JP2002351078A - Polymer compound for photoresist and photosensitive resin composition - Google Patents

Abstract

(57) Abstract: A polymer compound having high etching resistance when used for a photoresist is obtained. SOLUTION: The following formulas (Ia) and (Ib) (Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms,
A hydroxyl group which may be protected by a protecting group, -CO
OR ³ group, etc. R ³ represents a hydrogen atom, a tertiary hydrocarbon group which may have a substituent, a tetrahydrofuranyl group, or the like. Y represents a monovalent alicyclic group which may have a substituent. n represents 0, 1 or 2. R ² is a hydrogen atom,
And a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group which may be protected by a protecting group, and the like. L represents a 5- or more-membered lactone ring which may have a substituent. Wherein the norbornane ring in the formula may have a substituent in addition to the substituents shown in the formula).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer compound useful as a polymer for a photoresist or the like used in microfabrication of a semiconductor, a novel norbornene derivative useful as a raw material of the polymer compound, The present invention relates to a photoresist resin composition containing a molecular compound, and a method for producing a semiconductor.

[0002]

2. Description of the Related Art Positive photoresists used in a semiconductor manufacturing process have properties such as a property that an irradiated portion changes to alkali-soluble by light irradiation, adhesion to a silicon wafer, plasma etching resistance, and transparency to light used. Must have both. The positive photoresist is generally used as a solution containing a polymer as a main component, a photoacid generator, and several kinds of additives for adjusting the above properties. Is
It is extremely important that the polymer as the base agent has the above-mentioned properties in a well-balanced manner.

The exposure light source for lithography used in the manufacture of semiconductors is becoming shorter and shorter each year, and an ArF excimer laser having a wavelength of 193 nm is expected as a next-generation exposure light source. It has been proposed to use a unit containing an alicyclic hydrocarbon skeleton having high transparency to the wavelength and etching resistance as a monomer unit of a resist polymer used in the ArF excimer laser exposure machine. However, even if a conventional monomer unit containing an alicyclic hydrocarbon skeleton is incorporated into a resist polymer, sufficient etching resistance has not always been obtained.

[0004]

Accordingly, an object of the present invention is to provide a polymer compound which exhibits high etching resistance when used as a photoresist, and a novel norbornene derivative useful as a monomer of the polymer compound. Is to do. Another object of the present invention is to provide a polymer compound which can form a fine pattern with high accuracy when used for a photoresist, and a novel norbornene derivative useful as a monomer of the polymer compound. It is another object of the present invention to provide a polymer compound for a photoresist having a good balance between adhesion to a substrate, transparency, alkali solubility and etching resistance. Still another object of the present invention is to provide a photoresist resin composition capable of forming a fine pattern with high accuracy, and a method of manufacturing a semiconductor.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a norbornane ring to which an acyl group containing an alicyclic carbon ring is bonded or a norbornane ring to which a lactone ring is bonded are mainly used. When the polymer incorporated in the chain is used as a photoresist resin, the etching resistance is remarkably improved, and for example, by combining with a monomer unit having another function, it has been found that a fine pattern can be accurately formed, and the present invention has been completed. .

That is, the present invention provides the following formulas (Ia) and (Ib)

Embedded image (Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms,
A hydroxyl group optionally protected by a protecting group, a hydroxymethyl group optionally protected by a protecting group, or -CO
Represents an OR ³ group. R ³ represents a hydrogen atom, a tertiary hydrocarbon group which may have a substituent, a tetrahydrofuranyl group or a tetrahydropyranyl group. Y represents a monovalent alicyclic group which may have a substituent. n represents 0, 1 or 2. R ² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A hydroxyl group which may be protected with a protecting group or a hydroxymethyl group which may be protected with a protecting group.
L represents a 5- or more-membered lactone ring which may have a substituent. The norbornane ring in the formula may have a substituent in addition to the substituent shown in the formula) to provide a polymer compound containing at least one monomer unit selected from the group.

The polymer compound comprises at least one monomer unit selected from the above formulas (Ia) and (Ib) and the following formulas (IIa) to (IIo)

Embedded image

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹¹ and R ¹² are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ^{13 to} R ¹⁵ are the same or different. , Hydrogen atom,
It represents a methyl group or a hydroxyl group which may be protected by a protecting group. R ^{16 to} R ¹⁸ are the same or different and represent a hydrogen atom, a methyl group, a hydroxyl group which may be protected by a protecting group, or a —COOR ^b group. R ¹⁹ represents a methyl group or an ethyl group, R ²⁰ and R ²¹ are the same or different,
It represents a hydrogen atom, a hydroxyl group or an oxo group which may be protected by a protecting group. R ²² is a hydrogen atom or a carbon number of 1 to
Shows 10 hydrocarbon groups. R ²³ represents a tertiary hydrocarbon group which may have a substituent. R ²⁴ to R ²⁸ are the same or different, represent a hydrogen atom or a methyl group. R ^{29 to} R
³³ is the same or different and represents a hydrogen atom or a methyl group. R ³⁴ to R ³⁶ are the same or different and each represents a hydrogen atom or a methyl group, V ¹ ~V ³ are the same or different, -CH
_{It represents 2-} , -CO- or -COO-. R ³⁷ and R
³⁹ is the same or different and represents a hydrogen atom or a methyl group, and R ³⁸ represents a hydrogen atom, a methyl group, a hydroxyl group which may be protected by a protecting group, or a -COOR ^b group. R
⁴⁰ to R ⁴⁸ are the same or different, represent a hydrogen atom, a methyl group or an ethyl group. R ^{49 to} R ⁵⁷ are the same or different,
Represents a hydrogen atom, a methyl group or an ethyl group. R ⁵⁸ and R ⁵⁹
Is the same or different and represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyl group optionally protected by a protecting group, a hydroxymethyl group optionally protected by a protecting group, or a -COOR ^b group. Show. R ⁵⁸ and R ⁵⁹ may combine with each other to form a hydrocarbon ring, an acid anhydride ring or a lactone ring with two adjacent carbon atoms. p represents an integer of 1 to 3, and q represents 0 or 1. R ^b represents a hydrogen atom, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxepanyl group, a lower alkyl group or a tertiary hydrocarbon group which may have a substituent. Units may be included.

The value of the solubility parameter of the polymer compound according to the Fedors method is, for example, 19.5 to 2
It is in the range of 4.5 (J / cm ³ ) ^1/2 . The above polymer compound can be used as a polymer compound for a photoresist.

The present invention also provides a photosensitive resin composition containing at least the above polymer compound for a photoresist and a photoacid generator.

[0010] The present invention further provides a resist coating film by applying the above-mentioned photosensitive resin composition on a substrate or substrate.
Provided is a method of manufacturing a semiconductor including a step of forming a pattern through exposure and development.

The present invention further relates to the following formula (Ia) or (Ib)

Embedded image (Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms,
A hydroxyl group optionally protected by a protecting group, a hydroxymethyl group optionally protected by a protecting group, or -CO
Represents an OR ³ group. R ³ represents a hydrogen atom, a tertiary hydrocarbon group which may have a substituent, a tetrahydrofuranyl group or a tetrahydropyranyl group. Y represents a monovalent alicyclic group which may have a substituent. n represents 0, 1 or 2. R ² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A hydroxyl group which may be protected with a protecting group or a hydroxymethyl group which may be protected with a protecting group.
L represents a 5- or more-membered lactone ring which may have a substituent. The norbornene ring in the formula may have a substituent in addition to the substituent shown in the formula).

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”. In chemical formulas and the like,
The (meth) acryloyl group may be abbreviated as “(M) AL” and the t-butyl group may be abbreviated as “tBu”. Examples of the protecting group for the hydroxyl group and the hydroxymethyl group include protecting groups commonly used in the field of organic synthesis.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer compound of the present invention comprises, as a structural unit constituting a polymer molecule, at least one monomer unit (repeating unit) (hereinafter referred to as a repeating unit) selected from the formulas (Ia) and (Ib). "Monomer unit 1"). Since the monomer unit 1 has one non-aromatic ring in addition to the norbornane ring, the monomer unit 1 has a function of significantly improving etching resistance. Further, since the monomer unit represented by the formula (Ib) has a lactone ring, it has a function of increasing the adhesion to the substrate (substrate adhesion function). Further, by selecting R ¹ and R ² , a substrate adhesion function and an alkali-soluble function (acid-eliminating function) can be provided. Furthermore, in the production of a polymer, a polymer having various functions required as a resist can be obtained in a well-balanced manner by appropriately using a polymerizable monomer capable of expressing a substrate adhesion function or an alkali-soluble function as a comonomer. . Therefore, the polymer containing the above monomer unit 1 can be suitably used as a photoresist resin.

In the formula (Ia), R ¹ is a hydrogen atom, having 1 to 1 carbon atoms.
5 represents a hydrocarbon group, a hydroxyl group which may be protected by a protecting group, a hydroxymethyl group which may be protected by a protecting group, or a -COOR ³ group, wherein R ³ is a hydrogen atom;
And a tertiary hydrocarbon group, a tetrahydrofuranyl group or a tetrahydropyranyl group which may have a substituent. Examples of the hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and s.
Alkyl groups such as -butyl, t-butyl and pentyl groups;
Alkenyl groups such as vinyl and allyl groups; alkynyl groups such as 2-propynyl groups; and alicyclic hydrocarbon groups such as cyclopentyl groups.

The tertiary hydrocarbon group (hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom) for R ³ includes, for example, t-butyl group, t-amyl group, 2-methyl- Examples thereof include a 2-adamantyl group and a 1-methyl-1-adamantylethyl group. Examples of the substituent which the tertiary hydrocarbon group may have include a halogen atom, an alkyl group, a hydroxyl group which may be protected by a protecting group, and an oxo group. The tetrahydrofuranyl group includes a 2-tetrahydrofuranyl group, and the tetrahydropyranyl group includes a 2-tetrahydropyranyl group.

Y represents a monovalent alicyclic group which may have a substituent, and n represents 0, 1 or 2. As the alicyclic ring corresponding to the alicyclic group, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring,
A monocyclic alicyclic ring having about 3 to 20 carbon atoms (cycloalkane ring, cycloalkene ring) such as cyclohexene ring, cyclooctane ring, cyclodecane ring, cyclododecane ring; perhydroindene ring, decalin ring, perhydrofluorene ring, Perhydroanthracene ring, perhydrophenanthrene ring, perhydroacenaphthene ring, perhydrophenalene ring, norbornane ring, norbornene ring, pinane ring,
Bornan ring, isobornirane ring, adamantane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodecane ring and the like, a bridged ring having about 6 to 20 carbon atoms.

The alicyclic ring may be condensed with a non-aromatic heterocyclic ring (eg, an acid anhydride ring, a lactone ring, a cyclic ether ring, etc.) or an aromatic ring, particularly a non-aromatic heterocyclic ring. Good. Examples of the ring in which a non-aromatic heterocyclic ring is condensed to the ring include, for example, a 4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3-one ring and a 4-oxatricyclo [5.2] .
1.0 ^2,6 ] decane-3,5-dione ring, 3-oxatricyclo [4.2.1.0 ^{4 , 8} ] nonan-2-one ring,
3-oxatricyclo [4.3.1.1 ^4,8 ] undecane-2-one ring and the like are exemplified.

The substituent which the alicyclic group may have may be, for example, a halogen atom, an oxo group, a hydroxyl group which may be protected by a protecting group, or a protective group. A hydroxymethyl group, a substituted oxy group (eg, an alkoxy group, an aryloxy group, an acyloxy group, etc.), a carboxyl group or a substituted oxycarbonyl group (a group similar to the above-mentioned —COOR ³ ), a substituted or unsubstituted carbamoyl group, a cyano group A nitro group, a substituted or unsubstituted amino group, a formyl group, an alkyl group (for example, methyl,
Examples thereof include a C _1-5 alkyl group such as an ethyl group, a cycloalkyl group, an aryl group (eg, a phenyl and naphthyl group), a heterocyclic group and the like. Among these substituents, an oxo group, a hydroxyl group which may be protected with a protecting group, a hydroxymethyl group which may be protected with a protecting group, an alkyl group (for example, a C _1-5 alkyl group), a cycloalkyl A group, a carboxyl group, or a substituted oxycarbonyl group (such as the same group as the above-mentioned -COOR ³ ) is preferable.

In the formula (Ib), R ² is a hydrogen atom and has from 1 to 1 carbon atoms.
20 represents a hydrocarbon group, a hydroxyl group which may be protected by a protecting group, or a hydroxymethyl group which may be protected by a protecting group. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a hydrocarbon group in which a plurality of these groups are combined, and the like.

Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl,
Linear or branched aliphatic hydrocarbon groups having 1 to 20 carbon atoms (preferably about 1 to 10 carbon atoms) such as octyl, decyl, tetradecyl, hexadecyl, octadecyl, and allyl groups (alkyl groups, alkenyl groups, Alkynyl group).

Examples of the alicyclic hydrocarbon group include monocyclic alicyclic hydrocarbons having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclodecyl and cyclododecyl groups. Groups (cycloalkyl groups, cycloalkenyl groups); bridged ring hydrocarbon groups (bridged cyclic hydrocarbon groups);

Examples of the aromatic hydrocarbon group include C6-C20 aromatic hydrocarbon groups such as phenyl and naphthyl groups.

In the formula (Ib), L represents an optionally substituted 5- or more-membered lactone ring, and the norbornene ring in the formula (Ib) represents, in addition to the substituents shown in the formula, It may have a substituent. As a 5- or more-membered lactone ring, γ
-Butyrolactone ring, δ-valerolactone ring, ε-caprolactone ring and the like. The substituent of the lactone ring includes, for example, a hydrocarbon group having 1 to 20 carbon atoms. A plurality of substituents on the lactone ring may combine to form a ring. Examples of the lactone ring having such a ring include a 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring and a 4-oxatricyclo [5.2.
1.0 ^2,6 ] decane-3-one ring and the like.

In a preferred embodiment of the present invention, the above-mentioned formula (Ia)
And at least one monomer unit selected from (Ib) and at least one monomer unit (repeating unit) selected from the formulas (IIa) to (IIo) (hereinafter, referred to as “monomer unit 2”). There is). In the monomer unit represented by the formula (IIa), a site containing an adamantane skeleton is eliminated from the carboxylic acid portion bonded to the main chain by an acid to generate a free carboxyl group. In the monomer unit represented by the formula (IIc), the adamantane skeleton is eliminated from the carboxylic acid moiety bonded to the main chain by an acid to generate a free carboxyl group. Further, the monomer units represented by the formulas (IId), (IIe), (IIf) and (IIg) also decompose the carboxylic acid ester site with an acid,
Elimination produces a free carboxyl group. Therefore,
These monomer units function as alkali-soluble units for solubilizing the resin during alkali development.

The formulas (IIa), (IIb), (IIc) and (I
Since the monomer units represented by Id) and (IIn) have an alicyclic carbon skeleton, they have characteristics of being excellent in transparency and having extremely high etching resistance. Furthermore, the formula (II
a) and (IIb), a monomer unit having a hydroxyl group on the adamantane ring, and formulas (IIg), (IIh) and (IIb).
i), (IIj), (IIk), (IIl), (IIm) and (IIo)
Is highly hydrophilic and has an adhesive function. As described above, since these monomer units can impart various functions based on their structures, by incorporating each of the above monomer units into a polymer, the balance of various properties required as a resin for resist can be finely adjusted according to the application. Can be adjusted. In addition, the polymer compound for a photoresist of the present invention may contain a monomer unit other than the above, if necessary, in order to adjust the above-mentioned various properties.

In the formula (IIa), hydrocarbons having 1 to 8 carbon atoms in R ¹¹ and R ¹² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,
C _1-8 alkyl groups such as pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl, heptyl, 1-methylhexyl, octyl and 1-methylheptyl; cyclo C _3-8 such as propyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups
A cycloalkyl group; a phenyl group; Among these, C, such as methyl, ethyl and isopropyl groups,
_1-3 alkyl groups are preferred.

In the formula (IId), R ²² has 1 to 1 carbon atoms.
Examples of the 0 hydrocarbon group include the same hydrocarbon groups having 1 to 8 carbon atoms in R ¹¹ and R ¹² , as well as nonyl and decyl groups.

In the formula (IIe), examples of the tertiary hydrocarbon group (hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom) for R ²³ include, for example, t-butyl group, t-amyl Group, 2-methyladamantan-2-yl group, 1-methyl-1-adamantylethyl group and the like. The tertiary hydrocarbon group may have the same substituent as R ³ .

In the formula (IIn), examples of the hydrocarbon group having 1 to 8 carbon atoms for R ⁵⁸ and R ⁵⁹ are the same as the hydrocarbon groups having 1 to 8 carbon atoms for R ¹¹ and R ¹² . .

In the formulas (IIb), (IIj) and (IIn),
As the lower alkyl group for R ^b of the —COOR ^b group,
For example, an alkyl group having 1 to 5 carbon atoms such as a methyl, ethyl, propyl, isopropyl, butyl, and isobutyl group is exemplified. Examples of the tertiary hydrocarbon group (hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom) for R ^b include, for example, t-butyl group, t-amyl group, 2-methyladamantane-2- And a 1-methyl-1-adamantylethyl group. The tertiary hydrocarbon group may have the same substituent as R ³ .

In the polymer compound of the present invention, the content of the monomer unit 1 is, for example, 1 to 90 mol%, preferably 5 to 70 mol%, and more preferably 15 mol%, based on the whole monomer units constituting the polymer. About 50 mol%. In a preferred polymer compound, the monomer unit 2 is added in an amount of about 10 to 99 mol% (for example, 3
About 0 to 95 mol%), particularly about 50 to 85 mol%.

In the polymer compound of the present invention, among the above-mentioned combinations of the monomer units, particularly preferred combinations include the following. (1) A monomer unit of the formula (Ia) and at least a compound of the formula (II)
a) to (IIg) (in particular, a combination with at least one monomer unit selected from the formulas (IIa) and (IIc)) (2) a monomer unit of the formula (Ia) and at least a compound of the formula (II)
h) to (IIo) (especially, formulas (IIi), (IIn), and (IIo))
(3) a combination of at least one monomer unit of the formula (Ia) and at least a monomer unit of the formula (II)
a) to (IIg) (in particular, formulas (IIa), (IIc)) and at least one monomer unit selected from the formulas (IIh) to (Ih)
In) (in particular, a combination with at least one monomer unit selected from the formulas (IIi), (IIn) and (IIo)). (4) A monomer unit of the formula (Ib) and at least a compound of the formula (II)
a) to (IIg) (in particular, a combination with at least one monomer unit selected from the formulas (IIa) and (IIc)). (5) A monomer unit of the formula (Ib) and at least a compound of the formula (II)
h) to (IIo) (especially, formulas (IIi), (IIn), and (IIo))
(6) a combination of at least one monomer unit of the formula (Ib) with at least one monomer unit of the formula (II)
a) to (IIg) (in particular, formulas (IIa), (IIc)) and at least one monomer unit selected from the formulas (IIh) to (Ih)
In) (especially in combination with at least one monomer unit selected from the formulas (IIi), (IIn), (IIo))

The polymer compound of the present invention can be prepared using a solubility parameter [Polym. Eng. Sci., 1] according to the method of Fedors.
4, 147 (1974)] (hereinafter sometimes simply referred to as “SP value”) from 19.5 to 24.5 (J / cm ³ ) ^1/2.
Is preferably within the range. A resist coating formed by applying a photosensitive resin composition containing a polymer compound having such a solubility parameter to a semiconductor substrate (silicon wafer) has excellent adhesiveness (adhesion) to the substrate and alkali development. Thus, a high-resolution pattern can be formed. SP value is 19.5 (J / c
m ³ ) If it is lower than ^1/2 , the adhesiveness to the substrate decreases,
The problem that the pattern is not peeled off by development and does not remain tends to occur. Also, the SP value is 24.5 (J / cm ³ ) ^1/2
If it is larger, the composition tends to be repelled by the substrate, making it difficult to apply, and has a higher affinity for an alkali developing solution. As a result, the contrast of the solubility between the exposed and unexposed areas is deteriorated, and the resolution is reduced. Easier to do. The solubility parameter of the polymer compound can be adjusted by appropriately selecting the type of the constituent monomer (the solubility parameter of the monomer) and the composition ratio.

The weight average molecular weight (Mw) of the polymer compound of the present invention is, for example, about 1,000 to 100,000, preferably about 5,000 to 20,000, and the molecular weight distribution (Mw / Mn) is, for example, 1.5 to 3.5. It is about.
Here, Mn indicates a number average molecular weight (in terms of polystyrene). The polymer compound of the present invention can be used as a polymer compound for a photoresist.

The formulas (Ia), (Ib), (IIn) and (II)
o) each monomer unit represented by the corresponding ethylenically unsaturated compound as a (co) monomer,
Each of the monomer units represented by the formulas (IIa) to (IIm) can be formed by subjecting the corresponding (meth) acrylate to polymerization as a (co) monomer. The polymerization is
It can be carried out by a conventional method used for producing an acrylic polymer or a polyolefin polymer, such as solution polymerization or melt polymerization.

[Monomer unit of the formula (Ia)]
The monomer corresponding to the monomer unit of is represented by the above formula (1a). Although the compound represented by the formula (1a) has stereoisomers, they can be used alone or as a mixture.

Representative examples of the compound represented by the formula (1a) include the following compounds, but are not limited thereto.

[0038]

Embedded image

The compound represented by the formula (1a) can be obtained by utilizing a method for producing a ketone represented by the following reaction scheme.

Embedded image

In the above reaction scheme, formula (3) represents an aldehyde having an alicyclic group (such as a 2-norbornene-5-carbaldehyde derivative), and formula (4) represents an olefin having an alicyclic group. And formula (5) represents a ketone having an alicyclic skeleton on both sides of a carbonyl group. As the olefin represented by the formula (4), an olefin having an ethylenic double bond in a ring (cyclic olefin) [in the formula (1a), n
, Etc.], an alicyclic compound having an exomethylene group [eg, a compound having n = 1 in formula (1a)], an alicyclic compound having a vinyl group bonded to the ring A compound [for example, when producing a compound where n = 2 in the formula (1a)] is used.

The above reaction is carried out in the presence of an N-substituted cyclic imide compound. As the N-substituted cyclic imide compound, for example, an imide compound described in WO00 / 35835 can be used. Representative examples of N-substituted cyclic imide compounds include N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalic imide, N, N'-dihydroxycyclohexanetetracarboxylic imide, Hydroxyphthalimide, N
-Hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxyhettimide, N-hydroxyhymic imide, N-
Examples include hydroxytrimellitic imide, N, N'-dihydroxypyromellitic imide, and N, N'-dihydroxynaphthalenetetracarboxylic imide.

The amount of the N-substituted imide compound to be used can be selected from a wide range. For example, the reaction components (for example, a small amount of the compound represented by the formula (3) and the compound represented by the formula (4) may be used) Component) 0.0000 per mole
It is about 001 to 1 mol, preferably about 0.00001 to 0.5 mol, and more preferably about 0.0001 to 0.4 mol.

The aldehyde represented by the formula (3) and the aldehyde represented by the formula (4)
In the reaction with the olefin represented by the formula, it is preferable to allow a radical generator to be present in the system. Examples of the radical generator include halogens (eg, chlorine and bromine), peracids (eg, peracetic acid, m-chloroperbenzoic acid), and peroxides (eg, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide (TBHP)). ) And radical initiators (such as azobisisobutyronitrile). Of these, peroxides such as benzoyl peroxide are preferred. The amount of the radical generator used depends on the reaction components (for example, the compound represented by the formula (3) and the compound represented by the formula (4)).
Is usually about 0.001 to 0.5 mol per 1 mol of the compound represented by the formula (1).

The radical generator may be added to the system at once, but sometimes the intermittent or continuous addition of the radical generator can improve the yield of the target compound.

The reaction between the compound represented by the formula (3) and the compound represented by the formula (4) is carried out in the presence or absence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; chloroform, dichloromethane, dichloroethane, Halogenated hydrocarbons such as carbon chloride, chlorobenzene, and trifluoromethylbenzene; linear or cyclic ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone and methyl ethyl ketone; acetic acid, propionic acid; Organic acids such as fluoroacetic acid; nitriles such as acetonitrile, propionitrile, benzonitrile; formamide, acetamide, dimethylformamide (DMF), dimethylacetoyl Amides such as de;
Nitro compounds such as nitrobenzene, nitromethane and nitroethane; esters such as ethyl acetate and butyl acetate; water; and mixed solvents thereof. As the solvent, aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like are suitable.

The ratio of the compound represented by the formula (3) to the compound represented by the formula (4) can be appropriately selected depending on the kind (price, reactivity) and combination of both compounds. The reaction temperature can be appropriately selected according to the types of the compound represented by the formula (3) and the compound represented by the formula (4).
C., and preferably about 40 to 125.degree. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system.

The reaction produces the corresponding ketone of formula (5). After completion of the reaction, the reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, and column chromatography, or a combination thereof.

By utilizing the above reaction, for example, the compound of the formula [1a-1] can be produced according to the following reaction scheme.

Embedded image

That is, by reacting 2-norbornene-5-carbaldehyde (3a) and 2-norbornene (4a) in the presence of an N-substituted cyclic imide compound,
The norbornene derivative represented by the formula [1a-1] can be obtained.

The compound of the formula [1a-9] can be produced according to the following reaction scheme.

Embedded image

That is, 2-norbornene-5-carbaldehyde (3a) and 1-vinyl adamantane (4b) are
By reacting in the presence of an N-substituted cyclic imide compound, a norbornene derivative represented by the formula [1a-9] can be obtained.

Further, the compound of the above formula [1a-11] can be produced according to the following reaction scheme.

Embedded image

That is, by reacting 2-norbornene-5-carbaldehyde (3a) with 2-methylene adamantane (4c) in the presence of an N-substituted cyclic imide compound, a compound represented by the formula [1a-11] is obtained. To obtain a norbornene derivative.

[Monomer unit of the formula (Ib)]
The monomer corresponding to the monomer unit of is represented by the above formula (1b). Although the compound represented by the formula (1b) has stereoisomers, they can be used alone or as a mixture.

Representative examples of the compound represented by the formula (1b) include the following compounds, but are not limited thereto.

Embedded image

The compound represented by the formula (1b) can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein R ² and L are the same as above)

In the above reaction scheme, the reaction between the norbornanediene derivative represented by the formula (6) and the lactone compound represented by the formula (7) is carried out in the presence of a metal compound and molecular oxygen. Examples of the metal compound include a hydroxide, an oxide, a halide, an oxoacid salt, an oxoacid, an isopolyacid, and a heteropoly of a Group 5 to 9 element of the periodic table (particularly, a metal element of the fourth period such as Mn and Co). Acids, organic acid salts,
Complexes and the like can be used. The metal compounds can be used alone or in combination of two or more. Particularly when a manganese compound and a cobalt compound are used in combination, the reaction rate and the selectivity of the reaction are improved. The amount of the metal compound used is, for example, a reaction component (for example, a component of the compound represented by the formula (6) and the compound represented by the formula (7) which is used in a smaller amount) 1
It is about 0.0001 to 0.1 mol, preferably about 0.0002 to 0.05 mol, per mol.

As molecular oxygen, pure oxygen may be used, or oxygen or air diluted with an inert gas may be used. The amount of molecular oxygen to be used is 0.5 mol or more with respect to 1 mol of a reaction component (for example, a component used in a small amount of the compound represented by the formula (6) and the compound represented by the formula (7)). And preferably about 1 to 100 mol. To increase the initial reaction activity, an additive such as a radical generator may be present in the system. Preferred additives include peroxides such as benzoyl peroxide, peracids such as m-chloroperbenzoic acid,
Aldehydes such as benzaldehyde and cyclic ketones such as cyclohexanone are included.

The reaction between the compound represented by the formula (6) and the compound represented by the formula (7) is carried out in the presence or absence of a solvent. As the solvent, the same solvents as those used in the reaction between the compound (3) and the compound (4) can be used.

The ratio of the compound represented by the formula (6) to the compound represented by the formula (7) can be appropriately selected depending on the kind (price, reactivity) and combination of both compounds. The reaction temperature can be appropriately selected depending on the types of the compound represented by the formula (6) and the compound represented by the formula (7).
C., and preferably about 30 to 100.degree. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system under normal pressure or pressure.

The reaction produces a corresponding addition reaction product represented by the formula (8). After completion of the reaction, the reaction product is, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization,
Separation means such as adsorption and column chromatography, or a combination thereof can be used for separation and purification.

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹¹ and R ¹² are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ^{13 to} R ¹⁵ are the same or different. , Hydrogen atom,
Represents a methyl group or a hydroxyl group which may be protected by a protecting group)

The representative compounds include, but are not limited to, the following compounds. [2-1] 1- (1- (meth) acryloyloxy-1-
Methylethyl) adamantane (R ^a = H or CH ₃ , R ^{11
_{= R 12 = CH 3, R}} 13 = R 14 = R 15 = H) [2-2] 1- hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ^a =
H or _{^{CH 3, R 11 = R 12}} = CH 3, R 13 = OH, R 14 =
^{R 15 = H) [2-3]} 1- (1- ethyl-1 (meth) acryloyloxy propyl) adamantane (R ^a = H or CH _3, R
_{^{11 = R 12 = CH 2 CH}} 3, R 13 = R 14 = R 15 = H) [2-4] 1- hydroxy-3- (1-ethyl-1- (meth) acryloyloxy propyl) adamantane (R ^a
= H or _{^{CH 3, R 11 = R 12}} = CH 2 CH 3, R 13 = O
^{H, R 14 = R 15 =} H) [2-5] 1- (1- ( meth) acryloyloxy-1
Methylpropyl) adamantane (R ^a = H or CH ₃ , R
_{^{11 = CH 3, R 12 =}} CH 2 CH 3, R 13 = R 14 = R 1 5 =
H) [2-6] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane ( ^Ra
ＨH or CH ₃ , R ¹¹ ＣＨCH ₃ , R ¹² ＣＨCH ₂ CH ₃ , R ^{13
= OH, R 14 = R 15} = H) [2-7] 1- (1- ( meth) acryloyloxy-1,
2-dimethylpropyl) adamantane ( ^Ra = H or C
H ₃ , R ¹¹ 3CH ₃ , R ¹² ＣＨCH (CH ₃ ) ₂ , R ¹³ ＲR ^{14
= R 15 = H) [2-8} ] 1- hydroxy-3- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ^a = H or _{^{CH 3, R 11 = CH 3}} , R ¹² = CH (C
^{_{H 3) 2, R 13 =}} OH, R 14 = R 15 = H) [2-9] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ^a = H or CH ₃ , R ¹¹ = R ¹² = CH ₃ , R ¹³ = R ^{14
= OH, R 15 = H)} [2-10] 1- (1- ethyl-1 (meth) acryloyloxy propyl) -3,5-dihydroxy-adamantane (R ^a = H or CH _3, R ¹¹ = R ¹² = CH ₂ CH ₃ , R ¹³ =
^{R 14 = OH, R 15 =} H) [2-11] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R ^a = H or CH _3, R ¹¹ = CH ₃ , R ¹² = CH ₂ C
_{^{H 3, R 13 = R 14}} = OH, R 15 = H) [2-12] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ^a = H or CH ₃ , R ¹¹ ＣＨCH ₃ , R ¹² ＣＨCH
^{_{(CH 3) 2, R 13}} = R 14 = OH, R 15 = H)

The compound represented by the above formula (2a) can be obtained by, for example, obtaining a corresponding alcohol (adamantane methanol derivative) from an adamantane derivative by the method described in WO 99/54271 or a method analogous thereto.
It can be obtained by reacting the above-mentioned alcohol with (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst.

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

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{16 to} R
¹⁸ is the same or different and is a hydrogen atom, a methyl group, a hydroxyl group which may be protected by a protecting group, or -COOR
^b represents a group. R ^b represents a hydrogen atom, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxepanyl group, a lower alkyl group or a tertiary hydrocarbon group which may have a substituent)

Typical examples thereof include the following compounds, but are not limited thereto. [2-13] 1-hydroxy-3- (meth) acryloyloxyadamantane (R ^a = H or CH ₃ , R ¹⁶ = OH, R
^{17 = R 18 = H) [} 2-14] 1,3- dihydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ¹⁶ = R
^{17 = OH, R 18 = H} ) [2-15] 1- carboxy-3- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ¹⁶ = COO
^{H, R 17 = R 18 =} H) [2-16] 1,3- dicarboxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ¹⁶ = R
¹⁷ = COOH, R ¹⁸ = H) [2-17] 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane (R ^a = H or C
^{_{H 3, R 16 = COOH,}} R 17 = OH, R 18 = H) [2-18] 1-t- butoxycarbonyl-3- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R
¹⁶ = t-butoxycarbonyl ^{group, R 17 = R 18 = H} ) [2-19] 1,3- bis (t-butoxycarbonyl) -5
-(Meth) acryloyloxyadamantane [ ^Ra = H
Or CH ₃ , R ¹⁶ ＲR ¹⁷ = t-butoxycarbonyl group,
^{R 18 = H] [2-20]} 1-t- butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxy adamantane (R ^a
= H or ^{_{CH 3, R 16 = OH,}} R 17 = t- butoxycarbonyl ^{group, R 18 = H) [2-21} ] 1- (2- tetrahydropyranyloxy) -3- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ¹⁶ = 2- tetrahydropyranyloxy ^{group, R 17 = R 18 = H} ) [2-22] 1,3- bis (2-tetrahydropyranyloxy carbonyl) -5 - (meth) acryloyloxy adamantane (R ^a = H or _{^{CH 3, R 16 = R 17}} = 2- tetrahydropyranyloxy ^{group, R 18 = H) [2-23} ] 1- hydroxy-3- (2- tetrahydropyranyloxy carbonyl) -5- (meth) acryloyloxy adamantane (R ^a = H or ^{_{CH 3, R 16 = OH,}} R
¹⁷ = 2-tetrahydropyranyloxycarbonyl group, R
¹⁸ = H)

The compound represented by the above formula (2b) can be obtained, for example, by converting a corresponding 1-adamantanol derivative and (meth) acrylic acid or a reactive derivative thereof into a conventional ester using an acid catalyst or a transesterification catalyst. It can be obtained by reacting according to the chemical formula. The 1-adamantanol derivative used as a raw material can be prepared by introducing a hydroxyl group or a carboxyl group into an adamantane ring of an adamantane compound and, if necessary, performing esterification. Introduction of a hydroxyl group or a carboxyl group into the adamantane ring can be carried out by the method described in JP-A-9-327626, JP-A-11-239730 and the like.

[Monomer Unit of the Formula (IIc)]
The monomer corresponding to the monomer unit of c) is represented by the following formula (2)
c). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹⁹ represents a methyl group or an ethyl group, and R ²⁰ and R ²¹ may be the same or different and may be protected by a hydrogen atom or a protecting group. Represents a hydroxyl group or an oxo group)

Typical examples include the following compounds, but are not limited thereto. [2-24] 2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R ¹⁹ = CH ₃ , R ²⁰
= R ²¹ = H) [2-25] 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R
¹⁹ = CH ₃ , R ²⁰ = 1-OH, R ²¹ = H) [2-26] 5-Hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R
¹⁹ = CH ₃ , R ²⁰ = 5-OH, R ²¹ = H) [2-27] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane ( ^Ra = H or C
_{^{H 3, R 19 = CH 3}} , R 20 = 1-OH, R 21 = 3-OH) [2-28] 1,5- dihydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ^a = H or C
_{^{H 3, R 19 = CH 3}} , R 20 = 1-OH, R 21 = 5-OH) [2-29] 1,3- dihydroxy-6 (meth) acryloyloxy-6-methyl-adamantane (R ^a = H or C
_{^{H 3, R 19 = CH 3}} , R 20 = 1-OH, R 21 = 3-OH) [2-30] 2- ( meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R ¹⁹ = CH ₂ CH _3,
^{R 20 = R 21 = H)} [2-31] 1- hydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R
_{^{19 = CH 2 CH 3, R}} 20 = 1-OH, R 21 = H) [2-32] 5- hydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R
_{^{19 = CH 2 CH 3, R}} 20 = 5-OH, R 21 = H) [2-33] 1,3- dihydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or C
_{^{H 3, R 19 = CH 2}} CH 3, R 20 = 1-OH, R 21 = 3-
OH) [2-34] 1,5-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane ( ^Ra = H or C
_{^{H 3, R 19 = CH 2}} CH 3, R 20 = 1-OH, R 21 = 5-
OH) [2-35] 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane (R ^a = H or C
_{^{H 3, R 19 = CH 2}} CH 3, R 20 = 1-OH, R 21 = 3-
OH)

The compound represented by the above formula (2c) can be obtained, for example, by converting a corresponding 2-adamantanol derivative and (meth) acrylic acid or a reactive derivative thereof into a conventional ester using an acid catalyst or a transesterification catalyst. It can be obtained by reacting according to the chemical formula. In addition, the 2-adamantanol derivative used as a raw material can be obtained by reacting a 2-adamantanone derivative with a Grignard reagent (methyl Grignard reagent or ethyl Grignard reagent) according to a normal Grignard reaction.

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

Embedded image (In the formula, R ^a represents a hydrogen atom or a methyl group, and R ²² represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

Typical examples include the following compounds, but are not limited thereto. [2-36] 2- (meth) acryloyloxytricyclo [7.4.0.0 ^3,8 ] tridecane (R ^a = H or C
H ₃ , R ²² = H) [2-37] 2- (meth) acryloyloxy-2-methyltricyclo [7.4.0.0 ^3,8 ] tridecane (R ^a = H
Or _{^{CH 3, R 22 = CH 3}} ) [2-38] 2- ( meth) acryloyloxy-2-ethyl tricyclo [7.4.0.0 ^3,8] tridecane (R ^a = H
Or CH ₃ , R ²² ＣＨCH ₂ CH ₃ )

[Monomer Unit of the Formula (IIe)]
The monomer corresponding to the monomer unit of e) is represented by the following formula (2)
e). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (In the formula, R ^a represents a hydrogen atom or a methyl group, and R ²³ represents a tertiary hydrocarbon group which may have a substituent.)

Typical examples include the following compounds, but are not limited thereto. [2-39] t-butyl (meth) acrylate (R ^a = H or CH ₃ , R ²³ = t-butyl group)

[Monomer Unit of the Formula (IIf)]
The monomer corresponding to the monomer unit of f) is represented by the following formula (2)
f). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group;
Indicates an integer of 3)

Typical examples thereof include, but are not limited to, the following compounds. [2-40] 2-tetrahydropyranyl (meth) acrylate (R ^a = H or CH ₃ , p = 2) [2-41] 2-tetrahydrofuranyl (meth) acrylate (R ^a = H or CH ₃ , p = 1)

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ²⁴ to R
²⁸ is the same or different and represents a hydrogen atom or a methyl group)

Typical examples thereof include the following compounds, but are not limited thereto. [2-42] β- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁴ = R ²⁵ = R ²⁶ = R ²⁷
= R ²⁸ = H) [2-43] β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁴
= R ²⁵ = CH ₃ , R ²⁶ = R ²⁷ = R ²⁸ = H) [2-44] β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ^{27
_{= R 28 = CH 3, R}} 24 = R 25 = R 26 = H) [2-45] β- ( meth) acryloyloxy -α, α, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 24 = R 25}} = R 26 = CH 3, R 27 = R 28 = H) [2-46] β- ( meth) acryloyloxy-beta, gamma, gamma
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 26 = R 27}} = R 28 = CH 3, R 24 = R 25 = H) [2-47] β- ( meth) acryloyloxy-.alpha., alpha,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ²⁴ = R ²⁵ = R ²⁶ = R ²⁷ = R ²⁸ = C
H ₃ )

The compound represented by the above formula (2g) is obtained by, for example, using a corresponding β-hydroxy-γ-butyrolactone derivative and (meth) acrylic acid or a reactive derivative thereof using an acid catalyst or a transesterification catalyst. It can be obtained by reacting according to a conventional esterification method.

[Monomer Unit of the Formula (IIh)]
The monomer corresponding to the monomer unit of h) is represented by the following formula (2)
h). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, and R ^{29 to} R ^29
33 is the same or different and represents a hydrogen atom or a methyl group)

Representative examples include the following compounds, but are not limited thereto. [2-48] α- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁹ = R ³⁰ = R ³¹ = R ³²
= R ³³ = H) [2-49] α- (meth) acryloyloxy-α-methyl-γ-butyrolactone (R ^a = H or CH ₃ , R ²⁹ = CH
₃ , R ³⁰ = R ³¹ = R ³² = R ³³ = H) [2-50] α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone ( ^Ra = H or CH ₃ , R ³⁰
= R ³¹ = CH ₃ , R ²⁹ = R ³² = R ³³ = H) [2-51] α- (meth) acryloyloxy-α, β, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
H ₃ , R ²⁹ = R ³⁰ = R ³¹ = CH ₃ , R ³² = R ³³ = H) [2-52] α- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone ( ^Ra = H Or CH ₃ , R ³²
= R ³³ = CH ₃ , R ²⁹ = R ³⁰ = R ³¹ = H) [2-53] α- (meth) acryloyloxy-α, γ, γ
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 29 = R 32}} = R 33 = CH 3, R 30 = R 31 = H) [2-54] α- ( meth) acryloyloxy-beta, beta,
γ, γ-tetramethyl-γ-butyrolactone (R ^a = H
Or CH ₃ , R ³⁰ = R ³¹ = R ³² = R ³³ = CH ₃ , R ²⁹ =
H) [2-55] α- (meth) acryloyloxy-α, β,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ²⁹ = R ³⁰ = R ³¹ = R ³² = R ³³ = C
H ₃ )

The compound represented by the above formula (2h) can be obtained, for example, by subjecting a corresponding α-hydroxy-γ-butyrolactone derivative to (meth) acrylic acid or a reactive derivative thereof using an acid catalyst or a transesterification catalyst. It can be obtained by reacting according to a conventional esterification method. The α-hydroxy-γ-butyrolactone derivative used as a raw material can be obtained, for example, by the method described in WO 00/35835 or a method analogous thereto.

[Monomer Unit of the Formula (IIi)]
The monomer corresponding to the monomer unit of i) is represented by the following formula (2)
i). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{34 to} R ^34
36 is the same or different and represents a hydrogen atom or a methyl group; V ^{1 to} V ³ are the same or different and represent —CH ₂ — and —C
O- or -COO-)

Representative examples include the following compounds, but are not limited thereto. [2-56] 1- (meth) acryloyloxy-4-oxo-adamantane (R ^a = H or _{^{CH 3, R 34 = R 35}} = R 36 =
^{H, V 1 = -CO-, V} 2 = V 3 = -CH 2 -) [2-57] 3- hydroxy-1- (meth) acryloyloxy-4-oxo-adamantane (R ^a = H or CH _3, R
^{34 = OH, R 35 = R} 36 = H, V 1 = -CO-, V 2 = V 3
_{= -CH 2 -) [2-58]} 7- hydroxy-1- (meth) acryloyloxy-4-oxo-adamantane (R ^a = H or CH _3, R
^{36 = OH, R 34 = R} 35 = H, V 1 = -CO-, V 2 = V 3
= —CH ₂ —) [2-59] 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one (R ^a = H or CH ₃ , R ³⁴ = R ³⁵ = R ³⁶ = H, V ² =
—CO—O— (the left side is the carbon atom side to which R ³⁵ is bonded), V ¹ = V ³ = —CH ₂ —) [2-60] 1- (meth) acryloyloxy-4,7-dioxa Tricyclo [4.4.1.1 ^3,9 ] dodecane-
5,8-dione (R ^a = H or _{^{CH 3, R 34 = R 35}} = R 36
^{= H, V 1 = -CO-} O- ( left bonded to the carbon atom side of the ^{R 34), V 2 = -CO} -O- ( left bonded to the carbon atom side of the R ^35), V _{^{3 = -CH 2 -) [2-61}} ] 1- ( meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^{3, 9]} dodecane -
5,7-dione (R ^a = H or _{^{CH 3, R 34 = R 35}} = R 36
^{= H, V 1 = -O-} CO- ( left bonded to the carbon atom side of the ^{R 34), V 2 = -CO} -O- ( left bonded to the carbon atom side of the R ^35), V _{^{3 = -CH 2 -) [2-62}} ] 1- ( meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^{3, 9]} dodecane -
4,8-dione (R ^a = H or CH ₃ , R ³⁴ = R ³⁵ = R ³⁶
= H, V ¹ = —CO—O— (the left side is the carbon atom side to which R ³⁴ is bonded), V ² = —O—CO— (the left side is the carbon atom side to which R ³⁵ is bonded), V ³ = -CH ₂ -)

The compound represented by the above formula (2i) is prepared by subjecting the corresponding cyclic alcohol derivative to (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained by reacting.

Of the compounds represented by the above formula (2i), V
^The cyclic alcohol derivative (11) corresponding to the compound in which ² = —CO—O— and V ¹ = V ³ = —CH ₂ — can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein R ³⁴ , R ³⁵ and R ³⁶ are the same as above)

In this reaction scheme, the compound represented by the formula (10) is obtained by converting a 2-adamantanone compound represented by the formula (9) into an N-substituted cyclic imide catalyst such as N-hydroxyphthalimide. It can be obtained by reacting with oxygen in the presence of a vanadium compound (for example, vanadium (III) acetylacetonate or the like) and a manganese compound (for example, manganese (II) acetylacetonate or the like). At this time, the amount of the N-substituted cyclic imide-based catalyst used is, for example, 0.0 mol per mol of the compound represented by the formula (9).
00001-1 mol, preferably 0.00001-0.
It is about 5 mol. The total amount of the vanadium compound and the manganese compound is, for example, about 0.0001 to 0.7 mol, preferably about 0.001 to 0.5 mol, per 1 mol of the compound represented by the formula (9). It is. The ratio of the vanadium compound to the manganese compound (metal atomic ratio) is, for example, the former / the latter = 99/1 to 1/99, preferably 9
It is about 5/5 to 10/90. Oxygen is often used in excess with respect to the compound represented by the formula (9). The reaction is
For example, the reaction is carried out in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, a halogenated hydrocarbon such as dichloroethane, or the like under normal pressure or under pressure at a temperature of about 20 to 200 ° C., preferably about 30 to 150 ° C. .

The thus obtained 5- (5) represented by the equation (10)
Hydroxy-2-adamantanone compound is prepared by using an N-substituted cyclic imide-based catalyst such as N-hydroxyphthalimide and, if necessary, a metal-based co-catalyst such as a cobalt compound (for example, cobalt acetate, cobalt acetylacetonate or the like). When a primary or secondary alcohol is oxidized by molecular oxygen together with a primary or secondary alcohol, a Bayer-Villiger-type reaction proceeds, and 1-hydroxy-4-oxatricyclo [4.3 represented by the formula (11) is obtained. 1.1.1 ^3,8 ] undecane compound is produced. Examples of the primary or secondary alcohol include methanol, ethanol, 1-propanol,
-Propanol, s-butyl alcohol, cyclohexanol, 1-phenylethanol, benzhydrol and the like. Preferred are secondary alcohols.
The alcohol functions as a co-oxidant and is usually converted in the system to an aldehyde, carboxylic acid or ketone. N-
The amount of the substituted cyclic imide-based catalyst is, for example, about 0.000001 to 1 mol, and preferably about 0.00001 to 0.5 mol, per 1 mol of the compound of the formula (10). Further, the amount of the metal-based cocatalyst used is based on 1 mol of the compound of the formula (10).
For example, 0.0001 to 0.7 mol, preferably 0.00
It is about 1 to 0.5 mol. The amount of the alcohol used is, for example, 0.5 to 1 mol of the compound of the formula (10).
It is about 100 mol, preferably about 1 to 50 mol. Oxygen is often used in excess with respect to the compound of the formula (10).
The reaction is, for example, an organic acid such as acetic acid, acetonitrile,
In a solvent such as a nitrile such as benzonitrile, a halogenated hydrocarbon such as trifluoromethylbenzene, or an ester such as ethyl acetate, at normal pressure or under pressure, 20 to 200.
C., preferably at a temperature of about 30 to 150.degree. The compound of the formula (11) can be obtained by a general Bayer-Villiger reaction, that is, the reaction of the compound (10) with a peroxide such as hydrogen peroxide or a peracid such as m-chloroperbenzoic acid. it can.

Among the compounds represented by the above formula (2i), V
Correspond to compounds wherein - ¹ = -CO-O- in and _{^{V 2 = V 3 = -CH 2}} - , compound and V ³ = -CO-O- in and V ¹ = V _² = -CH ² The cyclic alcohol derivative can be produced from the corresponding adamantanone compound by the same method as described above. Further, the cyclic alcohol derivative corresponding to the compound having a plurality of —CO—O— groups can be produced from the corresponding adamantanedione or adamantanetrione compound according to the above method.

[Monomer Unit of the Formula (IIj)]
The monomer forming the monomer unit of j) is represented by the following formula (2j)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ³⁷ and R ³⁹ are the same or different and represent a hydrogen atom or a methyl group, and R ³⁸ is protected by a hydrogen atom, a methyl group, or a protecting group. and shows also good hydroxyl group or -COOR ^b group. the R ^b is a hydrogen atom, a tetrahydrofuranyl group, tetrahydropyranyl group, oxepanyl group, a lower alkyl group, or may have a substituent tertiary hydrocarbon Indicates a group)

Typical examples thereof include the following compounds.
However, the present invention is not limited to these. [2-63] 5- (meth) acryloyloxy-3-oxa
Tricyclo [4.2.1.0^4,8Nonan-2-one
(R^a= H or CH_Three, R³⁷= R³⁸= R³⁹= H) [2-64] 5- (meth) acryloyloxy-5-methyl
-3-oxatricyclo [4.2.1.0^4,8] Nonan
-2-one (R^a= H or CH_Three, R³⁷= CH_Three, R ³⁸=
R³⁹= H) [2-65] 5- (meth) acryloyloxy-9-carbo
Xy-3-oxatricyclo [4.2.1.0^4,8]
Nan-2-one (R^a= H or CH_Three, R³⁷= R³⁹= H,
R³⁸= COOH) [2-66] 5- (meth) acryloyloxy-9-methoxy
Cycarbonyl-3-oxatricyclo [4.2.1.0
^4,8] Nonan-2-one (R^a= H or CH_Three, R^{Three 7}= R
³⁹= H, R³⁸= Methoxycarbonyl group) [2-67] 5- (meth) acryloyloxy-9-ethoxy
Cycarbonyl-3-oxatricyclo [4.2.1.0
^4,8] Nonan-2-one (R^a= H or CH_Three, R^{Three 7}= R
³⁹= H, R³⁸= Ethoxycarbonyl group) [2-68] 5- (meth) acryloyloxy-9-t-butyl
Toxicarbonyl-3-oxatricyclo [4.2.
1.0^4,8] Nonan-2-one (R^a= H or CH_Three, R
³⁷= R³⁹= H, R³⁸= T-butoxycarbonyl group) [2-69] 5- (meth) acryloyloxy-9- (2-
Methyl-2-adamantyloxycarbonyl) -3-o
Xatricyclo [4.2.1.0^4,8Nonan-2-o
(R^a= H or CH_Three, R³⁷= R³⁹= H, R³⁸= 2-me
Butyl-2-adamantyloxycarbonyl group) [2-70] 5- (meth) acryloyloxy-9- (1-
Methyl-1-adamantylethoxycarbonyl) -3-
Oxatricyclo [4.2.1.0^4,8Nonan-2-
ON (R^a= H or CH_Three, R³⁷= R³⁹= H, R³⁸= 1-
Methyl-2-adamantylethoxycarbonyl group) [2-71] 5- (meth) acryloyloxy-9- (2-
Tetrahydropyranyloxycarbonyl) -3-oxa
Tricyclo [4.2.1.0^4,8Nonan-2-one
(R^a= H or CH_Three, R³⁷= R³⁹= H, R³⁸= 2-tet
Lahydropyranyloxycarbonyl group)

The compound represented by the above formula (2j) is prepared by subjecting a corresponding cyclic alcohol derivative to (meth) acrylic acid or a reactive derivative thereof according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can be obtained by reacting.

The cyclic alcohol derivative (13) used as a raw material is, for example, a 5-norbornene-2-carboxylic acid derivative represented by the formula (12) or an ester thereof as a peracid or It can be obtained by reacting with peroxide.

Embedded image (Wherein, R ³⁷ , R ³⁸ and R ³⁹ are the same as above)

5-norbornene-2 represented by the formula (12)
Examples of the ester of the carboxylic acid derivative include alkyl esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester (for example, C _1-4 alkyl). Esters); cycloalkyl esters such as cyclohexyl esters; aryl esters such as phenyl esters; aralkyl esters such as benzyl esters, and the like, but are not limited thereto.

The above-mentioned peracids include formic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid,
Organic peracids such as monoperoxyphthalic acid; and inorganic peracids such as permanganic acid. Peracids can also be used in salt form. The organic peracid may be an equilibrated peracid (eg, equilibrated formic acid, equilibrated peracetic acid, etc.). That is, for example, an organic acid such as formic acid or acetic acid may be used in combination with hydrogen peroxide to generate a corresponding organic peracid in the system. When using an equilibrium peracid, a small amount of a strong acid such as sulfuric acid may be added as a catalyst.

The amount of the peracid used is, for example, 0.8 to 2 mol, preferably 0.9 to 1 mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (12) or 1 mol of the ester thereof. ~ 1.5 mol, more preferably 0.95-1.
It is about 2 mol.

Examples of the peroxide include hydrogen peroxide, peroxide, hydroperoxide, peroxoacid, and salts of peroxoacid.

As the hydrogen peroxide, pure hydrogen peroxide may be used. However, from the viewpoint of handleability, usually an appropriate solvent,
For example, it is used in a form diluted with water (for example, 30% by weight hydrogen peroxide solution).

The amount of the peroxide such as hydrogen peroxide used is, for example, 0.9 to 0.9 mol per mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (12) or an ester thereof.
The amount is about 5 mol, preferably about 0.9 to 3 mol, and more preferably about 0.95 to 2 mol.

The hydrogen peroxide is often used together with a metal compound. Examples of the metal compound include W,
Oxides containing metal elements such as Mo, V, Mn, Re, oxo acids or salts thereof, sulfides, halides, oxyhalides, borides, carbides, silicides, nitrides, phosphides, peroxides, Complexes (inorganic complexes and organic complexes), organometallic compounds and the like. These metal compounds can be used alone or in combination of two or more.

Examples of the oxide include tungsten oxide (WO ₂ , WO ₃ etc.), molybdenum oxide (MoO
₂ , MoO _3, etc.), vanadium oxide (VO, V ₂ O ₃ , V
O ₂ , V ₂ O _5, etc.), manganese oxide (MnO, Mn)
₂ O ₃ , Mn ₃ O ₄ , MnO ₂ , Mn ₂ O ₇ etc.), W, M
A composite oxide containing a metal element such as o, V, and Mn may be used.

The oxo acids include tungstic acid, molybdic acid, vanadic acid, manganic acid and the like, isopolyacids such as isopolytungstic acid, isopolymolybdic acid and isopolyvanadate; phosphotungstic acid, silicotungstic acid, Phosphomolybdenum sun, silico molybdic acid,
Heteropoly acids composed of the above-mentioned metal element such as limbanadomolybdic acid and other metal elements are included. As the other metal element in the heteropoly acid, phosphorus or silicon, particularly phosphorus is preferable.

Examples of the oxo acid salt include alkali metal salts such as sodium and potassium salts of the above oxo acid; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; ammonium salts; transition metal salts and the like. Can be The salt of an oxo acid (for example, a salt of a heteropoly acid) may be a salt in which a part of a hydrogen atom corresponding to a cation is substituted with another cation.

The peroxide containing a metal element includes, for example, peroxo acids (eg, peroxotungstic acid, peroxomolybdic acid, peroxovanadate, etc.), and salts of peroxo acids (the alkali metal salts of the above peroxo acids, alkaline earths, etc.). Metal salts, ammonium salts, transition metal salts, etc.), peracids (permanganic acid, etc.), peracid salts (alkali metal salts of the above peracids, alkaline earth metal salts, ammonium salts, transition metal salts, etc.) and the like. No.

The amount of the metal compound used together with the hydrogen peroxide is, for example, 0.0001 to 2 mol per mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (12) or an ester thereof. Degree, preferably 0.0
About 005 to 0.5 mol, more preferably 0.001
About 0.2 mol.

5-norbornene-2 represented by the formula (12)
The reaction of the carboxylic acid derivative or its ester with the peracid or peroxide is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; chloroform, dichloromethane, 1,2-
Halogenated hydrocarbons such as dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide, N, N-dimethylacetamide Amides such as acetonitrile, propionitrile, benzonitrile, etc .; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; organic acids such as acetic acid; water and the like. These solvents may be used alone or as a mixture of two or more. When the reaction is performed in a heterogeneous system, water or a solvent containing water is often used as the solvent.

The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity.
Preferably it is about 10 to 80 ° C. The reaction is batch type,
It may be performed by any method such as a semi-batch type and a continuous type.

According to the above reaction, 3-
Oxatricyclo [4.2.1.0 ^4,8Nonan-2-
An on derivative is formed. In this reaction, first, in equation (12)
The represented 5-norbornene-2-carboxylic acid derivative or
Epoxidation of the ester double bond occurs and continues
And the intramolecular cyclization reaction involving the opening of the epoxy ring proceeds
3-oxatricyclo [4.2.
1.0^4,8A nonan-2-one derivative is formed
Guessed.

[0109] represented by formula (13) produced by the reaction of 3-oxatricyclo [4.2.1.0 ^{4, 8]} nonan-2-one derivatives, for example, filtration, concentration, distillation, extraction, Crystallization,
Separation and purification can be performed by separation means such as recrystallization, column chromatography, or a combination thereof.

5-norbornene-2 represented by the formula (12)
-The carboxylic acid derivative or its ester can be obtained by utilizing the Diels-Alder reaction. For example, by reacting a cyclopentadiene derivative (cyclopentadiene or 2-methylcyclopentadiene) with an α, β-unsaturated carboxylic acid (acrylic acid, methacrylic acid, crotonic acid, etc.) or an ester thereof,
The compound represented by 2) can be produced.

The cyclopentadiene derivative and α, β-
The reaction with an unsaturated carboxylic acid or its ester (Diels-Alder reaction) is carried out in the presence or absence of a solvent. Examples of the solvent include esters such as ethyl acetate; organic acids such as acetic acid; alcohols such as t-butyl alcohol; chloroform, dichloromethane, 1,2-
Halogenated hydrocarbons such as dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide, N, N-dimethylacetamide Amides; acetonitrile, propionitrile, benzonitrile and other nitriles; and linear or cyclic ethers such as ethyl ether and tetrahydrofuran. These solvents are used alone or in combination of two or more.

Reaction rate and reaction selectivity (stereoselectivity, etc.)
Lewis acid may be added to the system in order to improve the viscosity.
Examples of the Lewis acid include AlCl ₃ , SnCl ₄ , T
Examples include, but are not limited to, iCl ₄ , BF _{3, and the} like.

The reaction temperature can be appropriately selected according to the type of the reaction raw materials and the like, but is generally about -80 ° C to 300 ° C, preferably about -70 ° C to 250 ° C. The reaction is carried out under normal pressure or under pressure. The reaction may be performed by any method such as a batch system, a semi-batch system, and a continuous system.

[Monomer Unit of the Formula (IIk)]
The monomer forming the monomer unit of k) is represented by the following formula (2k)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{40 to} R
⁴⁸ is the same or different and represents a hydrogen atom, a methyl group or an ethyl group)

Representative examples include the following compounds, but are not limited thereto. [2-72] 4- (meth) acryloyloxy-6-oxabicyclo [3.2.1] octan-7-one (R ^a = H
Or CH ₃ , R ⁴⁰ = R ⁴¹ = R ⁴² = R ⁴³ = R ⁴⁴ = R ⁴⁵ = R
⁴⁶ = R ⁴⁷ = R ⁴⁸ = H) [2-73] 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one ( ^Ra = H or CH ₃ , R ⁴⁰ = R ⁴¹ = R ⁴³ = R ⁴⁴ = R ⁴⁵
= R ⁴⁶ = R ⁴⁷ = R ⁴⁸ = H, R ⁴² = CH ₃ ) [2-74] 4- (meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octane-7- on (R ^a = H or _{^{CH 3, R 40 = R 41}} = R 42 = R 44 = R 45
= R ⁴⁶ = R ⁴⁷ = R ⁴⁸ = H, R ⁴³ = CH ₃ ) [2-75] 4- (meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane-
7-one (R ^a = H or CH ₃ , R ⁴⁰ = R ⁴¹ = R ⁴⁴ = R ⁴⁵
= R ⁴⁶ = R ⁴⁷ = R ⁴⁸ = H, R ⁴² = R ⁴³ = CH ₃ )

[Monomer unit of the formula (IIl)]
The monomer forming the monomer unit of l) is represented by the following formula (2l)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, and R ^{49 to} R
⁵⁷ is the same or different and represents a hydrogen atom, a methyl group or an ethyl group)

Representative examples include the following compounds, but are not limited thereto. [2-76] 6- (meth) acryloyloxy-2-oxabicyclo [2.2.2] octan-3-one (R ^a = H
Or CH ₃ , R ⁴⁹ = R ⁵⁰ = R ⁵¹ = R ⁵² = R ⁵³ = R ⁵⁴ = R
^{55 = R 56 = R 57 =} H) [2-77] 6- ( meth) acryloyloxy-6-methyl-2- oxabicyclo [2.2.2] octan-3-one (R ^a = H or CH _{^{3, R 49 = R 50 =}} R 51 = R 53 = R 54
^{= R 55 = R 56 = R} 57 = H, R 52 = CH 3) [2-78] 6- ( meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octan-3 on (R ^a = H or _{^{CH 3, R 49 = R 50}} = R 52 = R 53 = R 54
^{= R 55 = R 56 = R} 57 = H, R 51 = CH 3) [2-79] 6- ( meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane -
3-one (R ^a = H or _{^{CH 3, R 49 = R 50}} = R 53 = R 54
= R ⁵⁵ = R ⁵⁶ = R ⁵⁷ = H, R ⁵¹ = R ⁵² = CH ₃ )

The compounds represented by the above formulas (2k) and (2l) can be prepared by converting a corresponding cyclic alcohol derivative and (meth) acrylic acid or a reactive derivative thereof into a conventional compound using an acid catalyst or a transesterification catalyst. It can be obtained by reacting according to the esterification method.

The cyclic alcohol derivative used as a raw material can be obtained, for example, according to the following reaction scheme.

Embedded image

[0120]

Embedded image

[0121]

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{41 to} R ^41
48 represents a hydrogen atom, a methyl group or an ethyl group, respectively)

In the above reaction scheme, the reaction between the diene represented by the formula (14) and the α, β-unsaturated carboxylic acid represented by the formula (15) is carried out under general Diels-Alder reaction conditions. be able to. This reaction produces cyclohexene carboxylic acid. It should be noted that two types of isomers (16a) and (16b) can be produced depending on the type of raw materials and reaction conditions. As the diene represented by the formula (14), isoprene, 2,3-
Dimethylbutadiene and the like are preferable, and acrylic acid, methacrylic acid, crotonic acid and the like are preferable as the α, β-unsaturated carboxylic acid represented by the formula (15).

Next, the produced cyclohexenecarboxylic acids (16a) and (16b) are reacted with hydrogen peroxide in the presence of (i) a metal compound containing a metal element selected from W, Mo, V and Mn. Or (ii) by reacting with a peroxide containing the metal element, a hydroxyl group is bonded to one carbon atom constituting a double bond of the cyclohexene ring, and a lactone ring is formed at the other carbon atom site. A hydroxyoxabicyclooctanone derivative is formed. Also in this reaction, 2
Species isomers can be formed. That is, the compounds represented by the formulas (17a) and (17b) are produced from the cyclohexenecarboxylic acid represented by the formula (16a), and the compound represented by the formula (17c) is produced from the cyclohexanecarboxylic acid represented by the formula (16b). ) And (1
The compound represented by 7d) can be produced.

W, Mo, V and Mn in the above (i)
Examples of metal compounds containing metal elements selected from
For example, tungsten oxide (WO_Two, WO_ThreeEtc.), oxidation
Ribden (MoO_Two, MoO_ThreeEtc.), vanadium oxide
(VO, V_TwoO_Three, VO_Two, V_TwoO _FiveManganese oxide)
(MnO, Mn_TwoO_Three, Mn_ThreeO_Four, MnO_Two, Mn_TwoO₇What
Etc.), oxides such as composite oxides containing said metals; tongues
Stynic acid, molybdic acid, vanadic acid, manganic acid,
Sopolytungstic acid, isopolymolybdic acid, isopo
Isopoly acids such as rivanadic acid, phosphotungsten
Acid, silicotungstic acid, phosphomolybdenum san, silicate
Heteropolyacids such as ribic acid, limbanamolybdic acid
Oxo acids or salts thereof; sulfurization corresponding to the oxides
Material; halide; oxyhalide; boride; charcoal
Silicide; nitride; phosphide; peroxide, arsenic
Dropperoxide, peroxoic acid (for example, peroxo
Tungstic acid, peroxomolybdic acid, peroxo
Vanadic acid, etc.), salts of peroxoacids
Alkali metal salts, alkaline earth metal salts of ammonium acid, ammonia
Salts, transition metal salts, etc.), peracids (such as permanganate)
Etc.), peracid salts (the above-mentioned alkali metal salts of peracid, alkali
Earth metal salts, ammonium salts, transition metal salts, etc.)
Peroxide; complex (inorganic complex and organic complex); organometallic
And the like. These metal compounds can be used alone or
Can be used in combination of two or more.

The amount of the metal compound used is, for example, based on 1 mol of cyclohexenecarboxylic acid used in the reaction.
About 0.0001 to 2 mol, preferably 0.0005 to
About 0.5 mol, more preferably 0.001 to 0.2
It is about a mole.

As the peroxide in the above (ii), those similar to the above can be used. In this case, peroxides can be used alone or in combination of two or more. The amount of the peroxide used is, for example, about 0.8 to 2 mol, preferably about 0.9 to 1.5 mol, and more preferably 0.95 to 1 mol per mol of cyclohexenecarboxylic acid used in the reaction.
It is about 1.2 mol.

As the hydrogen peroxide, pure hydrogen peroxide may be used. However, from the viewpoint of handleability, an appropriate solvent is usually used.
For example, it is used in a form diluted with water (for example, 30% by weight hydrogen peroxide solution). The amount of hydrogen peroxide used is, for example, about 0.9 to 5 moles, preferably about 0.9 to 3 moles, per mole of cyclohexenecarboxylic acid used in the reaction.
More preferably, it is about 0.95 to 2 mol.

The reaction is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; chloroform, dichloromethane,
Halogenated hydrocarbons such as 1,2-dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide; N
Amides such as dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; and organic acids such as acetic acid. These solvents may be used alone or as a mixture of two or more.

The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity.
Preferably it is about 10 to 60 ° C. The reaction is batch type,
It may be performed by any method such as a semi-batch type and a continuous type.

In this reaction, it is presumed that the epoxidation of the double bond occurs first, and then the intramolecular cyclization reaction involving the opening of the epoxy ring proceeds to produce the corresponding hydroxylactone. At this time, 2 forming a double bond
Which carbon atom of the two carbon atoms is cyclized is determined by the electrical properties and bulkiness of the substituent bonded to the carbon atom, steric restrictions, stability of the resulting lactone, and the like.

The reaction product can be separated and purified, for example, by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.

In the above series of reactions, the formula (1)
In place of the α, β-unsaturated carboxylic acid represented by 5),
Esters of the α, β-unsaturated carboxylic acid (eg, methyl ester, ethyl ester, isopropyl ester,
alkyl ester such as t-butyl ester; cycloalkyl ester such as cyclohexyl ester; aryl ester such as phenyl ester; aralkyl ester such as benzyl ester) with diene (14),
An ester corresponding to the cyclohexene carboxylic acid represented by the above formulas (16a) and (16b) is produced, and the same as above, (i) a metal containing a metal element selected from W, Mo, V and Mn By reacting with hydrogen peroxide in the presence of a compound, or (ii) reacting with a peroxide containing the metal element, a hydroxyoxabicyclooctanone derivative (cyclic alcohol derivative) (17a), (17b) ,
(17c) and (17d) can be obtained. The reaction conditions and the like are the same as in the case where the α, β-unsaturated carboxylic acid (14) is used.

The hydroxyoxabicyclooctanone derivatives (17a), (17b), (17c), (17
In d), the compounds represented by the formulas (17a) and (17c) correspond to the cyclic alcohol derivative which is a raw material of the compound represented by the formula (2k), and are represented by the formulas (17b) and (17d). The compound represented by the above formula corresponds to a cyclic alcohol derivative which is a raw material of the compound represented by the formula (2l).

[Monomer Unit of the Formula (IIm)]
The monomer forming the monomer unit of m) is represented by the following formula (2m)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group)

Representative examples include the following compounds, but are not limited thereto. [2-80] 8- (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^{2, 6]} decan-5-one (R ^a = H or CH ₃₎ [2-81] 9 - (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^{2, 6]} decan-5-one (R ^a = H or CH ₃₎

[Monomer unit of the formula (IIn)]
The monomer forming the monomer unit of n) is represented by the following formula (2n)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (In the formula, R ⁵⁸ and R ⁵⁹ may be the same or different and may be protected by a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyl group which may be protected by a protecting group, or a protecting group. a hydroxy methyl group or -COOR ^b group .R ⁵⁸
And R ⁵⁹ may combine with each other to form a hydrocarbon ring, an acid anhydride ring or a lactone ring with two adjacent carbon atoms. q represents 0 or 1. R ^b represents a hydrogen atom, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxepanyl group, a lower alkyl group or a tertiary hydrocarbon group.

Representative examples include the following compounds, but are not limited thereto. [2-82] 2-norbornene (R ⁵⁸ ＲR ^{59 、} H, q = 0) [2-83] 2-hydroxy-5-norbornene (R ⁵⁸ ＯO
H, R ⁵⁹ = H, q = 0) [2-84] 2- (t-butoxycarbonyl) -5-norbornene (R ⁵⁸ = t-butoxycarbonyl group, R ⁵⁹ = H,
q = 0) [2-85] 2- (2-tetrahydropyranyloxycarbonyl) -5-norbornene (R ⁵⁸ = 2-tetrahydropyranyloxycarbonyl group, R ⁵⁹ = H, q = 0) [2-86 2- (2-methyl-2-adamantyloxycarbonyl) -5-norbornene (R ⁵⁸ = 2-methyl-2)
Adamantyloxycarbonyl group, R ⁵⁹ = H, q =
0) [2-87] 2- (1-Methyl-1-adamantylethoxycarbonyl) -5-norbornene (R ⁵⁸ = 1-methyl-
1-adamantylethoxycarbonyl group, R ⁵⁹ ＨH, q
= 0) [2-88] 4-oxatricyclo [5.3.1.0 ^2,6 ]
Decane-8-en-3-one ^{(R 58 + R 59 = -CO} -O
—CH ₂ —, q = 0)

[Monomer unit of the formula (IIo)]
The monomer forming the monomer unit of o) is represented by the following formula (2)
o)

Embedded image The following compounds represented by [2-89] Maleic anhydride

The photosensitive resin of the present invention contains the polymer compound for a photoresist of the present invention and a photoacid generator.

Examples of the photoacid generator include common 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 photosensitive resin composition 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, a dye). For example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof, and the like. Is also good.

After coating the photosensitive resin composition on a substrate or a substrate and drying, the coating film (resist film) is exposed to a light beam through a predetermined mask (or further subjected to a post-exposure bake). (Perform) By forming a latent image pattern and then developing, a fine pattern can be formed with high accuracy.

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 beams having various wavelengths, for example, ultraviolet rays and X-rays can be used for exposure. For semiconductor resists, g-rays, i-rays, 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 .

An acid is generated from the photoacid generator by light irradiation,
By this acid, for example, a protective group (leaving group) such as a carboxyl group of the alkali-soluble unit of the polymer compound is rapidly eliminated, and a carboxyl group or the like contributing to solubilization is generated. Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developing solution.

[0147]

The polymer compound of the present invention has high etching resistance when used for a photoresist. Further, the resolution is high and a fine pattern can be formed with high accuracy. According to the photoresist polymer compound of the present invention,
Adhesion to the substrate, transparency, alkali solubility and etching resistance can be expressed in a well-balanced manner. According to the photoresist resin composition of the present invention and the method of manufacturing a semiconductor, since the photoresist polymer compound is used,
A fine pattern can be formed with high accuracy. Further, according to the present invention, there is provided a novel norbornene derivative useful as a monomer or the like of a polymer compound for a photoresist.

[0148]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. In addition, "acrylate" after the compound number (monomer number) indicates a compound having an acryloyloxy group among two compounds corresponding to the compound number described in the specification, and is referred to as "methacrylate". Represents a compound having a methacryloyloxy group among the above two compounds. The number at the lower right of the parenthesis in the structural formula indicates the mol% of the monomer unit.

Production Example 1 (Production of 2-norbornen-5-yl = norbornan-2-yl = ketone [1a-1]) 2-Norbornen-5-carbaldehyde 60 mmol,
20 mmol of 2-norbornene, 2 mmol of N-hydroxyphthalimide, 1 mmol of benzoyl peroxide and 10 ml of benzene were placed in a flask, and the mixture was stirred at 80 ° C. for 12 hours under an argon atmosphere, and then 1 mmol of benzoyl peroxide was added. The mixture was stirred under the conditions for 12 hours. As a result, 2-norbornen-5-yl = norbornane-
2-yl ketone was obtained in a yield of 52% (selectivity 79).
%). [Spectral data of 2-norbornen-5-yl = norbornan-2-yl = ketone] ¹ H-NMR (CDCl ₃ ) δ: 6.28 (dd, 1
H), 6.09 (dd, 1H), 4.0-0.8 (m,
18H) MS m / e: 39, 66, 91, 216.

According to the above method, 2-norbornene-
5-yl = 4-oxatricyclo [5.2.1.
0 ^2,6 ] decane-3-one-9-yl ketone [1a-
3], 2-norbornen-5-yl = 5 or 6-t-butoxycarbonylnorbornan-2-yl = ketone [1a
-8].

Production Example 2 (2-norbornen-5-yl = 2- (adamantane-
Preparation of 1-yl) ethyl ketone [1a-9] 60 mmol of 2-norbornene-5-carbaldehyde,
20 mmol of 1-vinyl adamantane, 2 mmol of N-hydroxyphthalimide, 1 mmol of benzoyl peroxide, and 10 ml of benzene were placed in a flask, and stirred at 80 ° C. for 12 hours under an argon atmosphere, and then 1 mmol of benzoyl peroxide was added. The mixture was stirred under the same conditions for 12 hours. As a result, 2-norbornen-5-yl = 2- (adamantan-1-yl) ethyl = ketone was obtained in a yield of 26% (selectivity 49%). [2-norbornen-5-yl = 2- (adamantane-
1-yl) ethyl = ketone spectral data] MS m / e: 66,135,285 (M + 1)

Production Example 3 (Production of 2-norbornen-5-yl = adamantan-2-ylmethyl ketone [1a-11]) 2-Norbornen-5-carbaldehyde 60 mmol,
20 mmol of 2-methylene adamantane, 2 mmol of N-hydroxyphthalimide, 1 mmol of benzoyl peroxide, and 10 ml of benzene were placed in a flask, and the mixture was stirred at 80 ° C. for 12 hours under an argon atmosphere, and then 1 mmol of benzoyl peroxide was added. The mixture was stirred under the same conditions for 12 hours. As a result, 2-norbornen-5-yl = adamantan-2-ylmethyl = ketone was obtained with a yield of 32% (selectivity 53%). [Spectral data of 2-norbornen-5-yl = adamantan-2-ylmethyl = ketone] MS m / e: 66, 94, 135, 272 (M + 1)

Production Example 4 (Production of α- (2-norbornen-5-yl) -γ-butyrolactone [1b-1]) Manganese (II) acetate (0.4 mmol), cobalt (II) acetate (0. 02 mmol) and benzaldehyde (1
Mmol) in an acetic acid solution (20 ml) containing norbornanediene (300 mmol) and γ-butyrolactone (2).
0 mmol) and reacted at 90 ° C. for 5 hours under normal pressure air. The unreacted raw materials and the solvent were distilled off under reduced pressure, and the obtained concentrate was purified by silica gel column chromatography to obtain α- (2-norbornene-5-
Il) -γ-butyrolactone was obtained in a yield of 23%. [Spectral data of α- (2-norbornen-5-yl) -γ-butyrolactone] MS m / e: 66, 84, 179

The same operation as described above was carried out except that δ-valerolactone was used instead of γ-butyrolactone.
(2-Norbornen-5-yl) -δ-valerolactone [1b-2] was obtained. Also, instead of γ-butyrolactone, 5-hydroxy-3-oxatricyclo [4.2.1.
The same operation as described above was carried out except that [ ^04,8 ] nonan-2-one was used to obtain 5-hydroxy-1- (2-norbornen-5-yl) -3-oxatricyclo [4.2.1]. .0
^4,8 ] nonan-2-one [1b-3] was obtained.

Production Example 5 (2- (2-norbornen-5-yl) -4-oxato
Licyclo [5.2.1.0^2,6] Decan-3-one [1b-
4] Production of manganese (II) acetate (0.4 mmol), cobalt acetate
(II) (0.02 mmol) and benzaldehyde (1
Acetic acid solution (20 ml) containing
(300 mmol) and 4-oxatricyclo
[5.2.1.0 ^2,6] Decane-3-one (20 mM
And reacted at 90 ° C. for 5 hours under normal pressure air.
The unreacted raw materials and the solvent are distilled off under reduced pressure, and the resulting concentrate is obtained.
Is purified by silica gel column chromatography.
By doing so, 2- (2-norbornen-5-yl)-
4-oxatricyclo [5.2.1.0^2,6] Decane-
3-one was obtained with a yield of 13%. [2- (2-norbornen-5-yl) -4-oxato
Licyclo [5.2.1.0^2,6] Decane-3-one
Spectrum data] MS m / e: 66, 69, 218, 246

Example 1 Synthesis of a polymer compound having the following structure

Embedded image In a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 4.50 g (17 mmol) of monomer [1a-3], 1.63 g (17 mmol) of monomer [2-89], and monomer [2
-1] 3.94 g (16 mmol) of (acrylate) and 1.00 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries) were added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. After drying the collected precipitate under reduced pressure, it was dissolved in 10 g of tetrahydrofuran,
By repeating the above-mentioned precipitation purification operation twice, 6.5 g of a desired resin was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 5000 and the molecular weight distribution was 2.3.
Met. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0
In addition to -3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed around 2.8, 3.5, and 4.7 ppm. The SP value of the polymer is 22.60 (J / c
m ³ ) ^1/2 .

Example 2 Synthesis of polymer compound having the following structure

Embedded image In a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 4.50 g (17 mmol) of monomer [1a-3], 1.63 g (17 mmol) of monomer [2-89], and monomer [2
-24] (acrylate) 3.94 g (16 mmol),
And 1.00 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries) was added, and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. After drying the collected precipitate under reduced pressure, it was dissolved in 10 g of tetrahydrofuran,
By repeating the above-mentioned precipitation purification operation twice, 6.0 g of a desired resin was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 4,500, and the molecular weight distribution was 2.3.
Met. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0
-3.0 ppm (broad), 2.1, 2.8,
Strong signals were observed at around 3.5 and 4.7 ppm. The SP value of the polymer is 22.10 (J / cm ³ ) ^1/2 .

Example 3 Synthesis of polymer compound having the following structure

Embedded image 4.10 g (15 mmol) of monomer [1a-3], 0.57 g (6 mmol) of monomer [2-82], and monomer [2-8] in a 50-ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
9] 1.63 g (21 mmol), monomer [2-1] (acrylate) 3.23 g (13 mmol), and 1.00 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries) were added, and n-acetic acid n-
Dissolved in 10 g of butyl. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate is dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation is repeated twice to obtain a desired resin 7.1.
g was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,200 and the molecular weight distribution was 2.1.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-3.0 p
pm (broad), 1.7, 2.1, 2.8,
Strong signals were observed at around 3.5 and 4.6 ppm. The SP value of the polymer is 21.92 (J / cm ³ ) ^1/2 .

Example 4 Synthesis of polymer compound having the following structure

Embedded image 4.10 g (15 mmol) of monomer [1a-3], 0.57 g (6 mmol) of monomer [2-82], and monomer [2-8] in a 50-ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
9] 1.63 g (21 mmol), 2.89 g (13 mmol) of monomer [2-24] (acrylate), and 0.95 g of initiator (V-601 manufactured by Wako Pure Chemical Industries) were added, and acetic acid n
-Dissolved in 10 g of butyl. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate is dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation is repeated twice to obtain a desired resin 6.9.
g was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,200 and the molecular weight distribution was 2.1.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-3.0 p
pm (broad), 2.1, 2.8, 3.5,
A strong signal was observed at around 4.6 ppm. SP value of the polymer is ^{21.92 (J / cm 3) 1} /2.

Example 5 Synthesis of polymer compound having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
3.5g (15mmol) of monomer [1a-3]
0.96 g (5 mmol) of monomer [1a-1], monomer [2-89]
1.76 g (18 mmol), monomer [2-1] (acrylic
Rate) 3.82 g (15 mmol) and initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of butyl. Next, dry the inside of the flask
After purging with nitrogen, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. Hexane and ethyl acetate
To a mixture (3: 1), and the resulting precipitate is filtered.
Purification was performed separately. The collected precipitate is dried under reduced pressure
Then, it was dissolved in 10 g of tetrahydrofuran,
By repeating the purification operation twice, the desired resin 6.9 was obtained.
g was obtained. The weight of the recovered polymer was determined by GPC analysis.
The average molecular weight was 6,200 and the molecular weight distribution was 2.1.
¹In H-NMR (in DMSO-d6) analysis, 1.0-3.0 p
pm (broad), 1.6, 2.1, 2.8,
Strong signals were observed around 3.5 and 4.6 ppm.
Was. The SP value of the polymer is 21.95 (J / cm ^Three)^1/2so
is there.

Example 6 Synthesis of polymer compound having the following structure

Embedded image 5.6 g (19 mmol) of monomer [1a-8], 1.66 g (19 mmol) of monomer [2-89], and monomer [2-5] in a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
9] (Acrylate) 2.25 g (9.5 mmol) and 1.0 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries)
It was dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated twice to obtain 7.4 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,000 and the molecular weight distribution was 2.0. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.6, 2.1,
Strong signals were observed at around 2.8, 3.5, 4.6 ppm. The SP value of the polymer is 22.24 (J / c
m ³ ) ^1/2 .

Example 7 Synthesis of polymer compound having the following structure

Embedded image 4.0 g (14 mmol) of monomer [1a-8], 1.33 g (14 mmol) of monomer [2-89], and monomer [2-
1] (acrylate) 1.12 g (4 mmol), monomer [2-59] (acrylate) 3.23 g (14 mmol)
l) and initiator (V-601 manufactured by Wako Pure Chemical Industries) 1.0 g
Was dissolved in 10 g of n-butyl acetate. continue,
After the atmosphere in the flask was replaced with dry nitrogen, the temperature of the reaction system was reduced to 70%.
The mixture was stirred at a temperature of 6 ° C. for 6 hours under a nitrogen atmosphere. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate,
Purification was performed by filtering off the resulting precipitate. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated twice to obtain 6.5 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,600 and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis,
1.0-3.0 ppm (broad), 1.7,
Strong signals were observed around 2.1, 2.8, 3.5, and 4.7 ppm. The SP value of the polymer is 22.20 (J
/ Cm ³ ) ^1/2 .

Example 8 Synthesis of polymer compound having the following structure

Embedded image 4.0 g (14 mmol) of monomer [1a-8], 1.33 g (14 mmol) of monomer [2-89], monomer [2-2] in a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
4] (acrylate) 0.89 g (4 mmol), monomer [2-59] (acrylate) 3.23 g (14 mmol)
l) and initiator (V-601 manufactured by Wako Pure Chemical Industries) 0.92
g was added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-described precipitation purification operation was repeated twice to obtain 6.1 g of a desired resin. G of recovered polymer
As a result of PC analysis, the weight average molecular weight was 6,300, and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-3.0 ppm (broad), and also
Strong signals were observed around 7, 2.1, 2.8, 3.5, and 4.7 ppm. The SP value of the polymer is 22.20
(J / cm ³ ) ^1/2 .

Example 9 Synthesis of polymer compound having the following structure

Embedded image 0.67 g (2.5 mmol) of monomer [1a-9] was placed in a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
4.0 g (15 mmol) of monomer [1a-3], monomer [2
-89] 1.69 g (18 mmol), 3.69 g (14 mmol) of monomer [2-1] (acrylate), and 1.0 g of an initiator (V-601, manufactured by Wako Pure Chemical Industries), and n-acetic acid n-
Dissolved in 10 g of butyl. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate is dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation is repeated twice to obtain a desired resin 6.9.
g was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 5,800 and the molecular weight distribution was 2.2.
^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-3.0 p
pm (broad), 1.7, 2.1, 2.8,
Strong signals were observed at around 3.5 and 4.7 ppm. The SP value of the polymer is 21.92 (J / cm ³ ) ^1/2 .

Example 10 Synthesis of polymer compound having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
0.81 g (3 mmol) of monomer [1a-9]
9.93 g (18 mmol) of monomer [2-88], monomer [2-8]
9] 2.05 g (21 mmol), monomer [2-1]
4.44 g (18 mmol) and initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of chill. Next, dry nitrogen inside the flask.
After the substitution, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. The reaction solution was diluted with hexane and ethyl acetate.
Drop into 100 ml of a 3: 1 mixture and filter off the resulting precipitate
To perform purification. After drying the collected precipitate under reduced pressure,
Dissolved in 10 g of tetrahydrofuran and purified by precipitation as described above.
By repeating the operation twice, 5.9 g of the desired resin was obtained.
Obtained. As a result of GPC analysis of the recovered polymer, the weight average
The molecular weight was 5,400 and the molecular weight distribution was 2.1.¹H
In NMR (in DMSO-d6) analysis, 1.0-3.0 pp
m (broad), 1.7, 2.1, 2.8, 3.
Strong signals were observed around 5, 4.6 ppm. Po
The SP value of the reamer is 22.02 (J / cm ^Three)^1/2It is.

Example 11 Synthesis of a polymer having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
0.81 g (3 mmol) of monomer [1a-9]
9.93 g (18 mmol) of monomer [2-88], monomer [2-8]
9] 2.05 g (21 mmol), monomer [2-24]
4.00 g (18 mmol) and initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of chill. Next, dry nitrogen inside the flask.
After the substitution, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. The reaction solution was diluted with hexane and ethyl acetate.
Drop into 100 ml of a 3: 1 mixture and filter off the resulting precipitate
To perform purification. After drying the collected precipitate under reduced pressure,
Dissolved in 10 g of tetrahydrofuran and purified by precipitation as described above.
By repeating the operation twice, 6.4 g of the desired resin is obtained.
Obtained. As a result of GPC analysis of the recovered polymer, the weight average
The molecular weight was 5,600 and the molecular weight distribution was 2.1.¹H
In NMR (in DMSO-d6) analysis, 1.0-3.0 pp
m (broad), 1.7, 2.1, 2.8, 3.
Strong signals were observed around 5, 4.6 ppm. Po
The SP value of the reamer is 22.02 (J / cm ^Three)^1/2It is.

Example 12 Synthesis of polymer compound having the following structure

Embedded image 0.47 g (2.5 mmol) of monomer [1a-1] was placed in a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
4.07 g (15 mmol) of monomer [1a-3], monomer
[2-89] 1.72 g (18 mmol), monomer [2-1]
3.74 g (15 mmol) of (acrylate) and 1.0 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries) were added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. After drying the collected precipitate under reduced pressure, the precipitate is dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation is repeated twice to obtain the desired resin 6.
3 g were obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,000 and the molecular weight distribution was 2.1. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-3.
In addition to 0 ppm (broad), 1.7, 2.1, 2..
Strong signals were observed around 8, 3.5, and 4.7 ppm. The SP value of the polymer is 22.03 (J / cm ³ ) ^1/2
It is.

Example 13 Synthesis of polymer compound having the following structure

Embedded image 0.47 g (2.5 mmol) of monomer [1a-1] was placed in a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
4.07 g (15 mmol) of monomer [1a-3], monomer
[2-89] 1.72 g (18 mmol), monomer [2-24]
3.22 g (15 mmol) of (acrylate) and 1.0 g of an initiator (V-601 manufactured by Wako Pure Chemical Industries) were added and dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. After drying the collected precipitate under reduced pressure, the precipitate is dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation is repeated twice to obtain the desired resin 6.
0 g was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 5,800 and the molecular weight distribution was 2.3. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-3.
In addition to 0 ppm (broad), 1.7, 2.1, 2..
Strong signals were observed around 8, 3.5, and 4.7 ppm. The SP value of the polymer is 22.03 (J / cm ³ ) ^1/2
It is.

Example 14 Synthesis of polymer compound having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
0.58 g (3 mmol) of monomer [1a-1]
2.76 g (18 mmol) of monomer [2-88], monomer [2-8]
9] 2.10 g (21 mmol), monomer [2-1] (ac
4.56 g (18 mmol) and initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of chill. Next, dry nitrogen inside the flask.
After the substitution, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. The reaction solution was diluted with hexane and ethyl acetate.
Drop into 100 ml of a 3: 1 mixture and filter off the resulting precipitate
To perform purification. After drying the collected precipitate under reduced pressure,
Dissolved in 10 g of tetrahydrofuran and purified by precipitation as described above.
By repeating the operation twice, 6.9 g of the desired resin is obtained.
Obtained. As a result of GPC analysis of the recovered polymer, the weight average
The molecular weight was 5,700 and the molecular weight distribution was 2.2.¹H
In NMR (in DMSO-d6) analysis, 1.0-3.0 pp
m (broad), 1.7, 2.1, 2.8, 3.
Strong signals were observed around 5, 4.7 ppm. Po
The SP value of the reamer is 22.12 (J / cm ^Three)^1/2It is.

Example 15 Synthesis of a polymer having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
0.58 g (3 mmol) of monomer [1a-1]
2.76 g (18 mmol) of monomer [2-88], monomer [2-8]
9] 2.10 g (21 mmol), monomer [2-24]
4.06 g (18 mmol) and initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of chill. Next, dry nitrogen inside the flask.
After the substitution, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. The reaction solution was diluted with hexane and ethyl acetate.
Drop into 100 ml of a 3: 1 mixture and filter off the resulting precipitate
To perform purification. After drying the collected precipitate under reduced pressure,
Dissolved in 10 g of tetrahydrofuran and purified by precipitation as described above.
By repeating the operation twice, 6.1 g of the desired resin is obtained.
Obtained. As a result of GPC analysis of the recovered polymer, the weight average
The molecular weight was 6,100 and the molecular weight distribution was 2.2.¹H
In NMR (in DMSO-d6) analysis, 1.0-3.0 pp
m (broad), 1.7, 2.1, 2.8, 3.
Strong signals were observed around 5, 4.7 ppm. Po
The SP value of the reamer is 22.12 (J / cm ^Three)^1/2It is.

Example 16 Synthesis of a polymer compound having the following structure

Embedded image In a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 3.64 g (20 mmol) of monomer [1b-1], 2.00 g (20 mmol) of monomer [2-89], and monomer [2
-1] (acrylate) 4.35 g (18 mmol) and 1.0 g of initiator (V-601 manufactured by Wako Pure Chemical Industries)
It was dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-described precipitation purification operation was repeated twice to obtain 7.0 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,000 and the molecular weight distribution was 2.3. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed at around 2.8, 3.5, 4.6 ppm. The SP value of the polymer is 21.79 (J / c
m ³ ) ^1/2 .

Example 17 Synthesis of a polymer compound having the following structure

Embedded image In a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 3.64 g (20 mmol) of monomer [1b-1], 2.00 g (20 mmol) of monomer [2-89], and monomer [2
-24] (acrylate) 4.00 g (18 mmol) and initiator (Wako Pure Chemical Industries V-601) 1.0 g,
It was dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-described precipitation purification operation was repeated twice to obtain 7.0 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,200 and the molecular weight distribution was 2.1. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 2.1, 2.8,
Strong signals were observed at around 3.5 and 4.6 ppm. The SP value of the polymer is 21.79 (J / cm ³ ) ^1/2 .

Example 18 Synthesis of a polymer having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
2.74 g (15 mmol) of monomer [1b-1]
Nomer [2-82] 0.57 g (6 mmol), monomer [2-8]
9] 2.11 g (22 mmol), monomer [2-1] (ac
4.58 g (18 mmol) and initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of chill. Next, dry nitrogen inside the flask.
After the substitution, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. The reaction solution was diluted with hexane and ethyl acetate.
Drop into 100 ml of a 3: 1 mixture and filter off the resulting precipitate
To perform purification. After drying the collected precipitate under reduced pressure,
Dissolved in 10 g of tetrahydrofuran and purified by precipitation as described above.
By repeating the operation twice, 5.8 g of the desired resin is obtained.
Obtained. As a result of GPC analysis of the recovered polymer, the weight average
The molecular weight was 5,500 and the molecular weight distribution was 2.0.¹H
In NMR (in DMSO-d6) analysis, 1.0-3.0 pp
m (broad), 1.7, 2.1, 2.8, 3.
Strong signals were observed around 5, 4.6 ppm. Po
The SP value of the limer is 21.70 (J / cm ^Three)^1/2It is.

Example 19 Synthesis of polymer compound having the following structure

Embedded image50 ml round bottom flask equipped with a reflux tube, stirrer, and 3-way cock
2.74 g (15 mmol) of monomer [1b-1]
Nomer [2-82] 0.57 g (6 mmol), monomer [2-8]
9] 2.11 g (22 mmol), monomer [2-24]
4.08 g (18 mmol) and an initiator
(V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
Dissolved in 10 g of chill. Next, dry nitrogen inside the flask.
After the substitution, keep the temperature of the reaction system at 70 ° C and maintain a nitrogen atmosphere.
The mixture was stirred for 6 hours. The reaction solution was diluted with hexane and ethyl acetate.
Drop into 100 ml of a 3: 1 mixture and filter off the resulting precipitate
To perform purification. After drying the collected precipitate under reduced pressure,
Dissolved in 10 g of tetrahydrofuran and purified by precipitation as described above.
By repeating the operation twice, 5.8 g of the desired resin is obtained.
Obtained. As a result of GPC analysis of the recovered polymer, the weight average
The molecular weight was 5,500 and the molecular weight distribution was 2.0.¹H
In NMR (in DMSO-d6) analysis, 1.0-3.0 pp
m (broad), 1.7, 2.1, 2.8, 3.
Strong signals were observed around 5, 4.6 ppm. Po
The SP value of the limer is 21.70 (J / cm ^Three)^1/2It is.

Example 20 Synthesis of a polymer having the following structure

Embedded image 3.84 g (20 mmol) of the monomer [1b-2], 2.00 g (20 mmol) of the monomer [2-89], and the monomer [2
-1] (acrylate) 4.35 g (18 mmol) and 1.0 g of initiator (V-601 manufactured by Wako Pure Chemical Industries)
It was dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated twice to obtain 6.8 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,100 and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed around 2.8, 3.5, and 4.8 ppm. The SP value of the polymer is 21.55 (J / c
m ³ ) ^1/2 .

Example 21 Synthesis of a polymer having the following structure

Embedded image 3.84 g (20 mmol) of the monomer [1b-2], 2.00 g (20 mmol) of the monomer [2-89], and the monomer [2
-24] (acrylate) 4.00 g (18 mmol) and initiator (Wako Pure Chemical Industries V-601) 1.0 g,
It was dissolved in 10 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-described precipitation purification operation was repeated twice to obtain 6.1 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 5,900 and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed at around 2.8, 3.5, 4.6 ppm. The SP value of the polymer is 21.55 (J / c
m ³ ) ^1/2 .

Example 22 Synthesis of a polymer having the following structure

Embedded image 4.66 g (20 mmol) of monomer [1b-3], 2.00 g (20 mmol) of monomer [2-89], and monomer [2
-1] (acrylate) 4.35 g (18 mmol), and initiator (Wako Pure Chemical Industries V-601) 1.1 g,
It was dissolved in 11 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The recovered precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated twice to obtain 5.9 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,700, and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed at around 2.8, 3.5, 4.5, 4.6 ppm. The SP value of the polymer is 22.90 (J
/ Cm ³ ) ^1/2 .

Example 23 Synthesis of a polymer having the following structure

Embedded image 4.66 g (20 mmol) of monomer [1b-3], 2.00 g (20 mmol) of monomer [2-89], and monomer [2
-1] (acrylate) 4.35 g (18 mmol), and initiator (Wako Pure Chemical Industries V-601) 1.1 g,
It was dissolved in 11 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The recovered precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated twice to obtain 5.9 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,700, and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed at around 2.8, 3.5, 4.5, 4.6 ppm. The SP value of the polymer is 22.90 (J
/ Cm ³ ) ^1/2 .

Example 24 Synthesis of a polymer having the following structure

Embedded image In a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 4.40 g (18 mmol) of monomer [1b-4], 1.76 g (18 mmol) of monomer [2-89], and monomer [2
-1] (acrylate) 3.83 g (15 mmol), and initiator (Wako Pure Chemical Industries V-601) 1.1 g,
It was dissolved in 11 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-described precipitation purification operation was repeated twice to obtain 7.0 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,200 and the molecular weight distribution was 2.2. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 1.7, 2.1,
Strong signals were observed at around 2.8, 3.5, 4.6 ppm. The SP value of the polymer is 21.41 (J / c
m ³ ) ^1/2 .

Example 25 Synthesis of a polymer having the following structure

Embedded image In a 50 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 4.40 g (18 mmol) of monomer [1b-4], 1.76 g (18 mmol) of monomer [2-89], and monomer [2
-24] (acrylate) 3.83 g (15 mmol) and initiator (Wako Pure Chemical Industries, Ltd. V-601) 1.1 g,
It was dissolved in 11 g of n-butyl acetate. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 70 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 100 ml of a 3: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was filtered off for purification. The collected precipitate was dried under reduced pressure, dissolved in 10 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated twice to obtain 6.5 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,800 and the molecular weight distribution was 2.1. ^{In 1} H-NMR (in DMSO-d6) analysis, 1.0-
In addition to 3.0 ppm (broad), 2.1, 2.8,
Strong signals were observed at around 3.5 and 4.6 ppm. The SP value of the polymer is 21.41 (J / cm ³ ) ^1/2 .

Test Example 100 parts by weight of the polymer obtained in the example and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were dissolved in ethyl lactate to prepare a resin composition for a photoresist having a polymer concentration of 20% by weight. 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. After pre-baking on a hot plate at a temperature of 110 ° C. for 120 seconds, exposure was performed at a dose of 30 mJ / cm ² through a mask using a KrF excimer laser having a wavelength of 247 nm, and then post-baking was performed at a temperature of 120 ° C. for 60 seconds. Next, the film was developed with a 0.3 M aqueous solution of tetramethylammonium hydroxide for 60 seconds, and then rinsed with pure water.
And space was obtained.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Keizo Inoue 62, Ogama, Higashi-machi, Himeji-shi, Hyogo (72) Inventor Katsunori Funaki 1367-5 Shinzai, Aboshi-ku, Himeji-shi, Hyogo 22-4 Arashiyama-cho (72) Inventor Akira Horai 940 F-term of new resident at Hibashi-ku, Hyogo Prefecture Abashiri-ku 940 F-term (reference) AR11Q BA03P BA11P BA12P BA20Q BC08P BC09P BC09Q BC12Q BC53P CA01 CA04 DA28 HA08 HC04 HC54 HC69 HE07 JA38

Claims (7)

[Claims] (1) The following formulas (Ia) and (Ib) (Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms,
A hydroxyl group optionally protected by a protecting group, a hydroxymethyl group optionally protected by a protecting group, or -CO
Represents an OR ³ group. R ³ represents a hydrogen atom, a tertiary hydrocarbon group which may have a substituent, a tetrahydrofuranyl group or a tetrahydropyranyl group. Y represents a monovalent alicyclic group which may have a substituent. n represents 0, 1 or 2. R ² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A hydroxyl group which may be protected with a protecting group or a hydroxymethyl group which may be protected with a protecting group.
L represents a 5- or more-membered lactone ring which may have a substituent. Wherein the norbornane ring in the formula may have a substituent in addition to the substituents shown in the formula). 2. At least one monomer unit selected from the formulas (Ia) and (Ib) and the following formulas (IIa) to (IIo): Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹¹ and R ¹² are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ^{13 to} R ¹⁵ are the same or different. , Hydrogen atom,
It represents a methyl group or a hydroxyl group which may be protected by a protecting group. R ^{16 to} R ¹⁸ are the same or different and represent a hydrogen atom, a methyl group, a hydroxyl group which may be protected by a protecting group, or a —COOR ^b group. R ¹⁹ represents a methyl group or an ethyl group, R ²⁰ and R ²¹ are the same or different,
It represents a hydrogen atom, a hydroxyl group or an oxo group which may be protected by a protecting group. R ²² is a hydrogen atom or a carbon number of 1 to
Shows 10 hydrocarbon groups. R ²³ represents a tertiary hydrocarbon group which may have a substituent. R ²⁴ to R ²⁸ are the same or different, represent a hydrogen atom or a methyl group. R ^{29 to} R
³³ is the same or different and represents a hydrogen atom or a methyl group. R ³⁴ to R ³⁶ are the same or different and each represents a hydrogen atom or a methyl group, V ¹ ~V ³ are the same or different, -CH
_{It represents 2-} , -CO- or -COO-. R ³⁷ and R
³⁹ is the same or different and represents a hydrogen atom or a methyl group, and R ³⁸ represents a hydrogen atom, a methyl group, a hydroxyl group which may be protected by a protecting group, or a -COOR ^b group. R
⁴⁰ to R ⁴⁸ are the same or different, represent a hydrogen atom, a methyl group or an ethyl group. R ^{49 to} R ⁵⁷ are the same or different,
Represents a hydrogen atom, a methyl group or an ethyl group. R ⁵⁸ and R ⁵⁹
Is the same or different and represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyl group optionally protected by a protecting group, a hydroxymethyl group optionally protected by a protecting group, or a -COOR ^b group. Show. R ⁵⁸ and R ⁵⁹ may combine with each other to form a hydrocarbon ring, an acid anhydride ring or a lactone ring with two adjacent carbon atoms. p represents an integer of 1 to 3, and q represents 0 or 1. R ^b represents a hydrogen atom, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxepanyl group, a lower alkyl group or a tertiary hydrocarbon group which may have a substituent. 2. The polymer compound according to claim 1, comprising a unit. 3. The polymer compound according to claim 1, wherein the solubility parameter value according to the Fedors method is in the range of 19.5 to 24.5 (J / cm ³ ) ^1/2 . 4. The polymer compound according to claim 1, which is a polymer compound for a photoresist. 5. A photosensitive resin composition comprising at least the photoresist polymer compound according to claim 4 and a photoacid generator. 6. A method for producing a semiconductor, comprising a step of applying the photosensitive resin composition according to claim 5 on a substrate or a substrate to form a resist coating film and forming a pattern through exposure and development. 7. A compound represented by the following formula (Ia) or (Ib): (Wherein, R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms,
A hydroxyl group optionally protected by a protecting group, a hydroxymethyl group optionally protected by a protecting group, or -CO
Represents an OR ³ group. R ³ represents a hydrogen atom, a tertiary hydrocarbon group which may have a substituent, a tetrahydrofuranyl group or a tetrahydropyranyl group. Y represents a monovalent alicyclic group which may have a substituent. n represents 0, 1 or 2. R ² is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A hydroxyl group which may be protected with a protecting group or a hydroxymethyl group which may be protected with a protecting group.
L represents a 5- or more-membered lactone ring which may have a substituent. The norbornene ring in the formula may have a substituent in addition to the substituent shown in the formula).