JP2008120758A - Cyclic (meth)acrylate compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (meth)acrylate monomer containing a heterocyclic group having high hydrophilicity. <P>SOLUTION: The cyclic (meth)acrylate compound has a structure expressed by general formula (1) [wherein R<SP>1</SP>and R<SP>2</SP>are each hydrogen or a (meth)acryloyl expressed by general formula (2) provided that at least one of R<SP>1</SP>and R<SP>2</SP>is the (meth)acryloyl expressed by general formula (2); R<SP>3</SP>is hydrogen or a methyl; and the wavy line shows a bonding site]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel cyclic (meth) acrylate compound and a method for producing the same in high yield and high purity.

  In the production of vinyl copolymer resins, (meth) acrylic acid esters are one of the important monomer groups for copolymerization and are used in a wide variety of applications. However, polymerization with a single monomer often fails to provide the desired performance. In that case, in order to obtain the required physical properties, it is possible to mix a plurality of different (meth) acrylate monomers and copolymerize them. Done. Among them, imparting polarity to the resin is one of the most important modifications of the resin, and a (meth) acrylic acid ester monomer having a polar group is used for that purpose. Typical examples thereof include linear hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Since these can be easily produced industrially from a compound having a corresponding epoxy skeleton or a corresponding diol and (meth) acrylic acid, they have been widely used because they are easily available in large quantities at low cost. However, depending on the application, hydroxy (meth) acrylates having these chain skeletons are not optimal for expressing the desired properties. Rather, although these polar polar monomers are added, these chain polar monomers are added. As a result, there was a problem that functions that were originally required were weakened or no longer developed.

  For example, it is disclosed that a composition containing a (meth) acrylic monomer having a heterocyclic ring is useful as a fluoride-release dental composition (Patent Document 1). However, although it is stated in the specification that a conventional chain-like hydroxyalkyl (meth) acrylate can be used as a comonomer when imparting hydrophilicity to this composition, these hydroxyalkyl (meth) acrylates are mentioned. Since no heterocyclic ring is present, the function of releasing a fluoride is considered to be insufficient, and the structure is not suitable as a dental composition for releasing fluoride. If a (meth) acrylic acid ester having a heterocyclic ring and exhibiting high hydrophilicity is present, it is considered useful for producing a vinyl polymer resin that requires a heterocyclic ring.

In another application, (meth) acrylic acid ester having a hydroxy group is used in combination with (meth) acrylate having a heterocyclic ring by reacting with diisocyanate to form urethane acrylate.
For example, as a radiation curable resin composition, a hydroxy (meth) acrylate such as hydroxyethyl methacrylate, a polyol, a polyfunctional urethane (meth) acrylate prepared from a mixture of diisocyanate (a component that gives viscosity to the resin), and tetrahydrofurfuryl It is disclosed that a composition in which a component having a heterocyclic compound such as (meth) acrylate is mixed is preferable (Patent Document 2). This is because unless the heterocyclic compound is added, the hardness of the cured coating layer is not sufficiently increased and the desired performance is not achieved. Therefore, if there is a heterocyclic compound (meth) acrylate having a hydroxy group, urethane acrylate having a heterocyclic structure can be produced, and thus its utility value is considered high.

In this way, (meth) acrylates, which have been improved in hydrophilicity by having both a heterocyclic ring and a hydrophilic group in the same monomer, can be used for various compounds based on the utilization of the high water affinity and the hydrophilic group. It was a compound that was expected to be developed because of its diversity of conversion.
Furthermore, in the field of ArF photoresists for semiconductors in recent years, (meth) acrylate-based resins are used as the mainstream of resist materials. In manufacturing this ArF photoresist resin, in order to increase the etching resistance. Introduction of a cyclic hydrocarbon structure such as an adamantane skeleton is required (Non-Patent Document 1). However, introduction of a large number of hydrocarbon groups, on the other hand, results in a decrease in the solubility of the resin in the developer, and therefore modification of the resin that increases the solubility in the aqueous developer is required. At present, for this purpose, a resin to which a monomer having a polar group such as hydroxyadamantyl methacrylate is added is used. However, since the affinity of these monomers with water is not sufficient, the addition amount must be increased. There is a problem that the manufacturing cost of the entire resist resin is increased because it is expensive. Therefore, also in this field, development of a (meth) acrylate monomer having a high water affinity capable of efficiently imparting hydrophilicity to a resin has been desired.
JP-A-8-301718 Japanese Patent Laid-Open No. 7-48422 J. Photopolym. Sci. Technol., 9. 509 (1996).

  An object of the present invention is to provide a heterocyclic ring which is a structure necessary for achieving physical properties required in many fields, and a (meth) acrylate in which a hydrophilic group is present in the same monomer molecule. Is to provide a process for producing a product from a commercially available raw material by a reaction that can be carried out industrially.

As a result of intensive studies to solve this problem, the cyclic (meth) acrylate compound represented by the general formula (1) has a structure in which a heterocyclic ring and a hydrophilic group are present in the same monomer molecule, and actually It has been found that it has very good solubility in an aqueous solvent and has a high affinity for water, and the present invention has been completed.
That is, the first gist of the present invention resides in a cyclic (meth) acrylate compound having a structure represented by the following general formula (1).

（式（１）中、Ｒ¹およびＲ²は、それぞれ水素原子または下記一般式（２）で表される（メタ）アクリロイル基であり、Ｒ¹およびＲ²のうち少なくとも一つは一般式（２）で表される（メタ）アクリロイル基である。）

(In formula (1), R ¹ and R ² are each a hydrogen atom or a (meth) acryloyl group represented by the following general formula (2), and at least one of R ¹ and R ² is represented by the general formula ( (It is a (meth) acryloyl group represented by 2).)

（式（２）中、Ｒ³は水素原子またはメチル基であり、波線は結合部位を示す。）
本発明の第２の要旨は、７−オキサビシクロ[２．２．１]ヘプタン−２，３−ジオールと（メタ）アクリル酸ハライドとを塩基の存在下に反応させることを特徴とする上記記載の環式（メタ）アクリレート化合物の製造方法、に存する。

(In Formula (2), R ³ is a hydrogen atom or a methyl group, and a wavy line indicates a binding site.)
The second gist of the present invention is the above description, characterized in that 7-oxabicyclo [2.2.1] heptane-2,3-diol and (meth) acrylic acid halide are reacted in the presence of a base. In the production method of the cyclic (meth) acrylate compound.

The hydroxy group-containing (meth) acrylate compound of the present invention has a structure in which a heterocyclic ring and a hydrophilic group are present in the same monomer molecule, and actually exhibits good solubility in an aqueous solvent. Since it has high affinity, it can be used for modification purposes to impart hydrophilicity to various (meth) acrylic resins. Examples of fields that can be used include resist resins such as color resists and semiconductor resists, medical material resins such as dentistry, paint resins, adhesive resins, and fiber treatment resins. Furthermore, recently, in the resist field, technological development by the immersion method has been actively carried out in the image forming technology using ArF laser, but the need for a top coat resin that can be dissolved in an alkaline developer is increasing. Considering the characteristics of the compound, it is considered possible to apply to this application.

  Further, according to the production method of the present invention, it is possible to produce this hydrophilic polymerizable monomer with high yield by an industrially simple operation.

Hereinafter, the present invention will be described in detail.
<Cyclic (meth) acrylate compound>
The polymerizable monomer of the present invention has a structure represented by the structure of the following general formula (1).

In formula (1), R ¹ and R ² are each a hydrogen atom or a (meth) acryloyl group represented by the following general formula (2), and at least one of R ¹ and R ² is represented by the general formula (2 ) Is a (meth) acryloyl group.

In the formula (2), R ³ is a hydrogen atom or a methyl group, and a wavy line indicates a binding site.
That is, at least one of the two hydroxyl groups of 7-oxabicyclo [2.2.1] heptane-2,3-diol (in formula (1), R ¹ and R ² are hydrogen atoms) is (meth) acrylic acid. It is a structure converted into an ester group. These compounds are compounds in which a (meth) acrylic ester is simply bonded to a hydrocarbon or a compound having a 7-oxabicyclo [2.2.1] heptane ring and a (meth) acrylic ester group is 1 as an oxygen functional group. It was found that the water affinity was remarkably superior to that of a single condensed compound.

In particular, in the general formula (1), 2- (meth) acryloyloxy-3-hydroxy-7-oxabicyclo [2. is a compound in which hydrogen and a (meth) acrylic ester group are condensed on R ¹ and R ² one by one. 2.1] Heptane was found to have high water affinity and excellent solubility in aqueous solvents. This is considered that the —OH group and the 7-membered cyclic ether structure, both of which are hydrophilic, and the ester group are located in the molecule without bias, and thus the entire molecule is likely to be solvated by water molecules. It is estimated that solubility is increasing. On the other hand, since it has sufficient solubility in organic solvents, it is easy to handle the monomer itself, and it has a great advantage in terms of handling and operation, such as a wide choice of solvents for polymerization. Yes.

<Method for producing cyclic (meth) acrylate compound>
The production route of the cyclic (meth) acrylate compound of the present invention is not particularly limited, and any production method can be adopted. For example, a method using an adduct of vinylene carbonate and furan as a raw material is preferable because these raw materials can be obtained on an industrial scale at low cost. In this case, first, an adduct is obtained by Diels-Alder reaction of vinylene carbonate and furan, followed by reduction and hydrolysis to form 7-oxabicyclo [2.2.1] heptane-2,3-diol. It can be produced by converting the number of hydroxyl groups to (meth) acrylate.

  The (meth) acrylated reaction in the next step using 7-oxabicyclo [2.2.1] heptane-2,3-diol as a raw material can be arbitrarily selected. Typical methods include esterifying a hydroxyl group using (meth) acrylic acid halide or (meth) acrylic anhydride, transesterification using a lower alcohol ester of (meth) acrylic acid, N A direct esterification reaction in which (meth) acrylic acid and the diol are subjected to dehydration condensation using a dehydration condensing agent such as N, N'-dicyclohexylcarbodiimide is preferably used.

  In addition, for the purpose of producing mono (meth) acrylate of 7-oxabicyclo [2.2.1] heptane-2,3-diol, first, 7-oxabicyclo [2.2.1] heptane-2 is first stepwise. , A method of protecting one of the hydroxyl groups of 3-diol and deprotecting the hydroxyl group after (meth) acrylate formation, modifying two hydroxyl groups to a carbonate structure and selectively nucleophilically A method of selectively producing mono (meth) acrylate, such as a method of converting to a (meth) acrylate group and performing a post-treatment with final water, can be employed without any particular limitation.

As the compound of the present invention and the reagent, a (meth) acrylic acid compound rich in polymerizability is used. Therefore, a polymerization inhibitor may be used as necessary so that polymerization does not proceed during reaction or storage. Examples of polymerization inhibitors include hydroquinones such as p-benzoquinone, hydroquinone, hydroquinone monomethyl ether and 2,5-diphenylparabenzoquinone, and N-oxy radicals such as tetramethylpiperidinyl-N-oxy radical (TEMPO). , Substituted catechol cages such as t-butylcatechol, amines such as phenothiazine, diphenylamine, and phenyl-β-naphthylamine, nitrosobenzene, picric acid, molecular oxygen, sulfur, copper (II) chloride, and the like. Of these, hydroquinones, phenothiazines and N-oxy radicals are preferred from the viewpoint of versatility and polymerization inhibition, and N-oxy radicals such as TEMPO are particularly preferred because they contribute strongly to polymerization inhibition at high temperatures.

The use amount of the polymerization inhibitor is 7-oxabicyclo [2.2.1] heptane-2,3-diol or the compound of the general formula (1) as a product, the lower limit is usually 10 ppm or more, Preferably it is 50 ppm or more, and an upper limit is 10,000 ppm or less normally, Preferably it is 1000 ppm or less. If the amount is too small, the effect as a polymerization inhibitor does not appear or is small, and there is a risk that the polymerization proceeds at the time of reaction or concentration in the post-treatment process. This is not preferable because it may become an impurity in the production of, and may have an adverse effect such as inhibiting polymerization reactivity.
The reaction conditions that can be employed for a typical esterification reaction of 7-oxabicyclo [2.2.1] heptane-2,3-diol are described below.

<Transesterification method>
A compound that can be used as a (meth) acrylate agent in the case of (meth) acrylate-converting 7-oxabicyclo [2.2.1] heptane-2,3-diol by transesterification is a lower compound of (meth) acrylic acid. It is an alcohol ester. The lower alcohol is preferably a C1-C4 aliphatic alcohol, and the number of alcohol residues is selected from 1 to 3. Particularly preferred are (meth) acrylic acid methyl ester, ethyl ester, n-propyl ester and i-propyl ester. Among these, (meth) acrylic acid methyl ester, ethyl ester and the like are preferable because they can be easily operated in terms of removing alcohol by-produced during the reaction.

The lower limit of the amount of (meth) acrylic acid ester used is usually 0.1 molar equivalents or more, preferably 0 with respect to the number of moles of the starting material 7-oxabicyclo [2.2.1] heptane-2,3-diol. .2 mole equivalent or more, more preferably 0.5 mole equivalent or more, and the upper limit is usually 20 mole equivalent or less, preferably 10 mole equivalent or less, more preferably 5 mole equivalent or less. However, when attempting to produce a diester of the general formula (1) (R ^1, R ² are both (meth) acrylic ester) is (meth) the amount of acrylic acid ester is 7-oxabicyclo [2.2. 1] It can be used excessively with respect to heptane-2,3-diol, and in an extreme case, it may be 50 mol equivalent or more.

Although these (meth) acrylic acid esters are added, there is no particular limitation, and the reaction is carried out by adding the total amount to 7-oxabicyclo [2.2.1] heptane-2,3-diol when the reaction is charged. In addition, it is possible to employ both adding in portions during the reaction.
The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone are preferably used. Among these, aromatic hydrocarbon solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are preferable in terms of reactivity. These solvents may be used singly or a plurality of arbitrary solvents may be mixed and used.

When using a solvent, the amount of the starting 7-oxabicyclo [2.2.1] heptane-2,3-diol has a lower limit of usually 1% or more, preferably 10% or more, The upper limit is not particularly limited, but is usually 80% or less, preferably 50% or less.
The transesterification reaction is usually performed in the presence of a catalyst. As the usable catalyst, those generally usable in transesterification can be applied, for example, transition metal compounds such as titanium tetraisopropoxysite, alkali metal or alkaline earth metal alcoholate such as sodium methoxide, and the like. Aluminum alkoxides such as aluminum triisopropoxide, alkali metal and alkaline earth metal hydroxides such as lithium hydroxide and sodium hydroxide, tin compounds such as dibutyltin oxide, dioctyltin oxide, and distanoxane compounds. . Of these, transition metal compounds such as titanium tetraisopropoxysite, alkali metals such as sodium methoxide and alcoholates of alkaline earth metals, and the like are preferable because of their catalytic activity and availability.

The lower limit of the amount of these catalysts used is usually 0.01 mol% or more, preferably 0.1 mol%, relative to the number of moles of the starting 7-oxabicyclo [2.2.1] heptane-2,3-diol. Or more, more preferably 0.5 mol% or more, and the upper limit is usually 50 mol% or less, preferably 20
The mol% or less, more preferably 10 mol% or less. When the amount of the catalyst is too small, the reaction activity tends to be low and the yield of the desired ester compound tends to be low. On the other hand, when the amount is too large, the load on the post-treatment step after the transesterification reaction increases, Moreover, it is not preferable also from an economical viewpoint.

  The reaction is preferably carried out in a reactor equipped with a normal stirring device. Further, it is preferable to carry out the reaction while transferring the equilibrium to the production system while distilling off the alcohol generated during the reaction. At this time, if the (meth) acrylic acid ester used as the reagent and the alcohol azeotropes and the (meth) acrylic acid ester is distilled off from the system, the (meth) acrylic acid ester is added as necessary. You may react by replenishing sequentially.

It is preferable to carry out the reaction with heating in order to obtain a sufficient reaction rate. Specifically, the lower limit is usually 30 ° C. or higher, preferably 50 ° C. or higher, and the upper limit is usually 200 ° C. or lower, preferably 150 ° C. or lower. When the reaction temperature is too high, the polymerization reaction of the raw material (meth) acrylic acid ester or the target product ester tends to occur, and when it is too low, the transesterification reaction does not proceed or the reactivity is extremely slow, There is a tendency to require a long reaction time.
The reaction time is arbitrarily selected, but since alcohol is produced as the reaction proceeds, it is preferable to continue the reaction until a predetermined amount of alcohol is produced. In general reaction time, the lower limit is usually 10 minutes or longer, preferably 30 minutes or longer, and the upper limit is not particularly limited, but is usually 50 hours or shorter, preferably 30 hours or shorter.

<(Meth) acrylic acid halide method, (meth) acrylic anhydride method>
7-oxabicyclo [2.2.1] heptane-2,3-diol is (meth) acrylated using (meth) acrylic acid halide or (meth) acrylic anhydride as (meth) acrylating agent can do. The compounds that can be used as the (meth) acrylic acid halide in that case are (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide.

The lower limit of the amount of (meth) acrylic acid halide or (meth) acrylic anhydride used is usually 0 with respect to the number of moles of raw material 7-oxabicyclo [2.2.1] heptane-2,3-diol. 01 mole equivalent or more, preferably 0.05 mole equivalent or more, more preferably 0.1 mole equivalent or more, and the upper limit is usually 20 mole equivalent or less, preferably 10 mole equivalent or less, more preferably 5 mole equivalent. Less than molar equivalent. However, when the monoester of the general formula (1) (at least one of R ¹ and R ² is (meth) acrylic ester) is to be produced, (meth) acrylic acid halide or (meth) acrylic anhydride The upper limit of the amount used must be further reduced with respect to 7-oxabicyclo [2.2.1] heptane-2,3-diol, preferably 3 molar equivalents or less, more preferably 1.5 molar equivalents. It is as follows.

It is a method of adding these (meth) acrylic acid halides or (meth) acrylic acid anhydrides, but avoiding direct contact with these (meth) acrylic reagents and basic substances for a long time before the reaction, There is no restriction | limiting in particular in the method of addition. For example, 7-oxabicyclo [2.2
. 1] Heptane-2,3-diol and (meth) acrylic acid halide or (meth) acrylic anhydride may be charged into the reactor at the same time, and a basic substance may be added later, or charged into the reactor in advance. The basic substance and 7-oxabicyclo [2.2.1] heptane-2,3-diol, or (meth) acrylic acid halide or (meth) acrylic anhydride are added dropwise to the solution to carry out the reaction. May be. When the mono (meth) acrylate of 7-oxabicyclo [2.2.1] heptane-2,3-diol is to be produced, the latter addition method is preferably used for suppressing by-products.

When the reaction is carried out using (meth) acrylic acid halide or (meth) acrylic anhydride, it is necessary to control the water content appropriately. If water is present in the system, the reagent cannot be used effectively by reacting with (meth) acrylic acid halide or (meth) acrylic anhydride. Substrates used in the present invention, for example 7-oxabicyclo [2.2
. 1] Heptane-2,3-diol is a compound that is easily miscible with water, but the smaller the amount of water contained in the substrate, the better. Specifically, it is 10 mol% or less, preferably 5 mol% or less, more preferably 1 mol% or less with respect to 7-oxabicyclo [2.2.1] heptane-2,3-diol.

  The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitrile solvents such as acetonitrile and benzonitrile, ester solvents such as ethyl acetate, butyl acetate and gamma butyrolactone, dimethylformamide and dimethylacetamide, N An amide solvent such as methylpyrrolidone is preferably used. Among these, aromatic hydrocarbon solvents, ketone solvents, nitrile solvents, and the like are preferable for allowing the reaction to proceed smoothly. Among them, ketone solvents and nitrile solvents are the starting materials such as 7-oxabicyclo [2.2.1] heptane-2, It is preferable at the point which can improve the solubility of 3-diol. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

When using a solvent, the amount is such that the concentration of the starting material 7-oxabicyclo [2.2.1] heptane-2,3-diol has a lower limit of usually 0.1% or more, preferably 1% or more. The upper limit is not particularly limited, but is usually 50% or less, preferably 30% or less.
The (meth) acrylation reaction with (meth) acrylic acid halide or (meth) acrylic anhydride is usually performed in the presence of a basic substance. Usable basic substances include metal hydroxides such as sodium hydroxide and barium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, metal phosphates such as monosodium phosphate and potassium phosphate It is possible to use salts, hydrogen phosphates, basic ion exchange resins, organic tertiary amines such as triethylamine and tributylamine, and aromatic amines such as pyridine. Of these, pyridine, triethylamine, and potassium carbonate are preferably used.

  Although it is the usage-amount of these basic substances, with respect to the (meth) acrylic acid halide or (meth) acrylic anhydride used, the lower limit is usually 0.1 mol equivalent, preferably 0.5 mol, etc. The upper limit is usually 10 mole equivalents or less, preferably 5 mole equivalents or less, more preferably 2 mole equivalents or less. If the amount of the basic substance is too small, it is not preferable because the progress of the reaction is slow or stopped, and if it is too large, there is a problem of coloring the reaction solution, which is not preferable from the viewpoint of economy. .

The reaction is preferably carried out in a reactor equipped with a normal stirring device.
The reaction temperature adopted is carried out in the range where the lower limit is usually −50 ° C. or higher, preferably −20 ° C. or higher, and the upper limit is usually 100 ° C. or lower, preferably 70 ° C. or lower. 7-oxabicyclo [2.
2.1] When producing mono (meth) acrylate of heptane-2,3-diol, the upper limit temperature is preferably set low, and the upper limit is usually 50 ° C or lower, preferably 30 ° C or lower. Will be implemented.

The reaction time is arbitrarily selected, but the general reaction time is usually 10 minutes or more, preferably 30 minutes or more, and the upper limit is not particularly limited. Time or less, preferably 10 hours or less.
In addition, when performing the (meth) acrylation reaction by a (meth) acrylic acid halide, it is necessary to pay attention to the purity of the (meth) acrylic acid halide used depending on the substrate. (Meth) acrylic acid halides are described in Chimia, 1985, 39, p. As described in 19-20, it is dimerized over time to produce impurities having a structure represented by the following (7) or (8), and the purity is lowered.

In the formulas (7) and (8), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom or a methyl group, and X represents a halogen atom, preferably a chlorine atom.
Usually, when a hydroxyl group having an environment that is sterically mixed to some extent is esterified with an acid halide, the acid halide site of these dimers is also sterically mixed, so the dimer is less active than the acid halide and is involved in the reaction. Sometimes it doesn't. However, for example, when 7-oxabicyclo [2.2.1] heptane-2,3-diol having a cyclic structure is used as a substrate, it is higher than the acid halide because the periphery of the hydroxyl group is relatively three-dimensionally rinsed. Has reactivity. Therefore, when an acid halide containing a large amount of the dimer having the above structure is used to (meth) acrylate 7-oxabicyclo [2.2.1] heptane-2,3-diol, these acid halides are In addition to the reaction, the dimer reacts to produce a by-product of the following structures (3) and (4).

In the formulas (3) and (4), R ² is a hydrogen atom or (meth) represented by the general formula (2).
It is an acryloyl group, and R ⁴ , R ⁵ and R ⁶ each represent a group represented by the following general formula (5) or (6).

式（５）および（６）中、Ｒ⁷、Ｒ⁸、Ｒ⁹およびＲ¹⁰はそれぞれ水素原子またはメチル
基であり、Ｘはハロゲン原子、好ましくは塩素原子を表す。また波線は結合部位を示す。
以上述べた理由により、７−オキサビシクロ[２．２．１]ヘプタン−２，３−ジオールなどの比較的立体的にすいた水酸基を（メタ）アクリル酸ハライドを用いて（メタ）アクリレート化する場合は、（メタ）アクリル酸ハライドの純度が高い試剤を使用する必要がある。具体的には、（メタ）アクリル酸ハライドの純度が通常、８５モル％以上、好ましくは９０モル％以上、より好ましくは９５モル％以上、さらに好ましくは９９モル％以上のものを使用する。

In the formulas (5) and (6), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, and X represents a halogen atom, preferably a chlorine atom. A wavy line indicates a binding site.
For the reasons described above, a relatively three-dimensionally hydroxyl group such as 7-oxabicyclo [2.2.1] heptane-2,3-diol is (meth) acrylated using (meth) acrylic acid halide. In this case, it is necessary to use a reagent having a high purity of (meth) acrylic acid halide. Specifically, a (meth) acrylic acid halide having a purity of usually 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more is used.

The total content of the dimers (7) and (8) in the (meth) acrylic acid halide is usually 15 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, particularly preferably. Is preferably esterified using 1 mol% or less.
More specifically, the total content of (7) in the (meth) acrylic acid halide is usually 15 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 1 mol%. It is preferable to esterify using the following.

The method for increasing the purity of the (meth) acrylic acid halide is not particularly limited, but it is convenient and preferable to carry out distillation using the boiling point difference between the acid halide and the dimer. As the distillation method, simple distillation, precision distillation, thin film distillation and the like can be employed without limitation. Among these, it is more preferable in terms of separation performance to employ simple distillation or precision distillation.
Specifically, the method will be specifically described as an example of simple distillation.

Although simple distillation does not pursue the precision in particular, since the acid halide to be purified this time is a polymerizable compound, a polymerization inhibitor may be used as necessary for distillation. As the usable polymerization inhibitor, a compound which can be used in the present specification at the time of reaction or storage can be used as it is in the main distillation.
The lower limit of the amount of the polymerization inhibitor used is usually 10 ppm or more, preferably 50 ppm or more, and the upper limit is usually 10,000 ppm or less, preferably 1000 ppm or less with respect to the acid halide. If the amount of the polymerization inhibitor is too small, the effect as a polymerization inhibitor is not manifested or is small, and there is a risk that polymerization proceeds during the distillation operation. This is not preferable because it is an impurity during production, and there is a risk of adverse effects such as inhibiting polymerization reactivity.

Distillation may be carried out at normal pressure or under reduced pressure. However, when the acid halide is methacrylic acid chloride, since the boiling point is 96 ° C. even at normal pressure, it is preferable to carry out the distillation at normal pressure or at a low reduced pressure, for example, 0.01 MPa or more.
As described above, the acid halide having an increased purity is dimerized with time and decreases in purity. Therefore, it is necessary to use the acid halide immediately after distillation. Even in the case of storage, it is necessary to store in a cool dark place to minimize the decrease in purity. The storage temperature is preferably 0 ° C. or lower, more preferably −10 ° C. or lower.

  When 7-oxabicyclo [2.2.1] heptane-2,3-diol is (meth) acrylated using (meth) acrylic acid halide having an increased purity in this way, structural formulas (3) and (4) It is possible to obtain a hydroxy group-containing (meth) acrylate compound represented by the above formula (1) with little by-product. In addition, when (3) and (4) are mixed as impurities in the desired compound represented by the formula (1), a difference in polymerization rate occurs in the subsequent polymerization, or an insoluble matter is generated. In addition to being a problem, it also affects the performance of the resin itself, which is not preferable. In the case of the composition containing the compound having the structure represented by the general formulas (3) and (4) in the compound represented by the above formula (1) of the present invention, it is represented by the general formulas (3) and (4). Is a compound composition represented by the general formula (1) in which the total content of the compounds having a structure is 15 mol% or less with respect to the compound represented by the above formula (1), preferably 10 The mol% or less, more preferably 5% or less, and still more preferably 0.1% or less.

<Direct dehydration method>
When esterifying with (meth) acrylic acid, the reaction proceeds rapidly when a dehydrating condensing agent is allowed to coexist. As the condensing agent, any condensing agent generally known for esterification can be used without particular limitation. For example, N, N′-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolium chloride can be used. Propanephosphonic anhydride is preferably used. In this case, an organic basic substance such as pyridine, 4-dimethylaminopyridine or triethylamine may be used in combination. Among these, N, N′-dicyclohexylcarbodiimide is preferable as the condensing agent, and pyridine and triethylamine are preferable as the basic substance from the viewpoint of condensation reactivity and availability.

The lower limit of the reaction temperature usually employed in this reaction is usually −20 ° C., preferably −10 ° C., and the upper limit is usually 100 ° C., preferably 50 ° C.
The amount of the dehydrating condensing agent used is theoretically sufficient if it is used in an equivalent amount or more with respect to the substrate 7-oxabicyclo [2.2.1] heptane-2,3-diol, but it can be used in excess. Absent. Preferably, it is 1.0 molar equivalent or more, more preferably 1.1 molar equivalent or more.

When a dehydrating condensing agent is not used, (meth) acrylic acid and 7-oxabicyclo [2.2.1] heptane-2,3-diol are reacted in the presence of an acid while distilling off generated water.
Any acid can be used without particular limitation as long as it is an acid used in a normal esterification reaction. For example, inorganic acids such as sulfuric acid and hydrochloric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid, acid type ion exchange resins, Lewis acids such as fluorinated boron and ether complexes, lanthanide trif And water-soluble Lewis acids such as rate. These acids may be used alone or in combination of two or more.

  The lower limit of the amount of the acid used is 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 7-oxabicyclo [2.2.1] heptane-2,3-diol as a substrate. Is 0.5 mol% or more. On the other hand, the upper limit is not limited and is 20 mol equivalent or less, preferably 10 mol equivalent or less. If the amount of the acid catalyst is too small, it is not preferable because the progress of the reaction is slow or stopped, and if the amount is too large, there is a tendency to cause coloring of the reaction solution or an undesirable side reaction occurs. Absent.

  The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, and the like are preferably used. Among these, an aromatic hydrocarbon solvent and a halogen-based solvent are preferable for allowing the reaction to proceed smoothly. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

When a solvent is used, the amount of the starting 7-oxabicyclo [2.2.1] heptane-2,3-diol concentration is usually at least 0.1%, preferably at least 1%. The upper limit is not particularly limited, but is usually 50% or less, preferably 30% or less.
The reaction is usually carried out at or above the boiling point of the solvent used, and the reaction is carried out while distilling off the produced water.
The reaction time is arbitrarily selected, but the end point of the reaction can be recognized by measuring the amount of water produced. In general reaction time, including the dropping time of the reagent, the lower limit is usually 10 minutes or longer, preferably 30 minutes or longer, and the upper limit is not particularly limited, but is usually 20 hours or shorter, preferably 10 hours or shorter.

<Purification method>
For example, purification of the compound represented by the general formula (1) produced by the above reaction can be employed without any particular limitation. For example, a distillation method, a recrystallization method, an extraction cleaning method, and the like. When performing distillation, the form can be arbitrarily selected from simple distillation, precision distillation, thin film distillation, molecular distillation and the like.
<Storage method of (meth) acrylic acid ester monomer>
Since the (meth) acrylic acid ester monomer of the present invention has a polymerizable functional group, it is desirable to store it in a cool dark place. In addition, in order to prevent polymerization, the above-described polymerization inhibitor can be used and stored.
<Use of (meth) acrylic acid ester monomer>
The cyclic (meth) acrylate compound obtained in the present invention can be used as an acid generator diffusion preventing monomer that is one of the raw materials for resist resins, as a raw material monomer for paints, adhesive resins, etc. It can be widely used as a raw material for agricultural chemicals.

<Polymer, resist resin>
As an example of the use of the (meth) acrylic acid ester monomer of the present invention, a polymer = resist resin when used as a raw material for a resist resin composition, and production conditions thereof are described.
In the case of producing a resist resin, three types of acid dissociable monomer, substrate adhesion monomer and acid generator diffusion preventing monomer are mixed and copolymerized.
Examples of the acid dissociable monomer that can be used include adamantyl such as 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and 1-adamantyl-1-methylethyl (meth) acrylate. In addition to tertiary methacrylate having a group, 8-ethyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, 8-methyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl (meth) Cyclic tertiary (meth) acrylates other than adamantyl groups, such as acrylate, 2-methyl-2-norbornyl (meth) acrylate, 2-ethyl-2-norbornyl (meth) acrylate, 1-alkylcyclohexyl-1- (meth) acrylate Monocyclic tertiary such as 1-alkylcyclopentyl-1- (meth) acrylate Meth) acrylate can be used.
The amount of the acid dissociable monomer used in the production of the resist resin depends on the acid dissociation performance of the monomer used, but the lower limit is usually 5 mol%, preferably 10 mol%, more preferably 15 mol%. The upper limit is usually 60 mol%, preferably 50 mol%, more preferably 40 mol%. If the content of the acid dissociable monomer is too small, the balance of solubility in a solvent as a resist, dry etching resistance, resolution, etc. tends to be reduced. There is a tendency for adhesion to decrease.

Examples of the substrate adhesion monomer include 3-methacryloyloxymethyl-2,6-norbornanecarbolactone, 5-methacryloyloxy-2,6-norbornanecarbolactone, 8-methacryloyloxy-4-oxatricyclo [5.2.1.0. ^2,6 ] decan-3-one, 5- (meth) acryloyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one (= 5- (meth) acryloyloxy- 2,6-norbornanecarbolactone), 5- (meth) acryloyloxy-5-methyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5- (meth) acryloyl oxy-1-methyl-3-oxa-tricyclo [4.2.1.0 ^{4, 8]} nonane-2-one, 5- (meth) acryloyloxy-9-methyl - - oxatricyclo [4.2.1.0 ^{4, 8]} nonane-2-one, 5- (meth) acryloyloxy-9-carboxy-3-oxatricyclo [4.2.1.0 ^{4, 8} ] Nonan-2-one, 5- (meth) acryloyloxy-9-methoxycarbonyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5- (meth) acryloyloxy -9-Ethoxycarbonyl-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5- (meth) acryloyloxy-9-t-butoxycarbonyl-3-oxatricyclo [ 4.2.1.0 ^4,8 ] nonan-2-one, 8- (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-5-one, 9- (Meth) acryloyloxy-4 Oxatricyclo [5.2.1.0 ^{2, 6]} decan-5-one, 4- (meth) acryloyloxy-6-oxabicyclo [3.2.1] octan-7-one, 4- (meth ) Acryloyloxy-4-methyl-6-oxabicyclo [3.2.1] octane-7-one, 4- (meth) acryloyloxy-5-methyl-6-oxabicyclo [3.2.1] octane- 7-one, 4- (meth) acryloyloxy-4,5-dimethyl-6-oxabicyclo [3.2.1] octane-7-one, 6- (meth) acryloyloxy-2-oxabicyclo [2. 2.2] octane-3-one, 6- (meth) acryloyloxy-6-methyl-2-oxabicyclo [2.2.2] octane-3-one, 6- (meth) acryloyloxy-1-methyl -2- Other lactone rings such as xabibicyclo [2.2.2] octane-3-one and 6- (meth) acryloyloxy-1,6-dimethyl-2-oxabicyclo [2.2.2] octane-3-one Lactone compounds condensed to the ring, β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-α-methyl-γ-butyrolactone , Α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, β, β-trimethyl-γ-butyrolactone, α- (meth) acryloyloxy-γ, γ -Dimethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, γ, γ-trimethyl-γ-butyrolactone, α- (meth) acrylo Methacryloyloxy on the γ-lactone ring such as ruoxy-β, β, γ, γ-tetramethyl-γ-butyrolactone, α- (meth) acryloyloxy-α, β, β, γ, γ-pentamethyl-γ-butyrolactone A lactone compound having a group bonded thereto can be used.
The use amount of the substrate adhesion monomer with respect to all monomers used for producing the resist resin is usually 5 mol%, preferably 10 mol%, more preferably 15 mol%, and the upper limit is usually 60 mol%, preferably 50 mol. %, More preferably 40 mol%. When the content of the adhesive monomer is too small, the adhesion to the substrate as a resist tends to be reduced, and when too much, the balance of solvent solubility, dry etching resistance, resolution, etc. as a resist is lowered. Tend.

  Furthermore, as a monomer considered to have an acid generator diffusion preventing effect, the (meth) acrylic acid ester monomer of the present invention is used, but in addition to this, an existing acid dissociable monomer is used by mixing with it. Also good. Examples of the acid dissociable monomer that can be used in combination include 3-hydroxy-1-adamantyl (meth) acrylate, 1,3-dihydroxy-5- (meth) acryloyloxyadamantane, and 1-carboxy-3- (meth). Acryloyloxyadamantane, 1,3-dicarboxy-5- (meth) acryloyloxyadamantane, 1-carboxy-3-hydroxy-5- (meth) acryloyloxyadamantane, isosorbide mono (meth) acrylate, erythritan mono ( A (meth) acrylate having a hydroxyl group such as (meth) acrylate can be used.

  The amount of the acid generator diffusion preventing monomer used relative to all the monomers used in the production of the resist resin is usually 1 mol%, preferably 5 mol%, more preferably 10 mol%, and the upper limit is usually 40 mol%, preferably 30 mol%, more preferably 25 mol%. If the amount of the acid generator diffusion preventing monomer is too small, the control of the diffusion phenomenon of the acid generated from the acid generator in the resist film is not successful and tends to cause an undesirable chemical reaction. The balance of solvent solubility, dry etching resistance, resolution, etc. required for the resist resin tends to decrease.

The polymerization of these compounds can be carried out by a generally known method, and the method is not particularly limited. For example, a polymerization method in the presence of a radical initiator, a photopolymerization method in the presence of a photopolymerization initiator, an anionic polymerization method, or the like can be employed.
As the photopolymerization initiator, for example, aromatic ketones such as benzophenone, aromatic compounds such as anthracene and α-chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used.

Examples of the radical polymerization initiator include benzoyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxycarbonate, t-butyl. Organic peroxides such as peroxyisopropyl monocarbonate and azo compounds such as 2,2′-azobisisobutyronitrile (AIBN) can be used.
If necessary, a photopolymerization initiator and a radical polymerization initiator may be used in combination.

What is necessary is just to select the usage-amount of a radical polymerization initiator and a photoinitiator according to a well-known polymerization reaction. For example, the photopolymerization initiator is usually used in an amount of 0.001 to 20 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the compound of the present invention represented by the formula (1). . The radical polymerization initiator is usually used in an amount of 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the compound of the present invention represented by the formula (1). .
The reaction temperature usually has a lower limit of 0 ° C., preferably 10 ° C., while the upper limit is 200 ° C., preferably 100 ° C. As for the reaction time, the lower limit is usually 10 minutes, preferably 30 minutes, and the upper limit is not particularly limited.

<Resist resin composition>
The resist composition manufactured using a polymer obtained by using the (meth) acrylic acid ester monomer having the acid generator diffusion preventing effect of the present invention as a raw material is obtained by adding components generally used as a resist agent. Can be manufactured.

  One component of the acid generator is one that generates acid by decomposition of the substance by applying radiation such as light or electron beam to the substance itself or to a resist composition containing the substance. It is. The acid generated from the acid generator acts on the resin and cleaves the group that is cleaved by the action of the acid present in the resin. Such acid generators include, for example, onium salt compounds, organic halogen compounds, sulfone compounds, sulfonate compounds and the like. Specifically, the following compounds can be mentioned.

Diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) Iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tri Phenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyl Diphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium trifluoro Romethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate,
1- (2-naphthoylmethyl) thiolanium hexafluoroantimonate, 1- (2
-Naphthoylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 2-methyl-
4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (benzo [d] [1,3] Dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (3,4 5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 1-benzoyl-1-phenylmethyl p-toluenesulfonate (commonly known as benzoin tosylate), 2-benzoyl-2-hydroxy-2-phenyl Phenylethyl p-toluenesulfonate (commonly known as α-methylolbenzointosylate), 1,2,3-benzenetriyl trismethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4- Nitrobenzyl p-toluenesulfonate, diphenyl disulfone, di-p-tolyl disulfone, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (4-tert-butylphenyl) Sulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, N- (pheny Rusulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) naphthalimide and the like can be mentioned.

In general, in a chemically amplified positive resist composition, a basic compound, particularly a basic nitrogen-containing organic compound, for example, amines, is added as a quencher to deactivate the acid accompanying holding after exposure. It is known that the performance deterioration due to can be improved, and it is preferable to add such a basic compound also in the present invention. Specific examples of the basic compound used for the quencher include those represented by the following formulas.

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent hydrogen, alkyl optionally substituted with a hydroxyl group, cycloalkyl, aryl or alkoxy, and A represents alkylene, carbonyl or imino. To express. Here, the alkyl and alkoxy represented by R ^{11 to} R ¹⁵ can have about 1 to 6 carbon atoms, the cycloalkyl can have about 5 to 10 carbon atoms, and the aryl is a carbon atom. It can be about several 6 to 10. Further, the alkylene represented by A can have about 1 to 6 carbon atoms, and may be linear or branched.
The resist composition of the present invention contains 80 to 99.9% by weight of resin based on the total solid weight.
The acid generator is preferably contained in the range of 0.1 to 20% by weight. When the amount of the acid generator used is too small, the sensitivity and developability as a resist tend to be reduced. On the other hand, when the amount is too large, transparency to radiation is lowered and it is difficult to obtain a bowl-shaped resist pattern. Tend to be.

When a basic compound as a quencher is used, it is preferably contained in the range of 0.01 to 10% by weight based on the total solid weight of the resist composition. When the amount of the basic compound is too small, there is a concern that the resist pattern shape and dimensional stability may be lowered, and when it is too much, there is a concern that sensitivity as a resist and developability may be lowered.
This composition can also contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, and dyes as required.

The resist composition produced by using a polymer obtained by using a (meth) acrylic acid ester monomer having an acid generator diffusion preventing effect of the present invention as a raw material is usually in a state where each of the above components is dissolved in a solvent. A resist solution is applied on a substrate such as a silicon wafer. The solvent used here may be any solvent that dissolves each component, has an appropriate drying speed, and gives a uniform and smooth coating film after the solvent has evaporated, and is usually used in this field. Can be. For example, glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate, esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate, acetone, methyl isobutyl ketone, 2-butanone 2-pentanone, 2-heptanone, 2-octanone, 3-methylcyclopentanone, cyclohexanone, ketones such as 2-methylcyclohexanone, cyclic esters such as γ-butyrolactone, methyl 2-hydroxypropionate, 2 -Alkyl 2-hydroxypropionates such as ethyl hydroxypropionate and n-butyl 2-hydroxypropionate. Among these, ketones, cyclic esters, alkyl 2-hydroxypropionates and the like are preferable. These solvents can be used alone or in combination of two or more.

  The resist film coated on the substrate and dried is subjected to an exposure process for patterning, followed by a heat treatment for promoting a deprotecting group reaction, and then developed with an alkali developer. The alkaline developer used here may be various alkaline aqueous solutions used in this field. For example, sodium hydroxide, potassium hydroxide, sodium silicate, aqueous ammonia, n-propylamine, diethylamine, triethylamine, An aqueous solution of triethanolamine, tetramethylammonium hydroxide, piperidine, pyrrole, 2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) or the like is used. Of these, tetramethylammonium hydroxide and 2-hydroxyethyl) trimethylammonium hydroxide are preferably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.

<Analysis of purity by gas chromatography>
Column: DB-1 manufactured by Agilent Technologies
0.25mmφ, 30m, 0.25μm
Carrier gas: Helium Detector: FID
Inlet temperature: 250 ° C
Column tank temperature: Initial temperature 100 ° C. (hold for 5 minutes)
Temperature increase rate 10 ℃ / min
Final temperature 250 ° C (20 minutes hold)
Injection volume: 1 μL

<Gel permeation chromatography (hereinafter abbreviated as GPC) analysis conditions>
Column: Tosoh TSK-GEL G2000HXL
7.8 mm (ID) x 300 mm (L) x 2 Mobile phase: THF 1 mL / min Detector: RI
Column bath temperature: 40 ° C
Injection volume: 50 μL (0.1% THF solution)

<Compound name> In the reference examples and examples, the following abbreviations in parentheses are used.
・ 3,5,10-Trioxatricyclo [5.2.1.0 ^2,6 ] dec-8-en-4-one; (FVC)
・ 3,5,10-Trioxatricyclo [5.2.1.0 ^2,6 ] decan-4-one; (FVCH)
7-oxabicyclo [2.2.1] heptane-2,3-diol; (FEG)
・ 2-Methacryl-3-hydroxy-7-oxabicyclo [2.2.1] heptane; (FEGMA)
・ 2,3-Dimethacryl-7-oxabicyclo [2.2.1] heptane; (FEG (MA) 2)
2,2,6,6-tetramethylpiperidine-1-oxyl free radical; (TEMPO)

(Production example)
<Synthesis of FEG>
A 20 L-SUS reaction vessel was charged with 5.9 kg (68.6 mol) of vinylene carbonate and 0.944 kg (13.8 mol) of furan, and Diels-Alder reaction was performed at 130 ° C. for 21 hours. After completion of the reaction, excess vinylene carbonate was distilled and separated under conditions of 70 ° C./1064 Pa to obtain 1.35 kg of a pale yellow oil as a distillation residue. Next, 6 L of ethyl acetate was added to the distillation residue to dissolve it, and the insoluble matter was separated by filtration. Then, the filtrate was concentrated and dried under reduced pressure to obtain 1.3 kg of crude FVC. Next, 1.3 kg of crude FVC, 10 L of ethanol, and 14 L of toluene were added to a 100 L autoclave, and 140 g of 5% Pd / C catalyst (wet) was added, and hydrogen gas was pressurized to 0.3 MPa and stirred at room temperature for 7 hours. Hydrogenation reaction was carried out. After completion of the hydrogenation reaction, the catalyst was filtered and separated under a nitrogen gas stream, and the filtrate was concentrated and dried under reduced pressure to obtain 1.2 kg of crude FVCH. Crude FVCH was purified by distillation under the conditions of 150 to 160 ° C./266 to 399 Pa to obtain purified FVCH having a GC purity of 99.1%. Next, 60 g of purified FVCH was dissolved in 300 ml of methanol and 300 ml of water, 20 g of NaOH was added thereto, and a hydrolysis reaction was performed while stirring at room temperature for 4 hours. After completion of the reaction, the reaction solution was acidified by adding 41.7 ml of 35% HCl, methanol was distilled off, 40 g of NaCl and 600 ml of ethyl acetate / THF were added to the remaining aqueous layer, and the mixture was extracted and separated. The organic layer was concentrated and dried under reduced pressure to obtain 41.0 g of FEG. The above-described hydrolysis reaction of FVCH was performed several times.

(Example 1)
A 1 L reactor in which nitrogen was circulated was charged with 50.0 g (0.38 mol) of FEG synthesized in the reference example, 106.4 g (0.77 mol) of potassium carbonate, and 500 ml of acetonitrile, and ice water so that the temperature inside the system would be 5 ° C. or less. The mixture was stirred for 1 hr while cooling. Distilled and purified methacrylic acid chloride (purity by H-NMR analysis = 99 mol% or more, methacrylic acid chloride dimer content is 1 mol% or less) 50.0 g (0.48 mol) was applied over 1 h. And slowly dropped. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, then raised to room temperature, and the reaction was further continued for 7 hours. After completion of the reaction, 20 ml of 0.5% aqueous sodium hydrogen carbonate was added to the reaction solution to quench excess methacrylic acid chloride, and then the precipitated inorganic salt was separated by filtration. Next, 100 ml of 0.5% aqueous sodium hydrogen carbonate and 10 mg of a polymerization inhibitor TEMPO were added to the filtrate, and most of acetonitrile was distilled off with a rotary evaporator to obtain a pale yellow residue. When 150 ml of demineralized water is added to this product and ice-cooled, white crystals are precipitated. The white crystals are once separated by filtration, and then extracted by adding a mixed solvent of 600 ml of demineralized water / 50 ml of acetonitrile / 100 ml of n-heptane. Processed.

  To the aqueous layer after extraction, 100 g of NaCl is added and extracted three times with 300 ml of ethyl acetate solvent. Thereafter, the combined amount of the organic layer is washed several times with 50 ml of demineralized water, and 5 mg of methoxyphenol is added to the organic layer. And 40.4 g of a white solid was obtained by concentrating with a rotary evaporator. When this was analyzed by 1H-NMR, 13C-NMR, and GC-mass spectrum, it was clear that it was monomethacrylate (FEGMA) of 7-oxabicyclo [2.2.1] heptane-2,3-diol. became. (Handling yield based on raw material FEG: 52.5 mol%, GC purity (area ratio) = 99% <, GPC purity = 100%, the above general formulas (3) and (4) are not detected).

  On the other hand, the n-heptane layer used for the above extraction treatment was extracted several times with 20 ml of demineralized water, and then n-heptane was distilled off with a rotary evaporator to obtain 1.7 g of a pale yellow oil. When this was analyzed by 1H-NMR, 13C-NMR, and GC-mass spectrum, it was 7-oxabicyclo [2.2.1] heptane-2,3-diol dimethacrylate (FEG (MA) 2). It became clear (handling yield 1.7% by mole based on raw material FEG, GC purity (area ratio) = 97%).

<FEGMA>
(1H-NMR (400 MHz), CDCl3, in ppm); 6.17 (1H, s), 5.64 (1H, S), 4.4 to 4.7 (4H, m), 4.28 (1H, brs, OH), 2.2 to 1.6 ( 4H, m), 1.97 (3H, s)
(13C-NMR (400MHz), CDCl3, in ppm); 167.19, 135.64, 126.43, 79.45, 78.17, 70.61, 67.85, 23.41, 21.58, 18.22
GC-mass (CI ionization method: isobutane); M + H = 199

<FEG (MA) 2>
(1H-NMR (400MHz), CDCl3, in ppm); 6.09 (2H, s), 5.58 (2H, s), 4.96 (2H, m), 4.76 (2H, m), 2.1 to 1.6 (4H, m) , 1.92 (6H, s)
(13C-NMR (400MHz), CDCl3, in ppm); 166.28, 135.81, 126.16, 68.86, 22.73, 17.91
GC-mass (CI ionization method: isobutane); M + H = 267

(Example 2)
A reactor in which nitrogen was circulated was charged with 10.0 g (76.8 mmol) of FEG synthesized in the reference example, 23.4 g (169.3 mmol) of potassium carbonate, and 100 ml of acetonitrile, and ice water was added so that the temperature inside the system would be 5 ° C. or less. Cooled down. To this, 9.8 g of a reagent having a purity of methacrylic acid chloride of about 85 mol% (about 14 mol% is a compound represented by the general formulas (5) and (6)) was slowly added dropwise over 30 minutes. After dropping, the mixture was stirred at 5 ° C. for 1 hour, then the temperature was raised to room temperature and the reaction was continued for another 6 hours. After completion of the reaction, 4 ml of 0.5% aqueous sodium hydrogen carbonate was added to the reaction solution to quench the excess methacrylic acid chloride, and then the precipitated inorganic salt was separated by filtration. Next, 20 ml of 0.5% -sodium bicarbonate water and 2 mg of a polymerization inhibitor TEMPO were added to the filtrate, and most of acetonitrile was distilled off by a rotary evaporator to obtain a pale yellow residue. When 30 ml of demineralized water is added to this and ice-cooled, white crystals are precipitated. The white crystals are once separated by filtration, and then extracted by adding a mixed solvent of 120 ml of demineralized water / 20 ml of acetonitrile / 20 ml of n-heptane. Processed.

To the aqueous layer after extraction, 20 g of NaCl was added and extracted three times with 60 ml of ethyl acetate solvent. Thereafter, the combined organic layer was washed several times with 10 ml of demineralized water, and 1 mg of methoxyphenol was added to the organic layer. And concentrated with a rotary evaporator to obtain 7.0 g of yellowish white solid. The FEGMA purity in the obtained solid was 94% by GC analysis (area ratio) and 86% by GPC analysis (in terms of molar ratio). The other component in the GPC analysis was the compound of the general formula (3) (wherein R ² = H, R ⁴ = (5) or (6)) and was 14%.

(Example 3)
FEG 10.0 g (76.8 mmol), triethylamine 8.6 g (85.0 mmol), dimethylaminopyridine 1.0 g (8.2 mmol), and acetonitrile 100 ml were charged into a reactor in which nitrogen was circulated, and the system temperature was 5 ° C. It cooled with ice water so that it might become the following. To this, 13.1 g (85.0 mmol) of methacrylic anhydride was slowly added dropwise over 30 minutes. After the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour, and then the temperature was raised to room temperature and the reaction was continued for another 6 hours.

After completion of the reaction, 20 ml of 0.5% aqueous sodium hydrogen carbonate and 2 mg of a polymerization inhibitor TEMPO were added to the reaction solution, and most of acetonitrile was distilled off with a rotary evaporator.
A pale yellow aqueous layer residue was obtained. To this was added 50 ml of demineralized water and extracted with 20 ml of n-heptane. Next, NaCl more than the dissolved amount is added to the aqueous layer after extraction, and the mixture is extracted three times with 30 ml of ethyl acetate. Then, the organic layer after extraction is washed several times with 5 ml of demineralized water, and the organic layer is TEMPO.
By adding 2 mg and concentrating with a rotary evaporator, white solid FEGMA4
. 1 g was obtained (handling yield based on raw material FEG 26.6 mol%, GC purity (area ratio) = 98%, GPC purity (mol ratio conversion) = 97%, the other components were the above general formula (3) And 2
. It was 5%. ).

Example 4
FEG 10.0 g (76.8 mmol), methacrylic acid 6.70 g (77.8 mmol), dimethylaminopyridine 0.10 g (0.90 mmol) and methylene chloride 100 ml were charged into a reactor in which nitrogen was circulated. It cooled with ice water so that it might become 5 degrees C or less. A solution of 16.1 g (78.0 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 10 ml of methylene chloride was slowly added dropwise thereto over 30 minutes. After dropping, the reaction was continued for 30 minutes, and then the temperature was slowly raised to room temperature and the reaction was continued for 3 hours. After completion of the reaction, the precipitated urea was separated by filtration. To the filtrate, 20 ml of 0.5% aqueous sodium hydrogen carbonate and 2 mg of a polymerization inhibitor TEMPO were added, and most of the methylene chloride was distilled off with a rotary evaporator. A residue was obtained. When 30 ml of demineralized water is added to this and ice-cooled, white crystals are precipitated. The white crystals are once separated by filtration, and then extracted by adding a mixed solvent of 120 ml of demineralized water / 20 ml of acetonitrile / 20 ml of n-heptane. Processed.

To the aqueous layer after extraction, 20 g of NaCl was added and extracted three times with 60 ml of ethyl acetate solvent. Thereafter, the combined organic layer was washed several times with 10 ml of demineralized water, and 1 mg of methoxyphenol was added to the organic layer. In addition, 7.9 g of a pale yellowish white solid was obtained by concentrating with a rotary evaporator. The FEGMA purity in the obtained solid was 99% <in GC analysis (area ratio) and 100% in GPC analysis (converted in molar ratio).

Claims (7)

The cyclic (meth) acrylate compound which has a structure represented by following General formula (1).

(In formula (1), R ¹ and R ² are each a hydrogen atom or a (meth) acryloyl group represented by the following general formula (2), and at least one of R ¹ and R ² is represented by the general formula ( (It is a (meth) acryloyl group represented by 2).)

(In Formula (2), R ³ is a hydrogen atom or a methyl group, and a wavy line indicates a binding site.) The total content of the compounds having the structures represented by the following general formulas (3) and (4) is 15 mol% with respect to the cyclic (meth) acrylate compound having the structure represented by the general formula (1). The cyclic (meth) acrylate composition according to claim 1, wherein:

(In the formulas (3) and (4), R ² is a hydrogen atom or (meth) represented by the above general formula (2).
It is an acryloyl group, and R ⁴ , R ⁵ and R ⁶ each represent a group represented by the following general formula (5) or (6). )

(In the formulas (5) and (6), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, X represents a halogen atom, and a wavy line represents a binding site.)   7. 7-oxabicyclo [2.2.1] heptane-2,3-diol and (meth) acrylic acid halide are reacted in the presence of a basic substance. The manufacturing method of cyclic (meth) acrylate compound of this.   The manufacturing method of the cyclic (meth) acrylate compound of Claim 3 using what has a purity of 85 mol% or more as a raw material (meth) acrylic acid halide.   The production of the cyclic (meth) acrylate compound according to claim 3 or 4, wherein the raw material (meth) acrylic acid halide is a (meth) acrylic acid halide dimer content of 15 mol% or less. Method.   Resin resin composition comprising a cyclic (meth) acrylate compound represented by formula (1) according to claim 1 as a constituent component   The resist resin composition according to claim 6, comprising an acid dissociable monomer as a constituent component as a copolymer composition.