TW201927739A - (meth)acrylate compound having fluorene skeleton - Google Patents

Abstract

An objective of the present invention is to provide a bifunctional (meth)acrylate compound which exhibits compatibility with a monofunctional (meth)acrylate compound and high refractive index. The objective of the present invention can be solved by a (meth)acrylate compound represented by the following general formula (1). (Wherein, R1 to R4 are the same or different and each represents an alkylene group, an aryl group or a halogen atom which may be branched, R5 and R6 are the same or different and each represents an alkylene group having 2 to 4 carbon atoms which may be branched, R7 and R8 are the same or different and each represents a hydrogen atom or a methyl group. k1 to k4 are the same or different and each represents an integer of 0 to 4, n1 and n2 are the same or different and each represents an integer of 1 or more, p1 and p2 are the same or different and each represents an integer of 1 or more. When k1 to k4 are 2 or more, the corresponding R1 to R4 may be the same or different.).

Description

(Meth) acrylate compound having fluorene skeleton

The present invention relates to a novel difunctional (meth) acrylate compound having a fluorene skeleton, a method for producing the same, a hardenable composition containing the (meth) acrylate compound, and a composition made of the hardenable composition. Of hardened.

In recent years, from the viewpoints of lightness, safety, and design, it has been used in cymbals, overcoat agents, hard coating agents, anti-reflection films, or so-called camera lenses and glasses for liquid crystal display devices. Among the optical materials of lenses, optical fibers, optical waveguides, and holograms, plastic (resin) is often used as a substitute for inorganic glass. Among these resins, (meth) acrylate compounds are polymerized The (meth) acrylate resin obtained by (hardening) is one of the resins often used as the aforementioned material because it has a feature that it can be easily hardened at a relatively low temperature by active energy rays.

On the other hand, because the refractive index of the resin is lower than that of the inorganic glass, when it is used instead of the inorganic glass, there is a problem that the thickness is likely to become larger than that of the inorganic glass. From the point of view, the system is required to further increase the refractive index.

Among the (meth) acrylate compounds used in the aforementioned optical materials, as a high refractive index compound, a bifunctional (meth) acrylate compound derived from a bisphenol compound having a fluorene skeleton is known [for example, Japanese special Kaihei 04-325508 (Patent Document 1)].

However, although a bifunctional (meth) acrylate compound derived from a bisphenol compound having a fluorene skeleton has a high refractive index, on the other hand, because of the single hardening of the difunctional (meth) acrylate compound The adhesion of the object to the substrate is poor, so in order to improve the adhesion with the target substrate, it is necessary to prepare a monofunctional (meth) acrylate compound.

However, since the bifunctional (meth) acrylate compound derived from a bisphenol compound having a fluorene skeleton is poorly compatible with the monofunctional (meth) acrylate compound described above, it is often difficult to prepare the difunctional compound at a high concentration. A hardening composition of a non-toxic (meth) acrylate compound.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 04-325508

It is an object of the present invention to provide a monofunctional (meth) acrylate compound which is excellent in compatibility with the monofunctional (meth) acrylate compound and shows a bifunctional (meth) acrylate compound derived from a bisphenol compound having a fluorene skeleton that has been conventionally known. Bifunctional (meth) acrylic acid with a refractive index of at least An ester compound, a curable composition containing the compound, and a cured product obtained by curing the curable composition.

In order to solve the aforementioned problems, the present inventors repeated the results of intensive studies and found that the bifunctional (meth) acrylate compound represented by the following general formula (1) is excellent in monofunctional (meth) acrylate compounds Compatibility. Specifically, the present invention includes the following inventions.

[1]

A (meth) acrylate compound is 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 each the same or different and represent a branched carbon number of 2 to 4 R ₇ and R ₈ are each the same or different and represent a hydrogen atom or a methyl group; k ₁ to k ₄ are each the same or different and represent an integer of 0 to 4; n ₁ and n ₂ are each the same or different and represent An integer of 1 or more; p ₁ and p ₂ are each the same or 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).

[2]

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

[3]

A diol compound is 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 each the same or different and represent a branched carbon number of 2 to 4 K ₁ to k ₄ are each the same or different and represent integers from 0 to 4; n ₁ and n ₂ are each the same or different and represent integers greater than 1; p ₁ and p ₂ are each the same or different and represent 1 The above integers; when k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ may be the same or different).

[4]

A method for producing a (meth) acrylate compound according to [1] or [2], comprising a step of reacting a bishydric compound represented by the following general formula (2) with a (meth) acrylic compound;

(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 each the same or different and represent a branched carbon number of 2 to 4 K ₁ to k ₄ are each the same or different and represent integers from 0 to 4; n ₁ and n ₂ are each the same or different and represent integers greater than 1; p ₁ and p ₂ are each the same or different and represent 1 The above integers; when k ₁ to k ₄ are 2 or more, the corresponding R ₁ to R ₄ may be the same or different).

[5]

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

[6]

A cured product, which is a cured product of the curable composition described in [5].

According to the present invention, it is possible to provide a difunctional (meth) acrylate compound having both of the following characteristics: excellent compatibility with monofunctional (meth) acrylate compounds, and exhibiting a fluorene skeleton from a conventionally known one Bifunctional (meth) acrylate compounds derived from bisphenol compounds It has the same or higher refractive index, has excellent transparency, and has a low Abbe number.

In particular, since the (meth) acrylate compound of the present invention is excellent in compatibility with the monofunctional acrylate compound, a curable composition containing the (meth) acrylate compound of the present invention at a high concentration can be prepared. The result is A hardening composition capable of producing the characteristics of the (meth) acrylate compound of the present invention having both high refractive index, high transparency, and low Abbe number, as well as low viscosity / adhesion properties of the monofunctional acrylate compound And its hardened matter.

For example, by mixing the (meth) acrylate compound of the present invention with 2-phenoxyethyl acrylate, which is a kind of monofunctional acrylate compound, it is possible to obtain a high refractive index and adhesion to a substrate such as polycarbonate. A hardened (meth) acrylate hardened product, and by making it compatible with 2- (2-phenylphenoxyethyl) acrylate, it is possible to obtain a hardened material having a higher refractive index and a hardened refractive index. Higher solidified matter.

FIG. 1 is a ¹ H-NMR chart of the bishydric compound represented by the following formula (2-1) obtained in Example 1 among the bishydric compounds represented by the general formula (2).

FIG. 2 is a ¹³ C-NMR chart of the bishydric compound represented by the following formula (2-1) obtained in Example 1 among the bishydric compounds represented by the general formula (2).

FIG. 3 shows the implementation of the bis-alcohol compound represented by the general formula (2). The mass analysis chart of the bishydric compound represented by the following formula (2-1) obtained in Example 1.

FIG. 4 is ¹ H- 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). NMR chart.

FIG. 5 is ¹³ C- 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). NMR chart.

FIG. 6 is a mass analysis 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). .

<(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).

The "(meth) acrylate" as used in this specification means at least one selected from the group consisting of acrylate and methacrylate. The "(meth) acrylfluorenyl group" means at least one selected from the group consisting of acrylfluorenyl and methacrylfluorenyl.

Examples of the alkyl group as the substituent (R ₁ to R ₄ ) in the general formula (1) include branched alkyl groups such as methyl, ethyl, propyl, and isopropyl, and cyclopentyl, Cycloalkyl such as cyclohexyl and the like.

Examples of the aryl group as the substituent (R ₁ to R ₄ ) include an aromatic group which may have a substituent such as a phenyl group and a tolyl group.

Examples of the halogen atom as the substituent (R ₁ to R ₄ ) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

From the viewpoint of the manufacturability of the bishydric compound represented by the above-mentioned general formula (2), which is a raw material, among these substituents, an alkyl group having 1 to 4 carbon atoms which is branched is preferred.

K ₁ to k ₄ representing the number of substituents (R ₁ to R ₄ ) are each the same or different, and represent an integer of 0 or 1 to 4 and belong to the production of a bishydric compound represented by the general formula (2) above as a raw material From the viewpoint of sex, 0 or 1 is more preferable, and 0 (without a substituent) is more preferable.

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 represent the number of a methylene group having a phenyl group having a (meth) acrylfluorenyl group and other phenyl groups, and n ₁ and n ₂ are each the same or different and represent an integer of 1 or more, preferably Is an integer from 1 to 4. From the viewpoint of the manufacturability of the bishydric compound represented by the general formula (2), which is a raw material, 1 or 2 is more preferable, and 1 is still more preferable.

R ₅ and R ₆ are each the same or different, and represent an alkylene group having 2 to 4 carbon atoms which may be branched. Examples of the alkylene group having a branched carbon number of 2 to 4 represented by R ₅ and R ₆ include, for example, ethylene, n-propylene, (methyl) ethyl, and butylene. (N-butylene), second (meth) propyl, and third (dimethyl) ethyl. Among these alkylene groups, ethylidene or (methyl) ethylidene is preferred.

In addition, p ₁ and p ₂ representing the number of oxyalkylene are the same or different, and represent an integer of 1 or more, preferably 1 or 2, and particularly preferably 1.

R ₇ and R ₈ are each the same or different and represent a hydrogen atom or a methyl group.

Since the (meth) acrylate compound of the present invention has excellent compatibility with monofunctional (meth) acrylate compounds, it has excellent operability and can be prepared to contain the (meth) acrylate of the present invention at a high concentration. Compound hardening composition. Therefore, a hardenable composition capable of sufficiently exerting the characteristics of the (meth) acrylate compound of the present invention, or a hardened product obtained by curing the hardenable composition can be easily obtained.

The refractive index of the (meth) acrylate compound of the present invention measured under the conditions described later is usually 1.59 or more, particularly 1.60 or more, and further 1.61 or more. In addition, the Abbe number is 29 or less, especially 27 or less. In particular, chromatic aberration can be eliminated by combining with a material with a high Abbe number. Therefore, it can be suitably used as a problem of chromatic aberration. High refractive index is the preferred optical material.

<The manufacturing method of the (meth) acrylate compound of this invention>

The (meth) acrylate compound represented by the general formula (1) of the present invention can be obtained by reacting a bisphenol compound represented by the following general formula (3) with an alkylene oxide or an alkylene carbonate. A bis-alcohol compound represented by formula (2), and produced by reacting the bis-alcohol compound with (meth) acrylates; (In the formula, R ₁ to R ₄ , k ₁ to k _4, and n ₁ and n _{2 have} the same meanings as described above).

Among the alkylene oxides or alkylene carbonates used in the production of the bis-alcohol compound represented by the above general formula (2), because the alkylene oxide is a gas at normal temperature or a liquid with a low boiling point, its operation requires special equipment . Moreover, since it is not easy to improve the purity of the obtained diol compound represented by the said General formula (2), it is preferable to use an alkylene carbonate. The reaction between the bisphenol compound represented by the general formula (3) and the alkylene carbonate will be described in detail below.

The amount of the alkylene carbonate used is usually 2 to 10 mol, preferably 2 to 4 mol, relative to 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 an amount of 10 mol or less, a bishydric compound represented by the general formula (2) can be obtained more economically. The alkylene carbonate may be used singly or in combination of two or more kinds as necessary.

When carrying out the above reaction, the reaction speed can be increased by carrying out the reaction in the presence of a basic compound. Examples of the basic compound used in this reaction include carbonates, bicarbonates, hydroxides, and organic bases. More specifically, carbonates may be exemplified: potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, etc .; bicarbonates may be exemplified: Potassium bicarbonate, sodium bicarbonate, lithium bicarbonate, cesium bicarbonate, etc .; hydroxides can be exemplified: sodium hydroxide, potassium hydroxide, lithium hydroxide, etc .; organic bases can be exemplified: triethylamine, dimethylamine Pyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride, and the like.

Among these basic compounds, potassium carbonate, sodium carbonate, and triphenylphosphine can be suitably used in terms of good operability. The amount used when using these basic compounds is generally 0.01 to 1.0 mol, preferably 0.03 to 0.2 mol, relative to 1 mol of the bisphenol compound represented by the general formula (3). These basic compounds may be used singly or in combination of two or more kinds as necessary.

When carrying out the above reaction, an organic solvent may be used in combination as necessary. The organic solvent that can be used in combination may be any one that is inert to the bisphenol compound and the alkylene carbonate represented by the general formula (3). Examples of such organic solvents include ketones, aromatic hydrocarbons, and halogenated aromatics. Hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, glycol dimethyl ethers (glyme), esters, aliphatic nitriles, fluorenes, etc., more specifically, ketones may Examples: acetone, methyl ethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclohexanone, etc .; aromatic Examples of the group of hydrocarbons include toluene, xylene, 1,3,5-mesitylene and the like; examples of halogenated aromatic hydrocarbons include chlorobenzene and dichlorobenzene; examples of the aliphatic hydrocarbons include pentane and hexane , Heptane, etc .; halogenated aliphatic hydrocarbons can be exemplified: methylene chloride, 1,2-dichloroethane, etc .; ethers can be exemplified: diethyl ether, diisopropyl ether, methyl tertiary butyl ether, cyclopentyl Methyl ether, diphenyl ether, etc .; ethylene glycol dimethyl ethers can be exemplified by methyl diethylene glycol dimethyl ether, ethyl diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether ,two Glycol butyl ether and the like; esters can be exemplified: Ethyl acetate, butyl acetate, and the like; aliphatic nitriles can be exemplified: acetonitrile and the like; fluorenes can be exemplified: dimethyl sulfene and the like.

Among these organic solvents that can be used in combination, aromatic hydrocarbons, ketones, ethers, or ethylene glycol dimethyl having a boiling point of 110 ° C or higher at 101.3 kPa can be suitably used in terms of good availability and operability. Ethers. These organic solvents may be used singly or in combination of two or more kinds as necessary.

The amount used when these organic solvents are used in combination is usually 0.1 to 5 parts by weight, and preferably 0.5 to 3 parts by weight, relative to 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 an alkylene carbonate is capable of reacting the bisphenol compound represented by the general formula (3) and an alkylene carbonate, and optionally a basic compound and / or The organic solvent that can be used in combination is added to the reaction vessel, and it is usually carried out at 30 to 150 ° C, preferably 100 to 130 ° C.

After completion of the reaction, the bishydric compound represented by the general formula (2) can be taken out of the obtained reaction solution by using conventional methods such as neutralization, washing, concentration, crystallization, and filtration, if necessary. The obtained diol compound represented by the general formula (2) can also be purified by conventional methods such as recrystallization, distillation, adsorption, and column chromatography.

The bishydric compound represented by the general formula (2) of the present invention can be used as a raw material for the (meth) acrylate compound represented by the general formula (1), and can also be made of polycarbonate, polyester, or polyester. A thermoplastic resin such as polycarbonate is epoxidized with a monomer or a conventional method to form an epoxy resin. In particular, because the refractive index is high, it can be suitably used as a light source. Lenses and optical films are represented by monomers for resins of optical members.

Next, a method for producing a (meth) acrylic acid ester compound represented by the general formula (1) by reacting a diol compound represented by the general formula (2) with a (meth) acrylic acid will be described in detail (hereinafter, this reaction (In the case of (meth) acrylate reaction).

Examples of the (meth) acrylic acid used in the (meth) acrylic acid esterification reaction include (meth) acrylic acid, (meth) acrylic lower alkyl esters (for example, (meth) acrylate, (Meth) acrylic acid ethyl ester, (meth) acrylic acid butyl (meth acrylic acid C _1-4 alkyl ester, etc.), (meth) acrylic acid halide (e.g. (meth) acrylic acid chloride, etc.) (Meth) acrylic anhydride.

The (meth) acrylic acid may be used singly or in combination of two or more kinds as necessary.

The amount of the (meth) acrylic acid used is 2 to 20 mol, preferably 2.2 to 10 mol, and more preferably 2.5 to 5 mol relative to 1 mol of the bishydric compound represented by the above general formula (2). ear.

In the (meth) acrylic acid esterification reaction, an acid or a base can be appropriately used. Examples of the acid usable in the (meth) acrylic acid esterification reaction include various acids such as inorganic acids and organic acids. Specifically, examples of the inorganic acid include sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, heteropoly acid, zeolite, clay mineral, and the like; examples of the organic acid include methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid , Ion exchange resin, etc. These acids may be used singly or in combination of two or more kinds as necessary.

Examples of the base that can be used in the (meth) acrylation reaction include inorganic bases and organic bases. Specifically, examples of the inorganic base include metal carbonates (alkali metal or alkaline earth metal carbonates such as sodium carbonate and sodium bicarbonate). And other alkali metal or alkaline earth metal bicarbonate, etc.), carboxylic acid metal salts (such as sodium acetate, calcium acetate and other alkali metal or alkaline earth metal salts, etc.), and metal hydroxides (such as sodium hydroxide and alkali metal hydroxides, hydrogen Alkaline earth metal hydroxides such as calcium oxide, etc.); organic bases can be exemplified: amines [such as tertiary amines (triethylamine, triisopropylamine, tributylamine, trialkylamines, N, N-dimethylamine Aromatic tertiary amines such as aniline, heterocyclic tertiary amines such as pyridine) and the like]. These alkalis may be used singly or in combination of two or more kinds as necessary.

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

The (meth) acrylic acid esterification reaction may be performed in the presence of a polymerization inhibitor (thermal polymerization inhibitor), if necessary. Examples of the polymerization inhibitor include hydroquinones (for example, hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone), and catechols (for example, alkyl groups such as third butyl catechol) Catechol, etc.), amines (such as diphenylamine, etc.), 2,2-diphenyl-1-picrylhydrazine, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl and the like. The polymerization inhibitor may be used singly or in combination of two or more kinds as 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, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of (meth) acrylics.

The (meth) acrylic acid esterification reaction is also performed without using a solvent, or an organic solvent may be used in combination. Examples of organic solvents that can be used in combination include hydrocarbons, halogenated hydrocarbons, ethers, ketones, and nitriles. Specific examples of the hydrocarbons include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; and examples of the halogenated hydrocarbons include dichloromethane, Aliphatic halogenated hydrocarbons such as chloroform and carbon tetrachloride; aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; examples of the ethers include dialkyl ethers such as diethyl ether; tetrahydrofuran; Cyclic ethers such as alkanes, anisole and the like; examples of ketones include dialkyl ketones such as acetone and methyl ethyl ketone; examples of nitriles include acetonitrile, propionitrile and benzonitrile . These organic solvents may be used singly or in combination of two or more kinds as necessary. When the acid or base is a 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, and preferably 1 to 10 parts by weight, based on 1 part by weight of the bishydric compound represented by the general formula (2).

The (meth) acrylic acid esterification reaction is usually carried out at 80 to 140 ° C, preferably at 100 to 130 ° C. When the (meth) acrylic acid esterification reaction is carried out, it may be performed simultaneously with removal of by-produced water and alcohols. The reaction can be carried out under pressure or under reduced pressure.

After the (meth) acrylic acid esterification reaction is completed, the (meth) acrylic acid ester compound represented by the general formula (1) may not be taken out from the obtained reaction liquid, and the reaction liquid may be used as it is to prepare a hardening composition described later Thing. In addition, if necessary, the (meth) acrylate compound represented by the general formula (1) may be removed by conventional methods such as neutralization, washing, concentration, crystallization, and filtration, and then the extracted general formula ( The (meth) acrylate compound represented by 1) is used to prepare a curable composition. In addition, the (meth) acrylate compound represented by the general formula (1) once taken out can be purified by conventional methods such as recrystallization, distillation, adsorption, and column chromatography, and then the purified The (meth) acrylate compound represented by the general formula (1) is used for preparing a curable composition.

<Curable composition containing (meth) acrylate compound of this invention>

The curable composition containing the (meth) acrylate compound of the present invention may contain other polyfunctional (meth) acrylates in addition to the (meth) acrylate compound represented by the general formula (1). Compounds, polymerization initiators, diluents, etc. In addition, since the (meth) acrylate compound represented by the general formula (1) has a low melt viscosity, a hardening composition can also be formed by using only the (meth) acrylate compound represented by the general formula (1). And hardened to obtain a hardened material.

Examples of other polyfunctional (meth) acrylate compounds that can be contained in the curable composition of the present invention include, for example, difunctional (meth) acrylate {alkanediol di (meth) acrylic acid Ester [C _2-10 alkanediol di (meth) acrylic acid such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate Esters, etc.], polyalkylene glycol di (meth) acrylates [di to tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, di to tetrapropylene glycol di (methyl) ) Acrylate, polytetramethylene glycol di (meth) acrylate, etc., poly C _2-4 alkanediol di (meth) acrylate, etc.], bisphenol A (or C _2-3 alkylene oxide Adduct), di (meth) acrylate, etc.}, trifunctional or higher polyfunctional (meth) acrylate [e.g. glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Esters, tris (hydroxyethyl) trimeric isocyanate tris (meth) acrylates, tri- or tetra-alcohols such as tri- or tetra-alcohols such as neopentaerythritol tri or tetra (meth) acrylates; Trimethylolpropane) tetra (meth) acrylate; Dipentaerythritol tetra to hexa (meth) acrylate, etc.], amine ester (meth) acrylate, (meth) acrylate epoxy, polyester (meth) acrylate, polyfunctional with fluorene skeleton (Meth) acrylate {9,9-bis (4- (meth) acryloxyphenyl) fluorene, 9,9-bis (4- (meth) acryloxy-3-methylbenzene) Group) fluorene and the like 9,9-bis ((meth) acryloxyphenyl) hydrazones; 9,9-bis [4- (2- (meth) acryloxyoxyethoxy) -3- Methylphenyl] fluorene and the like 9,9-bis [(meth) acrylfluorenoxy (poly) ethoxyphenyl] fluorene and the like} and the like. These other polyfunctional (meth) acrylate compounds may be used singly or in combination of two or more kinds as necessary.

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

Examples of the polymerization initiator that can be contained in the curable composition of the present invention include a thermal polymerization initiator and a photopolymerization initiator, and a thermal polymerization initiator and photopolymerization can be used in combination as necessary. Initiator. Examples of the thermal polymerization initiator include dialkyl peroxides (di-tertiary butyl peroxide, dicumyl peroxide, etc.) and difluorene peroxides [dioxane peroxide (laurel peroxide)醯, etc.), diaryl hydrazone peroxide (benzidine peroxide, etc.), etc., peresters (third butyl peracetate, etc.), ketone peroxides, percarbonates, and ketal peroxides And other organic peroxides; azonitrile compounds [2,2'-azobis (isobutyronitrile), etc.], azo compounds such as azoamine compounds, and azo compounds, etc. These thermal polymerization initiators may be used singly or in combination of two or more as needed. on.

Examples of the photopolymerization initiator include benzoin (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin isopropyl ether), and acetophenone (Acetophenone, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, etc.), aminoacetophenones {2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinaminoacetone-1, etc.}, anthraquinones (anthraquinone, 2-methylanthraquinone, etc.), thioxanthone ( 2,4-dimethylthiaxanthone, 2,4-diethylthiaxanthone, 2-chlorothiaxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketone) Ketal, etc.), diphenyl ketones (diphenyl ketone, etc.), xanthone (xanthone), and the like. These photopolymerization initiators may be used singly or in combination of two or more kinds as necessary.

The photopolymerization initiator may be used in combination with a photosensitizer. Examples of photosensitizers that can be used in combination include tertiary amines {such as trialkylamine, trialkanolamine (triethanolamine, etc.), ethyl N, N-dimethylaminobenzoate [p- (dimethylamine Group) ethyl benzoate, etc.], N, N-dimethylamino benzoic acid pentyl ester [p- (dimethylamino) pentyl benzoate, etc.] dialkylamino benzoic acid alkyl ester, 4,4- Bis (diethylamino) diphenyl ketone (Michler's ketone) and other bis (dialkylamino) diphenyl ketones, 4- (dimethylamino) diphenyl ketone, etc. Alkylaminodiphenyl ketones, etc.} and the like. These photosensitizers may be used singly or in combination of two or more kinds as necessary.

The amount of the polymerization initiator used is 100 parts by weight with respect to 100 parts by weight of the (meth) acrylate compound represented by the general formula (1) [when another polyfunctional (meth) acrylate compound is used in combination, it is relative to the general formula ( 1) The (meth) acrylate compound represented is esterified with other polyfunctional (meth) acrylates The total amount of the composition is 100 parts by weight], usually 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 1.5 to 10 parts by weight. When a polymerization initiator (photopolymerization initiator) and a photosensitizer are used together, the amount of the photosensitizer used is 5 to 200 parts by weight relative to 100 parts by weight of the polymerization initiator (photopolymerization initiator). It is preferably 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight.

Examples of the diluent that can be contained in the curable composition of the present invention include a reactive diluent and / or a non-reactive diluent (solvent). Specific examples of the reactive diluent include polymerizable monomers (alkyl (meth) acrylate) (methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. ) acrylic acid C _1-20 alkyl ester, preferably (meth) acrylic acid C _1-10 alkyl ester, etc.], alkyl methacrylate, cycloalkyl acrylate [(meth) acrylate, cyclohexyl (meth) acrylate, C _{5- 8} cycloalkyl esters, etc.], aryl (meth) acrylates [phenyl (meth) acrylates, etc.], hydroxyalkyl (meth) acrylates [(2-hydroxyethyl (meth) acrylate, (meth) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, etc. (hydroxy C _2-10 alkyl (meth) acrylate, etc.), (poly) oxanediol mono (meth) acrylate (diethyl) (Poly) oxy C _2-6 alkanediol mono (e.g., Glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. (Meth) acrylate), alkoxyalkyl (meth) acrylate [2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, etc.], (meth) Phenoxyalkyl acrylate [2-phenoxyethyl (meth) acrylate, 2- (2-phenylphenoxy) ethyl (meth) acrylate ], N- substituted (meth) acrylamide (N, N- dimethyl (meth) acrylamide, etc. N, N- two C _1-4 alkyl (meth) acrylamide, N- hydroxyethyl N-hydroxy C _1-4 alkyl (meth) acrylamide, such as meth (meth) acrylamide, amino alkyl (meth) acrylate (N, N-dimethylaminoethyl acrylate, etc.) 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 preferred, and particularly preferred are 2-phenoxyethyl (meth) acrylate, ( 2- (2-phenylphenoxy) ethyl meth) acrylate and cyclohexyl (meth) acrylate. These reactive diluents may be used singly or in combination of two or more kinds as necessary.

The amount used when using a reactive diluent is 100 parts by weight of the (meth) acrylate compound represented by the general formula (1) [when another polyfunctional (meth) acrylate compound is used in combination, it is based on the general The total amount of (meth) acrylate compound and other polyfunctional (meth) acrylate compound represented by formula (1) is 100 parts by weight], which is usually 1 to 1,000 parts by weight, preferably 5 to 500 parts by weight, More preferably, it is 10 to 200 parts by weight.

Examples of the non-reactive diluent include aliphatic hydrocarbons, ketones, aromatic hydrocarbons, alcohol ethers, esters, and petroleum solvents. Examples of the aliphatic hydrocarbons include hexane, heptane, and octane; examples of the ketones include ethyl methyl ketone and cyclohexanone; examples of the aromatic hydrocarbons include toluene and xylene Examples of alcohol ethers include ethyl cellosolve, methyl cellosolve, carbitol, methylcarbitol, propylene glycol monomethyl ether, and the like; Examples include: methyl acetate, ethyl acetate, butyl acetate, cythru acetate, butyl cythru acetate, carbitol acetate, butyl carbitol acetate, propylene glycol mono Methyl ether acetate, carbon Acrylic acid, etc .; Examples of petroleum solvents include petroleum ether, petroleum naphtha, solvent naphtha, and the like. These non-reactive diluents may be used singly or in combination of two or more kinds as necessary.

The amount used when a non-reactive diluent is used is based on 100 parts by weight of the (meth) acrylate compound represented by the above general formula (1) [when other polyfunctional (meth) acrylate compounds are used in combination, it is relative to the above The total amount of the (meth) acrylate compound and other polyfunctional (meth) acrylate compound represented by the general formula (1) is 100 parts by weight], usually 1 to 500 parts by weight, and preferably 20 to 300 parts by weight , More preferably 30 to 200 parts by weight.

The curable composition of the present invention may contain, in addition to the other polyfunctional (meth) acrylate compounds, polymerization initiators, and diluents described above, commonly used additives such as a coloring agent, a stabilizer (thermal Stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, flame retardant additives, 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 kinds as necessary.

<The hardened | cured material of the hardenable composition containing the (meth) acrylate compound of this invention>

The hardened | cured material of the hardenable composition containing the (meth) acrylate compound represented by the said General formula (1) of this invention can be obtained by performing the hardening process mentioned later on the said hardenable composition of this invention. For example, a film-like cured material can be formed by coating a substrate with a curable composition containing a (meth) acrylate compound represented by the general formula (1) to form a coating film (or film). Manufactured by hardening. The thickness of the film-like coating film (or film) can be selected depending on the application, and is, for example, 0.1 to 1000 μm, preferably 1 to 500 μm, and more preferably 5 to 300 μm.

In addition, a three-dimensionally shaped (e.g., 稜鏡 -shaped, lens-shaped, etc.) hardened product can be produced by casting, a 3D printer, or the like.

Furthermore, the hardening composition containing the (meth) acrylic acid ester compound represented by the said General formula (1) can also be made low-viscosity by heating before hardening process as needed.

Examples of the curing treatment include heat treatment and light irradiation treatment. In addition, a heat treatment and a light irradiation treatment may be combined. The heating temperature during the heat treatment is, for example, 50 to 250 ° C, preferably 60 to 200 ° C, and more preferably 70 to 150 ° C. In the light irradiation treatment (exposure treatment), although the light irradiation energy varies depending on the application, the film thickness of the coating film, etc., it is usually 0.1 to 10000 mJ / cm ² , preferably 1 to 8000 mJ / cm ² , More preferably, it is 10 to 5000 mJ / cm ² .

Because the (meth) acrylate compound represented by the general formula (1) of the present invention has excellent compatibility or solubility with diluents such as organic solvents and monofunctional (meth) acrylate compounds, It can be easily produced by diluting with a large amount of diluent. " Therefore, compared with the case where a bifunctional (meth) acrylate compound derived from a bisphenol compound having a fluorene skeleton is conventionally used, the cured product can be produced more easily, and at the same time, the above-mentioned general advantages can be obtained. The hardened | cured material of the characteristic (high refractive index, low Abbe number, etc.) which a (meth) acrylate compound represented by Formula (1) has.

[Example]

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

[1] HPLC analysis

(1-1) Diol compounds and HPLC analysis conditions when producing the compounds

‧Installation: LC-20A by Shimadzu Corporation

‧Column: XBridge Shield Rp18 (3.5μm, 4.6mm × 250mm)

‧Column temperature: 40 ℃

‧Mobile phase: liquid A = pure water, liquid B = acetonitrile

‧Mobile phase flow rate: 1.0mL / min

‧Mobile phase gradient: B liquid concentration: 70% (0 minutes) → 70% (10 minutes) → 100% (20 minutes) → 100% (30 minutes)

‧ Detection wavelength: UV 254nm

(1-2) (meth) acrylate compounds and HPLC analysis conditions at the time of production of the compounds

‧Installation: LC-20A by Shimadzu Corporation

‧Column: L-Column ODS (5μm, 4.6mm × 250mm)

‧Column temperature: 40 ℃

‧Mobile phase: A liquid = 30% methanol water, B liquid = methanol

‧Mobile phase flow rate: 1.0mL / min

‧Gradient of mobile phase: Concentration of liquid B: 30% (0 minutes) → 100% (10 minutes) → 100% (35 minutes)

‧ Detection wavelength: UV 254nm

[2] NMR measurement

^{The 1} H-NMR and ¹³ C-NMR systems use chloroform-d as a solvent, and recorded by a JEOL-ESC400 spectrometer.

[3] LC-MS determination

The target was identified by LC-MS separation and mass analysis under the following measurement conditions.

‧Installation: "Xevo G2 Q-Tof" made by Waters

‧Column: L-Column2 ODS (2μm, 2.1mm × 100mm)

‧Column temperature: 40 ℃

‧ Detection wavelength: UV 210-500nm

‧Mobile phase: liquid A = pure water, liquid B = acetonitrile

‧Mobile phase flow rate: 0.3mL / min

‧Mobile phase gradient: B liquid concentration: 80% (0 minutes) → 100% (15 minutes) → 100% (25 minutes)

‧Test method: Q-Tof

‧Ionization method: APCI (+) method

‧Ion source: voltage (+) 2.0kV, temperature 120 ℃

‧Sampling Cone: voltage 30V, airflow 50L / h

‧Desolvation gas: temperature 500 ℃, air flow 1000L / h

[4] Solubility to monofunctional acrylate compounds

70 parts by weight of the difunctional (meth) acrylate compound obtained in the following examples and the like were mixed with 30 parts by weight of the monofunctional acrylate compound described below, and the solubility was evaluated based on the following evaluation criteria.

<Monofunctional acrylate>

‧2-phenoxyethyl acrylate (PEA) (manufactured by Tokyo Chemical Industry)

‧2- (2-phenylphenoxy) ethyl acrylate (OPPEA) (manufactured by Shin Nakamura Chemical)

<Evaluation Criteria>

A: It dissolves within 2 hours when heated at 80 ° C, and no crystals are precipitated even when cooled.

B: It is dissolved by heating at 80 ° C for 2 hours or more, and no crystals are precipitated even when cooled.

C: Although dissolved during heating, crystals are precipitated during cooling or do not dissolve even when heated.

[5] Refractive index and Abbe number

The refractive index and Abbe at the following wavelengths were measured as follows. The number is the refractive index and Abbe number of the bifunctional (meth) acrylate compound obtained in the following examples and the like.

Each of the difunctional (meth) acrylate compounds was dissolved in N-methyl-2-pyrrolidone to prepare 5 wt%, 10 wt%, and 15 wt% solutions (Comparative Example 1 and Comparative Example 2 because it is not easy It is dissolved in an organic solvent, so it is 1% by weight, 3% by weight, and 5% by weight). For each solution, the refractive index at each wavelength is measured by the apparatus and conditions described later. Next, an approximate straight line was derived from the measured values at the three points obtained, and the value when extrapolated to 100% by weight was set as the refractive index of each difunctional (meth) acrylate compound at each wavelength. Then, the Abbe number is calculated based on the obtained refractive index of each wavelength.

<Measurement conditions of refractive index and Abbe number of each solution>

Device: Abbe refractometer ("Multi-wavelength Abbe refractometer DR-2M" manufactured by ATAGO)

Measurement wavelength; refractive index: 589nm (20 ° C), Abbe number: 486, 589, 656nm (20 ° C)

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

A glass reactor provided with a stirrer, a heating cooler, and a thermometer was fed with a bisphenol compound represented by the following formula (3-1) 120.0g (0.176 mole), 162.2g of toluene, 16.5g of triethylene glycol dimethyl ether, 38.7g of ethyl carbonate (0.439 mole), 2.0g of potassium carbonate (0.014 mole), and then the temperature was raised to 110 Stirring was performed at this temperature for 15 hours.

After the completion of the stirring, when the reaction liquid was analyzed by high-speed liquid chromatography, it was confirmed that the production rate of the bisphenol compound represented by the above formula (2-1) was 80.9%, and The residual rate was less than 1.0%, and the reaction was terminated.

An aqueous sodium hydroxide solution was added to the obtained reaction solution to neutralize the reaction solution, and then the water layer was removed and washed with water four times. After that, a part of toluene was distilled off by concentration, and then crystals were precipitated by adding heptane and cooling, and the precipitated crystals were separated by filtration and dried to obtain the formula (2-1). 132.0 g of a bishydric compound crystal (HPLC purity 97%, yield 97%). The measurement results of ¹ H-NMR, ¹³ C-NMR, and LC-MS of the bishydric compound represented by the formula (2-1) are as follows.

¹ H-NMR (CDCl ₃ )

δ = 1.38ppm (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 value (M + NH4) ⁺ : 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)>

In a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, 98.16 g (0.13 mol) of a bishydric compound represented by the above formula (2-1), 3.21 g (0.017 mol) of p-toluenesulfonic acid, and p-formyl 0.32 g (0.0026 mol) of oxyphenol, 24.20 g (0.34 mol) of acrylic acid and toluene, and refluxing at 110 ° C to 115 ° C while performing dehydration and esterification reaction to obtain Up to the theoretical amount of dehydration.

After the reaction, when the reaction solution was analyzed by HPLC, the acrylate compound represented by the formula (1-1) produced 87.0%.

After adding a 6% sodium hydroxide aqueous solution to the obtained reaction solution for neutralization, washing with water 4 times with water and concentrating under reduced pressure gave 115.1 g of an acrylate compound represented by the above formula (1-1) ( 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 formula (1-1). The measurement results of ¹ H-NMR, ¹³ C-NMR, and LC-MS of the acrylate compound represented by the formula (1-1) are as follows.

¹ H-NMR (CDCl ₃ , 400MHz)

δ = 3.4ppm (4H, t), 4.0ppm (4H, s), 4.1ppm (4H, t), 5.8ppm (2H, d), 6.0ppm (2H, dd), 6.313ppm (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 analysis value (M + NH4) ⁺ : 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 ): 8693.951)

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

In a glass reactor equipped with a stirrer, cooler, and thermometer, 9,20-bis (4- (2-hydroxyethoxy) -phenyl) fluorene 200.00 g (0.46 mol) and p-toluenesulfonic acid 11.28 were charged. g (0.059 mol), 1.13 g (0.0091 mol) of p-methoxyphenol, 84.08 g (1.17 mol) of acrylic acid and toluene, and refluxing at 110 ° C to 115 ° C while performing dehydration and esterification until the theoretical amount of dehydration is obtained.

When the reaction liquid was analyzed by HPLC after the reaction, the acrylate compound represented by the formula (4) produced 88.3%.

After adding 5% sodium bicarbonate water to the obtained reaction solution for neutralization, it was washed twice with brine and concentrated under reduced pressure to obtain 258.8 g of an acrylate compound represented by the formula (4) ( HPLC purity: 86.9%).

About the obtained acrylate compound represented by the above formula (4) Table 1 shows the measurement results of the emissivity, Abbe number, and compatibility with monofunctional acrylate compounds.

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

In a glass reactor equipped with a stirrer, a cooler, and a thermometer, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) 茀 60.00g (0.13mol), Toluenesulfonic acid 3.18 g (0.017 mol), p-methoxyphenol 0.32 g (0.0026 mol), acrylic acid 24.09 g (0.33 mol) and toluene, refluxing at 110 ° C to 115 ° C while performing dehydration and esterification reaction to obtain theoretical dehydration So far.

After the reaction, when the reaction solution was analyzed by HPLC, the acrylate compound represented by the formula (5) was 88.6%.

After adding 5% sodium bicarbonate water to the obtained reaction solution for neutralization, it was washed twice with brine and concentrated under reduced pressure, thereby obtaining 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 formula (5).

Claims (6)

A (meth) acrylate compound is 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 each the same or different and represent an alkylene group which may have branched carbon numbers of 2 to 4. ; R ₇ and R ₈ are each the same or different and represent a hydrogen atom or a methyl group; k ₁ to k ₄ are each the same or different and represent an integer of 0 to 4; n ₁ and n ₂ are each the same or different and represent 1 The above integers; p ₁ and p ₂ are each the same or 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. The (meth) acrylic acid ester compound according to item 1 of the scope of patent application, wherein n ₁ and n ₂ in the general formula (1) are 1, and k ₁ to k ₄ are 0. A diol compound is 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 each the same or different and represent an alkylene group which may have branched carbon numbers of 2 to 4. ; K ₁ to k ₄ are each the same or different and represent integers from 0 to 4; n ₁ and n ₂ are each the same or different and represent integers of 1 or more; p ₁ and p ₂ are each the same or different and represent 1 or more When k ₁ to k ₄ is 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 item 1 or 2 of the scope of patent application, comprising the step of reacting a bis-alcohol compound represented by the following general formula (2) with a (meth) acrylic compound; 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 each the same or different and represent an alkylene group which may have branched carbon numbers of 2 to 4. ; K ₁ to k ₄ are each the same or different and represent integers from 0 to 4; n ₁ and n ₂ are each the same or different and represent integers of 1 or more; p ₁ and p ₂ are each the same or different and represent 1 or more When k ₁ to k ₄ is 2 or more, the corresponding R ₁ to R ₄ may be the same or different. A hardening composition containing the (meth) acrylate compound described in item 1 or 2 of the scope of patent application. A hardened material is a hardened material of the hardenable composition described in the fifth item of the patent application.