JP5360502B2 - 4- (Acyloxy) -1-naphthyl (meth) acrylate compound, production method thereof and polymer obtained by polymerizing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound which is an aromatic polycyclic compound having a high refractive index, is free from such a problem that there is an absorption peak in an ultraviolet region or fluorescence is generated, is excellent in transparency and can be polymerized in a UV curing apparatus in which a high-pressure mercury lamp or the like is used and which is industrially advantageous and to provide a polymerizable composition containing the compound. <P>SOLUTION: A 4-(acyloxy)-1-naphthyl(meth)acrylate compound and the polymerizable composition containing the 4-(acyloxy)-1-naphthyl(meth)acrylate compound and a polymerization initiator are provided. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a 4- (acyloxy) -1-naphthyl (meth) acrylate compound, a production method thereof, and a polymer obtained by polymerizing 4- (acyloxy) -1-naphthyl (meth) acrylate compound.

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.

On the other hand, high refractive index materials having a benzene ring and a biphenyl ring have been known for introduction of an aromatic ring, and these are light and excellent in transparency and have a well-balanced high refractive index material (Patent Document 3). etc). However, when a benzene ring is used, it is difficult to obtain a monomer having a refractive index exceeding 1.54. In addition, when a biphenyl ring is used, the absorption shifts to a longer wavelength side compared to the monomer of the benzene ring, and in the case of photocuring, the initiator and the UV absorption overlap, so that the photoinitiating efficiency is lowered. was there. In addition, in order to obtain a higher refractive index, development of a monomer having an anthracene ring or a fluorene ring has been studied (Patent Documents 4, 8, and 9). Attempts have also been made to introduce an anthracene ring, a fluorene ring or the like into a polymer by transesterification (Patent Document 5).

However, introduction of anthracene ring or fluorene ring can yield a polymer with a relatively high refractive index. However, when a fluorene ring is introduced, it absorbs in the ultraviolet region and is easily colored by light irradiation, which causes problems with light resistance. Comes out. In addition, when an anthracene ring is introduced, the anthracene ring emits fluorescence, so that there are problems such as difficulty in application in the field of optical materials.

From the viewpoint of transparency, acrylic high refractive index resins have been studied as spectacle lenses, intraocular lenses, liquid crystal display panels, color filter protective films, and the like (Patent Documents 6, 7, 8, and 9). However, there are drawbacks that the refractive index is not sufficient, and that the viscosity is too high to be handled like fluorene acrylate.

On the other hand, since a high refractive index can be expected by introducing a naphthalene ring, the acrylate compound containing a naphthalene compound in the skeleton has been reported in recent years for its monoacrylate body and diacrylate body (Patent Documents 10 and 11). ). However, acrylates containing these naphthalene compounds have UV absorption around 350 nm. When the most common high-pressure mercury lamp is used as a UV lamp when photocuring, the light around 366 nm of the high-pressure mercury lamp is absorbed into the naphthalene compound. Due to the so-called internal filtering effect that is absorbed, there is the disadvantage that photocuring is slowed down. For this reason, conventional photocuring using phosphine oxide-based photoradical polymerization initiators such as Irgacure 819 and Darocur TPO (Irgacure, Darocur is a registered trademark of Ciba Specialty Chemicals Co., Ltd.) using ultraviolet LED lamps having a wavelength of around 400 nm. (Patent Document 11).

However, LED lamps and the like are not yet common, and have a drawback that it is difficult to produce a large device, and phosphine oxide-based photoradical polymerization initiators contain phosphorus compounds that are not good for the environment and are expensive. It has the disadvantage of being.

JP 05-170702 A JP 2002-20433 A JP 2003-064296 A JP 2004-083855 A JP 2006-312709 A JP 2003-144538 A JP 2003-049037 A Japanese Patent Laid-Open No. 06-220131 Japanese Patent Laid-Open No. 06-21936 JP 2001-276687 A JP 2008-81682 A

Therefore, it is an aromatic polycyclic compound having a high refractive index, there is no problem of absorption and fluorescence in the ultraviolet region as seen in biphenyl group, anthracene group and fluorene group, the viscosity is low and easy to handle, and excellent transparency. Development of acrylate compounds with a naphthalene skeleton that can be polymerized with a light source such as a general and most widely used high-pressure mercury lamp and can be polymerized without using a radical initiator as a radical photopolymerization initiator Is desired.

As a result of intensive studies on the structure and photocurability of the naphthalene compound, the present inventors have found that the 4- (acyloxy) -1-naphthyl (meth) acrylate compound is low in viscosity and easy to handle, and is easily polymerized with a high-pressure mercury lamp. Furthermore, it discovered that the obtained polymer had a high refractive index, and completed this invention.

The first invention provides a 4- (acyloxy) -1-naphthyl (meth) acrylate compound represented by the general formula (1).

(In the general formula (1), R represents a hydrogen atom or a methyl group, Z represents an alkyl group or an aryl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, a halogen atom, Indicates an atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.)

The second invention provides a method for producing the above 4- (acyloxy) -1-naphthyl (meth) acrylate compound, which comprises acylating a 4-hydroxy-1-naphthyl (meth) acrylate compound.

A third invention provides a method for producing a 4- (acyloxy) -1-naphthyl (meth) acrylate compound according to the first invention, which comprises (meth) acrylating a 4- (acyloxy) -1-naphthol compound. .

In 4th invention, the polymeric composition containing said 4- (acyloxy) -1-naphthyl (meth) acrylate compound and a polymerization initiator is provided.

In 5th invention, the polymer obtained by superposing | polymerizing said polymeric composition is provided.

In the sixth invention, a high refractive material containing the polymer is provided.

In the present invention, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl.

The 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention is a novel compound and is easily polymerized by a high-pressure mercury lamp which is the most common ultraviolet light source. Moreover, the polymer obtained by the polymerization is an industrially useful compound having a high refractive index.

FIG. 1 is a result of an experiment for reducing the melt viscosity of 9,9-bis [4- (2-acryloyloxy) ethoxyphenyl] fluorene by adding 4-propanoyloxy-1-naphthyl acrylate. (Example 25)

The 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention is a compound having the structure described in the general formula (1), and in the general formula (1), R is a hydrogen atom or a methyl group. Z represents an alkyl group or an aryl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group Indicates either.

In general formula (1), examples of the alkyl group represented by Z include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a cyclohexyl group, and a benzyl group. Examples of the aryl group include a phenyl group and a naphthyl group. These groups may have a substituent.

In the general formula (1), examples of the alkyl group represented by X and Y include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. As the halogen atom, a fluorine atom, a chlorine atom, Examples thereof include bromine and iodine atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the alkylthio group include a methylthio group and an ethylthio group, and examples of the arylthio group include a phenylthio group and a naphthylthio group.

Examples of the 4- (acyloxy) -1-naphthyl (meth) acrylate compound represented by the general formula (1) include the following.

That is, 4-acetyloxy-1-naphthyl acrylate, 4-acetyloxy-1-naphthyl methacrylate, 4-propanoyloxy-1-naphthyl acrylate, 4-propanoyloxy-1-naphthyl methacrylate, 4-butanoyloxy- 1-naphthyl acrylate, 4-butanoyloxy-1-naphthyl methacrylate, 4-benzoyloxy-1-naphthyl acrylate, 4-benzoyloxy-1-naphthyl methacrylate, 4- (2-naphthylcarbonyloxy) -1-naphthyl acrylate 4- (2-naphthylcarbonyloxy) -1-naphthyl methacrylate, 4- (1-naphthylcarbonyloxy) -1-naphthyl acrylate, 4- (1-naphthylcarbonyloxy) -1-naphthyl methacrylate, and the like. It is.

Further, examples of the compound in which an alkyl group is substituted on the naphthalene ring include 2-methyl-4-acetyloxy-1-naphthyl acrylate, 2-methyl-4-acetyloxy-1-naphthyl methacrylate, 2-methyl-4-propylene. Noyloxy-1-naphthyl acrylate, 2-methyl-4-propanoyloxy-1-naphthyl methacrylate, 2-methyl-4-butanoyloxy-1-naphthyl acrylate, 2-methyl-4-butanoyloxy-1- Naphthyl methacrylate, 2-methyl-4-benzoyloxy-1-naphthyl acrylate, 2-methyl-4-benzoyloxy-1-naphthyl methacrylate, etc., 5-methyl-4-acetyloxy-1-naphthyl acrylate, 5-methyl- 4-acetyloxy-1-naphthyl methacrylate 5-methyl-4-propanoyloxy-1-naphthyl acrylate, 5-methyl-4-propanoyloxy-1-naphthyl methacrylate, 5-methyl-4-butanoyloxy-1-naphthyl acrylate, 5-methyl-4 -Butanoyloxy-1-naphthyl methacrylate, 5-methyl-4-benzoyloxy-1-naphthyl acrylate, 5-methyl-4-benzoyloxy-1-naphthyl methacrylate, 6-methyl-4-acetyloxy-1-naphthyl Acrylate, 6-methyl-4-acetyloxy-1-naphthyl methacrylate, 6-methyl-4-propanoyloxy-1-naphthyl acrylate, 6-methyl-4-propanoyloxy-1-naphthyl methacrylate, 6-methyl- 4-butanoyloxynaphthyl acrylate 6-methyl-4-butanoyl-1- naphthyl methacrylate, 6-methyl-4-benzoyloxy-1-naphthyl acrylate, 6-methyl-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Furthermore, 2-ethyl-4-acetyloxy-1-naphthyl acrylate, 2-ethyl-4-acetyloxy-1-naphthyl methacrylate, 2-ethyl-4-propanoyloxy-1-naphthyl acrylate, 2-ethyl- 4-propanoyloxy-1-naphthyl methacrylate, 2-ethyl-4-butanoyloxy-1-naphthyl acrylate, 2-ethyl-4-butanoyloxy-1-naphthyl methacrylate, 2-ethyl-4-benzoyloxy- 1-naphthyl acrylate, 2-ethyl-4-benzoyloxy-1-naphthyl methacrylate, etc., 5-ethyl-4-acetyloxy-1-naphthyl acrylate, 5-ethyl-4-acetyloxy-1-naphthyl methacrylate, 5- Ethyl-4-propanoyloxy-1-naphthyl Acrylate, 5-ethyl-4-propanoyloxy-1-naphthyl methacrylate, 5-ethyl-4-butanoyloxy-1-naphthyl acrylate, 5-ethyl-4-butanoyloxy-1-naphthyl methacrylate, 5-ethyl -4-benzoyloxy-1-naphthyl acrylate, 5-ethyl-4-benzoyloxy-1-naphthyl methacrylate, 6-ethyl-4-acetyloxy-1-naphthyl acrylate, 6-ethyl-4-acetyloxy-1- Naphthyl methacrylate, 6-ethyl-4-propanoyloxy-1-naphthyl acrylate, 6-ethyl-4-propanoyloxy-1-naphthyl methacrylate, 6-ethyl-4-butanoyloxy-1-naphthyl acrylate, Ethyl-4-butanoyloxy-1-na Chill methacrylate, 6-ethyl-4-benzoyloxy-1-naphthyl acrylate, 6-ethyl-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Furthermore, 2,3-dimethyl-4-acetyloxy-1-naphthyl acrylate, 2,3-dimethyl-4-acetyloxy-1-naphthyl methacrylate, 2,3-dimethyl-4-propanoyloxy-1-naphthyl Acrylate, 2,3-dimethyl-4-propanoyloxy-1-naphthyl methacrylate, 1- (2,3-dimethyl-4-butanoyloxynaphthyl) acrylate, 1- (2,3-dimethyl-4-butanoyl Oxynaphthyl) methacrylate, 2,3-dimethyl-4-benzoyloxy-1-naphthyl acrylate, 2,3-dimethyl-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Furthermore, 2,6-dimethyl-4-acetyloxy-1-naphthyl acrylate, 2,6-dimethyl-4-acetyloxy-1-naphthyl methacrylate, 2,6-dimethyl-4-propanoyloxynaphthyl acrylate, 2 , 6-dimethyl-4-propanoyloxy-1-naphthyl methacrylate, 2,6-dimethyl-4-butanoyloxy-1-naphthyl acrylate, 2,6-dimethyl-4-butanoyloxy-1-naphthyl methacrylate, 2,6-dimethyl-4-benzoyloxy-1-naphthyl acrylate, 2,6-dimethyl-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Furthermore, 2,7-dimethyl-4-acetyloxy-1-naphthyl acrylate, 2,7-dimethyl-4-acetyloxy-1-naphthyl methacrylate, 2,7-dimethyl-4-propanoyloxy-1-naphthyl Acrylate, 2,7-dimethyl-4-propanoyloxy-1-naphthyl methacrylate, 2,7-dimethyl-4-butanoyloxy-1-naphthyl acrylate, 2,7-dimethyl-4-butanoyloxy-1- Naphthyl methacrylate, 2,7-dimethyl-4-benzoyloxy-1-naphthyl acrylate, 2,7-dimethyl-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Further, examples of the compound in which a halogen atom is substituted on the naphthalene ring include 2-chloro-4-acetyloxy-1-naphthyl acrylate, 2-chloro-4-acetyloxy-1-naphthyl methacrylate, 2-chloro-4-propylene. Noyloxy-1-naphthyl acrylate, 2-chloro-4-propanoyloxy-1-naphthyl methacrylate, 2-chloro-4-butanoyloxy-1-naphthyl acrylate, 2-chloro-4-butanoyloxy-1- Naphthyl methacrylate, 2-chloro-4-benzoyloxy-1-naphthyl acrylate, 2-chloro-4-benzoyloxy-1-naphthyl methacrylate, etc., 2-bromo-4-acetyloxy-1-naphthyl acrylate, 2-bromo- 4-acetyloxy-1-naphthyl methacrylate 2-bromo-4-propanoyloxy-1-naphthyl acrylate, 2-bromo-4-propanoyloxy-1-naphthyl methacrylate, 2-bromo-4-butanoyloxy-1-naphthyl acrylate, 2-bromo- 4-butanoyloxy-1-naphthyl methacrylate, 2-bromo-4-benzoyloxy-1-naphthyl acrylate, 2-bromo-4-benzoyloxy-1-naphthyl methacrylate, 2-fluoro-4-acetyloxy-1- Naphthyl acrylate, 2-fluoro-4-acetyloxy-1-naphthyl methacrylate, 2-fluoro-4-propanoyloxy-1-naphthyl acrylate, 2-fluoro-4-propanoyloxy-1-naphthyl methacrylate, 2-fluoro -4-butanoyloxy-1- Examples include butyl acrylate, 2-fluoro-4-butanoyloxy-1-naphthyl methacrylate, 2-fluoro-4-benzoyloxy-1-naphthyl acrylate, and 2-fluoro-4-benzoyloxy-1-naphthyl methacrylate. .

Furthermore, 5-chloro-4-acetyloxy-1-naphthyl acrylate, 5-chloro-4-acetyloxy-1-naphthyl methacrylate, 5-chloro-4-propanoyloxy-1-naphthyl acrylate, 5-chloro- 4-propanoyloxy-1-naphthyl methacrylate, 5-chloro-4-butanoyloxy-1-naphthyl acrylate, 5-chloro-4-butanoyloxy-1-naphthyl methacrylate, 5-chloro-4-benzoyloxy- 1-naphthyl acrylate, 5-chloro-4-benzoyloxy-1-naphthyl methacrylate, 5-bromo-4-acetyloxy-1-naphthyl acrylate, 5-bromo-4-acetyloxy-1-naphthyl methacrylate, 5-bromo -4-propanoyloxy-1-naphthyla Relate, 5-bromo-4-propanoyloxy-1-naphthyl methacrylate, 5-bromo-4-butanoyloxy-1-naphthyl acrylate, 5-bromo-4-butanoyloxy-1-naphthyl methacrylate, 5-bromo -4-benzoyloxy-1-naphthyl acrylate, 5-bromo-4-benzoyloxy-1-naphthyl methacrylate, 5-fluoro-4-acetyloxy-1-naphthyl acrylate, 5-fluoro-4-acetyloxy-1- Naphthyl methacrylate, 5-fluoro-4-propanoyloxy-1-naphthyl acrylate, 5-fluoro-4-propanoyloxy-1-naphthyl methacrylate, 5-fluoro-4-butanoyloxy-1-naphthyl acrylate, 5- Fluoro-4-butanoyloxy 1-naphthyl methacrylate, 5-fluoro-4-benzoyloxy-1-naphthyl acrylate, 5-fluoro-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Further, 2,3-dichloro-4-acetyloxy-1-naphthyl acrylate, 2,3-dichloro-4-acetyloxy-1-naphthyl methacrylate, 2,3-dichloro-4-propanoyloxy-1-naphthyl Acrylate, 2,3-dichloro-4-propanoyloxy-1-naphthyl methacrylate, 2,3-dichloro-4-butanoyloxy-1-naphthyl acrylate, 2,3-dichloro-4-butanoyloxy-1- Examples include naphthyl methacrylate, 2,3-dichloro-4-benzoyloxy-1-naphthyl acrylate, 2,3-dichloro-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Furthermore, as the compound in which alkoxy is substituted on the naphthalene ring, 2-methoxy-4-acetyloxy-1-naphthyl acrylate, 2-methoxy-4-acetyloxy-1-naphthyl methacrylate, 2-methoxy-4-propanoyl Oxy-1-naphthyl acrylate, 2-methoxy-4-propanoyloxy-1-naphthyl methacrylate, 2-methoxy-4-butanoyloxy-1-naphthyl acrylate, 2-methoxy-4-butanoyloxy-1-naphthyl Methacrylate, 2-methoxy-4-benzoyloxy-1-naphthyl acrylate, 2-methoxy-4-benzoyloxy-1-naphthyl methacrylate, 5-methoxy-4-acetyloxy-1-naphthyl acrylate, 5-methoxy-4- Acetyloxy-1-naphth Methacrylate, 5-methoxy-4-propanoyloxy-1-naphthyl acrylate, 5-methoxy-4-propanoyloxy-1-naphthyl methacrylate, 5-methoxy-4-butanoyloxy-1-naphthyl acrylate, 5- Methoxy-4-butanoyloxy-1-naphthyl methacrylate, 5-methoxy-4-benzoyloxy-1-naphthyl acrylate, 5-methoxy-4-benzoyloxy-1-naphthyl methacrylate, 2-ethoxy-4-acetyloxy- 1-naphthyl acrylate, 2-ethoxy-4-acetyloxy-1-naphthyl methacrylate, 2-ethoxy-4-propanoyloxy-1-naphthyl acrylate, 2-ethoxy-4-propanoyloxy-1-naphthyl methacrylate, 2 -Ethoxy 4-butanoyloxy-1-naphthyl acrylate, 2-ethoxy-4-butanoyloxy-1-naphthyl methacrylate, 2-ethoxy-4-benzoyloxy-1-naphthyl acrylate, 2-ethoxy-4-benzoyloxy-1 -Naphthyl methacrylate, 5-ethoxy-4-acetyloxy-1-naphthyl acrylate, 5-ethoxy 4-acetyloxy-1-naphthyl methacrylate, 5-ethoxy-4-propanoyloxy-1-naphthyl acrylate, 5-ethoxy- 4-propanoyloxy-1-naphthyl methacrylate, 5-ethoxy-4-butanoyloxy-1-naphthyl acrylate, 5-ethoxy 4-butanoyloxy-1-naphthyl methacrylate, 5-ethoxy-4-benzoyloxy-1 -Naphthyl acry Rate, 5-ethoxy-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Further, compounds in which aryloxy is substituted on the naphthalene ring include 2-phenoxy-4-acetyloxy-1-naphthyl acrylate, 2-phenoxy-4-acetyloxy-1-naphthyl methacrylate, 2-phenoxy-4-propaline. Noyloxy-1-naphthyl acrylate, 2-phenoxy-4-propanoyloxy-1-naphthyl methacrylate, 2-phenoxy-4-butanoyloxy-1-naphthyl acrylate, 2-phenoxy-4-butanoyloxy-1- Naphthyl methacrylate, 2-phenoxy-4-benzoyloxy-1-naphthyl acrylate, 2-phenoxy-4-benzoyloxy-1-naphthyl methacrylate, etc., 5-phenoxy-4-acetyloxy-1-naphthyl acrylate, 5-phenoxy- 4 Acetyloxy-1-naphthyl methacrylate, 5-phenoxy-4-propanoyloxy-1-naphthyl acrylate, 5-phenoxy-4-propanoyloxy-1-naphthyl methacrylate, 5-phenoxy-4-butanoyloxy-1- Examples include naphthyl acrylate, 5-phenoxy-4-butanoyloxy-1-naphthyl methacrylate, 5-phenoxy-4-benzoyloxy-1-naphthyl acrylate, 5-phenoxy-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Further, examples of the compound in which an alkylthio group is substituted on the naphthalene ring include 2-methylthio-4-acetyloxy-1-naphthyl acrylate, 2-methylthio-4-acetyloxy-1-naphthyl methacrylate, 2-methylthio-4-propapropene. Noyloxy-1-naphthyl acrylate, 2-methylthio-4-propanoyloxy-1-naphthyl methacrylate, 2-methylthio-4-butanoyloxy-1-naphthyl acrylate, 2-methylthio-4-butanoyloxy-1- Naphtyl methacrylate, 2-methylthio-4-benzoyloxy-1-naphthyl acrylate, 2-methylthio-4-benzoyloxy-1-naphthyl methacrylate, etc., 5-methylthio-4-acetyloxy-1-naphthyl acrylate, 5-methylthio- 4 Acetyloxy-1-naphthyl methacrylate, 5-methylthio-4-propanoyloxy-1-naphthyl acrylate, 5-methylthio-4-propanoyloxy-1-naphthyl methacrylate, 5-methylthio-4-butanoyloxy-1- Examples include naphthyl acrylate, 5-methylthio-4-butanoyloxy-1-naphthyl methacrylate, 5-methylthio-4-benzoyloxy-1-naphthyl acrylate, 5-methylthio-4-benzoyloxy-1-naphthyl methacrylate, and the like.

Further, compounds in which an arylthio group is substituted on the naphthalene ring include 2-phenylthio-4-acetyloxy-1-naphthyl acrylate, 2-phenylthio-4-acetyloxy-1-naphthyl methacrylate, 2-phenylthio-4-propaprop Noyloxy-1-naphthyl acrylate, 2-phenylthio-4-propanoyloxy-1-naphthyl methacrylate, 2-phenylthio-4-butanoyloxy-1-naphthyl acrylate, 2-phenylthio-4-butanoyloxy-1- Naphthyl methacrylate, 2-phenylthio-4-benzoyloxy-1-naphthyl acrylate, 2-phenylthio-4-benzoyloxy-1-naphthyl methacrylate, etc., 5-phenylthio-4-acetyloxy-1-naphthyl acrylate, -Phenylthio-4-acetyloxy-1-naphthyl methacrylate, 5-phenylthio-4-propanoyloxy-1-naphthyl acrylate, 5-phenylthio-4-propanoyloxy-1-naphthyl methacrylate, 5-phenylthio-4-buta Noyloxy-1-naphthyl acrylate, 5-phenylthio-4-butanoyloxy-1-naphthyl methacrylate, 5-phenylthio-4-benzoyloxy-1-naphthyl acrylate, 5-phenylthio-4-benzoyloxy-1-naphthyl methacrylate Etc.

Among these compounds, 4-acetyloxy-1-naphthyl acrylate, 4-acetyloxy-1-naphthyl methacrylate, 4-propanoyloxy-1-naphthyl acrylate and 4-benzoyloxy-1-naphthyl acrylate are easily synthesized. Particularly preferred is the high refractive index of the resulting product.

[Production method]
Next, the synthesis of these compounds will be described in detail. The 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention can be obtained by two routes as shown in the figure below. One is a route A in which a 1,4-naphthalenediol compound is first mono (meth) acrylated and then acylated, and the second is a method reverse in order to the first. , 4-Naphthalenediol compound is monoacylated and then (meth) acrylated.

<Route A>
First, route A will be described. In route A, the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention acylates the 4-hydroxy-1-naphthyl (meth) acrylate compound represented by the following general formula (2). Can get more. The 4-hydroxy-1-naphthyl (meth) acrylate compound can be obtained by mono (meth) acrylating a 1,4-naphthalenediol compound.

That is, as shown in the following reaction formula, a first reaction in which a 1,4-naphthalenediol compound is mono (meth) acrylated to form a 4-hydroxy-1-naphthyl (meth) acrylate compound, and the obtained 4-hydroxy- The 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention can be synthesized from the second reaction in which the 1-naphthyl (meth) acrylate compound is acylated.

In the first reaction, the 1,4-naphthalenediol compound is mono (meth) acrylated to give the corresponding 4-hydroxy-1-naphthyl (meth) acrylate compound.

Examples of the 1,4-naphthalenediol compound used in the first reaction include the following compounds. That is, 1,4-naphthalenediol, 2-methyl-1,4-naphthalenediol, 2-ethyl-1,4-naphthalenediol, 2-chloro-1,4-naphthalenediol, 2-fluoro-1,4- Naphthalenediol, 2-bromo-1,4-naphthalenediol, 2-methoxy-1,4-naphthalenediol, 2-ethoxy-1,4-naphthalenediol, 2-phenoxy-1,4-naphthalenediol, 2-methylthio -1,4-naphthalenediol, 2-phenylthio-1,4-naphthalenediol, and the like.

Furthermore, 5-methyl-1,4-naphthalenediol, 5-ethyl-1,4-naphthalenediol, 5-chloro-1,4-naphthalenediol, 5-fluoro-1,4-naphthalenediol, 5-bromo -1,4-naphthalenediol, 5-methoxy-1,4-naphthalenediol, 5-ethoxy-1,4-naphthalenediol, 5-phenoxy-1,4-naphthalenediol, 5-methylthio-1,4-naphthalene Diol, 5-phenylthio-1,4-naphthalenediol, 6-methyl-1,4-naphthalenediol, 6-ethyl-1,4-naphthalenediol, 6-chloro-1,4-naphthalenediol, 6-fluoro- 1,4-naphthalenediol, 5-bromo-1,4-naphthalenediol, 6-methoxy-1,4-naphthalene , 6-ethoxy-1,4-naphthalenediol, 6-phenoxy-1,4-naphthalenediol, 5-methylthio-1,4-naphthalenediol, 6-phenylthio-1,4-naphthalenediol, 2,3 -Dimethyl-1,4-naphthalenediol, 2,3-dichloro-1,4-naphthalenediol, 2,6-dimethyl-1,4-naphthalenediol, 2,7-dimethyl-1,4-naphthalenediol, etc. is there.

The method for producing a 4-hydroxy-1-naphthyl (meth) acrylate compound in the first reaction comprises reacting a 1,4-naphthalenediol compound with a (meth) acrylic acid halide in the presence of an inorganic base. Acrylic acid chloride is particularly preferred as the acrylic acid halide, and methacrylic acid chloride is particularly preferred as the methacrylic acid halide. If acrylic acid halide is used as a raw material, a 4-hydroxy-1-naphthyl acrylate compound is obtained. On the other hand, if a methacrylic acid halide is used as a raw material, a 4-hydroxy-1-naphthyl methacrylate compound is obtained.

The use ratio of 1,4-naphthalenediol compound to (meth) acrylic acid halide is a molar ratio of (meth) acrylic acid halide to 1,4-naphthalenediol compound, usually 0.5 or more, particularly 0.8 or more. In addition, it is usually preferably less than 2, particularly preferably 1.5 or less. If the ratio of (meth) acrylic acid halide is too low, the amount of unreacted 1,4-naphthalenediol compound increases, and treatment such as raw material recovery may be required. On the other hand, when the ratio of the (meth) acrylic acid halide is too high, the by-product amount of the diester in which both hydroxyl groups of the 1,4-naphthalenediol compound are (meth) acrylated tends to increase.

Examples of the inorganic base used include sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ) and the like. Of these, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable.

The use ratio of the inorganic base is an equivalent ratio of the inorganic base to the 1,4-naphthalenediol compound, usually 1.0 equivalent or more, especially 1.2 equivalents or more, and usually 3.0 equivalents or less, especially 2.0 equivalents. The following range is preferable. If the ratio of the inorganic base is too low, the pH of the aqueous layer becomes acidic during the dropping of the acid halide, and the selectivity may be significantly reduced. On the other hand, if the ratio of the inorganic base is too high, decomposition of the acid halide may increase.

The reaction between the 1,4-naphthalenediol compound and the (meth) acrylic acid halide is usually carried out in the presence of a reaction solvent. The type of the reaction solvent is not particularly limited, but the reaction is preferably performed in a two-phase system composed of an aqueous phase and an organic phase.

When the reaction is performed in a two-phase system composed of an aqueous phase and an organic phase, usually, water and one or more organic solvents that form the organic phase are used in combination as a reaction solvent. The type of the organic solvent that forms the organic phase is not particularly limited, but it is preferable to use an organic solvent that exhibits relatively low polarity and is not miscible with water. Examples of such an organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as heptane, cyclohexane and decalin. Any of these may be used alone, or two or more of these may be used in combination in any combination and ratio. Of these, toluene, xylene and heptane are preferable, and it is particularly preferable to use toluene alone or mixed with heptane.

The ratio of the aqueous phase to the organic phase is not particularly limited, but it is preferable that the volume ratio of the aqueous phase to the total amount of the aqueous phase and the organic phase is usually in the range of 50% to 95%. Even if the proportion of the aqueous phase is too small or too large, the selectivity of the 4-hydroxy-1-naphthyl (meth) acrylate compound tends to decrease. The concentration of the 1,4-naphthalenediol compound relative to the total amount of the aqueous phase and the organic phase is usually 0.005 g / ml or more, especially 0.03 g / ml or more, and usually 0.5 g / ml or less, especially 0.3 g. / Ml or less is preferable. If the concentration of the 1,4-naphthalenediol compound is too low, production efficiency may be reduced. On the other hand, if the concentration of the 1,4-naphthalenediol compound is too high, the selectivity may decrease. Further, it may be difficult to stir the slurry solution with the precipitated solid.

From the viewpoint of controlling the reaction temperature and improving the selectivity, a method of dropping (meth) acrylic acid halide is preferred. In particular, when the reaction is carried out in a two-phase system consisting of an aqueous phase and an organic phase, the 1,4-naphthalenediol compound is dissolved in a two-phase solvent of the aqueous phase and the organic phase, and a method such as stirring in a container is used. It is preferable that (meth) acrylic acid halide is dropped and reacted while mixing.

The reaction is preferably carried out while cooling the reaction system. Specifically, it is preferable that the temperature of the reaction system is usually 10 ° C. or lower, particularly 5 ° C. or lower, and a temperature at which the aqueous layer does not solidify. If the temperature during the reaction is too high, the selectivity tends to decrease, and hydrolysis of the 4-hydroxy-1-naphthyl (meth) acrylate compound, which is a reaction product, may occur.

The reaction time is preferably in the range of usually 30 minutes or more, particularly 60 minutes or more, and usually 5 hours or less, especially 2 hours or less. It is preferable to quench (stop) the reaction as soon as possible after the above reaction time has elapsed.

The reaction is quenched by, for example, adding an acid such as dilute hydrochloric acid (about 1 to 3 N) or dilute sulfuric acid (about 1 to 3 N) to the reaction system (aqueous phase) to make it acidic. After completion of the reaction, post-treatment such as rough purification and recrystallization purification may be performed as necessary.

The crude purification of the reaction product can be performed, for example, by the following procedure. For example, an extraction solvent such as ethyl acetate is added to the reaction system and mixed to perform two-layer separation. The organic phase is washed with water, a drying agent such as magnesium sulfate (MgSO ₄ ) is added and dried, and then the solvent is distilled off to obtain a crude product. The recrystallized purification of the crude purified product is performed, for example, by adding the crude purified product to a recrystallization solvent and dissolving it by heating, then allowing to cool and recrystallizing. As the solvent for recrystallization, for example, toluene, a mixed solvent of toluene and ethyl acetate, a mixed solvent of toluene and ethanol, or the like can be used.

Next, in the second reaction, the 4-hydroxy-1-naphthyl (meth) acrylate compound is acylated in the presence or absence of a base, and the corresponding 4- (acyloxy) -1-naphthyl) (meta ) An acrylate compound is obtained. Examples of acylating agents used include carboxylic acid halides such as acetyl chloride, acetyl bromide, propanoyl chloride, and butanoyl chloride, carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and benzoyl chloride, bromide. Examples thereof include carboxylic acid halides such as benzoyl, chloride-1-naphthoyl, and 2-naphthoyl chloride, and carboxylic anhydrides such as benzoic anhydride.

As a raw material for the second reaction, the 4-hydroxy-1-naphthyl (meth) acrylate compound obtained in the first reaction is used. For example, 4-hydroxy-1-naphthyl acrylate, 4-hydroxy-1-naphthyl methacrylate, 2-methyl-4-hydroxy-1-naphthyl acrylate having a naphthalene ring substituted with an alkyl group, 2-methyl-4-hydroxy-1-naphthyl methacrylate, 2-ethyl-4-hydroxy-1-naphthyl acrylate, 2-ethyl-4-hydroxy-1-naphthyl methacrylate, 2,6-dimethyl-4-hydroxy-1 -Naphtyl acrylate, 2,6-dimethyl-4-hydroxy-1-naphthyl methacrylate, etc. are mentioned.

Furthermore, 2-chloro-4-hydroxy-1-naphthyl acrylate, 2-chloro-4-hydroxy-1-naphthyl methacrylate, 5-chloro-4-hydroxy-1-naphthyl acrylate having a halogen atom substituted on the naphthalene ring, Examples include 5-chloro-4-hydroxy-1-naphthyl methacrylate.

Furthermore, 2-methoxy-4-hydroxy-1-naphthyl acrylate, 2-methoxy-4-hydroxy-1-naphthyl methacrylate, 2-ethoxy-4-hydroxy-1-naphthyl acrylate having an alkoxy group substituted on the naphthalene ring, 2-ethoxy-4-hydroxy-1-naphthyl methacrylate, 5-ethoxy-4-hydroxy-1-naphthyl acrylate, 5-ethoxy-4-hydroxy-1-naphthyl methacrylate, and an aryloxy group substituted on the naphthalene ring 2-phenoxy-4-hydroxy-1-naphthyl acrylate, 2-phenoxy-4-hydroxy-1-naphthyl methacrylate, and the like.

Furthermore, 2-methylthio-4-hydroxy-1-naphthyl acrylate, 2-methylthio-4-hydroxy-1-naphthyl methacrylate, 2-ethylthio-4-hydroxy-1-naphthyl acrylate having a naphthalene ring substituted with an alkylthio group, 2-Ethylthio-4-hydroxy-1-naphthyl methacrylate Furthermore, 2-phenylthio-4-hydroxy-1-naphthyl acrylate, 2-phenylthio-4-hydroxy-1-naphthyl methacrylate, etc. in which an arylthio group is substituted on the naphthalene ring Can be mentioned.

When the acylating agent is a carboxylic acid halide, the addition amount of the acylating agent relative to the 4-hydroxy-1-naphthyl (meth) acrylate compound is preferably 1 to 2 times, more preferably 1.1 times. To 1.3 mole times. When the amount is less than 1 mol, unreacted 4-hydroxy-1-naphthyl (meth) acrylate compound remains. When the amount exceeds 2 mol, a large amount of acylating agent remains in the reaction product. Are difficult to crystallize, both of which are not preferred. On the other hand, when the acylating agent is a carboxylic acid anhydride, it is preferably added at least 1 mol times. However, the addition of more than 2 mol times does not adversely affect the reaction. A large excess may also be added.

Examples of the base used in the second reaction include trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline, piperidine and the like. The amount of the base used is usually added in an equimolar to 3 molar amount relative to the starting 4-hydroxy-1-naphthyl (meth) acrylate compound.

The second reaction is generally performed in a solvent. 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 and dimethylformamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used. In some cases, an acylating agent may be used as a solvent. The concentration of the 4-hydroxy-1-naphthyl (meth) acrylate compound in the solvent is usually preferably 0.2 molar or higher.

When the solvent is an aromatic solvent, the 4-hydroxy-1-naphthyl (meth) acrylate compound, which is the raw material for the second reaction, may have a low solubility in the solvent, but may be in a slurry state, but as the reaction proceeds. Generally, it becomes solubilized.

The reaction temperature is 0 ° C to 80 ° C, preferably 0 ° C to 20 ° C. If the reaction temperature is too low, the reaction takes time, and if it exceeds 80 ° C., the impurity concentration increases, which is not preferable in either case.

The reaction time is about 15 minutes to 3 hours. After completion of the reaction, if the acylating agent is a carboxylic acid halide, water or methanol is added to hydrolyze the unreacted acylating agent, and then water is added to the filtrate to remove the precipitated hydrochloride by filtration. At the same time, the product is crystallized, and the precipitated crystals are filtered to obtain a white or yellowish white powder. When a water-soluble ketone such as acetone is used as the solvent, water is added after the reaction is completed to hydrolyze the unreacted acylating agent, and then water is added to dissolve the precipitated hydrochloride to obtain a homogeneous solution. To do. Thereafter, since the product gradually precipitates from the homogeneous solution, white or yellowish white powder can be obtained by filtering the precipitated crystals. The obtained crystals can be further recrystallized from, for example, methylene chloride / methanol to obtain white or white yellow crystals.

<Route B>
The route A for obtaining the 4- (acyloxy) -1-naphthyl (meth) acrylate compound has been described above. Next, the route B will be described. In Route B, the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention (meth) acrylates the 4- (acyloxy) -1-naphthol compound represented by the following general formula (3). You can get more than that. The 4- (acyloxy) -1-naphthol compound can be obtained by monoacylating a 1,4-naphthalenediol compound.

In the general formula (3), Z represents an alkyl group or an aryl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryloxy group, It represents either an alkylthio group or an arylthio group.

In general formula (3), examples of the alkyl group represented by Z include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a cyclohexyl group, and a benzyl group. Examples of the aryl group include a phenyl group and a naphthyl group. These groups may have a substituent.

In the general formula (3), examples of the alkyl group represented by X and Y include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and the halogen atom includes a fluorine atom, a chlorine atom, Examples thereof include bromine and iodine atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the alkylthio group include a methylthio group and an ethylthio group, and examples of the arylthio group include a phenylthio group and a naphthylthio group.

Examples of the 4- (acyloxy) -1-naphthol compound represented by the general formula (3) include the following. 4-acetyloxy-1-naphthol, 4-propanoyloxy-1-naphthol, 4-n-butanoyloxy-1-naphthol, 4-i-butanoyloxy-1-naphthol, 4-benzoyloxy-1- Examples include naphthol, 4- (1-naphthylcarbonyloxy) -1-naphthol, 4- (2-naphthylcarbonyloxy) -1-naphthol, and the like.

Further, 2-chloro-4-acetyloxy-1-naphthol, 2-chloro-4-propanoyloxy 1-naphthol, 2-chloro-4-n-butanoyloxy-1 having a halogen atom substituted on the naphthalene ring -Naphthol, 2-chloro-4-i-butanoyloxy-1-naphthol, 2-chloro-4-benzoyloxy-1-naphthol, 2-chloro-4- (1-naphthylcarbonyloxy) -1-naphthol, 2-chloro-4- (2-naphthylcarbonyloxy) -1-naphthol.

Still further, 2-methoxy-4-acetyloxy-1-naphthol, 2-methoxy-4-propanoyloxy 1-naphthol, 2-methoxy-4-n-butanoyloxy- in which an alkoxy group is substituted on the naphthalene ring 1-naphthol, 2-methoxy-4-i-butanoyloxy-1-naphthol, 2-methoxy-4-benzoyloxy-1-naphthol, 2-methoxy-4- (1-naphthylcarbonyloxy) -1-naphthol 2-methoxy-4- (2-naphthylcarbonyloxy) -1-naphthol.

Furthermore, 2-phenoxy-4-acetyloxy-1-naphthol, 2-phenoxy-4-propanoyloxy 1-naphthol, 2-phenoxy-4-n-butanoyloxy substituted with an aryloxy group on the naphthalene ring -1-naphthol, 2-phenoxy-4-i-butanoyloxy-1-naphthol, 2-phenoxy-4-benzoyloxy-1-naphthol, 2-phenoxy-4- (1-naphthylcarbonyloxy) -1- Examples thereof include naphthol and 2-phenoxy-4- (2-naphthylcarbonyloxy) -1-naphthol.

Furthermore, 2-methylthio-4-acetyloxy-1-naphthol, 2-methylthio-4-propanoyloxy 1-naphthol, 2-methylthio-4-n-butanoyloxy-, wherein the naphthalene ring is substituted with an alkylthio group 1-naphthol, 2-methylthio-4-i-butanoyloxy-1-naphthol, 2-methylthio-4-benzoyloxy-1-naphthol, 2-methylthio-4- (1-naphthylcarbonyloxy) -1-naphthol 2-methylthio-4- (2-naphthylcarbonyloxy) -1-naphthol and the like.

Still further, 2-phenylthio-4-acetyloxy-1-naphthol, 2-phenylthio-4-propanoyloxy 1-naphthol, 2-phenylthio-4-n-butanoyloxy- with an arylthio group substituted on the naphthalene ring 1-naphthol, 2-phenylthio-4-i-butanoyloxy-1-naphthol, 2-phenylthio-4-benzoyloxy-1-naphthol, 2-phenylthio-4- (1-naphthylcarbonyloxy) -1-naphthol 2-phenylthio-4- (2-naphthylcarbonyloxy) -1-naphthol and the like.

In Route B, as shown in the following reaction formula, the third reaction in which 1,4-naphthalenediol compound is monoacylated to give 4- (acyloxy) -1-naphthol compound, and the obtained 4- (acyloxy)- The 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention can be synthesized from the fourth reaction of (meth) acrylating the 1-naphthol compound.

In the third reaction, the 1,4-naphthalenediol compound is monoacylated to give the corresponding 4- (acyloxy) -1-naphthol compound.

As the 1,4-naphthalenediol compound used in the third reaction, the same compound as that used in the first reaction is used.

The method for producing a 4- (acyloxy) -1-naphthol compound in the third reaction comprises reacting a 1,4-naphthalenediol compound with a carboxylic acid halide in the presence of an inorganic base. Examples of the acylating agent used include carboxylic acid halides such as acetyl chloride, acetyl bromide, propanoyl chloride, butanoyl chloride, benzoyl chloride, benzoyl bromide, 1-naphthoyl chloride, and 2-naphthoyl chloride.

The ratio of 1,4-naphthalenediol compound to carboxylic acid halide is the molar ratio of carboxylic acid halide to 1,4-naphthalenediol compound, usually 0.5 or more, particularly 0.8 or more, and usually less than 2. Especially, it is preferable to set it as the range of 1.5 or less. If the ratio of the carboxylic acid halide is too low, the amount of unreacted 1,4-naphthalenediol compound increases, and treatment such as raw material recovery may be required. On the other hand, when the ratio of the carboxylic acid halide is too high, the amount of by-products of the diester in which both hydroxyl groups of the 1,4-naphthalenediol compound are acylated tends to increase.

Examples of the inorganic base used include sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ) and the like. Of these, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable.

The use ratio of the inorganic base is an equivalent ratio of the inorganic base to the 1,4-naphthalenediol compound, usually 1.0 equivalent or more, especially 1.2 equivalents or more, and usually 3.0 equivalents or less, especially 2.0 equivalents. The following range is preferable. If the ratio of the inorganic base is too low, the pH of the aqueous layer becomes acidic during the dropping of the acid halide, and the selectivity may be significantly reduced. On the other hand, if the ratio of the inorganic base is too high, decomposition of the acid halide may increase.

The reaction between the 1,4-naphthalenediol compound and the carboxylic acid halide is usually performed in the presence of a reaction solvent. The type of the reaction solvent is not particularly limited, but the reaction is preferably performed in a two-phase system composed of an aqueous phase and an organic phase.

When the reaction is performed in a two-phase system composed of an aqueous phase and an organic phase, usually, water and one or more organic solvents that form the organic phase are used in combination as a reaction solvent. The type of the organic solvent that forms the organic phase is not particularly limited, but it is preferable to use an organic solvent that exhibits relatively low polarity and is not miscible with water. Examples of such an organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as heptane, cyclohexane and decalin. Any of these may be used alone, or two or more of these may be used in combination in any combination and ratio. Of these, toluene, xylene and heptane are preferable, and it is particularly preferable to use toluene alone or mixed with heptane.

The ratio of the aqueous phase to the organic phase is not particularly limited, but it is preferable that the volume ratio of the aqueous phase to the total amount of the aqueous phase and the organic phase is usually in the range of 50% to 95%. If the proportion of the aqueous phase is too small or too large, the selectivity of the 4- (acyloxy) -1-naphthol compound tends to decrease. The concentration of the 1,4-naphthalenediol compound relative to the total amount of the aqueous phase and the organic phase is usually 0.005 g / ml or more, especially 0.03 g / ml or more, and usually 0.5 g / ml or less, especially 0.3 g. / Ml or less is preferable. If the concentration of the 1,4-naphthalenediol compound is too low, production efficiency may be reduced. On the other hand, if the concentration of the 1,4-naphthalenediol compound is too high, the selectivity may decrease. Further, it may be difficult to stir the slurry solution with the precipitated solid.

From the viewpoint of controlling the reaction temperature and improving the selectivity, a method of dropping carboxylic acid is preferred. In particular, when the reaction is carried out in a two-phase system consisting of an aqueous phase and an organic phase, the 1,4-naphthalenediol compound is dissolved in a two-phase solvent of the aqueous phase and the organic phase, and a method such as stirring in a container is used. It is preferable that (meth) acrylic acid halide is dropped and reacted while mixing.

The reaction is preferably carried out while cooling the reaction system. Specifically, it is preferable that the temperature of the reaction system is usually 10 ° C. or lower, particularly 5 ° C. or lower, and a temperature at which the aqueous layer does not solidify. If the temperature during the reaction is too high, the selectivity tends to decrease, and hydrolysis of the 4- (acyloxy) -1-naphthol compound, which is a reaction product, may occur.

The reaction time is preferably in the range of usually 30 minutes or more, particularly 60 minutes or more, and usually 5 hours or less, especially 2 hours or less. It is preferable to quench (stop) the reaction as soon as possible after the above reaction time has elapsed.

The reaction is quenched by, for example, adding an acid such as dilute hydrochloric acid (about 1 to 3 N) or dilute sulfuric acid (about 1 to 3 N) to the reaction system (aqueous phase) to make it acidic. After completion of the reaction, post-treatment such as rough purification and recrystallization purification may be performed as necessary.

The crude purification of the reaction product can be performed, for example, by the following procedure. For example, an extraction solvent such as ethyl acetate is added to the reaction system and mixed to perform two-layer separation. The organic phase is washed with water, a drying agent such as magnesium sulfate (MgSO ₄ ) is added and dried, and then the solvent is distilled off to obtain a crude product. The recrystallized purification of the crude purified product is performed, for example, by adding the crude purified product to a recrystallization solvent and dissolving it by heating, then allowing to cool and recrystallizing. As the solvent for recrystallization, for example, toluene, a mixed solvent of toluene and ethyl acetate, a mixed solvent of toluene and ethanol, or the like can be used.

Next, in the fourth reaction, the 4- (acyloxy) -1-naphthol compound is (meth) acrylated in the presence or absence of a base, and the corresponding 4- (acyloxy) -1-naphthyl (meta) ) An acrylate compound is obtained. As the (meth) acrylating agent used, acrylic acid halide and methacrylic acid halide are used. Specific examples of the compound include acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride, and methacrylic acid bromide.

The addition amount of the (meth) acrylating agent with respect to the 4- (acyloxy) -1-naphthol compound is preferably 1 to 2 mol times, more preferably 1.1 to 1.3 mol times. If it is lower than 1 mol, unreacted 4- (acyloxy) -1-naphthol compound remains, and if it exceeds 2 mol, a large amount of (meth) acrylating agent remains in the reaction product. Are difficult to crystallize, both of which are not preferred.

Examples of the base used in the fourth reaction include trimethylamine, triethylamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline, piperidine and the like. The amount of the base used is usually from 1 to 3 moles to the 4- (acyloxy) -1-naphthol compound as a raw material.

The fourth reaction is generally performed in a solvent. 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 and dimethylformamide, and ether solvents such as tetrahydrofuran and 1,4-dioxane are preferably used. In some cases, an alkanoylating agent or an arylcarbonylating agent can be used as a solvent. The concentration of the 4- (acyloxy) -1-naphthol compound in the solvent is usually preferably 0.2 molar or higher.

When the solvent is an aromatic solvent, the 4- (acyloxy) -1-naphthol compound, which is the raw material for the fourth reaction, may have a low solubility in the solvent, but may become a slurry state. Generally it is solubilized.

The reaction temperature is 0 ° C to 80 ° C, preferably 0 ° C to 20 ° C. If the reaction temperature is too low, the reaction takes time, and if it exceeds 80 ° C., the impurity concentration increases, which is not preferable in either case.

The reaction time is about 15 minutes to 3 hours. After completion of the reaction, water or methanol is added to hydrolyze the unreacted (meth) acrylating agent, and then water is added to the filtrate to remove the precipitated hydrochloride by filtration and crystallize the product. The precipitated crystals are filtered to obtain a white or yellowish white powder. When a water-soluble ketone such as acetone is used as the solvent, water is added after the reaction is completed to hydrolyze the unreacted (meth) acrylating agent, and then water is added to dissolve the precipitated hydrochloride. Make a homogeneous solution. Thereafter, since the product gradually precipitates from the homogeneous solution, white or yellowish white powder can be obtained by filtering the precipitated crystals. The obtained crystals can be further recrystallized from, for example, methylene chloride / methanol to obtain white or white yellow crystals.

The obtained compound was identified using a ¹ H-NMR spectrum and an IR spectrum and confirmed to be a corresponding 4- (acyloxy) -1-naphthyl (meth) acrylate compound.

[Polymerizable composition]
The 4- (acyloxy) -1-naphthyl (meth) acrylate compound thus obtained can be converted into a polymer by radical polymerization. In order to promote radical polymerization of the compound of the present invention, it is preferable to add a radical polymerization initiator. And it can be set as a radically polymerizable composition by mixing a 4- (acyloxy) -1-naphthyl (meth) acrylate compound and a radical polymerization initiator.

Such radical polymerization initiators include photo radical polymerization initiators and thermal radical polymerization initiators. Photoradical polymerization using active energy rays such as ultraviolet rays and visible rays is fast and can provide a polymer having high transparency and efficiency. Therefore, particularly when the compound of the present invention is used for optical applications, photoradical polymerization is used. Is preferred.

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, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine Examples thereof include oxide, 2-isopropylthioxanthone, and 2-t-butylanthraquinone. Examples of actual industrial products include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 907, Irgacure 369, Darocur TPO and Irgacure 819 manufactured by Ciba Specialty Chemicals (Irgacure and Darocur are registered trademarks of Ciba Specialty Chemicals).

In the photo-radical polymerizable composition of the present invention, the above naphthalene compound, that is, 4- (acyloxy) -1-naphthyl (meth) acrylate compound can be used alone to form a polymer. ) -1-Naphtyl (meth) acrylate compounds other than normal radical polymerizable monomers may be added to copolymerize as a copolymerizable photoradical polymerizable composition.

Examples of the radical polymerizable monomer to be copolymerized include tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, epoxy acrylate, urethane acrylate polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, silicone resin acrylate, Further, styrene acrylate, 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-to Acrylate, o-tolyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, biphenyl-4-yl-acrylate, biphenyl-4-yl-methacrylate, 4-phenoxyphenyl acrylate, 4-phenoxyphenyl methacrylate, 2- Examples include phenoxyphenyl acrylate, 2-phenoxyphenyl methacrylate, 2- (biphenyl-2-yloxy) ethyl acrylate, 2- (biphenyl-2-yloxy) ethyl methacrylate, and the like.

Radicals other than the 4- (acyloxy) -1-naphthyl (meth) acrylate compound by copolymerizing these radical polymerizable monomers and the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention. Compared with the polymerization using a polymerizable monomer alone, it is possible to improve the refractive index of the resulting polymer as well as the solvent resistance, hardness, oxygen impermeability, and the like. In addition, the composition which added the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of this invention to the said radically polymerizable compound is easy to handle with comparatively low viscosity, 4- (acyloxy) -1 of this invention -It can be said that a naphthyl (meth) acrylate compound is a practically excellent compound.

Also, biphenyl acrylates such as 2- (biphenyl-4-yloxy) ethyl acrylate and 2- (biphenyl-4-yloxy) ethyl methacrylate, 9,9-bis [4- (3-acryloyloxy-2-hydroxy) propoxy Phenyl] fluorene, 9,9-bis (4-methacryloyloxyphenyl) fluorene, 9,9-bis (4-acryloyloxyphenyl) fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis {4- [2- (3-acryloyloxy-2-hydroxy-propoxy) -ethoxy] phenyl} fluorene, 9,9-bis [4- (3-acryloyloxy-2-hydroxy) Roxy) propoxy-3-methylphenyl] fluorene, copolymerized with radically polymerizable monomers having a high refractive index such as fluorene acrylate such as acrylic acid adduct of glycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene You can also

These radically polymerizable monomers are generally high-viscosity compounds in the melt state, but the polymerizable composition obtained by adding the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention. Since the viscosity of the melted state of the product can be lowered, the coating film operation becomes easy. And since the refractive index of the polymer obtained is not reduced, it can be said that the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention is a practically effective compound.

The addition ratio of 4- (acyloxy) -1-naphthyl (meth) acrylate compound to these radical polymerizable monomers depends on the solubility of 4- (acyloxy) -1-naphthyl (meth) acrylate compound. It is preferable to add 10% by weight or more of the total composition. In order to obtain the effect of increasing the refractive index, 50% by weight or more is more preferable.

The addition concentration of the photo radical polymerization initiator is 0.1 to 5% by weight based on the total weight of the 4- (acyloxy) -1-naphthyl (meth) acrylate compound and the radical polymerizable compound used in combination as necessary. It is selected from the range, preferably 0.5 to 2% by weight. If it is less than 0.1% by weight, the polymerization rate is slow, and if it is more than 5% by weight, the physical properties of the polymer are deteriorated.

Moreover, 4- (acyloxy) -1-naphthyl (meth) acrylate compound can also be made into a polymer using a thermal radical polymerization initiator.

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-3,5,6-trimethylhexanoate, t-butyl. Peroxyesters such as peroxyisopropyl carbonates, peroxyketals such as 1,1-bis (t-hexylperoxy) -3,3,6-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).

The polymerizable composition of the present invention includes a diluent, a colorant, an organic or inorganic filler, a leveling agent, a surfactant, an antifoaming agent, a thickener, a flame retardant, and the like within a range not impairing the effects of the present invention. You may mix | blend various resin additives, such as antioxidant, a stabilizer, a lubricant, and a plasticizer.

[Polymerization method]
Polymerization of the radical photopolymerizable composition can be carried out in the form of a film or can be cured in the form of 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- (acyloxy) -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 to be 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. In particular, the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention can be polymerized using a high-pressure mercury lamp (wavelength 366 nm) which is a light source most widely used as a UV curing device. It is an industrially very useful compound.

Determination of photoradical polymerization was performed based on a tack-free test (finger 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- (acyloxy) -1-naphthyl (meth) acrylate compound thus obtained exhibits a high refractive index and, from its structure, absorbs ultraviolet rays. It is industrially useful and can be expected to have 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 on a weight basis.

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) Refractive index: Abbe refractometer: manufactured by Elmer, model ER-7MW-H
(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
(5) Mass spectrum: manufactured by Shimadzu Corporation, mass spectrometer, model GCMS-QP5000
(6) Gas chromatograph: GC-1700 manufactured by Shimadzu Corporation, column: CBP1-W25-500

(Example 1) <Synthesis of 4-hydroxy-1-naphthyl acrylate>
A reaction vessel was charged with 30.0 ml of water, 4.0 ml of toluene, 800 mg (20.0 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of 1,4-naphthalenediol. Next, while cooling and stirring under a nitrogen gas atmosphere, 1.4 g (15.0 mmol) of commercially available acrylic acid chloride was added dropwise to the mixture in the reaction vessel over 60 minutes using a syringe. During this time, the internal temperature was kept below 5 ° C. At this time, the seed crystal of 4-hydroxy-1-naphthyl acrylate was added to the reaction solution in two steps, before dropping of acrylic acid chloride and when 30% of acrylic acid chloride was dropped. When about 40% of acid chloride was dropped, a considerable amount of precipitate was observed. After completion of the dropping, stirring was continued for 15 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped.

Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. When the obtained organic phase was analyzed by gas chromatography (GC), the composition was as follows: 1,4-naphthalenediol, which is a remaining raw material, 5.5%, 4-hydroxy-1-naphthyl acrylate, 70.2%, , 4-dimethacryloyloxynaphthalene was 23.6%. The selectivity for 4-hydroxy-1-naphthyl acrylate determined from these values was 74.3%. To this crude product, 6.0 ml of toluene was added and dissolved under heating and stirring. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 1.2 g of off-white crystals. When this crystal was analyzed by gas chromatography, it was confirmed to be 4-hydroxy-1-naphthyl acrylate having a purity of 97.0%.

The physicochemical properties of this product are shown below.
(1) Melting point: 108.5-109.4 ° C
(2) Refractive index n _D = 1.628
(3) IR (KBr, cm ⁻¹ ): 1712, 1624, 1580, 1475, 1400, 1380, 1352, 1292, 1260, 1175, 1155, 1054, 963, 810, 793.759
(4) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 5.98 (bs, 1H), 6.10 (bd, 1H), 6.47 (d, 1H), 6.48 (dd, 1H) ), 6.73 (bd, 1H), 6.97 (d, 1H), 7.40 (bdd, 1H), 7.49 (bdd, 1H), 7.74 (bd, 1H), 8.05 (Bd, 1H).
(5) Mass spectrum (EI): 214 (M +)

(Example 2) <Synthesis of 4-hydroxy-1-naphthyl methacrylate>
A reaction vessel was charged with 75.0 ml of water, 15.0 ml of toluene, 1.2 g of sodium hydroxide, and 5.0 g of 1,4-naphthalenediol. Next, while cooling and stirring under a nitrogen gas atmosphere, 3.5 g (33.0 mmol) of methacrylic acid chloride obtained by re-distilling the commercial product was dropped into the mixture in the reaction vessel over 85 minutes using a dropping funnel. did. During this time, the internal temperature of the reaction vessel was kept at 5 ° C. or lower. From the middle of dropping, a large amount of crystals was observed. After completion of the dropping, stirring was continued for another 30 minutes while keeping the internal temperature of the reaction vessel at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped. Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water and dried by adding magnesium sulfate. Further, the solvent was distilled off with a rotary evaporator to obtain 7.4 g of a black solid crude product.

When this crude product was analyzed by GC, the compositions were 4-hydroxy-1-naphthyl methacrylate 87.8% and 1,4-dimethacryloyloxynaphthalene 6.7%.

To this crude product was added 23.0 ml of toluene, and the mixture was heated on an oil bath at 90 to 100 ° C. with stirring and dissolved. Next, the mixture was allowed to cool, and the precipitated crystals were collected by filtration and dried to obtain 6.0 g of off-white crystals. When this crystal was analyzed by GC, it was confirmed to be 4-hydroxy-1-naphthyl methacrylate having a purity of 93.4%.

The obtained crystals were recrystallized using toluene in the same procedure, and 5.3 g of off-white crystals were obtained. When this crystal was analyzed by GC, it was confirmed to be 4-hydroxy-1-naphthyl methacrylate having a purity of 97.5%. The yield of 4-hydroxy-1-naphthyl methacrylate throughout this example (yield from the raw material 1,4-naphthalenediol) was 74.0%.

The physicochemical properties of this product are shown below.
(1) Melting point: 151.0-151.7 ° C
(2) Refractive index n _D = 1.615
(3) IR (KBr, cm ⁻¹ ): 1705, 1636, 1588, 1392, 13559, 1330, 1268, 1210, 1172, 1140, 1062, 960, 810, 763
(4) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 2.16 (bs, 3H), 5.86 (bs, 1H), 5.95 (bs, 1H), 6.46 (d, 1H ), 6.53 (bs, 1H), 6.95 (d, 1H), 7.43 (bdd, 1H), 7.49 (bdd, 1H), 7.74 (bd, 1H), 8.04 (Bd, 1H).
(5) Mass spectrum (EI): 228 (M +)

(Example 3) <Synthesis of 4-acetyloxy-1-naphthyl acrylate>
In a 300 ml three-necked eggplant flask equipped with a thermometer and a stirrer, 8.56 g (40 mmol) of 4-hydroxy-1-naphthyl acrylate obtained in the same manner as in Example 1 was dissolved in 60 g of acetic anhydride and pyridine while being cooled with ice water. 3.16 g (40 mmol) was added. After maintaining the reaction temperature at 5 ° C. and stirring for 2 hours, the reaction solution was poured into 250 ml of ice water to gradually precipitate crystals. The precipitated crystals were separated and washed to obtain 8.06 g (32.0 mmol) of white crystals of 4-acetyloxy-1-naphthyl acrylate. The yield based on the raw material 4-hydroxy-1-naphthyl acrylate was 80 mol%.

(1) Melting point: 106-107 ° C
(2) Refractive index n _D = 1.591
(3) IR (KBr, cm ⁻¹ ): 1760, 1740, 1416, 1396, 1372, 1260, 1208, 1170, 1155, 1262, 1062, 802, 766.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 2.47 (s, 3H), 6.12 (d, J = 8 Hz, 1H), 6.47 (dd, J ₁ = 17 Hz, J ₂ = 8 Hz, 1H), 6.73 (d, J = 17 Hz, 1H), 7.24-7.30 (m, 2H), 7.50-7.60 (m, 2H), 7.84- 7.94 (m, 2H).

(Example 4) <Synthesis of 4-propanoyloxy-1-naphthyl acrylate>
In a 300 ml three-necked eggplant flask equipped with a thermometer and a stirrer, 8.56 g (40 mmol) of 4-hydroxy-1-naphthyl acrylate obtained in the same manner as in Synthesis Example 1 was dissolved in 40 g of propionic anhydride and cooled with ice water. 7.9 g (100 mmol) of pyridine was added. After maintaining the reaction temperature at 5 ° C. and stirring for 2 hours, the reaction solution is poured into 400 ml of ice water, the resulting oily substance is extracted with methylene chloride, washed with water, added with n-hexane and concentrated to 4-propanoyl. 5.0 g (18.5 mmol) of white crystals of oxy-1-naphthyl acrylate was obtained. The yield based on 4-hydroxy-1-naphthyl acrylate as a raw material was 46 mol%.

(1) Melting point: 44-45 ° C
(2) Refractive index n _D = 1.577
(3) IR (KBr, cm ⁻¹ ): 1760, 1750, 1604, 1462, 1390, 1242, 1213, 1132, 1080, 1060, 980, 892, 800, 760.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.37 (t, J = 7 Hz, 3H), 2.76 (q, J = 7 Hz, 2H), 6.13 (d, J = 8 Hz, 1 H), 6.49 (dd, J ₁ = 17 Hz, J ₂ = 8 Hz, 1 H), 6.75 (d, J = 17 Hz, 1 H), 7.23-7.33 (m, 2 H), 7.49-7.60 (m, 2H), 7.82-7.94 (m, 2H).

(Example 5) <Synthesis of 4-benzoyloxy-1-naphthyl acrylate>
In a 300 ml three-necked flask equipped with a thermometer and a stirrer, 8.56 g (40 mmol) of 4-hydroxy-1-naphthyl acrylate was dissolved in 80 ml of acetone, and 5.6 g (40 mmol) of benzoyl chloride was added while cooling with ice water. . Next, 4.04 g (40 mmol) of triethylamine in 10 ml of acetone was prepared, and the solution was slowly added while cooling the three-necked flask with ice water. Since a white precipitate immediately formed, the mixture was further stirred for 1 hour. Then, it post-processed by the usual method and obtained 9.2g (28.9 mmol) of the white crystal | crystallization of 4-benzoyloxy- 1-naphthyl acrylate. The yield based on 4-hydroxy-1-naphthyl acrylate as a raw material was 72 mol%.

(1) Melting point: 65-66 ° C
(2) Refractive index: n _D = 1.621
(3) IR (KBr, cm ⁻¹ ): 1750, 1738, 1600, 1464, 1450, 1390, 1260, 1220, 1140, 1082, 892, 800, 760, 704.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 6.13 (d, J = 8 Hz, 1H), 6.51 (dd, J ₁ = 17 Hz, J ₂ = 8 Hz, 1H), 6. 76 (d, J = 17 Hz, 1H), 7.33-7.43 (m, 2H), 7.50-7.64 (m, 4H), 7.64-7.73 (m, 1H), 7.90-8.00 (m, 1H), 8.34 (d, J = 6 Hz, 2H).

(Example 6) <Synthesis of 4-acetyloxy-1-naphthol>
A reaction vessel was charged with 30.0 ml of water, 10.0 ml of toluene, 800 mg (20.0 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of 1,4-naphthalenediol. Next, 1.2 g (15.0 mmol) of a commercially available acetyl chloride was added dropwise to the mixture in the reaction vessel over 40 minutes using a syringe while cooling and stirring in a nitrogen gas atmosphere. During this time, the internal temperature was kept below 5 ° C. After completion of the dropping, stirring was continued for 15 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped. Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water, and the obtained organic phase was analyzed by high performance liquid chromatography (LC). As a result, the composition was 17.6% of 1,4-naphthalenediol, 4-acetyloxy- 1-naphthol 66.9% and 1,4-diacetyloxynaphthalene 20.9%. The crude product was recrystallized from toluene to obtain off-white crystals, 1.37 g. When analyzed by high performance liquid chromatography (LC), the content of 4-acetyloxy-1-naphthol was 86.6%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 134.0-135.5 ° C
(2) Refractive index: n _D = 1.622
(3) IR (KBr, cm ⁻¹ ): 1745, 1588, 1480, 1393, 1375, 1358, 1230, 1068, 1010, 905, 828, 776, 760.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 2.45 (s, 3H), 6.20 (s, 1H), 6.45 (d, 1H), 6.92 (d, 1H ), 7.40-7.56 (m, 2H), 7.71-7.78 (m, 1H), 8.02-8.11 (m, 1H).

(Example 7) <Synthesis of 4-propanoyloxy-1-naphthol>
A reaction vessel was charged with 30.0 ml of water, 10.0 ml of toluene, 650 mg (16.2 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of 1,4-naphthalenediol. Next, 1.25 g (13.1 mmol) of commercially available propionyl chloride was added dropwise to the mixture in the reaction vessel over 60 minutes using a syringe while cooling and stirring under a nitrogen gas atmosphere. During this time, the internal temperature was kept below 5 ° C. After completion of the dropping, stirring was continued for 15 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped. Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water, and the obtained organic phase was analyzed by high performance liquid chromatography (LC). As a result, the composition was 4-propanoyloxy-1-naphthol 69.0%, naphthalene-1,4- Dipropanoate was 19.6%. The crude product was recrystallized from toluene to obtain 1.22 g of pale yellow crystals. When analyzed by high performance liquid chromatography (LC), the content of 4-acetyloxy-1-naphthol was 97.0%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 115.0-116.0 ° C
(2) Refractive index: n _D = 1.611
(3) IR (KBr, cm ⁻¹ ): 1734, 1602, 1588, 1390, 1357, 1268, 1175, 1158, 1010, 1084, 1062, 816, 764, 755.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.38 (t, 3H), 2.78 (q, 2H), 6.50 (d, 1H), 6.94 (d, 1H) ), 7.39-7.53 (m, 2H), 7.70-7.77 (m, 1H), 8.02-8.10 (m, 1H).

(Example 8) <Synthesis of 4- (n-butanoyloxy) -1-naphthol>
A reaction vessel was charged with 30.0 ml of water, 10.0 ml of toluene, 800 mg (20.0 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of 1,4-naphthalenediol. Next, 1.6 g (14.5 mmol) of a commercially available butyroyl chloride was dropped into the mixture in the reaction vessel over 40 minutes while cooling and stirring under a nitrogen gas atmosphere. During this time, the internal temperature was kept below 5 ° C. After completion of the dropwise addition, stirring was continued for another 30 minutes while maintaining the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped. Subsequently, ethyl acetate was added as an extraction solvent to separate into two layers, and the reaction product was recovered in the organic phase. The organic phase was washed with water, and the obtained organic phase was analyzed by high performance liquid chromatography (LC). As a result, the composition was 4-butanoyloxy-1-naphthol 68.6%, naphthalene-1,4- Dibutyrate was 18.0%. The crude product was recrystallized from toluene to obtain 1.07 g of light brown crystals. When analyzed by high performance liquid chromatography (LC), the content of 4-butanoyloxy-1-naphthol was 76.2%. Chloroform was added to this crystal and extracted. After removing the insoluble material by filtration, chloroform was distilled off to obtain pale brown crystals, 0.80 g. The purity of 4-butanoyloxy-1-naphthol was 93.0%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 157.2-158.5 ° C
(2) Refractive index: n _D = 1.584
(3) IR (KBr, cm ⁻¹ ): 1740, 1586, 1477, 1390, 1350, 1262, 1168, 1148, 824, 768, 752.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.12 (t, 3H), 1.83-1.97 (m, 2H), 2.73 (t, 2H), 5.92 (Brs, 1H), 6.46 (d, 1H), 6.91 (d, 1H), 7.40-7.53 (m, 2H), 7.72 (d, 1H), 8.04 ( d, 1H).

Example 9 <Synthesis of 4- (i-butanoyloxy) -1-naphthol>
A reaction vessel was charged with 20.0 ml of water, 20.0 ml of toluene, 580 mg (14.4 mmol) of sodium hydroxide, and 2.0 g (12.5 mmol) of 1,4-naphthalenediol. Next, while cooling and stirring under a nitrogen gas atmosphere, 1.4 g (13.1 mmol) of a commercial product isobutyryl chloride was added dropwise to the mixture in the reaction vessel over 55 minutes using a syringe. During this time, the internal temperature was kept below 5 ° C. After completion of the dropwise addition, stirring was continued for 20 minutes while keeping the internal temperature at 5 ° C. or lower. Thereafter, dilute hydrochloric acid was added to make the pH of the reaction system (aqueous phase) acidic, and the reaction was stopped. When the organic phase obtained by the usual post-treatment was analyzed by high performance liquid chromatography (LC), the composition was 7.6% of 1,4-naphthalenediol, 4- (i-butanoyloxy), which is the remaining raw material. -1-Naphthol 74.1% and naphthalene-1,4-diisobutyrate 14.0%. The crude product was recrystallized with a toluene-normal hexane mixed solvent to obtain 1.27 g of an off-white crystal. When analyzed by high performance liquid chromatography (LC), the amount of 4- (i-butanoyloxy) -1-naphthol was 93.7%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 159.5-162.4 ° C
(2) IR (KBr, cm ⁻¹ ): 1736, 1644, 1600, 1482, 1393, 1342, 1268, 1154, 1060, 824, 763, 743.
(3) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.46 (d, 6H), 2.94-3.08 (m, 1H), 5.91 (brs, 1H), 6.48 (T, 1H), 6.87-6.96 (m, 1H), 7.39-7.56 (m, 2H), 7.70-7.78 (m, 1H), 8.01-8 .08 (m, 1H).

Example 10 <Synthesis of 4- (i-pentanoyloxy) -1-naphthol>
The same procedure as in Example 9 was repeated except that a commercially available isovaleryl chloride was used in place of isobutyryl chloride as the acid chloride to obtain 2.4 g of a blackish brown crude product. Analysis by high performance liquid chromatography (LC) revealed that the composition was 1,4-naphthalenediol, which is a remaining raw material, 6.0%, 4- (i-pentanoyloxy) -1-naphthol, 78.1%, naphthalene. It was 11.5% of -1,4-diisopentanoate. When hexane was added to the crude product, brown crystals, 1.5 g, were obtained. When analyzed by high performance liquid chromatography (LC), the content of 4- (i-pentanoyloxy) -1-naphthol was 90.8%. This crystal was further recrystallized with a toluene / hexane mixed solvent to obtain 4- (i-pentanoyloxy) -1-naphthol having a purity of 97.0%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 56.3-57.8 ° C
(3) Refractive index: n _D = 1.574
(3) IR (KBr, cm ⁻¹ ): 1732, 1588, 1480, 1390, 1357, 1300, 1265, 1084, 836, 775, 757.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.13 (d, 6H), 2.30-2.44 (m, 1H), 2.62 (d, 2H), 6.00 (Brs, 1H), 6.52 (d, 1H), 6.94 (d, 1H), 7.40-7.56 (m, 2H), 7.77 (d, 1H), 8.07 ( d, 1H).

Example 11 <Synthesis of 4- (n-pentanoyloxy) -1-naphthol>
The same procedure as in Example 9 was repeated except that a commercially available valeryl chloride was used in place of isobutyryl chloride as the acid chloride to obtain 2.7 g of a blackish brown crude product. As a result of analysis by high performance liquid chromatography (LC), the composition was 2.9% of 1,4-naphthalenediol as the remaining raw material, 83.6% of 4- (n-pentanoyloxy) -1-naphthol, and naphthalene. It was 9.2% of -1,4-dipentanoate. The crude product was recrystallized with a mixed solvent of toluene-normal hexane to obtain 1.9 g of off-white crystals. When analyzed by high performance liquid chromatography (LC), the content of 4- (n-pentanoyloxy) -1-naphthol was 92.6%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 92.1-93.3 ° C
(2) Refractive index: n _D = 1.596
(3) IR (KBr, cm ⁻¹ ): 1743, 1643, 1600, 1594, 1387, 1355, 1262, 1170, 1157, 1064, 825, 764, 744.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.01 (t, 3H), 1.42-1.58 (m, 2H), 1.76-1.92 (m, 2H) 2.67-2.80 (m, 2H), 6.08 (s, 1H), 6.43 (d, 1H), 6.91 (d, 1H), 7.37-7.53 (m , 2H), 7.71 (d, 1H), 8.04 (d, 1H),

(Example 12) <Synthesis of 4-benzoyloxy-1-naphthol>
The same procedure as in Example 9 was repeated except that a commercially available benzoyl chloride was used in place of isobutyryl chloride as the acid chloride to obtain 3.1 g of a purple crude product. When analyzed by high performance liquid chromatography (LC), the composition was as follows: 1,4-naphthalenediol 0.2%, 4-benzoyloxy-1-naphthol 63.5%, naphthalene-1,4- Dibenzoate was 30.3%. The crude product was recrystallized from toluene to obtain 1.6 g of slightly yellow crystals. When analyzed by high performance liquid chromatography (LC), the content of 4-benzoyloxy-1-naphthol was 94.8%.

The melting point, IR spectrum and ¹ H-NMR spectrum of this compound are shown below. (1) Melting point: 153.6-154.9 ° C.
(2) Refractive index: n _D = 1.669
(3) IR (KBr, cm ⁻¹ ): 1718, 1605, 1590, 1395, 1357, 1264, 1097, 758, 712.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 6.07 (brs, 1H), 6.55 (d, 1H), 7.07 (d, 1H), 7.41-7.62 (M, 4H), 7.63-7.74 (m, 1H), 7.78-7.85 (m, 1H), 8.02-8.13 (m, 1H), 8.27-8 .35 (m, 2H).

(Example 13) <Synthesis of 4-acetyloxy-1-naphthyl methacrylate>
A reaction vessel was charged with 30 ml of acetonitrile, 6.6 g (65.7 mmol) of triethylamine, and 5.0 g (21.9 mmol) of 4-hydroxy-1-naphthyl methacrylate synthesized in the same manner as in Example 2. Next, a solution prepared by dissolving 2.75 g (21.9 mmol) of a commercially available acetyl chloride in 20 ml of acetonitrile was added dropwise to the mixture in the reaction vessel over 40 minutes while cooling and stirring in a nitrogen gas atmosphere. During this time, the internal temperature was kept below 5 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 30 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic layer. The organic layer was washed with saturated aqueous sodium bicarbonate and then with water, and the solvent was distilled off to obtain 4.6 g of a brown liquid crude product. When the mechanical phase was analyzed by high performance liquid chromatography (LC), it was 46.7% of 4-acetyloxy-1-naphthyl methacrylate. The crude product was recrystallized with a toluene-normal hexane mixed solvent to obtain 3.0 g of light brown crystals. When analyzed by high performance liquid chromatography (LC), the purity of 4-acetyloxy-1-naphthyl methacrylate was 97.9%. If desired, white crystals can be obtained by treating the crystals with activated carbon.

The melting point, refractive index, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 103-104 ° C
(2) Refractive index: n _D = 1.584
(3) IR (KBr, cm ⁻¹ ): 1770, 1735, 1640, 1605, 1396, 1378, 1320, 1205, 1128, 955, 900, 770.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 2.13 (s, 3H), 2.46 (s, 3H), 5.85 (s, 1H), 6.49 (s, 1H) ), 7.21-7.31 (m, 2H), 7.48-7.58 (m, 2H), 7.82-7.91 (m, 2H).

(Example 14) <Synthesis of 4- (i-butanoyloxy) -1-naphthyl acrylate>
A reaction vessel was charged with 30 ml of acetonitrile, 5.3 g (52.4 mmol) of triethylamine, and 4.0 g (17.5 mmol) of 4- (i-butanoyloxy) -1-naphthol synthesized in the same manner as in Example 9. It is. Next, a solution prepared by dissolving 2.8 g (31.4 mmol) of a commercial product acryloyl chloride in 10 ml of acetonitrile was added dropwise to the mixture in the reaction vessel over 55 minutes while cooling and stirring in a nitrogen gas atmosphere. During this time, the internal temperature was kept below 5 ° C. After completion of the dropwise addition, the temperature was returned to room temperature and stirring was continued for another 20 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic layer. The organic layer was washed with saturated aqueous sodium bicarbonate and then with water, and the solvent was distilled off to obtain 4.8 g of a reddish brown liquid crude product. When the mechanical phase was analyzed by high performance liquid chromatography (LC), it was 4- (i-butanoyloxy) -1-naphthyl acrylate 87.4%. The crude product was recrystallized with a mixed solvent of toluene-normal hexane to obtain 2.1 g of pale yellow crystals. When analyzed by high performance liquid chromatography (LC), the purity of 4- (i-butanoyloxy) -1-naphthyl acrylate was 89.2%. If desired, white crystals can be obtained by treating the crystals with activated carbon.

The melting point, refractive index, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 55-56 ° C
(2) Refractive index: n _D = 1.5640
(3) IR (KBr, cm ⁻¹ ): 1758, 1750, 1638, 1607, 1470, 1470, 1410, 1392, 1228, 1144, 1130, 988, 756.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.43 (d, 6H), 2.94-3.06 (m, 1H), 6.08 (d, 1H), 6.47 (Dd, 1H), 6.72 (d, 1H), 7.20-7.31 (m, 2H), 7.48-7.56 (m, 2H), 7.81-7.92 (m , 2H).

(Example 15) <Synthesis of 4- (n-pentanoyloxy) -1-naphthyl acrylate>
A reaction vessel was charged with 40 ml of acetonitrile, 5.7 g (56.0 mmol) of triethylamine, and 4.0 g (18.7 mmol) of 4-hydroxy-1-naphthyl acrylate synthesized in the same manner as in Example 1. Next, a solution obtained by dissolving 4.1 g (33.1 mmol) of a commercial product valeryl chloride in 10 ml of acetonitrile was added dropwise to the mixture in the reaction vessel over 52 minutes while cooling and stirring in a nitrogen gas atmosphere. . During this time, the internal temperature was kept below 5 ° C. After completion of the dropwise addition, the temperature was returned to room temperature, and stirring was further continued for 30 minutes. Thereafter, water and ethyl acetate were added, and two layers were separated to obtain an organic layer. The organic layer was washed with saturated aqueous sodium bicarbonate and then with water, and the solvent was distilled off to obtain 5.4 g of a brown liquid crude product. The organic phase was analyzed by high performance liquid chromatography (LC) and found to be 94.6% 4- (n-pentanoyloxy) -1-naphthyl acrylate. 3.7 g of the crude product was distilled under reduced pressure using a Kugel-Rohr distillation apparatus. Under a reduced pressure of 5-6 mmHg, 2.0 g of a pale yellow liquid was distilled at 235-245 ° C. When analyzed by high performance liquid chromatography (LC), the purity of 4- (n-pentanoyloxy) -1-naphthyl acrylate was 96.9%. This crystallized during storage.

The melting point, refractive index, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 27-28 ° C
(2) Refractive index: n _D = 1.560
(3) IR (KBr, cm ⁻¹ ): 1758, 1638, 1606, 1470, 1410, 1395, 1210, 1140, 1105, 990, 898, 760.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.03 (t, 3H), 1.42-1.60 (m, 2H), 1.80-1.92 (m, 2H) 2.92 (t, 2H), 6.10 (d, 1H), 6.47 (dd, 1H), 6.72 (d, 1H), 7.20-7.32 (m, 2H), 7.48-7.58 (m, 2H), 7.82-7.92 (m, 2H).

(Example 16) <Synthesis of 4- (i-pentanoyloxy) -1-naphthyl acrylate>
The same procedure as in Example 15 was carried out except that commercially available isovaleryl chloride was used in place of valeryl chloride as the acid chloride to obtain 4.7 g of a light brown solid as a crude product. When analyzed by high performance liquid chromatography (LC), it was 4- (i-pentanoyloxy) -1-naphthyl acrylate 96.8%. The crude product was dissolved in toluene, treated with activated carbon, and recrystallized with a toluene-normal hexane mixed solvent to obtain 1.5 g of white crystals. When analyzed by high performance liquid chromatography (LC), the purity of 4- (i-pentanoyloxy) -1-naphthyl acrylate was 98.3%.

The melting point, refractive index, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 69-70 ° C
(2) Refractive index: n _D = 1.564
(3) IR (KBr, cm ⁻¹ ): 1760, 1746, 1640, 1608, 1470, 1410, 1397, 1302, 1256, 1222, 1170, 1150, 1060, 995, 915, 773.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.4 (d, 6H), 2.27-2.43 (m, 1H), 2.61 (d, 2H), 6.10 (D, 1H), 6.49 (dd, 1H), 6.72 (d, 1H), 7.22-7.32 (m, 2H), 7.49-7.59 (m, 2H), 7.83-7.93 (m, 2H),

(Example 17) <Synthesis of 4-propanoyloxy-1-naphthyl methacrylate>
A dark brown liquid was obtained as a crude product in the same manner as in Example 13 except that commercially available propanoyl chloride was used instead of acetyl chloride as the acid chloride. When analyzed by high performance liquid chromatography (LC), it was 4-propanoyloxy-1-naphthyl methacrylate 96.8%. Crude 5.0 g was distilled under reduced pressure using a Kugel-Rohr distillation apparatus. Under a reduced pressure of 4 mmHg, 2.4 g of a pale yellow liquid was distilled at 210 to 225 ° C. When analyzed by high performance liquid chromatography (LC), the purity of 4-propanoyloxy-1-naphthyl methacrylate was 97.5%. If desired, it can be recrystallized from toluene.

The melting point, refractive index, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 35-36 ° C
(2) Refractive index: n _D = 1.571
(3) IR (KBr, cm ⁻¹ ): 1760, 1735, 1637, 1596, 1460, 1383, 1312, 1258, 1216, 1114, 883, 800, 752.
(4) ¹ H-NMR (270 MHz, CDCl ₃ ): δ = 1.38 (t, 3H), 2.17 (s, 3H), 2.78 (q, 2H), 5.84 (s, 1H) ), 6.50 (s, 1H), 7.22-7.30 (m, 2H), 7.48-7.59 (m, 2H), 7.82-7.92 (m, 2H).

(Example 18) <Synthesis of 4-benzoyloxy-1-naphthyl methacrylate>
In a 300 ml three-necked flask equipped with a thermometer and a stirrer, 4.56 g (20 mmol) of 4-hydroxy-1-naphthyl methacrylate was dissolved in 40 ml of acetone, and 2.8 g (20 mmol) of benzoyl chloride was added while cooling with ice water. . Next, a solution of 4.04 g (40 mmol) of triethylamine in 10 ml of acetone was prepared, and the solution was slowly added while cooling the three-necked flask with ice water. Since a white precipitate immediately formed, the mixture was further stirred for 1 hour. Then, it post-processed by the usual method and obtained 3.6 g (11 mmol) of the white crystal | crystallization of 4-benzoyloxy-1-naphthyl methacrylate. The yield based on the raw material 4-hydroxy-1-naphthyl methacrylate was 55 mol%.

The melting point, refractive index, IR spectrum and ¹ H-NMR spectrum of this compound are shown below.
(1) Melting point: 70-71 ° C
(2) Refractive index: n _D = 1.616
(3) IR (KBr, cm ⁻¹ ): 2970, 1740, 1720, 1640, 1600, 1452, 1390, 1320, 1256, 1220, 1120, 1082, 1068, 1020, 946, 892, 758, 711.
(4) ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 2.17 (s, 3H), 5.88 (s, 1H), 6.53 (s, 1H), 7.30-7.41 (M, 2H), 7.49-7.62 (m, 4H), 7.70-7.79 (m, 1H), 7.90-8.01 (m, 1H), 8.33 (d , J = 6 Hz, 2H).

(Example 19) <Copolymerization of 4-acetyloxy-1-naphthyl acrylate and trimethylolpropane triacrylate>
For 70 parts of 4-acetyloxy-1-naphthyl acrylate and 30 parts of trimethylolpropane triacrylate synthesized in the same manner as in Example 3, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) was mixed and immersed in an oil bath at 120 ° C. to melt. The melt of the obtained radically polymerizable composition was applied on a polyester film (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) so as to have a thickness of 0.2 mm, and then in a nitrogen atmosphere. In a state kept at 120 ° C., the surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm was 1 mW / cm ² ) for 3 minutes to obtain a radical photopolymer.

The refractive index of the polymer was measured (measuring instrument: Elmer ER-7MW-H) n _D = 1.591. In general, this type of compound is expected to have a higher refractive index than the original monomer when polymerized, but the refractive index of the original polymerizable composition is n _D = 1.555, The value was improved by 0.036, and it was confirmed that polymerization was carried out in this respect as well.

(Example 20) <Copolymerization of 4-benzoyloxy-1-naphthyl acrylate and trimethylolpropane triacrylate>
For 70 parts of 4-benzoyloxy-1-naphthyl acrylate and 30 parts of trimethylolpropane triacrylate synthesized in the same manner as in Example 5, 2-benzyl-2-dimethylamino-1- (4-morpholino was used as an initiator. 0.5 parts of phenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) was mixed and immersed in an oil bath at 85 ° C. to melt. The melt of the obtained radical photopolymerizable composition was applied on a polyester film (Toray Lumirror) so that the film thickness was 0.2 mm, and then kept at 80 ° C. in a nitrogen atmosphere, The surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm was 1 mW / cm ² ) for 3 minutes to obtain a radical photopolymer.

When the refractive index of the polymer was measured (measuring instrument: Elmer ER-7MW-H), n _D = 1.602. The refractive index of the original polymerizable composition is n _D = 1.576, the value of the refractive index is improved by 0.026, and it can be seen that polymerization has occurred.

(Example 21) <Copolymerization of 4-acetyloxy-1-naphthyl methacrylate and trimethylolpropane triacrylate>
For 46 parts of 4-acetyloxy-1-naphthyl methacrylate and 54 parts of trimethylolpropane triacrylate synthesized in the same manner as in Example 13, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) was mixed and immersed in an oil bath at 120 ° C. to melt. The melt of the obtained radically polymerizable composition was applied on a polyester film (Toray Lumirror, Lumirror is a registered trademark of Toray Industries, Inc.) so as to have a thickness of 0.2 mm, and then in a nitrogen atmosphere. In a state kept at 120 ° C., the surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm was 1 mW / cm ² ) for 3 minutes to obtain a radical photopolymer.

When the refractive index of the polymer was measured (measuring instrument: Elmer ER-7MW-H), n _D = 1.556. In general, this type of compound is expected to have a higher refractive index than the original monomer when polymerized, but the refractive index of the original polymerizable composition is n _D = 1.517, The value was improved by 0.04, and it was confirmed that polymerization was carried out in this respect as well.

(Comparative Example 1) <Trial of photocopolymerization of 4-methoxy-1-naphthyl acrylate and trimethylolpropane triacrylate>
2-Benzyl-2-dimethylamino-1- (70 parts of 4-methoxy-1-naphthyl acrylate (compound described in Example 3 of JP-A-62-192340) and 30 parts of trimethylolpropane triacrylate 0.5 part of 4-morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) was mixed and immersed in an oil bath at 70 ° C. to melt. The melt of the obtained radical photopolymerizable composition was applied on a polyester film (Toray Lumirror) to a film thickness of 0.3 mm, and then kept at 70 ° C. in a nitrogen atmosphere, Even after the surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm was 1 mW / cm ² ) for 10 minutes, it was not cured at all.

From the above results, it can be said that the 4- (acyloxy) naphthyl-1- (meth) acrylate compound of the present invention is an industrially advantageous compound that can be polymerized even in a high-pressure mercury lamp. Further, since the refractive index (n _D ) of the trimethylolpropane triacrylate homopolymer is 1.538, the 4- (acyloxy) naphthyl-1- (meth) acrylate compound of the present invention is copolymerized. It can be seen that the refractive index of the polymer can be increased.

Example 22 <9,9-bis [4- () for copolymerization of <4-acetyloxy-1-naphthyl acrylate with 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene Synthesis of 2-acryloyloxyethoxy) phenyl] fluorene>
In a 50 ml three-necked flask equipped with a thermometer and a stirrer, 1.0 g (2.3 mmol) of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 10 ml of toluene, 3.9 g of methyl acrylate (46 Mmol), 10 mg of TEMPO and 0.1 g (0.2 mmol) of titanium tetraisopropoxide were added, and the mixture was stirred for 9 hours while extracting methyl acrylate while heating to 105 ° C. in an oil bath. Thereafter, it was post-treated by a conventional method to obtain 0.9 g (1.6 mmol) of a light pink oil of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. The yield based on the starting 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene was 60 mol%.

(Example 23) <Copolymerization of 4-acetyloxy-1-naphthyl acrylate with 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene>
70 parts of 4-acetyloxy-1-naphthyl acrylate synthesized in the same manner as in Example 3 and 30 parts of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene synthesized by the method described above were mixed. Then, 0.5 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) was added as a radical photopolymerization initiator to the mixture. Then, it was immersed in an oil bath at 120 ° C. and melted. The viscosity of the melt of the obtained radical photopolymerizable composition was low, and could be easily applied on a polyester film (Toray Lumirror) so that the film thickness was 0.2 mm. After coating, the surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm: 1 mW / cm ² ) for 3 minutes while keeping the temperature at 120 ° C. under a nitrogen atmosphere to obtain a radical photopolymer.

Measurement of the refractive index of the polymer (measurement instrument: Elmer _ER-7MW-H) was n D = 1.618. The refractive index of the original polymerizable composition is n _D = 1.598, and the value of the refractive index is improved by 0.020.

(Example 24) <Copolymerization of 4-benzoyloxy-1-naphthyl acrylate with 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene>
70 parts of 4-benzoyloxy-1-naphthyl acrylate synthesized in the same manner as in Example 5, and 30 parts of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene synthesized in the same manner as in Example 21 On the other hand, 0.5 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) as a radical photopolymerization initiator was mixed, It was immersed in an oil bath and melted. The viscosity of the melt of the obtained radical photopolymerizable composition was low, and could be easily applied on a polyester film (Toray Lumirror) so that the film thickness was 0.2 mm. After coating, the surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm: 1 mW / cm ² ) for 3 minutes while keeping the temperature at 80 ° C. in a nitrogen atmosphere to obtain a radical photopolymer.

Measurement of the refractive index of the polymer (measurement instrument: Elmer _ER-7MW-H) was n D = 1.638. The refractive index of the original polymerizable composition is n _D = 1.619, the value of the refractive index is improved by 0.019, and it can be seen that polymerization has occurred.

Comparative Example 2 <Photocopolymerization of 4-methoxy-1-naphthyl acrylate and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene>
70 parts of 4-methoxy-1-naphthyl acrylate (compound described in Example 3 of JP-A-62-192340), 9,9-bis [4- (2-acryloyloxy) synthesized in the same manner as in Example 20 Ethoxy) phenyl] fluorene (30 parts) was mixed with 0.5 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369 manufactured by Ciba Specialty Chemicals) and 90 ° C. It was immersed in an oil bath and melted. The melt of the obtained radical photopolymerizable composition was applied on a polyester film (Toray Lumirror) to a film thickness of 0.3 mm, and then kept at 70 ° C. in a nitrogen atmosphere, Even after the surface was irradiated with a high-pressure mercury lamp (irradiation intensity at a wavelength of 366 nm was 1 mW / cm ² ) for 15 minutes, it was not cured at all.

(Example 25) Experiment for reducing melt viscosity of 9,9-bis [4- (2-acryloyloxy) ethoxyphenyl] fluorene by addition of 4-propanoyloxy-1-naphthyl acrylate Synthesis was performed in the same manner as in Example 4. 100 parts of 4-propanoyloxy-1-naphthyl acrylate and 100 parts of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene synthesized in the same manner as in Example 22 were mixed on a hot plate. To 60 ° C. to obtain a uniform melt. 10 g of this melt was taken, and the viscosity was measured using a viscometer Viscometer Model VM-10A manufactured by CBC while raising the temperature of the melt. Similarly, the viscosity of 4-propanoyloxy-1-naphthyl acrylate alone and the viscosity of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene alone were measured. The result is shown in FIG. In the figure, 4-propanoyloxy-1-naphthyl acrylate is abbreviated as Ac-HN (propionyl). 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene is abbreviated as fluorene acrylate.

From this result, it can be seen that 4-propanoyloxy-1-naphthyl acrylate has a very low viscosity in the melt state. Further, the mixture is obtained by adding the 4-propanoyloxy-1-naphthyl acrylate of the present invention on a one-to-one basis to the high-viscosity 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. It was found that the melt viscosity of was significantly reduced relative to the viscosity of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.

From the above results, it can be said that the 4- (acyloxy) -1-naphthyl (meth) acrylate compound of the present invention is an industrially advantageous compound that can be polymerized even in a high-pressure mercury lamp. Moreover, 4- (acyloxy) -1-naphthyl (meth) acrylate of the present invention is added to a compound such as 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene having a high refractive index but high viscosity. By mixing the compounds, the viscosity of the melt can be lowered, the coating can be facilitated, and a polymer having a high refractive index can be obtained.

Claims (6)

A 4- (acyloxy) -1-naphthyl (meth) acrylate compound represented by the general formula (1).

(In the general formula (1), R represents a hydrogen atom or a methyl group, Z represents an alkyl group or an aryl group, X and Y may be the same or different, and a hydrogen atom, an alkyl group, a halogen atom, Indicates an atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group.) The method for producing a 4- (acyloxy) -1-naphthyl (meth) acrylate compound according to claim 1, which comprises acylating the 4-hydroxy-1-naphthyl (meth) acrylate compound. The method for producing a 4- (acyloxy) -1-naphthyl (meth) acrylate compound according to claim 1, comprising (meth) acrylating the 4- (acyloxy) -1-naphthol compound. A polymerizable composition comprising the 4- (acyloxy) -1-naphthyl (meth) acrylate compound according to claim 1 and a polymerization initiator. A polymer obtained by polymerizing the polymerizable composition according to claim 4. A highly refractive material containing the polymer according to claim 5.