JP2002338627A - Polymer compound for photoresist and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer compound which exhibits a high etching resistance when used for a photoresist. SOLUTION: This polymer compound contains at least one kind of monomer unit selected from monomer units represented by formulas (Ia)-(Ig) [wherein Ra is H or methyl; R1 and R2 are each H or a 1-5C hydrocarbon group; R3 is an optionally substituted tertiary hydrocarbon group; R4 is H, a 1-20C hydrocarbon group, hydroxyl, etc.; A is a single bond, methylene, ethylene, etc.; L is an optionally substituted 5-membered or higher lactone ring; X is an optionally substituted divalent alicyclic group; Y, Y1, and Y2 are each an optionally substituted monovalent alicyclic group (with the proviso that n is 0, then Y in formula (Ic) excludes an optionally substituted adamantyl group); m is 0 or 1; and n, n1, and n2 are each 0, 1 or 2].

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 photoresist polymer or the like used in microfabrication of semiconductors, and a novel (meth) acrylate ester useful as a raw material for the polymer compound. The present invention relates to a derivative, a resin composition for a photoresist containing the polymer 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. Attention has also been drawn to units having a lactone skeleton as monomer units for imparting substrate adhesion. Furthermore, a unit having a 2-methyladamantan-2-yl group or the like is known as a monomer unit that imparts a function of being eliminated by an acid generated from a photoacid generator upon exposure to become soluble in an alkaline developer. I have. Conventionally, various photoresist resins have been proposed by appropriately combining these monomer units. However, conventional photoresist resins have not always been satisfactory in terms of substrate adhesion, etching resistance, acid desorption properties, balance of these properties, resolution, cost, and the like.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polymer compound having high etching resistance when used for a photoresist, and a novel (meth) acrylic acid useful as a monomer of the polymer compound. An object of the present invention is to provide an acid ester derivative. Another object of the present invention is to provide a high molecular compound capable of forming a fine pattern with high resolution when used for a photoresist, and a novel (meth) compound useful as a monomer of the high molecular compound. An object of the present invention is to provide an acrylate derivative.

Another object of the present invention is to provide a polymer compound which exhibits high performance as a photoresist resin and can be produced at low cost, and a novel (meth) acrylic acid useful as a monomer of the polymer compound. An object of the present invention is to provide an ester derivative. 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.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, when a (meth) acrylate derivative having a specific alicyclic skeleton is polymerized as a monomer, excellent performance is obtained. It has been found that a photoresist resin having the following formula is obtained, and the present invention has been completed.

That is, the present invention provides the following formulas (Ia) to (Ia)
g)

Embedded image [Wherein, ^Ra represents a hydrogen atom or a methyl group. R ¹ , R ²
Represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³
Represents a tertiary hydrocarbon group which may have a substituent, a tetrahydropyranyl group or a tetrahydrofuranyl group.
R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group which may be protected by a protecting group, or a hydroxymethyl group which may be protected by a protecting group. A represents a single bond, a methylene group, an ethylene group or a hydroxyethylene group. L represents a 5- or more-membered lactone ring which may have a substituent. X represents a divalent alicyclic group which may have a substituent. Y, Y ¹ and Y ² each represent a monovalent alicyclic group which may have a substituent (provided that when n in n in the formula (Ic) is 0, it has a substituent) Adamantyl group which may be substituted). m represents 0 or 1.
n, n1, and n2 each represent 0, 1, or 2]; and a polymer compound comprising at least one monomer unit selected from the group consisting of:

[0008] The polymer compound is represented by the above formulas (Ia) to (Ia).
g) at least one monomer unit selected from:
Formulas (IIa) to (IIo) below

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 above-mentioned 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-mentioned polymer compound for a photoresist and a photoacid generator.

[0011] The present invention further provides a resist coating film by applying the above 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 provides the following formula (1a):
(1b), (1c), (1d), (1e), (1f) or (Ig)

Embedded image [Wherein, ^Ra represents a hydrogen atom or a methyl group. R ¹ , R ²
Represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³
Represents a tertiary hydrocarbon group which may have a substituent, a tetrahydropyranyl group or a tetrahydrofuranyl group.
R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group which may be protected by a protecting group, or a hydroxymethyl group which may be protected by a protecting group. A represents a single bond, a methylene group, an ethylene group or a hydroxyethylene group. L represents a 5- or more-membered lactone ring which may have a substituent. X represents a divalent alicyclic group which may have a substituent. Y, Y ¹ and Y ² each represent a monovalent alicyclic group which may have a substituent (provided that when n in n in the formula (Ic) is 0, it has a substituent) Adamantyl group which may be substituted). m represents 0 or 1.
n, n1, n2 represent 0, 1, or 2] (meta)
Provide an acrylic ester.

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 is “(M) AL”, the t-butyl group is “tBu”, and the tetrahydropyranyl group is “THP”
May be abbreviated. As a protecting group for a hydroxyl group or a hydroxymethyl group, a protecting group commonly used in the field of organic synthesis is used.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer compound of the present invention is represented by the above formulas (Ia) to (I) as structural units constituting a polymer molecule.
g) at least one type of monomer unit (repeating unit) (hereinafter sometimes referred to as “monomer unit 1”).

Of these monomer units, formulas (Ia) and (Ia)
The monomer units represented by b), (If), and (Ig) have a function of significantly increasing etching resistance because one monomer unit contains two or more alicyclic skeletons.
The monomer unit represented by the formula (Ic) has an excellent alkali-soluble function (acid-eliminating function). The monomer unit represented by the formula (Id) has high resolution since one monomer unit contains two or more acid-labile groups. Since the lactone ring is bonded to the alicyclic skeleton, the monomer unit represented by the formula (Ie) exhibits not only etching resistance but also high adhesion to a substrate. In addition, among the monomer units represented by the formula (Ia), m = 1, among the monomer units represented by the formula (Ie), m = 1, and represented by the formula (Ig) The monomer unit also has an alkali-soluble function (acid-eliminating function). Further, at the time of polymer production, a monomer corresponding to each of the above monomer units may be appropriately combined, or a polymerizable monomer capable of exhibiting various functions (substrate adhesion function, alkali solubility function, etching resistance imparting function, etc.) together with the monomer. By appropriately using the compound as a comonomer, a polymer having various functions required as a resist in a well-balanced manner can be obtained. Therefore, the polymer containing the above monomer unit 1 can be used as a photoresist resin.

In the formula, Ra represents ^a hydrogen atom or a methyl group. R ¹ and R ² represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. Examples of the hydrocarbon group having 1 to 5 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl and pentyl groups; alkenyl groups such as vinyl and allyl groups; -An alkynyl group such as a propynyl group; an alicyclic hydrocarbon group such as a cyclopentyl group.

R ³ represents an optionally substituted tertiary hydrocarbon group, tetrahydropyranyl group or tetrahydrofuranyl group. Examples of the tertiary hydrocarbon group (hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom) include a t-butyl group, a t-amyl group, a 2-methyl-2-adamantyl group, And a 1-methyl-1-adamantylethyl group. The tertiary hydrocarbon group is
It may have a substituent (for example, a halogen atom, an alkyl group, a hydroxyl group optionally protected by a protecting group, an oxo group, etc.) as long as the acid-eliminating function is not impaired. R
The tetrahydropyranyl group in ³ includes a 2-tetrahydropyranyl group, and the tetrahydrofuranyl group has 2
-A tetrahydrofuranyl group is included. Two R ³ in the formula (Id) may be the same or different.

R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 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);

The aromatic hydrocarbon group includes, for example, an aromatic hydrocarbon group having 6 to 20 carbon atoms such as phenyl and naphthyl groups.

A represents a single bond, a methylene group, an ethylene group or a hydroxyethylene group. L represents a 5- or more-membered lactone ring which may have a substituent. Examples of the 5- or more-membered lactone ring include a γ-butyrolactone ring, a δ-valerolactone ring, and an ε-caprolactone ring.
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.

X represents a divalent alicyclic group which may have a substituent, and Y, Y ¹ and Y ² each represent a monovalent alicyclic group which may have a substituent. (However, as for Y in the formula (Ic), when n is 0, an adamantyl group which may have a substituent is excluded). m represents 0 or 1. n, n1,
n2 represents 0, 1 or 2.

The alicyclic ring corresponding to the divalent alicyclic group and the monovalent alicyclic group includes, 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 fused with a non-aromatic heterocyclic ring (for example, 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 a preferred embodiment of the present invention, the above-mentioned formula (Ia)
To (Ig) 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. The formula (II
In the monomer units represented by d), (IIe), (IIf) and (IIg), the carboxylic acid ester site is decomposed and eliminated by an acid to generate a free carboxyl group. Therefore, these monomer units function as alkali-soluble units for solubilizing the resin during alkali development.

Further, the formulas (IIa), (IIb), (IIc), (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), the hydrocarbon having 1 to 8 carbon atoms in R ¹¹ and R ¹² includes 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, about 1 to 95 mol%, preferably about 5 to 80 mol%, based on the entire monomer units constituting the polymer. In a preferred polymer compound, the monomer unit 2 is contained in an amount of about 5 to 99 mol% (for example, about 20 to 95 mol%) based on the entire monomer units constituting the polymer.

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 represented by the formula (Ia) and at least the formula units (IIa), (IIb), (IIi), (IIj) and (II)
combination with at least one monomer unit selected from m) (2) a monomer unit represented by formula (Ib) and at least one selected from formulas (IIb), (IIi), (IIj) and (IIm) And (3) a monomer unit represented by the formula (Ic) and at least one monomer selected from the formulas (IIb), (IIi), (IIj) and (IIm) Combination with unit (4) Combination of monomer unit represented by formula (Id) and at least one monomer unit selected from formulas (IIb), (IIi), (IIj) and (IIm) ( 5) a combination of a monomer unit represented by the formula (Ie) and at least one monomer unit selected from the formulas (IIa), (IIb), (IIi) and (IIm); ) And a monomer unit represented by At least the formulas (IIa), (IIb), (IIi), (IIj) and (II
(7) Combination with at least one monomer unit selected from m) (7) A monomer unit represented by the formula (Ig) and at least one of the formulas (IIa), (IIb), (IIi), (IIj) and (II)
m) a combination with at least one monomer unit selected from

The polymer compound of the present invention can be prepared using a solubility parameter [Polym. Eng. Sci.
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 suitably used as a polymer compound for a photoresist.

Formulas (Ia) to (Ig) and formulas (IIa) to (II)
m), each of the monomer units represented by the corresponding (meth) acrylate as a (co) monomer,
Further, each monomer unit represented by the formulas (IIn) and (IIo) represents a corresponding ethylenically unsaturated compound by (co)
It can be formed by subjecting to polymerization as a monomer. The polymerization 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). When stereoisomers exist in the compound represented by the formula (1a), they can be used alone or as a mixture.

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

[0041]

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[0042]

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[0043]

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[0044]

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

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In the above reaction scheme, the formula (3) represents an aldehyde having an alicyclic skeleton (such as an alicyclic aldehyde), the formula (4) represents an olefin having an alicyclic skeleton, and the formula (5) Represents a ketone having an alicyclic skeleton on both sides of a carbonyl group. Examples of the olefin represented by the formula (4) include an olefin having an ethylenic double bond in a ring (a cyclic olefin) [for example, when producing a compound where n = 0 in the formula (1a) or an intermediate thereof], exomethylene Alicyclic compound having a group [in the case of producing a compound of the formula (1a) wherein n = 1 or an intermediate thereof], an alicyclic compound having a vinyl group bonded to a ring [n = 2 in the formula (1a)]
For producing a compound or an intermediate thereof].

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, a small amount of a reaction component (for example, a compound represented by the formula (3) and a compound represented by the formula (4) is 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.

In producing the compound represented by the formula (1a) using the above reaction, the introduction of a (meth) acryloyloxy group or a hydroxyl group as a precursor thereof is carried out before and after the above reaction. It can be performed in any of the steps.

More specifically, for example, the above formula [1a-1]
Can be produced according to the following reaction scheme.

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That is, 2-norbornene-5-carbaldehyde (3a) and 2-norbornene (4a) are reacted in the presence of an N-substituted cyclic imide compound to obtain a corresponding ketone (5a). Is subjected to hydrosilylation or hydroboration to give a hydroxyl compound (6a), and then is reacted with (meth) acrylic acid or a reactive derivative thereof, whereby the (meth) compound represented by the formula [1a-1] is obtained.
An acrylate derivative can be obtained.

Hydrosilation or hydroboration can be performed by a conventional method (hydrosilation using a platinum or rhodium catalyst and hydrosilane, BH ₃ .THF).
And the like using a borane complex such as hydroboration. The reaction between the hydroxyl compound and (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.) can be carried out according to a conventional esterification method using an acid catalyst or a transesterification catalyst. it can.

The compound represented by the formula [1a-15] can be produced according to the following reaction scheme.

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That is, 3-hydroxyadamantane
1-carbaldehyde (3b) is reacted with 4-oxatricyclo [5.2.1.0 ^2,6 ] decane-8-en-3-one in the presence of an N-substituted cyclic imide compound, A ketone (6b) having a corresponding hydroxyl group is obtained, and reacted with (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.) to obtain a compound represented by the formula [1a-15]. (Meth) acrylic acid ester derivative can be obtained.

Further, the compound represented by the above formula [1a-34] can be produced according to the following reaction scheme.

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That is, α, α-dimethyl-2-norbornene-5-methanol (4c) and norbornane-2-carbaldehyde (3c) are reacted in the presence of an N-substituted cyclic imide compound to form a corresponding hydroxyl group. A ketone having a group (6c) is obtained, and is reacted with (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, or the like) to obtain a compound represented by the formula [1a-34] ( A (meth) acrylate derivative can be obtained.

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

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

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[0064]

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The compound represented by the formula (1b) wherein R ¹ is a hydrocarbon group having 1 to 5 carbon atoms can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein, R ^a , R ¹ , Y ¹ , Y ² , n1 and n2 are the same as above. X
¹ represents a halogen atom)

The halogen atom for X ¹ includes chlorine, bromine and iodine atoms. In the above reaction scheme, the reaction between the ketone represented by the formula (7) and the Grignard reagent represented by the formula (8) can be carried out in the same manner as a conventional Grignard reaction. The obtained alcohol (9) is reacted with (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.) according to a conventional esterification method using an acid catalyst or a transesterification catalyst. Can convert to the compound represented by the formula (1b). The ketone (7) used as a raw material in the above reaction scheme can be produced by using the above ketone production method.

More specifically, the compound represented by the above formula [1b-1] can be obtained by di (norbornan-2-yl) ketone (7a) and methylmagnesium bromide (8a) as shown in the following formula. And the corresponding alcohol form (9a)
And then reacting the alcohol (9a) with (meth) acrylic acid or a reactive derivative thereof.

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Among the compounds represented by the formula (1b), those in which R1 is a hydrogen atom are obtained by reducing the ketone represented by the above formula (7) to a corresponding alcohol compound, and then converting the alcohol compound to the above compound Similarly, it can be obtained by reacting with (meth) acrylic acid or a reactive derivative thereof.
For the reduction, a conventional reduction method (such as a method using a metal hydride complex compound such as sodium borohydride) can be used.

Further, the compound represented by the formula (1b) (for example, the compounds of [1b-22] to [1b-39]) is represented by the following formula (1b)
It can also be produced according to a method for obtaining the compound represented by f) (a method for obtaining a compound of the formula (39) from a compound of the formula (36)).

[Monomer unit of the formula (Ic)]
The monomer corresponding to the monomer unit of is represented by the above formula (1c). When stereoisomers exist in the compound represented by the formula (1c), they can be used alone or as a mixture.

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

[0072]

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[0073]

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The compound of the formula (1c) wherein R1 is a hydrocarbon group having 1 to 5 carbon atoms can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein, Ra, R1, R2, Y, n, and X1 are the same as described above)

In the above reaction scheme, the reaction between the ketone represented by the formula (10) and the Grignard reagent represented by the formula (8) can be carried out in the same manner as a conventional Grignard reaction. The obtained alcohol (11) was prepared in the same manner as in the case of the compound represented by the formula (1b),
By reacting with acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.), the compound of formula (1c)
Can be converted to the compound represented by The ketone (10) used as a raw material in the above reaction scheme can be produced by using the above-described ketone production method.

Further, among the compounds represented by the formula (1c), R
The compound in which 1 is a hydrogen atom is obtained by reducing the ketone represented by the above formula (10) to a corresponding alcohol compound, and then reacting the alcohol compound with (meth) acrylic acid or a reactive derivative thereof in the same manner as described above. Can be obtained. For the reduction, a conventional reduction method (such as a method using a metal hydride complex compound such as sodium borohydride) can be used.

[Monomer unit of the formula (Id)]
The monomer corresponding to the monomer unit of is represented by the above formula (1d). When stereoisomers exist in the compound represented by the formula (1d), they can be used alone or as a mixture.

Typical examples of the compound represented by the formula (1d) include, but are not limited to, the following compounds.

[0079]

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The compound of the formula (1d) wherein m = 1 can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein Ra, R3 and X are the same as described above)

In the above reaction scheme, the reaction between the alicyclic compound having a hydroxyl group represented by the formula (12) and the maleic acid ester or the fumaric acid ester represented by the formula (13) is carried out by an N-substituted cyclic compound. The reaction is performed in the presence of an imide compound and molecular oxygen. As the compound represented by the formula (12), a compound having a methine carbon atom (such as a bridged cyclic compound having a hydrogen atom at the bridgehead position) is preferable. The compounds described above can be used as the N-substituted cyclic imide compound.

The amount of the N-substituted imide compound to be used can be selected from a wide range.
0.00000 to 1 mole of the compound represented by 2) and the compound represented by formula (13)
The amount is about 01 to 1 mol, preferably about 0.00001 to 0.5 mol, and more preferably about 0.0001 to 0.4 mol.

As molecular oxygen, pure oxygen may be used, or oxygen or air diluted with an inert gas may be used. A radical generator can be used instead of molecular oxygen. The amount of the molecular oxygen or radical generator used may be a catalytic amount or an equivalent amount or more based on the reaction components.

In the reaction of the alicyclic compound having a hydroxyl group represented by the formula (12) with the maleic ester or fumaric ester represented by the formula (13), it is preferable to use a metal compound as a co-catalyst. . As the metal compound, for example, a hydroxide, oxide, halide, oxo acid salt, oxo acid, isopoly acid, heteropoly acid, organic acid salt, complex acid salt, or the like of a transition metal such as Co, Mn, V, and Mo is used. it can. The metal compounds can be used alone or in combination of two or more. The amount of the metal compound to be used is, for example, 0.0000001 to 1 mol of a reaction component (for example, a component used in a small amount of the compound represented by the formula (12) and the compound represented by the formula (13)). 0.1 mol, preferably 0.00
It is about 1 to 0.05 mol.

The reaction between the compound represented by the formula (12) and the compound represented by the formula (13) 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 (12) to the compound represented by the formula (13) 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 (12) and the compound represented by the formula (13).
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 under normal pressure or pressure.

The reaction produces a corresponding addition reaction product represented by the formula (14). 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.

The compound represented by the formula (14) is
By reacting with (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.) in the same manner as in the case of the compound represented by b), the compound represented by the formula (15)
[A compound represented by the formula (1d)
= 1).

Further, among the compounds represented by the formula (1d),
The compound wherein = 0 can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein, Z1 represents an alicyclic ring; R3 is the same as described above)

In the above reaction scheme, the reaction between the alicyclic compound (16) having a hydroxyl group and an ethylenically unsaturated bond in the ring and the malonic ester (17) is carried out in the presence of a metal compound and molecular oxygen. Done. Examples of the metal compound include hydroxides, oxides, halides, oxoacid salts, oxoacids, isopolyacids, and heteropolyacids of elements of Groups 5 to 9 of the periodic table (particularly, metal elements 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 to be used is, for example, from 0.0001 to 1 mol per 1 mol of the reaction component (for example, the component of the compound represented by the formula (16) and the compound represented by the formula (17) which is used in a small amount). It is about 0.1 mol, preferably about 0.0002 to 0.05 mol.

As the molecular oxygen, pure oxygen may be used, or oxygen or air diluted with an inert gas may be used. The amount of molecular oxygen used depends on the reaction components (for example, the formula (1
It is 0.5 mol or more, preferably about 1 to 100 mol, per 1 mol of the compound represented by 6) and the compound represented by the formula (17), which is used in a small amount. 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 (16) and the compound represented by the formula (17) 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 (16) to the compound represented by the formula (17) 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 (16) and the compound represented by the formula (17).
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 (18). 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.

The compound represented by the formula (18) is represented by the formula (1)
By reacting with (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.) in the same manner as in the case of the compound represented by b), the compound represented by the formula (19)
[A compound represented by the formula (1d)
= 0 compound].

[Monomer Unit of the Formula (Ie)]
The monomer corresponding to the monomer unit of is represented by the above formula (1e). When stereoisomers exist in the compound represented by the formula (1e), they can be used alone or as a mixture.

Typical examples of the compound represented by the formula (1e) include, but are not limited to, the following compounds.

[0098]

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The compound of the formula (1e) wherein m = 0 can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein R4 and L are the same as above)

In the above reaction scheme, the reaction between the norbornanediene derivative represented by the formula (20) and the lactone compound represented by the formula (21) is carried out by reacting the compound represented by the formula (16) with the compound represented by the formula (17) The reaction is performed in the presence of a metal compound and molecular oxygen as in the case of the reaction with the compound represented by the formula (1). Reaction conditions and the like are the same as described above.

The addition reaction product (2
2) is subjected to hydrosilylation or hydroboration to give a hydroxyl form (23), and then (meth)
By reacting acrylic acid or a reactive derivative thereof, a (meth) acrylic acid ester derivative represented by the formula (24) [a compound represented by the formula (1e) wherein m = 0 is obtained] Can be.

Hydrosilation or hydroboration can be carried out by a conventional method (hydrosilation using platinum or rhodium catalyst and hydrosilane, BH3.THF).
And the like using a borane complex such as hydroboration. The reaction between the hydroxyl compound and (meth) acrylic acid or a reactive derivative thereof (acid halide, acid anhydride, ester, etc.) can be carried out according to a conventional esterification method using an acid catalyst or a transesterification catalyst. it can.

Among the compounds represented by the formula (1e), the compound wherein m = 1 can be produced, for example, according to the following reaction scheme.

Embedded image (Wherein R1, R2, R4 and L are the same as above)

In the above reaction scheme, the reaction between the norbornene derivative represented by the formula (25) and the lactone compound represented by the formula (21) is carried out by reacting the compound represented by the formula (16) with the compound represented by the formula (17) The reaction is performed in the presence of a metal compound and molecular oxygen, as in the reaction with the compound represented by Reaction conditions and the like are the same as described above. Addition reaction product generated by this reaction (26)
Is reacted with (meth) acrylic acid or a reactive derivative thereof in the same manner as described above, whereby a (meth) acrylate derivative represented by the formula (27) [m of the compound represented by the formula (1e) 1) can be obtained.

[Monomer Unit of the Formula (If)]
The monomer corresponding to the monomer unit of is represented by the above formula (1f). When stereoisomers exist in the compound represented by the formula (1f), they can be used alone or as a mixture.

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

[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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Among the compounds represented by the formula (1f), the compound wherein n = 0 can be obtained by utilizing the method represented by the following reaction scheme. In addition, the compound in which n = 1 or 2 among the compounds represented by the formula (1f) can be produced according to this method.

Embedded image (Wherein, Z2 represents an alicyclic ring)

In the above reaction scheme, formula (28) is an alicyclic compound having a hydroxyl group and a hydrogen atom in the ring [in particular, an alicyclic compound having a methine carbon atom (a bridged ring having a hydrogen atom at the bridgehead position)] Formula compound etc.)], and the formula (2
9) represents an olefin having an alicyclic skeleton. Equation (29)
As the olefin represented by, an olefin having an ethylenic double bond in an alicyclic ring (cyclic olefin), an alicyclic compound having an exomethylene group, an alicyclic compound having a vinyl group bonded to an alicyclic ring, and the like are used.

The reaction between the compound represented by the formula (28) and the compound represented by the formula (29) is carried out in the presence of an N-substituted cyclic imide compound and molecular oxygen. The reaction can be carried out according to the reaction between the compound represented by the above (12) and the compound represented by the formula (13). This reaction can produce an addition reaction product represented by the formula (30) and a compound represented by the formula (31) in which the addition reaction product is further oxidized.

The compound represented by the formula (30) and the compound represented by the formula (31) are, as shown in the following reaction scheme, respectively (meth) acrylic acid or a reactive derivative thereof as described above. By reacting with (3), (meth) acrylic acid ester derivatives represented by the formulas (32) to (35) can be converted.

[0132]

Embedded image (Wherein Z2 is the same as above)

[0133]

Embedded image (Wherein Z2 is the same as above)

More specifically, as shown in the following reaction scheme, 1-adamantanol represented by the formula (28a) and 4-oxatricyclo [5.
2.1.02,6] decane-8-en-3-one;
When reacted with an N-substituted cyclic imide compound in the presence of molecular oxygen, an addition reaction product represented by the formula (30a) and a compound represented by the formula (3)
An addition-oxidation reaction product represented by 1a) is produced. These compounds are then converted to (meth)
By reacting with acrylic acid or a reactive derivative thereof, it is possible to derive the corresponding (meth) acrylic acid ester derivative represented by the formulas (32a) to (35a).

[0135]

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The compound represented by the formula (1f) can also be obtained by utilizing a method represented by the following reaction scheme.

Embedded image (Wherein, Z3 represents an alicyclic ring)

In the above reaction scheme, the formula (36) represents an alicyclic compound having a hydrogen atom in the ring [in particular, an alicyclic compound having a methine carbon atom (a bridged cyclic compound having a hydrogen atom at the bridgehead position, etc.)] )], And formula (37) represents an olefin having an alicyclic skeleton. Examples of the olefin represented by the formula (37) include an olefin having an ethylenic double bond in an alicyclic ring (cyclic olefin), an alicyclic compound having an exomethylene group, and an alicyclic compound having a vinyl group bonded to an alicyclic ring. Is used.

The reaction between the compound represented by the formula (36) and the compound represented by the formula (37) is carried out in the presence of an N-substituted cyclic imide compound and molecular oxygen. The reaction can be carried out according to the reaction between the compound represented by the above (12) and the compound represented by the formula (13). By this reaction, an alcohol having a plurality of alicyclic skeletons represented by the formula (38) can be produced. Then, the compound represented by the formula (38) is converted into a (meth) acrylic ester derivative represented by the formula (39) by reacting the compound with (meth) acrylic acid or a reactive derivative thereof as described above. it can.

More specifically, as shown in the following reaction scheme, 3-oxatricyclo [4.3.1.14,
8] undecane-2-one (36a) and 4-oxatricyclo [5.2.1.02,6] decane-8-en-3-
(37a) is reacted with an N-substituted cyclic imide compound in the presence of molecular oxygen, and then esterified with (meth) acrylic acid or a reactive derivative thereof to obtain a compound represented by the formula (39a). (Meth) acrylic acid ester can be obtained.

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[Monomer unit of the formula (Ig)]
The monomer corresponding to the monomer unit is represented by the above formula (1g). When stereoisomers exist in the compound represented by the formula (1g), they can be used alone or as a mixture.

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

[0142]

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[0143]

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[0144]

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[0145]

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The compound represented by the formula (1g) can be obtained, for example, by utilizing the method represented by the following reaction scheme.

Embedded image (In the formula, Z4 represents an alicyclic ring. R1 and R2 are the same as described above.)

In the above reaction scheme, the formula (40) represents an alcohol having an alicyclic ring having a hydrogen atom in the ring [in particular, a compound having a methine carbon atom in the alicyclic ring (a bridged cyclic compound having a hydrogen atom in the bridgehead position) And formula (41) represents an olefin having an alicyclic skeleton. Examples of the olefin represented by the formula (41) include an olefin having an ethylenic double bond in an alicyclic ring (cyclic olefin), an alicyclic compound having an exomethylene group, and an alicyclic compound having a vinyl group bonded to an alicyclic ring. Is used.

The reaction between the compound represented by the formula (40) and the compound represented by the formula (41) is carried out in the presence of an N-substituted cyclic imide compound and molecular oxygen. The reaction can be carried out according to the reaction between the compound represented by the above (12) and the compound represented by the formula (13). This reaction can produce an addition reaction product represented by the formula (42) and a compound represented by the formula (43) in which the addition reaction product is further oxidized.

The compound represented by the formula (42) and the compound represented by the formula (43) are, as shown in the following reaction scheme, respectively (meth) acrylic acid or a reactive derivative thereof as described above. By reacting with the above, it can be converted to (meth) acrylate derivatives represented by the formulas (44) to (47).

[0150]

Embedded image (Wherein, Z4 is the same as above)

[0151]

Embedded image (Wherein, Z4 is the same as above)

More specifically, as shown in the following reaction scheme, α, α-dimethyl-1 represented by the formula (40a)
-Adamantane methanol and 4 represented by the formula (41a)
-Oxatricyclo [5.2.1.02,6] decane-
When 8-ene-3-one is reacted with an N-substituted cyclic imide compound in the presence of molecular oxygen, the addition reaction product represented by the formula (42a) and the addition reaction product represented by the formula (43a) are obtained. -Oxidation reaction products are formed. And these compounds,
By reacting with (meth) acrylic acid or a reactive derivative thereof according to a conventional method, the corresponding formula (44a)-
A (meth) acrylate derivative represented by (47a) is produced.

[0153]

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The compound represented by the formula (1g) can also be obtained by utilizing the method represented by the following reaction scheme.

Embedded image (In the formula, Z5 and Z6 each represent an alicyclic ring; R1 and R2 are the same as described above.)

In the above reaction scheme, formula (48) represents an alcohol having an alicyclic ring having an ethylenic double bond in the ring, and formula (49) represents an alicyclic compound having a hydrogen atom in the ring [particularly, Compounds having a methine carbon atom in the ring (bridged cyclic compounds having a hydrogen atom at the bridgehead)].

The reaction between the compound represented by the formula (48) and the compound represented by the formula (49) is carried out in the presence of an N-substituted cyclic imide compound and molecular oxygen. The reaction can be carried out according to the reaction between the compound represented by the above (12) and the compound represented by the formula (13). This reaction can produce an addition reaction product represented by the formula (50) and a compound represented by the formula (51) in which the addition reaction product is further oxidized.

The compound represented by the formula (50) and the compound represented by the formula (51) are, as shown in the following reaction scheme, respectively (meth) acrylic acid or a reactive derivative thereof as described above. By reacting with the above, it can be converted to (meth) acrylate derivatives represented by the formulas (52) to (55).

[0158]

Embedded image (Wherein, Z5, Z6, R1, R2 are the same as above)

[0159]

Embedded image (Wherein, Z5, Z6, R1, R2 are the same as above)

More specifically, as shown in the following reaction scheme, α, α-dimethyl-2 represented by the formula (48a)
-Norbornene-5-methanol and adamantane represented by the formula (49a) are reacted with an N-substituted cyclic imide compound in the presence of molecular oxygen to obtain an addition reaction product represented by the formula (50a) And an addition-oxidation reaction product represented by the formula (51a). Then, by reacting these compounds with (meth) acrylic acid or a reactive derivative thereof according to a conventional method, the corresponding formulas (52a) to (5
The (meth) acrylate derivative represented by 5a) is produced.

[0161]

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[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 Ra represents a hydrogen atom or a methyl group, R11 and R12 are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R13 to R15 are the same or different and represent a hydrogen atom or methyl Represents a hydroxyl group which may be protected by a group or a protecting group)

The representative compounds include, but are not limited to, the following compounds. [2-1] 1- (1- (meth) acryloyloxy-1-
Methylethyl) adamantane (Ra = H or CH3, R
11 = R12 = CH3, R13 = R14 = R15 = H) [2-2] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (Ra =
H or CH3, R11 = R12 = CH3, R13 = O
H, R14 = R15 = H) [2-3] 1- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane (Ra = H or CH3,
R11 = R12 = CH2CH3, R13 = R14 = R1
5 = H) [2-4] 1-hydroxy-3- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane (Ra
= H or CH3, R11 = R12 = CH2CH3, R1
3 = OH, R14 = R15 = H) [2-5] 1- (1- (meth) acryloyloxy-1-)
Methylpropyl) adamantane (Ra = H or CH3,
R11 = CH3, R12 = CH2CH3, R13 = R1
4 = R15 = H) [2-6] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (Ra
= H or CH3, R11 = CH3, R12 = CH2CH
3, R13 = OH, R14 = R15 = H) [2-7] 1- (1- (meth) acryloyloxy-1,
2-dimethylpropyl) adamantane (Ra = H or C
H3, R11 = CH3, R12 = CH (CH3) 2, R
13 = R14 = R15 = H) [2-8] 1-hydroxy-3- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (Ra = H or CH3, R11 = CH3, R12 = CH
(CH3) 2, R13 = OH, R14 = R15 = H [2-9] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (Ra = H or CH3, R11 = R12 = CH3, R1
3 = R14 = OH, R15 = H) [2-10] 1- (1-ethyl-1- (meth) acryloyloxypropyl) -3,5-dihydroxyadamantane (Ra = H or CH3, R11 = R12 = CH2CH)
3, R13 = R14 = OH, R15 = H) [2-11] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (Ra = H or CH3, R11 = CH3 , R12 = CH
2CH3, R13 = R14 = OH, R15 = H) [2-12] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (Ra = H or CH3, R11 = CH3, R12
= CH (CH3) 2, R13 = R14 = OH, R15 =
H)

The compound represented by the above formula (2a) can be prepared 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;
R18 is the same or different and is a hydrogen atom, a methyl group, a hydroxyl group optionally protected by a protecting group, or -CO
Represents an ORb group. Rb is a hydrogen atom, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxepanyl group,
Represents a lower alkyl group or a tertiary hydrocarbon group which may have a substituent)

Representative examples include the following compounds, but are not limited thereto. [2-13] 1-hydroxy-3- (meth) acryloyloxyadamantane (Ra = H or CH3, R16 = O
H, R17 = R18 = H) [2-14] 1,3-dihydroxy-5- (meth) acryloyloxyadamantane (Ra = H or CH3, R16
= R17 = OH, R18 = H) [2-15] 1-carboxy-3- (meth) acryloyloxyadamantane (Ra = H or CH3, R16 = CO
OH, R17 = R18 = H) [2-16] 1,3-dicarboxy-5- (meth) acryloyloxyadamantane (Ra = H or CH3, R16
= R17 = COOH, R18 = H) [2-17] 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane (Ra = H or C
H3, R16 = COOH, R17 = OH, R18 = H) [2-18] 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane (Ra = H or CH3,
R16 = t-butoxycarbonyl group, R17 = R18 =
H) [2-19] 1,3-bis (t-butoxycarbonyl) -5
-(Meth) acryloyloxyadamantane [Ra = H
Or CH3, R16 = R17 = t-butoxycarbonyl group, R18 = H] [2-20] 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxyadamantane (Ra
= H or CH3, R16 = OH, R17 = t-butoxycarbonyl group, R18 = H) [2-21] 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane (Ra = H Or CH3, R16 = 2-tetrahydropyranyloxycarbonyl group, R17 = R18 = H) [2-22] 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (Ra = H or CH3, R16 = R17 = 2-
Tetrahydropyranyloxycarbonyl group, R18 =
H) [2-23] 1-hydroxy-3- (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (Ra = H or CH3, R16 = O
H, R17 = 2-tetrahydropyranyloxycarbonyl group, R18 = 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 Ra represents a hydrogen atom or a methyl group, R19 represents a methyl group or an ethyl group, and R20 and R21 are the same or different and are each a hydrogen atom, a hydroxyl group or an oxo group which may be protected by a protecting group. Indicates a group)

Typical examples include the following compounds, but are not limited thereto. [2-24] 2- (meth) acryloyloxy-2-methyladamantane (Ra = H or CH3, R19 = CH3,
R20 = R21 = H) [2-25] 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (Ra = H or CH3,
R19 = CH3, R20 = 1-OH, R21 = H) [2-26] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (Ra = H or CH3,
R19 = CH3, R20 = 5-OH, R21 = H) [2-27] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (Ra = H or C
H3, R19 = CH3, R20 = 1-OH, R21 = 3
-OH) [2-28] 1,5-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (Ra = H or C
H3, R19 = CH3, R20 = 1-OH, R21 = 5
-OH) [2-29] 1,3-dihydroxy-6- (meth) acryloyloxy-6-methyladamantane (Ra = H or C
H3, R19 = CH3, R20 = 1-OH, R21 = 3
-OH) [2-30] 2- (meth) acryloyloxy-2-ethyladamantane (Ra = H or CH3, R19 = CH2C
H2, R20 = R21 = H) [2-31] 1-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane (Ra = H or CH3,
R19 = CH2CH3, R20 = 1-OH, R21 =
H) [2-32] 5-hydroxy-2- (meth) acryloyloxy-2-ethyladamantane (Ra = H or CH3;
R19 = CH2CH3, R20 = 5-OH, R21 =
H) [2-33] 1,3-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (Ra = H or C
H3, R19 = CH2CH3, R20 = 1-OH, R2
1 = 3-OH) [2-34] 1,5-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (Ra = H or C
H3, R19 = CH2CH3, R20 = 1-OH, R2
1 = 5-OH) [2-35] 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane (Ra = H or C
H3, R19 = CH2CH3, R20 = 1-OH, R2
1 = 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, Ra represents a hydrogen atom or a methyl group, and R22 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

Representative examples include the following compounds, but are not limited thereto. [2-36] 2- (meth) acryloyloxytricyclo [7.4.0.03,8] tridecane (Ra = H or C
H3, R22 = H) [2-37] 2- (meth) acryloyloxy-2-methyltricyclo [7.4.0.03,8] tridecane (Ra
= H or CH3, R22 = CH3) [2-38] 2- (meth) acryloyloxy-2-ethyltricyclo [7.4.0.03,8] tridecane (Ra
= H or CH3, R22 = CH2CH3)

[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, Ra represents a hydrogen atom or a methyl group, and R23 represents a tertiary hydrocarbon group which may have a substituent.)

Representative examples include the following compounds, but are not limited thereto. [2-39] t-butyl (meth) acrylate (Ra = H or CH3, R23 = 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 (Where Ra represents a hydrogen atom or a methyl group, and p represents 1 to
Indicates an integer of 3)

Representative examples include the following compounds, but are not limited thereto. [2-40] 2-tetrahydropyranyl (meth) acrylate (Ra = H or CH3, p = 2) [2-41] 2-tetrahydrofuranyl (meth) acrylate (Ra = H or CH3, 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, Ra represents a hydrogen atom or a methyl group;
R28 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. [2-42] β- (meth) acryloyloxy-γ-butyrolactone (Ra = H or CH3, R24 = R25 = R2
6 = R27 = R28 = H) [2-43] β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone (Ra = H or CH3, R
24 = R25 = CH3, R26 = R27 = R28 = H) [2-44] β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (Ra = H or CH3, R
27 = R28 = CH3, R24 = R25 = R26 = H) [2-45] β- (meth) acryloyloxy-α, α, β
-Trimethyl-γ-butyrolactone (Ra = H or CH
3, R24 = R25 = R26 = CH3, R27 = R28
= H) [2-46] β- (meth) acryloyloxy-β, γ, γ
-Trimethyl-γ-butyrolactone (Ra = H or CH
3, R26 = R27 = R28 = CH3, R24 = R25
= H) [2-47] β- (meth) acryloyloxy-α, α,
β, γ, γ-pentamethyl-γ-butyrolactone (Ra
= H or CH3, R24 = R25 = R26 = R27 = R
28 = CH3)

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, Ra represents a hydrogen atom or a methyl group;
R33 is the same or different and represents a hydrogen atom or a methyl group)

Typical examples include the following compounds, but are not limited thereto. [2-48] α- (meth) acryloyloxy-γ-butyrolactone (Ra = H or CH3, R29 = R30 = R3
1 = R32 = R33 = H) [2-49] α- (meth) acryloyloxy-α-methyl-γ-butyrolactone (Ra = H or CH3, R29 =
CH3, R30 = R31 = R32 = R33 = H) [2-50] α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone (Ra = H or CH3, R
30 = R31 = CH3, R29 = R32 = R33 = H) [2-51] α- (meth) acryloyloxy-α, β, β
-Trimethyl-γ-butyrolactone (Ra = H or CH
3, R29 = R30 = R31 = CH3, R32 = R33
= H) [2-52] α- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (Ra = H or CH3, R
32 = R33 = CH3, R29 = R30 = R31 = H) [2-53] α- (meth) acryloyloxy-α, γ, γ
-Trimethyl-γ-butyrolactone (Ra = H or CH
3, R29 = R32 = R33 = CH3, R30 = R31
= H) [2-54] α- (meth) acryloyloxy-β, β,
γ, γ-tetramethyl-γ-butyrolactone (Ra = H
Or CH3, R30 = R31 = R32 = R33 = CH
3, R29 = H) [2-55] α- (meth) acryloyloxy-α, β,
β, γ, γ-pentamethyl-γ-butyrolactone (Ra
= H or CH3, R29 = R30 = R31 = R32 = R
33 = CH3)

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 (In the formula, Ra represents a hydrogen atom or a methyl group;
R36 is the same or different and represents a hydrogen atom or a methyl group, and V1 to V3 are the same or different and represent -CH2-,
Represents -CO- or -COO-)

Representative examples include the following compounds, but are not limited thereto. [2-56] 1- (meth) acryloyloxy-4-oxoadamantane (Ra = H or CH3, R34 = R35 =
R36 = H, V1 = -CO-, V2 = V3 = -CH2
-) [2-57] 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (Ra = H or CH3;
R34 = OH, R35 = R36 = H, V1 = -CO-,
V2 = V3 = -CH2-) [2-58] 7-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (Ra = H or CH3,
R36 = OH, R34 = R35 = H, V1 = -CO-,
V2 = V3 = -CH2-) [2-59] 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.13,8] undecane-5
ON (Ra = H or CH3, R34 = R35 = R36 =
H, V2 = -CO-O- (the left side is the side of the carbon atom to which R35 is bonded), V1 = V3 = -CH2-) [2-60] 1- (meth) acryloyloxy-4,7-dioxa Tricyclo [4.4.1.13,9] dodecane-
5,8-dione (Ra = H or CH3, R34 = R35
= R36 = H, V1 = -CO-O- (left side is a carbon atom side bonded to R34), V2 = -CO-O- (left side is a carbon atom side bonded to R35), V3 =- CH2
-) [2-61] 1- (meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.13,9] dodecane-
5,7-dione (Ra = H or CH3, R34 = R35
= R36 = H, V1 = -O-CO- (left side is a carbon atom side bonded to R34), V2 = -CO-O- (left side is a carbon atom side bonded to R35), V3 =- CH2
-) [2-62] 1- (meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.13,9] dodecane-
4,8-dione (Ra = H or CH3, R34 = R35
= R36 = H, V1 = -CO-O- (left side is a carbon atom side bonded to R34), V2 = -O-CO- (left side is a carbon atom side bonded to R35), V3 =- CH2
−)

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 (58) corresponding to the compound in which 2 = —CO—O— and V1 = V3 = —CH2- is, for example,
It can be obtained according to the following reaction scheme.

Embedded image (Wherein R34, R35 and R36 are the same as above)

In the reaction scheme, the compound represented by the formula (57) is obtained by converting a 2-adamantanone compound represented by the formula (56) 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). In this case, the amount of the N-substituted cyclic imide-based catalyst used is, for example, 0.0
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 (56). 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 (56). 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 formula (57)
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 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 (58) is obtained. 1.1.13,8] undecane compounds are produced. As the primary or secondary alcohol,
For example, methanol, ethanol, 1-propanol,
Examples thereof include 2-propanol, s-butyl alcohol, cyclohexanol, 1-phenylethanol, and benzhydrol. 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.
The amount of the N-substituted cyclic imide-based catalyst is, for example, about 0.000001 to 1 mol, preferably about 0.00001 to 0.5 mol, per 1 mol of the compound of the formula (57). The amount of the metal-based cocatalyst to be used is, for example, 0.0001 to 0.7 mol, preferably 0.1 mol, per 1 mol of the compound of the formula (57).
It is about 001 to 0.5 mol. The amount of the alcohol used is, for example, 0.5 to 1 mol of the compound of the formula (57).
It is about 100 mol, preferably about 1-50 mol. Oxygen is often used in excess with respect to the compound of the formula (57). The reaction may be performed, for example, in a solvent such as an organic acid such as acetic acid, acetonitrile, a nitrile such as benzonitrile, a halogenated hydrocarbon such as trifluoromethylbenzene, an ester such as ethyl acetate, or the like under a normal pressure or a pressure of 20 to 20. 2
It is carried out at a temperature of about 00C, preferably about 30 to 150C. The compound of the formula (58) can be obtained by a general Bayer-Villiger reaction, that is, the reaction of the compound (57) with a peroxide such as hydrogen peroxide or a peracid such as m-chloroperbenzoic acid. it can.

Of the compounds represented by the above formula (2i), V
A compound wherein 1 = -CO-O- and V2 = V3 = -CH2- and a compound wherein V3 = -CO-O- and V1 = V2 = -C
The cyclic alcohol derivative corresponding to each of the compounds represented by H2- can be produced from the corresponding adamantanone compound by the same method as described above. Further, a cyclic alcohol derivative corresponding to a compound having a plurality of -CO-O- groups,
It 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 Ra represents a hydrogen atom or a methyl group, R37 and R39 are the same or different and represent a hydrogen atom or a methyl group, and R38 is a hydrogen atom, a methyl group, a hydroxyl group which may be protected with a protecting group. Rb 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)

Representative examples include the following compounds, but are not limited thereto. [2-63] 5- (meth) acryloyloxy-3-oxatricyclo [4.2.1.04,8] nonan-2-one (Ra = H or CH3, R37 = R38 = R39 = H) [ 2-64] 5- (meth) acryloyloxy-5-methyl-3-oxatricyclo [4.2.1.04,8] nonan-2-one (Ra = H or CH3, R37 = CH3,
R38 = R39 = H) [2-65] 5- (meth) acryloyloxy-9-carboxy-3-oxatricyclo [4.2.1.04,8]
Nonan-2-one (Ra = H or CH3, R37 = R3
9 = H, R38 = COOH) [2-66] 5- (meth) acryloyloxy-9-methoxycarbonyl-3-oxatricyclo [4.2.1.0
4,8] nonan-2-one (Ra = H or CH3, R3
7 = R39 = H, R38 = methoxycarbonyl group) [2-67] 5- (meth) acryloyloxy-9-ethoxycarbonyl-3-oxatricyclo [4.2.1.0
4,8] nonan-2-one (Ra = H or CH3, R3
7 = R39 = H, R38 = ethoxycarbonyl group) [2-68] 5- (meth) acryloyloxy-9-t-butoxycarbonyl-3-oxatricyclo [4.2.
1.04,8] nonan-2-one (Ra = H or CH
3, R37 = R39 = H, R38 = t-butoxycarbonyl group) [2-69] 5- (meth) acryloyloxy-9- (2-
Methyl-2-adamantyloxycarbonyl) -3-oxatricyclo [4.2.1.04,8] nonane-2-
ON (Ra = H or CH3, R37 = R39 = H, R3
8 = 2-methyl-2-adamantyloxycarbonyl group) [2-70] 5- (meth) acryloyloxy-9- (1-
Methyl-1-adamantylethoxycarbonyl) -3-
Oxatricyclo [4.2.1.04,8] nonane-2
-On (Ra = H or CH3, R37 = R39 = H, R
38 = 1-methyl-1-adamantylethoxycarbonyl group) [2-71] 5- (meth) acryloyloxy-9- (2-
Tetrahydropyranyloxycarbonyl) -3-oxatricyclo [4.2.1.04,8] nonan-2-one (Ra = H or CH3, R37 = R39 = H, R38 =
2-tetrahydropyranyloxycarbonyl group)

The compound represented by the above formula (2j) 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.

The cyclic alcohol derivative (60) used as a raw material can be obtained, for example, by converting a 5-norbornene-2-carboxylic acid derivative represented by the formula (59) or an ester thereof into a peracid or It can be obtained by reacting with peroxide.

Embedded image (Wherein R37, R38 and R39 are the same as above)

5-norbornene-2 represented by the formula (59)
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, C1-4 alkyl ester). );
Cycloalkyl esters such as cyclohexyl esters;
Examples thereof include aryl esters such as phenyl esters; aralkyl esters such as benzyl esters, but are not limited thereto.

Examples of the peracid include performic 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 (59) or 1 mol 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 to be used is, for example, 0.9 to 0.9 mol per mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (59) 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 above-mentioned 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 (WO2, WO3, etc.) and molybdenum oxide (Mo
O2, MoO3, etc.), vanadium oxide (VO, V2O
3, VO2, V2O5, etc.), manganese oxide (MnO,
Mn2O3, Mn3O4, MnO2, Mn2O7, and the like, and a composite oxide containing a metal element such as W, Mo, V, and Mn.

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 salts of oxo acids include alkali metal salts such as the sodium and potassium salts of the above oxo acids; alkaline earth metal salts such as magnesium salts, calcium salts and barium salts; 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.

Examples of the peroxide containing a metal element include peroxoacids (eg, peroxotungstic acid, peroxomolybdic acid, peroxovanadate, etc.), and salts of peroxoacids (the alkali metal salts of the above peroxoacids, 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 1 mol of the 5-norbornene-2-carboxylic acid derivative represented by the formula (59) 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 (59)
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- (formula (60))
Oxatricyclo [4.2.1.04,8] nonane-2
An -one derivative is formed. In this reaction, first, equation (59)
The epoxidation of the double bond of the 5-norbornene-2-carboxylic acid derivative or its ester represented by the following formula (1) occurs, followed by the intramolecular cyclization reaction involving ring opening of the epoxy ring, and the formula (60) 3-oxatricyclo [4.2.
1.04,8] Nonan-2-one derivative is presumed to be produced.

The 3-oxatricyclo [4.2.1.04,8] nonan-2- represented by the formula (60) produced by the reaction
The ON derivative can be separated and purified, for example, by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.

5-norbornene-2 represented by the formula (59)
-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 (eg, acrylic acid, methacrylic acid, crotonic acid) or an ester thereof,
The compound represented by 9) can be produced.

The above 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 AlCl3, SnCl4,
Examples include TiCl4, BF3, and the like, but are not limited thereto.

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 (In the formula, Ra represents a hydrogen atom or a methyl group;
R48 is the same or different and represents a hydrogen atom, a methyl group or an ethyl group)

Typical examples thereof include the following compounds, but are not limited thereto. [2-72] 4- (meth) acryloyloxy-6-oxabicyclo [3.2.1] octan-7-one (Ra = H
Or CH3, R40 = R41 = R42 = R43 = R44
= R45 = R46 = R47 = R48 = H) [2-73] 4- (meth) acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octan-7-one (Ra = H or CH3 , R40 = R41 = R43 = R
44 = R45 = R46 = R47 = R48 = H, R42 =
CH3) [2-74] 4- (meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octan-7-one (Ra = H or CH3, R40 = R41 = R42 = R
44 = R45 = R46 = R47 = R48 = H, R43 =
CH3) [2-75] 4- (meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane-
7-one (Ra = H or CH3, R40 = R41 = R4
4 = R45 = R46 = R47 = R48 = H, R42 = R
43 = CH3)

[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 Ra represents a hydrogen atom or a methyl group;
R57 is the same or different and represents a hydrogen atom, a methyl group or an ethyl group)

Typical examples thereof include the following compounds, but are not limited thereto. [2-76] 6- (meth) acryloyloxy-2-oxabicyclo [2.2.2] octan-3-one (Ra = H
Or CH3, R49 = R50 = R51 = R52 = R53
= R54 = R55 = R56 = R57 = H) [2-77] 6- (meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octan-3-one (Ra = H or CH3 , R49 = R50 = R51 = R
53 = R54 = R55 = R56 = R57 = H, R52 =
CH3) [2-78] 6- (meth) acryloyloxy-1-methyl-2-oxabicyclo [2.2.2] octan-3-one (Ra = H or CH3, R49 = R50 = R52 = R
53 = R54 = R55 = R56 = R57 = H, R51 =
CH3) [2-79] 6- (meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane-
3-one (Ra = H or CH3, R49 = R50 = R5
3 = R54 = R55 = R56 = R57 = H, R51 = R
52 = CH3)

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 an esterification method.

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

Embedded image

[0220]

Embedded image

[0221]

Embedded image (Wherein Ra represents a hydrogen atom or a methyl group;
R48 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 (61) and the α, β-unsaturated carboxylic acid represented by the formula (62) is carried out under the general Diels-Alder reaction conditions. be able to. This reaction produces cyclohexene carboxylic acid. It should be noted that two types of isomers (63a) and (63b) can be produced depending on the type of raw materials and reaction conditions. As the diene represented by the formula (61), 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 (62).

Next, the produced cyclohexenecarboxylic acids (63a) and (63b) 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 the 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 (64a) and (64b) are produced from the cyclohexenecarboxylic acid represented by the formula (63a), and the compounds represented by the formula (64c) are produced from the cyclohexanecarboxylic acid represented by the formula (63b). ) And (6
The compound represented by 4d) can be produced.

W, Mo, V and Mn in the above (i)
Examples of the metal compound containing a metal element selected from the group consisting of tungsten oxide (WO2, WO3, etc.), molybdenum oxide (MoO2, MoO3, etc.), vanadium oxide (VO, V2O3, VO2, V2O5, etc.), manganese oxide (MnO2) , Mn2O3, Mn3O4, MnO2,
Oxides such as complex oxides containing the above metals; isopolyacids such as tungstic acid, molybdic acid, vanadic acid, manganic acid, isopolytungstic acid, isopolymolybdic acid, isopolyvanadate, and phosphotungstic acid Oxoacids such as heteropolyacids such as silicotungstic acid, phosphomolybdenumsan, silicomolybdic acid, and lyvanadomolybdic acid, or salts thereof; sulfides corresponding to the oxides; halides; oxyhalides; borides; carbides; Silicides; nitrides; phosphides; peroxides, hydroperoxides, peroxoacids (eg, peroxotungstic acid, peroxomolybdic acid, peroxovanadate, etc.), salts of peroxoacids (the alkali metal salts of the peroxoacids, alkaline earth metals) salt,
Peroxides such as ammonium salts, transition metal salts, etc., peracids (permanganic acid, etc.), peracid salts (alkali metal salts, alkaline earth metal salts, ammonium salts, transition metal salts, etc. of the above peracids) 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.

The amount of the metal compound used is, for example, based on 1 mole 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, a suitable 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 performed 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, but is generally about 0 to 100 ° C.
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, followed by the intramolecular cyclization reaction involving the opening of the epoxy ring 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 (6
In place of the α, β-unsaturated carboxylic acid represented by 2),
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 (61),
An ester corresponding to the cyclohexene carboxylic acid represented by the above formulas (63a) and (63b) is produced, and the same as the 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) (64a), (64b) ,
(64c) and (64d) can be obtained. The reaction conditions and the like are the same as in the case where the α, β-unsaturated carboxylic acid (61) is used.

The hydroxyoxabicyclooctanone derivatives (64a), (64b), (64c), (64
In d), the compounds represented by the formulas (64a) and (64c) correspond to the cyclic alcohol derivative serving as a raw material of the compound represented by the formula (2k), and the compounds represented by the formulas (64b) and (64d) The compound represented by the above 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)

Typical examples thereof include the following compounds, but are not limited thereto. [2-80] 8- (meth) acryloyloxy-4-oxatricyclo [5.2.1.02,6] decane-5-one (Ra = H or CH3) [2-81] 9- (meta ) Acryloyloxy-4-oxatricyclo [5.2.1.02,6] decane-5-one (Ra = H or CH3)

[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 (Wherein, R58 and R59 are the same or different and are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyl group optionally protected by a protecting group, a hydroxymethyl optionally protected by a protecting group; R represents a group or a -COORb group.
58 and R59 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. Rb represents a hydrogen atom, a tetrahydrofuranyl group, a tetrahydropyranyl group, an oxepanyl group, a lower alkyl group or a tertiary hydrocarbon group.

Typical examples thereof include the following compounds, but are not limited thereto. [2-82] 2-norbornene (R58 = R59 = H, q =
0) [2-83] 2-hydroxy-5-norbornene (R58 =
OH, R59 = H, q = 0) [2-84] 2- (t-butoxycarbonyl) -5-norbornene (R58 = t-butoxycarbonyl group, R59 =
H, q = 0) [2-85] 2- (2-tetrahydropyranyloxycarbonyl) -5-norbornene (R58 = 2-tetrahydropyranyloxycarbonyl group, R59 = H, q = 0) [2-86 2- (2-methyl-2-adamantyloxycarbonyl) -5-norbornene (R58 = 2-methyl-
2-adamantyloxycarbonyl group, R59 = H, q
= 0) [2-87] 2- (1-methyl-1-adamantylethoxycarbonyl) -5-norbornene (R58 = 1-methyl-1-adamantylethoxycarbonyl group, R59 =
H, q = 0) [2-88] 4-oxatricyclo [5.3.1.02
6] decane-8-en-3-one (R58 + R59 = −
CO-O-CH2-, 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 photoresist polymer compound of the present invention and a photoacid generator.

Examples of the photoacid generator include commonly used or known compounds which efficiently generate an acid upon exposure, 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 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 / cm2, preferably about 10 to 500 mJ / cm2.

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.

[0247]

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. Further, it can be manufactured at low cost. ADVANTAGE OF THE INVENTION According to the polymer compound for photoresists of this invention, adhesiveness with respect to a board | substrate, transparency, alkali solubility, and etching resistance can be expressed in a well-balanced manner. According to the photoresist resin composition and the method for producing a semiconductor of the present invention, a fine pattern can be formed with high accuracy because the above-mentioned photoresist polymer compound is used. Further, according to the present invention, there is provided a novel (meth) acrylate ester useful as a monomer or the like of a polymer compound for a photoresist.

[0248]

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 (5 (or 6) -methacryloyloxynorbornane-
Preparation of 2-yl = norbornan-2-yl = ketone [1a-1 (methacrylate)] 60 mmol of 2-norbornene-5-carbaldehyde, 20 mmol of 2-norbornene, 2 mmol of N-hydroxyphthalimide, benzoyl peroxide 1 10 mmol of benzene 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. As a result, 2-norbornene-5
-Yl = norbornan-2-yl = ketone in 52% yield
(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 0.01 mmol of H2PtCl and 2-norbornen-5-yl = norbornan-2- obtained by the above method.
To a mixture of 50 mmol of il = ketone was added 55 mmol of trichlorosilane at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours. The obtained mixture was suspended in 249 mmol of potassium fluoride and 500 mmol of potassium hydrogen carbonate (2000
ml, solvent: tetrahydrofuran / methanol = 1 /
1) at 0 ° C. with vigorous stirring, and at room temperature for 30 minutes.
Aqueous hydrogen peroxide solution (41.5 ml) was added. Thereafter, the mixture was stirred for 12 hours. Furthermore, Na2S2O3.5H
50 g of 2O was added and stirred for 1 hour. After filtering the mixture,
The filtrate was concentrated, and the concentrate was subjected to silica gel column chromatography to obtain 5 (or 6) -hydroxynorbornan-2-yl = norbornan-2-yl = ketone (mixture) in a yield of 86%. 10 mmol of 5 (or 6) -hydroxynorbornan-2-yl = norbornan-2-yl ketone (mixture) and 15 mmol of triethylamine obtained by the above method are dissolved in 50 ml of tetrahydrofuran, and methacrylic acid chloride Mmol was added at room temperature and stirred at room temperature for 24 hours. The reaction mixture was washed sequentially with water, an aqueous sodium hydrogen carbonate solution and an aqueous sodium chloride solution, and the organic layer was concentrated. The concentrate was subjected to silica gel column chromatography to give the title 5 (or 6) -methacryloyloxynorbornan-2-yl = norbornan-2-yl = ketone (mixture) in an 82% yield. [5 (or 6) -methacryloyloxynorbornane-
Spectrum data of 2-yl = norbornan-2-yl = ketone] MS m / e: 39, 69, 81, 302

According to the above method, 5- (or 6) -methacryloyloxynorbornan-2-yl = 4-oxatricyclo [5.2.1.02,6] decan-3-one-9-yl = Ketone [1a-4 (methacrylate)], 5
(Or 6) -methacryloyloxynorbornane-2-
Yl = 5 (or 6) -hydroxynorbornan-2-yl = ketone [1a-5 (methacrylate)] and 5 (or 6) -methacryloyloxynorbornan-2-yl =
5 (or 6) -t-butoxycarbonylnorbornane-
2-yl ketone [1a-8 (methacrylate)] was prepared.

Production Example 2 (3-methacryloyloxyadamantan-1-yl =
Preparation of 4-oxatricyclo [5.2.1.02,6] decane-3-one-8 (or 9) -yl = ketone [1a-15 (methacrylate)] 3-hydroxyadamantane-1-carba 60 mmol of aldehyde, 4-oxatricyclo [5.2.1.02,6] decane-8-en-3-
On 20 mmol, N-hydroxyphthalimide 2 mmol, benzoyl peroxide 1 mmol, and benzene 10
ml in a flask.
After stirring for 2 hours, 1 mmol of benzoyl peroxide was further added, and the mixture was stirred for 12 hours under the same conditions. As a result, 3-hydroxyadamantan-1-yl = 4-oxatricyclo [5.2.1.02,6] decane-3-one-8 (or 9) -yl = ketone (mixture) was obtained in a yield of 23. %. [Spectral data of 3-hydroxyadamantan-1-yl = 4-oxatricyclo [5.2.1.02,6] decane-3-one-8 (or 9) -yl = ketone] MS m / e: 66,135,331 (M + 1) 3-hydroxyadamantane obtained by the above method
1-yl = 4-oxatricyclo [5.2.1.02,
6] 10 mmol of decane-3-one-8 (or 9) -yl ketone (mixture) and 15 mmol of triethylamine are dissolved in 50 ml of tetrahydrofuran, and 15 mmol of methacrylic chloride is added to this solution at room temperature.
Stirred at room temperature for 24 hours. The reaction mixture was washed sequentially with water, an aqueous sodium hydrogen carbonate solution and an aqueous sodium chloride solution, and the organic layer was concentrated. The concentrate is subjected to silica gel column chromatography to give the title 3-methacryloyloxyadamantan-1-yl = 4-oxatricyclo [5.2.1.02,6] decane-3-one-8.
(Or 9) -yl = ketone (mixture) was obtained in 69% yield. [3-methacryloyloxyadamantan-1-yl =
Spectral data of 4-oxatricyclo [5.2.1.02,6] decan-3-one-8 (or 9) -yl = ketone] MS m / e: 66, 135, 330, 339 (M +
1)

According to the above method, 3-methacryloyloxyadamantan-1-yl = 5 (or 6) -hydroxynorbornan-2-yl ketone [1a-17 (methacrylate)], 3-methacryloyloxyadamantan-1 -Yl = 5 (or 6) -t-butoxycarbonylnorbornan-2-yl ketone [1a-20 (methacrylate)], 3-methacryloyloxy-5,7-dimethyladamantan-1-yl = 4-oxatricyclo [5.
2.1.02,6] decane-3-one-8 (or 9)-
Il = ketone [1a-25 (methacrylate)], 3-methacryloyloxy-5,7-dimethyladamantane-1
-Yl = 5 (or 6) -hydroxynorbornane-2-
Il = ketone [1a-27 (methacrylate)], and 3-
Methacryloyloxy-5,7-dimethyladamantan-1-yl = 5 (or 6) -t-butoxycarbonylnorbornan-2-yl ketone [1a-30 (methacrylate)] was produced.

Production Example 3 (5 (or 6)-(1-methacryloyloxy-1-methylethyl) norbornan-2-yl = norbornan-
Preparation of 2-yl ketone [1a-34 (methacrylate)] 60 mmol of norbornane-2-carbaldehyde,
α, α-dimethyl-2-norbornene-5-methanol 20 mmol, N-hydroxyphthalimide 2 mmol, benzoyl peroxide 1 mmol, and benzene 10 m
1 to a flask and placed in an argon atmosphere at 80 ° C. for 12 hours.
After stirring for 1 hour, 1 mmol of benzoyl peroxide was further added, and the mixture was stirred for 12 hours under the same conditions. As a result, 5 (or 6)-(1-hydroxy-1-methylethyl) norbornan-2-yl = norbornan-2-yl = ketone (mixture) was obtained with a yield of 52%. [Spectral data of 5 (or 6)-(1-hydroxy-1-methylethyl) norbornan-2-yl = norbornan-2-yl = ketone] MS m / e: 66,259,277 (M + 1) 10 mmol of the obtained 5 (or 6)-(1-hydroxy-1-methylethyl) norbornan-2-yl = norbornan-2-yl = ketone (mixture),
15 mmol of triethylamine is dissolved in 50 ml of tetrahydrofuran, and methacrylic acid chloride 1 is added to this solution.
5 mmol was added at room temperature, and the mixture was stirred at room temperature for 24 hours.
The reaction mixture was washed sequentially with water, an aqueous sodium hydrogen carbonate solution and an aqueous sodium chloride solution, and the organic layer was concentrated. By subjecting the concentrate to silica gel column chromatography, the title 5 (or 6)-(1-methacryloyloxy-1-methylethyl) norbornan-2-yl = norbornan-2-yl = ketone (mixture) was 79%. In the yield of [5 (or 6) -methacryloyloxynorbornane-
Spectrum data of 2-yl = norbornan-2-yl = ketone] MS m / e: 66,259,345 (M + 1)

Production Example 4 (Production of 2- [1-methacryloyloxy-1- (norbornan-2-yl) ethyl] norbornane [1b-1 (methacrylate)]) A 1M methylmagnesium bromide-tetrahydrofuran solution (12 Mmol)
Was charged. To this solution, a solution of di (norbornan-2-yl) ketone (10 mmol) dissolved in 70 ml of tetrahydrofuran was added dropwise while maintaining the internal temperature at 0 ° C. After the addition, the mixture was stirred at 0 ° C. for 4 hours. After quenching with a 10% by weight aqueous solution of sulfuric acid, the mixture was neutralized with a 5% by weight aqueous solution of sodium hydroxide, and separated. The aqueous layer was extracted with toluene.
The organic layers were combined, concentrated, and the concentrate was subjected to silica gel column chromatography to give 2- [1-hydroxy-1
-(Norbornan-2-yl) ethyl] norbornane was obtained in a yield of 87%. [Spectral data of 2- [1-hydroxy-1- (norbornan-2-yl) ethyl] norbornane] MS m / e: 68,217,235 (M + 1) 2- [1-hydroxy-1] obtained by the above method. -(Norbornan-2-yl) ethyl] To a mixture of 10 mmol of norbornane, 15 mmol of triethylamine and 70 ml of tetrahydrofuran, 15 mmol of methacrylic acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give the title 2- [1-methacryloyloxy-1- (norbornan-2-yl) ethyl] norbornane in a yield. Obtained at 77%. [Spectral data of 2- [1-methacryloyloxy-1- (norbornan-2-yl) ethyl] norbornane] MS m / e: 68,216,303 (M + 1)

According to the above method, 1- [1-methacryloyloxy-1- (norbornan-2-yl) ethyl] adamantane [1b-7 (methacrylate)],
[3- (Adamantane-1-yl) -1-methacryloyloxy-1-methylpropyl] adamantane [1b-10
(Methacrylate)], 1- [1-methacryloyloxy-1- (norbornan-2-yl) ethyl] -3,5
-Dimethyladamantane [1b-13 (methacrylate)], 3- [1-methacryloyloxy-1- (norbornan-2-yl) ethyl] tetracyclo [4.4.
0.12, 5.17, 10] dodecane [1b-19 (methacrylate)].

Production Example 5 (Production of 2- (3-methacryloyloxy-3-methylbutyl) norbornane [1c-10 (methacrylate)]) 60 mmol of acetaldehyde, 20 mmol of 2-vinylnorbornane, 2 mmol of N-hydroxyphthalimide 1 mmol of benzoyl oxide and 1 of benzene
After placing 0 ml in a flask and stirring at 80 ° C. for 12 hours under an argon atmosphere, 1 mmol of benzoyl peroxide was further added, and the mixture was stirred under the same conditions for 12 hours. As a result, methyl 2- (norbornan-2-yl) ethyl ketone was obtained in a yield of 28%. The flask was charged with a 1 M methylmagnesium bromide-tetrahydrofuran solution (12 mmol). In this solution, while keeping the internal temperature at 0 ° C., methyl 2- (norbornane-
A solution of 2-yl) ethyl ketone (10 mmol) in 70 ml of tetrahydrofuran was added dropwise. After the addition, the mixture was stirred at 0 ° C. for 4 hours. After quenching with a 10% by weight aqueous solution of sulfuric acid, the mixture was neutralized with a 5% by weight aqueous solution of sodium hydroxide, and separated. The aqueous layer was extracted with toluene. The organic layers were combined, concentrated, and the concentrated solution was subjected to silica gel column chromatography to obtain 2- (3-hydroxy-3-methylbutyl) norbornane in a yield of 92%. To a mixture of 10 mmol of 2- (3-hydroxy-3-methylbutyl) norbornane, 15 mmol of triethylamine and 100 ml of tetrahydrofuran obtained by the above method, 15 mmol of methacrylic acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to obtain the title compound, 2- (3
-Methacryloyloxy-3-methylbutyl) norbornane was obtained in a yield of 82%. [Spectral data of 2- (3-methacryloyloxy-3-methylbutyl) norbornane] MS m / e: 66, 69, 182, 251

The same operation as above was carried out except that propionaldehyde was used instead of acetaldehyde and 2-norbornene was used instead of 2-vinylnorbornane.
(1-Methacryloyloxy-1-methylpropyl) norbornane [1c-2 (methacrylate)] was obtained. Also,
Propionaldehyde instead of acetaldehyde, 2
Tetracyclo [4.- instead of vinylnorbornane];
4.0.12, 5.17, 10] The same operation as above was performed except that dodecane-3-ene was used, and 3- (1-methacryloyloxy-1-methylpropyl) tetracyclo [4.4.0] was used. .12, 5.17, 10] dodecane [1c-5
(Methacrylate)].

Production Example 6 (Production of 1- (3-methacryloyloxy-3-methylbutyl) adamantane [1c-13 (methacrylate)]) 60 mmol of acetaldehyde, 20 mmol of 1-vinyladamantane, 2 mmol of N-hydroxyphthalimide 1 mmol of benzoyl oxide and 1 of benzene
After placing 0 ml in a flask and stirring at 80 ° C. for 12 hours under an argon atmosphere, 1 mmol of benzoyl peroxide was further added, and the mixture was stirred under the same conditions for 12 hours. As a result, 2-
(Adamantan-1-yl) ethyl methyl ketone was obtained in 32% yield. The flask was charged with a 1 M methylmagnesium bromide-tetrahydrofuran solution (12 mmol). To this solution, a solution of 2- (adamantan-1-yl) ethyl methyl ketone (10 mmol) obtained in the above method in 70 ml of tetrahydrofuran was added dropwise while maintaining the internal temperature at 0 ° C. After the addition, the mixture was stirred at 0 ° C. for 4 hours. After quenching with a 10% by weight aqueous solution of sulfuric acid, the mixture was neutralized with a 5% by weight aqueous solution of sodium hydroxide, and separated. The aqueous layer was extracted with toluene. The organic layers were combined, concentrated, and the concentrate was subjected to silica gel column chromatography to obtain 1- (3-hydroxy-3-methylbutyl) adamantane in a yield of 91%. To a mixture of 10 mmol of 1- (3-hydroxy-3-methylbutyl) adamantane, 15 mmol of triethylamine and 100 ml of tetrahydrofuran obtained by the above method, 15 mmol of methacrylic acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to obtain the title 1- (3
-Methacryloyloxy-3-methylbutyl) adamantane was obtained with a yield of 78%. [Spectral data of 3-methacryloyloxy-3-methylbutyl) adamantane MS m / e: 69, 135, 291

Production Example 7 (1- [1,2-bis (t-butoxycarbonyl) ethyl] -3-methacryloyloxyadamantane [1d-1]
Production of (methacrylate)] 1-adamantanol was added to a benzonitrile solution (80 ml) containing N-hydroxyphthalimide (9 mmol) and cobalt (III) acetylacetonate [Co (acac) 3] (0.3 mmol). (270 mmol) and t-butyl maleate (3
(0 mmol) and reacted at 75 ° C. for 14 hours under a 20% oxygen atmosphere diluted with nitrogen. The unreacted raw materials and the solvent are distilled off under reduced pressure, and the obtained concentrate is purified by silica gel column chromatography,
1- [1,2-Bis (t-butoxycarbonyl) ethyl] -3-hydroxyadamantane was obtained in a yield of 21%. To a mixture of 10 mmol of 1- [1,2-bis (t-butoxycarbonyl) ethyl] -3-hydroxyadamantane, 15 mmol of triethylamine and 100 ml of tetrahydrofuran obtained by the above method, 15 mmol of methacrylic acid chloride is applied for about 30 minutes. And dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give the title 1- [1,2-bis (t-butoxycarbonyl) ethyl] -3-methacryloyloxyadamantane. Obtained in 79% yield. [Spectral data of 1- [1,2-bis (t-butoxycarbonyl) ethyl] -3-methacryloyloxyadamantane] MS m / e: 135,247,335,449

Instead of 1-adamantanol, 3,5-
By performing the same operation as described above except that dimethyl-1-adamantanol was used, 1- [1,2-bis (t
-Butoxycarbonyl) ethyl] -3-methacryloyloxy-5,7-dimethyladamantane [1d-2 (methacrylate)] was obtained.

Production Example 8 (2- [1,1-bis (t-butoxycarbonyl) methyl] -5-methacryloyloxynorbornane [1d-3]
(Methacrylate)]) Manganese acetate (II)
(0.4 mmol) and cobalt (II) acetate (0.02
5-hydroxy-2-norbornene (300 mmol) and t-butyl malonate (20 mmol) were added to an acetic acid solution (20 ml) containing
The reaction was performed at 5 ° C. for 5 hours. 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 give 2- [1,1-
Bis (t-butoxycarbonyl) methyl] -5-hydroxynorbornane was obtained in a yield of 35%. 10 mmol of 2- [1,1-bis (t-butoxycarbonyl) methyl] -5-hydroxynorbornane obtained by the above method, 15 mmol of triethylamine and tetrahydrofuran 1
To a mixture of 00 ml, 15 mmol of methacrylic acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, at room temperature 12
Stirred for hours. After adding water to the reaction mixture, it was concentrated,
The concentrate was subjected to silica gel column chromatography to give the title 2- [1,1-bis (t-butoxycarbonyl) methyl] -5-methacryloyloxynorbornane in a yield of 83%. [Spectral data of 2- [1,1-bis (t-butoxycarbonyl) methyl] -5-methacryloyloxynorbornane] MS m / e: 39,68,321,395

Production Example 9 (Production of α- (5 (or 6) -methacryloyloxynorbornan-2-yl) -γ-butyrolactone [1e-1 (methacrylate)]) Manganese (II) acetate (0.4 mmol) Acetic acid solution containing acetic acid, cobalt (II) acetate (0.02 mmol) and benzaldehyde (1 mmol) (20
ml), norbornanediene (300 mmol) and γ
-Butyrolactone (20 mmol) was added and reacted at 90 ° C. for 5 hours under normal pressure air. Unreacted raw materials and the solvent are distilled off under reduced pressure, and the obtained concentrate is purified by silica gel column chromatography to obtain α-
(2-Norbornen-5-yl) -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 0.01 mmol of H2PtCl6 and α- (2-norbornene-5) obtained by the above method. To a mixture with 50 mmol of yl) -γ-butyrolactone was added 55 mmol of trichlorosilane at 0 ° C, and the mixture was stirred at 25 ° C for 2 hours.
The obtained mixture was suspended in 249 mmol of potassium fluoride and 500 mmol of potassium hydrogen carbonate (2000 m 2).
1, solvent: tetrahydrofuran / methanol = 1/1)
Was added at 0 ° C. with vigorous stirring, and 30% by weight aqueous hydrogen peroxide (41.5 ml) was added at room temperature. Then 1
Stir for 2 hours. Further, 50 g of Na2S2O3 / 5H2O was added, and the mixture was stirred for 1 hour. After the mixture was filtered, the filtrate was concentrated. The obtained concentrate is washed with tetrahydrofuran 200
and dissolved in 60 ml of triethylamine. 60 mmol of methacrylic acid chloride was added to this solution at room temperature, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was washed sequentially with water, an aqueous sodium hydrogen carbonate solution and an aqueous sodium chloride solution, and the organic layer was concentrated. The concentrate was subjected to silica gel column chromatography to give the title α- (5 (or 6) -methacryloyloxynorbornan-2-yl) -γ-butyrolactone (mixture).
Obtained in 9% yield. [Spectral data of α- (5 (or 6) -methacryloyloxynorbornan-2-yl) -γ-butyrolactone] MS m / e: 66, 84, 265

Instead of γ-butyrolactone, 5-hydroxy-3-oxatricyclo [4.2.1.04,8]
The same operation as described above was performed except that nonan-2-one was used, and 5-hydroxy-1- (5 (or 6) -methacryloyloxynorbornan-2-yl) -3-oxatricyclo [4.2. 1.04,8] nonan-2-one [1e
-5 (methacrylate)].

Production Example 10 (α- [5 (or 6)-(1-methacryloyloxy-
Production of 1-methylethyl) norbornan-2-yl] -γ-butyrolactone [1e-2 (methacrylate)] A 1M methylmagnesium bromide-tetrahydrofuran solution (120 mmol) was charged into a flask. To this solution, 5-acetyl-2-norbornene (100 mmol) was added to tetrahydrofuran 70 while maintaining the internal temperature at 0 ° C.
A solution dissolved in 0 ml was added dropwise. After the addition, the mixture was stirred at 0 ° C. for 4 hours. After quenching with 10% by weight sulfuric acid aqueous solution,
The mixture was neutralized with a 5% by weight aqueous sodium hydroxide solution and separated. The aqueous layer was extracted with toluene. The organic layers were combined and concentrated, and the concentrated solution was subjected to silica gel column chromatography to obtain α, α-dimethyl-2-norbornene-5-methanol in a yield of 82%. Manganese (II) acetate (0.
4 mmol), cobalt (II) acetate (0.02 mmol) and benzaldehyde (1 mmol) in an acetic acid solution (20 ml) containing the α, α-dimethyl-
2-norbornene-5-methanol (300 mmol)
And γ-butyrolactone (20 mmol) were added and reacted at 90 ° C. for 5 hours under normal pressure air. Unreacted raw materials and the solvent are distilled off under reduced pressure, and the obtained concentrate is purified by silica gel column chromatography to obtain α-
[5 (or 6)-(1-hydroxy-1-methylethyl) norbornan-2-yl] -γ-butyrolactone (mixture) was obtained in a yield of 35%. Α obtained by the above method
-[5 (or 6)-(1-hydroxy-1-methylethyl) norbornan-2-yl]-[gamma] -butyrolactone (mixture) 10 mmol, triethylamine 15 mmol and tetrahydrofuran 100 ml were mixed with 15 mmol of methacrylic acid chloride. Was added dropwise over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to obtain the α- [5
(Or 6)-(1-methacryloyloxy-1-methylethyl) norbornan-2-yl] -γ-butyrolactone (mixture) was obtained with a yield of 71%. [Α- [5 (or 6)-(1-methacryloyloxy-
Spectrum data of 1-methylethyl) norbornan-2-yl] -γ-butyrolactone] MS m / e: 66, 69, 84, 307

Production Example 11 (2- (5 (or 6) -methacryloyloxynorbornan-2-yl) -4-oxatricyclo [5.2.
1.02,6] Decan-3-one [1e-7 (methacrylate)]) Manganese (II) acetate (0.4 mmol), cobalt (II) acetate (0.02 mmol) and benzaldehyde (1 mmol) ) Containing acetic acid solution (20m
l) has norbornanediene (300 mmol) and 4-
Oxatricyclo [5.2.1.02,6] decane-3
-One (20 mmol) was added, and the mixture was reacted at 90 ° C. for 5 hours under normal pressure air. The unreacted raw material and the solvent were distilled off under reduced pressure, and the obtained concentrate was purified by silica gel column chromatography to give 2- (2-norbornen-5-yl) -4-oxatricyclo. [5.2.
1.02,6] Decan-3-one was obtained in a yield of 13%. [Spectral data of 2- (2-norbornen-5-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one] MS m / e: 66, 69, 218, 246 To a mixture of 0.01 mmol of H2PtCl6 and 50 mmol of 2- (2-norbornen-5-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one obtained by the above method. Then, 55 mmol of trichlorosilane was added at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours. The obtained mixture was suspended in 249 mmol of potassium fluoride and 500 mmol of potassium hydrogen carbonate (2000 ml, solvent:
Tetrahydrofuran / methanol = 1/1) at 0 ° C. with vigorous stirring, and 30% by weight aqueous hydrogen peroxide (41.5 ml) was added at room temperature. Thereafter, the mixture was stirred for 12 hours. Further, 50 g of Na2S2O3 / 5H2O was added, and the mixture was stirred for 1 hour. After the mixture was filtered, the filtrate was concentrated. The obtained concentrate was dissolved in 200 ml of tetrahydrofuran, and 60 mmol of triethylamine was added thereto. 60 mmol of methacrylic acid chloride was added to this solution at room temperature, and the mixture was stirred at room temperature for 24 hours. The reaction mixture is
The organic layer was washed sequentially with water, an aqueous sodium hydrogen carbonate solution and an aqueous sodium chloride solution, and the organic layer was concentrated. The concentrate was subjected to silica gel column chromatography to give the title 2
-(5 (or 6) -methacryloyloxynorbornan-2-yl) -4-oxatricyclo [5.2.1.0
2,6] Decan-3-one (mixture) was obtained in a yield of 47%. [2- (5 (or 6) -methacryloyloxynorbornan-2-yl) -4-oxatricyclo [5.2.
1.02,6] Spectral data of decane-3-one] MS m / e: 66,245,332

Production Example 12 (2- [5 (or 6)-(1-methacryloyloxy-
1-methylethyl) norbornan-2-yl] -4-oxatricyclo [5.2.1.02,6] decane-3-
Preparation of ON [1e-8 (methacrylate)] manganese (II) acetate (0.4 mmol), cobalt (II) acetate (0.
02 mmol) and benzaldehyde (1 mmol) in an acetic acid solution (20 ml).
Norbornene-5-methanol (300 mmol) and 4
-Oxatricyclo [5.2.1.02,6] decane-
3-one (20 mmol) was added, and the mixture was heated to 90 ° C under normal pressure air.
For 5 hours. The unreacted raw materials and the solvent are distilled off under reduced pressure, and the obtained concentrate is purified by silica gel column chromatography to give 2- [5 (or 6)-(1-hydroxy-1-methyl). Ethyl) norbornan-2-yl] -4-oxatricyclo [5.2.
1.02,6] decane-3-one (mixture) in a yield of 16
%. 2- [5 (or 6)-obtained by the above method
(1-hydroxy-1-methylethyl) norbornane-
2-yl] -4-oxatricyclo [5.2.1.0
2,6] decane-3-one (mixture) 10 mmol, triethylamine 15 mmol and tetrahydrofuran 1
To a mixture of 00 ml, 15 mmol of methacrylic acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, at room temperature 12
Stirred for hours. After adding water to the reaction mixture, it was concentrated,
The concentrate was subjected to silica gel column chromatography to give the title 2- [5 (or 6)-(1-methacryloyloxy-1-methylethyl) norbornane-2-
Yl] -4-oxatricyclo [5.2.1.02
6] Decan-3-one (mixture) was obtained with a yield of 79%. [2- [5 (or 6)-(1-methacryloyloxy-
1-methylethyl) norbornan-2-yl] -4-oxatricyclo [5.2.1.02,6] decane-3-
ON spectrum data] MS m / e: 66, 68, 305, 374

Production Example 13 (8 (or 9)-(3-acryloyloxyadamantan-1-yl) -4-oxatricyclo [5.2.1.
02,6] decane-3-one [1f-159 (acrylate)], 9 (or 8)-(3-acryloyloxyadamantan-1-yl) -8 (or 9) -hydroxy-4
-Oxatricyclo [5.2.1.02,6] decane-
3-one [1f-3 (acrylate)], 8 (or 9) -acryloyloxy-9 (or 8)-(3-hydroxyadamantan-1-yl) -4-oxatricyclo [5.
2.1.02,6] decane-3-one [1f-25 (acrylate)] and 8 (or 9) -acryloyloxy-
9 (or 8)-(3-acryloyloxyadamantan-1-yl) -4-oxatricyclo [5.2.1.0
Preparation of 2,6] decan-3-one) N-hydroxyphthalimide (9 mmol) and cobalt (III) acetylacetonate [Co (acac) 3] (0.3 mmol)
1-adamantanol (270 mmol) and 4-oxatricyclo [5.2.1.02,6] decane-8-en-3-one (30 mmol) were added to a benzonitrile solution (80 ml) containing The reaction was carried out at 75 ° C. for 14 hours in a 20% oxygen atmosphere diluted with nitrogen. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography. The obtained mixture was dissolved in tetrahydrofuran (50 ml), triethylamine (30 mmol) was added thereto, and acrylic acid chloride (30 mmol) was added to about 30 mmol. Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 8 (or 9)-(3-acryloyloxyadamantan-1-yl) -4-oxatricyclo [5. .2.
1.02,6] Decan-3-one (mixture) in yield 24
%, 9 (or 8)-(3-acryloyloxyadamantan-1-yl) -8 (or 9) -hydroxy-4-oxatricyclo [5.2.1.02,6] decane-3-
On (mixture) in 3% yield, 8 (or 9) -acryloyloxy-9 (or 8)-(3-hydroxyadamantan-1-yl) -4-oxatricyclo [5.2.1.
02,6] decane-3-one (mixture) in 5% yield, 8%
(Or 9) -acryloyloxy-9 (or 8)-(3
-Acryloyloxyadamantan-1-yl) -4-
Oxatricyclo [5.2.1.02,6] decane-3
-One (mixture) was obtained in 9% yield. [8 (or 9)-(3-acryloyloxyadamantan-1-yl) -4-oxatricyclo [5.2.1.
02,6] decane-3-one spectral data] MS m / e: 66,135,357 (M + 1) [9 (or 8)-(3-acryloyloxyadamantan-1-yl) -8 (or 9) -Spectral data of -hydroxy-4-oxatricyclo [5.2.1.02,6] decan-3-one] MS m / e: 66,135,355,373 (M +
1) [8 (or 9) -acryloyloxy-9 (or 8)-
Spectrum data of (3-hydroxyadamantan-1-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one] MS m / e: 66,135,373 (M + 1) [ 8 (or 9) -acryloyloxy-9 (or 8)-
(3-acryloyloxyadamantan-1-yl)-
Spectral data of 4-oxatricyclo [5.2.1.02,6] decan-3-one] MS m / e: 66,135,427 (M + 1)

By performing the same operation as described above except that methacrylic acid chloride was used instead of acrylic acid chloride, the corresponding methacrylic acid ester derivatives were obtained.

Production Example 14 (1-Acryloyloxy-3- [2- (adamantan-1-yl) ethyl] adamantane [1f-165 (acrylate)], 1-acryloyloxy-3- [2- (adamantan-1 Preparation of -yl) -2-hydroxyethyl] adamantane [1f-9 (acrylate)] and 1-acryloyloxy-3- [2-acryloyloxy-2- (adamantan-1-yl) ethyl] adamantane) N
-Hydroxyphthalimide (9 mmol) and cobalt (III) acetylacetonate [Co (acac) 3]
(0.3 mmol) in a benzonitrile solution (80 m
l), 1-adamantanol (270 mmol) and 1
-Vinyl adamantane (30 mmol) was added, and the mixture was reacted at 75 ° C for 14 hours under a 20% oxygen atmosphere diluted with nitrogen. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography. The obtained mixture was dissolved in 50 ml of tetrahydrofuran, 30 mmol of triethylamine was added, and 15 mmol of acrylic acid chloride was added to about 30 mmol. Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 1-acryloyloxy-3.
-[2- (Adamantane-1-yl) ethyl] adamantane was obtained in a yield of 12% and 1-acryloyloxy-3- [2
-(Adamantan-1-yl) -2-hydroxyethyl] adamantane in a yield of 8% and 1-acryloyloxy-3- [2-acryloyloxy-2- (adamantan-1-yl) ethyl] adamantane in a yield of 14%. %. [Spectral data of 1-acryloyloxy-3- [2- (adamantan-1-yl) ethyl] adamantane] MS m / e: 135,300,369 (M + 1) [1-acryloyloxy-3- [2- ( Spectral data of adamantane-1-yl) -2-hydroxyethyl] adamantane] MS m / e: 135,367,385 (M + 1) [1-acryloyloxy-3- [2-acryloyloxy-2- (adamantan-1) -Yl) ethyl] adamantane spectral data] MS m / e: 135,301,439 (M + 1)

By performing the same operation as described above except that methacrylic acid chloride was used instead of acrylic acid chloride, corresponding methacrylic acid ester derivatives were obtained.

Production Example 15 (8 (or 9) -acryloyloxy-9 (or 8)-
(3-oxatricyclo [4.3.1.14,8] undecane-2-one-6-yl) -4-oxatricyclo [5.2.1.02,6] decan-3-one [ 1f-115
Preparation of (acrylate)] 3-oxatriene was added to a benzonitrile solution (80 ml) containing N-hydroxyphthalimide (9 mmol) and cobalt (III) acetylacetonate [Co (acac) 3] (0.3 mmol). Cyclo [4.3.1.14,8] undecane-2-one (270 mmol) and 4-oxatricyclo [5.2.
1.02,6] decane-8-en-3-one (30 mmol) was added and reacted at 75 ° C. for 14 hours under a 20% oxygen atmosphere diluted with nitrogen. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel chromatography. The obtained mixture was dissolved in tetrahydrofuran (40 ml), triethylamine (20 mmol) was added thereto, and acrylic acid chloride (20 mmol) was added for about 30 minutes. It dripped over. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 8 (or 9) -acryloyloxy-9 (or 8)-(3-oxatricyclo [4.3]. .1.14,8] undecane-2
-On-6-yl) -4-oxatricyclo [5.2.
1.02,6] Decan-3-one (mixture) in a yield of 34
%. [8 (or 9) -acryloyloxy-9 (or 8)-
Of (3-oxatricyclo [4.3.1.14,8] undecane-2-one-6-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one Spectrum data] MS m / e: 66, 290, 318, 387 (M +
1)

By performing the same operation as described above except that methacrylic acid chloride was used instead of acrylic acid chloride, the corresponding methacrylic acid ester derivatives were obtained.

Production Example 16 (8 (or 9) -acryloyloxy-9 (or 8)-
(Production of (2-oxoadamantan-5-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one [1f-126 (acrylate)]) N-hydroxyphthalimide (9 mmol) ) And cobalt (III) acetylacetonate [Co (acac) 3] (0.3 mmol) in a benzonitrile solution (80 ml), 2-oxoadamantane (270 mmol) and 4-oxatricyclo [5.2. .1.02,6] decane-8-ene-3
-One (30 mmol) and 20% diluted with nitrogen
The reaction was performed at 75 ° C. for 14 hours under an oxygen atmosphere. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel chromatography. The obtained mixture was dissolved in tetrahydrofuran (40 ml), triethylamine (20 mmol) was added thereto, and acrylic acid chloride (20 mmol) was added for about 30 minutes. It dripped over. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 8 (or 9) -acryloyloxy-9 (or 8).
-(2-oxoadamantan-5-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one (mixture) was obtained at a yield of 45%. [8 (or 9) -acryloyloxy-9 (or 8)-
(Spectral data of (2-oxoadamantan-5-yl) -4-oxatricyclo [5.2.1.02,6] decan-3-one] MS m / e: 66, 134, 302, 371 (M +
1)

By performing the same operation as above except that methacrylic acid chloride was used instead of acrylic acid chloride, the corresponding methacrylic acid ester derivatives were obtained.

Production Example 17 (9 (or 8)-(2-acryloyloxy-2-methyladamantan-5-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one [1f-210
(Acrylate)], 9 (or 8)-(2-acryloyloxy-2-methyladamantan-5-yl) -8
(Or 9) -hydroxy-4-oxatricyclo [5.
2.1.02,6] decane-3-one [1f-137 (acrylate)], 8 (or 9) -acryloyloxy-9
(Or 8)-(2-hydroxy-2-methyladamantan-5-yl) -4-oxatricyclo [5.2.1.
02,6] decane-3-one [1f-148 (acrylate)] and 8 (or 9) -acryloyloxy-9
(Or 8)-(2-acryloyloxy-2-methyladamantan-5-yl) -4-oxatricyclo [5.
2.1.02,6] Decan-3-one) N-hydroxyphthalimide (9 mmol) and cobalt (II
I) Acetylacetonate [Co (acac) 3] (0.
Benzonitrile solution (3 ml) (80 ml)
2-methyl-2-adamantanol (270 mmol) and 4-oxatricyclo [5.2.1.02,6]
Decane-8-en-3-one (30 mmol) was added,
In a 20% oxygen atmosphere diluted with nitrogen, 14
Allowed to react for hours. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel chromatography. The obtained mixture was dissolved in tetrahydrofuran (40 ml), triethylamine (20 mmol) was added thereto, and acrylic acid chloride (20 mmol) was added for about 30 minutes. It dripped over. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 9 (or 8)-(2-acryloyloxy-2-methyladamantan-5-yl)-.
4-oxatricyclo [5.2.1.02,6] decane-3-one (mixture) was obtained in a yield of 32% and 9 (or 8)-
(2-acryloyloxy-2-methyladamantane-
5-yl) -8 (or 9) -hydroxy-4-oxatricyclo [5.2.1.02,6] decane-3-one (mixture) in 4% yield, 8 (or 9) -acryloyl Oxy-9 (or 8)-(2-hydroxy-2-methyladamantan-5-yl) -4-oxatricyclo [5.
2.1.02,6] Decan-3-one (mixture) in 6% yield, 8 (or 9) -acryloyloxy-9 (or 8)-(2-acryloyloxy-2-methyladamantane-5- Yl) -4-oxatricyclo [5.2.
1.02,6] Decan-3-one (mixture) in yield 11
%. [Spectral data of 9 (or 8)-(2-acryloyloxy-2-methyladamantan-5-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one] MS m / E: 66, 135, 240, 269, 371
(M + 1) [9 (or 8)-(2-acryloyloxy-2-methyladamantan-5-yl) -8 (or 9) -hydroxy-4-oxatricyclo [5.2.1.02,6] Spectrum data of decane-3-one] MS m / e: 69, 135, 315, 387 (M +
1) [8 (or 9) -acryloyloxy-9 (or 8)-
(2-hydroxy-2-methyladamantan-5-yl) -4-oxatricyclo [5.2.1.02,6]
Spectrum data of decane-3-one] MS m / e: 66,135,361,387 (M +
1) [8 (or 9) -acryloyloxy-9 (or 8)-
(2-acryloyloxy-2-methyladamantane-
5-yl) -4-oxatricyclo [5.2.1.0
2,6] Decan-3-one spectral data] MS m / e: 66, 135, 369, 441 (M +
1)

By performing the same operation as described above except that methacrylic acid chloride was used instead of acrylic acid chloride, the corresponding methacrylic acid ester derivatives were obtained.

Also, 1- (meth) acryloyloxy-3- (3-hydroxynorbornan-2-yl) adamantane [1f-
1], 1- (meth) acryloyloxy-3- (5 (or 6) -t-butoxycarbonyl-3-hydroxynorbornan-2-yl) adamantane [1f-6], 1- (meth) acryloyloxy-3 -(3,5 (or 6) -dihydroxynorbornan-2-yl) adamantane [1f
-7], 1-hydroxy-3- [3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f-2
3], 1-hydroxy-3- [5 (or 6) -t-butoxycarbonyl-3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f-28], 1-hydroxy-3- [5 ( Or 6) -hydroxy-3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f-29], 1-hydroxy-3-[(2-
(Meth) acryloyloxyadamantan-2-yl)
Methyl] adamantane [1f-31], 1-hydroxy-3
-[3-hydroxy-5 (or 6)-(meth) acryloyloxymethylnorbornan-2-yl] adamantane [1f-33], 1-t-butoxycarbonyl-3- (meth) acryloyloxy-5- [3 -Hydroxynorbornan-2-yl] adamantane [1f-45], 1-t-
Butoxycarbonyl-3-hydroxy-5- [3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f-56], 1- [3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f- 6
9], 8 (or 9)-(meth) acryloyloxy-9
(Or 8)-(adamantan-1-yl) -4-oxatricyclo [5.2.1.02,6] decane-3-one [1f-71], 1- [5 (or 6) -t -Butoxycarbonyl-3- (meth) acryloyloxynorbornane-
2-yl] adamantane [1f-74], 1-t-butoxycarbonyl-3- [3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f-91], 8
(Or 9)-(meth) acryloyloxy-9 (or 8)-(3-t-butoxycarbonyloxyadamantan-1-yl) -4-oxatricyclo [5.2.1.
02,6] decane-3-one [1f-93], 1-tert-butoxycarbonyl-3- [5 (or 6) -tert-butoxycarbonyl-3- (meth) acryloyloxynorbornan-2-yl] adamantane [1f-96], 8- (3-
(Meth) acryloyloxynorbornan-2-yl)
-3-oxatricyclo [4.3.1.14,8] undecane-2-one [1f-113], 8 (or 9)-(4-oxatricyclo [5.2.1.02,6 ] Decane-3-
On-9 (or 8) -yl) -3-oxatricyclo [4.3.1.14,8] undecane-2-one [1f-1
15], 8- (5 (or 6) -t-butoxycarbonyl-
3- (meth) acryloyloxynorbornan-2-yl) -3-oxatricyclo [4.3.1.14,8]
Undecane-2-one [1f-118], 8-[(2- (meth) acryloyloxyadamantan-1-yl) methyl] -3-oxatricyclo [4.3.1.14,8]
Undecane-2-one [1f-121], 9 (or 8)-[2
-Oxoadamantan-5-yl] -8 (or 9)-
[(Meth) acryloyloxy] -4-oxatricyclo [5.2.1.02,6] decane-3-one [1f-12
6], 2- (meth) acryloyloxy-2-methyl-
5- (3-hydroxynorbornan-2-yl) adamantane [1f-135], 9 (or 8)-[2- (meth) acryloyloxy-2-methyladamantan-5-yl]
-8 (or 9) -hydroxy-4-oxatricyclo [5.2.1.02,6] decane-3-one [1f-13
7], 2-hydroxy-5- [3- (meth) acryloyloxynorbornan-2-yl] -2-methyladamantane [1f-146].

Production Example 18 (9 (or 8)-[3- (1-acryloyloxy-1)
-Methylethyl) adamantan-1-yl] -4-oxatricyclo [5.2.1.02,6] decane-3-one [1g-21 (acrylate)], 9 (or 8)-[3-
(1-acryloyloxy-1-methylethyl) adamantan-1-yl] -8 (or 9) -hydroxy-4-
Oxatricyclo [5.2.1.02,6] decane-3
-One [1g-3 (acrylate)], 8 (or 9) -acryloyloxy-9 (or 8)-[3- (1-hydroxy-1-methylethyl) adamantan-1-yl] -4
-Oxatricyclo [5.2.1.02,6] decane-
3-one and 8 (or 9) -acryloyloxy-9
(Or 8) Production of-[3- (1-acryloyloxy-1-methylethyl) adamantan-1-yl] -4-oxatricyclo [5.2.1.02,6] decane-3-one) N-hydroxyphthalimide (9 mmol) and cobalt (III) acetylacetonate [Co (aca
c) In a benzonitrile solution (80 ml) containing 3] (0.3 mmol), α, α-dimethyl-1-adamantanemethanol (270 mmol) and 4-oxatricyclo [5.2.1.02,6 Decane-8-en-3-one (30 mmol) was added, and the mixture was reacted at 75 ° C. for 14 hours under a 20% oxygen atmosphere diluted with nitrogen. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography. The obtained mixture was dissolved in 40 ml of tetrahydrofuran, 20 mmol of triethylamine was added thereto, and about 30 mmol of acrylic acid chloride was added. Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 9 (or 8)-[3- (1-acryloyloxy-
1-methylethyl) adamantan-1-yl] -4-oxatricyclo [5.2.1.02,6] decane-3-
On (mixture) was obtained in a yield of 13%, 9 (or 8)-[3-
(1-acryloyloxy-1-methylethyl) adamantan-1-yl] -8 (or 9) -hydroxy-4-
Oxatricyclo [5.2.1.02,6] decane-3
-One (mixture) in 3% yield, 8 (or 9) -acryloyloxy-9 (or 8)-[3- (1-hydroxy-
1-methylethyl) adamantan-1-yl] -4-oxatricyclo [5.2.1.02,6] decane-3-
On (mixture) in 5% yield, 8 (or 9) -acryloyloxy-9 (or 8)-[3- (1-acryloyloxy-1-methylethyl) adamantan-1-yl]-
4-oxatricyclo [5.2.1.02,6] decane-3-one (mixture) was obtained with a yield of 7%. [9 (or 8)-[3- (1-acryloyloxy-1)
-Methylethyl) adamantan-1-yl] -4-oxatricyclo [5.2.1.02,6] decan-3-one] MS m / e: 66,135,327,399 (M +
1) [9 (or 8)-[3- (1-acryloyloxy-1)
-Methylethyl) adamantan-1-yl] -8 (or 9) -hydroxy-4-oxatricyclo [5.2.
1.02,6] Spectral data of decane-3-one] MS m / e: 66,135,343,397,415
(M + 1) 1 H-NMR (CDCl 3) δ: 1.5 (CH 3,6
H) [8 (or 9) -acryloyloxy-9 (or 8)-
[3- (1-Hydroxy-1-methylethyl) adamantan-1-yl] -4-oxatricyclo [5.2.
1.02,6] Spectral data of decane-3-one] MS m / e: 66,135,415 (M + 1) 1H-NMR (CDCl3) δ: 1.2 (CH3,6
H) [8 (or 9) -acryloyloxy-9 (or 8)-
[3- (1-acryloyloxy-1-methylethyl)
Spectral Data of Adamantan-1-yl] -4-oxatricyclo [5.2.1.02,6] decan-3-one] MS m / e: 66,135,469 (M + 1)

By performing the same operation as described above except that methacrylic acid chloride was used instead of acrylic acid chloride, the corresponding methacrylic acid ester derivatives were obtained.

Production Example 19 (1- (1-Acryloyloxy-1-methylethyl)
-3- [2- (adamantan-1-yl) ethyl] adamantane [1g-27 (acrylate)], 1- (1-acryloyloxy-1-methylethyl) -3- [2- (adamantan-1-yl) ) -2-Hydroxyethyl] adamantane [1g-9 (acrylate)], 1- (1-acryloyloxy-1-methylethyl) -3- [2-acryloyloxy-2- (adamantan-1-yl) ethyl] Adamantane and 1- (1-hydroxy-1-methylethyl) -3- [2-acryloyloxy-2-
(Production of (adamantan-1-yl) ethyl] adamantane) N-hydroxyphthalimide (9 mmol) and cobalt (III) acetylacetonate [Co (acac)
3] (0.3 mmol) in a benzonitrile solution (8
0 ml), α, α-dimethyl-1-adamantanemethanol (270 mmol) and 1-vinyladamantane (30 mmol) were added, and the mixture was reacted at 75 ° C. for 14 hours under a 20% oxygen atmosphere diluted with nitrogen. . The reaction mixture is concentrated under reduced pressure, the concentrate is subjected to silica gel chromatography, and the resulting mixture is treated with tetrahydrofuran 40
Then, 20 mmol of triethylamine was added thereto, and 20 mmol of acrylic acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography,
1- (1-acryloyloxy-1-methylethyl)-
3- (2-adamantan-1-ylethyl) adamantane was obtained at a yield of 22% and 1- (1-acryloyloxy-1-).
Methylethyl) -3- [2- (adamantan-1-yl) -2-hydroxyethyl] adamantane in a yield of 2
%, 1- (1-acryloyloxy-1-methylethyl) -3- [2-acryloyloxy-2- (adamantan-1-yl) ethyl] adamantane in a yield of 3%,
-(1-hydroxy-1-methylethyl) -3- [2-
Acryloyloxy-2- (adamantan-1-yl)
[Ethyl] adamantane was obtained in a yield of 5%. [1- (1-acryloyloxy-1-methylethyl)
Spectrum data of -3- (2-adamantan-1-ylethyl) adamantane] MS m / e: 135, 338, 410 (M + 1) [1- (1-acryloyloxy-1-methylethyl)
-3- [2- (Adamantan-1-yl) -2-hydroxyethyl] adamantane spectral data] MS m / e: 135, 355, 409, 427 (M +
1) 1H-NMR (CDCl3) δ: 1.5 (CH3,6)
H) [1- (1-Acryloyloxy-1-methylethyl)
Spectral data of -3- [2-acryloyloxy-2- (adamantan-1-yl) ethyl] adamantane] MS m / e: 72,135,481 (M + 1) [1- (1-hydroxy-1-methylethyl) ) -3-
[2-acryloyloxy-2- (adamantane-1-
Il) Ethyl] Spectrum data of adamantane] MS m / e: 135, 409, 427 (M + 1)

By performing the same operation as described above except that methacrylic chloride was used instead of acrylic chloride, the corresponding methacrylic ester derivatives were obtained.

Production Example 20 (1- [5 (or 6)-(1-acryloyloxy-1)
-Methylethyl) norbornan-2-yl] adamantane [1g-33 (acrylate)], 1- [5 or 6- (1
-Acryloyloxy-1-methylethyl) -3-hydroxynorbornan-2-yl] adamantane [1g-15
(Acrylate)], 1- [3-acryloyloxy-
5 (or 6)-(1-acryloyloxy-1-methylethyl) norbornan-2-yl] adamantane and 1- [3-acryloyloxy-5 or 6- (1-hydroxy-1-methylethyl) norbornane- 2-yl]
Production of adamantane) N-hydroxyphthalimide (9
Ammantane (270 ml) in a benzonitrile solution (80 ml) containing (mmol) and cobalt (III) acetylacetonate [Co (acac) 3] (0.3 mmol).
Mmol) and 5- (1-hydroxy-1-methylethyl) -2-norbornene (30 mmol), and reacted at 75 ° C. for 14 hours under a 20% oxygen atmosphere diluted with nitrogen. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography. The obtained mixture was dissolved in 40 ml of tetrahydrofuran, and 20 mmol of triethylamine was added thereto. Dropped over minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After adding water to the reaction mixture, the mixture was concentrated, and the concentrate was subjected to silica gel column chromatography to give 1- [5 (or 6)-(1).
-Acryloyloxy-1-methylethyl) norbornan-2-yl] adamantane in 15% yield, 1- [5
(Or 6)-(1-acryloyloxy-1-methylethyl) -3-hydroxynorbornan-2-yl] adamantane at a yield of 5% and 1- [3-acryloyloxy-
5 (or 6)-(1-acryloyloxy-1-methylethyl) norbornan-2-yl] adamantane at a yield of 10% and 1- [3-acryloyloxy-5 (or 6)
-(1-Hydroxy-1-methylethyl) norbornan-2-yl] adamantane was obtained with a yield of 8%. [1- [5 (or 6)-(1-acryloyloxy-1)
-Methylethyl) norbornan-2-yl] adamantane] MS m / e: 66,135,271,343 (M +
1) [1- [5 (or 6)-(1-acryloyloxy-1)
-Methylethyl) -3-hydroxynorbornane-2-
Il] Spectral data of adamantane] MS m / e: 66, 73, 135, 359 (M + 1) 1H-NMR (CDCl3) δ: 1.5 (CH3, 6
H) [1- [3-acryloyloxy-5 (or 6)-(1
Spectrum data of -acryloyloxy-1-methylethyl) norbornan-2-yl] adamantane] MS m / e: 66,135,413 (M + 1) [1- [3-acryloyloxy-5 (or 6)-(1
-Hydroxy-1-methylethyl) norbornane-2-
Il] adamantane spectral data] MS m / e: 66,135,341,359 (M +
1)

By performing the same operation as described above except that methacrylic acid chloride was used instead of acrylic acid chloride, the corresponding methacrylic acid ester derivatives were obtained.

Further, 1- [1- (meth) acryloyloxy-1-methylethyl] -3- (3-hydroxynorbornan-2-
Il) adamantane [1g-1], 1- [1- (meth) acryloyloxy-1-methylethyl] -3- (norbornan-2-yl) adamantane [1g-19], and 1-
[5 (or 6)-(1- (meth) acryloyloxy-
1-Methylethyl) norbornan-2-yl] adamantane [1g-33] was produced.

Example 1 Synthesis of a polymer compound having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer and a three-way cock, monomer [1a-4] (methacrylate) 4.85
g (13.5 mmol), 1.60 g (6.8 mmol) of monomer [2-13] (methacrylate), and monomer [2-
1] (methacrylate) 3.55 g (13.5 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.35 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,200 and the molecular weight distribution was 2.21. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.7, 4.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.
59 (J / cm3) 1/2.

Example 2 Synthesis of a polymer compound having the following structure

Embedded image Monomer [2-63] (methacrylate) 1.82 in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (8.2 mmol), monomer [2-13] (methacrylate) 1.93 g (8.2 mmol), monomer [1a-
8] (methacrylate) 6.25 g (16.4 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.92 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,700, and the molecular weight distribution was 2.01. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 22.14 (J / cm
3) 1/2.

Example 3 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 2.50 of monomer [2-63] (methacrylate) was added.
g (11.3 mmol), monomer [1a-5] (methacrylate) 3.58 g (11.3 mmol), monomer [2-1] (methacrylate) 3.92 g (15.0 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.38 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,500, and the molecular weight distribution was 2.22. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.97 (J / cm3) 1/2.

Example 4 Synthesis of a polymer compound having the following structure

Embedded image Monomer [1a-15] (methacrylate) 5.1 in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock
1 g (12.8 mmol), monomer [2-13] (methacrylate) 1.52 g (6.4 mmol), monomer [2-1] (methacrylate) 3.37 g (12.9 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.22 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,000 and the molecular weight distribution was 2.12. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.7, 4.2, and 4.6 ppm. The SP value of the polymer is 21.28
(J / cm3) 1/2.

Example 5 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 1.65 of monomer [2-63] (methacrylate) was added.
g (7.4 mmol), monomer [2-13] (methacrylate) 1.76 g (7.5 mmol), monomer [1a-2
0] (methacrylate) 6.59 g (14.9 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.82 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,500 and the molecular weight distribution was 2.11. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.95 (J / cm
3) 1/2.

Example 6 Synthesis of a polymer compound having the following structure

Embedded image 2.39 monomer (2-63) (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock.
g (10.8 mmol), 3.85 g (10.8 mmol) of monomer [1a-17] (methacrylate), and 3.76 g (14.4 mm) of monomer [2-1] (methacrylate).
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.22 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,300 and the molecular weight distribution was 1.99. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.75 (J / cm3) 1/2.

Example 7 Synthesis of a polymer compound having the following structure

Embedded image Monomer [1a-25] (methacrylate) 5.2 in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock
9 g (12.4 mmol), monomer [2-13] (methacrylate) 1.46 g (6.2 mmol), monomer [2-1] (methacrylate) 3.25 g (12.4 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g and the above-mentioned precipitation purification operation was repeated to obtain 6.82 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,900 and the molecular weight distribution was 2.15. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.7, 4.2, and 4.6 ppm. The SP value of the polymer is 21.08
(J / cm3) 1/2.

Example 8 Synthesis of a polymer compound having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.59 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (7.2 mmol), 1.69 g (7.2 mmol) of monomer [2-13] (methacrylate), and monomer [1a-3]
0] (methacrylate) 6.72 g (14.3 mmol
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.62 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,700, and the molecular weight distribution was 2.01. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.75 (J / cm
3) 1/2.

Example 9 Synthesis of a polymer having the following structure

Embedded image 2.32 monomer [2-63] (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer and three-way cock
g (10.5 mmol), 4.03 g (10.4 mmol) of monomer [1a-27] (methacrylate), 3.65 g (13.9 mm) of monomer [2-1] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.67 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,100 and the molecular weight distribution was 2.21. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.55 (J / cm3) 1/2.

Example 10 Synthesis of a polymer compound having the following structure

Embedded image 2.58 monomer [2-63] (methacrylate)
g (11.6 mmol), 2.74 g (11.6 mmol) of monomer [2-13] (methacrylate), 4.68 g (15.5 mm) of monomer [1b-1] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.75 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,800, and the molecular weight distribution was 2.02. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.88 (J / c
m3) １ ／.

Example 11 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [2-63] (methacrylate) 2.43
g (10.9 mmol), 2.58 g (10.9 mmol) of monomer [2-13] (methacrylate), 4.99 g (14.6 mm) of monomer [1b-7] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g and the above-mentioned precipitation purification operation was repeated to obtain 6.82 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,600 and the molecular weight distribution was 2.11. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.78 (J / c
m3) １ ／.

Example 12 Synthesis of a polymer having the following structure

Embedded image 2.33 Monomer [2-63] (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer and three-way cock
g (10.5 mmol), 2.48 g (10.5 mmol) of monomer [2-13] (methacrylate), 5.19 g (14.0 m) of monomer [1b-13] (methacrylate)
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and 7.28 g of a desired resin was obtained by repeating the above-mentioned precipitation purification operation. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7100,
The molecular weight distribution was 2.23. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer was 21.58 (J /
cm3) 1/2.

Example 13 Synthesis of a polymer having the following structure

Embedded image 2.21 monomer [2-63] (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer and three-way cock
g (10.0 mmol), 2.35 g (10.0 mmol) of monomer [2-13] (methacrylate), and 5.44 g (13.3 m) of monomer [1b-10] (methacrylate).
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.22 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,000,
The molecular weight distribution was 2.12. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.80 (J /
cm3) 1/2.

Example 14 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 2.34 of monomer [2-63] (methacrylate) was added.
g (10.5 mmol), monomer [2-13] (methacrylate) 2.49 g (10.5 mmol), monomer [1b-19] (methacrylate) 5.17 g (14.0 m)
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and 6.95 g of the desired resin was obtained by repeating the above-mentioned precipitation purification operation. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,500,
The molecular weight distribution was 1.99. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer was 21.55 (J /
cm3) 1/2.

Example 15 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 2.87 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (12.9 mmol), monomer [2-13] (methacrylate) 3.05 g (12.9 mmol), monomer [1c-2] (methacrylate) 4.07 g (17.3 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.65 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,900 and the molecular weight distribution was 2.22. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.88 (J / c
m3) １ ／.

Example 16 Synthesis of a polymer having the following structure

Embedded image 2.58 monomer [2-63] (methacrylate)
g (11.6 mmol), 2.74 g (11.6 mmol) of monomer [2-13] (methacrylate), 4.69 g (15.5 mm) of monomer [1c-5] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 6.92 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,300 and the molecular weight distribution was 1.88. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.69 (J / c
m3) １ ／.

Example 17 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [2-63] (methacrylate) 2.74
g (12.3 mmol), 2.91 g (12.3 mmol) of monomer [2-13] (methacrylate), and 4.35 g (16.4 m) of monomer [1c-10] (methacrylate).
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.22 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8300,
The molecular weight distribution was 2.12. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.88 (J /
cm3) 1/2.

Example 18 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer and a three-way cock, monomer [2-63] (methacrylate) 2.63
g (11.8 mmol), monomer [2-13] (methacrylate) 2.79 g (11.8 mmol), monomer [1c-13] (methacrylate) 4.58 g (15.8 m)
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and 6.90 g of the desired resin was obtained by repeating the above-described precipitation purification operation. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8200,
The molecular weight distribution was 1.95. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.68 (J /
cm3) 1/2.

Example 19 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [2-63] (methacrylate) 2.17
g (9.8 mmol), 2.31 g (9.8 mmol) of monomer [2-13] (methacrylate), and monomer [1d-
1] (methacrylate) 5.52 g (13.0 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.11 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,900 and the molecular weight distribution was 2.10. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.81 (J / cm
3) 1/2.

Example 20 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 2.09 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (9.4 mmol), 2.23 g (9.5 mmol) of monomer [2-13] (methacrylate), and monomer [1d-
2] (methacrylate) 5.68 g (12.6 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.82 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,600 and the molecular weight distribution was 2.11. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.43 (J / cm
3) 1/2.

Example 21 Synthesis of a polymer having the following structure

Embedded image 2.26 monomer (2-63) (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock
g (10.2 mmol), monomer [2-13] (methacrylate) 2.40 g (10.2 mmol), monomer [1d-3] (methacrylate) 5.34 g (13.6 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.28 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,100, and the molecular weight distribution was 2.23. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.95 (J / c
m3) １ ／.

Example 22 Synthesis of a polymer having the following structure

Embedded image Monomer [1e-1] (methacrylate) 4.10 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (15.5 mmol), 1.83 g (7.8 mmol) of monomer [2-13] (methacrylate), monomer [2-
1] (methacrylate) 4.07 g (15.5 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.35 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,200 and the molecular weight distribution was 2.21. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.7, 4.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.
47 (J / cm3) 1/2.

Example 23 Synthesis of a polymer having the following structure

Embedded image A monomer [1e-7] (methacrylate) 3.61 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (10.9 mmol), 2.58 g (10.9 mmol) of monomer [2-13] (methacrylate), 3.82 g (14.6 mm) of monomer [2-1] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.22 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,000 and the molecular weight distribution was 2.12. 1H-NMR (DMSO-d6
In the (middle) analysis, strong signals were observed at around 3.7, 4.2, 4.4, and 4.6 ppm in addition to 1.5-2.7 ppm (broad). The SP value of the polymer is 21.71
(J / cm3) 1/2.

Example 24 Synthesis of a polymer having the following structure

Embedded image A monomer [1e-5] (methacrylate) 3.62 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (10.9 mmol), monomer [2-13] (methacrylate) 2.57 g (10.9 mmol), monomer [2-1] (methacrylate) 3.81 g (14.5 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g and the above-mentioned precipitation purification operation was repeated to obtain 6.82 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,900 and the molecular weight distribution was 2.15. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 21.71
(J / cm3) 1/2.

Example 25 Synthesis of a polymer having the following structure

Embedded image A monomer [1e-2] (methacrylate) 4.55 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (14.9 mmol), 3.51 g (14.9 mmol) of monomer [2-13] (methacrylate), 1.95 g (7.4 mmol) of monomer [2-1] (methacrylate)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.21 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,800, and the molecular weight distribution was 1.99. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.7, 4.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.
27 (J / cm3) 1/2.

Example 26 Synthesis of polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 3.92 monomer (1e-8) (methacrylate)
g (10.5 mmol), 3.32 g (14.1 mmol) of monomer [2-13] (methacrylate), and 2.76 g (10.5 mm) of monomer [2-1] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.31 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,500 and the molecular weight distribution was 2.12. 1H-NMR (DMSO-d6
In the (middle) analysis, strong signals were observed at around 3.7, 4.2, 4.4, and 4.6 ppm in addition to 1.5-2.7 ppm (broad). The SP value of the polymer is 21.51
(J / cm3) 1/2.

Example 27 Synthesis of a polymer having the following structure

Embedded image 3.97 monomer (1f-3) (methacrylate) was placed in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock.
g (10.5 mmol), 2.43 g (10.3 mmol) of monomer [2-13] (methacrylate), and 3.60 g (13.7 mm) of monomer [2-1] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 6.88 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,300 and the molecular weight distribution was 2.26. 1H-NMR (DMSO-d6
In the middle) analysis, in addition to 1.5-2.7 ppm (broad), 3.2, 3.4, 3.7, 3.9, 4.2, and 4.
Strong signals were observed around 4, 4.6 ppm. The SP value of the polymer is 21.51 (J / cm3) 1/2.

Example 28 Synthesis of polymer having the following structure

Embedded image 1.68 monomer (2-63) (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock.
g (7.6 mmol), monomer [2-13] (methacrylate) 1.79 g (7.6 mmol), monomer [1f-
6] (methacrylate) 6.53 g (15.2 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.92 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,700, and the molecular weight distribution was 2.01. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.4, 3.9, 4.4 and 4.6 ppm. The SP value of the polymer is 22.
23 (J / cm3) 1/2.

Example 29 Synthesis of polymer having the following structure

Embedded image 2.58 monomer [2-63] (methacrylate)
g (10.9 mmol), monomer [1f-1] (methacrylate) 3.61 g (10.9 mmol), monomer [2-1] (methacrylate) 3.82 g (14.6 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.38 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,500, and the molecular weight distribution was 2.22. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.45 (J / cm3) 1/2.

Example 30 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 3.42 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (15.4 mmol), 2.54 g (7.7 mmol) of monomer [1f-23] (methacrylate), 4.04 g (15.4 mm) of monomer [2-1] (methacrylate)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.02 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,800, and the molecular weight distribution was 2.25. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 4.4, and 4.6 ppm. The SP value of the polymer is 21.80 (J / c
m3) １ ／.

Example 31 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.81 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (8.2 mmol), 8.19 g (19.0 mmol) of monomer [1f-28] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 6.32 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 1.92.
Met. In 1H-NMR (in DMSO-d6) analysis,
In addition to 5-2.7 ppm (broad), 3.2 and 4.
Strong signals were observed around 4, 4.6 ppm. The SP value of the polymer is 22.13 (J / cm3) 1/2.

Example 32 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 3.49 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (15.7 mmol), monomer [1f-7] (methacrylate) 1.36 g (3.9 mmol), monomer [2-
1] (methacrylate) 5.15 g (19.7 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.22 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,300 and the molecular weight distribution was 1.99. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.4, 3.9, 4.4 and 4.6 ppm. The SP value of the polymer is 21.
72 (J / cm3) 1/2.

Example 33 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 3.49 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (15.7 mmol), monomer [1f-33] (methacrylate) 1.36 g (3.9 mmol), monomer [2-1] (methacrylate) 5.15 g (19.7 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 6.52 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 1.89. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.72 (J / cm3) 1/2.

Example 34 Synthesis of polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 3.49 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (15.7 mmol), monomer [1f-29] (methacrylate) 1.36 g (3.9 mmol), monomer [2-1] (methacrylate) 5.15 g (19.7 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 6.61 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 1.84. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5 to 2.7 ppm (broad), strong signals were observed at around 3.2, 3.4, 3.9, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.72 (J / cm3) 1/2.

Example 35 Synthesis of a polymer having the following structure

Embedded image Monomer [2-63] (methacrylate) 1.99 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (9.0 mmol), 8.01 g (20.9 mmol) of monomer [1f-31] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries) were added and dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and 6.52 g of a desired resin was obtained by repeating the above-mentioned precipitation purification operation. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,900 and the molecular weight distribution was 1.98.
Met. In 1H-NMR (in DMSO-d6) analysis,
In addition to 5-2.7 ppm (broad), 3.2 and 4.
Strong signals were observed around 4, 4.6 ppm. The SP value of the polymer is 22.67 (J / cm3) 1/2.

Example 36 Synthesis of a polymer having the following structure

Embedded image A monomer [1f-25] (methacrylate) 3.9 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
7g (10.3 mmol), monomer [2-13] (methacrylate) 2.43 g (10.3 mmol), monomer [2-1] (methacrylate) 3.60 g (13.7 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.28 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,500, and the molecular weight distribution was 2.16. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 3.7, 4.2, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.38 (J / cm3) 1/2.

Example 37 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [1f-45] (methacrylate) 7.8 was added.
3 g (16.1 mmol), 2.17 g (6.9 mmol) of monomer [1f-69] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries) were added and dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C.
The mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, it was again dissolved in 40 g of tetrahydrofuran,
By repeating the above-mentioned precipitation purification operation, 6.32 g of a desired resin was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,700, and the molecular weight distribution was 1.89.
Met. In 1H-NMR (in DMSO-d6) analysis,
5-2.7 ppm (broad), 3.2 and 3.
Strong signals were observed around 4, 3.7, 3.9, 4.2 and 4.6 ppm. The SP value of the polymer is 21.90
(J / cm3) 1/2.

Example 38 Synthesis of a polymer having the following structure

Embedded image 1.68 monomer (2-63) (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, stirrer, and three-way cock.
g (7.6 mmol), monomer [2-13] (methacrylate) 1.79 g (7.6 mmol), monomer [1f-4
5] (methacrylate) 6.53 g (15.2 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.96 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,900 and the molecular weight distribution was 2.21. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.4, 3.9, 4.4 and 4.6 ppm. The SP value of the polymer is 22.
21 (J / cm3) 1/2.

Example 39 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.81 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (8.2 mmol), 8.19 g (19.0 mmol) of monomer [1f-56] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries) were added and dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 6.33 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,500 and the molecular weight distribution was 1.83.
Met. In 1H-NMR (in DMSO-d6) analysis,
In addition to 5-2.7 ppm (broad), 3.2 and 4.
Strong signals were observed around 4, 4.6 ppm. The SP value of the polymer is 22.06 (J / cm3) 1/2.

Example 40 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 2.04 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (9.2 mmol), 2.17 g (9.2 mmol) of monomer [2-13] (methacrylate), and monomer [1f-7]
4] (methacrylate) 5.78 g (18.4 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.86 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,500 and the molecular weight distribution was 2.14. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.60 (J / cm
3) 1/2.

Example 41 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 1.73 monomer (2-63) (methacrylate) was added.
g (7.8 mmol), 1.84 g (7.8 mmol) of monomer [2-13] (methacrylate), and monomer [1f-9]
1] (methacrylate) 6.44 g (15.6 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.76 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,200 and the molecular weight distribution was 2.12. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.60 (J / cm
3) 1/2.

Example 42 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.49 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (6.7 mmol), 1.59 g (6.7 mmol) of monomer [2-13] (methacrylate), and monomer [1f-9]
6] (methacrylate) 6.92 g (13.5 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.56 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 1.92. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.2, 4.4, 4.6 ppm. The SP value of the polymer is 21.47 (J / cm
3) 1/2.

Example 43 Synthesis of a polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.19 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (5.4 mmol), 1.26 g (5.3 mmol) of monomer [2-13] (methacrylate), and monomer [1f-9]
3] (methacrylate) 7.55 g (16.1 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.78 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 1.98. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.7, 4.2, 4.4, and 4.6 ppm. The SP value of the polymer is 22.
25 (J / cm3) 1/2.

Example 44 Synthesis of polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.86 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (7.9 mmol), 8.14 g (18.3 mmol) of monomer [1f-118] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. The collected precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.33 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 6,900 and the molecular weight distribution was 1.87.
Met. In 1H-NMR (in DMSO-d6) analysis,
In addition to 5-2.7 ppm (broad), 3.0 and 3.0.
A strong signal was observed at around 2,4.6 ppm. The SP value of the polymer is 22.03 (J / cm3) 1/2.

Example 45 Synthesis of polymer having the following structure

Embedded image A monomer [1f-113] (methacrylate) 3.7 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
0 g (10.8 mmol), monomer [2-13] (methacrylate) 2.54 g (10.8 mmol), monomer [2-1] (methacrylate) 3.76 g (14.4 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-described precipitation purification operation was repeated to obtain 7.18 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,900 and the molecular weight distribution was 2.26. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.0, 3.2, and 4.6 ppm. The SP value of the polymer is 21.03 (J / c
m3) １ ／.

Example 46 Synthesis of polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [1f-115] (methacrylate) 3.4
5 g (8.6 mmol), 2.03 g (8.6 mmol) of monomer [2-13] (methacrylate), and monomer [2-
1] (methacrylate) 4.52 g (17.3 mmol
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.06 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,200 and the molecular weight distribution was 2.12. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
3.0, 3.2, 3.7, 4.2, 4.4, 4.6 pp
m, a strong signal was observed. The SP value of the polymer is 21.73 (J / cm3) 1/2.

Example 47 Synthesis of a polymer having the following structure

Embedded image A monomer [1f-121] (methacrylate) 3.4 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
4 g (8.6 mmol), monomer [2-13] (methacrylate) 2.04 g (8.6 mmol), monomer [2-
1] (methacrylate) 4.53 g (17.3 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.47 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,200 and the molecular weight distribution was 2.17. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed at around 3.0 and 4.6 ppm. The SP value of the polymer is 20.66 (J / cm3) 1 /
2.

Example 48 Synthesis of polymer having the following structure

Embedded image A monomer [1f-137] (methacrylate) 3.4 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
5 g (8.6 mmol), 2.03 g (8.6 mmol) of monomer [2-13] (methacrylate), and monomer [2-
1] (methacrylate) 4.52 g (17.3 mmol
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 7.37 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,600 and the molecular weight distribution was 2.13. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
3.2, 3.4, 3.7, 3.9, 4.2, 4.6 pp
m, a strong signal was observed. The SP value of the polymer is 21.12 (J / cm3) 1/2.

Example 49 Synthesis of polymer having the following structure

Embedded image A monomer [2-63] (methacrylate) 1.49 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (6.7 mmol), 1.58 g (6.7 mmol) of monomer [2-13] (methacrylate), and monomer [1f-1]
35] (methacrylate) 6.93 g (20.1 mmo
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.82 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 1.78. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.4, 3.9, 4.4 and 4.6 ppm. The SP value of the polymer is 22.
26 (J / cm3) 1/2.

Example 50 Synthesis of a polymer having the following structure

Embedded image 4.9 Monomer [1f-71] (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
3g (13.3 mmol), monomer [2-13] (methacrylate) 1.57 g (6.7 mmol), monomer [2-1] (methacrylate) 3.49 g (13.3 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
The resin was dissolved in 0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.55 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,300 and the molecular weight distribution was 2.26. 1H-NMR (DMSO-d6
In the (middle) analysis, in addition to 1.5-2.7 ppm (broad), strong signals were observed at around 3.2, 3.7, 4.2, 4.4, and 4.6 ppm. The SP value of the polymer is 2
1.00 (J / cm3) 1/2.

Example 51 Synthesis of a polymer having the following structure

Embedded image A monomer [1f-126] (methacrylate) 5.0 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
3g (13.1 mmol), monomer [2-13] (methacrylate) 1.54 g (6.5 mmol), monomer [2-1] (methacrylate) 3.43 g (13.1 mm)
ol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.00
g was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification.
After drying the collected precipitate under reduced pressure, tetrahydrofuran 4
0 g, and the above-mentioned precipitation purification operation was repeated to obtain 7.12 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,900 and the molecular weight distribution was 2.32. 1H-NMR (DMSO-d6
In the middle) analysis, in addition to 1.5-2.7 ppm (broad), 3.0, 3.2, 3.7, 4.2, 4.4, 4.6 were used.
A strong signal was observed around ppm. Polymer S
The P value is 21.37 (J / cm3) 1/2.

Example 52 Synthesis of a polymer having the following structure

Embedded image 6.6 Monomer [1f-146] (methacrylate) in a 100 ml round bottom flask equipped with a reflux tube, a stirrer and a three-way cock.
3 g (19.3 mmol), 3.37 g (12.9 mmol) of monomer [2-1] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries) were added and dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C.
The mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, it was again dissolved in 40 g of tetrahydrofuran,
By repeating the above-described precipitation purification operation, 7.12 g of a desired resin was obtained. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8,900 and the molecular weight distribution was 2.32.
Met. In 1H-NMR (in DMSO-d6) analysis,
In addition to 5-2.7 ppm (broad), 4.4, 4.6
A strong signal was observed around ppm. Polymer S
The P value is 20.43 (J / cm3) 1/2.

Example 53 Synthesis of a polymer having the following structure

Embedded image A monomer [2-1] (methacrylate) 2.08 was placed in a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock.
g (7.9 mmol), 7.92 g (18.5 mmol) of monomer [1g-3] (methacrylate), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 40 g of tetrahydrofuran. . Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the recovered precipitate under reduced pressure, it is dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation is repeated to obtain the desired resin 7.
75 g were obtained. As a result of GPC analysis of the recovered polymer,
The weight average molecular weight was 7,800 and the molecular weight distribution was 2.02. In 1H-NMR (in DMSO-d6) analysis, 1.5-
In addition to 2.7 ppm (broad), 3.2, 3.4,
Strong signals were observed around 3.7, 3.9, 4.2 and 4.6 ppm. The SP value of the polymer is 21.85 (J
/ Cm3) 1/2.

Example 54 Synthesis of polymer compound having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 1.85 of monomer [2-63] (methacrylate) was added.
g (8.3 mmol), monomer [2-13] (methacrylate) 1.96 g (8.3 mmol), monomer [1 g-
1] (methacrylate) 6.19 g (16.6 mmol)
l), and 1.00 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries)
Was dissolved in 40 g of tetrahydrofuran. Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. The reaction solution was dropped into 500 ml of a 9: 1 mixture of hexane and ethyl acetate, and the resulting precipitate was separated by filtration for purification. After drying the collected precipitate under reduced pressure, tetrahydrofuran 40
g, and the above-mentioned precipitation purification operation was repeated to obtain 6.82 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7,600 and the molecular weight distribution was 2.11. 1H-NMR (in DMSO-d6)
In the analysis, in addition to 1.5-2.7 ppm (broad),
Strong signals were observed around 3.2, 3.4, 3.9, 4.4 and 4.6 ppm. The SP value of the polymer is 22.
10 (J / cm3) 1/2.

Example 55 Synthesis of a polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [2-63] (methacrylate) 2.38
g (10.7 mmol), 2.53 g (10.7 mmol) of monomer [2-13] (methacrylate), 5.09 g (14.3 m) of monomer [1g-19] (methacrylate)
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and the above-mentioned precipitation purification operation was repeated to obtain 7.32 g of a desired resin. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 7900,
The molecular weight distribution was 2.21. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), 3.2, 3.4, 3.9, 4.4, 4.6 ppm
A strong signal was observed in the vicinity. The SP value of the polymer is 21.32 (J / cm3) 1/2.

Example 56 Synthesis of polymer having the following structure

Embedded image In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, monomer [2-63] (methacrylate) 2.38
g (10.7 mmol), monomer [2-13] (methacrylate) 2.53 g (10.7 mmol), monomer [1g-33] (methacrylate) 5.09 g (14.3 m)
mol) and an initiator (V-65 manufactured by Wako Pure Chemical Industries) 1.0
0 g was added and dissolved in 40 g of tetrahydrofuran.
Subsequently, after the inside of the flask was replaced with dry nitrogen, the temperature of the reaction system was maintained at 60 ° C., and the mixture was stirred under a nitrogen atmosphere for 6 hours. 500 ml of a 9: 1 mixture of hexane and ethyl acetate
And the resulting precipitate was filtered off to purify. The recovered precipitate was dried under reduced pressure, dissolved again in 40 g of tetrahydrofuran, and 7.55 g of a desired resin was obtained by repeating the above-described precipitation purification operation. As a result of GPC analysis of the recovered polymer, the weight average molecular weight was 8200,
The molecular weight distribution was 2.23. 1H-NMR (DMSO-d
6) In the analysis, in addition to 1.5-2.7 ppm (broad), 3.2, 3.4, 3.9, 4.4, 4.6 ppm
A strong signal was observed in the vicinity. The SP value of the polymer is 21.32 (J / cm3) 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 prebaking 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, followed by postbaking 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 Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/08 C08F 232/08 G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Keizo Inoue 62 Ogama, Shizuma-Higashi-cho, Himeji City, Hyogo Prefecture (72) Inventor, Katsunori Funaki 1367-5, Shinzai, Aboshi-ku, Himeji City, Hyogo Prefecture ) Inventor Akira Horai 940F F-term (Reference) 2H025 AA01 AA02 AA09 AA14 AB16 AC08 AD03 BE00 BE10 BG00 BJ10 CB14 CB41 CB52 FA17 4J100 AL08P AL08Q BA11 BA12 BA20 BC07 BC08 BC09 BC12 BC

Claims (7)

[Claims] (1) The following formulas (Ia) to (Ig) [Wherein, ^Ra represents a hydrogen atom or a methyl group. R ¹ , R ²
Represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³
Represents a tertiary hydrocarbon group which may have a substituent, a tetrahydropyranyl group or a tetrahydrofuranyl group.
R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group which may be protected by a protecting group, or a hydroxymethyl group which may be protected by a protecting group. A represents a single bond, a methylene group, an ethylene group or a hydroxyethylene group. L represents a 5- or more-membered lactone ring which may have a substituent. X represents a divalent alicyclic group which may have a substituent. Y, Y ¹ and Y ² each represent a monovalent alicyclic group which may have a substituent (provided that when n in n in the formula (Ic) is 0, it has a substituent) Adamantyl group which may be substituted). m represents 0 or 1.
n, n1, and n2 each represent 0, 1, or 2], and a polymer compound containing at least one monomer unit selected from the group consisting of: 2. At least one monomer unit selected from the formulas (Ia) to (Ig) 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. The following formulas (1a), (1b), (1c), (1
d), (1e), (1f) or (Ig) [Wherein, ^Ra represents a hydrogen atom or a methyl group. R ¹ , R ²
Represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. R ³
Represents a tertiary hydrocarbon group which may have a substituent, a tetrahydropyranyl group or a tetrahydrofuranyl group.
R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group which may be protected by a protecting group, or a hydroxymethyl group which may be protected by a protecting group. A represents a single bond, a methylene group, an ethylene group or a hydroxyethylene group. L represents a 5- or more-membered lactone ring which may have a substituent. X represents a divalent alicyclic group which may have a substituent. Y, Y ¹ and Y ² each represent a monovalent alicyclic group which may have a substituent (provided that when n in n in the formula (Ic) is 0, it has a substituent) Adamantyl group which may be substituted). m represents 0 or 1.
n, n1, n2 represent 0, 1, or 2] (meta)
Acrylic esters.