , R ⁴⁴ = R ⁴⁵ = H, R ⁴⁶ = 2-tetrahydropyranyl group) [3-17] 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meta ) acryloyloxyadamantane (R ^a = H or CH _3, R ⁴⁴ = 2- tetrahydropyranyloxy ^{group, R 45 = H, R 46} = 2- tetrahydropyranyl group) [3-18] 1- (2- tetrahydropyranyloxy carbonyl) -3-hydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or ^{_{CH 3, R 44 = OH,}} R
⁴⁵ = H, the monomers corresponding to the monomer units of the R ⁴⁶ = 2-tetrahydropyranyl group) Formula [monomer units of formula (IIIc)] (IIIc) is expressed by the following formula (3c). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0076]

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[0077] (In the above formula, R ^a represents a hydrogen atom or a methyl group, R ⁴⁷ represents a methyl group or an ethyl group, R ⁴⁸
And R ⁴⁹ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group. Representative examples include, but are not limited to, the following compounds. [3-19] 2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R ⁴⁷ = CH ₃ , R ^{48
= R 49 = H) [3-20} ] 1- hydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ^a = H or CH _3, R
⁴⁷ ＣＨCH ₃ , R ⁴⁸ = 1-OH, R ⁴⁹ ） H) [3-21] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane ( ^Ra = H or CH ₃ , R
⁴⁷ = CH ₃ , R ⁴⁸ = 5-OH, R ⁴⁹ = H) [3-22] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane ( ^Ra = H or C
_{^{H 3, R 47 = CH 3}} , R 48 = 1-OH, R 49 = 3-OH) [3-23] 1,5- dihydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ^a = H or C
_{^{H 3, R 47 = CH 3}} , R 48 = 1-OH, R 49 = 5-OH) [3-24] 1,3- dihydroxy-6 (meth) acryloyloxy-6-methyl-adamantane (R ^a = H or C
_{^{H 3, R 47 = CH 3}} , R 48 = 1-OH, R 49 = 3-OH) [3-25] 2- ( meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R ⁴⁷ = CH ₂ CH ₃ ,
R ⁴⁸ = R ⁴⁹ = H) [3-26] 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R ^a = H or CH ₃ , R
⁴⁷ ＣＨCH ₂ CH ₃ , R ⁴⁸ = 1-OH, R ⁴⁹ ＨH) [3-27] 5-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane ( ^Ra = H or CH ₃ , R
⁴⁷ = CH ₂ CH ₃ , R ⁴⁸ = 5-OH, R ⁴⁹ = H) [3-28] 1,3-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R ^a = H or C
_{^{H 3, R 47 = CH 2}} CH 3, R 48 = 1-OH, R 49 = 3-
OH) [3-29] 1,5-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R ^a = H or C
_{^{H 3, R 47 = CH 2}} CH 3, R 48 = 1-OH, R 49 = 5-
OH) [3-30] 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane (R ^a = H or C
_{^{H 3, R 47 = CH 2}} CH 3, R 48 = 1-OH, R 49 = 3-
OH) [Monomer unit of formula (IIId)] A monomer corresponding to the monomer unit of formula (IIId) is represented by the following formula (3d). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0078]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, and R ⁵⁰ represents a tertiary hydrocarbon group which may have a substituent.) Typical examples include the following compounds. However, the present invention is not limited to these. [3-31] t-butyl (meth) acrylate (R ^a = H or CH ₃ , R ⁵⁰ = t-butyl group) [Monomer unit of formula (IIIe)] Monomer corresponding to the monomer unit of formula (IIIe) Is represented by the following formula (3e). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0080]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, and m represents an integer of 1 to 3.) Representative examples include the following compounds, but are not limited thereto. . [3-32] 2-Tetrahydropyranyl (meth) acrylate (R ^a = H or CH ₃ , m = 2) [3-33] 2-Tetrahydrofuranyl (meth) acrylate (R ^a = H or CH ₃ , m = 1) [Monomer unit of formula (IIIf)] A monomer corresponding to the monomer unit of formula (IIIf) is represented by the following formula (3f). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0082]

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(In the above formula, Ra represents ^a hydrogen atom or a methyl group, and R ⁵¹ to ⁵⁵ are the same or different and represent a hydrogen atom or a methyl group.) Typical examples include the following compounds. However, the present invention is not limited to these. [3-34] β- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ⁵¹ = R ⁵² = R ⁵³ = R ⁵⁴
= R ⁵⁵ = H) [3-35] β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ⁵¹
= R ⁵² = CH ₃ , R ⁵³ = R ⁵⁴ = R ⁵⁵ = H) [3-36] β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ⁵⁴
= R ⁵⁵ = CH ₃ , R ⁵¹ = R ⁵² = R ⁵³ = H) [3-37] β- (meth) acryloyloxy-α, α, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 51 = R 52}} = R 53 = CH 3, R 54 = R 55 = H) [3-38] β- ( meth) acryloyloxy-beta, gamma, gamma
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 53 = R 54}} = R 55 = CH 3, R 51 = R 52 = H) [3-39] β- ( meth) acryloyloxy-.alpha., alpha,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ⁵¹ = R ⁵² = R ⁵³ = R ⁵⁴ = R ⁵⁵ = C
H ₃ ) [Monomer unit of formula (IIIg)] A monomer corresponding to the monomer unit of formula (IIIg) is represented by the following formula (3g). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

[0084]

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(In the above formula, R^aIs a hydrogen atom or methyl
And R represents⁵⁶Is a secondary hydrocarbon which may have a substituent
Group, 2-tetrahydrofuranyl group, 2-tetrahydro
It represents a pyranyl group or a 2-oxepanyl group. n is 0 or
1 is shown. Representative examples include the following compounds.
It is not limited. [2-40] 5-t-butoxycarbonylnorbornene (R
⁵⁶= T-butyl group, n = 0) [2-41] 9-t-butoxycarbonyltetracyclo
[6.2.1.1^3,6. 0^2,7] Dodeca-4-ene (R⁵⁶
= T-butyl group, n = 1) [2-42] 5- (2-tetrahydropyranyloxycarbo)
Nyl) norbornene (R ⁵⁶= T-butyl group, n = 0) [2-41] 9- (2-tetrahydropyranyloxycarbo)
Nyl) tetracyclo [6.2.1.1^3,6. 0^2,7] Dode
Car-4-ene (R⁵⁶= T-butyl group, n = 1) The resin composition for photoresist of the present invention is the same as that of the present invention
Including polymer compound for photoresist and photoacid generator
I have.

Examples of the photoacid generator include conventional or known compounds which efficiently generate an acid upon exposure to light, such as diazonium salts, iodonium salts (eg, diphenyliodohexafluorophosphate), and sulfonium salts (eg, triphenylsulfonium). Hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonic acid ester [for example, 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1
-Benzoylmethane, 1,2,3-trisulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl)
-1-hydroxy-1-benzoylmethane, etc.], oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (eg, diphenyldisulfone), imide compounds, oxime sulfonates, diazonaphthoquinone, benzoin tosylate, and the like. These photoacid generators can be used alone or in combination of two or more.

The amount of the photoacid generator used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each monomer unit in the polymer compound, and the like. For example, based on 100 parts by weight of the polymer compound 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.

The resin composition for a photoresist includes an alkali-soluble component such as an alkali-soluble resin (eg, a novolak resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a coloring agent (eg, a dye), and an organic solvent. (Eg, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof, and the like). May be.

After coating the photoresist resin composition on a substrate or substrate and drying, the coating film (resist film) is exposed to a light beam (or further baked after exposure) through a predetermined mask. The fine pattern can be formed with high precision by forming a latent image pattern and then developing.

As the substrate or substrate, a silicon wafer,
Examples include metal, plastic, glass, and ceramic. The application of the resin composition for a photoresist can be performed using a conventional application means such as a spin coater, a dip coater, and a roller coater. The thickness of the coating film is, for example, about 0.1 to 20 μm, and preferably about 0.3 to 2 μm.

Light of various wavelengths, for example, ultraviolet rays and X-rays can be used for exposure. For semiconductor resists, g-rays, i-rays, and excimer lasers (for example, XeC
1, KrF, KrCl, ArF, ArCl, etc.) are used. Exposure energy is, for example, 1 to 1000 m
J / cm ² , preferably about 10 to 500 mJ / cm ² . Upon irradiation with light, an acid is generated from the photoacid generator, and the acid quickly removes a protecting group (leaving group) such as a carboxyl group of the alkali-soluble unit of the polymer compound, thereby contributing to solubilization. A carboxyl group is generated. Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developing solution.

[0092]

According to the present invention, a polymer compound using fluorenone as a starting material has an economical advantage, and furthermore, has a high transparency and an alkali-soluble function, and has a high etching property. Resistance can be expected, and Ar
F to activate next-generation semiconductor development.

[0093]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. In the first half of the synthesis example, the synthesis example of the polymerizable compound newly proposed in the present invention is described, in the second half, the example of the polymer compound using the polymerizable compound is applied, and further, the semiconductor is formed from the polymer compound as a resist material. An application example of is shown. Synthesis Example 1 Synthesis of 2-hydroxy-tricyclo [7.4.0.0 ^3,8 ] tridecane In a pressure vessel equipped with a stirrer and a hydrogen gas inlet tube, 18.2 g (0.10 mol) of fluorenone was added to methanol 20.
It was dissolved in 0 ml and charged, and 10 g of a 5% ruthenium carbon-supported catalyst (hereinafter referred to as 5% Ru-carbon) was added.
After replacing the inside with hydrogen, a hydrogen pressure of 50 Pa at 120 ° C.
For 2 hours. After cooling to room temperature, the reacted solution was filtered and charged again into a pressure vessel equipped with a stirrer and a hydrogen gas inlet tube, and 10 g of Raney Ni catalyst was charged. The reaction was carried out at a hydrogen pressure of 50 Pa and a temperature of 80 ° C. for 2 hours, and after cooling to room temperature, filtration was performed. The filtered liquid was transferred to an evaporator, and methanol was removed under reduced pressure of 100 to 150 mmHg. 14.5 g of 2-hydroxy-tricyclo [7.4.0.0 ^3,8 ] tridecane having a purity of 97% (0.
075 mol). The yield was 75%. ¹ H-
In NMR (in DMSO-d6) analysis, 1.4 ppm
(8H, m), 1.5 ppm (8H, m), 2.1 pp
m (2H, m), 2.6 ppm (2H, m), 4.5 p
A signal of pm (1H, m) was observed. Synthesis Example 2 2-methacryloyloxy-tricyclo [7.4.0.
0 ^3,8 ] tridecane 2 flasks equipped with dropping funnel, condenser and stirrer
-Hydroxy-tricyclo [7.4.0.0 ^3,8 ] tridecane 15.2 g (0.078 mol), triethylamine 27 g (0.27 mol) and toluene 88 g were added, and 50
20. methacrylic chloride containing 400 ppm of hydroquinone monomethyl ether while controlling the temperature at 20 ° C.
3 g (0.19 mol) was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 50 ° C. for 24 hours. When the liquid after the reaction was analyzed by gas chromatography, 2-methacryloyloxy-tricyclo [7.4.0.0 ^3,8 ] tridecane was produced in a yield of 17.8 g (0.068 mol), 87%. I was The reaction solution was subjected to column chromatography to separate the desired product. ¹ H-NMR (in DMSO-d6)
The analysis revealed 1.4 ppm (8H, m) and 1.5 ppm (8 H, m).
H, m), 2.0 ppm (3H, s), 2.1 ppm
(2H, m), 3.3 ppm (2H, m), 5.3 pp
m (1H, m), 5.6 ppm (1H, d), 6.0p
A signal of pm (1H, d) was observed. Synthesis Example 3 Synthesis of 9-hydroxy-9-methylfluorene In a flask equipped with a dropping funnel, a condenser and a stirrer, 36.4 g (0.20 mol) of fluorenone and 60 g of tetrahydrofuran were added, and the temperature was controlled at 50 ° C. or lower. tetrahydrofuran solution 122g of methyl magnesium bromide _{(CH 3 MgBr) (CH 3} 0.2 as MgBr
25 mol) in about 1 hour. Then 60
Continue stirring at 1 ° C. for 1 hour and cool the contents to room temperature.

In a flask equipped with a dropping funnel, a condenser and a stirrer, 100 ml of a 10% aqueous sulfuric acid solution was added, and the temperature of the reaction mixture obtained above was reduced to about 1 under a nitrogen gas atmosphere while controlling the temperature to 10 ° C. or lower. Drop in time. Then 5
Neutralize with caustic soda and concentrate with an evaporator at normal pressure until the internal temperature reaches 100 ° C. 200 ml of toluene
And 200 ml of water were added, and the mixture was stirred and mixed.
Separate the lower layer. After the upper layer is further washed with 200 ml of water, the upper layer is transferred to an evaporator and concentrated under reduced pressure. 55 g of a concentrated liquid was obtained and contained 31.0 g (0.156 mol) of 9-hydroxy-9-methylfluorene. Synthesis Example 4 2-Hydroxy-2-methyltricyclo [7.4.0.
[0 ^3,8 ] Tridecane The total amount of the liquid obtained in Synthesis Example 3 and 200 ml of methanol are mixed and charged into a pressure vessel equipped with a stirrer and a hydrogen gas inlet tube. Further, 20 g of 5% Ru-carbon was added. After replacing the inside with hydrogen, at 120 ° C. and a hydrogen pressure of 50
The reaction was performed at Pa for 2 hours. After cooling to room temperature, the reacted solution was filtered, charged again into a pressure vessel equipped with a stirrer and a hydrogen gas inlet tube, and charged with 20 g of Raney Ni catalyst. The reaction is performed at a hydrogen pressure of 50 Pa and a temperature of 80 ° C. for 2 hours.
After cooling to room temperature, it was filtered. The filtered liquid was transferred to an evaporator, and methanol was removed under reduced pressure of 100 to 150 mmHg. 2-hydroxy-2-methyltricyclo [7.4.0.0 ^3,8 ] tridecane having a purity of 97% is 2
6.0 g (0.125 mol) were obtained. The yield based on fluorenone used in Synthesis Example 3 was 62.5%. ¹
1.4 ppm by H-NMR (in DMSO-d6) analysis
(11H, m), 1.5 ppm (8H, m), 2.1p
A signal of pm (2H, m) and 2.7 ppm (2H, m) was observed. Synthesis Example 5 2-methacryloyloxy-2-methyltricyclo
Synthesis of [7.4.0.0 ^3,8 ] tridecane A flask equipped with a dropping funnel, a condenser and a stirrer was charged with 2
-Hydroxy-2-methyltricyclo [7.4.0.0
^3,8 ] tridecane 16.3 g (0.078 mol), triethylamine 27 g (0.27 mol), toluene 88 g, and while controlling the temperature at 50 ° C., 20.3 g of methacrylic acid chloride containing 400 ppm of hydroquinone monomethyl ether. (0.19 mol) was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 50 ° C. for 24 hours. When the liquid after the reaction was analyzed by gas chromatography, 2-methacryloyloxy-2-methyltricyclo was obtained.
[7.4.0.0 ^3,8 ] tridecane 16.5 g (0.0
(60 mol) with a yield of 77%. The reaction solution was subjected to column chromatography to separate the desired product. ¹ H-NM
R (in DMSO-d6) 1.4 ppm (8H,
m), 1.5 ppm (8H, m), 2.0 ppm (3
H, s), 2.1 ppm (5H, m), 3.4 ppm
(2H, m), 5.6 ppm (1H, d), 6.0 pp
m (1H, d) signal was observed. Example 1 Synthesis of polymer compound having the following structure

[0095]

Embedded image

[0096] A 10-tube equipped with a reflux tube, stirrer and 3-way cock
In a 0 ml round bottom flask, 13.0 g (47.1 mmol) of monomer [1-2] (methacrylate) and monomer [2
-13] (methacrylate) 7.0 g (31.5 mmol
l) and initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 80 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction mixture was prepared as a 9: 1 mixture of hexane and ethyl acetate (1000 m).
and purified by filtering off the resulting precipitate. The collected precipitate was dried under reduced pressure, dissolved again in 80 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 16.2 g of a desired resin. GPC analysis of the recovered polymer showed a weight average molecular weight of 880.
0 and the molecular weight distribution was 1.98. ¹ H-NMR (D
In MSO-d6) analysis, in addition to 1.5 to 2.5 ppm (broad), 3.1 ppm, 3.4 ppm, 4.6
A strong signal at ppm was observed. Example 2 Synthesis of polymer compound having the following structure

[0097]

Embedded image

[0098] A 10-tube equipped with a reflux pipe, a stirrer and a three-way cock
In a 0 ml round bottom flask, 11.0 g (40.0 mmol) of monomer [1-2] (methacrylate) and monomer [2
-1] (methacrylate) 3.7 g (15.7 mmol)
l), monomer [2-13] (methacrylate) 5.3
g (23.8 mmol) and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and tetrahydrofuran 8
0 g was dissolved. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and under a nitrogen atmosphere,
Stir for 6 hours. The reaction solution was mixed with hexane and ethyl acetate 9:
One mixture was dropped into 1000 ml, and the resulting precipitate was separated by filtration for purification. The recovered precipitate was dried under reduced pressure, dissolved again in 80 g of tetrahydrofuran, and 15.1 g of the desired resin was obtained by repeating the above-mentioned precipitation purification operation. GPC analysis of the recovered polymer revealed a weight average molecular weight of 7,500 and a molecular weight distribution of 1.88. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.
5 to 2.5 ppm (broad), 3.1 ppm,
Strong signals were observed at 3.4 ppm, 4.6 ppm, and 4.7 ppm.

Test Example 100 parts by weight of the polymer obtained in the example and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with ethyl lactate as a solvent to give a polymer concentration of 17%.
A weight percent of a photoresist resin composition was prepared. The photoresist resin composition was applied to a silicon wafer by spin coating to form a photosensitive layer having a thickness of 1.0 μm. 15 on a hot plate at 100 ° C
After pre-baking for 0 second, using a KrF excimer laser having a wavelength of 247 nm, a dose of 30 mJ was applied through a mask.
/ Cm ² , and post-baked at a temperature of 100 ° C. for 60 seconds. Subsequently, the film was developed with a 0.3 M aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water. In each case, a line and space pattern of 0.30 μm was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/08 C08F 232/08 C08K 5/00 C08K 5/00 C08L 33/04 C08L 33/04 G03F 7 / 027 G03F 7/027 7/039 601 7/039 601 H01L 21/027 H01L 21/30 502R F-term (reference) 2H025 AA01 AA02 AA09 AA14 AB16 AC04 AC08 AD03 BC13 BC34 BE00 BE10 BG00 CB08 CB10 CB14 4CB46 4B006A01 BG031 BG071 BH021 BK001 EB116 EQ016 EU186 EV246 EV326 EW176 FD206 GP03 4J100 AJ02Q AJ02R AK32Q AL01Q AL08P AL08Q AL08R AQ01Q AR09Q BA11Q BA11R BA20Q BA20R BC07P BC09Q BC09R BC53Q BC53 CA04

Claims (8)

[Claims] [Claim 1] The following formula (1) (In the above formula, Ra represents ^a hydrogen atom or a methyl group,
R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms). 2. The following formula (I): (In the above formula, Ra represents ^a hydrogen atom or a methyl group,
R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms), and at least one monomer unit represented by the formula (I): 3. At least one monomer unit selected from the monomer units represented by the formula (I) and the following formulas (IIa) to (IIj): (In the above formula, Ra represents ^a hydrogen atom or a methyl group,
R ² and R ³ are the same or different and represent a hydrogen atom, a hydroxyl group or a carboxyl group, and R ⁴ represents a hydroxyl group, an oxo group or a carboxyl group. X ¹ to X ³ are the same or different and represent —CH ₂ — or —CO—O—.
R ⁵ to R ⁷ are the same or different and each represent a hydrogen atom or a methyl group. R ⁸ and R ⁹ are the same or different and each represent a hydrogen atom or a methyl group. R ¹⁰ to R ¹⁴ are the same or different and each represent a hydrogen atom or a methyl group. R ¹⁵ represents a hydrogen atom or a linear, branched, cyclic or bridged cyclic hydrocarbon having 1 to 20 carbon atoms which may have a polar substituent. R ¹⁶ to R ¹⁹ are the same or different and each represent a hydrogen atom or a methyl group. R ²⁰ represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group, or a carboxyl group. R ²¹ to ³⁸ each represent a hydrogen atom, a methyl group or an ethyl group. o, p, q and r each represent 0 or 1. The polymer compound for a photoresist according to claim 2, comprising at least one monomer unit selected from the group consisting of: 4. At least one monomer unit selected from the monomer units represented by the formula (I) and the following formulas (IIIa) to (IIIg): (In the above formula, Ra represents ^a hydrogen atom or a methyl group,
R ³⁹ and R ⁴⁰ are the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, R ⁴¹ ~ ⁴³ are the same or different and each represents a hydrogen atom, a hydroxyl group or a methyl group, R ⁴⁴ and R
⁴⁵ are the same or different, a hydrogen atom, a hydroxyl group or -COOR ^46, R ⁴⁶ is t- butyl, 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group, R ⁴⁷ Represents a methyl group or an ethyl group, R ⁴⁸ and R ⁴⁹ are the same or different and each represent a hydrogen atom, a hydroxyl group or an oxo group, and R ⁵⁰ represents a tertiary hydrocarbon group which may have a substituent. And R ⁵¹ to ⁵⁵ are
The same or different and each represents a hydrogen atom or a methyl group, R ⁵⁶
Is an optionally substituted tertiary hydrocarbon group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group or 2
-Represents an oxepanyl group. m represents an integer of 1 to 3, and n
Represents 0 or 1. The polymer compound for a photoresist according to claim 2, comprising at least one monomer unit selected from the monomer units represented by (3). 5. At least one monomer unit selected from the monomer units represented by the formula (I):
To (IIj), and at least one monomer unit selected from the monomer units represented by the formulas (IIIa) to (IIIg). The polymer compound for a photoresist according to the above. 6. A photoresist resin composition comprising at least the polymer compound for a photoresist according to claim 2 and a photoacid generator. 7. A method for producing a semiconductor, comprising: applying the photoresist resin composition according to claim 6 onto a substrate or a substrate to form a resist coating film, and exposing and developing to form a pattern. 8. A method for producing the compound represented by the formula (1).