JP2002116542A - High molecular compound for photoresist and resin composition for photoresist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new high molecular compound for a photoresist having adhesion to a substrate and etching resistance in a well-balanced state. SOLUTION: The high molecular compound contains at least one of monomer units of formulae (Ia) and (Ib) (where Ra is H or methyl and R1-R18 are each H, methyl or ethyl), may contain 0.1-50 mol%, based on the total amount, of a monomer unit having a group containing an alicyclic hydrocarbon ring other than the monomer units of the formulae (Ia) and (Ib) and may further contain 0.1-50 mol% monomer unit corresponding to a monomer whose solubility parameter by the Fedors method is <=11 (cal/cm3)1/2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art A photoresist resin used in a semiconductor manufacturing process includes a portion exhibiting substrate adhesion and a portion which becomes soluble in an alkali developing solution by being desorbed by an acid generated from a photoacid generator upon exposure. is necessary. Further, the photoresist resin must also have dry etching resistance.

Hitherto, a lactone skeleton has attracted attention as a skeleton for imparting substrate adhesion. And as a structure with dry etching resistance in addition to this substrate adhesion,
Alicyclic hydrocarbon skeletons containing a lactone ring are known. However, few photoresist resins have a good balance between substrate adhesion and dry etching resistance.
On the other hand, a lactone skeleton having a tertiary carbon atom has been proposed as a skeleton having both substrate adhesion and acid desorption properties (Japanese Patent Application Laid-Open No. 10-207069). However, almost no skeleton having a lactone ring and having all of substrate adhesion, dry etching resistance and acid desorption properties is known.

[0004]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a novel polymer compound for photoresists having a good balance between adhesion to a substrate and etching resistance. It is another object of the present invention to provide a novel photoresist polymer compound having high adhesion to a substrate and exhibiting excellent acid desorption and etching resistance. Still another object of the present invention is to provide a resin composition for a photoresist capable of forming a fine pattern with high accuracy, and a method for manufacturing a semiconductor.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a polymer containing a monomer unit having an alicyclic skeleton having a specific structure in which a lactone ring is condensed is used as a resin for a photoresist. As a result, the present inventors have found that a polymer compound for photoresist having a good balance between adhesion to a substrate and etching resistance can be obtained, and the present invention has been completed.

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

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{1 to} R ¹⁸
Represents a hydrogen atom, a methyl group or an ethyl group, respectively).

The polymer compound for a photoresist comprises at least one monomer unit selected from the formulas (Ia) and (Ib) and the following formulas (IIa) to (IIg):

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹⁹ and R ²⁰ are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ²¹ , R ²² and R ²³ are the same. R ²⁴ and R ²⁵ are the same or different and represent a hydrogen atom, a hydroxyl group or a —COOR ²⁶ group, and R ²⁶ is a t-butyl group,
It represents a tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group. R ²⁷ represents a methyl group or an ethyl group, and R ²⁸ and R ²⁹ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group. R ³⁰ is
A hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom shown in the formula is shown. R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are the same or different and represent a hydrogen atom or a methyl group. R ³⁶ represents a t-butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group. m represents an integer of 1 to 3, and n represents 0 or 1.).

In addition, in addition to at least one monomer unit selected from the formulas (Ia) and (Ib),
In addition to at least one monomer unit selected from (Ib) and at least one monomer unit selected from Formulas (IIa) to (IIg), the following Formulas (IIIa) to (III)
h)

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ³⁷ and R ³⁸ are the same or different and represent a hydrogen atom, a hydroxyl group or a carboxyl group, and R ³⁹ represents a hydroxyl group, an oxo group or a carboxyl group. X ¹ , X ² and X
³ are the same or different, -CH ₂ - shows or -CO-O- and. R ⁴⁰ , R ⁴¹ and R ⁴² are the same or different and each represent a hydrogen atom or a methyl group. R ⁴³ and R ⁴⁴ are the same or different and each represent a hydrogen atom or a methyl group. R ⁴⁵ , R ⁴⁶ , R
⁴⁷ , R ⁴⁸ and R ⁴⁹ are the same or different and each represent a hydrogen atom or a methyl group. R ⁵⁰ represents a hydrogen atom or a linear, branched, cyclic or bridged cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ⁵¹ , R ⁵² , R ⁵³
And R ⁵⁴ are the same or different and each represent a hydrogen atom or a methyl group. R ⁵⁵ represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group. o, p, q and r each represent 0 or 1), and may include at least one monomer unit selected from the monomer units represented by:

The polymer compound for a photoresist is a monomer unit having a group containing an alicyclic hydrocarbon ring (formula (I)
a) and (Ib) (excluding the monomer units represented by (Ib)). Also, Fed
ors method has a solubility parameter value of 11 (c
al / cm ³ ) It is also preferred to contain 0.1 to 50 mol% of a monomer unit corresponding to ^1/2 or less of the monomer. Further, the polymer compound for photoresist has a solubility parameter value of 9.5 to 12 (cal) according to the Fedors method.
/ Cm ³ ) ^1/2 .

The present invention also provides a photoresist resin composition comprising at least the above-mentioned polymer compound for a photoresist and a photoacid generator. The present invention further provides a method for producing a semiconductor, comprising a step of applying the above-described resin composition for photoresist on a substrate or a substrate to form a resist coating film, and forming a pattern through exposure and development. . 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”.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer compound for a photoresist of the present invention comprises, as a structural unit constituting a polymer molecule, at least one monomer unit (repeating unit) selected from the formulas (Ia) and (Ib). (Hereinafter may be referred to as “monomer unit 1”). Since this monomer unit 1 has a lactone ring having high hydrophilicity, it functions as an adhesion imparting unit that enhances adhesion to a substrate. Further, since it also has an alicyclic carbon ring (cyclohexane ring), it also has a function of improving etching resistance. Further, when R ³ or R ¹³ is a methyl group or an ethyl group, since the bonding site of the oxygen atom constituting the ester bond becomes a tertiary carbon atom, the alicyclic carbon ring is eliminated by an acid. Also, since a free carboxyl group is generated, it also has an alkali-soluble (acid-eliminating) function. In the case where R ³ and R ¹³ are hydrogen atoms, the polymer can be used as a resist by appropriately using a polymerizable monomer capable of expressing an alkali-soluble (acid-eliminating) function as a comonomer in the production of a polymer. It can be a polymer having all the functions. Therefore, the polymer containing the above monomer unit 1 can be suitably used as a photoresist resin.

In a preferred embodiment of the present invention, the above-mentioned formula (Ia)
And at least one monomer unit selected from (Ib) and at least one monomer unit (repeating unit) selected from the formulas (IIa) to (IIg) (hereinafter, referred to as “monomer unit 2”). There is).

In the formulas (Ia) and (Ib), R ^{1 to} R ¹⁸ each represent a hydrogen atom, a methyl group or an ethyl group, but are often a hydrogen atom or a methyl group. It is preferable that R ³ and R ¹³ be a methyl group or an ethyl group, since the monomer unit represented by the formula (Ia) or (Ib) has an acid elimination function as described above.

In the formula (IIa), hydrocarbons having 1 to 8 carbon atoms in R ¹⁹ and R ²⁰ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,
C _1-8 alkyl groups such as pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl, heptyl, 1-methylhexyl, octyl and 1-methylheptyl; cyclo C _3-8 such as propyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups
A cycloalkyl group; a phenyl group; Among these, C, such as methyl, ethyl and isopropyl groups,
_1-3 alkyl groups are preferred.

In the formula (IId), examples of the “hydrocarbon group having a tertiary carbon atom at the bonding site to an oxygen atom shown in the formula” for R ³⁰ include, for example, a t-butyl group and a t-amyl group And the like. These hydrocarbon groups may have a substituent.

In the monomer unit represented by the formula (IIa), a site containing an adamantane skeleton is eliminated from the carboxylic acid moiety bonded to the main chain by an acid to generate a free carboxyl group. In the monomer unit represented by the formula (IIb), a carboxyl group protected by a protecting group bonded to the adamantane skeleton is deprotected by an acid to generate a free carboxyl group. Further, the monomer unit represented by the formula (IIc) generates a free carboxyl group by removing the adamantane skeleton from the carboxylic acid moiety bonded to the main chain by an acid. Further, the formulas (IId), (IIe), (IIf) and (I
In the monomer unit represented by Ig), a carboxylic acid ester site is decomposed and eliminated by an acid to generate a free carboxyl group. Therefore, the monomer unit 2 functions as an alkali-soluble unit for solubilizing the resin during alkali development.

Since the monomer units represented by the formulas (IIa), (IIb), (IIc) and (IIg) have an alicyclic carbon skeleton, they have excellent transparency and extremely high etching resistance. Has features. In addition, in the formula (IIa), R
²¹ at least one monomeric unit is a hydroxyl group to R ^23, and monomer units represented by the formula (IIf) is
It is highly hydrophilic and has an adhesive function.

The polymer compound for a photoresist according to the present invention comprises the monomer unit 1 or the monomer unit 1
And at least one monomer unit (repeating unit) selected from the monomer units represented by the formulas (IIIa) to (IIIh) (hereinafter referred to as “monomer unit 3”)
May be included).

In the formula (IIIb), X¹~ X^Three-CO-
The orientation of the O-group does not matter. Further, in the formula (IIIe), R⁵⁰To
Linear, branched, cyclic or cyclic having 1 to 20 carbon atoms
Is a bridged cyclic hydrocarbon group (bridged cyclic group)
, Ethyl, propyl, isopropyl, butyl, isobu
Tyl, t-butyl, pentyl, hexyl, octyl, de
Syl, dodecyl, tetradecyl, octadecyl groups, etc.
A linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms
(Especially alkyl group); cyclopentyl, cyclohexyl
, Cyclooctyl, cyclododecyl, etc.
-20 cycloalkyl or cycloalkenyl groups;
Hydroindene ring, perhydrofluorene ring, perhydride
Ronaphthalene ring (decalin ring), perhydroanthrace
Ring, norbornane ring, norbornene ring, pinane ring,
Lunane ring, isobornirane ring, tricyclo [5.2.
1.0^2,6] Decane ring, tetracyclo [4.4.0.1
^2,5. 1 ^7,106 to 20 carbon atoms corresponding to a dodecane ring or the like
Bridged cyclic hydrocarbon groups (bridged cyclic hydrocarbon groups);
Cyclo [5.2.1.0^2,6] Decylmethyl group, tetra
Cyclo [4.4.0.1^2,5. 1^7,10] Dodecylmethyl
Or each of the above hydrocarbon groups such as a 2-norbornylmethyl group
And the like. These hydrocarbon groups
Is protected by an alkyl group, a halogen atom, or a protecting group.
May be protected by a hydroxyl group or a protecting group.
Hydroxymethyl group, may be protected with a protecting group
Carboxyl group (for example, carboxyl group, t-butyl
Oxycarbonyl group, 2-tetrahydrofuranyloxy
Carbonyl group, 2-tetrahydropyranyloxycarbo
Nyl group, 2-oxepanyloxycarbonyl group, etc.)
It may have a substituent such as a xo group. The protecting group and
Thus, protecting groups commonly used in the field of organic synthesis can be used.

The monomer unit represented by the formula (IIIa) has a highly hydrophilic group (hydroxyl group, carboxyl group, oxo group) bonded to the adamantane skeleton.
It has the function of improving the adhesion to the substrate. The formula (III
a), (IIIb) (e.g., X ^{1 to} X ³ are all methylene groups), (IIIc), (IIIe) (R ⁵⁰ is a cyclic or bridged cyclic hydrocarbon group), (IIIg) and Since the monomer unit represented by (IIIh) has an alicyclic carbon skeleton, it contributes to improvement in transparency, etching resistance, and the like. Formula (IIIb)
(Where at least one of X ^{1 to} X ³ is a —CO—O— group), a monomer unit having a lactone skeleton represented by (IIIc), (IIId) and (IIIg), a compound represented by the formula (IIIe) (R ⁵⁰ Is a hydrogen atom), (IIIf), (IIIh) (where R ⁵⁵ is a hydroxyl group, a hydroxymethyl group or a carboxyl group) contains a hydrophilic group and has an adhesion property. Has functions. 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 resist resin 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 those described above, if necessary, in order to adjust the above various properties.

In the polymer compound for photoresist of the present invention, the content of the monomer unit 1 is, for example, 1 to 1 with respect to the entire monomer units constituting the polymer.
It is about 95 mol%, preferably about 10 to 90 mol%, and more preferably about 20 to 80 mol%. In a preferred polymer compound, the monomer unit 2 is added in an amount of 5 to 99% by mole based on the entire monomer units constituting the polymer.
Degree (for example, about 10 to 80 mol%), especially 30 to 6
About 0 mol% is contained. The content of the monomer unit 3 in the polymer compound containing the monomer unit 3 is, for example, 1 to 50 mol%, preferably 3 to 40 mol%, more preferably 5 to 50 mol%, based on the entire monomer units constituting the polymer. About 30 mol%.

Further, in the polymer compound for a photoresist of the present invention, the ratio of monomer units having a group containing an alicyclic hydrocarbon ring (excluding the monomer units represented by formulas (Ia) and (Ib)) Is 0.1 to 50 mol%, especially 5 to 35 mol%, based on the whole monomer units constituting the polymer.
Preferably it is mol%. Such a polymer compound exhibits particularly high etching resistance while maintaining the substrate adhesion and the acid detachability (alkali solubility).

Examples of the monomer unit having a group containing an alicyclic hydrocarbon ring include, for example, a group containing an alicyclic hydrocarbon ring to which a heterocyclic ring such as a lactone ring is not condensed (particularly a bridged ring) is an ester. A monomer unit linked to the main chain through a bond is exemplified. More specifically, for example, the above formulas (IIa), (IIb), (IIc), (IIIa), (IIIb) (X ¹
To X ³ are all methylene groups), (IIIe) (R
⁵⁰ is a cyclic or bridged cyclic hydrocarbon group).

In the polymer compound of the present invention, among the above combinations of the monomer units, particularly preferred combinations include the following. (1) at least one selected from the formulas (Ia) and (Ib)
Species monomer units and at least one of the formulas (IIa) to (IIg)
At least one monomer unit selected from
At least one monomer unit selected from the formulas (IIa), (IIb) and (IIc))

(2) at least one monomer unit selected from the formulas (Ia) and (Ib);
At least one monomer unit selected from
At least one monomer unit selected from the formulas (IIa), (IIb) and (IIc)) and at least one monomer unit selected from the formulas (IIIa) to (IIIh) (particularly, the formulas (IIIa), (IIIa) IIIf) and at least one monomer unit selected from (IIIh))

(3) At least one monomer unit selected from the formulas (Ia) and (Ib) and at least a compound represented by the formula (II)
Combination with at least one monomer unit selected from Ia) to (IIIg) (particularly at least one monomer unit selected from formulas (IIIa), (IIIf) and (IIIh))

In the present invention, the solubility parameter according to the method of Fedors [Polym. Eng. Sci., 14, 147 (1974)]
The value of the reference (hereinafter, simply referred to as "SP value") of 11 (cal / cm ³⁾ monomer units from 0.1 to 50 mol%, corresponding to a ^half or less of the monomer (in particular, 5 3
5 mol%). SP value is 11 (cal /
The polymer compound containing a monomer unit corresponding to a monomer of cm ^{3 1/2 1/2} or less has the above-described specific amount, and particularly has a good balance between substrate adhesion and etching resistance.

As a typical example of a monomer having an SP value of 11 (cal / cm ³ ) ^1/2 or less, 1-methacryloyloxy-3-hydroxyadamantane [SP value = 10.86
(Cal / cm ³ ) ^1/2 ], 1-acryloyloxyadamantan-4-one [SP value = 10.95 (cal / c)
m ^{3) 1/2],} 1- methacryloyloxyadamantane -
4-one [SP value = 10.66 (cal / c)
m ³ ) ^1/2 ], 1-acryloyloxy-3-carboxyadamantane [SP value = 10.71 (cal / cm ³ )
^1/2 ], 1- (meth) acryloyloxy-3-carboxyadamantane [SP value = 10.58 (cal / cm
³ ) ^1/2 ].

The polymer compound for a photoresist of the present invention can be prepared by the method of Fedors [Polym. Eng. Sci., 14,
147 (1974)] (see “S
P value) is 9.5 (cal / cm ³ ) ^{1/2 to} 12 (cal
/ Cm ³ ) ^1/2 [= 19.4 (J / cm ³ ) ^1/2 ２４24.6
(J / cm ³ ) ^1/2 ].

A resist coating film formed by applying a photoresist resin composition containing a polymer compound having such a solubility parameter to a semiconductor substrate (silicon wafer) has excellent adhesiveness (adhesion) to the substrate. At the same time, a high-resolution pattern can be formed by alkali development. SP value is 9.5 (cal / cm ³ )
^{If it} is lower than ^1/2 [= 19.4 (J / cm ³ ) ^1/2 ], the problem that the adhesiveness to the substrate is reduced and the pattern is not peeled off by development and remains is likely to occur. Further, the SP value is 12 (cal / cm ³ ) ^1/2 [= 24.6 (J / c
m ³ ) ^1/2 ], the composition tends to be repelled on the substrate, making it difficult to apply, and has a high affinity for an alkali developing solution. As a result, the solubility contrast between exposed and unexposed areas is increased. And the resolution tends to decrease.

In the present invention, the weight average molecular weight (Mw) of the polymer compound is, for example, about 5,000 to 50,000, preferably about 7000 to 20,000, and the molecular weight distribution (Mw / Mn) is, for example, 1.8 to 3. It is about 5.
Here, Mn indicates a number average molecular weight (in terms of polystyrene).

Each of the monomer units represented by the above formulas (IIg), (IIIf), (IIIg) and (IIIh) has a corresponding ethylenically unsaturated compound as a (co) monomer and a compound of the formula (Ia) , (Ib), (IIa)-(IIf), (IIIa)-
Each monomer unit represented by (IIIe) can be formed by subjecting the corresponding (meth) acrylic acid or its ester to polymerization as a (co) 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) or (Ib)] The monomer corresponding to the monomer unit of the formula (Ia) is represented by the following formula (1a), and the monomer corresponding to the monomer unit of the formula (Ib) is represented by the following formula: It is represented by (1b). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{1 to} R ¹⁸
Represents a hydrogen atom, a methyl group or an ethyl group, respectively)

The representative represented by the above formula (1a) or (1b)
Typical examples include the following compounds. [1-1] 4- (meth) acryloyloxy-6-oxa
Bicyclo [3.2.1] octan-7-one (R^a= H
Or CH_Three, R¹= R^Two= R^Three= R^Four= R^Five= R⁶= R⁷= R⁸
= R⁹= H) [1-2] 4- (meth) acryloyloxy-4-methyl
-6-oxabicyclo [3.2.1] octane-7-o
(R^a= H or CH_Three, R¹= R^Two= R^Four= R^Five= R ⁶= R⁷
= R⁸= R⁹= H, R^Three= CH_Three[1-3] 4- (meth) acryloyloxy-5-methyl
-6-oxabicyclo [3.2.1] octane-7-o
(R^a= H or CH_Three, R¹= R^Two= R^Three= R^Five= R ⁶= R⁷
= R⁸= R⁹= H, R^Four= CH_Three) [1-4] 4- (meth) acryloyloxy-4,5-di
Methyl-6-oxabicyclo [3.2.1] octane-
7-on (R^a= H or CH_Three, R¹= R^Two= R^Five= R⁶= R
⁷= R⁸= R⁹= H, R^Three= R^Four= CH_Three) [1-5] 6- (meth) acryloyloxy-2-oxa
Bicyclo [2.2.2] octan-3-one (R^a= H
Or CH_Three, R^Ten= R¹¹= R¹²= R¹³= R¹⁴= R^Fifteen= R
¹⁶= R¹⁷= R¹⁸= H) [1-6] 6- (meth) acryloyloxy-6-methyl
-2-oxabicyclo [2.2.2] octane-3-o
(R^a= H or CH_Three, R^Ten= R¹¹= R¹²= R¹⁴= R^Fifteen
= R¹⁶= R¹⁷= R¹⁸= H, R¹³= CH_Three) [1-7] 6- (meth) acryloyloxy-1-methyl
-2-oxabicyclo [2.2.2] octane-3-o
(R^a= H or CH_Three, R^Ten= R¹¹= R¹³= R¹⁴= R^Fifteen
= R¹⁶= R¹⁷= R¹⁸= H, R¹²= CH_Three) [1-8] 6- (meth) acryloyloxy-1,6-di
Methyl-2-oxabicyclo [2.2.2] octane-
3-one (R^a= H or CH_Three, R^Ten= R¹¹= R¹⁴= R^Fifteen
= R¹⁶= R¹⁷= R¹⁸= H, R¹²= R¹³= CH_Three)

The compounds represented by the above formulas (1a) and (1b) can be obtained, for example, according to the following reaction scheme.

Embedded image

Embedded image

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{1 to} R ⁹
Represents a hydrogen atom, a methyl group or an ethyl group, respectively. R ^X represents a halogen atom, a hydroxyl group, an alkoxy group or an alkenyloxy group)

In the above reaction scheme, the reaction between the diene represented by the formula (4) and the α, β-unsaturated carboxylic acid represented by the formula (5) is carried out under general Diels-Alder reaction conditions. be able to. This reaction produces cyclohexene carboxylic acid. It should be noted that two types of isomers (6a) and (6b) can be produced depending on the type of raw materials and reaction conditions. As the diene represented by the formula (4), 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 (5).

Next, the produced cyclohexenecarboxylic acids (6a) and (6b) 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, two types of isomers may be generated depending on reaction conditions and the like. That is, the compounds represented by the formulas (7a) and (7b) are produced from the cyclohexenecarboxylic acid represented by the formula (6a), and the compounds represented by the formula (7c) are produced from the cyclohexanecarboxylic acid represented by the formula (6b). ) And (7d).

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

The amount of the metal compound used is, for example, based on 1 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 to be used is, for example, about 0.8 to 2 mol, preferably about 0.9 to 1.5 mol, 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, usually, a suitable solvent,
For example, it is used in a form diluted with water (for example, 30% by weight of hydrogen peroxide solution). The amount of hydrogen peroxide used is, for example, about 0.9 to 5 moles, preferably about 0.9 to 3 moles, per mole of cyclohexenecarboxylic acid used in the reaction.
More preferably, it is about 0.95 to 2 mol.

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

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

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, and column chromatography, or a combination thereof.

In the above series of reactions, instead of the α, β-unsaturated carboxylic acid represented by the formula (5), an ester of the α, β-unsaturated carboxylic acid (for example,
Alkyl ester such as methyl ester, ethyl ester, isopropyl ester, t-butyl ester; cycloalkyl ester such as cyclohexyl ester; aryl ester such as phenyl ester; aralkyl ester such as benzyl ester) with diene (4). To form an ester corresponding to the cyclohexene carboxylic acid represented by the formulas (6a) and (6b), and containing the same as the above (i) containing a metal element selected from W, Mo, V and Mn. By reacting with hydrogen peroxide in the presence of a metal compound, or (ii) by reacting with a peroxide containing the metal element, a hydroxyoxabicyclooctanone derivative (7a), (7b), (7c), (7d) can be obtained. The reaction conditions and the like are the same as in the case where the α, β-unsaturated carboxylic acid (5) is used.

The hydroxyoxabicyclooctanone derivatives (7a), (7b), (7c) and (7d) thus obtained
Is reacted with (meth) acrylic acid or its derivative (8) to give the corresponding (meth) acrylic esters (9a), (9b), (9c) and (9d). Here, the compounds represented by the formulas (9a) and (9c) correspond to the compounds represented by the formula (1a), and the compounds represented by the formulas (9b) and (9d) correspond to the compounds represented by the formula (1b) This corresponds to the compound represented by The compounds represented by the formulas (9a), (9b), (9c) and (9d) can be subjected to polymerization either alone or as a mixture of two or more.

The above esterification reaction can be carried out by a conventional method using an acid catalyst or a transesterification catalyst. Further, hydroxyoxabicyclooctanone derivatives (7a), (7b), (7c), (7d) and (meth) alkenyl acrylate such as vinyl (meth) acrylate and 2-propenyl (meth) acrylate, When the reaction (ester exchange reaction) is carried out in the presence of a catalyst of a Group 3 element compound of the periodic table (for example, a samarium compound such as samarium acetate, samarium trifluoromethanesulfonate, or a samarium complex), the target compound can be efficiently produced under mild conditions. Can be obtained. In this case, the amount of the alkenyl (meth) acrylate used is the amount of the hydroxyoxabicyclooctanone derivative 1
0.8 to 5 moles, preferably 1 to 5 moles,
It is about 1.5 mol. The amount of the Group 3 element compound catalyst used is, for example, about 0.001 to 1 mol, preferably about 0.01 to 0.25 mol, per 1 mol of the hydroxyoxabicyclooctanone derivative. This reaction is performed in a solvent inert to the reaction, for example, at a temperature of about 0 to 150 ° C, preferably about 25 to 120 ° C.

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹⁹ and R ²⁰ are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ²¹ , R ²² and R ²³ are the same. Or, differently, a hydrogen atom, a hydroxyl group or a methyl group)

Typical examples include the following compounds. [2-1] 1- (1- (meth) acryloyloxy-1-
Methylethyl) adamantane (R ^a = H or CH ₃ , R ^{19
_{= R 20 = CH 3, R}} 21 = R 22 = R 23 = H) [2-2] 1- hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ^a =
H or CH ₃ , R ¹⁹ = R ²⁰ = CH ₃ , R ²¹ = OH, R ²² =
^{R 23 = H) [2-3]} 1- (1- ethyl-1 (meth) acryloyloxy propyl) adamantane (R ^a = H or CH _3, R
_{^{19 = R 20 = CH 2 CH}} 3, R 21 = R 22 = R 23 = H) [2-4] 1- hydroxy-3- (1-ethyl-1- (meth) acryloyloxy propyl) adamantane (R ^a
ＨH or CH ₃ , R ¹⁹ ＲR ²⁰ ＣＨCH ₂ CH ₃ , R ²¹ ＯO
^{H, R 22 = R 23 =} H) [2-5] 1- (1- ( meth) acryloyloxy-1
Methylpropyl) adamantane (R ^a = H or CH ₃ , R
_{^{19 = CH 3, R 20 =}} CH 2 CH 3, R 21 = R 22 = R 2 3 =
H) [2-6] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylpropyl) adamantane ( ^Ra
ＨH or CH ₃ , R ¹⁹ ＣＨCH ₃ , R ²⁰ ＣＨCH ₂ CH ₃ , R ^{21
= OH, R 22 = R 23} = H) [2-7] 1- (1- ( meth) acryloyloxy-1,
2-dimethylpropyl) adamantane ( ^Ra = H or C
_{^{H 3, R 19 = CH 3}} , R 20 = CH (CH 3) 2, R 21 = R 22
^{= R 23 = H) [2-8} ] 1- hydroxy-3- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ^a = H or _{^{CH 3, R 19 = CH 3}} , R ²⁰ = CH (C
^{_{H 3) 2, R 21 =}} OH, R 22 = R 23 = H) [2-9] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ^a = H or CH ₃ , R ¹⁹ ＲR ²⁰ ＣＨCH ₃ , R ²¹ ＲR ^{22
= OH, R 23 = H)} [2-10] 1- (1- ethyl-1 (meth) acryloyloxy propyl) -3,5-dihydroxy-adamantane (R ^a = H or CH _3, R ¹⁹ = R ²⁰ = CH ₂ CH ₃ , R ²¹ =
^{R 22 = OH, R 23 =} H) [2-11] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R ^a = H or CH _3, R ¹⁹ = CH ₃ , R ²⁰ = CH ₂ C
_{^{H 3, R 21 = R 22}} = OH, R 23 = H) [2-12] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ^a = H or CH ₃ , R ¹⁹ ＣＨCH ₃ , R ²⁰ ＣＨCH
(CH ₃ ) ₂ , R ²¹ = R ²² = OH, R ²³ = H)

The compound represented by the above formula (2a) can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein X represents a halogen atom. ^Ra , R ¹⁹ , R ²⁰ ,
R ²¹ , R ²² , R ²³ and R ^X are the same as described above)

In this reaction scheme, a compound in which any of R ^{21 to} R ²³ among the adamantane derivatives (10) used as a raw material is a hydroxyl group can be obtained by introducing a hydroxyl group into the adamantane ring.
For example, an adamantane compound is contacted with oxygen in the presence of an N-hydroxyimide catalyst such as N-hydroxyphthalimide and, if necessary, a metal promoter such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.). By doing so, a hydroxyl group can be introduced into the adamantane ring. In this method, the amount of the N-hydroxyimide-based catalyst used is, for example, about 0.000001 to 1 mol, preferably about 0.00001 to 0.5 mol, per 1 mol of the adamantane compound. The amount of the metal promoter used is, for example, 0.0001 to 0.7 mol, preferably 0.1 mol, per 1 mol of the adamantane compound.
It is about 001 to 0.5 mol. Oxygen is often used in excess with respect to the adamantane compound. The reaction is performed, for example, in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, or a halogenated hydrocarbon such as dichloroethane, at normal pressure or under pressure, at a temperature of about 0 to 200 ° C, preferably about 30 to 150 ° C. Done in By selecting the reaction conditions, a plurality of hydroxyl groups can be introduced into the adamantane ring.

The reaction of the adamantane derivative (10) with a 1,2-dicarbonyl compound (eg, biacetyl) (11) and oxygen is carried out by a metal compound such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.). And / or in the presence of an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide. 1,
The amount of the 2-dicarbonyl compound (11) to be used is 1 mol or more (for example, 1 to 1 mol) per 1 mol of the adamantane derivative (10).
50 mol), preferably 1.5 to 20 mol, more preferably about 3 to 10 mol. The amount of the metal compound to be used is, for example, about 0.0001 to 0.1 mol per 1 mol of the adamantane derivative (10). The amount of the N-hydroxyimide-based catalyst used is determined based on the adamantane derivative (10).
The amount is, for example, about 0.001 to 0.7 mol per 1 mol. Oxygen is often used in excess with respect to the adamantane derivative (10). The reaction is usually performed in an organic solvent. Examples of the organic solvent include nitriles such as benzonitrile, an organic acid such as acetic acid, and halogenated hydrocarbons such as trifluoromethylbenzene. The reaction is carried out at normal pressure or under pressure, for example, at a temperature of about 30 to 250 ° C, preferably about 40 to 200 ° C.

The reaction between the acyladamantane derivative (12) thus obtained and the Grignard reagent (13) can be carried out according to a usual Grignard reaction. The amount of the Grignard reagent (13) used is, for example, about 0.7 to 3 mol, preferably about 0.9 to 1.5 mol, per 1 mol of the acyladamantane derivative (12). When the acyl adamantane derivative (12) has a hydroxyl group on the adamantane ring, the amount of the Grignard reagent is increased according to the number thereof. The reaction is performed in, for example, ethers such as diethyl ether and tetrahydrofuran. The reaction temperature is, for example, 0 to 150 ° C, preferably 20 to 10 ° C.
It is about 0 ° C.

The reaction (esterification reaction) between the adamantane methanol derivative (14) produced in the above reaction and (meth) acrylic acid or its derivative (8) is carried out by the above-mentioned hydroxyoxabicyclooctanone derivative (7a) or the like ) The reaction can be carried out according to the reaction with acrylic acid or its derivative (8).

Further, among the compounds represented by the above formula (2a), those in which R ¹⁹ and R ²⁰ are the same group include, for example,
It can be obtained according to the following reaction scheme.

Embedded image (Wherein, R ^y represents a hydrocarbon group. X, R ^a , R ²⁰ ,
R ²¹ , R ²² , R ²³ and R ^X are the same as described above)

Examples of the hydrocarbon group for R ^y include a C _1-6 aliphatic hydrocarbon group such as a methyl, ethyl, propyl, and isopropyl group; and a phenyl group.

In this reaction scheme, the adamantanecarboxylic acid derivative (15) used as a raw material can be produced by introducing a carboxyl group into the adamantane ring of the adamantane compound. For example, an adamantane compound may be combined with an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide and, if necessary, a cobalt compound (for example,
Carboxyl groups can be introduced into the adamantane ring of the adamantane compound by contacting with carbon monoxide and oxygen in the presence of a metal-based cocatalyst such as cobalt acetate, cobalt acetylacetonate and the like. In the carboxylation reaction, the amount of the N-hydroxyimide-based catalyst used is, for example, 0.0000 with respect to 1 mol of the adamantane compound.
It is about 01 to 1 mol, preferably about 0.00001 to 0.5 mol. The amount of the metal promoter used is, for example, from 0.0001 to 0.
It is about 7 mol, preferably about 0.001 to 0.5 mol. The amounts of carbon monoxide and oxygen used are, for example, 1 mol or more and 0.5 mol or more, respectively, per 1 mol of the adamantane compound. The ratio between carbon monoxide and oxygen is, for example, the former / the latter (molar ratio) = 1/99 to 99/1, preferably about 50/50 to 95/5. The carboxylation reaction is carried out, for example, in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, or a halogenated hydrocarbon such as dichloroethane in a solvent such as 0 to 2 at normal pressure or under pressure.
It is carried out at a temperature of about 00 ° C, preferably about 10 to 150 ° C. By selecting reaction conditions, a plurality of carboxyl groups can be introduced into the adamantane ring.

The reaction between the adamantanecarboxylic acid derivative (15) and the hydroxy compound (16) can be carried out, for example, according to a conventional esterification method using an acid catalyst or the like.

The reaction between the adamantanecarboxylic acid ester represented by the formula (17) and the Grignard reagent (13) is usually carried out in a solvent inert to the reaction, for example, diethyl ether,
It is carried out in ethers such as tetrahydrofuran. The reaction temperature is, for example, about 0 to 100 ° C, preferably about 10 to 40 ° C. The amount of the Grignard reagent (13) used is, for example, about 2 to 4 equivalents based on the adamantanecarboxylic acid ester (17).

The adamantane methanol derivative (18)
Reaction with (meth) acrylic acid or its derivative (8)
The sterelation reaction) is carried out by the aforementioned hydroxyoxabicyclooctane.
Tanone derivative (7a) etc. and (meth) acrylic acid or its derivative
The reaction can be performed according to the reaction with the conductor (8). This
Thus, among the compounds represented by the formula (2a), R¹⁹And R
²⁰Are the same hydrocarbon group (for example, R¹⁹= R²⁰=
(Ethyl group) Compound (2a ') can be easily prepared
You.

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ²⁴ and R ²⁵ are the same or different and represent a hydrogen atom, a hydroxyl group or a —COOR ²⁶ group, R ²⁶ is a t-butyl group, 2-
Represents a tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group)

Typical examples include the following compounds.
You. [2-13] 1-t-butoxycarbonyl-3- (meth) a
Cryloyloxyadamantane (R^a= H or CH_Three, R
^{twenty four}= R^{twenty five}= H, R²⁶= T-butyl group) [2-14] 1,3-bis (t-butoxycarbonyl) -5
-(Meth) acryloyloxyadamantane [R^a= H
Or CH_Three, R^{twenty four}= T-butoxycarbonyl group, R ^{twenty five}=
H, R²⁶= T-butyl group] [2-15] 1-t-butoxycarbonyl-3-hydroxy
-5- (meth) acryloyloxyadamantane (R^a
= H or CH_Three, R^{twenty four}= OH, R^{twenty five}= H, R²⁶= T-bu
[2-16] 1- (2-tetrahydropyranyloxycarbo)
Nyl) -3- (meth) acryloyloxyadamantane
(R^a= H or CH_Three, R^{twenty four}= R^{twenty five}= H, R²⁶= 2-tet
Lahydropyranyl group) [2-17] 1,3-bis (2-tetrahydropyranyloxy)
(Cicarbonyl) -5- (meth) acryloyloxyada
Mantan (R^a= H or CH_Three, R^{twenty four}= 2-tetrahydro
Pyranyloxycarbonyl group, R^{twenty five}= H, R²⁶= 2-te
Trahydropyranyl group) [2-18] 1-hydroxy-3- (2-tetrahydropyran
Nyloxycarbonyl) -5- (meth) acryloylo
Kisia Damantane (R^a= H or CH_Three, R^{twenty four}= OH, R
^{twenty five}= H, R²⁶= 2-tetrahydropyranyl group)

The compound represented by the above formula (2b) can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein, R ^X , R ^a , R ²⁴ , R ²⁵ , and R ²⁶ are the same as described above)

In this reaction scheme, the conversion of the carboxyadamantanol derivative (19) to the 1-adamantanol derivative (20) (protection of the carboxyl group) is carried out by a conventional method, for example, the carboxyadamantanol derivative (19) And isobutylene, dihydrofuran, dihydropyran and the like.

At this time, the carboxyadamantanol derivative (19) used as a raw material can be obtained by introducing a hydroxyl group and a carboxyl group into the adamantane ring of the adamantane compound. Introduction of a hydroxyl group and a carboxyl group into the adamantane ring can be performed in the same manner as described above.

The reaction (esterification reaction) between the 1-adamantanol derivative (20) and (meth) acrylic acid or its derivative (8) is carried out by the above-mentioned hydroxyoxabicyclooctanone derivative (7a) or the like and (meth) acrylic acid. Alternatively, the reaction can be carried out according to the reaction with the derivative (8).

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ²⁷ represents a methyl group or an ethyl group, and R ²⁸ and R ²⁹ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group)

Typical examples include the following compounds. [2-19] 2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or CH ₃ , R ²⁷ = CH ₃ , R ^{28
= R 29 = H) [2-20} ] 1- hydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ^a = H or CH _3, R
²⁷ ＣＨCH ₃ , R ²⁸ = 1-OH, R ²⁹ ） H) [2-21] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane ( ^Ra = H or CH ₃ , R
²⁷ = CH ₃ , R ²⁸ = 5-OH, R ²⁹ = H) [2-22] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ^a = H or C
_{^{H 3, R 27 = CH 3}} , R 28 = 1-OH, R 29 = 3-OH) [2-23] 1,5- dihydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ^a = H or C
_{^{H 3, R 27 = CH 3}} , R 28 = 1-OH, R 29 = 5-OH) [2-24] 1,3- dihydroxy-6 (meth) acryloyloxy-6-methyl-adamantane (R ^a = H or C
_{^{H 3, R 27 = CH 3}} , R 28 = 1-OH, R 29 = 3-OH) [2-25] 2- ( meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R ²⁷ = CH ₂ CH _3,
^{R 28 = R 29 = H)} [2-26] 1- hydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R
_{^{27 = CH 2 CH 3, R}} 28 = 1-OH, R 29 = H) [2-27] 5- hydroxy-2- (meth) acryloyloxy-2-ethyl adamantane (R ^a = H or CH _3, R
²⁷ = CH ₂ CH ₃ , R ²⁸ = 5-OH, R ²⁹ = H) [2-28] 1,3-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane ( ^Ra = H or C
_{^{H 3, R 27 = CH 2}} CH 3, R 28 = 1-OH, R 29 = 3-
OH) [2-29] 1,5-dihydroxy-2- (meth) acryloyloxy-2-ethyladamantane (R ^a = H or C
_{^{H 3, R 27 = CH 2}} CH 3, R 28 = 1-OH, R 29 = 5-
OH) [2-30] 1,3-dihydroxy-6- (meth) acryloyloxy-6-ethyladamantane ( ^Ra = H or C
_{^{H 3, R 27 = CH 2}} CH 3, R 28 = 1-OH, R 29 = 3-
OH)

The compound represented by the above formula (2c) can be obtained, for example, according to the following reaction scheme.

Embedded image ^{(Wherein, X, R a, R 27} , R 28, R 29, R X have the same meanings as defined above)

In this reaction scheme, the reaction between the adamantanone derivative (21) and the Grignard reagent (22) can be carried out according to a conventional Grignard reaction. The amount of the Grignard reagent (22) to be used is, for example, about 0.7 to 3 mol, preferably about 0.9 to 1.5 mol, per 1 mol of the adamantanone derivative (21). When the adamantane derivative (21) has a hydroxyl group on the adamantane ring, the amount of the Grignard reagent is increased according to the number of the hydroxyl groups. The reaction is carried out in a solvent inert to the reaction, for example, ethers such as diethyl ether and tetrahydrofuran. The reaction temperature is, for example, about 0 to 150 ° C, preferably about 20 to 100 ° C.

The 2-adamantanol derivative (23) thus obtained is converted from (meth) acrylic acid or its derivative (8)
(Esterification reaction) to give a compound represented by the formula (2c). The esterification reaction can be carried out according to the reaction between the hydroxyoxabicyclooctanone derivative (7a) or the like and (meth) acrylic acid or its derivative (8).

The adamantane derivative (21) having a hydroxyl group on the adamantane ring among the adamantanone derivatives (21) used as a raw material in the above method can be obtained by converting 2-adamantanones to an N-hydroxyimide catalyst such as N-hydroxyphthalimide. If necessary, it can be produced by contacting with oxygen in the presence of a metal-based cocatalyst such as a cobalt compound, a manganese compound and a vanadium compound to introduce a hydroxyl group into the adamantane ring. In this method, the amount of the N-hydroxyimide-based catalyst used is, for example, 0.000001 to 1 mol of 2-adamantanones.
To 1 mol, preferably about 0.00001 to 0.5 mol. The amount of the metal promoter used is, for example, 0.0001 to 0.7 with respect to 1 mol of 2-adamantanones.
Mol, preferably about 0.001 to 0.5 mol.
Oxygen is often used in excess relative to 2-adamantanones. The reaction is carried out, for example, 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 a normal pressure or a pressure of 0 to 200.
C., preferably at a temperature of about 30 to 150.degree.

Among the adamantanone derivatives (21), compounds having a hydroxyl group on the adamantane ring include the adamantane and oxygen, the N-hydroxyimide-based catalyst and a strong acid (eg, hydrogen halide, sulfuric acid, etc.). ,
If necessary, it can be produced by reacting in the presence of the metal-based cocatalyst. The amount of the strong acid used is
For example, 0.00001 per 1 mol of adamantane
To 1 mol, preferably about 0.0005 to 0.7 mol. Other reaction conditions are the same as the above-mentioned hydroxyl group introduction reaction.

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, and R ³⁰ is
Which represents a hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom shown in the formula)

Representative examples include the following compounds. [2-31] t-butyl (meth) acrylate (R ^a = H or CH ₃ , R ³⁰ = t-butyl group) [Monomer unit of the formula (IIe)] A monomer corresponding to the monomer unit of the above formula (IIe) Is represented by the following equation (2e). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and m represents 1 to
Indicates an integer of 3)

Typical examples include the following compounds. [2-32] 2-tetrahydropyranyl (meth) acrylate (R ^a = H or _{CH 3, m = 2) [} 2-33] 2- tetrahydrofuranyl (meth) acrylate (R ^a = H or CH _3, m = 1)

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

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ³¹ to R
³⁵ is the same or different and represents a hydrogen atom or a methyl group)

Typical examples include the following compounds. [2-34] β- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ³¹ = R ³² = R ³³ = R ³⁴
= R ³⁵ = H) [2-35] β- (meth) acryloyloxy-α, α-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ³¹
= R ³² = CH ₃ , R ³³ = R ³⁴ = R ³⁵ = H) [2-36] β- (meth) acryloyloxy-γ, γ-dimethyl-γ-butyrolactone (R ^a = H or CH ₃ , R ^{34
_{= R 35 = CH 3, R}} 31 = R 32 = R 33 = H) [2-37] β- ( meth) acryloyloxy -α, α, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 31 = R 32}} = R 33 = CH 3, R 34 = R 35 = H) [2-38] β- ( meth) acryloyloxy-beta, gamma, gamma
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 33 = R 34}} = R 35 = CH 3, R 31 = R 32 = H) [2-39] β- ( meth) acryloyloxy-.alpha., alpha,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ³¹ = R ³² = R ³³ = R ³⁴ = R ³⁵ = C
H ₃ )

The compound represented by the formula (2f) can be obtained, for example, by reacting the corresponding β-hydroxy-γ-butyrolactone with the compound represented by the formula (8). This esterification reaction can be carried out in accordance with the reaction between the hydroxyoxabicyclooctanone derivative (7a) or the like and (meth) acrylic acid or its derivative (8).

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

Embedded image (Wherein, R ³⁶ represents a t-butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, or a 2-oxepanyl group; n represents 0 or 1)

Typical examples include the following compounds.
You. [2-40] 5-t-butoxycarbonylnorbornene (R
³⁶= T-butyl group, n = 0) [2-41] 9-t-butoxycarbonyltetracyclo
[6.2.1.1^3,6. 0^2,7] Dodeca-4-ene (R³⁶
= T-butyl group, n = 1) [2-42] 5- (2-tetrahydropyranyloxycarbo)
Nyl) norbornene (R ³⁶= 2-tetrahydropyranyl
Group) [2-43] 9- (2-tetrahydropyranyloxycarbo)
Nyl) tetracyclo [6.2.1.1^3,6. 0^2,7] Dode
Car-4-ene (R³⁶= 2-tetrahydropyranyl group, n
= 1)

[Monomer Unit of the Formula (IIIa)]
The monomer corresponding to the monomer unit of Ia) is represented by the following formula (3)
a). When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, R ³⁷ and R ³⁸ are the same or different and represent a hydrogen atom, a hydroxyl group or a carboxyl group, and R ³⁹ represents a hydroxyl group, an oxo group or a carboxyl group. Show)

Representative compounds include the following: [3-1] 1-hydroxy-3- (meth) acryloyloxy adamantane (R ^a = H or ^{_{CH 3, R 39 = OH,}} R
^{37 = R 38 = H) [} 3-2] 1,3- dihydroxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ³⁹ = R
^{37 = OH, R 38 = H} ) [3-3] 1- carboxy-3- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ³⁹ = COO
^{H, R 37 = R 38 =} H) [3-4] 1,3- dicarboxy-5- (meth) acryloyloxy adamantane (R ^a = H or CH _3, R ³⁹ = R
³⁷ = COOH, R ³⁸ = H) [3-5] 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane ( ^Ra = H or C
^{_{H 3, R 39 = OH,}} R 37 = COOH, R 38 = H) [3-6] 1- ( meth) acryloyloxy-4-oxo-adamantane (R ^a = H or CH _3, R ³⁹ = 4- oxo Group, R ³⁷ = R ³⁸ = H) [3-7] 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ^a = H or CH ₃ , R
³⁹ = 4-oxo group, R ³⁷ = 3-OH, R ³⁸ = H) [3-8] 7-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ^a = H or CH ₃ , R
³⁹ = 4-oxo group, ^R37 = 7-OH, ^R38 = H)

The compound represented by the formula (3a) can be obtained, for example, by reacting the corresponding 1-adamantanol derivative with the compound represented by the formula (8). This esterification reaction can be carried out in accordance with the reaction between the hydroxyoxabicyclooctanone derivative (7a) or the like and (meth) acrylic acid or its derivative (8).

[Monomer unit of the formula (IIIb)]
The monomer corresponding to the monomer unit of Ib) is represented by the following formula (3b)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, ^Ra represents a hydrogen atom or a methyl group, and X ^{1 to} X ³
Are the same or different, -CH ₂ - or -CO-O- are shown, R ⁴⁰ to R ^42, identical or different, represent a hydrogen atom or a methyl group)

Representative examples of the compound represented by the formula (3b) include the following compounds. [3-9] 1- (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one (R ^a = H or CH ₃ , R ⁴⁰ = R ⁴¹ = R ⁴² = H, X ² =
—CO—O— (the left side is the carbon atom side to which R ⁴¹ is bonded), X ¹ ＸX ³ −—CH ₂ —) [3-10] 1- (meth) acryloyloxy-4,7-dioxa Tricyclo [4.4.1.1 ^3,9 ] dodecane-
5,8-dione (R ^a = H or CH ₃ , R ⁴⁰ = R ⁴¹ = R ⁴²
= H, X ¹ = —CO—O— (left side is a carbon atom side to which R ⁴⁰ is bonded), X ² = —CO—O— (left side is a carbon atom side to which R ⁴¹ is bonded), X _{^{3 = -CH 2 -) [3-11}} ] 1- ( meth) acryloyloxy-4,8-dioxatricyclo [4.4.1.1 ^{3, 9]} dodecane -
5,7-dione (R ^a = H or CH ₃ , R ⁴⁰ = R ⁴¹ = R ^{42
= H, X 1 = -O-} CO- ( left carbon atoms side bonded to ^{R 40), X 2 = -CO} -O- ( left carbon atoms side bonded to R ^41), X _{^{3 = -CH 2 -) [3-12}} ] 1- ( meth) acryloyloxy-5,7-dioxatricyclo [4.4.1.1 ^{3, 9]} dodecane -
4,8-dione (R ^a = H or CH ₃ , R ⁴⁰ = R ⁴¹ = R ^{42
= H, X 1 = -CO-} O- ( left bonded to the carbon atom side of the ^{R 40), X 2 = -O} -CO- ( left bonded to the carbon atom side of the R ^41), X ³ = -CH ₂ -)

Among the compounds represented by the above formula (3b), X
^The compound (3b-1) in which ² = —CO—O— and X ¹ = X ³ = —CH ₂ — can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein, R ^X , R ^a , R ⁴⁰ , R ⁴¹ and R ⁴² are the same as above)

In this reaction scheme, the compound represented by the formula (25) is obtained by converting a 2-adamantanone compound represented by the formula (24) into an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide and vanadium. Compound (for example, vanadium (III) acetylacetonate, etc.) and manganese compound (for example, manganese (II) acetylacetonate, etc.)
By reacting with oxygen in the presence of At this time, the amount of the N-hydroxyimide-based catalyst used is
For example, 0.1 mol per 1 mol of the compound represented by the formula (24).
00000-1 mol, preferably 0.00001-
It is about 0.5 mol. Further, the total amount of the vanadium compound and the manganese compound is, for example, 0.0001 to 0.7 mol, relative to 1 mol of the compound represented by the formula (24),
Preferably it is about 0.001-0.5 mol. Ratio of vanadium compound to manganese compound (metal atomic ratio)
Is, for example, the former / the latter = 99/1 to 1/99, preferably about 95/5 to 10/90. Oxygen is formula (24)
Is often used in excess with respect to the compound represented by The reaction may be carried out, for example, in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, or a halogenated hydrocarbon such as dichloroethane at a normal pressure or under a pressure of about 20 to 200 ° C., preferably about 30 to 150 ° C. Done in

The thus obtained 5- (5) represented by the equation (25)
A hydroxy-2-adamantanone compound, an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide;
If necessary, a cobalt compound (for example, cobalt acetate,
When oxidized by molecular oxygen together with a primary or secondary alcohol in the presence of a metal promoter such as cobalt acetylacetonate), a Bayer-Villiger-type reaction proceeds and is represented by the formula (26). 1-hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane compound is 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-hydroxyimide-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 (25). The amount of the metal-based cocatalyst to be used is, for example, 0.0001 to 0.7 mol, preferably 0.1 mol, per mol of the compound of the formula (25).
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 (25).
It is about 100 mol, preferably about 1-50 mol. Oxygen is often used in excess with respect to the compound of the formula (25). The reaction may be performed, for example, in a solvent such as an organic acid such as acetic acid, acetonitrile, nitriles such as benzonitrile, a halogenated hydrocarbon such as trifluoromethylbenzene, or an ester such as ethyl acetate, at normal pressure or under 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 (26) can be obtained by a general Bayer-Villiger reaction, that is, the reaction of the compound (25) with a peroxide such as hydrogen peroxide or a peracid such as m-chloroperbenzoic acid. it can.

The 1-hydroxy-4-produced by the above reaction
Oxatricyclo [4.3.1.1] ^3,8] Undecane
Compound (26) and (meth) acrylic acid or its derivative (8)
Reaction (esterification reaction) with the hydroxy oxa
Bicyclooctanone derivative (7a) etc. and (meth) acryl
It can be carried out according to the reaction with an acid or its derivative (8).
Wear.

Among the compounds represented by the above formula (3b), X
¹ = -CO-O-in and _{^{X 2 = X 3 = -CH 2}} - , compound, X ³ = -CO-O- in and _{^{X 1 = X 2 = -CH 2}} - Compounds that are the corresponding It can be produced from the adamantanone compound by the same method as described above. Further, the compound having a plurality of —CO—O— groups can be produced from the corresponding adamantanedione or adamantanetrione compound according to the above method.

[Monomer unit of the formula (IIIc)]
The monomer forming the monomer unit of Ic) is represented by the following formula (3c)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, and R ⁴³ and R ⁴⁴ are the same or different and represent a hydrogen atom or a methyl group)

Representative examples include the following compounds.
You. [3-13] 2- (meth) acryloyloxy-4-oxa
Tricyclo [4.2.1.0^3,7Nonan-5-one
(R^a= H or CH_Three, R⁴³= R⁴⁴= H) [3-14] 2- (meth) acryloyloxy-2-methyl
-4-oxatricyclo [4.2.1.0^3,7] Nonan
-5-one (R^a= H or CH_Three, R⁴³= CH_Three, R ⁴⁴=
H)

[Monomer Unit of the Formula (IIId)]
The monomer forming the monomer unit of Id) is represented by the following formula (3d)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, and R ⁴⁵ , R
⁴⁶ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are the same or different and each represent a hydrogen atom or a methyl group)

Representative examples include the following compounds. [3-15] α- (meth) acryloyloxy-γ-butyrolactone (R ^a = H or CH ₃ , R ⁴⁵ = R ⁴⁶ = R ⁴⁷ = R ^{48
= R 49 = H) [3-16} ] α- ( meth) acryloyloxy -α- methyl -γ- butyrolactone (R ^a = H or CH _3, R ⁴⁵ = CH
₃ , R ⁴⁶ = R ⁴⁷ = R ⁴⁸ = R ⁴⁹ = H) [3-17] α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone ( ^Ra = H or CH ₃ , R ^{45
= R 48 = R 49 = H} , R 46 = R 47 = CH 3) [3-18] α- ( meth) acryloyloxy -α, β, β
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 45 = R 46}} = R 47 = CH 3, R 48 = R 49 = H) [3-19] α- ( meth) acryloyloxy-gamma, .gamma.-dimethyl -γ- butyrolactone (R ^a = H Or CH ₃ , R ^{48
_{= R 49 = CH 3, R}} 45 = R 46 = R 47 = H) [3-20] α- ( meth) acryloyloxy -α, γ, γ
-Trimethyl-γ-butyrolactone (R ^a = H or C
_{^{H 3, R 45 = R 48}} = R 49 = CH 3, R 46 = R 47 = H) [3-21] α- ( meth) acryloyloxy-beta, beta,
γ, γ-tetramethyl-γ-butyrolactone (R ^a = H
Or CH ₃ , R ⁴⁶ = R ⁴⁷ = R ⁴⁸ = R ⁴⁹ = CH ₃ , R ⁴⁵ =
H) [3-22] α- (meth) acryloyloxy-α, β,
β, γ, γ-pentamethyl-γ-butyrolactone ( ^Ra
= H or CH ₃ , R ⁴⁵ = R ⁴⁶ = R ⁴⁷ = R ⁴⁸ = R ⁴⁹ = C
H ₃ )

The compound represented by the formula (3d) can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein, R ^z represents a hydrocarbon group. ^Ra , R ⁴⁵ , R ⁴⁶ , R
⁴⁷ , R ⁴⁸ , R ⁴⁹ and R ^X are the same as described above)

In the above reaction scheme, the hydrocarbon group for R ^z includes methyl, ethyl, propyl, s-butyl,
aliphatic hydrocarbon groups having about 1 to 6 carbon atoms such as t-butyl, vinyl and allyl groups (alkyl groups, alkenyl groups or alkynyl groups); aromatic hydrocarbon groups such as phenyl group and naphthyl group; cycloalkyl groups Alicyclic hydrocarbon group, and the like.

Α, β-unsaturated carboxylic acid ester (27)
The reaction between alcohol and alcohol (28) with oxygen is carried out by an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide and, if necessary, a metal-based co-catalyst such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.). Done in the presence of The ratio between the α, β-unsaturated carboxylic acid ester (27) and the alcohol (28) can be appropriately selected depending on the type (price, reactivity, etc.) of both compounds. For example, the alcohol (28) may be used in excess (for example, about 2 to 50 times by mole) relative to the α, β-unsaturated carboxylic acid ester (27). The ester (27) may be used in excess with respect to the alcohol (28). The amount of the N-hydroxyimide-based catalyst used is α, β-
For example, 0.1 mol of the unsaturated carboxylic acid ester (27) and the alcohol (28) may be used with respect to 1 mol of the compound used in a small amount.
00000-1 mol, preferably 0.00001-
It is about 0.5 mol. The amount of the metal-based cocatalyst used is, for example, 0.0001 to 0.7 mol based on 1 mol of the compound used in a smaller amount among the α, β-unsaturated carboxylic acid ester (27) and the alcohol (28). , Preferably 0.
It is about 001 to 0.5 mol. Oxygen is often used in excess of the α, β-unsaturated carboxylic acid ester (27) and the alcohol (28), which are used in small amounts.
The reaction is, for example, in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, a halogenated hydrocarbon such as trifluoromethylbenzene, or an ester such as ethyl acetate, at about 0 to 150 ° C. under normal pressure or pressure. And preferably at a temperature of about 30 to 100 ° C.

The reaction of the α-hydroxy-γ-butyrolactone derivative (29) thus obtained with (meth) acrylic acid or its derivative (8) is carried out by the above-mentioned hydroxyoxabicyclooctanone derivative (7a) and the like. The reaction can be carried out according to the reaction with acrylic acid or its derivative (8).

[Monomer Unit of the Formula (IIIe)]
The monomer forming the monomer unit of Ie) is represented by the following formula (3e)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ^a represents a hydrogen atom or a methyl group, and R ⁵⁰ is
A hydrogen atom or a carbon number of 1 to 2 which may have a substituent
0 represents a linear, branched, cyclic or bridged cyclic hydrocarbon group)

Representative examples include the following compounds. [3-23] (meth) acrylic acid (R ^a = H or CH ₃ , R ⁵⁰
= H) [3-24] Methyl (meth) acrylate (R ^a = H or C
H ₃ , R ⁵⁰ = methyl group) [3-25] Ethyl (meth) acrylate (R ^a = H or C
H ₃ , R ⁵⁰ = ethyl group) [3-26] isopropyl (meth) acrylate ( ^Ra = H or CH ₃ , R ⁵⁰ = isopropyl group) [3-27] n-butyl (meth) acrylate (R ^a = H or CH ₃ , R ⁵⁰ = n-butyl group) [3-28] Cyclohexyl (meth) acrylate ( ^Ra = H
Or CH ₃ , R ⁵⁰ = cyclohexyl group) [3-29] Decahydronaphthyl (meth) acrylate (R ^a
= H or CH ₃ , R ⁵⁰ = decahydronaphthyl group) [3-30] norbornyl (meth) acrylate (R ^a = H or CH ₃ , R ⁵⁰ = norbornyl group) [3-31] (meth) acrylic acid Isobornyl (R ^a = H or CH ₃ , R ⁵⁰ = isobornyl group) [3-32] Adamantyl (meth) acrylate (R ^a = H or CH ₃ , R ⁵⁰ = adamantyl group) [3-33] (meth) Dimethyl adamantyl acrylate (R
^a = H or CH ₃ , R ⁵⁰ = dimethyladamantyl group) [3-34] tricyclo (meth) acrylate [5.2.1.
0 ^2,6 ] decyl (R ^a = H or CH ₃ , R ⁵⁰ = tricyclo [5.2.1.0 ^2,6 ] decyl group) [3-35] tetracyclo [meth] acrylate [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodecyl (R ^a = H or CH ₃ , R
⁵⁰ = tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecyl group)

Compounds in which a substituent such as a hydroxy group, a hydroxymethyl group, a carboxyl group or an oxo group is bonded to the group corresponding to R ⁵⁰ of these compounds are also preferred.

[Monomer Unit of the Formula (IIIf)]
The monomer forming the monomer unit of If) is represented by the following formula (3f)
It is represented by

Embedded image [3-36] maleic anhydride

[Monomer Unit of the Formula (IIIg)]
The monomer forming the monomer unit of Ig) is the following formula (3g)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are the same or different and each represent a hydrogen atom or a methyl group. O, p and q each represent 0 or 1)

Representative examples of the compound represented by the formula (3g) include the following compounds. [3-37] 4-oxatricyclo [5.2.1.0 ^2,6 ]
Decane-8-en-5-one ( ^R53 = ^R54 = H, o = p
= 0, q = 1) [3-38] 3-oxatricyclo [5.2.1.0 ^2,6 ]
Decane-8-en-4-one (R ⁵¹ = R ⁵² = H, o = q
= 0, p = 1) [3-39] 5-oxatricyclo [6.2.1.0 ^2,7 ]
Undecane-9-en-6-one ( ^R53 = ^R54 = H, o
= P = 0, q = 2) [3-40] 4-oxatricyclo [6.2.1.0 ^2,7 ]
Undecane-9-en-5-one ^{(R 51 = R 52 = R} 53 =
R ⁵⁴ = H, o = 0, p = q = 1) [3-41] 4-oxapentacyclo [6.5.5.1.
^19,12 . 0 ^2,6 . 0 ^8,13 ] pentadecane-10-ene-
5-one ( ^R53 = ^R54 = H, o = 1, p = 0, q = 1) [3-42] 3-oxapentacyclo [6.5.1.
^19,12 . 0 ^2,6 . 0 ^8,13 ] pentadecane-10-ene-
4- On ^{(R 51 = R 52 = H} , o = 1, p = 1, q = 0) [3-43] 5- oxa penta cyclo [6.6.1.1
^10,13 . 0 ^2,7 . 0 ^9,14 ] hexadecane-11-ene-6
-One (R ⁵³ = R ⁵⁴ = H, o = 1, p = 0, q = 2) [3-44] 4-oxapentacyclo [6.6.1.1]
^10,13 . 0 ^2,7 . 0 ^9,14 ] hexadecane-11-ene-5
-On (R ⁵¹ = R ⁵² = R ⁵³ = R ⁵⁴ = H, o = 1, p = q
= 1)

These compounds can be obtained by a known method or a method analogous thereto. For example, the compound [3-
37] is cyclopentadiene and 2,5-dihydrofuran-
It can be obtained by a Diels-Alder reaction with 2-one or the like. In addition, compound [3-38] is described in Journal of Organic Chemistry (J. Org. Chem.), No. 41.
Vol. 7, No. 7, (1976), p. 1221, compound [3-39] is disclosed in Journal of Organic Chemistry (J. Org. Chem.), Vol. 50, No. 25, 5193 pages (1
985), compound [3-40] can be obtained by the method described in Tetrahedron Lett., P. 4099, (1976).
Can be produced. Compounds [3-41] to [3-
44] can be obtained by a Diels-Alder reaction between compounds [3-37] to [3-40] or a derivative thereof and cyclopentadiene, respectively.

[Monomer Unit of the Formula (IIIh)]
The monomer forming the monomer unit of Ih) is represented by the following formula (3h)
It is represented by When stereoisomers exist in these monomers, they can be used alone or as a mixture.

Embedded image (Wherein, R ⁵⁵ represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group; r represents 0 or 1)

Representative examples include the following compounds. [3-45] norbornene (R ⁵⁵ H, r = 0) [3-46] 5-hydroxy-2-norbornene (R ⁵⁵ ＲO
H, r = 0)

The photoresist resin composition of the present invention comprises:
It contains the polymer compound for photoresist of the present invention and a photoacid generator.

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

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

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

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

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

Light beams having various wavelengths, for example, ultraviolet rays and X-rays can be used for exposure. For semiconductor resists, g-rays, i-rays, excimer lasers (for example, XeC
1, KrF, KrCl, ArF, ArCl, etc.) are used. Exposure energy is, for example, 1 to 1000 m
J / cm ² , preferably about 10 to 500 mJ / cm ² .

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

[0118]

The polymer compound for photoresist of the present invention contains a monomer unit having an alicyclic skeleton having a specific structure in which a lactone ring is condensed, and thus has a good balance between adhesion to a substrate and etching resistance. . In particular,
When the alicyclic skeleton has a tertiary carbon atom at the bonding site with the oxygen atom constituting the ester bond, the alicyclic skeleton has high adhesion to the substrate and exhibits excellent acid desorption and etching resistance.

According to the photoresist resin composition and the method for producing a semiconductor of the present invention, a high molecular compound having the above excellent properties is used as a resist, so that a fine pattern can be formed with high precision. it can.

[0120]

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. The term “methacrylate” after the compound number (monomer number) indicates a compound having a methacryloyloxy group among two compounds corresponding to the compound numbers described in the specification.

Production Example 1 [First Step] 72 g (1.0 mol) of acrylic acid and 81.6 g (1.2 mol) of isoprene were charged into a pressure-resistant reactor.
Further, 0.5 g of hydroquinone was added.
The mixture was heated and stirred for hours. The reaction mixture was applied to a rotary evaporator under reduced pressure to obtain 130 g of methylcyclohexenecarboxylic acid (yield: 83%).

[Second Step] 1.4 g (10 mmol) of the above methylcyclohexenecarboxylic acid, tungstic acid 5
0 mg (0.2 mmol) and t-butyl alcohol 1
While stirring, 2 ml of a 30% by weight aqueous hydrogen peroxide solution was added dropwise at room temperature to 5 ml of the mixture, and the mixture was further stirred at room temperature for 5 hours. As a result, the following equations (7a-1), (7a-2), (7b
The four kinds of oxabicyclooctanone derivatives (hydroxylactone) represented by (-1) and (7b-2) have a total yield of 90%
Was generated by The reaction mixture was purified by silica gel column chromatography to obtain a mixture of the four hydroxylactones.

Embedded image

[Third Step] 15.6 g (0.1 mol) of a mixture of the four kinds of hydroxylactones obtained in the second step,
12 g (0.12 mol) of triethylamine and 0.1 g of hydroquinone were added to 100 m of tetrahydrofuran (THF).
10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise with stirring while controlling the temperature of the solution to 10 ° C. or lower. After the addition, the mixture was further stirred at 10 ° C. for 30 minutes. As a result, the following formulas (1a-1), (1a-2), (1b-1) and (1b-1)
The corresponding four types of methacrylates represented by -2) were produced in an amount of 21 g (94% in total yield). The reaction mixture was purified by silica gel column chromatography,
A mixture of different methacrylates was obtained.

Embedded image

Production Example 2 [First Step] Acrylic acid 72 g (1.0 mol), 2, 3
-98.4 g (1.2 mol) of dimethylbutadiene was charged into a pressure-resistant reactor, and 0.5 g of hydroquinone was further added thereto, followed by heating and stirring at 160 ° C for 1 hour. The reaction mixture was applied to a rotary evaporator under reduced pressure to obtain 134 g of dimethylcyclohexenecarboxylic acid (87% yield).

[Second Step] In a mixed solution of 1.54 g (10 mmol) of the above dimethylcyclohexenecarboxylic acid, 50 mg (0.2 mmol) of tungstic acid and 15 ml of t-butyl alcohol, 30% by weight of the mixture was stirred. 2 ml of hydrogen oxide water was added dropwise at room temperature, and
Stirred for hours. As a result, the following equations (7a-3) and (7b-3)
The two oxabicyclooctanone derivatives (hydroxylactone) represented by were produced with a total yield of 90%.
The reaction mixture was purified by silica gel column chromatography to obtain a mixture of the two types of hydroxylactone.

Embedded image

[Third Step] 17 g (0.1 mol) of a mixture of the two kinds of hydroxylactones obtained in the second step, 12 g (0.12 mol) of triethylamine and 0.1 g of hydroquinone were added to 100 ml of tetrahydrofuran (THF). After dissolution, 10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise with stirring while controlling the temperature of the solution to 10 ° C. or lower. After the addition, the mixture was further stirred at 10 ° C. for 30 minutes. As a result, the corresponding 2 represented by the following formulas (1a-3) and (1b-3)
22 g of various methacrylates (92% in total yield)
Had been generated. The reaction mixture was purified by silica gel column chromatography to obtain a mixture of two methacrylates.

Embedded image

Example 1 In a 100 ml round-bottomed flask equipped with a reflux tube, a stirrer and a three-way cock, 5.62 g (25.1 mmol) of a mixture of the four methacrylic esters obtained in Production Example 1 was added. (1-
4.38 g of (methacryloyloxy-1-methylethyl) adamantane ([2-1] (methacrylate))
6.7 mmol), and an initiator (V- Pure Chemical Industries V-
65) 1.00 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. 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 7.35 g of a desired resin.
GPC analysis of the recovered polymer showed a weight average molecular weight of 6,500 and a molecular weight distribution of 2.25. ¹ H
-NMR In (DMSO-d of ₆₎ analysis, 1.5-2.
In addition to 5 ppm (broad), 3.1 ppm, 4.6 p
A strong signal was observed at pm.

Example 2 In a 100 ml round-bottom flask equipped with a reflux tube, a stirrer and a three-way cock, 6.79 g (28.5 mmol) of a mixture of the two methacrylates obtained in Production Example 2, 1- (1-
3.21 g (1) of methacryloyloxy-1-methylethyl) adamantane ([2-1] (methacrylate))
6.9 mmol), and an initiator (V- Pure Chemical Industries, Ltd.)
65) 1.00 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. 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 7.11 g of a desired resin.
GPC analysis of the recovered polymer showed a weight average molecular weight of 6,800 and a molecular weight distribution of 2.18. ¹ H
-NMR In (DMSO-d of ₆₎ analysis, 1.5-2.
In addition to 5 ppm (broad), a strong signal was observed at 3.1 ppm.

Example 3 In a 100 ml round bottom flask equipped with a reflux tube, a stirrer, and a three-way cock, 4.21 g (18.8 mmol) of the mixture of the four methacrylates obtained in Production Example 1 was added. (1-
3.83 g (1) of methacryloyloxy-1-methylethyl) adamantane ([2-1] (methacrylate))
4.6 mmol), 1.97 g (8.35 mmol) of 1-hydroxy-3-methacryloyloxyadamantane ([3-1] (methacrylate)), and an initiator (V-65 manufactured by Wako Pure Chemical Industries). 00 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.
The mixture was stirred for 6 hours under a nitrogen atmosphere. 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, 7.87 g of a desired resin was obtained. GPC analysis of the recovered polymer showed a weight average molecular weight of 6,200 and a molecular weight distribution of 2.
02. ^{In 1} H-NMR (in DMSO-d ₆ ) analysis, in addition to 1.5-2.5 ppm (broad), 3.1
Strong signals were observed at ppm, 4.6 ppm, and 4.7 ppm.

Example 4 In a 100 ml round-bottom flask equipped with a reflux tube, a stirrer and a three-way cock, 5.37 g (22.6 mmol) of the mixture of the two methacrylates obtained in Production Example 2 was added. (1-
2.69 g of (methacryloyloxy-1-methylethyl) adamantane ([2-1] (methacrylate))
0.3 mmol), 1.94 g (8.22 mmol) of 1-hydroxy-3-methacryloyloxyadamantane ([3-1] (methacrylate)), and an initiator (V-65 manufactured by Wako Pure Chemical Industries). 00 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.
The mixture was stirred for 6 hours under a nitrogen atmosphere. 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, 7.55 g of a desired resin was obtained. GPC analysis of the recovered polymer showed a weight average molecular weight of 6,400 and a molecular weight distribution of 2.
It was 11. ^{In 1} H-NMR (in DMSO-d ₆ ) analysis, in addition to 1.5-2.5 ppm (broad), 3.1
A strong signal was observed at ppm and 4.7 ppm.

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA02 AA04 AA14 AB16 AC08 AD03 BE00 BE10 BG00 BJ01 CB08 CB14 CB41 FA17 4J002 BG071 EE036 EQ016 EU186 EV216 EV246 EV296 EV326 FD146 GP03 4J100 AK32R AL02Q AL03Q AL08P AL08Q AL08R AR11Q AR11R BA11P BA11Q BA11R BA16Q BA20Q BC04P BC09Q BC09R BC12Q BC12R CA53BC053

Claims (8)

[Claims] (1) The following formulas (Ia) and (Ib) (Wherein, ^Ra represents a hydrogen atom or a methyl group, and R ^{1 to} R ¹⁸
Represents a hydrogen atom, a methyl group or an ethyl group, respectively). 2. At least one monomer unit selected from the formulas (Ia) and (Ib) and the following formulas (IIa) to (IIg): (Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹⁹ and R ²⁰ are the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, and R ²¹ , R ²² and R ²³ are the same. R ²⁴ and R ²⁵ are the same or different and represent a hydrogen atom, a hydroxyl group or a —COOR ²⁶ group, and R ²⁶ is a t-butyl group,
It represents a tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group. R ²⁷ represents a methyl group or an ethyl group, and R ²⁸ and R ²⁹ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group. R ³⁰ is
A hydrocarbon group having a tertiary carbon atom at the bonding site with an oxygen atom shown in the formula is shown. R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are the same or different and represent a hydrogen atom or a methyl group. R ³⁶ represents a t-butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group. m represents an integer of 1 to 3, and n represents 0 or 1.) and at least one monomer unit selected from the group consisting of: 3. In addition to at least one monomer unit selected from the formulas (Ia) and (Ib) or at least one monomer unit selected from the formulas (Ia) and (Ib) and the formula (IIa) ) To (IIg) and at least one monomer unit selected from the following formulas (IIIa) to (IIIh): (Wherein, R ^a represents a hydrogen atom or a methyl group, R ³⁷ and R ³⁸ are the same or different and represent a hydrogen atom, a hydroxyl group or a carboxyl group, and R ³⁹ represents a hydroxyl group, an oxo group or a carboxyl group. X ¹ , X ² and X
³ are the same or different, -CH ₂ - shows or -CO-O- and. R ⁴⁰ , R ⁴¹ and R ⁴² are the same or different and each represent a hydrogen atom or a methyl group. R ⁴³ and R ⁴⁴ are the same or different and each represent a hydrogen atom or a methyl group. R ⁴⁵ , R ⁴⁶ , R
⁴⁷ , R ⁴⁸ and R ⁴⁹ are the same or different and each represent a hydrogen atom or a methyl group. R ⁵⁰ represents a hydrogen atom or a linear, branched, cyclic or bridged cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ⁵¹ , R ⁵² , R ⁵³
And R ⁵⁴ are the same or different and each represent a hydrogen atom or a methyl group. R ⁵⁵ represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group. 3. The polymer compound for a photoresist according to claim 1, comprising at least one monomer unit selected from monomer units represented by the following: o, p, q, and r each represent 0 or 1. 4. The composition according to claim 1, wherein the monomer units having a group containing an alicyclic hydrocarbon ring (excluding the monomer units represented by the formulas (Ia) and (Ib)) are contained in an amount of 0.1 to 50 mol%. ~ 3
The polymer compound for photoresist according to any one of the above items. 5. The method according to claim 1, wherein the solubility parameter according to the method of Fedors contains 0.1 to 50 mol% of a monomer unit corresponding to a monomer having a value of 11 (cal / cm ³ ) ^1/2 or less. 12. The polymer compound for a photoresist according to item 9. 6. The photoresist polymer according to claim 1, wherein the solubility parameter value according to the Fedors method is in the range of 9.5 to 12 (cal / cm ³ ) ^1/2. Compound. 7. A photoresist resin composition comprising at least the polymer compound for a photoresist according to claim 1 and a photoacid generator. 8. A method for producing a semiconductor, comprising the steps of: applying the photoresist resin composition according to claim 7 onto a substrate or substrate to form a resist coating film, and exposing and developing to form a pattern.