JP6098876B2 - 4-[(Disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound, process for producing the same, radical polymerizable composition containing them, and polymer thereof - Google Patents

Description

The present invention relates to a radically polymerizable compound and a polymer thereof, and in particular, a 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound and a process for producing the same, and 4-[(disubstituted phosphoryl) oxy]. The present invention relates to a radically polymerizable composition containing a -1-naphthyl (meth) acrylate compound and a polymer thereof.

In recent years, plastic has been actively used as a glass substitute material in the optical field. For example, polycarbonate and polymethyl methacrylate are well known. These plastic materials have light weight, safety, and design, but have a disadvantage that they are lower in refractive index than inorganic glass and easily become thick. Therefore, in recent years, there has been an increasing demand for plastic materials having a high refractive index. In particular, the advancement of high refractive index plastic materials to optical products has been remarkable, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, prism lens sheets for TFT, aspherical lenses, optical disks, holograms, and optical fibers. Studies on optical waveguides and the like have been actively conducted.

There is a positive correlation between the refractive index of the plastic and the refractive index of the monomer as the raw material, and in order to obtain a plastic with a high refractive index, the monomer part constituting the polymer must have a high refractive index. is necessary.

As a method for increasing the refractive index of an organic compound as a monomer, it is already well known that it is useful to introduce a halogen atom (excluding fluorine), a sulfur atom and an aromatic ring into the molecular structure. For example, a high refractive index polymer in which a halogen atom is introduced into a biphenyl ring using a high intrinsic refractive index of a halogen atom has been reported (Patent Document 1). However, due to halogenation, the light resistance is remarkably deteriorated and the specific gravity is high. In addition to the halogen, a monomer composition having a sulfur atom having a high intrinsic refractive index has also been reported (Patent Document 2). However, although these have a high refractive index and excellent impact resistance, the light resistance of the obtained polymer is remarkably inferior, and there is a disadvantage that an unpleasant odor peculiar to sulfur becomes a problem. Moreover, when plastics using these are treated as waste, there is a concern that harmful gases and compounds are generated.

Regarding the introduction of an aromatic ring, high refractive index materials having a benzene ring and a biphenyl ring have been known so far, and these are light and excellent in transparency and have a well-balanced high refractive index material (Patent Document 3, etc.). . However, when the benzene ring is used, the refractive index of the monomer is high, but it is still not sufficient. When the biphenyl ring is used, the absorption shifts to the long wavelength side compared to the monomer of the benzene ring, and in the case of photocuring Has a problem in that the photoinitiating efficiency decreases because the initiator and UV absorption overlap.

On the other hand, since a high refractive index can be expected by introducing a naphthalene ring, a monoacrylate, a diacrylate and the like have recently been reported for acrylate compounds containing a naphthalene compound in the skeleton (Patent Document 4). , 5, 6, 7). However, these 1,4-bis (meth) acryloyloxynaphthalene compounds have a problem of being colored brown when the cured product is exposed to sunlight. Furthermore, all of these (meth) acrylate compounds containing a naphthalene skeleton are solid at room temperature, and there is a problem that they are difficult to handle when preparing a radical polymerizable composition. There is a need for a (meth) acrylate compound containing a naphthalene skeleton that is liquid around room temperature.

In addition, plastics have good processability, but have the drawback of being flammable compared to metal and ceramic products. Therefore, various flame retardants have been studied for these plastics. In general, flame retardancy is achieved by adding a compound having a flame retardant element such as halogen or phosphorus. As a result, the excellent characteristics of the polymer are often impaired. There is a need for an efficient flame retardant that does not impair the physical properties possessed.

Among flame retardants, bromine-based flame retardants or combinations of brominated flame retardants and antimony-based flame retardants are often used because a flame-retardant effect can be obtained with a small amount of addition. Due to environmental issues, flame retardants are also being studied for non-halogen and non-antimony conversion.

Metal halides and phosphorus flame retardants are widely used except for halogen-based and antimony-based materials. Among them, phosphate ester flame retardants are often used as flame retardants that rarely impair the physical properties of polymers. In the phosphate ester flame retardant, an aliphatic phosphate compound and an aromatic phosphate compound are used.

These flame retardants are used by adding them to the polymer material. In that case, the flame retardant added is separated from the polymer material by bleed-out or volatilization, causing problems such as mold contamination or molding defects. Will occur. In order to solve this problem, there is a demand for a reactive phosphate ester flame retardant having reactivity that can be incorporated into a polymer, particularly in applications such as electricity / electronics, automobiles, and building materials.

It is already known that 1,4-hydroquinone compounds and 1,4-dihydroxynaphthalene compounds in which a dialkyl phosphoryl group or a diaryl phosphoryl group is substituted at the 2-position are effective as this reactive phosphate ester flame retardant. (Patent Documents 8 and 9).

However, a monomer having excellent flame retardancy that can be applied to a polyacrylic resin such as polymethyl methacrylate is not known.

JP 05-170702 A JP 2002-20433 A JP 2003-064296 A JP 1987-192340 A JP 2001-276687 A JP 2008-81682 A JP 2010-138331 A JP 2003-206350 A JP 2011-084597 A

An object of the present invention is to provide a (meth) acrylate compound having a naphthalene skeleton capable of producing a highly refractive polymer and a compound having a flame retardant phosphorus atom in the skeleton. is there.

As a result of intensive studies on the structure and photopolymerizability of the naphthalene compound, the inventor is a monofunctional (meth) acrylate obtained by (meth) acryloylating a disubstituted-4-hydroxy-1-naphthyl phosphate compound. -[(Disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound can be expected to have flame retardancy because it contains a phosphorus atom in its structure, and can be easily polymerized and obtained with a high-pressure mercury lamp. It was found that the obtained polymer had a high refractive index, and the present invention was completed.

The first invention provides a 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound represented by the following general formula (1).

In general formula (1), R ³ represents a hydrogen atom or a methyl group, and R ¹ and R ² may be the same or different, and an alkyl group having 1 to 4 carbon atoms, or 6 or 7 carbon atoms. And X and Y may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the second invention, radical polymerizability containing a 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound represented by the general formula (1) described in the first invention and a radical polymerization initiator. A composition is provided.

In the third invention, there is provided a polymer obtained by polymerizing the radically polymerizable composition described in the second invention.

In a fourth invention, the 4-[(disubstituted phosphoryl) oxy described in the first invention, which comprises (meth) acryloylating a di-substituted-4-hydroxy-1-naphthyl phosphate compound represented by the general formula (2). ] The manufacturing method of a 1-naphthyl (meth) acrylate compound is provided.

In general formula (2), R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 or 7 carbon atoms, X, Y may be the same or different and represents either a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the present invention, (meth) acryloylation represents acryloylation or methacryloylation, and (meth) acryloyl represents acryloyl or methacryloyl.

The 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention is a novel naphthalene compound having a (meth) acryloyl group having a phosphorus atom and radical polymerizability in its structure. . Furthermore, the hardened | cured material obtained after hardening | curing the radically polymerizable composition containing the said compound shows a high refractive index.

The 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention is a compound having the structure described in the general formula (1).

In general formula (1), R ³ represents a hydrogen atom or a methyl group, and R ¹ and R ² may be the same or different, and an alkyl group having 1 to 4 carbon atoms, or 6 or 7 carbon atoms. And X and Y may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In general formula (1), the alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, i- A propyl group, n-butyl group, etc. are mentioned, As an aryl group, a C6-C7 aryl group is preferable, and a phenyl group, a tolyl group, etc. are specifically mentioned.

In general formula (1), the alkyl group represented by X and Y is preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, or n-butyl. Group, n-heptyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

Next, specific examples of the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl-2- (meth) acrylate compound represented by the general formula (1) are shown. For example, when both X and Y are hydrogen atoms, 4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 4-[(dipropoxy Phosphoryl) oxy] -1-naphthyl acrylate, 4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 4-[(ditolyloxyphosphoryl) ) Oxy] -1-naphthyl acrylate, 4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 4-[(dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 4 -[(Diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate, 4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl methacrylate, and the like.

When either X or Y is an alkyl group, 2-methyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-methyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-methyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-methyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-methyl- 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-methyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl acrylate, 2-methyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-methyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-methyl-4-[(di Propoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-methyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-methyl-4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate 2-methyl-4-[(ditolyloxyxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-ethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-ethyl-4-[(di Ethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-ethyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-ethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate 2-ethyl-4-[(diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-ethyl Ru-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl acrylate, 2-ethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-ethyl-4-[(diethoxyphosphoryl) Oxy] -1-naphthyl methacrylate, 2-ethyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-ethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2- Examples include ethyl-4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-ethyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl methacrylate, and the like.

Further, 6-methyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-methyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-methyl-4-[(di Propoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-methyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-methyl-4-[(diphenoxyphosphoryl) oxy] -1-naphthyl acrylate 6-methyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl acrylate, 6-methyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-methyl-4-[(di Ethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-methyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate , 6-methyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-methyl-4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-methyl-4-[( Ditolyloxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-ethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-ethyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl Acrylate, 6-ethyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-ethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-ethyl-4-[( Diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-ethyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphth Acrylate, 6-ethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-ethyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-ethyl-4-[( Dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-ethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-ethyl-4-[(diphenoxyphosphoryl) oxy] -1-naphthyl And methacrylate, 6-ethyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl methacrylate, and the like.

Furthermore, 2-n-propyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-propyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n- Propyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-propyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-propyl-4-[( Diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-propyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-propyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-propyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-propiyl -4-[(dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-propyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-propyl-4-[(di Phenoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-propyl-4-[(ditolyloxyxyphosphoryl) oxy] -1-naphthyl methacrylate, and the like.

Further, 2-n-butyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-butyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n- Butyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-butyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-butyl-4-[( Diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-butyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl acrylate, 2-n-butyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-butyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-butyl-4-[(dipropo Xyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-butyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2-n-butyl-4-[(diphenoxyphosphoryl) oxy]- Examples include 1-naphthyl methacrylate and 2-n-butyl-4-[(ditolyloxyxyphosphoryl) oxy] -1-naphthyl methacrylate.

Furthermore, 6-n-propyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-n-propyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-n -Propyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-n-propyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-n-propyl-4- [ (Diphenoxyphosphoryl) oxy] -1-naphthyl acrylate, 6-n-propyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl acrylate, 6-n-propyl-4-[(dimethoxyphosphoryl) oxy ] -1-naphthyl methacrylate, 6-n-propyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-n- Lopyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-n-propyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-n-propyl-4-[( And diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate, 6-n-propyl-4-[(ditolyloxyphosphoryl) oxy] -1-naphthyl methacrylate, and the like.

When both X and Y are alkyl groups, 2,6-dimethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-dimethyl-4-[(diethoxyphosphoryl) Oxy] -1-naphthyl acrylate, 2,6-dimethyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-dimethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl Acrylate, 2,6-dimethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-dimethyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-dimethyl -4-[(Dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-dimethyl-4-[(dibutoxyphosphoryl) oxy] -1-na Tyl methacrylate, 2,6-diethyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-diethyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6- Diethyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-diethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-diethyl-4-[( Dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-diethyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-diethyl-4-[(dipropoxyphosphoryl) oxy]- 1-naphthyl methacrylate, 2,6-diethyl-4-[(dibutoxyphosphoryl) oxy] -1-naphthyl methacrylate, etc. It is.

Furthermore, 2,6-di-n-propyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-di-n-propyl-4-[(diethoxyphosphoryl) oxy] -1- Naphthyl acrylate, 2,6-di-n-propyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl acrylate, 2,6-di-n-propyl-4-[(dibutoxyphosphoryl) oxy]- 1-naphthyl acrylate, 2,6-di-n-propyl-4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-di-n-propyl-4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-di-n-propyl-4-[(dipropoxyphosphoryl) oxy] -1-naphthyl methacrylate, 2,6-di-n-propyl-4-[(dibutoxyfo Digging) oxy] -1-naphthyl methacrylate, and the like.

Among these compounds, those which are easy to synthesize and particularly preferred include 4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate, 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate and 4- [(Diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate.

[Production method]
The 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention (meth) acryloylates the disubstituted-4-hydroxy-1-naphthyl phosphate compound represented by the general formula (2). Can be obtained.

In general formula (2), R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 or 7 carbon atoms, X, Y may be the same or different and represents either a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In general formula (2), the alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group as in general formula (1). Group, n-propyl group, i-propyl group, n-butyl group and the like, and the aryl group is preferably an aryl group having 6 or 7 carbon atoms, specifically, phenyl group, tolyl group and the like. .

In the general formula (2), the alkyl group represented by X and Y is preferably an alkyl group having 1 to 8 carbon atoms as in the general formula (1), specifically, a methyl group, an ethyl group, Examples include n-propyl group, n-butyl group, n-heptyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

The di-substituted-4-hydroxy-1-naphthyl phosphate compound is obtained by reacting a 1,4-naphthoquinone compound and a phosphorous acid diester in the presence of a basic compound such as triethylamine.

Examples of the starting 1,4-naphthoquinone compound include 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, and 2-n-propyl-1,4-naphthoquinone. 2-n-butyl-1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 6-ethyl-1,4-naphthoquinone, 6-n-propyl-1,4-naphthoquinone, 6-butyl-1 , 4-naphthoquinone, 2,6-dimethyl-1,4-naphthoquinone, 2,6-diethyl-1,4-naphthoquinone, 2,6-di-n-propyl-1,4-naphthoquinone, 2,6-di -N-butyl-1,4-naphthoquinone etc. are mentioned.

Examples of the phosphite diester include dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, diphenyl phosphite, and ditolyl phosphite.

In the reaction of the 1,4-naphthoquinone compound and phosphorous acid diester, a basic compound is used as a catalyst. Examples of the basic compound include diethylamine, triethylamine, di-n-propylamine, diisopropylamine, tri-n-propylamine, triisopropylamine, 1,8-diazabicyclo [5,4,0] -7-undecene ( DBU), alkylamines such as diazadicyclo [2,2,2] octane, diazabicyclononene, guanidine; benzylamines such as methylbenzylamine, dimethylbenzylamine, ethylbenzylamine, diethylbenzylamine; methylaniline, dimethyl Examples include anilines such as aniline, ethylaniline, and diethylaniline; pyridines such as pyridine, methylpyridine, and dimethylaminopyridine; and quinolines such as quinoline and isoquinoline.

The amount of catalyst used varies depending on the catalyst used, but it is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.5 mol% or more and 10 mol, relative to the raw material 1,4-naphthoquinone compound. % Or less can be used.

Any solvent can be used as long as it has an appropriate solubility in the raw materials, has an appropriate boiling point from the viewpoint of reaction temperature and solvent recovery, and does not impair the catalytic effect. Specific examples include aromatic hydrocarbons such as toluene and xylene, ketone compounds such as methyl isobutyl ketone, ether compounds such as diethoxyethane and dimethoxyethane, ester compounds such as butyl acetate, acetonitrile, and the like. Nitrile compounds and the like.

The reaction temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 10 ° C. or higher and 110 ° C. or lower. When the reaction temperature is less than 0 ° C., a practical reaction rate cannot be obtained. On the other hand, when the temperature exceeds 150 ° C., the production of higher by-products increases.

The amount of phosphorous acid diester used is preferably in the range of 1 to 3 times, more preferably 1.1 to 2 times the naphthoquinone compound. When the usage-amount of phosphorous acid diester is less than 1 mol times, the quantity of an unreacted naphthoquinone compound will increase. On the other hand, when the amount of the phosphite diester exceeds 3 mole times, there is a disadvantage that a by-product of successive reaction in which two phosphite diester groups are substituted with a naphthohydroquinone skeleton is increased.

Thus, using the disubstituted-4-hydroxy-1-naphthyl phosphate compound represented by the general formula (2) obtained by the reaction of the 1,4-naphthoquinone compound and the phosphorous acid diester as a raw material, the general formula (1) 4-[(Disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound represented by the formula:

Examples of the di-substituted-4-hydroxy-1-naphthyl phosphate compound represented by the general formula (2) used as a raw material include dimethyl-4-hydroxy-1-naphthyl phosphate, diethyl-4-hydroxy-1- Naphthyl phosphate, di-n-propyl-4-hydroxy-1-naphthyl phosphate, di-n-butyl-4-hydroxy-1-naphthyl phosphate, diphenyl-4-hydroxy-1-naphthyl phosphate, ditolyl-4-hydroxy- 1-naphthyl phosphate, dimethyl-4-hydroxy-2-methyl-1-naphthyl phosphate, diethyl-4-hydroxy-2-methyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-2-methyl-1 -Naphthyl phosphate, di-n-butyl-4- Roxy-2-methyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-methyl-1-naphthyl phosphate, diphenyl-4-hydroxy-2-methyl-1-naphthyl phosphate, ditolyl-4-hydroxy-2-methyl -1-naphthyl phosphate, dimethyl-4-hydroxy-2-ethyl-1-naphthyl phosphate, diethyl-4-hydroxy-2-ethyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-2-ethyl- 1-naphthyl phosphate, di-n-butyl-4-hydroxy-2-ethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-ethyl-1-naphthyl phosphate, diphenyl-4-hydroxy-2-ethyl-1 -Naphthyl phosphate, ditolyl-4-hydroxy 2-ethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-n-propyl-1-naphthyl phosphate, diethyl-4-hydroxy-2-n-propyl-1-naphthyl phosphate, di-n-propyl-4 -Hydroxy-2-n-propyl-1-naphthyl phosphate, di-n-butyl-4-hydroxy-2-n-propyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-n-propyl-1-naphthyl Phosphate, diphenyl-4-hydroxy-2-n-propyl-1-naphthyl phosphate, ditolyl-4-hydroxy-2-n-propyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-n-butyl-1- Naphthyl phosphate, diethyl-4-hydroxy-2-n-butyl-1-naphthyl Phosphate, di-n-propyl-4-hydroxy-2-n-butyl-1-naphthyl phosphate, di-n-butyl-4-hydroxy-2-n-butyl-1-naphthyl phosphate, dimethyl-4-hydroxy- Examples include 2-n-butyl-1-naphthyl phosphate, diphenyl-4-hydroxy-2-n-butyl-1-naphthyl phosphate, ditolyl-4-hydroxy-2-n-butyl-1-naphthyl phosphate, and the like.

Dimethyl-4-hydroxy-6-methyl-1-naphthyl phosphate, diethyl-4-hydroxy-6-methyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-6-methyl-1-naphthyl phosphate Di-n-butyl-4-hydroxy-6-methyl-1-naphthyl phosphate, dimethyl-4-hydroxy-6-methyl-1-naphthyl phosphate, diphenyl-4-hydroxy-6-methyl-1-naphthyl phosphate, Ditolyl-4-hydroxy-6-methyl-1-naphthyl phosphate, dimethyl-4-hydroxy-6-ethyl-1-naphthyl phosphate, diethyl-4-hydroxy-6-ethyl-1-naphthyl phosphate, di-n-propyl -4-hydroxy-6-ethyl-1-naphthyl phosphate Di-n-butyl-4-hydroxy-6-ethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-ethyl-1-naphthyl phosphate, diphenyl-4-hydroxy-6-ethyl-1-naphthyl phosphate, Ditolyl-4-hydroxy-6-ethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-6-n-propyl-1-naphthyl phosphate, diethyl-4-hydroxy-6-n-propyl-1-naphthyl phosphate, di -N-propyl-4-hydroxy-6-n-propyl-1-naphthyl phosphate, di-n-butyl-4-hydroxy-6-n-propyl-1-naphthyl phosphate, dimethyl-4-hydroxy-6-n -Propyl-1-naphthyl phosphate, diphenyl-4-hydroxy-6-n Propyl-1-naphthyl phosphate, ditolyl-4-hydroxy -6-n-propyl-1-naphthyl phosphate,
Dimethyl-4-hydroxy-6-n-butyl-1-naphthyl phosphate, diethyl-4-hydroxy-6-n-butyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-6-n-butyl- 1-naphthyl phosphate, di-n-butyl-4-hydroxy-6-n-butyl-1-naphthyl phosphate, dimethyl-4-hydroxy-n-6-butyl-1-naphthyl phosphate, diphenyl-4-hydroxy-6 -N-butyl-1-naphthyl phosphate, ditolyl-4-hydroxy-6-n-butyl-1-naphthyl phosphate, and the like.

Furthermore, dimethyl-4-hydroxy-2,6-dimethyl-1-naphthyl phosphate, diethyl-4-hydroxy-2,6-dimethyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-2,6 -Dimethyl-1-naphthyl phosphate, di-n-butyl-4-hydroxy-2,6-dimethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2,6-dimethyl-1-naphthyl phosphate, diphenyl-4- Hydroxy-2,6-dimethyl-1-naphthyl phosphate, ditolyl-4-hydroxy-2,6-dimethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2,6-diethyl-1-naphthyl phosphate, diethyl-4 -Hydroxy-2,6-diethyl-1-naphthyl phosphate, di-n-propyl Pill-4-hydroxy-2,6-diethyl-1-naphthyl phosphate, di-n-butyl-4-hydroxy-2,6-diethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2-ethyl-1- Naphthyl phosphate, diphenyl-4-hydroxy-2,6-diethyl-1-naphthyl phosphate, ditolyl-4-hydroxy-2,6-diethyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2,6-di-n -Propyl-1-naphthyl phosphate, diethyl-4-hydroxy-2,6-di-n-propyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-2,6-di-n-propyl-1 Naphthyl phosphate, di-n-butyl-4-hydroxy-2,6-di-n-propyl-1-naphthylphos , Dimethyl-4-hydroxy-2,6-di-n-propyl-1-naphthyl phosphate, diphenyl-4-hydroxy-2,6-di-n-propyl-1-naphthyl phosphate, ditolyl-4-hydroxy- 2,6-di-n-propyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2,6-di-n-butyl-1-naphthyl phosphate, diethyl-4-hydroxy-2,6-di-n- Butyl-1-naphthyl phosphate, di-n-propyl-4-hydroxy-2,6-di-n-butyl-1-naphthyl phosphate, di-n-butyl-4-hydroxy-2,6-di-n- Butyl-1-naphthyl phosphate, dimethyl-4-hydroxy-2,6-di-n-butyl-1-naphthyl phosphate, diphenyl-4-hydroxy- Examples include 2,6-di-n-butyl-1-naphthyl phosphate and ditolyl-4-hydroxy-2,6-di-n-butyl-1-naphthyl phosphate.

Next, although it is (meth) acryloylation, the di-substitution represented by the general formula (2) obtained by heating a 1,4-naphthoquinone compound and a phosphorous acid diester in a solvent in the presence of a base compound. As shown in the following reaction formula, the 4-hydroxy-1-naphthyl phosphate compound is reacted with a (meth) acryloylating agent in the presence of a basic compound or in the absence of a basic compound. A 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound represented by the general formula (1) is obtained.

Examples of the (meth) acryloylating agent used in the reaction include acryloyl chloride, methacryloyl chloride, acryloyl bromide, methacryloyl bromide, acrylic anhydride, and methacrylic anhydride.

The addition amount of the (meth) acryloylating agent with respect to the di-substituted-4-hydroxy-1-naphthyl phosphate compound is 2 mol times to 4 mol times, preferably 2.5 mol times to 3 mol times.

If it is less than 2 mol times, the raw material di-substituted-4-hydroxy-1-naphthyl phosphate compound is unreacted and the purity of the remaining product is lowered. If it exceeds 4 mol times, the (meth) acryloylating agent remains and polymerizes. As a result, the isolation yield decreases, and neither is preferable.

Examples of the basic compound used in the reaction include trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline, piperidine and the like.

Solvents include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, halogenated carbon solvents such as methylene chloride, dichloroethane and dichloroethylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, N- Amide solvents such as methylpyrrolidone, dimethylformamide, dimethylacetamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used.

The reaction temperature is 0 ° C. or higher and 80 ° C. or lower, preferably 0 ° C. or higher and 20 ° C. or lower. If it is less than 0 ° C., the reaction time is too long, and if it exceeds 80 ° C., side reaction occurs and the purity of the product is lowered, which is not preferable.

The reaction time depends on the reaction temperature, but is usually about 15 minutes or longer and 60 minutes or shorter.

The obtained compound was identified using a ¹ H-NMR spectrum, an IR spectrum, and a Mass spectrum, and confirmed to be a 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound.

[Radical polymerization initiator]
The 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound thus obtained can be radically polymerized into a polymer by using a radical polymerization initiator. As the radical polymerization initiator, a thermal radical polymerization initiator and a photo radical polymerization initiator can be used.

As the thermal radical polymerization initiator, either an organic peroxide or an azo compound can be used. Examples of the organic peroxide include t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butyl. Peroxyesters such as peroxyisopropyl carbonates, peroxyketals such as 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, diacyl peroxides such as lauroyl peroxide, etc. Can be mentioned. Examples of the initiator of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobi (cyclohexane-1- And azonitriles such as (carbonitrile).

Examples of the photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-isopropylthioxanthone, 2-t-butylanthraquinone, and the like. Examples of actual industrial products include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 907, Irgacure 369, Irgacure 819, etc. manufactured by BASF (Irgacure and Darocur are registered trademarks of BSF Corporation).

Photoradical polymerization using active energy rays such as ultraviolet rays and visible rays is fast, and photoradical polymerization is preferred when the compound of the present invention is used for optical applications.

[Radically polymerizable composition]
The radically polymerizable composition can be prepared and then polymerized by mixing the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention and the above radical polymerization initiator.

In the radically polymerizable composition of the present invention, the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound can be polymerized alone as a homopolymer. A radically polymerizable compound other than the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention is added together with the substituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound to form a copolymerizable compound. It can also be set as a radically polymerizable composition. Examples of the radical polymerizable compound include tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, and imide. Acrylates, styrene, vinyl acetate, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, acrylic ester, methacrylic ester, phenyl acrylate, phenyl methacrylate, p-tolyl acrylate, p-tolyl methacrylate, m-tolyl Acrylate, m-tolyl methacrylate, o-tolyl acrylate Rate, o- tolyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 4-phenoxyphenyl acrylate, 4-phenoxyphenyl methacrylate, 2-phenoxyphenyl acrylate, 2-phenoxyphenyl methacrylate.

Since the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention is a compound having a high refractive index, it is copolymerized with a radical polymerizable compound such as trimethylolpropane triacrylate. Thus, the refractive index of the polymer obtained can be increased as compared with the case where the trimethylolpropane triacrylate is polymerized alone. Moreover, the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention contains a phosphorus atom, and the effect of improving the flame retardancy of the resulting polymer can also be expected. .

The concentration of the radical polymerization initiator used in the present invention is the total of the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention and the radical polymerizable compound used in combination as necessary. It is selected from the range of 0.1 to 5% by weight, preferably 0.5 to 2% by weight. If it is less than 0.1% by weight, the polymerization rate is slow, and if it exceeds 5% by weight, the physical properties of the polymer are deteriorated.

Further, the radically polymerizable composition of the present invention is a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, within a range not impairing the effects of the present invention. Various resin additives such as flame retardants, antioxidants, stabilizers, lubricants, and plasticizers may be blended.

[polymerization]
The polymerization of the radical polymerizable composition can be performed in the form of a film or can be cured in a lump. When polymerizing in the form of a film, the liquid polymerizable composition is applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 microns using, for example, a bar coater. The 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound of the present invention can be easily polymerized not only in a thin film but also in a thick film.

The coating film thus prepared can be polymerized by irradiating it with active energy rays. The light source used is an active energy ray having a wavelength of 250 to 500 nm, although it varies depending on the radical photopolymerization initiator used. Therefore, a light source such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a halogen lamp, a metal halide lamp, a UV-LED, a blue LED, or a white LED can be used as a light source capable of irradiating the active energy ray having the above wavelength. Sunlight can also be used.

The radically polymerizable compound of the present invention can be polymerized and cured by a generally used high-pressure mercury lamp.

The photopolymerization was determined based on a tack free test (finger touch test). That is, the time until the photoradical polymerizable composition on the surface of the film can be tacked by light irradiation was taken as the curing time.

The film, sheet or block obtained by polymerizing the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (meth) acrylate compound thus obtained exhibits a high refractive index and has a structure. It is industrially useful because it can be expected to have flame retardancy, ultraviolet absorption, high heat resistance, high hardness, high glossiness, and the like.

The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise noted, all parts and percentages are by weight.

The product was confirmed by measurement using the following equipment.
(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Refractometer: Model ER-7MWH manufactured by Elmer
(3) Infrared (IR) spectrophotometer: manufactured by JASCO Corporation, model IR-810
(4) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer

(Synthesis Example 1) Synthesis of dimethyl-4-hydroxy-1-naphthyl phosphate In a reaction vessel, 5.0 g (31.6 mmol) of 1,4-naphthoquinone, 5.2 g (47.4 mmol) of dimethyl phosphite and toluene as a solvent 40 ml was charged. While stirring this mixture in a nitrogen stream at room temperature, a solution of 200 mg of 1,8-diazabicyclo [5,4,0] -7-undecene (hereinafter referred to as DBU) as a catalyst in 10 ml of toluene was added thereto. Added over minutes. During this time, the reaction solution temperature rose from 19 ° C to 43 ° C. After returning to room temperature by cooling, the mixture was heated to 55 ° C. on an oil bath and stirred for 30 minutes. At the end of the reaction, a large amount of crystals were observed on the vessel wall. After leaving the reactor immersed in ice water, the precipitated crystals were obtained by filtration. The brown crystals (6.0 g) were further recrystallized from toluene to obtain light brown crystals (5.1 g). As a result of analysis, this was dimethyl-4-hydroxy-1-naphthyl phosphate, and the high performance liquid chromatography (LC) purity was 93.5% in peak area ratio. The yield through to crystal was 60.7 mol%. On the other hand, the reaction mother liquor from which crystals had been removed was washed with water, and then the solvent was distilled off from the obtained organic layer under reduced pressure to obtain 2.3 g of a brown liquid. When this product was analyzed by LC, the composition was 33.9% dimethyl-4-hydroxy-1-naphthyl phosphate and 48.1% 2-dimethoxyphosphoryl-1,4-dihydroxynaphthalene in peak area ratio. there were.

The melting point, IR spectrum and MS-spectrum measured values of the compound obtained as this crystal are shown below.
(1) Melting point: 141.0-141.6 ° C
(2) IR (KBr, cm ⁻¹ ): 3205, 1635, 1595, 1460, 1388, 1358, 1270, 1240, 1190, 1042, 935, 918, 857, 830, 773
(3) MS-spectrum: M ⁺ = 268

(Synthesis Example 2) Synthesis of diethyl-4-hydroxy-1-naphthyl phosphate In a reaction vessel, 2.0 g (12.6 mmol) of 1,4-naphthoquinone, 2,6 g (18.9 mmol) of diethyl phosphite and toluene as a solvent 20 ml was charged. The mixture was stirred under cooling with ice water under a simple air stream. A solution in which 67 mg of DBU was dissolved in toluene was added as a catalyst over 17 minutes. During this time, the reaction solution temperature was kept in the range of 20 ° C to 25 ° C. After addition of the catalyst, stirring was further performed at room temperature for 1 hour. Toluene was further added as an extraction solvent to the reaction solution, and the mixture was washed with 1N hydrochloric acid and then with water, and then the solvent was distilled off from the obtained organic layer under reduced pressure to obtain 3.6 g of a reddish brown liquid. When this product was analyzed by high performance liquid chromatography (LC), the composition was 69.8% diethyl-4-hydroxy-1-naphthyl phosphate in terms of peak area ratio, and 2-diethoxyphosphoryl-1,4-dihydroxy. Naphthalene was 17.8%. When left at room temperature, a large amount of crystals precipitated. This was washed with a mixed solvent of ethyl acetate-hexane to obtain 1.89 g of white crystals. As a result of analysis, this product was diethyl-4-hydroxy-1-naphthyl phosphate, and the purity was 98% in terms of peak area ratio. The yield to crystals was 49.7%.

The melting point, IR spectrum and MS-spectrum measured values of this compound are shown below.
(1) Melting point: 102.3-104.2 ° C
(2) IR (KBr, cm ⁻¹ ): 3190, 1635, 1598, 1580, 1476, 1445, 1387, 1358, 1263, 1248, 1157, 1035, 960, 903, 823, 762
(3) MS-spectrum: M ⁺ = 296

(Synthesis Example 3) Synthesis of diphenyl-4-hydroxy-1-naphthyl phosphate 3.0 g (15.9 mmol) of 1,4-naphthoquinone, 4,4 g (19.1 mmol) of diphenyl phosphite, dimethyl catalyst Aminopyridine, 20 mg, and 30 ml of toluene as a solvent were charged. This mixture was heated and stirred at 70 ° C. for 50 minutes under a simple air stream. After cooling, ethyl acetate was added to the reaction solution as an extraction solvent, and the mixture was washed with 1N hydrochloric acid and then with water. Then, the solvent was distilled off from the obtained organic layer under reduced pressure to obtain 6.8 g of a dark red liquid. When this product was analyzed by high performance liquid chromatography (LC), the composition was 41.4% diphenyl-4-hydroxy-1-naphthyl phosphate in terms of peak area ratio, and 2-diphenylphosphoryl-1,4-dihydroxynaphthalene. Of 9.1% and diphenyl phosphite of 8.8%. This reaction crude was subjected to column chromatography purification using silica gel. A mixed solvent of ethyl acetate and hexane was allowed to flow as an eluent. Elution was carried out in the order of diphenyl phosphite, 2-diphenylphosphoryl-1,4-dihydroxynaphthalene, and then the desired product diphenyl-4-hydroxy-1-naphthyl phosphate. When the solvent was distilled off from the fraction containing the desired product, pale brown crystals were obtained. This was recrystallized from ethyl acetate-hexane to obtain white crystals, 1.31 g. As a result of analysis, this was diphenyl-4-hydroxy-1-naphthyl phosphate, and the purity was 97.3% in terms of peak area ratio.

The melting point, IR spectrum and MS-spectrum measured values of the compound obtained as white crystals are shown below.
(1) Melting point: 101.2-103.4 ° C
(2) IR (KBr, cm ⁻¹ ): 3230, 1635, 1590, 1488, 1383, 1362, 1260, 1208, 1183, 1065, 965, 820, 762
(3) MS-spectrum: M ⁺ = 392

(Synthesis Example 1) Synthesis of 4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate Dithyl-4-hydroxy-1-naphthyl synthesized in the same manner as in Synthesis Example 1 in a reactor sufficiently purged with nitrogen Phosphate, 1.0 g (3.7 mmol), 1.1 g (11.2 mmol) of triethylamine and 10 ml of acetonitrile as a solvent were charged and dissolved under stirring. This solution was cooled with ice water, the temperature of the reaction solution was kept at 10-15 ° C., and 590 mg (5.6 mmol) of methacryloyl chloride was added dropwise over 20 minutes with stirring in a nitrogen stream. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 20 minutes to complete the reaction. Ethyl acetate as an extraction solvent and water for removing the generated triethylamine / hydrochloride were added to the reaction solution, and after stirring, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The organic phase was taken out, washed with water, and the solvent was distilled off to obtain 770 mg of a pale yellow oil. When this product was analyzed by high performance liquid chromatography (LC), the purity of 4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate was 95.7% in terms of peak area ratio.

The measured values of melting point, refractive index, IR spectrum, ¹ H-NMR spectrum and MS-spectrum of this compound are shown below.
(1) Melting point: liquid at room temperature (2) Refractive index: n _D = 1.5562
(3) IR (neat, cm ⁻¹ ): 3080, 2960, 2860, 1740, 1638, 1602, 1465, 1392, 1295, 1222, 1123, 1043, 905, 875, 797, 763
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 8.13-8.18 (m, 1H), 7.82-7.87 (m, 1H), 7.44-7.62 ( m, 3H), 7.20-7.27 (m, 1H), 6.50 (s, 1H), 6.83-6.86 (m, 1H), 3.87-3.92 (m, 6H), 2.13 (s, 3H)
(5) MS-spectrum: M ⁺ = 336

The 4-[(dimethoxyphosphoryl) oxy] -1-naphthyl methacrylate is liquid at room temperature and can be said to be easy to handle in the preparation of a radical polymerizable composition such as when mixed with a commercially available monomer.

Synthesis Example 2 Synthesis of 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate Diethyl-4-hydroxy-1-synthesized in the same manner as in Synthesis Example 2 in a reactor sufficiently substituted with nitrogen. Naphthyl phosphate, 2.0 g (6.8 mmol), triethylamine 2.0 g (20 mmol) and 20 ml of acetonitrile as a solvent were charged and dissolved under stirring. This solution was cooled with ice water, the temperature of the reaction solution was kept at 10-15 ° C., and 1.1 g (10.1 mmol) of methacryloyl chloride was added dropwise over 12 minutes with stirring in a nitrogen stream. After completion of the dropping, the temperature was returned to room temperature, and stirring was continued for another hour to complete the reaction. Ethyl acetate as an extraction solvent and water for removing the generated triethylamine / hydrochloride were added to the reaction solution, and after stirring, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The organic phase was taken out, washed with water, and the solvent was distilled off to obtain 2.23 g of a tan oil. When this product was analyzed by high performance liquid chromatography (LC), the purity of 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate in terms of peak area ratio was 91.6%. 1.85 g of this oily substance was distilled under reduced pressure using a glass tube oven apparatus (manufactured by Shibata Kagaku Co., Ltd., GTO-250RS type). Under a reduced pressure of 200 Pa, 1.41 g of a pale yellow liquid was obtained at an oven temperature of 220-240 ° C. The product was 94.6% pure by high performance liquid chromatography analysis.

The measured values of melting point, refractive index, IR spectrum, ¹ H-NMR spectrum and MS-spectrum of this compound are shown below.
(1) Melting point: liquid at room temperature (2) Refractive index: n _D = 1.5404
(3) IR (neat, cm ⁻¹ ): 3070, 2990, 2940, 1740, 1638, 1602, 1467, 1392, 1297, 1222, 1122, 1044, 950, 895, 808, 764, 704
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 8.14-8.19 (m, 1H), 7.78-7.86 (m, 1H), 7.47-7.58 ( m, 3H), 7.17-7.25 (m, 1H), 6.49 (s, 1H), 5.85 (s, 1H), 4.19-4.30 (m, 4H), 2 .13 (s, 3H), 1.30-1.37 (m, 6H)
(5) MS-spectrum: M ⁺ = 364

The 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate is also liquid at room temperature, and can be said to be easy to handle in the preparation of a radical polymerizable composition such as when mixed with a commercially available monomer.

(Synthesis Example 3) Synthesis of 4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate Diethyl-4-hydroxy-1-naphthyl phosphate synthesized in the same manner as in Synthesis Example 2, 3.0 g (6. 8 mmol), 3.0 g (30 mmol) of triethylamine, and 1.4 g (15.2 mmol) of acryloyl chloride in place of methacryloyl chloride were used in substantially the same manner as in Example 2 to obtain crude 4-[( Diethoxyphosphoryl) oxy] -1-acrylate was obtained as 3.0 g of a tan liquid. When this product was analyzed by high performance liquid chromatography (LC), the purity of 4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate was 95.4%. 3.0 g of this oily substance was distilled under reduced pressure using a glass tube oven apparatus in the same manner as in Example 2. Under a reduced pressure of 150 Pa, a pale yellow liquid, 2.10 g, was obtained at 220-230 ° C. at an oven temperature. As a result of analysis by high performance liquid chromatography, this product was a target product having a peak area ratio of 96.5% purity.

The measured values of melting point, refractive index, IR spectrum, ¹ H-NMR spectrum and MS-spectrum of this compound are shown below.
(1) Melting point: liquid at room temperature (2) Refractive index: n _D = 1.5476
(3) IR (neat, cm ⁻¹ ): 3080, 2990, 2905, 1748, 1635, 1600, 1465, 1390, 1280, 1221, 1142, 1044, 905, 800, 764,
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 8.12-8.20 (m, 1H), 7.80-7.87 (m, 1H), 7.47-7.58 ( m, 3H), 7.19-7.25 (m, 1H), 6.66-6.73 (m, 1H), 6.40-6.48 (m, 1H), 6.07-6. 11 (m, 1H), 4.17-4.28 (m, 4H), 1.27-1.37 (m, 6H)
(5) MS-spectrum: M ⁺ = 350

The 4-[(diethoxyphosphoryl) oxy] -1-naphthyl acrylate is also liquid at room temperature and can be said to be easy to handle in the preparation of a radical polymerizable composition such as when mixed with a commercially available monomer.

(Synthesis Example 4) Synthesis of 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate Diphenyl-4-hydroxy-1-synthesized in the same manner as in Synthesis Example 3 in a sufficiently nitrogen-substituted reactor. Naphthyl phosphate, 750 mg (1.9 mmol), 570 mg (5.7 mmol) of triethylamine and 10 ml of the solvent acetonitrile were charged and dissolved under stirring. This solution was cooled with ice water, the temperature of the reaction solution was kept at 10-15 ° C., and 300 mg (2.9 mmol) of methacryloyl chloride was added dropwise over 15 minutes with stirring in a nitrogen stream. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 30 minutes to complete the reaction. Ethyl acetate and water were added to the reaction solution as extraction solvents, and after stirring, the mixture was allowed to stand to separate into two phases, an aqueous phase and an organic phase. The organic phase was taken out, washed with water, and the solvent was distilled off to obtain 820 mg of a brown oily substance. When this product was analyzed by high performance liquid chromatography (LC), the purity of 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate was 93.5% in terms of peak area ratio. This reaction crude product, 700 mg, was subjected to column chromatography purification using silica gel. A mixed solvent of ethyl acetate and hexane was allowed to flow as an eluent. When the solvent was distilled off from the fraction containing the desired product, white crystals (70 mg) were obtained. As a result of analysis, this was 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate, and the purity was 98.5% in terms of peak area ratio.

The measured values of melting point, refractive index, IR spectrum, ¹ H-NMR spectrum and MS-spectrum of this compound are shown below.
(1) Melting point: 48.5-49.3 ° C
(2) Refractive index: n _D = 1.614
(3) IR (KBr, cm ⁻¹ ): 1732, 1635, 1590, 1488, 1463, 1390, 1296, 1215, 1195, 1125, 1064, 1010, 962, 900, 775, 762
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 8.00-8.03 (m, 1H), 7.82-7.86 (m, 1H), 7.46-7.58 ( m, 3H), 7.18-7.38 (m, 11H), 6.50-6.52 (m, 1H), 5.84-5.88 (m, 1H), 2.15 (s- 3H)
(5) MS-spectrum: M ⁺ = 460

(Evaluation Example 1) 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate was photopolymerized and the refractive index of the polymer was 100 parts by weight of trimethylolpropane triacrylate, and synthesized in the same manner as in Synthesis Example 2. 1 part by weight of radical photopolymerization initiator Irgacure 819 (manufactured by BASF) is added to 50 parts by weight of 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate to form a radically polymerizable composition. A product was prepared. Next, the composition prepared on the polyester film (Toray Lumirror film thickness 100 microns, Lumirror is a registered trademark of Toray Industries, Inc.) was applied using a bar coater so that the film thickness was 100 microns. After application, it was confirmed to be cured when irradiated with light using an ultraviolet LED (RX Firefly, manufactured by Phoseon Technology, center wavelength: 395 nm, irradiation intensity: 1.0 w / cm ² ) under a nitrogen atmosphere. The refractive index of the obtained photocured product was n _D = 1.535.

(Evaluation Example 2) Co-photopolymerization of 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate and trimethylolpropane triacrylate and refractive index of polymer 100 parts by weight of trimethylolpropane triacrylate, Synthesis Example 4 1 part by weight of photo radical polymerization initiator Irgacure 819 (manufactured by BASF) with respect to 50 parts by weight of 4-[(diphenoxyphosphoryl) oxy] -1-naphthyl methacrylate synthesized in the same manner as above The radical photopolymerizable composition was prepared by addition. Next, the composition prepared on the polyester film (Toray Lumirror film thickness 100 microns, Lumirror is a registered trademark of Toray Industries, Inc.) was applied using a bar coater so that the film thickness was 100 microns. After application, it was confirmed to be cured when irradiated with light using an ultraviolet LED (RX Firefly, manufactured by Phoseon Technology, center wavelength: 395 nm, irradiation intensity: 1.0 w / cm ² ) under a nitrogen atmosphere. The refractive index of the obtained photocured product was n _D = 1.548.

(Evaluation Comparative Example 1) Evaluation except that photopolymerization of trimethylolpropane triacrylate and refractive index of 4-[(diethoxyphosphoryl) oxy] -1-naphthyl methacrylate was 0 parts and trimethylolpropane triacrylate was 100 parts. When the same procedure as in Example 1 was carried out, the stickiness disappeared in 10 seconds and cured. The obtained polymer had a refractive index of 1.512.

From Evaluation Examples 1 and 2 and Evaluation Comparative Example 1, the following is clear. That is, a photocured product was obtained by irradiating a radical polymerizable composition comprising the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl methacrylate compound of the present invention and a radical polymerizable compound in Evaluation Examples 1 and 2 with light. It can be seen that the photocured product has a high refractive index. On the other hand, when the 4-[(disubstituted phosphoryl) oxy] -1-naphthyl methacrylate compound of the present invention is not used in the comparative example for evaluation, the photocurability is low and the refractive index is low.

Claims (4)

4-[(Disubstituted phosphoryl) oxy] -1-naphthyl methacrylate compound represented by the general formula (1).

(In the general formula (1), R ³ represents a hydrogen atom or a methyl group, R ¹ and R ² may be the same or different, and an alkyl group having 1 to 4 carbon atoms, or 6 or 6 carbon atoms. Any one of 7 aryl groups, X and Y may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) A radically polymerizable composition comprising a 4-[(disubstituted phosphoryl) oxy] -1-naphthyl methacrylate compound represented by the general formula (1) according to claim 1 and a radical polymerization initiator. A polymer obtained by polymerizing the radically polymerizable composition according to claim 2. The 4-[(disubstituted phosphoryl) oxy] -1-naphthyl (1) according to claim 1, which comprises (meth) acryloylating a di-substituted-4-hydroxy-1-naphthyl phosphate compound represented by the general formula (2). A method for producing a (meth) acrylate compound.

(In the general formula (2), R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 or 7 carbon atoms; Y may be the same or different, and represents either a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)