KR20010051365A - Polymer Compounds for Photoresist and Resin Compositions for Photoresist - Google Patents

Abstract

PURPOSE: To obtain a polymeric compound which not only is excellent in clarity, alkali resistance, and adhesive properties but also has a high etching resistance. CONSTITUTION: This polymeric compound contains at least one of monomer units represented by formula I (wherein R1 is H or methyl; and R2 and R3 are each H or hydroxyl) and may further contain at least one of monomer units selected from among monomer units represented by formulas II a and II b (wherein R1 is H or methyl; R4 and R5 are each H, hydroxyl, oxo, carboxyl, or the like provided they are not simultaneously H; and R7 and R8 are each H, hydroxyl, or oxo).

Description

Polymer Compounds for Photoresist and Resin Compositions for Photoresist

This invention relates to the high molecular compound useful as a resin for photoresists used when performing a micro process of a semiconductor, etc., and the resin composition for photoresists containing this high molecular compound.

The positive photoresist used in the semiconductor manufacturing process should have characteristics such as the property that the irradiated portion changes to alkali solubility by light irradiation, adhesion to a silicon wafer, plasma etching resistance, transparency to light used, and the like. The positive photoresist generally uses a solution containing a main polymer, a photoacid generator and various types of additives for adjusting the above properties, but the main polymer balances each of the above properties to prepare a resist according to the use. It is very important to have.

The lithography exposure light source used for the manufacture of a semiconductor is becoming short wavelength year by year, and the ArF excimer laser of 193 nm wavelength is promising as a next generation exposure light source. As a monomer unit of the polymer for resists used for this ArF excimer laser exposure machine, it is proposed to use the unit containing the alicyclic hydrocarbon backbone which has high transparency with respect to the said wavelength, and is etch resistant (Japanese Patent No. 2776273 etc.). ). Moreover, it is also known to use the polymer which has the adamantane skeleton which is especially excellent in etching resistance among alicyclic hydrocarbon backbone as a polymer for resist. However, although the alicyclic hydrocarbon backbone is excellent in etching resistance as mentioned above, since it has high hydrophobicity, there exists a fault that adhesiveness with respect to a board | substrate is low. Therefore, the said document proposes the copolymer which incorporated the high hydrophilic monomer unit (adhesion-adhering monomer unit) which has a carboxyl group, a lactone ring, etc. in order to improve this. However, since these monomer units do not have etching resistance, when they are incorporated into the polymer in an amount that satisfies the adhesion, there is a problem that the etching resistance of the entire polymer is insufficient.

On the other hand, Japanese Patent Laid-Open No. 11-109632 discloses an attempt to impart hydrophilicity by introducing a hydroxyl group into an adamantane skeleton. However, since (meth) acrylic acid t-butylester is used as the monomer unit (alkali-soluble monomer unit) which becomes alkali-soluble by the acid generated by light irradiation, it is also vulnerable to the etching resistance of the whole polymer.

In addition, attempts have been made to make the monomer unit itself having an adamantane skeleton as an alkali-soluble monomer unit (Japanese Patent Laid-Open No. 9-73173, Japanese Patent Laid-Open No. 9-90637, and Japanese Patent Laid-Open No. 10-274852). Publication, Japanese Patent Laid-Open No. 10-319595, Japanese Patent Laid-Open No. 11-12326, Japanese Patent Laid-Open No. 11-119434, etc.). However, also in these cases, the monomer which does not have etching resistance is used as an adhesive provision monomer unit, and it cannot be said that etching resistance of the whole polymer is enough.

Accordingly, an object of the present invention is to provide a polymer compound having not only excellent transparency, alkali solubility and adhesion, but also high etching resistance, and a resin composition for photoresists comprising the polymer compound.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, when the polymer characterized by including the monomer unit which has the adamantane skeleton of a specific structure is used as resin for photoresists, not only transparency, alkali solubility, adhesiveness but also Finally, the inventors found that etching resistance was also satisfied, thus completing the present invention.

That is, the present invention provides a polymer compound characterized in that it comprises at least one monomer unit represented by the following formula (1).

In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> and R <^3> is the same or different, and represents a hydrogen atom or a hydroxyl group.

The polymer compound may include at least one monomer unit represented by Formula 1 and at least one monomer unit selected from Formulas 2a and 2b.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom, a hydroxyl group, an oxo group, a carboxyl group or a -COOR ⁶ group, and R ⁶ is a t-butyl group , 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group or 2-oxepanyl group. However, R ⁴ and R ⁵ may not be a hydrogen atom at the same time. R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group.

Further, a monomer unit represented by the following formula (3), a monomer unit represented by the following formula (4), a monomer unit represented by the following formulas 5a and 5b, a monomer unit represented by the formula (6) and a monomer unit represented by the formula (7) It may be characterized by including one or more monomer units.

In the formula, R ¹ and R ⁹ are the same or different and represent a hydrogen atom or a methyl group.

In formula, R <^10> is tricyclo [5.2.1.0 ^2,6 ] decyl group, tetracyclo [4.4.O.1 ^2,5 . 1 ^7,10 ] a dodecyl group, a norbornyl group, an isobornyl group or a 2-norbornylmethyl group, R ¹¹ is a substituent of R ¹⁰ , a hydrogen atom, a hydroxyl group, a hydroxymethyl group, a carboxyl group or -COOR ¹² A group, R ¹² represents a t-butyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group or a 2-oxepanyl group. R ¹ is the same as above.

In formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> and R <^20> are the same or different, and represent a hydrogen atom or a methyl group. R ¹ is the same as above.

In formula, n represents the integer of 1-3. R ¹ is the same as above.

In formula, R <^1> is the same as the above.

In the polymer compound, the total content of monomer units having an adamantane skeleton is, for example, 50 to 100% by weight, preferably 70 to 100% by weight of the total monomer units constituting the polymer.

The said high molecular compound can be used as resin for photoresists.

This invention also provides the resin composition for photoresists containing the said high molecular compound and a photo-acid generator.

In addition, in this specification, "acryl" and "methacryl" may be generically called "(meth) acryl."

<Embodiment of the Invention>

The polymer compound of the present invention is characterized by including one or more monomer units (hereinafter sometimes referred to as "monomer unit 1") represented by Chemical Formula 1 as structural units constituting the polymer molecule.

The monomer unit represented by the formula (1) detaches from the carboxylic acid moiety in which the moiety containing the adamantane skeleton is bonded to the main chain depending on the acid to generate a free carboxyl group. Therefore, the monomer unit 1 functions as an alkali-soluble unit which solubilizes at the time of alkali image development. Moreover, since the said monomer unit has an adamantane frame | skeleton, it has the characteristics that it is excellent in transparency and very high etching tolerance. In addition, the monomer units of the general formula (1) in which at least one (preferably two) of R ² and R ³ are hydroxyl groups have high hydrophilicity and have an adhesive function. Therefore, by incorporating such a monomeric unit and another hydrophilic monomeric unit suitably, the outstanding adhesive function can also be expressed. Therefore, the high molecular compound of this invention can be used suitably as resin for photoresists.

As a preferable aspect of this invention, it is characterized by including the said monomer unit 1 and the at least 1 monomer unit chosen from the said General formula (2a) and (2b) (Hereinafter, it may be called "monomer unit 2.").

In formula (2a), R ⁴ and R ⁵ are groups bonded to the carbon atoms constituting the adamantane ring, and when they are a hydroxyl group, a carboxyl group or a -COOR ⁶ group, they are usually bonded to the intersection of the adamantane ring. In formula (2b), R ⁷ and R ⁸ are a group bonded to the carbon atom constituting the adamantane ring, and when it is a hydroxyl group, it is usually bonded to the bridgehead of the adamantane ring.

Monomer unit 2 is equipped with high etching tolerance by an adamantane skeleton. Moreover, in the monomer unit 2, the thing with which the high hydrophilic group (hydroxyl group, a carboxyl group, an oxo group) couple | bonded with the adamantane frame | skeleton functions as an adhesive provision unit which raises adhesiveness to a board | substrate. Moreover, since at least one of R <^4> and R <^5> in the monomer unit of Formula (2a) is a -COOR <^6> group, and the monomer unit of Formula (2b) produces | generates a free carboxyl group by acid, it also has alkali-soluble function. The monomer unit of formula (2a) wherein R ⁴ is a hydrogen atom and R ⁵ is -COOR ⁶ or a monomer unit of formula (2b) wherein R ⁷ and R ⁸ are both hydrogen atoms does not have an adhesive function but does not have an alkali soluble function as described above. Therefore, by combining with at least one (preferably two) of the monomer unit of the general formula (1) in which one or more of R ² and R ³ is a hydroxyl group, it is possible to equilibrate the alkali-soluble function and the adhesive function.

In the polymer compound having both the monomer unit 1 and the monomer unit 2, both of the units have an adamantane skeleton, so that high etching resistance is obtained and alkali solubility, adhesion to the substrate, plasma etching resistance and transparency Each of the characteristics is very well equipped. In such a polymer compound, the ratio of monomer unit 1 and monomer unit 2 is, for example, the former / the latter (molar ratio) = 1/99 to 99/1, preferably 5/95 to 80/20, and more preferably 15 /. 85 to 65/35 degrees.

The polymer compound of the present invention is also a monomer unit having an adamantane skeleton represented by the formula (3) (having no adhesive function and an alkali-soluble function), and a crosslinked alicyclic type other than adamantane represented by the formula (4). At least one monomer unit selected from monomer units having a hydrocarbon skeleton, monomer units having a lactone skeleton represented by the formulas (5a) and (5b), acetal monomer units represented by the formula (6), and monomer units having a carboxyl group represented by the formula (7) Hereinafter, the "monomer unit 3" may be referred to).

Polymers composed solely of structural units having an adamantane skeleton generally have low molecular entanglement and are easy to have relatively fragile properties, but such fragility is improved by incorporating the monomer units of Formulas 4 to 7 into the polymer. In addition, since the monomer units of Formulas 3 and 4 have high etching resistance, the monomer units of Formulas 5a and 5b have an adhesion imparting function, and the monomer units of Formulas 5b and 6 have an alkali-soluble function. The balance of various characteristics required as the resin can be finely adjusted according to the use.

In the high molecular compound containing such a monomer unit 3, the total content of the monomer unit 3 is, for example, about 1 to 50 mol%, preferably about 5 to 40 mol% of the total monomer units constituting the polymer.

In the high molecular compound of this invention, the following are mentioned as especially preferable combination among the combination of each said monomer unit.

(1) Combination of monomer units of formula (1) wherein R ² and R ³ are hydrogen atoms and monomer units of formula (1) wherein at least one of R ² and R ³ is a hydroxyl group

(2) Combination of monomer unit of formula 1 and monomer unit of formula 2a

(3) a combination of a monomer unit of formula (1) wherein at least one of R ² and R ³ is a hydroxyl group and a monomer unit of formula (2a) wherein R ⁴ or R ⁵ is a -COOR ⁶ group;

(4) a combination of a monomer unit of formula (1) and a monomer unit of formula (2b) wherein at least one of R ⁷ and R ⁸ is a hydroxyl group (particularly a monomer unit of R ⁷ = R ⁸ = OH)

(5) Combination of monomer units of formula (1) and monomer units of formula (2b) wherein at least one of R ² and R ³ is a hydroxyl group

(6) a combination of a monomer unit of formula (1) and a monomer unit of formula (5a) (e.g., a monomer unit wherein at least one of R ¹³ to R ¹⁷ is a methyl group)

(7) a combination of a monomer unit of formula (1) and a monomer unit of formula (5b) (e.g., a monomer unit in which at least one of R ¹⁸ to R ²⁰ is a methyl group, especially a monomer unit in which R ¹⁹ and R ²⁰ are methyl groups)

(8) Combination of monomer unit of formula 1 and monomer unit of formula 6

(9) Combination of monomer unit of formula 1, monomer unit of formula 2a and monomer unit of formula 5a

(10) Combination of monomer unit of formula 1, monomer unit of formula 2a and monomer unit of formula 5b

(11) Combination of monomer unit of formula 1, monomer unit of formula 2a and monomer unit of formula 6

In the polymer compound of the present invention, the total content of monomer units having an adamantane skeleton (Formulas 1, 2a, 2b, and 3, in particular, Formulas 1, 2a, and 2b is, for example, 50 to 100 weights of the total monomer units constituting the polymer). %, Preferably on the order of 70 to 100. Such high molecular compounds exhibit particularly good etching resistance.

In the present invention, the weight average molecular weight (M _w ) of the polymer compound is, for example, about 5000 to 50000, preferably about 7000 to 20000, and the molecular weight distribution (M _w / M _n ) is about 1.8 to 3.0, for example. In addition, said M _n represents a number average molecular weight (polystyrene conversion).

Each monomer unit represented by said Formula (1)-(7) can be formed by superposing | polymerizing a corresponding (meth) acrylic acid ester as a (co) monomer, respectively. Polymerization can be performed by the usual method used when manufacturing an acrylic polymer, such as solution polymerization and melt polymerization.

Monomer Unit of Formula 1

The monomer corresponding to the monomer unit of Formula 1 is represented by the following Formula 1a.

In formula, R <^1> , R <^2> , R <^3> is the same as the above.

The following compound is mentioned as a typical example of the monomer of the said General formula (1a).

[1a-1] 1- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ¹ = H or CH ₃ , R ² = R ³ = H)

[1a-2] 1-hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ¹ = H or CH ₃ , R ² = OH, R ³ = H)

[1a-3] 1,3-dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ¹ = H or CH ₃ , R ² = R ³ = OH )

The compound represented by Chemical Formula 1a can be obtained, for example, according to Scheme 1 below.

In the formula, X represents a halogen atom, and R ^X represents a halogen atom, a hydroxyl group, an alkoxy group or an alkenyloxy group. R ¹ , R ² and R ³ are the same as above.

In the said Reaction Formula 1, the compound whose at least one of R <^2> and R <^3> is a hydroxyl group in the adamantane derivative (8) used as a raw material can be obtained by introducing a hydroxyl group into an adamantane ring. For example, adamantane is replaced with an N-hydroxyimide catalyst such as N-hydroxyphthalimide and, if necessary, a metal-based promoter such as a cobalt compound (for example, cobalt acetate, cobalt acetylacetonate, etc.). The hydroxyl group can be introduced into the adamantane ring by contact with oxygen in the presence of. In this method, the amount of N-hydroxyimide catalyst used is, for example, 0.0001 to 1 mol, preferably 0.001 to 0.5 mol, per 1 mol of adamantane. In addition, the usage-amount of a metal type cocatalyst is 0.0001-0.7 mol, for example, about 0.001-0.5 mol with respect to 1 mol of adamantanes. Oxygen is often used in an excessive amount relative to adamantane. The reaction is carried out at a temperature of about 0 to 200 ° C., preferably about 30 to 150 ° C., under normal pressure or pressure in a solvent such as an organic acid such as acetic acid, nitriles such as acetonitrile, and halogenated hydrocarbons such as dichloroethane. By selecting the reaction conditions, a plurality of hydroxyl groups can be introduced into the adamantane ring.

The reaction of the adamantane derivative (8) with the 1,2-dicarbonyl compound (nonacetyl) (9) and oxygen may be carried out with a metal compound such as a cobalt compound (for example, cobalt acetate, cobaltacetylacetonato, etc.). And / or N-hydroxyimide catalysts such as N-hydroxyphthalimide. The amount of the 1,2-dicarbonyl compound (9) to be used is 1 mole or more (for example, 1 to 50 moles), preferably 1.5 to 20 moles, more preferably 1 mole of adamantane derivative (8) per mole. Is about 3 to 10 mol. The usage-amount of the said metal compound is about 0.0001-0.1 mol with respect to 1 mol of adamantane derivatives (8), for example. The amount of the N-hydroxyimide catalyst used is, for example, about 0.001 to 0.7 mol per mole of adamantane derivative (8). Oxygen is often used in an excessive amount relative to the adamantane derivative (8). The reaction is usually carried out in an organic solvent. As an organic solvent, organic acids, such as acetic acid, nitriles, such as benzonitrile, halogenated hydrocarbons, such as trifluoromethylbenzene, etc. are mentioned, for example. The reaction is carried out at normal temperature or under pressure, for example, at a temperature of about 30 to 250 캜, preferably about 40 to 200 캜.

The reaction between the acyl adamantane derivative (10) and the Grignard reagent (11) thus obtained can be carried out in accordance with the usual Grignard reaction. The use amount of the Grignard reagent (11) is, for example, 0.7 to 3 moles, preferably 0.9 to 1.5 moles, per 1 mole of the acyl adamantane derivative (10). When the acyl adamantane derivative (10) has a hydroxyl group on the adamantane ring, the amount of the Grignard reagent is increased according to the number thereof. The reaction is carried out, for example, in ethers such as diethyl ether and tetrahydrofuran. Reaction temperature is 0-150 degreeC, for example, Preferably it is about 20-100 degreeC.

The reaction (esterification reaction) of the adamantanemethanol derivative (12) produced by the above reaction and (meth) acrylic acid or its derivative (13) can be carried out by a conventional method using an acid catalyst or a transesterification catalyst. In addition, an almanyl (meth) acrylate such as adamantanemethanol derivative (12), vinyl (meth) acrylate, 2-propenyl (meth) acrylate, and the like can be used as a Group 3 element compound catalyst (e.g., samarium acetate, Reaction (ester exchange reaction) in the presence of samarium compounds such as samarium trifluoromethanesulfonate, samarium complex, and the like) can be efficiently used to obtain a compound represented by the general formula (1a) under mild conditions. In this case, the usage-amount of the alkenyl (meth) acrylate is 0.8-5 mol, for example, about 1-1.5 mol with respect to 1 mol of adamantanemethanol derivatives (12). The amount of the Group 3 element compound catalyst used in the periodic table is, for example, from O.OO1 to 1 mole, preferably from O.O1 to 0.25 mole, per 1 mole of adamantanemethanol derivative (12). This reaction is carried out in a solvent inert to the reaction, for example, at a temperature of from 0 to 150 캜, preferably from 25 to 120 캜.

In addition, the compound represented by Formula 1a may be obtained according to the following Scheme 2, for example.

In the formula, R ^y represents a hydrocarbon group. X, R ¹ , R ² , R ³ and R ^x are the same as above.

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

In the said Reaction Formula 2, the adamantanecarboxylic acid derivative (14) used as a raw material can be manufactured by introducing a carboxyl group into the adamantane ring of an adamantane compound. For example, an adamantane compound may be reacted with an N-hydroxyimide catalyst such as N-hydroxyphthalimide and, if necessary, a metal-based bath such as a cobalt compound (for example, cobalt acetate, cobalt acetylacetonate, etc.). By contacting with carbon monoxide and oxygen in the presence of a catalyst, a carboxyl group can be introduced into the adamantane ring of the adamantane compound. In this carboxylation reaction, the amount of the N-hydroxyimide catalyst used is, for example, 0.0001 to 1 mole, preferably 0.001 to 0.5 mole, per 1 mole of adamantane compound. In addition, the usage-amount of a metal type cocatalyst is 0.0001-0.7 mol, for example, about 0.001-0.5 mol with respect to 1 mol of adamantane compounds. The amount of carbon monoxide and oxygen used is, for example, 1 mol or more and 0.5 mol or more, based on 1 mol of the adamantane compound. The ratio of carbon monoxide and oxygen is, for example, about the former / the latter (molar ratio) = 1/99 to 99/1, preferably about 50/50 to 95/5. The carboxylation reaction is, for example, in an organic acid such as acetic acid, nitriles such as acetonitrile, halogenated hydrocarbons such as dichloroethane, and the like at about 0 to 200 ° C. under normal pressure or under pressure, preferably at a temperature of about 10 to 150 ° C. Is done in. In addition, a plurality of carboxyl groups can be introduced into the adamantane ring by selecting the reaction conditions.

The reaction of the adamantanecarboxylic acid derivative (14) with the hydroxy compound (15) can be carried out according to a conventional esterification method using an acid catalyst or the like, for example.

The reaction of adamantanecarboxylic acid ester represented by the formula (16) with the Grignard reagent (11) is usually carried out in a solvent inert to the reaction, for example, ethers such as diethyl ether and tetrahydrofuran. Reaction temperature is about 0-100 degreeC, for example, Preferably it is about 10-40 degreeC. The use amount of Grignard reagent (11) is, for example, about 2 to 4 equivalents relative to adamantanecarboxylic acid ester (16).

The reaction (esterification reaction) of an adamantanemethanol derivative (12) and (meth) acrylic acid or its derivative (13) is the same as the above.

Monomer Unit of Formula 2a

The monomer corresponding to the monomer unit of Formula 2a is represented by the following Formula 2aa.

In formula, R <^1> , R <^4> and R <^5> are the same as the above.

Representative examples of the monomer of Formula 2aa include the following compounds.

[2a-1] 1-hydroxy-3- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = OH, R ⁵ = H)

[2a-2] 1,3-dihydroxy-5- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = R ⁵ = OH)

[2a-3] 1-carboxy-3- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = COOH, R ⁵ = H)

[2a-4] 1,3-dicarboxy-5- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = R ⁵ = COOH)

[2a-5] 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = COOH, R ⁵ = OH)

[2a-6] 1- (meth) acryloyloxy-4-oxoadamantane (R ¹ = H or CH ₃ , R ⁴ = 4-oxo group, R ⁵ = H)

[2a-7] 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ¹ = H or CH ₃ , R ⁴ = 4-oxo group, R ⁵ = 3-OH)

[2a-8] 7-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ¹ = H or CH ₃ , R ⁴ = 4-oxo group, R ⁵ = 7-OH)

[2a-9] 1-t-butoxycarbonyl-3- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = t-butoxycarbonyl group, R ⁵ = H)

[2a-10] 1,3-bis (t-butoxycarbonyl) -5- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = R ⁵ = t-butoxycarbonyl group )

[2a-11] 1-t-butoxycarbonyl-3-hydroxy-5- (meth) acrylooxyadamantane (R ¹ = H or CH ₃ , R ⁴ = t-butoxycarbonyl group, R ⁵ = OH)

[2a-12] 1- (2-tetrahydropyranyloxycarbonyl) -3- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = 2-tetrahydropyranyloxycarbonyl group , R ⁵ = H)

[2a-13] 1,3-bis (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = R ⁵ = 2- Tetrahydropyranyloxycarbonyl group)

[2a-14] 1-hydroxy-3- (2-tetrahydropyranyloxycarbonyl) -5- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁴ = 2-tetra Hydropyranyloxycarbonyl group, R ⁵ = OH)

The compound represented by Formula 2aa may be obtained, for example, according to Scheme 3 below.

In formula, R <^1> , R <^4> , R <^5> and R <^X> are the same as the above.

In the above Reaction Scheme 3, the compound represented by the formula (17) used as a raw material can be obtained by introducing a hydroxyl group or a carboxyl group into the adamantane ring of the adamantane compound. The said method is mentioned as a method of introducing a hydroxyl group and a carboxyl group into an adamantane ring. In addition, the carboxylic acid and the alcohol R ⁶ OH are R ⁴ or R ⁵ of the compound represented by the formula -COOR ⁶ to 17 due to corresponding compounds can be prepared by esterification of tolerance.

Reaction (esterification reaction) of compound (17) and (meth) acrylic acid or its derivative (13) can be performed according to reaction of the compound represented by the said Formula (12), and (meth) acrylic acid or its derivative (13).

Monomer Unit of Formula 2b

The monomer corresponding to the monomer unit of Formula 2b is represented by the following Formula 2ba.

In formula, R <^1> , R <^7> and R <^8> are the same as the above.

The following compound is mentioned as a typical example of the monomer of the said General formula (2ba).

[2a-15] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ¹ = H or CH ₃ , R ⁷ = 1-OH, R ⁸ = 3- OH)

[2a-16] 1,5-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ¹ = H or CH ₃ , R ⁷ = 1-OH, R ⁸ = 5- OH)

[2a-17] 1,3-dihydroxy-6- (meth) acryloyloxy-6-methyladamantane (R ¹ = H or CH ₃ , R ⁷ = 1-OH, R ⁸ = 3- OH)

[2a-18] 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ¹ = H or CH ₃ , R ⁷ = 1-OH, R ⁸ = H)

[2a-19] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ¹ = H or CH ₃ , R ⁷ = 5-OH, R ⁸ = H)

[2a-20] 2- (meth) acryloyloxy-2-methyladamantane (R ¹ = H or CH ₃ , R ⁷ = R ⁸ = H)

The compound represented by Chemical Formula 2ba may be obtained, for example, according to Scheme 4 below.

In formula, X, R <^1> , R <^7> , R <^8> and R <^X> are the same as the above.

In the reaction scheme 4, the reaction between the adamantanone derivative 18 and the Grignard reagent 19 can be carried out in accordance with a conventional Grignard reaction. The amount of Grignard reagent 19 used is, for example, 0.7 to 3 moles, preferably 0.9 to 1.5 moles, per 1 mole of adamantanone derivative (18). When the adamantanone derivative (18) has a hydroxyl group on the adamantane ring, the amount of the Grignard reagent is increased according to the number thereof. The reaction is carried out in a solvent which is inert to the reaction, for example, ethers such as diethyl ether and tetrahydrofuran. Reaction temperature is 0-150 degreeC, for example, Preferably it is about 20-100 degreeC.

By reacting the thus obtained 2-adamantanol derivative (20) with (meth) acrylic acid or its derivative (13) (esterification reaction), a compound represented by the above formula (2ba) can be obtained. The esterification reaction can be carried out in accordance with the reaction of the compound of formula 12 with (meth) acrylic acid or its derivative (13).

Moreover, in the said method, the compound which has a hydroxyl group in the adamantane ring among the adamantanone derivatives 18 used as a raw material has 2-adamantanes as N-hydroxy imide, such as N-hydroxyphthalimide. In the presence of a metal catalyst and a metal promoter such as a cobalt compound, a manganese compound, a vanadium compound, and the like, it can be produced by contacting with oxygen to introduce a hydroxyl group into the adamantane ring. In this method, the amount of the N-hydroxyimide catalyst used is, for example, 0.0001 to 1 mol, preferably 0.001 to 0.5 mol, per 1 mol of 2-adamantanes. In addition, the usage-amount of a metal type cocatalyst is 0.0001-0.7 mol, for example, about 0.001-0.5 mol with respect to 1 mol of 2-adamantanes. Oxygen is often used in an excessive amount relative to 2-adamantanes. The reaction is carried out at a temperature of about 0 to 200 ° C., preferably about 30 to 150 ° C. under normal pressure or pressure in a solvent such as organic acids such as acetic acid, nitriles such as acetonitrile, and halogenated hydrocarbons such as dichloroethane. .

In addition, the compound which has a hydroxyl group in the adamantane ring in the adamantanone derivative (18) is required to combine adamantanes and oxygen with the said N-hydroxyimide type catalyst and a strong acid (for example, hydrogen halide, sulfuric acid, etc.). Can be prepared by reacting in the presence of the metal-based promoter. The amount of the strong acid used is, for example, 0.00001 to 1 mol, preferably 0.0005 to 0.7 mol, per 1 mol of adamantanes. Other reaction conditions are the same as the hydroxyl group introduction reaction.

Monomer Unit of Formula 3

The monomer corresponding to the monomer unit of Formula 3 is represented by the following Formula 3a.

In the formula, R ¹ and R ⁹ are the same as above.

The following compound is mentioned as a specific example of the monomer of the said General formula (3a). These compounds can be manufactured by a well-known and usual method.

[3a-1] 1- (meth) acryloyloxyadamantane (R ¹ = H or CH ₃ , R ⁹ = H)

[3a-2] 1- (meth) acryloyloxy-3,5-dimethyladamantane (R ¹ = H or CH ₃ , R ⁹ = CH ₃ )

Monomer Unit of Formula 4

The monomer forming the monomer unit of Formula 4 is represented by the following Formula 4a.

In formula, R <^1> , R <^10> and R <^11> are the same as the above.

Representative examples of the monomer of Formula 4a include the following compounds. These compounds can be obtained by a known or common method.

[4a-1] 8-hydroxymethyl-4- (meth) acryloyloxymethyltricyclo [5.2.1.0 ^2,6 ] decane

[4a-2] 4-hydroxymethyl-8- (meth) acryloyloxymethyltricyclo [5.2.1.O ^2,6 ] decane

[4a-3] 4- (meth) acryloyloxymethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane

[4a-4] 2- (meth) acryloyloxynorbornane

[4a-5] 2- (meth) acryloyloxyisobornane

[4a-6] 2- (meth) acryloyloxymethylnorbornane

Monomer Unit of Formula 5a

The monomer which forms the monomer unit of the said Formula (5a) is represented by following formula (5aa).

In formula, R <^1> , R <^13> , R <^14> , R <^15> , R <^16> and R <^17> are the same as the above.

Representative examples of the monomer of Formula 5aa include the following compounds.

[5a-1] 2- (meth) acryloyloxy-γ-butylarolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H)

[5a-2] 2- (meth) acryloyloxy-2-methyl-γ-butyrolactone (R ¹ = H or CH ₃ , R ¹³ = CH ₃ , R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = H)

[5a-3] 2- (meth) acryloyloxy-4,4-dimethyl-γ-butylolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁴ = R ¹⁵ = H, R ¹⁶ = R ¹⁷ = CH ₃ )

[5a-4] 2- (meth) acryloyloxy-2,4,4-trimethyl-γ-butyrolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁶ = R ¹⁷ = CH ₃ , R ¹⁴ = R ¹⁵ = H)

[5a-5] 2- (meth) acryloyloxy-3,4,4-trimethyl-γ-butyrolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁵ = H, R ¹⁴ = R ¹⁶ = R ¹⁷ = CH ₃ )

[5a-6] 2- (meth) acryloyloxy-2,3,4,4-tetramethyl-γ-butylolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁴ = R ¹⁶ = R ¹⁷ = CH ₃ , R ¹⁵ = H)

[5a-7] 2- (meth) acryloyloxy-3,3,4-trimethyl-γ-butyrolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁷ = H, R ¹⁴ = R ¹⁵ = R ¹⁶ = CH ₃ )

[5a-8] 2- (meth) acryloyloxy-2,3,3,4-tetramethyl-γ-butylarolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = CH ₃ , R ¹⁷ = H)

[5a-9] 2- (meth) acryloyloxy-3,3,4,4-tetramethyl-γ-butylarolactone (R ¹ = H or CH ₃ , R ¹³ = H, R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = CH ₃ )

[5a-10] 2- (meth) acryloyloxy-2,3,3,4,4-pentamethyl-γ-butyrolactone (R ¹ = H or CH ₃ , R ¹³ = R ¹⁴ = R ¹⁵ = R ¹⁶ = R ¹⁷ = CH ₃ )

The compound represented by Chemical Formula 5aa may be obtained, for example, according to Scheme 5 below.

In the formula, R ^Z represents a hydrocarbon group. R ¹ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^X are the same as above.

In the scheme 5, as the hydrocarbon group of R ^Z , an aliphatic hydrocarbon group having 1 to 6 carbon atoms (alkyl group, alkenyl group or alkynyl group) such as methyl, ethyl, propyl, s-butyl, t-butyl, vinyl, and allyl group, Aromatic hydrocarbon groups, such as a phenyl group and a naphthyl group, Alicyclic hydrocarbon groups, such as a cycloalkyl group, etc. are mentioned.

The reaction between the α, β-unsaturated carboxylic acid ester (21), the alcohol (22) and oxygen is carried out using an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide and cobalt compounds as necessary (for example, Cobalt acetate, cobalt acetylacetonate and the like). The ratio of the α, β-unsaturated carboxylic acid ester (21) to the alcohol (22) can be appropriately selected depending on the kind (price, reactivity, etc.) of both compounds. For example, alcohol (22) may be used in excess (for example, about 2 to 50 molar times) relative to the α, β-unsaturated carboxylic acid ester 21, and conversely, the α, β-unsaturated carboxylic acid ester ( 21) may be used in excess of alcohol (22). The amount of the N-hydroxyimide-based catalyst used is, for example, 0.0001 to 1 mol, preferably 0.001 to 1 mol of the compound on the smaller side of the α, β-unsaturated carboxylic acid ester (21) and the alcohol (22). To about 0.5 moles. The amount of the metal-based promoter is, for example, O.O001 to 0.7 mole, preferably 0.001 to 1 mole of the compound used in the small amount of the α, β-unsaturated carboxylic acid ester (21) and the alcohol (22). To about 0.5 moles. Oxygen is often used in an excessive amount with respect to the compound of the one used in a small amount in the α, β-unsaturated carboxylic acid ester (21) and the alcohol (22). The reaction is, for example, in an organic acid such as acetic acid, nitriles such as acetonitrile, halogenated hydrocarbons such as trifluoromethylbenzene, esters such as ethyl acetate, and the like at about 0 to 150 캜, preferably at atmospheric pressure or under pressure. It is performed at the temperature of about 30-100 degreeC.

Reaction of the (alpha) -hydroxy- (gamma)-butyrolactone derivative (23) and (meth) acrylic acid or its derivative (13) which were obtained in this way was carried out by the said 1-adamantanol derivative (12) and (meth) acrylic acid or its derivative (13). Can be carried out in accordance with the reaction with).

Monomer Unit of Formula 5b

The monomer forming the monomer unit of Formula 5b is represented by the following Formula 5ba.

In formula, R <^1> , R <^18> , R <^19> and R <^20> are the same as the above.

The following compound is mentioned as a typical example of the monomer of the said General formula (5ba).

[5a-11] 3- (meth) acryloyloxy-γ-butylolactone (R ¹ = H or CH ₃ , R ¹⁸ = R ¹⁹ = R ²⁰ = H)

[5a-12] 3- (meth) acryloyloxy-3-methyl-γ-butylolactone (R ¹ = H or CH ₃ , R ¹⁸ = CH ₃ , R ¹⁹ = R ²⁰ = H)

[5a-13] 3- (meth) acryloyloxy-4-methyl-γ-butylolactone (R ¹ = H or CH ₃ , R ¹⁸ = R ²⁰ = H, R ¹⁹ = CH ₃ )

[5a-14] 3- (meth) acryloyloxy-3,4-dimethyl-γ-butylolactone (R ¹ = H or CH ₃ , R ¹⁸ = R ¹⁹ = CH ₃ , R ²⁰ = H)

[5a-15] 3- (meth) acryloyloxy-4,4-dimethyl-γ-butylolactone (R ¹ = H or CH ₃ , R ¹⁸ = H, R ¹⁹ = R ²⁰ = CH ₃ )

[5a-16] 3- (meth) acryloyloxy-3,4,4-trimethyl-γ-butyrolactone (R ¹ = H or CH ₃ , R ¹⁸ = R ¹⁹ = R ²⁰ = CH ₃ )

The compound represented by Chemical Formula 5ba can be obtained, for example, according to Scheme 6 below.

In formula, R <^1> , R <^18> , R <^19> , R <^20> and R <^X> are the same as the above.

In the above Scheme 6, the conversion (isomerization) of the α-hydroxy-γ-butyrolactones represented by the formula (24) to the β-hydroxy-γ-butyrolactones represented by the formula (25) is a compound of the formula (24). If necessary, it can be carried out by dissolving an acid such as water, sulfuric acid or hydrochloric acid in a small amount of solvent. A solvent is not specifically limited, For example, acetonitrile, acetic acid, ethyl acetate, etc. can be used. Reaction temperature is 0-150 degreeC, for example, Preferably it is about 20-100 degreeC. (Alpha) -hydroxy- (gamma)-butyrolactone (24) used as a raw material can be manufactured similarly to the compound represented by the said General formula (23). In addition, the compound of formula (25) reacts the compound of formula (24) with phosphorus pentoxide (dehydration reaction) to give the corresponding α, β-unsaturated-γ-butylolactone, which is reacted with peracid such as hydrogen peroxide or m-chloroperbenzoic acid. It can also be obtained by epoxidizing a double bond and then hydrogenating in the presence of a catalyst such as Pd-C. In addition, the compound of the formula (25) can also be produced by a known method for obtaining β-hydroxy-γ-butyrolactones.

Reaction of (meth) acrylic acid or its derivative represented by (beta) -hydroxy- (gamma)-butyrolactone (25) with Formula (13) based on reaction of the compound of Formula (12) with (meth) acrylic acid or its derivative (13) I can do it.

Monomer Unit of Formula 6

The monomer forming the monomer unit of Chemical Formula 6 is represented by the following Chemical Formula 6a.

In formula, R <^1> and n are the same as the above.

Representative examples of the monomer of Formula 6a include the following compounds.

[6a-1] 2-tetrahydropyranyl (meth) acrylate (R ¹ = H or CH ₃ , n = 2)

[6a-2] 2-tetrahydrofuranyl (meth) acrylate (R ¹ = H or CH ₃ , n = 1)

Monomer Unit of Formula 7

The monomer forming the monomer unit of Formula 7 is represented by the following Formula 7a.

In formula, R <^1> is the same as the above.

Specific examples of the monomer of Formula 7a are the following compounds.

[7a-1] (meth) acrylic acid (R ¹ = H or CH ₃ )

Since the high molecular compound of this invention is equipped with all transparency, alkali solubility, adhesiveness, and etching tolerance as mentioned above, it can be used suitably as resin for photoresists.

The resin composition for photoresists of the present invention is characterized by comprising the polymer compound of the present invention and a photoacid generator.

As the photoacid generator, conventional to known compounds which efficiently generate an acid by exposure, for example, diazonium salt, iodonium salt (for example, diphenyl iodide hexafluorophosphate), and sulfonium salt (for example, tri Phenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonic acid esters (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-methylphenylsulfonyl Oxymethyl) -1-hydroxy-1-benzoylmethane, etc.), oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (such as diphenyldisulfone), imide compounds, oxime sulfonates, diazonapto Quinone, benzointosylate, etc. can be used. These photoacid generators can be used individually or in combination of 2 or more types.

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

The resin composition for photoresist may be an alkali-soluble component such as alkali-soluble resin (e.g., novolak resin, phenol resin, imide resin, carboxyl group-containing resin, etc.), colorant (e.g., dye, etc.), organic solvent (e.g., For example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof, and the like) may be included.

After apply | coating this resin composition for photoresists on a base material or a board | substrate, and drying, after exposing a light beam to a coating film (resist film) through a predetermined mask (or baking further after exposure), a latent image pattern is formed and it continues. By developing by developing, a fine pattern can be formed with high precision.

Examples of the substrate or substrate include silicon wafers, metals, plastics, glass, ceramics, and the like. Application | coating of the resin composition for photoresists can be performed using usual coating means, such as a spin quarter, a dip quarter, and a roller quarter. The thickness of a coating film is 0.1-20 micrometers, for example, Preferably it is about 0.3-2 micrometers.

Light rays of various wavelengths, for example, ultraviolet rays and X-rays, can be used for exposure, and g-rays, i-rays, and excimer lasers (for example, XeCl, KrF, KrCl, ArF, ArCl, etc.) are usually used for semiconductor resists. Etc. are used. The exposure energy is, for example, 1 to 100 mJ / cm ² , preferably about 10 to 50mJ / cm ² .

By irradiation with light, an acid is generated from the photoacid generator, and the acid rapidly escapes the protecting group (desorbable group) of the carboxyl group in the polymer compound to produce a carboxyl group that contributes to solubilization. Therefore, a predetermined pattern can be formed with high precision by image development by water or an alkaline developing solution.

<Example>

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example. In addition, what is called "acrylate" after a compound number (monomer number) represents the compound which has acryloyloxy group among two compounds corresponded to the compound number described in this application, and what is called "methacrylate" is said The compound which has methacryloyloxy group is shown in two compounds. The lower right number in parentheses in the structural formula represents the mole% of the monomer unit.

<Production example 1>

(Production of 1- (1-acryloyloxy-1-methylethyl) adamantane [1a-1 (acrylate)])

The flask was charged with 59.63 g (0.063 mol) of a 12 wt% methylmagnesium bromide-tetrahydrofuran solution prepared from methyl bromide and metal magnesium in advance. The solution which melt | dissolved 4.73 g (0.02 mol) of 1-adamantanecarboxylic acid n-butyl ester in 7.21 g of tetrahydrofuran was dripped at this solution, maintaining internal temperature at 35 degrees C or less. After dropping, the mixture was stirred at room temperature for 1 hour.

The reaction mixture obtained above was dripped in 32.37 g of 10 weight% aqueous sulfuric acid aqueous solution, maintaining the internal temperature at 35 degrees C or less, and it neutralized and separated into 5 weight% sodium hydroxide aqueous solution. The aqueous layer was extracted twice with 20 g of benzene. The organic layers were combined and washed with 20 g of saturated brine and then dried over anhydrous sodium sulfate. After drying, the mixture was filtered and the filtrate was concentrated under a reduced pressure to obtain α, α-dimethyl-1-adamantanemethanol. The yield on the basis of 1-adamantanecarboxylic acid n-butylester was 88.7%.

15 mmol of acrylic acid chloride was added dropwise to the mixture of 10 mmol of α, α-dimethyl-1-adamantanemethanol, 20 mmol of triethylamine and 40 ml of tetrahydrofuran obtained by the above method over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. Water was added to the reaction mixture, followed by concentration. The concentrate was purified by silica gel column chromatography to obtain the title compound in a yield of 76%.

[Spectrum data]

¹ H-NMR (500 MHz, CDCl ₃ ) δ: 1.49 (s, 6H), 1.60-1.75 (m, 12H), 2.02 (m, 3H), 5.71 (dd, 1H), 6.05 (dd, 1H), 6.28 (dd, 1 H)

<Production example 2>

(Production of 1- (1-methacryloyloxy-1-methylethyl) adamantane [1a-1 (methacrylate)])

The title compound was obtained in the same manner as in Production Example 1 except that methacrylic acid chloride was used instead of acrylic acid chloride.

[Spectrum data]

¹ H-NMR (500 MHz, CDCl ₃ ) δ: 1.49 (s, 6H), 1.56-1.80 (m, 12H), 1.92 (brs, 3H), 2.02 (m, 3H), 5.46 (brs, 1H), 6.02 (brs, 1 H)

<Production example 3>

(Preparation of 1- (1-acryloyloxy-1-methylethyl) -3-hydroxyadamantane [1a-2 (acrylate)])

A mixture of 0.3 mol of 1-adamantanol, 1.8 mol of nonacetyl, 1.5 mmol of cobalt (II) acetate and 300 ml of acetic acid was stirred at 60 ° C. for 4 hours under oxygen atmosphere (1 atm). The reaction mixture was concentrated to about 20% by weight, extracted with ethyl acetate, dried and washed with hexane to give 1-acetyl-3-adamantanol in 20% yield. In addition, the conversion rate of 1-adamantanol was 82%.

[Spectral data of 1-acetyl-3-adamantanol]

IR (cm ^-1 ): 3401, 2897, 2854, 1683, 1430, 1019, 605

¹³ C-NMR (CDCl ₃ ) δ: 24.3, 29.9, 34.8, 36.8, 43.9, 45.4, 49.6, 67.9, 212.4

1.1 mol of metal magnesium was added to the flask, and after nitrogen replacement, a solution of 1.0 mol of methyl bromide dissolved in 500 ml of ethyl ether was charged to the extent that the metal magnesium was immersed. Subsequently, a small amount of iodine was added to initiate the reaction, and the remaining ethyl ether solution of methyl bromide was added dropwise at a rate such that the solvent was gently refluxed, and the mixture was refluxed for an additional 2 hours after the completion of dropping.

To the obtained reaction mixture, a solution obtained by dissolving 1 mol of 1-acetyl-3-adamantanol in 100 ml of ethyl ether was added dropwise at a rate such that the solvent was gently refluxed. It was refluxed for 2 hours. The obtained reaction mixture was slowly added dropwise while stirring in ice-cold 10% hydrochloric acid (HCl: 1 molar equivalent), followed by further stirring at 0 ° C to room temperature for 2 hours.

10% sodium hydroxide was added to the reaction mixture to adjust the liquidity to neutral, and the liquid layer was separated into an organic layer and an aqueous layer, the aqueous layer was extracted twice with 1000 ml of ethyl ether, the organic layers were combined, concentrated, and cooled to determine 3- Hydroxy-α, α-dimethyl-l-adamantanemethanol was obtained in yield 67%.

[Spectral data of 3-hydroxy-α, α-dimethyl-1-adamantanmethanol]

MS (CI) m / e: 197, 179, 135

10 mmol of 3-hydroxy-α, α-dimethyl-l-adamantanemethanol, 10 mmol of triethylamine and 40 ml of tetrahydrofuran obtained by the above method were added dropwise over about 30 minutes to 10 mmol of acrylic acid chloride. It was. After completion of dropping, the mixture was stirred at room temperature for 6 hours. Water was added to the reaction mixture, followed by concentration. The concentrate was purified by silica gel column chromatography to obtain the title compound in a yield of 23%.

[Spectrum data]

¹ H-NMR (CDCl ₃ ) δ: 1.52 (s, 6H), 1.54-1.70 (m, 13H), 2.27 (m, 2H), 5.73 (dd, 1H), 6.04 (dd, 1H), 6.28 (dd , 1H)

<Production example 4>

(Preparation of 1-hydroxy-3- (1-methacryloyloxy-1-methylethyl) adamantane [1a-2 (methacrylate)]

The title compound was obtained in the same manner as in Production Example 3, except that methacrylic acid chloride was used instead of acrylic acid chloride.

[Spectrum data]

¹ H-NMR (CDCl ₃ ) δ: 1.52 (s, 6H), 1.54-1.70 (m, 13H), 1.92 (brs, 3H), 2.27 (m, 2H), 5.46 (brs, 1H), 6.02 (brs , 1H)

<Production example 5>

(Preparation of 1,3-dihydroxy-5- (1-methacryloyloxy-1-methylethyl) adamantane [1a-3 (methacrylate)])

A mixture of 1 mol of 1-adamantanecarboxylic acid, 0.1 mol of N-hydroxyphthalimide, 1 mmol of cobaltacetylacetonato (II), and 2.5 L of acetic acid was added at 75 ° C. under oxygen atmosphere (1 atm). Stir for hours. The reaction mixture was concentrated and then silica gel column chromatography to obtain 3,5-dihydroxy-1-adamantanecarboxylic acid.

A mixture of 300 mmol of 3,5-dihydroxy-1-adamantanecarboxylic acid obtained by the above method, 450 mmol of n-butanol, 15 mmol of sulfuric acid, and 900 ml of toluene was stirred under toluene reflux for 5 hours. The reaction mixture was concentrated and silica gel column chromatography gave 3,5-dihydroxy-1-adamantanecarboxylic acid n-butyl.

200 mmol of 3,5-dihydroxy-1-adamantanecarboxylic acid n-butyl obtained by the above method, 440 mmol of 2-methoxyethoxymethylchloride, 440 mmol of triethylamine and tetrahydrofuran (THF) 400 ml of the mixture was refluxed for 3 hours. The reaction mixture was concentrated and silica gel column chromatography gave 3,5-bis (2-methoxyethoxymethoxy) -1-adamantanecarboxylic acid n-butyl.

0.55 mol of metal magnesium was added to the flask and nitrogen-substituted, and a solution in which 0.5 mol of bromomethane was dissolved in 250 ml of THF was charged to the extent that the metallic magnesium was immersed. Subsequently, a small amount of iodine was added to initiate the reaction, and the remaining bromomethane THF solution was added dropwise at a rate such that the solvent was gently refluxed. After completion of the dropwise addition, the mixture was refluxed for an additional 2 hours to obtain a methylmagnesium bromide solution. .

A solution obtained by dissolving 100 mmol of 3,5-bis (2-methoxyethoxymethoxy) -1-adamantanecarboxylic acid n-butyl obtained by the above method in 150 ml of THF was dissolved in the methylmagnesium bromide solution. Was added dropwise at a rate of mild reflux, and refluxed for an additional 2 hours after completion of dropping. The obtained reaction mixture was added dropwise while stirring in ice-cold 10 wt% hydrochloric acid, and further stirred at O ° C to room temperature for 2 hours. 10% by weight of aqueous sodium hydroxide solution was added to the reaction mixture to adjust the liquidity to neutral, and the liquid layer was separated into an organic layer and an aqueous layer, the aqueous layer was extracted with toluene, the organic layer was concentrated, and the concentrated solution was purified by silica gel column chromatography to form α, α-dimethyl. -3,5-bis (2-methoxyethoxymethoxy) -1-adamantanemethanol was obtained.

Methacrylic to a mixture of 20 mmol of α, α-dimethyl-3,5-bis (2-methoxyethoxymethoxy) -1-adamantanemethanol, 40 mmol of triethylamine and 80 ml of THF obtained by the above method. 30 mmol of acid chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After adding water to the reaction mixture, the mixture was extracted with ethyl acetate, the organic layer was concentrated, and the concentrate was purified by silica gel column chromatography to obtain 1- (1-methacryloyloxy-1-methylethyl) -3,5-bis ( 2-methoxyethoxymethoxy) adamantane was obtained.

10 mmol of 1- (1-methacryloyloxy-1-methylethyl) -3,5-bis (2-methoxyethoxymethoxy) adamantane obtained by the above method, 1 mmol of 6N-HCl (HCl ), And 40 ml of acetone were stirred at room temperature for 5 hours. An aqueous ammonium chloride solution was added to the reaction mixture, extraction was performed with ethyl acetate, the organic layer was concentrated, and the concentrate was purified by silica gel column chromatography to obtain the title compound.

[Spectrum data]

¹ H-NMR (500 MHz, DMSO-d ₆ ) δ: 1.33-1.97 (m, 21H), 2.22 (m, 1H), 4.68 (brs, 2H), 5.74 (brs, 1H), 5.91 (brs, 1H )

<Production example 6>

(Preparation of 1-acryloyloxy-3-hydroxyadamantane [2a-1 (acrylate)])

To the mixture of 10 mmol of 1,3-adamantanediol, 15 mmol of triethylamine and 100 ml of tetrahydrofuran, 13 mmol of acrylic acid chloride was added dropwise over about 30 minutes. After completion of dropwise addition, the mixture was stirred at 50 ° C for 1.5 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate, the organic layer was concentrated, and the concentrate was purified by silica gel column chromatography to obtain the title compound in a yield of 63%.

[Spectrum data]

¹ H-NMR (CDCl ₃ ) δ: 1.47-1.61 (m, 2H), 1.62-1.80 (m, 5H), 2.00-2.17 (m, 6H), 2.34 (m, 2H), 5.75 (dd, 1H) , 6.03 (dd, 1H), 6.30 (dd, 1H)

<Production example 7>

(Preparation of 1-hydroxy-3-methacryloyloxyadamantane [2a-1 (methacrylate)])

The title compound was obtained in the same manner as in Production Example 6 except that methacrylic acid chloride was used instead of acrylic acid chloride.

[Spectrum data]

¹ H-NMR (CDCl ₃ ) δ: 1.48-1.61 (m, 6H), 1.89 (s, 3H), 2.00-2.16 (m, 7H), 2.34 (m, 2H), 5.49 (brs, 1H), 6.01 (brs, 1H)

<Production example 8>

(Production of 1-acryloyloxy-3,5-dihydroxyadamantane [2a-2 (acrylate)])

The title compound was obtained in the same manner as in Production Example 6 except that 1,3,5-adamantanetriol was used instead of 1,3-adamantanediol.

[Spectrum data]

¹ H-NMR (CDCl ₃ ) δ: 1.54-1.87 (m, 6H), 1.90-2.80 (m, 9H), 5.78 (dd, 1H), 6.04 (dd, 1H), 6.31 (dd, 1H)

<Production example 9>

(Preparation of 1,3-dihydroxy-5-methacryloyloxyadamantane [2a-2 (methacrylate)])

The title compound was obtained in the same manner as in Production Example 6, except that 1,3,5-adamantanetriol was used instead of 1,3-adamantanediol and methacrylic acid chloride was used instead of acrylic acid chloride.

[Spectrum data]

¹ H-NMR (DMSO-d ₆ ) δ: 1.35-1.95 (m, 13H), 2.23 (m, 1H), 4.73 (s, 2H), 5.59 (brs, 1H), 5.92 (brs, 1H)

<Production example 10>

(Preparation of 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone [5a-3 (methacrylate)])

A mixture of 3 mmol of ethyl acrylate, 3 ml of 2-propanol, 0.6 mmol of N-hydroxyphthalimide, 0.003 mmol of cobalt acetate (II), 0.015 mmol of cobaltacetylacetonato (III), and 1 ml of acetonitrile was oxygenated. Under atmosphere (1 atm), the mixture was stirred at 60 ° C. for 12 hours. The reaction mixture was concentrated and the concentrate was purified by silica gel chromatography to give 2-hydroxy-4,4-dimethyl-γ-butylolactone in a yield of 75%.

[Spectral data of 2-hydroxy-4,4-dimethyl-γ-butyrolactone]

¹ H-NMR (CDCl ₃ ) δ: 1.42 (s, 3H), 1.51 (s, 3H), 2.06 (dd, 1H), 2.52 (dd, 1H), 3.03 (brs, 1H), 4.63 (t, 1H )

A mixture of 100 mmol of 2-hydroxy-4,4-dimethyl-γ-butyrolactone obtained by the above method, 150 mmol of methacrylic acid chloride, 150 mmol of triethylamine and 300 ml of toluene was stirred at 25 ° C. for 4 hours. It was. After adding water to the reaction mixture, the organic layer was concentrated and the concentrated solution was purified by silica gel column chromatography to give 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone in a yield of 85%.

[Spectral data of 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone]

¹ H-NMR (CDCl ₃ ) δ: 1.47 (s, 3H), 1.54 (s, 3H), 1.92 (s, 3H), 2.10 (dd, 1H), 2.63 (dd, 1H), 5.63 (brs, 1H ), 5.94 (m, 1 H), 6.18 (brs, 1 H)

<Production example 11>

(Production of 2-acryloyloxy-2,4,4-trimethyl-γ-butyrolactone [5a-4 (acrylate)])

The title compound was obtained in the same manner as in Production Example 10 except that ethyl methacrylate was used instead of ethyl acrylate and acrylate was used instead of methacrylic acid chloride.

[Spectrum data]

¹ H-NMR (CDCl ₃ ) δ: 1.47 (s, 3H), 1.59 (s, 3H), 1.68 (s, 3H), 2.20 (dd, 1H), 2.63 (dd, 1H), 5.90 (dd, 1H ), 6.13 (dd, 1H), 6.46 (dd, 1H)

<Production example 12>

(Preparation of 3-methacryloyloxy-4,4-dimethyl-γ-butyrolactone [5a-15 (methacrylate)])

By reacting the 2-hydroxy-4,4-dimethyl-γ-butylarolactone obtained by the method of Production Example 10 with an equivalent of P ₂ O ₅ at room temperature in dioxane (dehydration reaction), the corresponding α, β- Unsaturated- [gamma] -butyrolactone was obtained (yield 30%). This was then reacted with m-chloroperbenzoic acid (MCPBA) in methylene chloride at room temperature to give 2,3-epoxy-4,4-dimethyl-γ-butyrolactone (yield 85%). Hydrogen was bubbled at room temperature for 11 hours in a mixture of 10 mmol of 2,3-epoxy-4,4-dimethyl-γ-butylarolactone, 1 g of 5 wt% Pd-C, and 20 ml of tetrahydrofuran. The reaction mixture was filtered and concentrated, and the concentrate was purified by silica gel column chromatography to give 3-hydroxy-4,4-dimethyl-γ-butylolactone in a yield of 63%.

The title compound was obtained by yielding the obtained 3-hydroxy-4,4-dimethyl-γ-butylolactone in the same manner as in Production Example 10 to react with methacrylic acid chloride (yield 87%).

[Spectrum data]

MS m / e: 199 (M ⁺ )

IR (cm ^-1 ): 3045, 1772, 1190

<Production example 13>

(Production of 3-acryloyloxy-3,4,4-trimethyl-γ-butyrolactone [5a-16 (acrylate)])

Except having used ethyl crotonate instead of ethyl acrylate, it carried out similarly to manufacture example 10, and obtained 2-hydroxy-3,4,4-trimethyl- (gamma)-butyrolactone in 15% yield. By reacting the obtained 2-hydroxy-3,4,4-trimethyl-γ-butylolactone with an equivalent amount of P ₂ O _{5 in} dioxane at room temperature (dehydration reaction), the corresponding α, β-unsaturated-γ-butyl Lolactone was obtained (yield 34%). This was then reacted with m-chloroperbenzoic acid (MCPBA) in methylene chloride at room temperature to give 2,3-epoxy-3,4,4-trimethyl- [gamma] -butyrolactone (yield 75%). Hydrogen was bubbled at room temperature for 11 hours in a mixture of 10 mmol of 2,3-epoxy-3,4,4-trimethyl-γ-butylarolactone, 1 g of 5 wt% Pd-C, and 20 ml of tetrahydrofuran. . The reaction mixture was filtered and concentrated, and the concentrate was purified by silica gel column chromatography to give 3-hydroxy-3,4,4-trimethyl-γ-butyrolactone in 82% yield.

The title compound was obtained (yield 85%) by reacting the obtained 3-hydroxy-3,4,4-trimethyl-γ-butyrolactone with acrylic acid chloride according to the method of Preparation Example 10.

[Spectrum data]

MS m / e: 199 (M ⁺ )

IR (cm ^-1 ): 3020, 1768, 1210

¹ H-NMR (CDCl ₃ ) δ: 1.43 (s, 3H), 1.51 (s, 3H), 1.63 (s, 3H), 2.92 (d, 1H), 3.30 (d, 1H), 5.92 (dd, 1H ), 6.14 (dd, 1H), 6.44 (dd, 1H)

<Example 1>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 2.00 g (8.1 mmole) of monomer [1a-1] (acrylate), 7.17 g (32.3 mmole) of monomer [2a-1] (acrylate) and initiator (Va65 manufactured by Wako Pure Chemical Industries, Ltd.) 0.92 g) was dissolved in 25 g of THF (tetrahydrofuran) to make a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C., stirred for 10 hours, the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Moreover, the target resin 6.82 g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8500 and dispersion degree (M _w / M _n ) of 2.06. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.6, 1.9, 2.1 and 4.6 ppm.

<Example 2>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 2.00 g (7.6 mmole) of monomer [1a-1] (methacrylate), 7.17 g (30.4 mmole) of monomer [2a-2] (methacrylate), and an initiator (product of Wako Pure Chemical Industries, Ltd. V) -65) 0.92 g was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Moreover, the target resin 6.82 g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8200 and dispersion degree (M _w / M _n ) of 2.26. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.9 (brs), 1.5, 1.9, 2.1 and 4.6 ppm.

<Example 3>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 2.OO g (7.6 mmole) of monomer [1a-1] (methacrylate), 8.51 g (30.4 mmole) of monomer [1a-2] (methacrylate) and initiator (Wako Pure Chemical Industries, Ltd.) 1.05 g of product V-65) was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Moreover, 6.52 g of the target resin was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8100 and dispersion degree (M _w / M _n ) of 2.37. ^{In the 1} NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.6, 1.9, 2.1 and 4.6 ppm.

<Example 4>

Synthesis of the Following Structural Resins

4.5 g (17.2 mmole) of monomer [1a-1] (methacrylate), 4.82 g (17.2 mmole) of monomer [1a-3] (methacrylate) and initiator (Wako Pure Chemical Industries, Ltd. product V) in an Erlenmeyer flask -65) 0.98 g was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.52 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 8300 and dispersion degree (M _w / M _n ) of 2.21. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1 and 4.6 ppm.

<Example 5>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 3.66 g (14.0 mmole) of monomer [1a-1] (methacrylate), 5.5O g (23.3 mmole) of monomer [2a-1] (methacrylate), monomer [5a-3] (methacrylate) ) 1.84 g (9.3 mmole) and an initiator (1.10 g of Wako Pure Chemical Industries, Ltd. V-65) were added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes under a nitrogen atmosphere using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was dropped into 500 ml of hexane, and the resulting precipitate was filtered out. Furthermore, the target resin 8.76 g was obtained by performing re-precipitation operation once again. GPC analysis of the recovered polymer showed M _w of 7200 and dispersion degree (M _w / M _n ) of 1.99. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 4.6 and 5.3 ppm.

<Example 6>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 3.33 g (13.4 mmole) of monomer [1a-1] (acrylate), 4.95 g (22.3 mmole) of monomer [2a-1] (acrylate), 1.65 g of monomer [5a-4] (acrylate) ( 8.3 mmole) and 0.96 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.42 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 7200 and dispersion degree (M _w / M _n ) of 1.99. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1 and 4.6 ppm.

<Example 7>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 2.20 g (8.4 mmole) of monomer [1a-1] (methacrylate), 7.88 g (33.3 mmole) of monomer [2a-1] (methacrylate), monomer [5a-15] (methacrylate) A monomer solution was prepared by dissolving 1.11 g (4.2 mmole) and 1.11 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) in 25 g of THF. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, 8.62 g of the target resin was obtained by performing the reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 9400 and dispersion degree (M _w / M _n ) of 2.38. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.9 (brs), 1.6, 1.9, 2.1, 4.3 and 4.6 ppm.

<Example 8>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 3.45 g (13.9 mmole) of monomer [1a-1] (acrylate), 5.18 g (23.2 mmole) of monomer [2a-1] (acrylate), 1.85 g of monomer [5a-16] (acrylate) 9.3 mmole) and 1.08 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes in a nitrogen atmosphere using a liquid pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Moreover, the target resin 8.23g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8800 and dispersion degree (M _w / M _n ) of 2.15. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 4.3 and 4.6 ppm.

<Example 9>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 2.23 g (8.5 mmole) of monomer [1a-1] (methacrylate), 6.05 g (24.6 mmole) of monomer [2a-1] (methacrylate), monomer [6a-1] (methacrylate) 1.57 g (8.6 mmole) and 0.98 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the prepared monomer solution was introduced into the reaction system over 90 minutes in a nitrogen atmosphere using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.68 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 8400 and dispersion degree (M _w / M _n ) of 2.38. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 3.6, 3.9, 4.6, and 5.9 ppm.

<Example 10>

Synthesis of the Following Structural Resins

In an Erlenmeyer flask, 5.1O g (19.3 mmole) of monomer [1a-2] (acrylate), 4.33 g (19.3 mmole) of monomer [2a-1] (acrylate) and initiator (Vako Sanya Kogyo Co., Ltd. product V- 65) 0.94 g was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.91 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 8900 and dispersion degree (M _w / M _n ) of 2.28. ^{In the 1} H-NMR (in DMS0-d ₆ ) spectrum, signals were observed at 0.8-2.4 (brs), 1.6, 1.9, 2.1 and 4.6 ppm.

<Example 11>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 5.O5 g (18.2 mmole) of monomer [1a-2] (methacrylate), 4.58 g (18.2 mmole) of monomer [2a-2] (methacrylate) and initiator (Wako Pure Chemical Industries, Ltd.) 0.96 g of product V-65) was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the end of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was filtered and separated and again subjected to reprecipitation purification operation. 8.04 g was obtained. GPC analysis of the recovered polymer showed M _w of 8300 and dispersion degree (M _w / M _n ) of 2.18. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.6, 1.9, 2.1 and 4.6 ppm.

<Example 12>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 8.O3 g (28.9 mmole) of monomer [1a-2] (methacrylate), 2.28 g (12.4 mmole) of monomer [6a-1] (methacrylate) and initiator (Wako Pure Chemical Industries, Ltd.) 1.03 g of product V-65) was added and dissolved in 25 g of THF to make a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the prepared monomer solution was introduced into the reaction system over 90 minutes in a nitrogen atmosphere using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 8.11g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8700 and dispersion degree (M _w / M _n ) of 2.31. Signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1 and 4.6 ppm in the ¹ H-NMR (in DMSO-d ₆ ) spectrum.

<Example 13>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 8.O1 g (28.8 mmole) of monomer [1a-2] (methacrylate), 1.43 g (7.20 mmole) of monomer [5a-3] (methacrylate) and initiator (Wako Pure Chemical Industries, Ltd.) 0.94 g of product V-65) was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.68 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 8500 and dispersion degree (M _w / M _n ) of 2.21. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 4.6 and 5.3 ppm.

<Example 14>

Synthesis of the Following Structural Resins

In an Erlenmeyer flask, 8.5O g (32.2 mmole) of monomer [1a-2] (acrylate), 1.51 g (8.1 mmole) of monomer [5a-4] (acrylate) and initiator (Vaco Co., Ltd. product V- 65) 1.00 g was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 8.24 g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8700 and dispersion degree (M _w / M _n ) of 2.38. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1 and 4.6 ppm.

<Example 15>

Synthesis of the Following Structural Resins

In an Erlenmeyer flask, 8.5O g (30.8 mmole) of monomer [1a-2] (methacrylate), 1.5O g (7.6 mmole) of monomer [5a-15] (methacrylate) and initiator (Wako Pure Chemical Industries, Ltd.) 1.00 g of product V-65) was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 8.24 g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8700 and dispersion degree (M _w / M _n ) of 2.38. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 4.3, 4.6 and 5.3 ppm.

<Example 16>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 8.40 g (30.2 mmole) of monomer [1a-2] (methacrylate), 1.6O g (7.6 mmole) of monomer [5a-16] (methacrylate) and initiator (from Wako Pure Chemical Industries, Ltd.) 1.00 g of V-65) was added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Moreover, the target resin 8.64g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8200 and dispersion degree (M _w / M _n ) of 2.29. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.6, 1.9, 2.1, 4.3 and 4.6 ppm.

<Example 17>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 4.55 g (16.4 mmole) of monomer [1a-2] (methacrylate), 3.86 g (16.4 mmole) of monomer [2a-1] (methacrylate), monomer [5a-3] (methacrylate) 1.62 g (8.2 mmole) and 1.01 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced into the reaction system over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 8.18 g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8100 and dispersion degree (M _w / M _n ) of 2.07. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 4.6 and 5.3 ppm.

<Example 18>

Synthesis of the Following Structural Resins

In an Erlenmeyer flask, 4.54 g (17.2 mmole) of monomer [1a-2] (acrylate), 3.83 g (17.2 mmole) of monomer [2a-1] (acrylate), 1.62 g of monomer [5a-4] (acrylate) ( 8.6 mmole) and 1.00 g of an initiator (V-65 from Wako Pure Chemical Industries, Ltd.) were added thereto and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.99 g was obtained by performing reprecipitation operation once again. GPC analysis of the recovered polymer showed M _w of 8100 and dispersion degree (M _w / M _n ) of 2.07. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.6, 1.9, 2.1 and 4.6 ppm.

<Example 19>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 4.54 g (16.4 mmole) of monomer [1a-2] (methacrylate), 3.83 g (16.2 mmole) of monomer [2a-1] (methacrylate), monomer [5a-15] (methacrylate) 1.81 g (8.2 mmole) and 1.02 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 8.29 g was obtained by performing reprecipitation refinement | purification operation once again. GPC analysis of the recovered polymer showed M _w of 8700 and dispersion degree (M _w / M _n ) of 2.02. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 4.3 and 5.3 ppm.

<Example 20>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 4.76 g (18.0 mmole) of monomer [1a-2] (acrylate), 4.04 g (18.0 mmole) of monomer [2a-1] (acrylate), 1.81 g of monomer [5a-16] (acrylate) 9.0 mmole) and 1.06 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 50 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.99 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 8100 and dispersion degree (M _w / M _n ) of 2.07. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.6, 1.9, 2.1 and 4.6 ppm.

<Example 21>

Synthesis of the Following Structural Resins

In a Erlenmeyer flask, 3.54 g (12.7 mmole) of monomer [1a-2] (methacrylate), 6.2 g (25.5 mmole) of monomer [2a-1] (methacrylate), monomer [6a-1] (methacryl) 0.78 g (8.2 mmole) and 1.03 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved in 25 g of THF to prepare a monomer solution. On the other hand, 15 g of THF was put into a 100 ml flask equipped with a reflux tube and a three-way coke, and the monomer solution prepared first was introduced in a nitrogen atmosphere over 90 minutes using a liquid feeding pump. After the completion of the liquid feeding, the temperature was maintained at 60 ° C. and stirred for 10 hours, and then the reaction solution was poured into 500 ml of hexane, and the resulting precipitate was separated by filtration. Furthermore, the target resin 7.63 g was obtained by performing reprecipitation purification operation once again. GPC analysis of the recovered polymer showed M _w of 8400 and dispersion degree (M _w / M _n ) of 2.28. ^{In the 1} H-NMR (in DMSO-d ₆ ) spectrum, signals were observed at 0.8-2.5 (brs), 1.5, 1.9, 2.1, 3.6, 3.9, 4.6, and 5.9 ppm.

<Test Example>

100 parts by weight of the polymer obtained in the examples and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with ethyl lactate as a solvent to prepare a resin composition for photoresist having a polymer concentration of 17% by weight. This resin composition for photoresist was apply | coated to a silicon wafer by the spin coating method, and the photosensitive layer of 1.0 micrometer thickness was formed. After prebaking at a temperature of 100 ° C. for 150 seconds on a hot plate, the composition was exposed to a dose of 30 mJ / cm ² through a mask using a KrF excimer laser having a wavelength of 247 nm, and then post-baked at a temperature of 100 ° C. for 60 seconds. Subsequently, development was performed with 0.3 M tetramethylammonium hydroxide aqueous solution for 60 seconds, and it wash | cleaned with pure water, and the line and space pattern of 0.25 micrometer was obtained in all cases.

According to the present invention, since the polymer includes a monomer unit having an adamantane skeleton having a specific structure, it is possible to provide high etching resistance while maintaining excellent transparency, alkali solubility and adhesion.

Claims (7)

A polymer compound comprising at least one monomer unit represented by the following formula (1). <Formula 1> In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> and R <^3> is the same or different, and represents a hydrogen atom or a hydroxyl group. The polymer compound according to claim 1, comprising at least one monomer unit represented by Formula 1 and at least one monomer unit selected from Formulas 2a and 2b. <Formula 2a> <Formula 2b> In the formula, R ¹ represents a hydrogen atom or a methyl group, R ⁴ and R ⁵ are the same or different, and represent a hydrogen atom, a hydroxyl group, an oxo group, a carboxyl group or a -COOR ⁶ group, and R ⁶ is a t-butyl group , 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group or 2-oxepanyl group. However, R ⁴ and R ⁵ may not be a hydrogen atom at the same time. R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a hydroxyl group or an oxo group. The monomer unit represented by the following formula (3), the monomer unit represented by the following formula (4), the monomer unit represented by the following formulas (5a) and 5b, the monomer unit represented by the following formula (6), and the following formula: A polymer compound comprising at least one monomer unit selected from monomer units represented by 7. <Formula 3> In the formula, R ¹ and R ⁹ are the same or different and represent a hydrogen atom or a methyl group. <Formula 4> In the formula, R ¹⁰ is a tricyclo [5.2.1.0 ^2,6 ] decylmethyl group, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] a dodecylmethyl group, a norbornyl group, an isobornyl group, or a 2-norbornylmethyl group, R ¹¹ is a substituent of R ¹⁰ , a hydrogen atom, a hydroxyl group, a hydroxymethyl group, a carboxyl group or- Represents a COOR ¹² group, and R ¹² represents a t-butyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group or 2-oxepanyl group. R ¹ is the same as above. <Formula 5a> <Formula 5b> In formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> and R <^20> are the same or different, and represent a hydrogen atom or a methyl group. R ¹ is the same as above. <Formula 6> In formula, n represents the integer of 1-3. R ¹ is the same as above. <Formula 7> In formula, R <^1> is the same as the above. The polymer compound according to any one of claims 1 to 3, wherein the total content of monomer units having an adamantane skeleton is 50 to 100% by weight of the total monomer units constituting the polymer. The polymer compound according to any one of claims 1 to 3, wherein the total content of monomer units having an adamantane skeleton is 70 to 100% by weight of the total monomer units constituting the polymer. The high molecular compound in any one of Claims 1-5 used as resin for photoresists. A resin composition for photoresists comprising the polymer compound according to any one of claims 1 to 5 and a photoacid generator.