JP2008115148A - Polymerizable monomer and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable monomer and its production method that can give a polymer having a naphthyl-group skeleton containing a hydrophilic group for contributing to improvement in line edge roughness in a resist, good copolymerizability with a polymerizable monomer such as (meth)acrylic acid or a (meth)acrylic ester, uniform composition and high light transmittance at a wave length of 193 nm. <P>SOLUTION: In the production method for the polymerizable monomer, a polymerizable monomer with a specific naphthalene skeleton is reacted with a specific monomer under specific conditions. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymerizable monomer useful for a (meth) acrylic polymer and a method for producing the same. In particular, it relates to a monomer useful for a resist polymer and a method for producing the monomer.

In recent years, in the field of microfabrication in the manufacture of semiconductor elements and liquid crystal elements, miniaturization has rapidly progressed due to advances in lithography technology. As a technique for miniaturization, generally, the wavelength of irradiation light is shortened. Specifically, the irradiation light has changed from conventional ultraviolet rays represented by g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm) to DUV (Deep Ultra Violet) having a shorter wavelength.
At present, KrF excimer laser (wavelength: 248 nm) lithography technology has been introduced to the market, and ArF excimer laser (wavelength: 193 nm) lithography technology for further shortening the wavelength is being studied. Furthermore, recently, these immersion lithography techniques have also been studied. As a high-resolution resist using such short-wavelength irradiation light or electron beam, a “chemically amplified resist” containing a photoacid generator has been proposed, and improvement and development of this chemically amplified resist are currently underway. It has been.

For example, as a chemically amplified resist polymer used in ArF excimer laser lithography, an acrylic polymer that is transparent to light having a wavelength of 193 nm has attracted attention. As such an acrylic polymer, a polymer obtained by polymerizing a (meth) acrylic acid ester having an adamantane skeleton in an ester portion and a (meth) acrylic acid ester monomer having a lactone skeleton in an ester portion has been studied ( For example, see Patent Document 1 and Patent Document 2).
However, the acrylic polymers described in Patent Document 1 and Patent Document 2 may have a large sidewall roughness (hereinafter referred to as “line edge roughness”) of the resist pattern. Moreover, there is a concern that the resist is insufficient in dry etching resistance due to the thinning of the resist film thickness.

On the other hand, in order to improve the problem of line edge roughness, Patent Document 3 describes a polymer having a hydroxyvinylnaphthalene monomer unit.
However, although the polymer having a hydroxyvinylnaphthalene monomer unit has a hydrophilic group-containing naphthyl skeleton, the problem of line edge roughness is improved, but hydroxyvinylnaphthalene and (meth) acrylic acid or (meth) acrylic acid ester, etc. When it is copolymerized with the polymerizable monomer, it cannot be said that the copolymerizability is sufficient, the composition distribution of the polymer is wide, and the uniformity of the polymer composition is not sufficient. Moreover, when this polymer is used for ArF excimer laser (wavelength: 193 nm) lithography, the light transmittance of the polymer at the exposure wavelength may not be sufficient, which may adversely affect the sensitivity and resolution of the resist composition. is there.
JP 10-319595 A JP-A-10-274852 JP 2004-163877 A

  The present invention has a hydrophilic group-containing naphthyl group skeleton to contribute to the improvement of the line edge roughness of the resist, and is copolymerized with a polymerizable monomer such as (meth) acrylic acid or (meth) acrylic acid ester. An object of the present invention is to provide a polymerizable monomer capable of obtaining a polymer having good copolymerizability, a uniform composition, and a high light transmittance at a wavelength of 193 nm, and a method for producing the same.

In the present invention, a polymerizable monomer having a naphthalene skeleton represented by the following formula (1) is a first invention.
The present invention also provides a polymerizable monomer represented by the following formula (3), wherein the following formula (1-11) and the following formula (1-12) are reacted at a temperature of 0 to 50 ° C. under basic conditions. This manufacturing method is the second invention.

（式（１）中、Ｒ¹⁰は水素原子又はメチル基を表す。Ｇは−Ｃ(＝Ｏ)−Ｏ−、−Ｏ−又はＯ−Ｃ(＝Ｏ)−のいずれかを表す。Ｌ¹は直接結合又は炭素数１〜２０の直鎖、分岐若しくは環状の２価の炭化水素基を表す。この２価の炭化水素基はヘテロ原子を有していてもよい。Ｙは−Ｃ(＝Ｏ)−ＯＨ、−ＯＨ、−Ｃ(＝Ｏ)−Ｏ−Ｒ^１１又はＯ−Ｒ^１１を表す。Ｒ^１１は炭素数１〜２０の直鎖、分岐又は環状の炭化水素基を表す。この炭化水素基はヘテロ原子を有していてもよい。ｇ１は０又は１である。ｈ２は１〜７の整数である。）

(In the formula (1), R ¹⁰ represents a hydrogen atom or a methyl group. G represents any of —C (═O) —O—, —O—, or O—C (═O) —. L ¹ Represents a direct bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and this divalent hydrocarbon group may have a hetero atom, Y represents —C (= O) -OH, -OH, -C ( = O) .R 11 representing a ^{-O-R 11} or ^{O-R 11} represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. the (The hydrocarbon group may have a hetero atom. G1 is 0 or 1. h2 is an integer of 1 to 7.)

（式（１−１１）中、Ｙは−Ｃ(＝Ｏ)−ＯＨ、−ＯＨ、−Ｃ(＝Ｏ)−ＯＲ¹³又は−ＯＲ¹³を表す。Ｒ¹³は炭素数１〜２０の直鎖、分岐又は環状の炭化水素基を表す。この炭化水素基はヘテロ原子を有していてもよい。Ｌ¹”は炭素数１〜４の直鎖炭化水素基を表す。）

(In formula (1-11), Y represents —C (═O) —OH, —OH, —C (═O) —OR ¹³ or —OR ¹³ , where R ¹³ is a straight chain having 1 to 20 carbon atoms. Represents a branched or cyclic hydrocarbon group. This hydrocarbon group may have a hetero atom. L ¹ ″ represents a straight-chain hydrocarbon group having 1 to 4 carbon atoms.)

（式（１−１２）中、Ｒ¹⁰は水素原子又はメチル基を表す。Ｚはハロゲン原子又はＯ−Ｃ（＝Ｏ）Ｃ（ＣＨ_２）Ｒ¹⁰を表す。）

(In formula (1-12), R ¹⁰ represents a hydrogen atom or a methyl group. Z represents a halogen atom or O—C (═O) C (CH ₂ ) R ^10. )

（式（３）中、Ｒ¹⁰は水素原子又はメチル基を表す。Ｙは−Ｃ(＝Ｏ)−ＯＨ、−ＯＨ、−Ｃ(＝Ｏ)−ＯＲ¹³又は−ＯＲ¹³を表す。Ｒ¹³は炭素数１〜２０の直鎖、分岐又は環状の炭化水素基を表す。この炭化水素基はヘテロ原子を有していてもよい。また、Ｌ¹”は炭素数１〜４の直鎖炭化水素基を表す。）

(In the formula (3), R ¹⁰ represents a hydrogen atom or a methyl group. Y represents —C (═O) —OH, —OH, —C (═O) —OR ¹³ or —OR ¹³ .R ¹³ Represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. This hydrocarbon group may have a hetero atom. L ¹ ″ represents a linear carbon atom having 1 to 4 carbon atoms. Represents a hydrogen group.)

  When the polymerizable monomer of the present invention is copolymerized with a monomer such as (meth) acrylic acid or (meth) acrylic acid ester, the copolymerizability is good, and a polymer having a uniform composition can be obtained. Moreover, since the obtained polymer has a high light transmittance at a wavelength of 193 nm, the resist obtained is excellent in dry etching resistance and line edge roughness, particularly when used in ArF excimer laser lithography and this immersion lithography.

A polymerizable monomer having a naphthalene skeleton represented by the formula (1)

The polymerizable monomer of the present invention (hereinafter referred to as “the present polymerizable monomer”) has a naphthalene skeleton represented by the following formula (1).

Here, G in Formula (1) represents either -C (= O) -O-, -O-, or O-C (= O)-.
Among these, —C (═O) —O— is preferable from the viewpoint of copolymerization with a monomer such as (meth) acrylic acid or (meth) acrylic acid ester.
L ¹ in the formula (1) represents a direct bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms. This divalent hydrocarbon group may have a hetero atom.
Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
Examples of the linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms include the following formulas (2-1) to (2-33).

L ¹ is a point of light transmittance at a wavelength of 193 nm and a point of copolymerization with a monomer such as (meth) acrylic acid or (meth) acrylic acid ester, and the formulas (2-1) to (2-4) Formula (2-8) to Formula (2-13), Formula (2-16), and Formula (2-18) to Formula (2-20) are preferable.
G1 is 0 or 1. g1 is preferably 0 in terms of light transmittance at a wavelength of 193 nm.
Y represents —C (═O) —OH, —OH, —C (═O) —O—R ¹¹ or —O—R ¹¹ . R ¹¹ represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. This hydrocarbon group may have a hetero atom.
Y is preferably —OH or —O—R ^{11 and} more preferably —OH in terms of light transmittance at a wavelength of 193 nm.
Examples of R ¹¹ include the following formulas (3-1) to (3-27).

In order to facilitate the deprotection of R ¹¹ with an acid, Formula (3-1), Formula (3-2), Formula (3-4), Formula (3-5), Formula (3-7), Formula (3-8), formula (3-13), formula (3-23), formula (3-25) and formula (3-27) are preferred, and formula (3-2), formula (3-4), Formula (3-5), formula (3-7), formula (3-8), formula (3-13), formula (3-23), and formula (3-25) are more preferable.

  Examples of the polymerizable monomer include monomers represented by the following formulas (8-1) to (8-24).

Among these, the present polymerizable monomer is represented by formulas (8-3) to (8) in terms of copolymerizability with (meth) acrylic acid and (meth) acrylic acid ester and light transmittance of the polymer with respect to a wavelength of 193 nm. (8-16), Formula (8-19), Formula (8-12), and Formula (8-20) to Formula (8-24) are preferable, and Formula (8-3), Formula (8-4), Formula (8-10) and formula (8-13) to formula (8-16) are more preferable. Particularly preferred are the formulas (8-3) and (8-16).
Among the present polymerizable monomers, a polymerizable monomer represented by the following formula (2) is preferable in terms of copolymerizability and light transmittance of the polymer with respect to a wavelength of 193 nm, and a monomer represented by the following formula (3) Is more preferable, and the polymerizable monomer represented by the following formula (4) is particularly preferable.

In formula (2), R ¹⁰ , G, g1 and Y have the same meaning as in formula (1). L ¹ ′ represents a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms. This divalent hydrocarbon group may have a hetero atom.
In formula (3), R ¹⁰ and Y have the same meaning as in formula (1). L ¹ ″ represents a linear hydrocarbon group having 1 to 4 carbon atoms.
In formula (4), L ¹ ″ has the same meaning as in formula (3).
Examples of the monomer represented by formula (2) include formula (8-3) to formula (8-16) and formula (8-19) to formula (8-24).
Examples of the monomer represented by Formula (3) include Formula (8-4), Formula (8-10), and Formula (8-13) to Formula (8-16).
As a monomer represented by Formula (4), Formula (8-3) is mentioned, for example.

Production method of the present polymerizable monomer

（Ｒ¹⁰は水素原子又はメチル基を表す。） The polymerizable monomer can be produced by a known method. Specific examples will be described below by using Expression (8-1), Expression (8-3), Expression (8-7), and Expression (8-16) as examples.
The polymerizable monomer represented by the formula (8-1) can be esterified with one alcohol of 2,6-dihydroxynaphthalene represented by the following formula (9-1) to form a (meth) acryloyloxy group.

(R ¹⁰ represents a hydrogen atom or a methyl group.)

Examples of the esterification method include a method of reacting 2,6-dihydroxynaphthalene with anhydrous (meth) acrylic acid or (meth) acrylic acid chloride in the presence of an acid catalyst or a base.
Examples of the acid catalyst include acids such as hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid, and acetic acid, and Lewis acids containing atoms such as hafnium, zirconium, yttrium, and ytterbium.
As the usage-amount of an acid catalyst, 0.1-10 mol part is preferable with respect to 100 mol part of 2, 6- dihydroxy naphthalene. When the amount of the acid catalyst used is 0.1 mol part or more, the reaction rate tends to be increased, and when it is 10 mol part or less, the production of by-products tends to be suppressed. The lower limit value of the amount of the acid catalyst used is more preferably 0.5 mol parts or more, and the upper limit value is more preferably 3 mol parts or less.

Examples of the base include bases containing alkali metals such as potassium carbonate, sodium hydroxide, potassium hydroxide, sodium (meth) acrylate, potassium (meth) acrylate, triethylamine, pyridine, dimethylaminopyridine and the like. An organic base is mentioned.
The amount of base used is preferably 0.5 to 10 mole parts per 100 mole parts of 2,6-dihydroxynaphthalene. As for the usage-amount of a base, 1-8 mol part is more preferable at the point of a by-product.
The amount of anhydrous (meth) acrylic acid or (meth) acrylic acid chloride to be used is preferably 50 to 500 mol parts per 100 mol parts of 2,6-dihydroxynaphthalene. When the amount of anhydrous (meth) acrylic acid or (meth) acrylic acid chloride used is 50 mol parts or more, the present polymerizable monomer of the formula (8-1) tends to be obtained with good yield. Moreover, when the amount of anhydrous (meth) acrylic acid or (meth) acrylic acid chloride is 500 mol parts or less used, the production of di (meth) acrylate as a by-product tends to be suppressed. The amount of anhydrous (meth) acrylic acid or (meth) acrylic acid chloride used is more preferably 95 to 150 mol parts.

The reaction temperature is preferably -20 ° C to 100 ° C. When the reaction temperature is −20 ° C. or higher, the present polymerizable monomer tends to be obtained with good yield. Moreover, when reaction temperature is 100 degrees C or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product. The reaction temperature is more preferably 0 to 60 ° C.
In the present invention, a solvent can be used for the above reaction. Examples of the solvent include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform and benzene. Of these, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and acetonitrile are preferred from the viewpoint of the solubility of 2,6-dihydroxynaphthalene.

  Further, the polymerizable monomer represented by the formula (8-1) can be produced by a method other than the above method. For example, 2-bromo-6-t-butoxycarbonyloxynaphthalene represented by the following formula (9-2) or 2-chloro-6-t-butoxycarbonyloxynaphthalene represented by the following formula (9-3) and (meta ) Acrylic acid metal salt is esterified in the presence of an interlayer catalyst to obtain 2- (meth) acryloyloxy-6-t-butoxycarbonyloxynaphthalene represented by the following formula (10-1). Next, an acid is allowed to act on 2- (meth) acryloyloxy-6-t-butoxycarbonyloxynaphthalene, and the t-butoxycarbonyloxy group is deprotected by a deprotection reaction, and this polymerization represented by the following formula (8-1) Can be obtained.

（Ｒ¹⁰は水素原子又はメチル基を表す。）

(R ¹⁰ represents a hydrogen atom or a methyl group.)

As the (meth) acrylic acid metal salt used for the esterification reaction, sodium (meth) acrylate and potassium (meth) acrylate are preferable in terms of availability.
The amount of (meth) acrylic acid metal salt used is 2-bromo-6-t-butoxycarbonyloxynaphthalene of formula (9-2) or 2-chloro-6-t-butoxycarbonyloxy of formula (9-3). 80-500 mol part is preferable with respect to 100 mol part of naphthalene. When the amount of the (meth) acrylic acid metal salt used is 80 mol parts or more, the main polymerizable monomer of the formula (8-1) tends to be obtained with good yield. Moreover, it exists in the tendency which can suppress a by-product when the usage-amount of (meth) acrylic-acid metal salt is 500 mol part or less. The lower limit of the amount of the (meth) acrylic acid metal salt is more preferably 100 parts by mole or more, and particularly preferably 120 parts by mole or more. Further, the upper limit of the amount of the (meth) acrylic acid metal salt is more preferably 300 parts by mole or less, and particularly preferably 250 parts by mole or less.

  Examples of the interlayer catalyst include tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetraethylammonium chloride, tri-n-octylmethylammonium bromide, tri-n-octylmethylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium chloride. Quaternary ammonium salts such as tetra n-butylammonium bromide and tetra n-butylammonium chloride; tetraethylphosphonium bromide, tetra n-butylphosphonium bromide, tetraphenylphosphonium bromide, triphenylbenzylphosphonium bromide, triphenylmethylphosphonium bromide, Tetraethylphos Quaternary phosphonium salts such as nium chloride, tetra-n-butylphosphonium chloride, tetraphenylphosphonium chloride, triphenylbenzylphosphonium chloride, triphenylmethylphosphonium chloride; 18-crown-6-ether, dibenzo-18-crown-6 And crown ethers such as ether, dibenzo-24-crown-8-ether, and dicyclohexano-18-crown-6-ether. These can be used alone or in combination of two or more.

The amount of the interlayer catalyst used is preferably 0.00001 to 1 mol part per 1 mol part of the (meth) acrylic acid alkali metal salt. When the amount of the interlayer catalyst used is 0.00001 mol part or more, the yield tends to improve. Further, when the amount of the interlayer catalyst used is 1 mol part or less, the production of by-products tends to be suppressed. As for the usage-amount of an interlayer catalyst, 0.0005-0.05 mol part is more preferable.
The reaction temperature is preferably -20 ° C to 100 ° C. When the reaction temperature is −20 ° C. or higher, the present polymerizable monomer tends to be obtained with good yield. Moreover, when reaction temperature is 100 degrees C or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product. The reaction temperature is more preferably 0 to 50 ° C.

A solvent can also be used for this reaction. Examples of the solvent include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform and benzene. Of these, toluene and tetrahydrofuran are preferred from the viewpoint of the solubility of 2,6-dihydroxynaphthalene.
Examples of the acid that can be used for the deprotection reaction include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, pyridinium paratoluenesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, acetic acid, and an ion exchange resin. Among these, hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid and camphorsulfonic acid are preferable in terms of yield improvement.

The amount of the acid used for the deprotection reaction is preferably 0.001 to 10 mole parts relative to 1 mole part of 2- (meth) acryloyloxy-6-t-butoxycarbonyloxynaphthalene. When the amount of acid used is 0.001 mol part or more, the reaction time tends to be short, and when it is 10 mol parts or less, the production of by-products tends to be suppressed. As for the usage-amount of an acid, 0.01-2 mol part is more preferable.
The reaction temperature for the deprotection reaction is preferably -20 to 100 ° C. When the reaction temperature is −20 ° C. or higher, the reaction time tends to be shortened, and when it is 100 ° C. or lower, the formation of by-products tends to be suppressed. The reaction temperature is more preferably 0 to 70 ° C.

Next, the manufacturing method of this polymerizable monomer shown to Formula (8-3) is demonstrated.
The present polymerizable monomer represented by the formula (8-3) esterifies an alcohol of a hydroxymethyl group in 2-hydroxy-6-hydroxymethylnaphthalene represented by the following formula (9-4) to form a (meth) acryloyloxy group. be able to.

（Ｒ¹⁰は水素原子又はメチル基を表す。）

(R ¹⁰ represents a hydrogen atom or a methyl group.)

Examples of the esterification method include (meth) acrylic acid, anhydrous (meth) acrylic acid or (meth) with respect to 2-hydroxy-6-hydroxymethylnaphthalene in the presence of an acid, a Lewis acid catalyst or a base. The method of making an acrylic acid chloride react is mentioned.
Examples of the acid catalyst include Lewis acids containing atoms such as hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid, acetic acid or funium, zirconium, yttrium, and ytterbium.
The amount of the acid catalyst used is preferably 0.1 to 10 parts by mole with respect to 100 parts by mole of 2-hydroxy-6-hydroxymethylnaphthalene. When the amount of the acid catalyst used is 0.1 mol part or more, the reaction rate tends to be increased, and when it is 10 mol part or less, the production of by-products tends to be suppressed. The lower limit value of the amount of the acid catalyst used is more preferably 0.5 mol parts or more, and the upper limit value is more preferably 3 mol parts or less.

Examples of the base include bases containing alkali metals such as potassium carbonate, sodium hydroxide, potassium hydroxide, sodium (meth) acrylate, and potassium (meth) acrylate, and organic substances such as triethylamine, pyridine, and dimethylaminopyridine. A base.
As for the usage-amount of a base, 0.5-10 mol part is preferable with respect to 100 mol part of 2-hydroxy-6-hydroxymethyl naphthalene. As for the usage-amount of a base, 1-8 mol part is more preferable at the point of a by-product.
Among (meth) acrylic acid and anhydrous (meth) acrylic acid, (meth) acrylic acid is preferable from the viewpoint of suppressing the formation of a by-product di (meth) acrylate.

  As for the usage-amount of (meth) acrylic acid or anhydrous (meth) acrylic acid, 50-500 mol part is preferable with respect to 100 mol part of 2-hydroxy-6-hydroxymethylnaphthalene. When the amount of (meth) acrylic acid or anhydrous (meth) acrylic acid used is 50 mol parts or more, the present polymerizable monomer of formula (8-1) tends to be obtained in good yield. Moreover, when this usage-amount is 500 mol part or less, it exists in the tendency which can suppress the production | generation of the dimethacrylate body which is a by-product. As for this usage-amount, 95-150 mol part is more preferable.

The reaction temperature is preferably 0 ° C to 50 ° C. When the reaction temperature is 0 ° C. or higher, the polymerizable monomer tends to be obtained with good yield. Moreover, when reaction temperature is 50 degrees C or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product.
Moreover, a solvent can be used for this reaction. Examples of the solvent include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform and benzene. Among these, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and acetonitrile are more preferable from the viewpoint of solubility of 2-hydroxy-6-hydroxymethylnaphthalene.

  The amount of (meth) acrylic acid chloride used is preferably 50 to 500 mol parts per 100 mol parts of 2-hydroxy-6-hydroxymethylnaphthalene. When the amount of (meth) acrylic acid chloride used is 50 mol parts or more, the main polymerizable monomer of the formula (8-3) tends to be obtained with good yield. Moreover, it exists in the tendency which can suppress the production | generation of a di (meth) acrylate body, when the usage-amount of (meth) acrylic acid chloride is 500 mol part or less. As for the usage-amount of (meth) acrylic acid chloride, 95-150 mol part is more preferable.

Examples of the base include organic bases such as triethylamine, pyridine, dimethylaminopyridine and the like.
As for the usage-amount of a base, 75-300 mol part is preferable with respect to 100 mol part of (meth) acrylic acid chloride. When the amount of the base used is 75 mol parts or more, the yield and reaction rate tend to be improved. Further, when the amount of base used is 300 mol parts or less, impurities after purification tend to be reduced. As for the usage-amount of a base, 100-150 parts is more preferable.

The reaction temperature is preferably 0 ° C to 50 ° C. When the reaction temperature is 0 ° C. or higher, the polymerizable monomer tends to be obtained with good yield. Moreover, when reaction temperature is 50 degrees C or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product.
Moreover, a solvent can be used for this reaction. Examples of the solvent include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform and benzene. From the viewpoint of the solubility of 2,6-dihydroxynaphthalene, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and acetonitrile are more preferable.

Next, the manufacturing method of this polymerizable monomer shown to Formula (8-7) is demonstrated.
The present polymerizable monomer represented by the formula (8-7) is, for example, 2-bromo-6-t-butoxycarbonyloxynaphthalene represented by the following formula (9-2) or 2 represented by the following formula (9-3). -Chloro-6-t-butoxycarbonyloxynaphthalene and sodium (meth) acrylate ethyl oxide represented by the following formula (11-1) or potassium (meth) acrylate ethyl oxide represented by the following formula (11-2) Can be obtained by reacting.

（Ｒ¹⁰は水素原子又はメチル基を表す。）

(R ¹⁰ represents a hydrogen atom or a methyl group.)

  Sodium (meth) acrylic acid ethyl oxide or potassium (meth) acrylic acid ethyl oxide is used in an amount of 100 parts by mole of 2-bromo-6-t-butoxycarbonyloxynaphthalene or 2-chloro-6-t-butoxycarbonyloxynaphthalene. The amount is preferably 70 to 500 mole parts. When the amount used is 70 mol parts or more, the present polymerizable monomer of the formula (8-5) tends to be obtained with good yield. Moreover, when this usage-amount is 500 mol part or less, it exists in the tendency which can suppress a by-product production | generation. As for this usage-amount, 100-200 mol part is more preferable.

The reaction temperature is preferably -20 ° C to 100 ° C. When the reaction temperature is −20 ° C. or higher, the polymerizable monomer tends to be obtained with good yield. Moreover, when reaction temperature is 100 degrees C or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product. The reaction temperature is more preferably 0 to 50 ° C.
Moreover, a solvent can be used for this reaction. Examples of the solvent include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform and benzene. From the viewpoint of the solubility of 2-bromo-6-t-butoxycarbonyloxynaphthalene or 2-chloro-6-t-butoxycarbonyloxynaphthalene, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and acetonitrile are more preferable.

Next, the manufacturing method of this polymerizable monomer shown to Formula (8-16) is demonstrated.
The present polymerizable monomer represented by the formula (8-16) can be produced by a method other than the above method. For example, an alcohol of the hydroxymethyl group of 2-t-butoxycarbonyloxy-6-hydroxymethylnaphthalene represented by the following formula (9-5) can be esterified to form a (meth) acryloyloxy group.

Examples of the esterification method include a method of reacting 2-t-butoxycarbonyloxy-6-hydroxymethylnaphthalene with (meth) acrylic acid anhydride or (meth) acrylic acid chloride in the presence of a base. It is done.
Examples of the base include bases containing alkali metals such as potassium carbonate, sodium hydroxide, potassium hydroxide, sodium (meth) acrylate and potassium (meth) acrylate, and organic bases such as triethylamine, pyridine and dimethylaminopyridine. Can be mentioned.
The amount of the base used is preferably 100 to 200 parts by mole based on 100 parts by mole of 2-t-butoxycarbonyloxy-6-hydroxymethylnaphthalene. The amount of the base used is more preferably from 105 to 150 mol parts in terms of yield and suppression of by-products.
Of the anhydrous (meth) acrylic acid or (meth) acrylic acid chloride, anhydrous (meth) acrylic acid is preferred in terms of yield and by-products.

  The amount of (meth) acrylic anhydride used is preferably 50 to 500 mole parts per 100 mole parts 2-t-butoxycarbonyloxy-6-hydroxymethylnaphthalene. When the amount of anhydrous (meth) acrylic acid used is 50 mol parts or more, the main polymerizable monomer of the formula (8-33) tends to be obtained with good yield. Moreover, when this usage-amount is 500 mol part or less, it exists in the tendency which can suppress the production | generation of the dimethacrylate body which is a by-product. As for this usage-amount, 95-150 mol part is more preferable.

The reaction temperature is preferably 0 ° C to 50 ° C. When the reaction temperature is 0 ° C. or higher, it is preferable from the viewpoint of the raw material conversion rate, and the present polymerizable monomer tends to be obtained with good yield. Further, when the reaction temperature is 50 ° C. or lower, the (meth) acrylation reaction tends to proceed with good reaction selectivity. The lower limit of the reaction temperature is more preferably 10 ° C or higher, and the upper limit of the reaction temperature is more preferably 40 ° C or lower.
Moreover, a solvent can be used for this reaction. Examples of the solvent include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform and benzene. Among these, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and acetonitrile are more preferable from the viewpoint of solubility of 2-hydroxy-6-hydroxymethylnaphthalene.

Examples of the base include organic bases such as triethylamine, pyridine, dimethylaminopyridine and the like.
As for the usage-amount of a base, 75-300 mol part is preferable with respect to 100 mol part of (meth) acrylic acid chloride. When the amount of the base used is 75 mol parts or more, the yield and reaction rate tend to be improved. Further, when the amount of base used is 300 mol parts or less, impurities after purification tend to be reduced. As for the usage-amount of a base, 100-150 parts is more preferable.

  As a method for recovering the present polymerizable monomer such as the formula (8-1), the formula (8-3), the formula (8-7) and the formula (8-16) from the reaction solution, a known method may be mentioned. And a method of distilling off the solvent under reduced pressure and a method of recovering crystals by crystallization. Among these, the crystallization operation is preferable from the viewpoint of the chemical purity of the recovered polymerizable monomer. The main polymerizable monomer crystal may be precipitated from the reaction solution, but usually the main monomer monomer crystal is precipitated by substituting the solvent with a suitable solvent in terms of yield, chemical purity and the like.

Examples of the solvent used for crystallization include water; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, n-amyl alcohol, cyclopropanol, n-hexyl alcohol, cyclohexane. Alcohol solvents such as hexanol, 1-octanol and isooctanol; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, methyl lactate and ethyl lactate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone System solvents: petroleum ether, dimethyl ether, diethyl ether, dimethoxymethane, diethoxyethane, diisopropyl ether, methyl-tert-butyl ether, 1,4-dioxane, tetrahydroph And hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, cyclopentane, cyclohexane, benzene, toluene, xylene, chloroform, methylene chloride, dichloroethane and the like. It is done.
After replacing the solvent in the reaction solution of the present polymerizable monomer with a solution containing at least one of these solvents, crystals of the present polymerizable monomer can be precipitated.
The solvent is preferably at least one solvent selected from water, alcohols, ethers and hydrocarbons, more preferably at least one solvent selected from water, alcohols and hydrocarbons in terms of recovery yield and chemical purity. .
Moreover, you may perform impurity removal operation, such as filtration, washing | cleaning, adsorption | suction, before depositing a crystal | crystallization.
The precipitated crystals are isolated, for example, by a vacuum filtration method, a pressure filtration method, or a centrifugal separation method, and the present polymerizable monomer is recovered. The isolation temperature is preferably -40 to 40 ° C. When the isolation temperature is −40 ° C. or higher, the chemical purity of the recovered hydroxyvinyl naphthalene compound tends to increase, and when the isolation temperature is 40 ° C. or lower, the recovery rate of the hydroxyvinyl naphthalene compound tends to increase. is there.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Moreover, in each Example and Comparative Example, “part” means “part by mass” unless otherwise specified.
Moreover, evaluation of the polymerizable monomer and the polymer was performed by the following method.

1. Evaluation of polymerizable monomer The structure of the polymerizable monomer was evaluated by ¹ H-NMR measurement and IR measurement.
(1) Structural evaluation by ¹ H-NMR measurement JNM-GX270 type FT-NMR (trade name) manufactured by JEOL Ltd. was used. About 5% by mass of a polymerizable monomer deuterated dimethyl sulfoxide solution was put in a test tube having a diameter of 5 mmφ, and measurement was performed 16 times in an observation frequency of 270 MHz and a single pulse mode. The measurement temperature was 24 ° C.

(2) Structural evaluation by IR measurement It measured by KBr method using Nexus 470FT-IR (trade name) manufactured by Thermo Nicolet.

2. Evaluation of copolymerizability of polymerizable monomer The polymerization solution is sampled every 1 hour of polymerization, the amount of unreacted monomer present in the polymerization solution is measured, and the ratio of the amount of reactive monomer to the amount of monomer charged is calculated. The consumption ratio was compared for the monomers.
The amount of unreacted monomer remaining in the polymerization solution was measured by the following method. First, in each polymerization time, 0.5 g of the polymerization solution collected from the polymerization reactor was diluted with acetonitrile, and the total volume was adjusted to 50 ml using a volumetric flask. This diluted solution was filtered through a 0.2 μm membrane filter, and the amount of unreacted monomers of each monomer was measured using a high performance liquid chromatograph HPLC-8020 (product name) manufactured by Tosoh Corporation.

The separation column used was one of Inertsil ODS-2 (trade name) manufactured by GL Sciences.
In addition, the mobile phase is a water / acetonitrile gradient system, the flow rate is 0.8 ml L / min, the detector is manufactured by Tosoh Corporation, UV / visible absorptiometer UV-8020 (trade name), detection wavelength 220 nm, measurement temperature 40 ° C. , Measured with an injection volume of 4 μl.
Inertsil ODS-2 (trade name), which is a separation column, had a silica gel particle diameter of 5 μm and a column inner diameter of 4.6 mm × column length of 450 mm.
The gradient conditions of the mobile phase were as follows, with the liquid A being water and the liquid B being acetonitrile.

Measurement time 0 to 3 minutes: A liquid / B liquid = 90/10 (volume%)
Measurement time 3 to 40 minutes: Liquid A / liquid B = 90/10 (volume%) → 50/50 (volume%)
Measurement time 40 to 62 minutes: A liquid / B liquid = 50/50 (volume%) → 0/100 (volume%)
Measurement time 62-70 minutes: A liquid / B liquid = 0/100 (volume%)
In addition, the consumption ratio of each monomer in each polymerization time was calculated | required by the following formula | equation from the amount of unreacted monomers.
Consumption ratio of each monomer = [(amount of monomer dropped into reaction vessel) − (amount of unreacted monomer)] / (amount of monomer dropped into reaction vessel)
It can be said that the smaller the difference in the consumption ratio of each monomer in each polymerization time, the better the copolymerization of the monomers and the formation of a polymer having a uniform composition. On the other hand, when the difference of the consumption ratio of each monomer is large, the copolymerizability is poor and it can be said that a polymer having an uneven copolymer composition ratio is generated.

3. The content of the constituent unit content polymer of Evaluation (1) each of the structural units of the polymer, in the case where it can be determined by the ¹ H-NMR measurement was determined by ¹ H-NMR measurement. Moreover, when it cannot obtain | require by 1H-NMR measurement by the overlap of a proton peak etc., it calculated | required by ¹³ C-NMR measurement.

^For measurement of ¹ H-NMR, JNM-GX270 type FT-NMR (trade name) manufactured by JEOL Ltd. was used. About 5% by mass of a polymer sample solution (deuterated chloroform solution or deuterated dimethyl sulfoxide solution) is put in a test tube with a diameter of 5 mmφ, and the measurement is performed with 64 observations in an observation frequency of 270 MHz and a single pulse mode. Carried out. The measurement temperature was 40 ° C. when deuterated chloroform was used as the solvent, and 60 ° C. when deuterated dimethyl sulfoxide was used as the solvent.

^In the case of ¹³ C-NMR measurement, UNITY-INOVA type FT-NMR (trade name) manufactured by Varian Technologies, Inc. was used. A proton complete decoupling method in which a deuterated dimethyl sulfoxide solution of about 20% by mass of a polymer sample is put in a test tube having a diameter of 5 mmφ, a measurement temperature of 60 ° C., an observation frequency of 125 MHz, and a nuclear overhauser effect (NOE) is removed. The measurement was carried out at 50,000 times.

(2) Mass average molecular weight and molecular weight distribution About 20 mg of polymer was dissolved in 5 ml of tetrahydrofuran (hereinafter referred to as “THF”), and filtered through a 0.5 μm membrane filter to prepare a sample solution. The mass average molecular weight and molecular weight distribution of this sample solution were measured by using gel permeation chromatography (GPC) manufactured by Tosoh Corporation.
In addition, the separation column used the Showa Denko Co., Ltd. product and three Shodex GPC K-805L (brand name) in series. In the measurement, THF was used as a solvent, and a differential refractometer was used as a detector. The measurement was performed at a flow rate of 1.0 ml / min, a measurement temperature of 40 ° C., and an injection amount of 0.1 ml, and polystyrene was used as a standard polymer.

(3) Light transmittance 5 parts of the polymer and 45 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) as a solvent were mixed to obtain a uniform solution. This was filtered through a membrane filter having a pore size of 0.1 μm to prepare a polymer solution.
Next, the polymer solution was spin-coated on a quartz wafer as a substrate, and prebaked at 120 ° C. for 60 seconds using a hot plate to produce a resist film having a thickness of 1 μm.
The resist film produced on the quartz wafer was installed on the sample side of the UV-3100 (trade name) made by Shimadzu Corporation, and the untreated quartz wafer was placed on the reference side. The light transmittance was measured. In the measurement, the wavelength range was 192 to 194 nm, the scan speed was medium, the sampling pitch was automatic, and the slit width was 2.0.

4). Calculation of raw material conversion rate and reaction selectivity during synthesis of polymerizable monomer The raw material conversion rate and reaction selectivity were calculated from the amount of raw material alcohol remaining in the reaction solution and the amount of polymerizable monomer produced. For detection of both compounds, high performance liquid chromatography (HPLC) was used.
<HPLC analysis conditions>
Sample preparation: 1.00 g of the reaction solution was precisely weighed in a 25 ml eggplant flask and adjusted to 25 ml with acetonitrile.
Column: manufactured by GL Sciences, Inertsil ODS-3V (4.6 × 250 mm), column oven temperature: 40 ° C.
Moving bed: water / acetonitrile (30/70, volume ratio)
Flow rate: 1.0 ml / min Detection: RI
Sample injection volume: 10 μl

Retention time of 2-t-butyroxycarbonyloxy-6-hydroxynaphthalene: about 5.0 minutes Retention time of 6- (1-butoxyethoxy) -2-hydroxynaphthalene: about 6.8 minutes 6-t-methacrylic acid Butyloxycarbonyloxyxynaphthalen-2-ylmethyl ester retention time: about 13.3 minutes Methacrylic acid 6- (1-butoxyethoxy) naphthalen-2-ylmethyl ester retention time: about 17.0 minutes Raw material conversion (%) = [(Raw alcohol remaining amount) × 100] / (raw alcohol charge)
Reaction selectivity (%) = [(polymerizable monomer production yield (%)) × 100] / ((raw material conversion rate (%))

[Example 1] (Production of methacrylic acid 6-hydroxynaphthalen-2-ylmethyl ester)
Into a 2 liter flask, 100.0 g (580.8 mmol) of 6-hydroxy-2-naphthaldehyde (manufactured by Aldrich, hereinafter referred to as “HNAL”) was added, and further 970 ml of ethyl acetate was added and stirred at 25 ° C. . After adding 13.14 g (52.3 mmol) of pyridinium p-toluenesulfonate, 143.12 g (1428.9 mmol) of n-butyl vinyl ether (manufactured by Nippon Carbide Industries Co., Ltd.) while adjusting the reaction temperature to 65 to 75 ° C. After dripping, it was aged for 16 hours. To this reaction solution, 250 ml of a saturated aqueous sodium hydrogen carbonate solution was added and stirred. After separating the ethyl acetate layer, it was washed with 250 ml of saturated aqueous sodium hydrogen carbonate solution. The ethyl acetate layer was separated again, and sodium sulfate was added for drying treatment. After removing sodium sulfate by filtration, using an evaporator, ethyl acetate was distilled off from the filtrate under conditions of 35 ° C. and 2660 Pa, and 6- (1-butoxyethoxy) -2-naphthylaldehyde (hereinafter referred to as “BANAL”). ) Was obtained (219.0 g).

  Next, 22.25 g (588.0 mmol) of sodium borohydride and 445 ml of ethanol were put into a 2 liter flask and stirred to suspend sodium borohydride in ethanol. To this suspension, a solution of 200.17 g (735 mmol) of BANAL crude in 98.5 ml of ethanol was added to a 1 ml while maintaining the temperature of the reaction solution at 0 to 10 ° C. using a 500 ml dropping funnel. Added dropwise over 75 hours. After aging at 0-25 ° C. for 5 hours, 735 ml of water was added and stirred. Ethanol was distilled off using an evaporator under the conditions of 25 ° C. and 2660 Pa, 1470 ml of ethyl acetate was added, and the ethyl acetate layer and the aqueous layer were separated. Next, the aqueous layer was re-extracted with 1470 ml of ethyl acetate, combined with the previously separated ethyl acetate layer, and dried by adding sodium sulfate. After removing sodium sulfate by filtration, using an evaporator, ethyl acetate was distilled off under the conditions of 35 ° C. and 2660 Pa, and 6- (1-butoxyethoxy) -2-hydroxynaphthalene (hereinafter referred to as “HMPAN”) was removed. A crude product (183.28 g) was obtained.

  Next, 181.1 g (660 mmol) of HMPAN crude material was charged into a 2 liter flask and dissolved in 330 ml of THF while stirring at 0 ° C. To this THF solution, 80.1 g (792 mmol) of triethylamine was added, and 0.969 g (7.9 mmol) of dimethylaminopyridine was added. Thereafter, 111.9 g (726 mmol) of methacrylic anhydride was added dropwise using a 200 ml dropping funnel while maintaining the temperature of the reaction solution at 0 to 10 ° C. After completion of the enemy, the reaction temperature was raised to 25 ° C. and stirred for 5.5 hours. The raw material conversion rate at this time was 99%, and the reaction selectivity was 99%. To this reaction solution, 330 ml of ethyl acetate and 330 ml of water were added, and the ethyl acetate layer was separated using a separatory funnel. Next, the ethyl acetate layer was washed with 330 ml of a saturated aqueous sodium hydrogen carbonate solution and further washed with 330 ml of water. Sodium sulfate was added to the ethyl acetate layer for drying treatment, followed by filtration. Ethyl acetate was distilled off at 35 ° C. and 2660 Pa using an evaporator to give 6- (1-butoxyethoxy) naphthalen-2-yl methacrylate. A crude product (206.1 g) of methyl ester (hereinafter referred to as “BANMA”) was obtained.

  In a 2 liter flask, 180.8 g (528.0 mmol) of a BANMA crude material was added, 180 ml of methanol was added, and the mixture was stirred and dissolved at 25 ° C. An aqueous hydrochloric acid solution (diluted 15.4 g of concentrated hydrochloric acid with 540 ml of water) was gradually added dropwise while maintaining the reaction temperature at 20 to 25 ° C. Then, after aging for 18.5 hours, 100 ml of a saturated aqueous sodium hydrogen carbonate solution was added. Methanol was distilled off at 25 ° C. and 2660 Pa using an evaporator, 250 ml of ethyl acetate was added, and the ethyl acetate layer and the aqueous layer were separated. The aqueous layer was re-extracted with 250 ml of ethyl acetate, combined with the previously separated ethyl acetate layer, and dried by adding sodium sulfate. After removing sodium sulfate by filtration, using an evaporator, ethyl acetate was distilled off under conditions of 35 ° C. and 2660 Pa, and methacrylic acid 6-hydroxynaphthalen-2-ylmethyl ester (hereinafter referred to as the following formula (81)) , “HNMMA”) (117.7 g) was obtained. The crude HNMMA was purified by column chromatography (filler: silica gel, eluent: hexane: ethyl acetate = 4: 1) to obtain 60.0 g of purified HNMMA. The NMR chart of purified HNMMA is shown in FIG. 1, and the IR chart is shown in FIG.

  Instead of column chromatography purification, 400 ml of ethanol / n-hexane mixed solvent (solubility ratio 1/10) was added to 117 g of crude HNMMA, and the mixture was heated and stirred at 50 ° C. After filtration under reduced pressure, the solution was cooled to 0 ° C. at a cooling rate of 10 to 13 ° C./hour, and further maintained at 0 ° C. for 10 hours. After cooling, the precipitated HNMMA crystals were separated by filtration under reduced pressure, washed with a small amount of n-hexane, and then obtained wet crystals were dried at 40 ° C. and 1330 to 13300 Pa for 6 hours to obtain purified HNMMA crystals 52. 1 g was obtained. The NMR chart of this purified HNMMA crystal was the same as in FIG. 1, and no impurities were observed.

[Example 2] (Production of methacrylic acid 6-tbutyroxycarbonyloxyoxynaphthalen-2-ylmethyl ester)
201.5 g (1170 mmol) of HNAL was put into a 2 liter flask, 702 ml of THF was added, and the mixture was stirred at 25 ° C. To this was added 101.8 g (1300 mmol) of pyridine, and then 280.9 g (1290 mmol) of di-t-butyl dioxide was added dropwise while adjusting the reaction temperature to be 0 to 5 ° C. The mixture was stirred and aged for 3.6 hours while adjusting the reaction temperature to 0 to 25 ° C. 465 ml of water was added dropwise to the reaction solution while maintaining the reaction temperature at -30 ° C. Subsequently, after stirring for 20 minutes, THF was distilled off with an evaporator to obtain a white slurry. After centrifuging this slurry, the obtained white wet powder was dried at 30 ° C. and 1330 to 13300 Pa for 5 hours to obtain a crude product of 6-t-butyoxycarbonyloxy-2-naphthaldehyde (hereinafter referred to as “BOCNAL”). A body (333.44 g) was obtained. This crude product was completely dissolved at 45 ° C. in a solvent of acetone / hexane = 1/2 (volume ratio). The solution was then recrystallized by cooling to 10 ° C. Furthermore, after filtering under reduced pressure, it dried at 40 degreeC and 1330-13300Pa for 5 hours, and obtained purified BOCNAL297.85g.

  Next, 16.3 g (432 mmol) of sodium borohydride and 326 ml of ethanol were put into a 2 liter flask and stirred to suspend sodium borohydride in ethanol. To this suspension, a solution of purified BOCNAL 294.1 (1080 mmol) dissolved in 667 ml of THF was added dropwise over 3 hours using a 1 liter dropping funnel while maintaining the temperature of the reaction solution at 0 to 10 ° C. . After aging for 0.5 hour, 204 ml of ethyl acetate was added and stirred. Further, 380 ml of water was added and stirred, and the organic layer was separated. Thereafter, toluene was distilled off at 60 ° C. and 2660 Pa with an evaporator to obtain a crude product (295.2 g) of 2-t-butyroxycarbonyloxy-6-hydroxynaphthalene (hereinafter referred to as “HMBOCN”). This crude HMBOCN was dissolved at 60 ° C. in a solvent of hexane / ethanol = 1.8 / 1 (volume ratio). The solution was cooled to 25 ° C. and recrystallized. Subsequently, after filtering under reduced pressure, it dried at 40 degreeC and 1330-13300Pa for 5 hours, and purified HMBOCN264.2g was obtained.

  Next, 98.75 g (360 mmol) of purified HMBOCN was charged into a 1 liter flask, and then dissolved in 296 ml of THF while stirring at 0 ° C. After adding 43.72 g (432 mmol) of triethylamine and 0.5418 g (4.4 mmol) of dimethylaminopyridine to this THF solution, 61.08 g (396 mmol) of methacrylic anhydride was added, and the reaction solution was maintained at 0 to 10 ° C. While dripping. After completion of the dropping, the reaction temperature was raised to 25 ° C. and stirred for 7.5 hours. The raw material conversion rate at this time was 99%, and the reaction selectivity was 99%. To this reaction solution, 180 ml of toluene and 180 ml of a saturated aqueous sodium hydrogen carbonate solution were added, and the toluene layer was separated using a separatory funnel. Next, the toluene layer was washed with 180 ml of a saturated saturated sodium hydrogen carbonate aqueous solution, and further washed with 180 ml of water. To the toluene layer, 0.012 g of p-methoxyphenol as a polymerization inhibitor was added, and toluene was distilled off at 50 ° C. and 2660 Pa with an evaporator. 6-tert-butyloxycarbonyloxymethacrylic acid methacrylate represented by the following formula (82) A crude product (129.67 g) of naphthalen-2-ylmethyl ester (hereinafter referred to as “BOCNMA”) was obtained. This crude product was dissolved in heptane at 50 ° C., cooled to 25 ° C., and recrystallized. After filtering this under reduced pressure, it was dried at 40 ° C. and 1330 to 13300 Pa for 5 hours to obtain 106.6 g of purified BOCNMA. The NMR chart of purified BOCNMA is shown in FIG. 3, and the IR chart is shown in FIG.

  Instead of purification by column chromatography, the reaction solution was washed with 200 ml of pure water, 500 ml of isopropyl alcohol was added to the THF layer which was separated and collected, and heated in a water bath at 40 to 60 ° C. while being heated at 1330 to 4000 Pa. The solution was concentrated under reduced pressure until the amount of the solution reached 446 g, and the same operation was further performed twice. The obtained concentrated liquid was heated to 50 ° C. and filtered under reduced pressure, and then the solution was cooled to 10 ° C. at a cooling rate of 5 to 10 ° C./hour, and further maintained at 10 ° C. for 2 hours. After cooling, the precipitated BOCNMA crystals were filtered off under reduced pressure, and the crystals were washed with a small amount of isopropyl alcohol. The obtained wet crystals were dried at 40 ° C. and 1330 to 13300 Pa for 6 hours to obtain 106.0 g of purified BOCNMA crystals. The NMR chart of this purified BOCNMA crystal was the same as in FIG. 3, and no impurities were observed.

[Example 3] (Production of 6-hydroxynaphthalen-2-yl methacrylate)
In a 500 ml flask, 56.06 g (350 mmol) of 2,6-dihydroxynaphthalene (manufactured by Aldrich) was dissolved in a mixed solution of 100 ml of THF and 27.7 g (350 mmol) of pyridine at 0 ° C. and stirred. To this solution, 36.6 g of methacrylic acid chloride was added dropwise over 1 hour while controlling the reaction temperature to be 10 ° C. or lower. Then, after stirring for 1 hour, 200 ml of water was added to terminate the reaction. Using 200 ml of ethyl acetate, methacrylic acid 6-hydroxynaphthalen-2-yl ester (hereinafter referred to as “HNMA”) represented by the following formula (83) is extracted from the reaction solution, separated, and dried by adding sodium sulfate. And concentrated. The concentrate was purified by column chromatography (hexane: ethyl acetate = 1: 10 (volume ratio)) to obtain 40.7 g (179 mmol) of purified HNMA.

[Examples 4 to 7 and Comparative Example 1]
In the methacrylation reaction of purified HMBOCN with methacrylic anhydride, the reaction temperature of 25 ° C. after completion of dropwise addition of methacrylic anhydride was changed to the temperature and reaction time shown in Table 1. Other conditions were the same as in Example 2 to produce purified BOCNMA. The results of the raw material conversion rate and the reaction selectivity are shown in Table 1.

  As is clear from Examples 1 to 3 and 4 to 7, the production method of the present polymerizable monomer of the present invention showed high raw material conversion and reaction selectivity. On the other hand, in Comparative Example 1, the reaction selectivity was low.

[Example 8] (Production of polymer (Y-2))
A flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer was charged with 50.8 parts of ethyl lactate under a nitrogen atmosphere, and the temperature in the flask was raised to 80 ° C. while stirring.
Next, 25.50 parts of α-methacryloyloxy-γ-butyrolactone (hereinafter referred to as “GBLMA”) represented by the following formula (51), 2-methacryloyloxy-2-methyladamantane represented by the following formula (52) 24.57 parts (hereinafter referred to as “MAdMA”), 10.89 parts of purified HNMMA obtained in Example 1, 91.4 parts of ethyl lactate and dimethyl-2,2′-azobisisobutyrate (hereinafter referred to as “DAIB”) A monomer solution in which 2.070 parts were mixed was prepared. This monomer solution was put into a dropping device and dropped into the flask at a constant rate over 4 hours. After completion of the dropping, the temperature was maintained at 80 ° C. for 3 hours to obtain a polymer (Y-2) solution.

Next, the polymer (Y-2) solution was added dropwise to 1.4 liters of methanol as a precipitation solvent while stirring to obtain a pale yellow precipitate. After this precipitate was filtered off, it was again poured into 1.4 liters of methanol as a washing solvent, and the precipitate was washed while stirring. Thereafter, the precipitate was filtered off and dried at 60 ° C. under reduced pressure for about 40 hours. The obtained polymer (Y-2) was evaluated, and the results are shown in Table 2.
The reaction solution was sampled every 1 hour or 1.5 hours after the start of dropping of the monomer solution, the amount of unreacted monomer was measured, and the consumption ratio of each monomer was determined. The results are shown in Table 3.

[Example 9] (Production of polymer (Y-1))
The initial amount of ethyl lactate in the flask was 58.2 parts, the monomer solution in the dropping apparatus was 27.20 parts GBLMA, 26.21 parts MAdMA, 16.42 parts purified BOCNMA obtained in Example 2, and 104.7 parts ethyl lactate. And a monomer solution in which 2.355 parts of DAIB were mixed. Other conditions were the same as in Example 8, and a polymer (Y-1) solution was obtained.

Subsequently, 1.6 liters of methanol / water = 85/15 (volume%) was used as the precipitation solvent, and 1.6 liters of methanol / water = 90/10 (volume%) was used as the cleaning solvent. Other conditions were the same as in Example 8, precipitation, filtration, and drying to obtain a polymer (Y-1). The obtained polymer (Y-1) was evaluated, and the results are shown in Table 2.
The reaction solution was sampled every 1 hour or 1.5 hours after the start of dropping of the monomer solution, the amount of unreacted monomer was measured, and the consumption ratio of each monomer was determined. The results are shown in Table 3.

[Example 10] (Production of polymer (Y-3))
The initial charged ethyl lactate in the flask was 69.5 parts, and the monomer solution in the dropping apparatus was 1-methacryloyloxy-3-hydroxyadamantane (hereinafter referred to as “HAdMA”) 9.44 represented by the following formula (53). Part, GBLMA 27.20 parts, MAdMA 37.44 parts, HNMMA 9.28 parts, ethyl lactate 125.0 parts and DAIB 2.760 parts. Other conditions were the same as in Example 8, and a polymer (Y-3) solution was obtained.

Subsequently, the solvent was changed to 1.5 liters of methanol as a precipitation solvent and 1.5 liters of methanol as a washing solvent. Other conditions were the same as in Example 8, precipitation, filtration, and drying to obtain a polymer (Y-3). The obtained polymer (Y-3) was evaluated, and the results are shown in Table 2.
The reaction solution was sampled every 1 hour or 1.5 hours after the start of dropping of the monomer solution, the amount of unreacted monomer was measured, and the consumption ratio of each monomer was determined. The results are shown in Table 3.

[Comparative Example 2] (Production of polymer (B-1))
6-Hydroxy-2-vinylnaphthalene (hereinafter referred to as “HVN”) represented by the following formula (91) was produced by the following method.
HVN was produced in 3 steps starting from 6-hydroxy-2-naphthaldehyde (manufactured by Aldrich) (hereinafter referred to as “HNAL”).
First, HMAL was protected with ethyl vinyl ether to obtain 6- (1-ethoxyethoxy) -2-naphthaldehyde (hereinafter referred to as “EENAL”). Subsequently, EENAL's Wittig reaction was performed to obtain 6- (1-ethoxyethoxy) -2-vinylnaphthalene. This 6- (1-ethoxyethoxy) -2-vinylnaphthalene was deprotected using pyridinium paratoluenesulfonate to obtain HVN.

  The initial charge of ethyl lactate in the flask was 52.9 parts, the monomer solution in the dropping apparatus was 28.05 parts of GBLMA, 27.03 parts of MAdMA, 8.415 parts of HVN obtained above, 95.2 parts of ethyl lactate and DAIB2. A monomer solution was mixed with 277 parts. Other conditions were the same as in Example 8, and a polymer (B-1) solution was obtained.

Then, precipitation, filtration and drying were conducted in the same manner as in Example 8 to obtain a polymer (B-1). The obtained polymer (B-1) was evaluated, and the results are shown in Table 2.
The reaction solution was sampled every 1 hour or 1.5 hours after the start of dropping of the monomer solution, the amount of unreacted monomer was measured, and the consumption ratio of each monomer was determined. The results are shown in Table 4.

  As is clear from Examples 8 to 10, the polymer having the present polymerizable monomer as a constituent unit was excellent in copolymerizability and light transmittance at the exposure wavelength. On the other hand, the polymer of Comparative Example 2 containing no present polymerizable monomer was inferior in light transmittance at the exposure wavelength.

NMR chart of methacrylic acid 6-hydroxynaphthalen-2-ylmethyl ester (Example 1) IR chart of methacrylic acid 6-hydroxynaphthalen-2-ylmethyl ester (Example 1) NMR chart of methacrylic acid 6-t-butyroxycarbonyloxyoxynaphthalen-2-ylmethyl ester (Example 2) IR chart of methacrylic acid 6-t-butyroxycarbonyloxyxynaphthalen-2-ylmethyl ester (Example 2)

Claims (5)

A polymerizable monomer having a naphthalene skeleton represented by the following formula (1).

(In the formula (1), R ¹⁰ represents a hydrogen atom or a methyl group. G represents any of —C (═O) —O—, —O—, or O—C (═O) —. L ¹ Represents a direct bond or a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms, and this divalent hydrocarbon group may have a hetero atom, and Y represents —C ( = O) -OH, -OH, -C (= O) .R 11 representing a ^{-O-R 11} or ^{O-R 11} represents a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. (This hydrocarbon group may have a hetero atom. G1 is 0 or 1. h2 is an integer of 1 to 7.) In the formula (1), [L ¹ — (O) g ¹ ] — is bonded to the 2-position of the naphthalene skeleton, L ¹ is L ¹ ′, h 2 is 1, and — [Y] h 2 is naphthalene. The polymerizable monomer according to claim 1, which is bonded to the 6-position of the skeleton, and thus the polymerizable monomer has a structure represented by the following formula (2).

(In the formula (2), R ¹⁰ represents a hydrogen atom or a methyl group. G represents —C (═O) —O—, —O— or O—C (═O) —, Y represents —C (═O) —OH, —OH, —C (═O) —O—R ¹¹ or O—R ¹¹ , where R ¹¹ is a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. This hydrocarbon group may have a hetero atom, g1 is 0 or 1. L ¹ ′ is a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms. (This divalent hydrocarbon group may have a hetero atom.) In the formula (2), G is —C (═O) —O—, g1 is 0, L ¹ ′ is L ¹ ″, and the polymerizable monomer has the structure represented by the following formula (3). The polymerizable monomer according to claim 2, comprising:

(In formula (3), R ¹⁰ represents a hydrogen atom or a methyl group. Y represents —C (═O) —OH, —OH, —C (═O) —O—R ¹¹ or O—R ¹¹ . R ¹¹ represents a straight-chain, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. This hydrocarbon group may have a hetero atom. L ¹ ″ is a straight chain having 1 to 4 carbon atoms. Represents a hydrocarbon group.) The polymerizable monomer according to claim 3, wherein in the formula (3), Y is a hydroxy group, and thus the polymerizable monomer has a structure represented by the following formula (4).

(In formula (4), R ¹⁰ represents a hydrogen atom or a methyl group. L ¹ ″ represents a straight-chain hydrocarbon group having 1 to 4 carbon atoms.) The manufacturing method of the polymerizable monomer of Claim 3 which makes the following formula (1-11) and following formula (1-12) react at the temperature of 0-50 degreeC on basic conditions.

(In formula (1-11), Y represents —C (═O) —OH, —OH, —C (═O) —OR ¹³ or —OR ¹³ , where R ¹³ is a straight chain having 1 to 20 carbon atoms. Represents a chain, branched or cyclic hydrocarbon group. This hydrocarbon group may have a hetero atom. L ¹ ″ represents a straight-chain hydrocarbon group having 1 to 4 carbon atoms.)

(In the formula (1-12), Z is .R ¹⁰ represents a halogen atom or a O-C (= O) C (CH 2) R 10 represents a hydrogen atom or a methyl group.)

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