JP7137286B2 - (Meth)acrylate compound with fluorene skeleton - Google Patents

Description

The present invention relates to a novel bifunctional (meth)acrylate compound having a fluorene skeleton, a method for producing the same, a curable composition containing the (meth)acrylate compound, and a cured product obtained by curing the curable composition. .

In recent years, optical materials such as prism sheets, overcoat agents, hard coat agents, anti-reflection films, camera lenses, spectacle lenses, optical fibers, optical waveguides, and holograms used in liquid crystal display devices are lightweight, safe, and design. Plastics (resins) are often used as substitute materials for inorganic glass from the viewpoint of their properties. It is a type of resin that is frequently used as the above-mentioned material because it is characterized by being able to be cured at a relatively low temperature and easily.

On the other hand, the resin has a lower refractive index than inorganic glass, and when used as a substitute for inorganic glass, there is a problem that the thickness tends to be larger than that of inorganic glass. From this point of view, there is a demand for a higher refractive index.

Among the (meth)acrylate compounds used in the optical materials described above, bifunctional (meth)acrylate compounds derived from bisphenol compounds having a fluorene skeleton are known as compounds having a high refractive index [for example, Japanese Unexamined Patent Application Publication No. 2001-193004]. 04-325508 (Patent Document 1)].

However, while a bifunctional (meth)acrylate compound derived from a bisphenol compound having a fluorene skeleton has a high refractive index, a single cured product of the bifunctional (meth)acrylate compound has poor adhesion to a substrate. Therefore, it is necessary to blend a monofunctional (meth)acrylate compound for the purpose of improving the adhesion to the target substrate.

However, a bifunctional (meth)acrylate compound derived from a bisphenol compound having a fluorene skeleton has poor compatibility with the aforementioned monofunctional (meth)acrylate compound. It has often been difficult to prepare curable compositions containing concentrations.

JP-A-04-325508

An object of the present invention is to have excellent compatibility with monofunctional (meth)acrylate compounds and have a refractive index equal to or higher than that of bifunctional (meth)acrylate compounds derived from conventionally known bisphenol compounds having a fluorene skeleton. and a curable composition containing the compound, and a cured product obtained by curing the curable composition.

As a result of extensive research by the present inventors to solve the above problems, the bifunctional (meth)acrylate compound represented by the following general formula (1) has compatibility with a monofunctional (meth)acrylate compound. found to be superior to Specifically, the present invention includes the following inventions.

[1]
A (meth)acrylate compound represented by the following general formula (1).

（式中、Ｒ_１～Ｒ_４はそれぞれ同一又は異なってアルキル基、アリール基又はハロゲン原子を表し、Ｒ_５及びＲ_６はそれぞれ同一又は異なって分岐を有してもよい炭素数２～４のアルキレン基を表し、Ｒ_７及びＲ_８はそれぞれ同一又は異なって水素原子又はメチル基を示す。ｋ_１～ｋ_４はそれぞれ同一又は異なって０～４の整数を表し、ｎ_１及びｎ_２はそれぞれ同一又は異なって１以上の整数を表し、ｐ_１及びｐ_２はそれぞれ同一又は異なって１以上の整数を表す。ｋ_１～ｋ_４が２以上である場合、それぞれ対応するＲ_１～Ｒ_４は同一であっても異なってもよい。）

(In the formula, R ₁ to R ₄ are each the same or different and represent an alkyl group, an aryl group or a halogen atom, R ₅ and R ₆ are represents an alkylene group, R ₇ and R ₈ are the same or different and each represents a hydrogen atom or a methyl group, k ₁ to k ₄ are the same or different and represent an integer of 0 to 4, and n ₁ and n ₂ are each p 1 and p 2 are the same or different and each represents an integer of 1 or more, and each of p ₁ and p ₂ is the same or different and represents an integer of 1 or more, and when k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ are may be the same or different).

[2]
The (meth)acrylate compound according to [1], wherein n ₁ and n ₂ are 1 and k ₁ to k ₄ are 0 in the general formula (1).

[3]
A bis alcohol compound represented by the following general formula (2).

（式中、Ｒ_１～Ｒ_４はそれぞれ同一又は異なってアルキル基、アリール基又はハロゲン原子を表し、Ｒ_５及びＲ_６はそれぞれ同一又は異なって分岐を有してもよい炭素数２～４のアルキレン基を表す。ｋ_１～ｋ_４はそれぞれ同一又は異なって０～４の整数を表し、ｎ_１及びｎ_２はそれぞれ同一又は異なって１以上の整数を表し、ｐ_１及びｐ_２はそれぞれ同一又は異なって１以上の整数を表す。ｋ_１～ｋ_４が２以上である場合、それぞれ対応するＲ_１～Ｒ_４は同一であっても異なってもよい。）

(In the formula, R ₁ to R ₄ are each the same or different and represent an alkyl group, an aryl group or a halogen atom, R ₅ and R ₆ are represents an alkylene group, k ₁ to k ₄ are the same or different and represent an integer of 0 to 4, n ₁ and n ₂ are the same or different and represent an integer of 1 or more, and p ₁ and p ₂ are the same or are different and represent an integer of 1 or more.When k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ may be the same or different.)

[4]
The following general formula (2):

（式中、Ｒ_１～Ｒ_４はそれぞれ同一又は異なってアルキル基、アリール基又はハロゲン原子を表し、Ｒ_５及びＲ_６はそれぞれ同一又は異なって分岐を有してもよい炭素数２～４のアルキレン基を表す。ｋ_１～ｋ_４はそれぞれ同一又は異なって０～４の整数を表し、ｎ_１及びｎ_２はそれぞれ同一又は異なって１以上の整数を表し、ｐ_１及びｐ_２はそれぞれ同一又は異なって１以上の整数を表す。ｋ_１～ｋ_４が２以上である場合、それぞれ対応するＲ_１～Ｒ_４は同一であっても異なってもよい。）
で表わされるビスアルコール化合物と（メタ）アクリル酸類とを反応させる工程を含む、〔１〕又は〔２〕に記載の（メタ）アクリレート化合物の製造方法。

(In the formula, R ₁ to R ₄ are each the same or different and represent an alkyl group, an aryl group or a halogen atom, R ₅ and R ₆ are represents an alkylene group, k ₁ to k ₄ are the same or different and represent an integer of 0 to 4, n ₁ and n ₂ are the same or different and represent an integer of 1 or more, and p ₁ and p ₂ are the same or are different and represent an integer of 1 or more.When k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ may be the same or different.)
A method for producing a (meth)acrylate compound according to [1] or [2], comprising the step of reacting a bis alcohol compound represented by with (meth)acrylic acids.

[5]
A curable composition containing the (meth)acrylate compound according to [1] or [2].

[6]
A cured product of the curable composition according to [5].

According to the present invention, a bifunctional (meth)acrylate compound derived from a conventionally known bisphenol compound having a fluorene skeleton, which is said to have excellent compatibility with monofunctional (meth)acrylate compounds and to have a high refractive index. It is possible to provide a bifunctional (meth)acrylate compound that exhibits a refractive index equal to or higher than that of , and further has excellent transparency and a low Abbe number.

In particular, since the (meth)acrylate compound of the present invention has excellent compatibility with monofunctional acrylate compounds, it is possible to prepare a curable composition containing the (meth)acrylate compound of the present invention at a high concentration. Preparation of a curable composition and a cured product thereof that combine the properties of the (meth)acrylate compound of the present invention, such as refractive index, high transparency, and low Abbe, with the properties of a monofunctional acrylate compound, such as low viscosity and adhesion. becomes possible.

For example, by making the (meth)acrylate compound of the present invention compatible with 2-phenoxyethyl acrylate, which is a type of monofunctional acrylate compound, the (meth)acrylate cures with a high refractive index and high adhesion to a substrate such as polycarbonate. Also, by making it compatible with 2-(2-phenylphenoxyethyl) acrylate, it is possible to obtain a cured product with a higher refractive index than the cured product while having adhesion. It becomes possible.

1 is a ¹ H-NMR chart of a bisalcohol compound represented by the following formula (2-1) obtained in Example 1 among the bisalcohol compounds represented by the general formula (2). 1 is a ¹³ C-NMR chart of a bisalcohol compound represented by the following formula (2-1) obtained in Example 1 among the bisalcohol compounds represented by the general formula (2). 1 is a mass spectrometry chart of a bisalcohol compound represented by the following formula (2-1) obtained in Example 1, among the bisalcohol compounds represented by the general formula (2). 1 is a ¹ H-NMR chart of a (meth)acrylate compound represented by the following formula (1-1) obtained in Example 2 among the (meth)acrylate compounds represented by the general formula (1). . 13 is a ¹³ C-NMR chart of the (meth)acrylate compound represented by the following formula (1-1) obtained in Example 2 among the (meth)acrylate compounds represented by the general formula (1). . 1 is a mass spectrometry chart of a (meth)acrylate compound represented by the following formula (1-1) obtained in Example 2 among the (meth)acrylate compounds represented by the general formula (1).

<(Meth)acrylate compound of the present invention>
The (meth)acrylate compound of the present invention is a (meth)acrylate compound having a structure represented by the general formula (1).
In addition, in this specification, "(meth)acrylate" represents at least one selected from acrylate and methacrylate. A "(meth)acryloyl group" represents at least one selected from an acryloyl group and a methacryloyl group.

In the general formula (1), the alkyl group in the substituents (R ₁ to R ₄ ) includes an optionally branched alkyl group such as a methyl group, an ethyl group, a propyl group and an isopropyl group, a cyclopentyl group, A cyclic alkyl group such as a cyclohexyl group is exemplified.
Examples of the aryl group in the substituents (R ₁ to R ₄ ) include aromatic groups which may have a substituent such as a phenyl group and a tolyl group.
The halogen atoms in the substituents (R ₁ to R ₄ ) are exemplified by fluorine, chlorine, bromine and iodine atoms.
Among these substituents, an alkyl group having 1 to 4 carbon atoms, which may have a branch, is preferable from the viewpoint of the productivity of the bis alcohol compound represented by the general formula (2), which is a starting material.

k ₁ to k ₄ representing the number of substituents (R ₁ to R ₄ ) are the same or different, and each is an integer of 0 or 1 to 4; From the viewpoint of compound manufacturability, it is preferably 0 or 1, more preferably 0 (having no substituents).
When at least one of k ₁ to k ₄ is 2 or more, the corresponding substituents may be the same or different.

n ₁ and n ₂ representing the number of methylene groups connecting a phenyl group having a (meth)acryloyl group and another phenyl group are the same or different and represent an integer of 1 or more, preferably an integer of 1 to 4. , more preferably 1 or 2, more preferably 1, from the viewpoint of the manufacturability of the bisalcohol compound represented by the general formula (2), which is the raw material.

R ₅ and R ₆ are the same or different and each represent an optionally branched alkylene group having 2 to 4 carbon atoms. Examples of the optionally branched alkylene group having 2 to 4 carbon atoms represented by R ₅ and R ₆ include ethylene group, n-propylene group, (methyl)ethylene group, n-butylene group, s-( A methyl)propylene group and a t-(dimethyl)ethylene group can be mentioned. Among these alkylene groups, an ethylene group or a (methyl)ethylene group is preferred.
In addition, p ₁ and p ₂ representing oxyalkylene numbers are the same or different and represent an integer of 1 or more, preferably 1 or 2, particularly preferably 1.
_R7 and R8 are the _same or different and represent a hydrogen atom or a methyl group.

The (meth)acrylate compound of the present invention has excellent compatibility with monofunctional (meth)acrylate compounds, so that it is excellent in handleability, and a curable composition containing the (meth)acrylate compound of the present invention at a high concentration. can be prepared. Therefore, it is possible to easily obtain a curable composition capable of sufficiently exhibiting the properties of the (meth)acrylate compound of the present invention, or a cured product obtained by curing the curable composition.

The (meth)acrylate compound of the present invention usually has a refractive index of 1.59 or more, particularly 1.60 or more, further 1.61 or more, measured under the conditions described later. In addition, the Abbe number is 29 or less, especially 27 or less, and since it is possible to cancel chromatic aberration by combining it with a material with a high Abbe number, chromatic aberration is a problem, and it is preferable to have a high refractive index Various optical materials It can be suitably used as.

<Method for producing the (meth)acrylate compound of the present invention>
The (meth)acrylate compound represented by the general formula (1) of the present invention has the following general formula (3):

（式中、Ｒ_１～Ｒ_４、ｋ_１～ｋ_４並びにｎ_１及びｎ_２の意味は上記の通りである。）
で表されるビスフェノール化合物とアルキレンオキサイド又はアルキレンカーボネートとを反応させることによって上記一般式（２）で表されるビスアルコール化合物を得、該ビスアルコール化合物と（メタ）アクリレート類とを反応させることによって製造することができる。

(In the formula, the meanings of R ₁ to R ₄ , k ₁ to k ₄ and n ₁ and n ₂ are as described above.)
By reacting a bisphenol compound represented by and an alkylene oxide or alkylene carbonate to obtain a bis alcohol compound represented by the general formula (2), and reacting the bis alcohol compound with (meth)acrylates can be manufactured.

Among the alkylene oxides or alkylene carbonates used in the production of the bis alcohol compound represented by the above general formula (2), the alkylene oxide is a gas at room temperature or a liquid with a low boiling point. Alkylene carbonate is preferably used because it requires equipment and is difficult to improve the purity of the resulting bisalcohol compound represented by the general formula (2). The reaction between the bisphenol compound represented by the general formula (3) and the alkylene carbonate is described in detail below.

The amount of alkylene carbonate to be used is usually 2 to 10 mol, preferably 2 to 4 mol, per 1 mol of the bisphenol compound represented by the general formula (3). By using 2 mol or more, a sufficient reaction rate can be obtained, and by using 10 mol or less, the bisalcohol compound represented by the general formula (2) can be obtained more economically. . Alkylene carbonates may be used singly or in combination of two or more if necessary.

When carrying out the above reaction, it is possible to improve the reaction rate by carrying out the reaction in the presence of a basic compound. Examples of the basic compound used in this reaction include carbonates, hydrogen carbonates, hydroxides, organic bases, and the like. More specifically, the carbonates include potassium carbonate, sodium carbonate, carbonate Lithium, cesium carbonate, etc., as hydrogen carbonates such as potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, etc., as hydroxides, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. Examples of organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like.
Among these basic compounds, potassium carbonate, sodium carbonate, and triphenylphosphine are preferably used from the viewpoint of ease of handling. When using these basic compounds, the amount used is usually 0.01 to 1.0 mol, preferably 0.03 to 0.2 mol, per 1 mol of the bisphenol compound represented by the general formula (3). use. These basic compounds may be used singly or in combination of two or more, if necessary.

When carrying out the above reaction, an organic solvent may be used in combination, if necessary. Organic solvents that can be used in combination may be those that are inert to the bisphenol compound and alkylene carbonate represented by the general formula (3). Examples of such organic solvents include ketones and aromatic hydrocarbons. , halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, glymes, esters, aliphatic nitriles, sulfoxides, etc., more specifically ketones Examples include acetone, methyl ethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclohexanone, etc. Examples of aromatic hydrocarbons include toluene, xylene, mesitylene, etc. Halogen Examples of aromatic hydrocarbons include chlorobenzene and dichlorobenzene; examples of aliphatic hydrocarbons include pentane, hexane, and heptane; examples of halogenated aliphatic hydrocarbons include dichloromethane and 1,2-dichloroethane; are diethyl ether, diisopropyl ether, methyl t-butyl ether, cyclopentyl methyl ether, diphenyl ether, etc.; glymes such as methyl diglyme, ethyl diglyme, triglyme, diethylene glycol butyl methyl ether; etc., examples of aliphatic nitriles include acetonitrile, and examples of sulfoxides include dimethyl sulfoxide and the like.
Among these organic solvents that can be used in combination, aromatic hydrocarbons, ketones, ethers, or glymes having a boiling point of 110° C. or higher at 101.3 kPa are preferably used because of their availability and ease of handling. These organic solvents may be used singly or in combination of two or more if necessary.
When these organic solvents are used in combination, the amount used is usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 1 part by weight of the bisphenol compound represented by the general formula (3). .

The reaction between the bisphenol compound represented by the general formula (3) and the alkylene carbonate includes the bisphenol compound represented by the general formula (3) and the alkylene carbonate, and optionally a basic compound and / or can be used in combination. An organic solvent is added to the reaction vessel, and the reaction is usually carried out at 30-150°C, preferably 100-130°C.

After completion of the reaction, the bis-alcohol compound represented by the above general formula (2) can be taken out from the resulting reaction solution by a conventional method such as neutralization, washing with water, concentration, crystallization, filtration, etc., if necessary. The obtained bis-alcohol compound represented by the general formula (2) can be purified by standard methods such as recrystallization, distillation, adsorption and column chromatography.

The bis alcohol compound represented by the above general formula (2) of the present invention is used as a raw material for the (meth)acrylate compound represented by the above general formula (1), as well as thermoplastics such as polycarbonate, polyester, and polyester polycarbonate. Epoxy resins can also be obtained by epoxidizing resin monomers or conventional methods. In particular, since it has a high refractive index, it can be suitably used as a monomer for resins constituting optical members represented by optical lenses and optical films.

Subsequently, a method for producing a (meth)acrylate compound represented by the general formula (1) by reacting a bis alcohol compound represented by the general formula (2) with a (meth)acrylic acid (hereinafter referred to as This reaction is sometimes called a (meth)acrylate reaction) will be described in detail.

Examples of (meth)acrylic acids used in the (meth)acrylate reaction include (meth)acrylic acid, (meth)acrylic acid lower alkyl esters (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, (meth) ) C _1-4 alkyl (meth)acrylates such as butyl acrylate, etc.), (meth)acrylic acid halides (eg, (meth)acrylic acid chloride, etc.), (meth)acrylic anhydrides, and the like.
(Meth)acrylic acids may be used singly or in combination of two or more if necessary.

The amount of (meth)acrylic acid used is usually 2 to 20 mol, preferably 2.2 to 10 mol, more preferably 2.5 to 1 mol, per 1 mol of the bis alcohol compound represented by the general formula (2). 5 mol.

Acids or bases can be used as appropriate in the (meth)acrylate reaction. Examples of acids that can be used in the (meth)acrylate reaction include various acids such as inorganic acids and organic acids. Specifically, examples of inorganic acids include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, heteropolyacid, zeolite, clay minerals, etc. Organic acids include methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and ion exchange resins. etc. are exemplified. These acids may be used singly or in combination of two or more if necessary.

Bases that can be used in the (meth)acrylate reaction include, for example, inorganic bases and organic bases. Specifically, as inorganic bases, metal carbonates (alkali metal or alkaline earth metal carbonates such as sodium carbonate, alkali metal or alkaline earth metal hydrogen carbonates such as sodium hydrogen carbonate, etc.), metal carboxylates (acetic acid sodium, alkali metal acetate or alkaline earth metal salts such as calcium acetate), metal hydroxides (alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, etc.), etc. Examples include amines as organic bases [e.g., tertiary amines (trialkylamines such as triethylamine, triisopropylamine, and tributylamine; aromatic tertiary amines such as N,N-dimethylaniline; cyclic tertiary amine)] and the like. These bases may be used singly or in combination of two or more if necessary.

The amount of the acid or base used is usually 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 1 mol, per 1 mol of the bisalcohol compound represented by the general formula (2). 3 mol.

Moreover, the (meth)acrylate reaction may be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor), if necessary. Examples of polymerization inhibitors include hydroquinones (e.g., hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (methoquinone)), catechols (e.g., alkyl catechols such as t-butylcatechol), amines (e.g., , diphenylamine, etc.), 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl and the like. One kind of polymerization inhibitor may be used, or two or more kinds thereof may be used in combination, if necessary.

When a polymerization inhibitor is used, the amount used is usually 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 parts by weight, based on 100 parts by weight of (meth)acrylic acids. ~5 parts by weight.

The (meth)acrylate reaction may be carried out without using a solvent, or may be used in combination with an organic solvent. Organic solvents that can be used in combination include, for example, hydrocarbons, halogenated hydrocarbons, ethers, ketones, nitriles and the like. Specific examples of hydrocarbons include aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; Aliphatic halogenated hydrocarbons such as methylene, chloroform and carbon tetrachloride; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; ethers such as dialkyl ethers such as diethyl ether; Examples of ketones include dialkyl ketones such as acetone and methyl ethyl ketone, and examples of nitriles include acetonitrile, propionitrile, and benzonitrile. These organic solvents may be used singly or in combination of two or more if necessary. Also, when the acid or base is liquid, the acid or base may be used as a solvent.

When an organic solvent is used in combination, the amount used is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of the bis alcohol compound represented by the general formula (2).

The (meth)acrylate reaction is usually carried out at 80-140°C, preferably 100-130°C. Moreover, when carrying out the (meth)acrylate reaction, it may be carried out while removing by-produced water and alcohols. Also, the reaction can be carried out under pressure or under reduced pressure.

After completion of the (meth)acrylate reaction, the reaction mixture is directly used for the preparation of a curable composition to be described later, without taking out the (meth)acrylate compound represented by the general formula (1) from the obtained reaction mixture. good too. Further, if necessary, the (meth)acrylate compound represented by the general formula (1) is taken out by a conventional method such as neutralization, washing with water, concentration, crystallization, filtration, etc., and then the taken out general formula (1) You may use the (meth)acrylate compound represented by for preparation of a curable composition. Furthermore, the (meth)acrylate compound represented by the general formula (1) once taken out is purified by a conventional method such as recrystallization, distillation, adsorption, or column chromatography, and then the purified general formula (1) The represented (meth)acrylate compounds may be used in the preparation of curable compositions.

<Curable composition containing the (meth)acrylate compound of the present invention>
The curable composition containing the (meth)acrylate compound of the present invention includes, in addition to the (meth)acrylate compound represented by the general formula (1), other polyfunctional (meth)acrylate compounds, a polymerization initiator, A diluent or the like may be included. Since the (meth)acrylate compound represented by the general formula (1) has a low melt viscosity, only the (meth)acrylate compound represented by the general formula (1) is used as a curable composition and cured. It is also possible to obtain a cured product.

Other polyfunctional (meth)acrylate compounds that can be contained in the curable composition of the present invention include, for example, bifunctional (meth)acrylate {alkylene glycol di(meth)acrylate [ethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, C _2-10 alkylene glycol di(meth)acrylate such as 1,4-butanediol di(meth)acrylate], polyalkylene glycol di(meth)acrylate [di to tetraethylene glycol di(meth)acrylate (meth)acrylates, polyethylene glycol di(meth)acrylates, di- or tetrapropylene glycol di(meth)acrylates, poly- _C2-4 alkylene glycol di(meth)acrylates such as polytetramethylene glycol di(meth)acrylates], Di(meth)acrylate of bisphenol A (or C _2-3 alkylene oxide adduct thereof)}, trifunctional or higher polyfunctional (meth)acrylates [e.g., glycerin tri(meth)acrylate, trimethylolpropane tri(meth) ) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate tri or tetraol tri or tetra (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate; Pentaerythritol tetra to hexa (meth) acrylate, etc.], urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyfunctional (meth) acrylate having a fluorene skeleton {9,9-bis(4- 9,9-bis((meth)acryloyloxyphenyl)fluorenes such as (meth)acryloyloxyphenyl)fluorene and 9,9-bis(4-(meth)acryloyloxy-3-methylphenyl)fluorene;9,9 -9,9-bis[(meth)acryloyloxy(poly)ethoxyphenyl]fluorenes such as bis[4-(2-(meth)acryloyloxyethoxy)-3-methylphenyl]fluorene, etc.) and the like. These other polyfunctional (meth)acrylate compounds may be used singly or in combination of two or more if necessary.

When used in combination with other polyfunctional (meth)acrylate compound, the amount used is usually 1 to 300 parts by weight, preferably 100 parts by weight of the (meth)acrylate compound represented by the general formula (1). 2 to 200 parts by weight, more preferably 5 to 100 parts by weight.

Polymerization initiators that can be contained in the curable composition of the present invention include, for example, thermal polymerization initiators and photopolymerization initiators, and thermal polymerization initiators and photopolymerization initiators can be used in combination, if necessary. Thermal polymerization initiators include, for example, dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide ( benzoyl peroxide, etc.)], organic peroxides such as peresters (t-butyl peracetate, etc.), ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2'- azobis(isobutyronitrile), etc.], azo compounds such as azoamide compounds, azoamidine compounds, and the like. These thermal polymerization initiators may be used singly or in combination of two or more if necessary.

Examples of photopolymerization initiators include benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin isopropyl ether), acetophenones (acetophenone, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy -2-methyl-1-phenylpropan-1-one, etc.), aminoacetophenones {2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1, etc.}, anthraquinones (anthraquinone , 2-methylanthraquinone, etc.), thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (benzophenone, etc.) ), xanthones, and the like. These photopolymerization initiators may be used singly or in combination of two or more if necessary.

Moreover, you may use a photoinitiator in combination with a photosensitizer. Photosensitizers that can be used in combination include, for example, tertiary amines {e.g., trialkylamine, trialkanolamine (triethanolamine, etc.), ethyl N,N-dimethylaminobenzoate [p-(dimethylamino) ethyl benzoate, etc.], N,N-dimethylaminobenzoic acid amyl [p-(dimethylamino)benzoic acid amyl, etc.], dialkylaminobenzoic acid alkyl esters such as 4,4-bis(diethylamino)benzophenone (Michler's ketone), etc. dialkylaminobenzophenone such as bis(dialkylamino)benzophenone, 4-(dimethylamino)benzophenone, etc.} and the like. These photosensitizers may be used singly or in combination of two or more if necessary.

The amount of the polymerization initiator used is based on 100 parts by weight of the (meth)acrylate compound represented by the general formula (1) (when other polyfunctional (meth)acrylate compounds are used in combination, the general formula (1) with respect to 100 parts by weight of the total amount of the (meth)acrylate compound represented by and other polyfunctional (meth)acrylate compounds), usually 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 .5 to 10 parts by weight. Further, when the photosensitizer is used together with the polymerization initiator (photopolymerization initiator), the amount of the photosensitizer used is 5 to 200 parts by weight with respect to 100 parts by weight of the polymerization initiator (photopolymerization initiator). parts, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight.

Examples of diluents that can be included in the curable composition of the present invention include reactive diluents and/or non-reactive diluents (solvents). Specific examples of reactive diluents include polymerizable monomers such as alkyl (meth)acrylates [(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate and butyl (meth)acrylate]. acid C _1-20 alkyl, preferably C _1-10 alkyl (meth)acrylate, etc.], cycloalkyl methacrylate [C _5-8 cycloalkyl (meth)acrylate, such as cyclohexyl (meth)acrylate, etc.], Aryl (meth)acrylate [phenyl (meth)acrylate, etc.], hydroxyalkyl (meth)acrylate [(2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate hydroxy C2-10 alkyl (meth)acrylates such as acrylate], (poly)oxyalkylene glycol mono (meth) acrylate (diethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) (poly)oxy C _2-6 alkylene glycol mono(meth)acrylates such as acrylates), alkoxyalkyl (meth)acrylates [2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, etc.], phenoxy Alkyl (meth)acrylates [2-phenoxyethyl (meth)acrylate, 2-(2-phenylphenoxy)ethyl (meth)acrylate, etc.], N-substituted (meth)acrylamides (N,N-dimethyl (meth)acrylamide, etc. N,N-diC 1-4 alkyl (meth)acrylamide, N-hydroxy C _1-4 alkyl (meth)acrylamide such as N-methylol (meth)acrylamide), aminoalkyl (meth)acrylate (N,N-dimethyl aminoethyl acrylate, etc.), monofunctional (meth)acrylate compounds such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, or non-(meth)acrylic monomers (e.g., aromatic vinyl monomers (styrene, etc. ), etc.).
Among these reactive diluents, monofunctional (meth)acrylate compounds are preferable, especially 2-phenoxyethyl (meth)acrylate and 2-(2-phenylphenoxy)ethyl, since the adhesiveness of the cured product can be easily improved. (Meth)acrylates and cyclohexyl (meth)acrylates are preferred. These reactive diluents may be used singly or in combination of two or more if necessary.

When using a reactive diluent, the amount used is relative to 100 parts by weight of the (meth)acrylate compound represented by the general formula (1) (when using other polyfunctional (meth)acrylate compounds, the above Per 100 parts by weight of the total amount of the (meth)acrylate compound represented by the general formula (1) and other polyfunctional (meth)acrylate compounds), usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, and further It is preferably 10 to 200 parts by weight.

Examples of non-reactive diluents include aliphatic hydrocarbons, ketones, aromatic hydrocarbons, glycol ethers, esters, petroleum solvents and the like. Aliphatic hydrocarbons such as hexane, heptane and octane; ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; and glycol ethers such as ethyl cellosolve and methyl cellosolve. , carbitol, methyl carbitol, propylene glycol monomethyl ether, etc. are esters such as methyl acetate, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene carbonate and petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha and the like. These non-reactive diluents may be used singly or in combination of two or more if necessary.

When using a non-reactive diluent, the amount used is relative to 100 parts by weight of the (meth)acrylate compound represented by the general formula (1) (when using other polyfunctional (meth)acrylate compounds together, usually 1 to 500 parts by weight, preferably 20 to 300 parts by weight, relative to 100 parts by weight of the total amount of the (meth)acrylate compound represented by the general formula (1) and other polyfunctional (meth)acrylate compounds; More preferably 30 to 200 parts by weight.

The curable composition of the present invention contains other polyfunctional (meth)acrylate compounds, polymerization initiators, and diluents as described above, as well as conventional additives such as colorants, stabilizers (heat stabilizers, oxidation inhibitors, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, flame retardant aids, leveling agents, silane coupling agents, polymerization inhibitors (or thermal polymerization inhibitors), and the like. These additives may be used singly or in combination of two or more if necessary.

<Cured product of curable composition containing (meth)acrylate compound of the present invention>
A cured product of the curable composition containing the (meth)acrylate compound represented by the general formula (1) of the present invention is obtained by subjecting the curable composition of the present invention described above to a curing treatment described below. be done. For example, a film-like cured product is obtained by applying a curable composition containing a (meth)acrylate compound represented by the above general formula (1) to a substrate to form a coating film (or thin film). , can be produced by applying a curing treatment. The thickness of the film-like coating (or thin film) can be selected depending on the application, and is, for example, 0.1 to 1000 μm, preferably 1 to 500 μm, more preferably 5 to 300 μm.
Moreover, a cured product having a three-dimensional shape (for example, a prism shape, a lens shape, etc.) can be produced using cast molding, a 3D printer, or the like.
In addition, if necessary, the viscosity of the curable composition containing the (meth)acrylate compound represented by the general formula (1) may be reduced by heating prior to the curing treatment.

Examples of curing treatment include heat treatment and light irradiation treatment. Alternatively, heat treatment and light irradiation treatment may be combined. The heating temperature for heat treatment is, for example, 50 to 250°C, preferably 60 to 200°C, more preferably 70 to 150°C. ^In light irradiation treatment ⁽ exposure treatment), the amount of light irradiation energy varies depending on the application, the film thickness of the coating film, etc. More preferably 10 to 5000 mJ/cm ² .

The (meth)acrylate compound represented by the general formula (1) of the present invention has excellent compatibility or solubility in diluents such as organic solvents and monofunctional (meth)acrylate compounds. It is characterized in that a cured product can be easily produced without diluting with an agent. Therefore, compared with the case of using a conventionally known bifunctional (meth)acrylate compound derived from a bisphenol compound having a fluorene skeleton, a cured product can be produced more easily, and at the same time, it is represented by the above general formula (1). A cured product can be obtained which can sufficiently exhibit the properties (high refractive index, low Abbe, etc.) of the (meth)acrylate compound.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these. In the following examples, etc., each measured value was obtained according to the following method and measurement conditions. In addition, the production rate (remaining rate) and purity (HPLC purity) of each component described in Examples below are area percentages of HPLC measured under the following conditions.

[1] HPLC analysis (1-1) Bis-alcohol compound and HPLC analysis conditions for manufacturing the compound Apparatus: LC-20A manufactured by Shimadzu Corporation
・Column: XBridge Shield RP18 (3.5 μm, 4.6 mmφ×250 mm)
・Column temperature: 40°C
・ Mobile phase: A liquid = pure water, B liquid = acetonitrile ・ Mobile phase flow rate: 1.0 mL / min
- Mobile phase gradient: B solution concentration: 70% (0 min) → 70% (10 min) → 100% (20 min) → 100% (30 min)
・Detection wavelength: UV 254 nm

(1-2) (Meth) acrylate compound and HPLC analysis conditions at the time of manufacturing the compound Apparatus: LC-20A manufactured by Shimadzu Corporation
・Column: L-Column ODS (5 μm, 4.6 mmφ×250 mm)
・Column temperature: 40°C
・ Mobile phase: A solution = 30% methanol water, B solution = methanol ・ Mobile phase flow rate: 1.0 mL / min
- Mobile phase gradient: B solution concentration: 30% (0 min) → 100% (10 min) → 100% (35 min)
・Detection wavelength: UV 254 nm

[2] NMR measurement
¹ H-NMR and ¹³ C-NMR were recorded on a JEOL-ESC400 spectrometer using chloroform-d as solvent.

[3] LC-MS measurement Separation by LC-MS and mass spectrometry were performed under the following measurement conditions to identify the desired product.

・ Apparatus: "Xevo G2 Q-Tof" manufactured by Waters Co., Ltd.
・Column: L-Column2 ODS (2 μm, 2.1 mmφ×100 mm)
・Column temperature: 40°C
・Detection wavelength: UV 210-500 nm
・ Mobile phase: A liquid = pure water, B liquid = acetonitrile ・ Mobile phase flow rate: 0.3 mL / min
- Mobile phase gradient: B solution concentration: 80% (0 min) → 100% (15 min) → 100% (25 min)
・Detection method: Q-Tof
・Ionization method: APCI (+) method ・Ion Source: voltage (+) 2.0 kV, temperature 120 ° C.
・Sampling Cone: voltage 30V, gas flow 50L/h
・Desolvation Gas: temperature 500°C, gas flow 1000L/h

[4] Solubility in Monofunctional Acrylate Compound 70 parts by weight of the bifunctional (meth)acrylate compound obtained in Examples below and 30 parts by weight of the monofunctional acrylate compound described below were mixed, and the following evaluation was performed. Solubility was evaluated based on standards.
<Monofunctional acrylate>
・ 2-Phenoxyethyl acrylate (PEA) (manufactured by Tokyo Kasei)
・ 2-(2-phenylphenoxy) ethyl acrylate (OPPEA) (manufactured by Shin-Nakamura Chemical)
<Evaluation Criteria>
A: When heated at 80° C., it dissolves within 2 hours, and no crystals precipitate even after cooling.
B: Dissolves when heated at 80°C for 2 hours or more, does not crystallize when cooled. C: Dissolves when heated, crystals precipitate when cooled, or does not dissolve when heated.

[5] Refractive index and Abbe number number.
Each bifunctional (meth)acrylate compound was dissolved in N-methyl-2-pyrrolidone to obtain 5% by weight, 10% by weight, and 15% by weight solutions (for Comparative Examples 1 and 2, it was difficult to dissolve in organic solvents). Therefore, 1% by weight, 3% by weight, and 5% by weight) were prepared, and the refractive index at each wavelength was measured for each solution using the apparatus and conditions described later. Next, an approximate straight line was derived from the measured values obtained at three points, and the value obtained by extrapolating this to 100% by weight was defined as the refractive index of each bifunctional (meth)acrylate compound at each wavelength. Also, the Abbe number was calculated based on the obtained refractive index at each wavelength.
<Conditions for measurement of refractive index and Abbe number of each solution>
Apparatus: Abbe refractometer ("Multi-wavelength Abbe refractometer DR-2M" manufactured by Atago Co., Ltd.)
Measurement wavelength; refractive index: 589 nm (20°C), Abbe number: 486, 589, 656 nm (20°C)

<Example 1 Production of a bisalcohol compound represented by the following formula (2-1)>

In a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, the following formula (3-1):

で表されるビスフェノール化合物１２０．０ｇ（０．１７６モル）、トルエン１６２．２ｇ、トリグライム１６．５ｇ、エチレンカーボネート３８．７ｇ（０．４３９モル）、炭酸カリウム２．０ｇ（０．０１４モル）を仕込んだ後、１１０℃まで昇温し、同温度で１５時間撹拌を実施した。撹拌終了後、反応液を高速液体クロマトグラフィーにて分析を行ったところ、上記式（２－１）で表されるビスアルコール化合物の生成率が８０．９％、上記式（３－１）で表されるビスフェノール化合物の残存率が１．０％未満であることを確認し、反応終了とした。
得られた反応液に水酸化ナトリウム水溶液を添加し反応液を中和後、水層を除去し、さらに水を用いて４回水洗した。その後、トルエンを一部濃縮により留去した後、ヘプタンを加え、冷却することで結晶を析出させ、析出した結晶をろ別、乾燥することにより、上記式（２－１）で表されるビスアルコール化合物の結晶１３２．０ｇ（ＨＰＬＣ純度９７％、収率９７％）を得た。上記式（２－１）で表されるビスアルコール化合物の^１Ｈ－ＮＭＲ、^１３Ｃ－ＮＭＲ、ＬＣ－ＭＳの測定結果は下記の通りであった。

120.0 g (0.176 mol) of the bisphenol compound represented by After charging, the temperature was raised to 110° C., and stirring was carried out at the same temperature for 15 hours. After the stirring was completed, the reaction solution was analyzed by high-performance liquid chromatography. After confirming that the residual ratio of the represented bisphenol compound was less than 1.0%, the reaction was terminated.
An aqueous sodium hydroxide solution was added to the obtained reaction solution to neutralize the reaction solution, the aqueous layer was removed, and the reaction solution was washed with water four times. Thereafter, toluene is partially distilled off by concentration, heptane is added, and the crystals are precipitated by cooling. The precipitated crystals are separated by filtration and dried to obtain the bis 132.0 g of alcohol compound crystals (HPLC purity 97%, yield 97%) were obtained. The measurement results of ¹ H-NMR, ¹³ C-NMR and LC-MS of the bisalcohol compound represented by the above formula (2-1) were as follows.

¹ H-NMR (CDCl ₃ )
δ = 1.38 ppm (2H, t), 3.32-3.40 (8H, m), 3.97 (4H, s), 6.98 (2H, d), 7.05-7.37 ( 28H, m), 7.72 (2H, d)

¹³ C-NMR (CDCl ₃ )
δ = 36.49ppm, 62.04ppm, 64.63ppm, 74.18ppm, 120.32ppm, 126.06ppm, 127.36ppm, 127.58ppm, 127.79ppm, 128.35ppm, 128.43ppm, 128.60ppm, 128.92ppm, 129.28ppm, 130.93ppm, 133.75ppm, 134.76ppm, 138.86ppm, 140.12ppm, 140.93ppm, 141.63ppm, 151.16ppm, 153.08ppm

Mass spectrum value (M+NH ₄ ) ⁺ : 788.3746
(Calculated molecular weight of the compound represented by the above formula (2-1) (TOF MS APCI ⁺ ; C ₅₅ H ₄₆ O ₄ +NH ₄ ): 788.3740)

<Example 2 Production of an acrylate compound represented by the following formula (1-1)>

98.16 g (0.13 mol) of the bisalcohol compound represented by the above formula (2-1) and 3.21 g of p-toluenesulfonic acid were placed in a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. (0.017 mol), 0.32 g (0.0026 mol) of p-methoxyphenol, 24.20 g (0.34 mol) of acrylic acid and toluene are added, and the mixture is refluxed at 110°C to 115°C until the theoretical amount of dehydration is obtained. A dehydration esterification reaction was carried out.
After the reaction, HPLC analysis of the reaction solution revealed that 87.0% of the acrylate compound represented by the above formula (1-1) was produced.
A 6% sodium hydroxide aqueous solution was added to the obtained reaction solution to neutralize it, then washed with pure water four times, and concentrated under reduced pressure to obtain an acrylate compound 115.1 represented by the above formula (1-1). 1 g was obtained (HPLC purity: 86.3%).
Table 1 shows the measurement results of the refractive index, Abbe number, and compatibility with the monofunctional acrylate compound of the obtained acrylate compound represented by the above formula (1-1). Further, the measurement results of ¹ H-NMR, ¹³ C-NMR and LC-MS of the acrylate compound represented by the above formula (1-1) were as follows.

¹ H-NMR (CDCl ₃ , 400 MHz)
δ = 3.4 ppm (4H, t), 4.0 ppm (4H, s), 4.1 ppm (4H, t), 5.8 ppm (2H, d), 6.0 ppm (2H, dd), 6.313 ppm (2H,d), 6.98-7.40ppm (30H,m), 7.7ppm (2H,d)

¹³ C-NMR (CDCl ₃ )
δ = 21.56ppm, 36.38ppm, 63.65ppm, 64.68ppm, 70.14ppm, 120.32ppm, 125.41ppm, 125.99ppm, 126.13ppm, 127.23ppm, 127.57ppm, 127.78ppm, 128.32ppm, 128.37ppm, 128.80ppm, 128.99ppm, 129.15ppm, 129.19ppm, 130.63ppm, 131.04ppm, 134.18ppm, 134.40ppm, 137.97ppm, 138.72ppm, 140. 15ppm, 141.11ppm, 141.69ppm, 151.22ppm, 152.96ppm, 165.99ppm

Mass spectrometric value (M+NH ₄ ) ⁺ : 896.3946
(Calculated molecular weight of the compound represented by the above formula (1-1) (TOF MS APCI ⁺ ; C ₅₇ H ₄₂ O ₄ +NH ₄ ): 896.3951)

<Comparative Example 1 Production of an acrylate compound represented by the following formula (4)>

攪拌器、冷却器及び温度計を備えた５００ｍＬのガラス製反応容器に、９，９－ビス（４－（２－ヒドロキシエトキシ）－フェニル）フルオレン２００．００ｇ（０．４６ｍｏｌ）、ｐ－トルエンスルホン酸１１．２８ｇ（０．０５９ｍｏｌ）、ｐ－メトキシフェノール１．１３ｇ（０．００９１ｍｏｌ）、アクリル酸８４．０８ｇ（１．１７ｍｏｌ）及びトルエンを投入し、１１０℃～１１５℃で還流しながら理論脱水量を得るまで脱水エステル化反応を行った。
反応後、反応液をＨＰＬＣ分析したところ上記式（４）で表されるアクリレート化合物が８８．３％生成していた。
得られた反応液に５％重曹水を加えて中和した後、食塩水で２回洗浄し、減圧下で濃縮することで上記式（４）で表されるアクリレート化合物２５８．８ｇを得た（ＨＰＬＣ純度：８６．９％）。
得られた上記式（４）で表されるアクリレート化合物の屈折率、アッベ数、及び単官能性アクリレート化合物に対する相溶性の測定結果について表１に示す。

In a 500 mL glass reaction vessel equipped with stirrer, condenser and thermometer, 200.00 g (0.46 mol) of 9,9-bis(4-(2-hydroxyethoxy)-phenyl)fluorene, p-toluenesulfone Add 11.28 g (0.059 mol) of acid, 1.13 g (0.0091 mol) of p-methoxyphenol, 84.08 g (1.17 mol) of acrylic acid and toluene, and theoretically dehydrate under reflux at 110°C to 115°C. The dehydration esterification reaction was carried out until the mass was obtained.
After the reaction, HPLC analysis of the reaction solution revealed that 88.3% of the acrylate compound represented by the above formula (4) was produced.
The obtained reaction solution was neutralized by adding 5% aqueous sodium bicarbonate, washed twice with brine, and concentrated under reduced pressure to obtain 258.8 g of the acrylate compound represented by the above formula (4). (HPLC purity: 86.9%).
Table 1 shows the measurement results of the refractive index, Abbe number, and compatibility with the monofunctional acrylate compound of the obtained acrylate compound represented by the above formula (4).

<Comparative Example 2 Production of an acrylate compound represented by the following formula (5)>

攪拌器、冷却器及び温度計を備えた５００ｍＬのガラス製反応容器に、９，９－ビス（４－（２－ヒドロキシエトキシ）－３－メチルフェニル）フルオレン６０．００ｇ（０．１３ｍｏｌ）、ｐ－トルエンスルホン酸３．１８ｇ（０．０１７ｍｏｌ）、ｐ－メトキシフェノール０．３２ｇ（０．００２６ｍｏｌ）、アクリル酸２４．０９ｇ（０．３３ｍｏｌ）及びトルエンを投入し、１１０℃～１１５℃で還流しながら理論脱水量を得るまで脱水エステル化反応を行った。
反応後、反応液をＨＰＬＣ分析したところ上記式（５）で表されるアクリレート化合物が８８．６％生成していた。
得られた反応液に５％重曹水を加えて中和した後、食塩水で２回洗浄し、減圧下で濃縮することで上記式（５）で表されるアクリレート化合物６６．４ｇを得た（ＨＰＬＣ純度：８８．６％）。
得られた上記式（５）で表されるアクリレート化合物の屈折率、アッベ数、及び単官能性アクリレート化合物に対する相溶性の測定結果について表１に示す。

In a 500 mL glass reaction vessel equipped with stirrer, condenser and thermometer, 60.00 g (0.13 mol) of 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, p - 3.18 g (0.017 mol) of toluenesulfonic acid, 0.32 g (0.0026 mol) of p-methoxyphenol, 24.09 g (0.33 mol) of acrylic acid and toluene were added and refluxed at 110°C to 115°C. The dehydration esterification reaction was continued until the theoretical amount of dehydration was obtained.
After the reaction, HPLC analysis of the reaction solution revealed that 88.6% of the acrylate compound represented by the above formula (5) was produced.
The obtained reaction solution was neutralized by adding 5% aqueous sodium bicarbonate solution, washed twice with brine, and concentrated under reduced pressure to obtain 66.4 g of an acrylate compound represented by the above formula (5). (HPLC purity: 88.6%).
Table 1 shows the measurement results of the refractive index, Abbe number, and compatibility with the monofunctional acrylate compound of the obtained acrylate compound represented by the above formula (5).

Claims (6)

A (meth)acrylate compound represented by the following general formula (1).

(In the formula, R ₁ to R ₄ are each the same or different and represent an alkyl group, an aryl group or a halogen atom, R ₅ and R ₆ are represents an alkylene group, R ₇ and R ₈ are the same or different and each represents a hydrogen atom or a methyl group, k ₁ to k ₄ are the same or different and represent an integer of 0 to 4, and n ₁ and n ₂ are each are the same or different and represent an integer of 1 to 4 , and p ₁ and p ₂ are the same or different and represent 1 or 2. When k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ are may be the same or different). 2. The (meth)acrylate compound according to claim 1, wherein n ₁ and n ₂ are 1 and k ₁ to k ₄ are 0 in the general formula (1). A bis alcohol compound represented by the following general formula (2).

(In the formula, R ₁ to R ₄ are each the same or different and represent an alkyl group, an aryl group or a halogen atom, R ₅ and R ₆ are represents an alkylene group, k ₁ to k ₄ are the same or different and represent an integer of 0 to 4, n ₁ and n ₂ are the same or different and represent an integer of 1 to 4 , and p ₁ and p ₂ are each are the same or different and represent 1 or 2. When k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ may be the same or different.) The following general formula (2):

(In the formula, R ₁ to R ₄ are each the same or different and represent an alkyl group, an aryl group or a halogen atom, R ₅ and R ₆ are represents an alkylene group, k ₁ to k ₄ are the same or different and represent an integer of 0 to 4, n ₁ and n ₂ are the same or different and represent an integer of 1 to 4 , and p ₁ and p ₂ are each are the same or different and represent an integer of 1 or 2. When k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ may be the same or different.)
The method for producing a (meth)acrylate compound according to claim 1 or 2, comprising the step of reacting the bis alcohol compound represented by with (meth)acrylic acids. A curable composition comprising the (meth)acrylate compound according to claim 1 or 2. A cured product of the curable composition according to claim 5 .

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