JP2013234127A - 9,10-bis{[2-(meth)acryloyloxy]alkoxy}-1,2,3,4-tetrahydro-1,4-methanoanthracene compound, method for producing the same, and polymer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a (meth)acrylate compound whose polymer has a high refractive index, and to provide a production method and a composition.SOLUTION: This invention relates to a 9,10-bis{[2-(meth)acryloyloxy]alkoxy}-1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by formula (1), (meth)acryloylating a compound represented by formula (2), and a method for producing the same.

Description

The present invention relates to a 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound, a process for producing the compound, and the 9,10- The present invention relates to a polymer obtained by polymerizing a bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene 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 properties, but have a drawback that they easily become thick because their refractive index is lower than that of inorganic glass. 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 used as the raw material. In order to obtain a plastic with a high refractive index, the monomer constituting the plastic needs to have a high refractive index.

As a method for increasing the refractive index of a monomer, it is already widely known that a halogen atom (excluding fluorine) or a sulfur atom is introduced into a 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, the halogenation significantly deteriorates the light resistance of the obtained polymer and has a disadvantage of high specific gravity.

A monomer composition having a sulfur atom having a high intrinsic refractive index in addition to halogen has also been reported (Patent Document 2). However, although the monomer composition having a sulfur atom has a high refractive index and excellent impact resistance, the light resistance of the polymer obtained in the same manner is remarkably inferior, and there are problems such as giving off an unpleasant odor peculiar to sulfur. there were. Furthermore, when plastics using a monomer composition having sulfur atoms are treated as waste, there is a concern that harmful gases and sulfur compounds are generated.

On the other hand, aromatic compounds have been conventionally introduced as a method for increasing the refractive index of acrylate monomers, and bisphenol A ring, biphenyl ring, fluorene ring, and the like are used as the aromatic rings. . As a method using these high refractive index aromatic acrylates, these high refractive index aromatic compounds are used with respect to monoacrylate compounds which are monofunctional main ingredients such as benzyl acrylate, phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, and the like. These bifunctional acrylates are generally used as additives for improving the refractive index. When bifunctional acrylates of these high refractive index aromatic compounds are used, if the acryloyl group is introduced directly into the aromatic ring, the skeleton is too stiff and poorly soluble in the main monomer, and the bifunctionality of the aromatic compound Since the melting point of acrylate is high, there is a drawback that it is difficult to handle. Therefore, by interposing an alkylene oxide such as ethylene oxide or propylene oxide between the aromatic ring and the acryloyl group (hereinafter referred to as EO-mediated bifunctional acrylate), the solubility with the main monomer can be improved, or the melting point can be reduced. It is common to use compounds that are made easier to handle by lowering. In terms of handling, it is preferably a liquid having a low viscosity at room temperature.

However, in these EO-mediated bifunctional acrylates, when a bisphenol A ring or a biphenyl ring is used as an aromatic compound, a monomer that does not contain a halogen atom or a sulfur atom in the skeleton has a refractive index exceeding 1.55. This is difficult, and EO-mediated bifunctional acrylates having a biphenyl ring are solid at room temperature and are hardly obtained in liquid form. Moreover, it is convenient that the alkylene oxide-mediated bifunctional acrylate having a bisphenol A skeleton is liquid at room temperature, but their refractive index is low and does not exceed 1.55. On the other hand, an EO-mediated bifunctional acrylate having a fluorene ring is known, and the EO-mediated bifunctional acrylate having a fluorene ring has a high refractive index of 1.615 and is liquid at room temperature. Although it is liquid, its viscosity is very high and its fluidity is extremely poor at room temperature, so it had a major disadvantage that it must be heated at the time of addition to lower the viscosity (patent) Literatures 3, 4, 5, 6).

In addition, an EO-mediated bifunctional acrylate compound in which an acryloyl group is introduced into a polycyclic aromatic naphthalene ring, anthracene ring, or 1,4-dihydroanthracene ring via an alkylene oxide such as ethylene oxide or propylene oxide. A report has been made. However, the obtained EO-mediated bifunctional acrylate containing a naphthalene ring, an anthracene ring and a 1,4-dihydroanthracene ring was solid at room temperature (Patent Documents 7, 8, 9, 10, 11, 12). , 13, 14).

JP 05-170702 A JP 2002-20433 A JP 2003-064025 A JP 2004-083855 A Japanese Patent Laid-Open No. 06-220131 JP 2008-001641 A JP 2008-024694 A JP 2007-204438 A JP 2008-169156 A JP 2009-040811 A JP 2010-018746 A JP 2010-254585 A JP 2010-275236 A

Therefore, development of polycyclic aromatic EO-mediated bifunctional (meth) acrylate compounds that are liquid at room temperature and have a high refractive index of the polymer obtained by UV irradiation. Was desired.

As a result of intensive studies on the structure and properties of the polycyclic aromatic EO-mediated bifunctional (meth) acrylate compound, the present inventor has found 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1, The 2,3,4-tetrahydro-1,4-methanoanthracene compound is liquid at room temperature and is easily polymerized by UV irradiation, and the obtained polymer has a high refractive index. As a result, the present invention has been completed.

Hereinafter, the contents of the invention will be described in detail.
The first invention provides a 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (1). .

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, R ⁷ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

In the second invention, the 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (2) is (meth) acryloylated. And a process for producing a 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound according to the first invention. .

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

In the third invention, the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound described in the first invention and radical polymerization initiation A polymerizable composition comprising an agent is provided.

In the fourth invention, the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound described in the first invention; , 10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound other than the polymerizable monomer and the radical polymerization initiator Offer things.

The fifth invention provides a polymer obtained by polymerizing the polymerizable composition described in the third invention or the fourth invention.

In the present invention, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl. Moreover, in this invention, alkyleneoxy shows the bivalent group shown by the following structure, for example, ethyleneoxy group, 2-methylethyleneoxy group (it may be called a propyleneoxy group), 2-ethylethylene. And an oxy group (sometimes referred to as a butyleneoxy group).

(In general formula (3), R ⁶ represents any one of a hydrogen atom, a methyl group, and an ethyl group, and * represents a bond.)

The position numbers of the substituents in the 1,2,3,4-tetrahydro-1,4-methanoanthracene skeleton are given as follows.

The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention is a novel compound that is liquid at room temperature. And it is easily polymerized by UV (ultraviolet) light irradiation. Moreover, the polymer obtained by the polymerization is an industrially useful compound having a high refractive index.

<Compound>
The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention is a compound represented by the following general formula (1). is there.

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, R ⁷ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

In general formula (1), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, etc., and the alkyl group is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, An ethyl group, n-propyl group, i-propyl, n-butyl group, etc. are mentioned.

Specific examples of the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (1) include the following: Can be mentioned.

That is, when X is a hydrogen atom, for example, 9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 9,10-bis [2 -(Methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro- 1,4-methanoanthracene, 9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 9,10-bis [2- (acryloyloxy) ) Butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 9,10-bis [2- (methacryloyloxy) butoxy] -1, , 3,4-tetrahydro-1,4-methanoanthracene, 1-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1-methyl-9,10-bis [2- (acryloyl) Oxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro -1,4-methanoanthracene, 1-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-meta Anthracene, 1-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl-9,10-bis [2- (Acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 2-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl- 9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl-9,10- Bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2 , 3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis [2- (acryloyl) Oxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis [2- (methacryloyloxy) Propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1 , 4-methanoanthracene, 11-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and the like.

When X is an alkyl group, 6-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-methyl- 9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4 -Methanoanthracene, 6-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-methyl 9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6-dimethyl-9,10-bis [2- (acryloyloxy) Ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6-dimethyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro -1,4-methanoanthracene, 1,6-dimethyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6- Dimethyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6-dimethyl-9, 0-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6-dimethyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1 , 4-Methanoanthracene, 2,6-dimethyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl- 9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl-9,10-bis [ 2- (Methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2 , 3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methano Anthracene, 6,11-dimethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6,11-dimethyl-9,10- Bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6,11-dimethyl-9,10-bis [2 (Acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6,11-dimethyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3 , 4-tetrahydro-1,4-methanoanthracene, 6,11-dimethyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, Examples include 6,11-dimethyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene.

Further, 5-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-methyl-9,10-bis [2- (Methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 5-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-methyl- 9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-methyl-9,10-bis [2 (Methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3 , 4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis [ 2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis [2- (a Liloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2, 5-dimethyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis [2- (Acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis [2- (methacryloyl) Oxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5, 11-dimethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis [2- (Methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis [2- (acryloyloxy) ) Propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4 Tetrahydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5,11 -Dimethyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and the like.

Also, 6-ethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-9,10-bis [2- (Methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 6-ethyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl- 9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-9,10-bis [2- Methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2, 3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4- Methanoanthracene, 6-ethyl-1-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl -9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl -9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl-9,10-bis [2- ( Methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-2-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2, 3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-2-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4- Methanoanthracene, 6-ethyl-2-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6 -Ethyl-2-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-2-methyl-9,10 -Bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-2-methyl-9,10-bis [2- (methacryloyloxy) butoxy ] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-11-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4 Tetrahydro-1,4-methanoanthracene, 6-ethyl-11-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1, -Methanoanthracene, 6-ethyl-11-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-11 Methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-11-methyl-9,10-bis [2- (Acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-11-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2 3,4-tetrahydro-1,4-methanoanthracene and the like.

Furthermore, 5-ethyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-9,10-bis [2 -(Methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3 4-tetrahydro-1,4-methanoanthracene, 5-ethyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl -9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-9,10-bis 2- (Methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1 , 2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1 , 4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl- 1-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-1 Methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis [2- (Methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-2-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2 , 3,4-Tetrahydro-1,4-methanoanthracene, 5-ethyl-2-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4 -Methanoanthracene, 5-ethyl-2-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracase 5-ethyl-2-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-2-methyl- 9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-2-methyl-9,10-bis [2- (methacryloyl) Oxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro 1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl -11-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis [2- (Acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis [2- (methacryloyloxy) butoxy]- 1,2,3,4-tetrahydro-1,4-methanoanthracene and the like.

When X is a halogen atom, for example, 6-chloro-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-9 , 10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-9,10-bis [2- (acryloyloxy) propoxy]- 1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4- Methanoanthracene, 6-chloro-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, Rho-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-1-methyl-9,10-bis [2- (Acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-1-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2 , 3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-1-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4 -Methanoanthracene, 6-chloro-1-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthra 6-chloro-1-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-1-methyl- 9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-2-methyl-9,10-bis [2- (acryloyl) Oxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-2-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene, 6-chloro-2-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1, 4-methanoanthracene, 6-chloro-2-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-2 -Methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-2-methyl-9,10-bis [2 -(Methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1, 2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2, , 4-Tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methano Anthracene, 6-chloro-11-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl- 9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl-9,10-bis [2- (methacryloyl) Oxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-9,10-bis [2- (acryloyloxy) e Xyl] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1 , 4-Methanoanthracene, 5-chloro-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-9,10- Bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-9,10-bis [2- (acryloyloxy) butoxy] -1,2 , 3,4-Tetrahydro-1,4-methanoanthracene, 5-chloro-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro -1,4-methanoanthracene, 5-chloro-1-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5- Chloro-1-methyl-9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10- Bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10-bis [2- (methacryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2 3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4- Methanoanthracene, 5-chloro-2-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl -9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl-9,10-bis [2- ( Acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl-9,10-bis [2- (methacryloyloxy) ) Propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3 4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene 5-chloro-11-methyl-9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-11-methyl-9 , 10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-11-methyl-9,10-bis [2- (acryloyloxy) propoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-11-methyl-9,10-bis [2- (methacryloyloxy) propoxy]- 1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-11-methyl-9,10-bis [2- (acryloyloxy) butoxy] -1,2,3,4-tetrahydro- 1,4-methanoanthracene, 5-chloro-11-methyl-9,10-bis [2- (methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene .

Among these compounds, 9,10-bis [2- (acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene (Structural Formula 1- having the structural formula shown below) 1) 9,10-bis [2- (methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene (Structure 1-2) is easily synthesized and obtained It is particularly preferable because the refractive index of the object is high.

[Production method]
The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (1) is easily industrially available. 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione obtained by hydrogenating a Diels-Alder reaction product of a 1,4-naphthoquinone compound and a cyclopentadiene compound A first reaction in which a compound (compound of the following general formula (4)) is reacted with an alkylene oxide or a halogenoalkanol in the presence of an alkali (a reaction with an alkylene oxide is referred to as a 1-1 reaction, and a reaction with a halogenoalkanol is a first reaction). -2 reaction), and 9,10-bis (2-hydroxyal) represented by the general formula (2) obtained by the 1-1 reaction or the 1-2 reaction. Carboxymethyl) -1,2,3,4-tetrahydro-1,4-methanonaphthalen anthracene compound (meth) may be obtained by the second reaction and to acryloylated.

(In the 1-1 reaction formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, It represents either a methyl group or an ethyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

(In the reaction formula 1-2, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and each represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, It represents either a methyl group or an ethyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

(In the second reaction formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom or a methyl group. Or an ethyl group, R ⁷ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

Specific examples of the halogen atom and the alkyl group represented by each X in the above-mentioned 1-1 reaction formula, 1-2 reaction formula and second reaction formula are the same as X in formula (1).

The 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound used as a raw material in the 1-1 reaction or 1-2 reaction is 1,4-naphthoquinone. It is obtained by hydrogenating a 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione compound which is a Diels-Alder reaction product of a compound and a cyclopentadiene compound.

Diels-Alder reaction between a 1,4-naphthoquinone compound and a cyclopentadiene compound can be performed by a conventionally known method. For example, it can be synthesized by the method described in Step 1 of JP-A-6-321950.

  Examples of the 1,4-naphthoquinone compound that is a raw material for the first reaction include the following compounds. That is, 1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 6-ethyl-1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 5-ethyl-1,4-naphthoquinone, 6- Examples include chloro-1,4-naphthoquinone, 5-chloro-1,4-naphthoquinone, 6-bromo-1,4-naphthoquinone, 5-bromo-1,4-naphthoquinone, and the like.

Examples of the cyclopentadiene compound include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, and 5-methylcyclopentadiene. These can be used alone or in combination. The cyclopentadiene compound may be used by heating the corresponding dicyclopentadiene compound and decomposing it into a cyclopentadiene compound.

For example, when dicyclopentadiene is heated to 150 ° C. or higher, it is thermally decomposed into cyclopentadiene. By cooling this, cyclopentadiene can be isolated. Similarly, methylcyclopentadiene can be obtained by thermally decomposing methyldicyclopentadiene. The cyclopentadiene or methylcyclopentadiene thus obtained is preferably dimerized again at room temperature, so that it is preferably used immediately in the next reaction. When cyclopentadiene or methylcyclopentadiene is mixed with a naphthoquinone compound, heat is generated and a Diels-Alder reaction occurs to produce a cyclic adduct. When methylcyclopentadiene is a mixture of isomers with different methyl substitution positions, the Diels-Alder reaction product is often a low melting point product compared to when cyclopentadiene is used. The hydrogenation reaction, the first reaction, and the second reaction can be carried out by substantially the same reaction operation, and 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4- Tetrahydro-1,4-methanoanthracene compounds can be synthesized.

Next, catalytic hydrogenation will be described. The 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione compound obtained by the above reaction can easily contact the double bond at the 2- and 3-positions in the presence of a catalytic hydrogenation catalyst. Can be hydrogenated. As the catalyst, a catalyst generally used for catalytic hydrogenation reaction of carbon-carbon double bond can be used. For example, palladium-supported activated carbon, Raney nickel, Raney cobalt, platinum oxide, platinum-supported activated carbon, nickel diatomaceous earth, copper Heterogeneous catalysts such as chromite; or homogeneous catalysts such as chlorotris (triphenylphosphine) rhodium, platinum-tin complexes, tertiary phosphine-cobaltcarbonyl complexes. The catalytic hydrogenation reaction is performed in the presence of hydrogen gas. Depending on the type of catalyst used, it can be carried out at normal pressure, but it is desirable to carry out under pressure because the reaction rate is often large. When carried out under pressure, the pressure is 30 MPa or less, preferably 20 MPa or less, more preferably 10 MPa or less, which is industrially advantageous from the standpoint of reaction equipment, operability and the like.

1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10- obtained by catalytic hydrogenation of Diels-Alder reaction product of 1,4-naphthoquinone compound and cyclopentadiene compound Examples of the dione compound include the following compounds. That is, 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-methyl-1,2,3,4,4a, 9a-hexahydro-1,4 -Methanoanthracene-9,10-dione, 5-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-ethyl-1,2,3 , 4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-ethyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10 -Dione, 6-chloro-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-chloro-1,2,3,4,4a, 9a- Hexahydro-1,4-methano Nthracene-9,10-dione, 6-bromo-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-bromo-1,2,3,4 , 4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione 6-methyl-1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-methyl-1-methyl-1,2,3 4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-ethyl-1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene- 9,10-dione 5-ethyl-1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-chloro-1-methyl-1,2,3,4 , 4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 5-chloro-1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9 , 10-dione, 6-bromo-1-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-bromo-1-methyl-1, 2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene- 9,10-dione, 6-me Tyl-2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-methyl-2-methyl-1,2,3,4,4a , 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 6-ethyl-2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10 -Dione, 5-ethyl-2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-chloro-2-methyl-1,2, 3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-chloro-2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methano Anthracene-9,10-dione, -Bromo-2-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-bromo-2-methyl-1,2,3,4, 4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 11-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-methyl-11-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-methyl-11-methyl-1,2,3,4 , 4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-ethyl-11-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9 , 10-dione 5-ethyl-11-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 6-chloro-11-methyl-1,2,3,4 , 4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione, 5-chloro-11-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9 , 10-dione, 6-bromo-11-methyl-1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione, 5-bromo-11-methyl-1, 2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione and the like.

Examples of the alkylene oxide used in the first reaction include ethylene oxide, propylene oxide, butylene oxide, and the like.

Examples of the alkali used in the 1-1 reaction include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and usually an aqueous solution thereof is used.

Solvents for the 1-1 reaction include alcohol solvents such as methanol, ethanol and isopropyl alcohol; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and 1,4-dioxane; dimethylformamide and dimethylacetamide. And amide solvents such as

In the 1-1 reaction, the alkylene oxide is preferably 2 mol times or more and 15 mol times based on the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound. Less than, more preferably 4 mol times or more and less than 10 mol times is added. If it is less than 2 mole times, 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound remains unreacted, and if it is more than 15 mole times, the solubility of the product is low. Too high, yield decreases.

In the 1-1 reaction, the alkali is added in an amount of 2 mol times or more and less than 3 mol times with respect to 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound. To do. If it is less than 2 mol times, the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound remains unreacted, and even if added more than 3 mol times, the yield Does not go up.

In the 1-1 reaction, the reaction temperature is preferably 0 ° C. or more and less than 60 ° C., more preferably 10 ° C. or more and less than 40 ° C. If it is less than 0 ° C., the reaction takes too much time, and if it is 60 ° C. or more, impurities increase and the yield decreases.

Examples of the 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound obtained by the 1-1 reaction include the following compounds. That is, 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 9,10-bis (2-hydroxypropoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1-methyl-9,10-bis (2 -Hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1, 4-methanoanthracene, 1-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl-9, 0-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 2-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10 -Bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4 Tetrahydro-1,4-methanoanthracene, 11-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, -Methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-methyl-9,10-bis (2-hydroxypropoxy) -1, 2,3,4-tetrahydro-1,4-methanoanthracene, 6-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1, 6-dimethyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6-dimethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,6-dimethyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1 , 4-methanoanthracene, 2,6-dimethyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl-9,10 -Bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,6-dimethyl-9,10-bis (2-hydroxybutoxy) -1,2,3 4-tetrahydro-1,4-methanoanthracene, 6,11-dimethyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6,11- Dimethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6,11-dimethyl-9,10-bis (2-H Roxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4 -Methanoanthracene, 5-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-methyl-9,10-bis (2-hydroxy) Butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1, 4-methanoanthracene, 1,5-dimethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 1,5-dimethyl Ru-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis (2-hydroxyethoxy) -1 , 2,3,4-Tetrahydro-1,4-methanoanthracene, 2,5-dimethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene 2,5-dimethyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis (2- Hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetra Hydro-1,4-methanoanthracene, 5,11-dimethyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-9, 10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 6-ethyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl -9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl-9,10-bis (2-hydride) Xypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-1-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro -1,4-methanoanthracene, 6-ethyl-2-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-2 -Methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-2-methyl-9,10-bis (2-hydroxybutoxy) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl-11-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetra Dro-1,4-methanoanthracene, 6-ethyl-11-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-ethyl- 11-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-9,10-bis (2-hydroxyethoxy) -1 , 2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5, -Ethyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis ( 2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 5-ethyl-1-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl 2-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-2-methyl-9,10-bis (2- Hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-2-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4 Torahydro-1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl- 11-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-ethyl-11-methyl-9,10-bis (2-hydroxy) Butoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene and the like.

Furthermore, 6-chloro-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene 6-chloro-1-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-1-methyl-9,10- Bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-1-methyl-9,10-bis (2-hydroxybutoxy) -1, , 3,4-Tetrahydro-1,4-methanoanthracene, 6-chloro-2-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene 6-chloro-2-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-2-methyl-9,10- Bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3 , 4-Tetrahydro-1,4-methanoanthracene, 6-chloro-11-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-meta Anthracene, 6-chloro-11-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-9,10-bis (2 -Hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1, 4-methanoanthracene, 5-chloro-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10- Bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10-bis (2-hydroxypropoxy) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-1-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1 , 4-methanoanthracene, 5-chloro-2-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl -9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-2-methyl-9,10-bis (2-hydroxybutoxy)- 1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-11-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4 − Tanoanthracene, 5-chloro-11-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-chloro-11-methyl-9, 10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-9,10-bis (2-hydroxyethoxy) -1,2,3,4 -Tetrahydro-1,4-methanoanthracene, 6-bromo-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-9,10 -Bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-1-methyl-9,10-bis (2-hydroxy) Toxi) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-1-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro- 1,4-methanoanthracene, 6-bromo-1-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-2- Methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-2-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-2-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1 , 4-methanoanthracene, 6-bromo-11-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-11-methyl -9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 6-bromo-11-methyl-9,10-bis (2-hydroxybutoxy)- 1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-9,10-bis (2-hydroxy) Roxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-1-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro -1,4-methanoanthracene, 5-bromo-1-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-1 -Methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-2-methyl-9,10-bis (2-hydroxyethoxy) ) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-2-methyl-9,10-bis (2-hydroxypropoxy) -1,2,3,4-tetra Dro-1,4-methanoanthracene, 5-bromo-2-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo- 11-methyl-9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-11-methyl-9,10-bis (2-hydroxy) Propoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene, 5-bromo-11-methyl-9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro- 1,4-methanoanthracene and the like can be mentioned.

Next, the 1-2 reaction will be described. Examples of the halogenoalkanol used in the 1-2 reaction include 1-bromo-2-ethanol, 1-chloro-2-ethanol, 1-bromo-2-propanol, 1-chloro-2-propanol, 1-bromo Examples include bromo-2-butanol and 1-chloro-2-butanol.

Examples of the alkali used in the 1-2 reaction include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like, and usually an aqueous solution thereof is used.

In the 1-2 reaction, the halogenoalkanol is preferably 2 mol times or more and less than 4 mol times with respect to the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound. More preferably, 2.5 mol times or more and less than 3.5 mol times are added. If it is less than 2 mole times, 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound remains unreacted, and if it is more than 4 mole times, the solubility of the product is low. Too high, yield decreases.

In the 1-2 reaction, the alkali is added in an amount of 2 mol times or more and less than 5 mol times to 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound. To do. If it is less than 2 mol times, the 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione compound remains unreacted, and even if it is added more than 5 mol times, the yield Does not go up.

In the 1-2 reaction, the reaction temperature is preferably 40 ° C. or higher and lower than 130 ° C., more preferably 60 ° C. or higher and lower than 100 ° C. If it is less than 40 degreeC, reaction will take time too much, and if it is 130 degreeC or more, an impurity will increase and a yield will fall.

The reaction time depends on the reaction temperature, but is usually 2 hours or more and less than 12 hours.

A specific example of the 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound obtained by the 1-2 reaction is obtained by the 1-1 reaction. This is the same as the specific example of the compound.

Next, the second reaction will be described. By subjecting the 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (2) to (meth) acryloylation, the general formula (1 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound shown in FIG.

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, R ⁷ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.)

The diol compound having a 1,2,3,4-tetrahydro-1,4-methanoanthracene skeleton represented by the general formula (2), which is a raw material for the second reaction, is a first reaction or a first reaction. It is a compound obtained by.

As the (meth) acryloylating agent used in the second reaction, halogenated (meth) acryloyl is used. Halogenated (meth) acryloyl includes acryloyl chloride, methacryloyl chloride, acryloyl bromide or methacryloyl bromide. Among them, acryloyl chloride or methacryloyl chloride is particularly preferable because the target product can be obtained with high yield.

  The amount of halogenated (meth) acryloyl added in the second reaction is usually based on 1 mol of 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound. It is 2.0 mol times or more and less than 4.0 mol times, preferably 2.2 mol times or more and less than 3 mol times. In the case of less than 2.0 mole times, the starting 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound remains unreacted, On the other hand, in the case of 4.0 mol times or more, the halogenated (meth) acryloyl partially polymerized and the resulting 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3 The purity of the 1,4-tetrahydro-1,4-methanoanthracene compound is lowered, which is not preferable.

Examples of the base used in the second reaction include alkalis and organic bases. As an alkali, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, and sodium carbonate are preferable, and sodium hydroxide is more preferable. Examples of the organic base include pyridine, α-picoline, γ-picoline, triethylamine, tributylamine, diethylamine, dibutylamine, ethylamine, butylamine and the like. Among these, triethylamine is more preferable because it easily reacts.

The amount of base used in the second reaction is usually 1.5 with respect to 1 mol of 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound. It is more than mol times and less than 3 mol times. When the amount of the base used is less than 1.5 mol, the pH of the aqueous layer becomes acidic during the dropwise addition of the halogenated (meth) acryloyl, and the selectivity may decrease. On the other hand, when the amount of the base used is 3 mol times or more, the halogenated (meth) acryloyl may be decomposed, which is not preferable.

The second reaction is usually performed in the presence of a solvent. The type of solvent is not particularly limited, but when the base is an organic base, aromatic solvents such as benzene, toluene, o-xylene, halogenated hydrocarbon solvents such as methylene chloride, dichloroethane, dichloroethylene, acetone, methyl ethyl ketone , Ketone solvents such as methyl-i-butyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran and 1,4-dioxane, and amide solvents such as dimethylformamide, dimethylacetamide and n-methylpyrrolidone are preferably used.

When the base is an alkali, a water-soluble solvent is preferable, a ketone solvent such as acetone or methyl ethyl ketone, an ether solvent such as tetrahydrofuran or 1,4-dioxane, an alcohol solvent such as methanol, ethanol, or isopropanol, Amide solvents such as dimethylacetamide and dimethylformamide are preferably used.

The time required for the (meth) acryloylation reaction is not particularly limited, but when the base is an organic base, a range of usually 0.1 hour or more and less than 4 hours, particularly 0.4 hour or more and less than 1.0 hour is preferable, When the base is an alkali, it is usually preferably 0.1 hours or more and less than 2 hours, particularly preferably 0.2 hours or more and less than 0.5 hours.

The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound thus obtained is liquid at room temperature, In addition, it is fluid and easy to handle.

Identification of the obtained compound was performed using ¹ H-NMR spectrum and IR spectrum, and the corresponding 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro It was confirmed that it was a -1,4-methanoanthracene compound or its precursor 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound.

[Polymerizable composition]
The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound thus obtained is converted into a polymer by radical polymerization. Can do. In order to promote radical polymerization of the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention, radical polymerization is performed. It is preferable to add an initiator.

Such radical polymerization initiators include photo radical polymerization initiators and thermal radical polymerization initiators.

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 BASF (Irgacure and Darocur are registered trademarks of BASF).

Then, 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound and a radical polymerization initiator are mixed to produce radical polymerizability. It can be a composition.

In the photoradical polymerizable composition of the present invention, the 9,10-bis [2- (meth) acryloyloxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene compound is used alone. Although it can also be made into a polymer, known radical polymerizability other than the 9,10-bis [2- (meth) acryloyloxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene compound A monomer 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.

By copolymerizing these radical polymerizable monomers and the 9,10-bis [(meth) acryloyloxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention, 9, In addition to improving the refractive index of the resulting polymer compared to the case where no radical polymerizable monomer of 10-bis [(meth) acryloyloxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene compound is used. , Heat resistance, solvent resistance, hardness, oxygen impermeability and the like can be improved.

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

The addition concentration of the photo radical polymerization initiator is 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound and, if necessary, It is selected from the range of 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the total weight of the radically polymerizable compounds used in combination. 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.

In addition, the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound should be converted into a polymer using a thermal radical polymerization initiator. You can also.

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]
The polymerization of the radical polymerizable composition can be performed in the form of a film or can be cured in a lump. When polymerizing in the form of a film, the liquid polymerizable composition is applied to a substrate such as a polyester film so as to have a film thickness of 5 to 300 microns using, for example, a bar coater. The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention can be easily used not only in a thin film but also in a thick film. It can be polymerized.

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 9,10-bis [(meth) acryloyloxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention is the most widely used light source as a UV curing device. Since it can be polymerized using a high-pressure mercury lamp (wavelength 366 nm), it is an industrially very useful compound.

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.

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.

[Polymerized product]
The film obtained by polymerizing the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound thus obtained. The sheet or lump is industrially useful because it exhibits a high refractive index and can be expected to have high heat resistance, high hardness, high glossiness and the like from its structure.

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, FTNMR Spectrometer
(5) Viscosity: CBC, VISCOMATE, VM-10A

[Synthesis Example 1] Synthesis of 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione 120 g of dicyclopentadiene (manufactured by Wako Pure Chemical Industries, Ltd.), an eggplant flask with a volume of 300 ml and Friedrich A cyclopentadiene (distilling temperature of 40 ° C) is charged by distillation into a distillation apparatus equipped with a cooling pipe and heated in an oil bath at 185 ° C, and 60 g of methylene chloride (manufactured by Wako Pure Chemical Industries) is contained. The collected volume was collected in a 200 ml eggplant flask. The eggplant flask to be collected was cooled with dry ice / acetone. The methylene chloride solution of 64 g of cyclopentadiene collected by the above method was transferred to a four-necked flask having a volume of 500 ml and cooled to −60 ° C. with dry ice / acetone. Prepare a slurry of 128 g of 1,4-naphthoquinone (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) and 200 g of methylene chloride (manufactured by Wako Pure Chemical Industries) in a separate container, and add the slurry to the methylene chloride solution of 64 g of cyclopentadiene over 15 minutes. did. When the cooling of dry ice / acetone was stopped after completion of the addition, the internal temperature rose to 45 ° C. due to an exothermic reaction. Stirring was continued until the internal temperature decreased, and when the internal temperature began to decrease, the bath temperature was adjusted to 35 ° C. and further stirred for 30 minutes. Thereafter, the reaction solution was transferred to a 1 L eggplant type flask, 300 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, 250 g of methylene chloride in the reaction solution was heated to 50 ° C. and distilled, and crystals were obtained. Crystallized. The precipitated crystals were suction filtered, and the obtained crystals were washed three times with 50 ml of methanol. The obtained crystals were white and the yield was 170 g. When this crystal was identified, it was 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione. The yield based on the raw material 1,4-naphthoquinone was 94 mol%.

Synthesis Example 2 Synthesis of 1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10-dione 1,4,4a, 9a obtained in the same manner as Synthesis Example 1 -70 g of tetrahydro-1,4-methanoanthracene-9,10-dione was weighed into a glass autoclave having a volume of 300 ml, 150 g of orthoxylene (manufactured by Wako Pure Chemical Industries) as a solvent, and 5% palladium carbon (Pd / C) 1 g was added, and hydrogen was supplied under the condition of 0.2 MpaG to cause a hydrogenation reaction. After completion of the reaction, Pd / C was filtered, the reaction solution was concentrated under reduced pressure, 130 g of orthoxylene was distilled off, and 50 g of methanol was added for crystallization. The precipitated crystals were suction filtered, washed with 50 ml of methanol and dried to obtain 60 g of white crystals. When this crystal was identified, it was 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione. The yield based on 1,4,4a, 9a-tetrahydro-1,4-methanoanthracene-9,10-dione was 85 mol%.

(1) Melting point: 116-117 ° C
(2) IR (KBr, cm ⁻¹ ): 2980, 2960, 2880, 1670, 1590, 1478, 1452, 1322, 1302, 1262, 1168, 1050, 998, 900, 820, 757, 730, 540
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 11-11-1.21 (2H, m), 1.41-1.46 (1H, m), 1.46-1.54 ( 2H, m), 1.58-1.65 (1H, m), 3.03 (2H, s), 3.20 (2H, s), 7.72-7.80 (2H, m), 8 .08-8.16 (2H, m).

Synthesis Example 3 Synthesis of 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene (1-2 reaction)
1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10- obtained in the same manner as in Synthesis Example 2 in a 500 ml three-necked flask equipped with a stirrer and a thermometer in a nitrogen atmosphere Dione 11.3 g (50 mmol) and degassed water 70 g were added. Then a solution of 30 g of degassed water of sodium hydroxide (200 mmol) was added. Since the white slurry became light red, it was heated at an internal temperature of 55 ° C. for 1 hour. Since it became a bright red solution, it was cooled to room temperature and a solution of 19.0 g (150 mmol) of 1-bromo-2-ethanol in 50 g of dimethylacetamide was added. When heated at an internal temperature of 60 ° C. for 5 hours and then allowed to cool, a large amount of crystals precipitated. The crystals are filtered off with suction, washed with water, then with methanol and dried to give a white powder of 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene. 2 g (32.2 mmol) were obtained. The yield based on the raw materials 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione was 64 mol%.

(1) Melting point: 163-164 ° C
(2) Refractive index: n _D = 1.614
(3) IR (KBr, cm ⁻¹ ): 3490, 3400, 2930, 2875, 1654, 1610, 1460, 1388, 1346, 1312, 1280, 1178, 1090, 1077, 1046, 1033, 072, 902, 773 759.
(4) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.32-1.40 (m, 2H), 1.60-1.66 (m, 1H), 1.75-1.82 ( m, 1H), 1.98-2.08 (m, 2H), 2.28 (bs, 2H), 3.75 (s, 2H), 3.99-4.07 (m, 4H), 4 10-4.17 (m, 2H), 4.21-4.27 (m, 2H), 7.39-7.46 (m, 2H), 8.04-8.12 (m, 2H)

Synthesis Example 4 Synthesis of 9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene (first reaction)
1,2,3,4,4a, 9a-Hexahydro-1,4-methanoanthracene-9,10 obtained in the same manner as in Synthesis Example 2 in a 300 ml three-necked flask equipped with a stirrer and a thermometer under a nitrogen atmosphere -Dione 11.3 g (50 mmol) and dimethylacetamide 80 g were added to give a colorless solution, sodium hydroxide 4.80 g (120 mmol) in 30 g of degassed water was added, and the mixture was heated at an internal temperature of 55 ° C for 30 minutes. Subsequently, 2 g (300 mmol) of butylene oxide was added to the resulting red solution and heated at an internal temperature of 60 ° C. for 8 hours. After cooling the resulting red-black solution, 10% sulfuric acid aqueous solution was added to make the pH of the solution slightly acidic. As a result, a thin khaki colored starch candy sank. After discarding the supernatant, the candy cake was washed thoroughly with water. did. Thereafter, it was stored in 100 ml of hexane. Since the crystallization gradually progressed, the produced crystals were suction filtered and dried, and a white powder of 9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene. 5 g (28.4 mmol) were obtained. The isolated yield based on the raw materials 1,2,3,4,4a, 9a-hexahydro-1,4-methanoanthracene-9,10-dione was 57 mol%.

(1) Melting point: 135-136 ° C
(2) Refractive index: n _D = 1.587
(3) IR (KBr, cm ⁻¹ ): 3500, 3425, 2975, 2947, 2880, 1612, 1460, 1350, 1312, 1282, 1180, 1128, 1090, 1050, 1017, 978, 954, 914, 764.
(4) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.05 (t, J = 8 Hz, 6H), 1.31-1.39 (m, 2H), 1.60-1.70 ( m, 5H), 1.74-1.81 (m, 1H), 1.98-2.08 (m, 2H), 2.57 (d, J = 9 Hz, 2H), 3.74 (s, 2H), 3.90-4.12 (m, 6H), 7.40-7.47 (m, 2H), 8.02-8.09 (m, 2H).

<Synthesis Example>
Example 1 Synthesis of 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene In a 200 ml three-necked flask with stirrer and thermometer 9.32 g (20 mmol) of 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene obtained in the same manner as in Synthesis Example 3 under a nitrogen atmosphere 30 g of methylene chloride and 4.50 g (50 mmol) of acryloyl chloride were added. When a methylene chloride solution of 4.04 g (40 mmol) of triethylamine in ice water was added to the resulting white slurry, it immediately became a sol. After stirring at room temperature for 3 hours, 8 g of water was added to form two layers, and the methylene chloride layer was washed with 14 g of water. Next, 25 g of acetone was added to the methylene chloride layer and passed through a silica gel column. The color of the effluent became colorless. The effluent was concentrated and colorless candy-like 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene 4.20 g (10 mmol) Got. 9,10-bis [(2-acryloyloxy) ethoxy] -1,2, against the starting 9,10-bis (2-hydroxyethoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene The isolated yield of 3,4-tetrahydro-1,4-methanoanthracene was 50 mol%. The melting point of this product was determined by dispersing the obtained candy-like substance in methanol, solidifying it in a dry ice / acetone refrigerant, returning to room temperature, and having a temperature at which it melts in the middle.

(1) Melting point: −32 ° C., liquid at room temperature (2) Refractive index: n _D = 1.573
(3) IR (neat, cm ⁻¹ ): 2960, 2880, 1730, 1642, 1460, 1412, 1349, 1302, 1278, 1200, 1176, 1096, 1060, 976, 812, 775. .
(4) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.32-1.41 (m, 2H), 1.62-1.67 (m, 1H), 1.76-1.82 ( m, 1H), 1.98-2.08 (m, 2H), 3.73 (s, 2H), 4.23-4.32 (m, 2H), 4.32-4.41 (m, 2H), 4.52-4.61 (m, 4H), 5.88 (d, J = 9 Hz, 2H), 6.20 (dd, J ₁ = 17 Hz, J ₂ = 9 Hz, 2H), 6. 46 (d, J = 17 Hz, 2H), 7.37-7.46 (m, 2H), 8.04-8.13 (m, 2H).
(5) Viscosity: 425 mPa · s / 70 ° C, 590 mPa · s / 60 ° C, 710 mPa · s / 50 ° C

Example 2 Synthesis of 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene In a 200 ml three-necked flask equipped with a stirrer and thermometer Under nitrogen atmosphere, 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene obtained in the same manner as in Synthesis Example 3 6.32 g ( 20 mmol), 30 g of methylene chloride and 5.20 g (50 mmol) of methacryloyl chloride were added. A solution of 4.04 g (40 mmol) of triethylamine in 8 g of methylene chloride in ice water was added to the resulting white slurry. Since it immediately became sol, it was stirred at room temperature for 3 hours. Thereafter, 10 g of water was added to form two layers, and the methylene chloride layer was further washed with 10 g of water. 25 g of acetone was added to the methylene chloride layer and passed through a silica gel column. The color of the effluent became colorless. Concentration gave 4.98 g (11 mmol) of a colorless candy cake. 9,10-bis [(2-methacryloyloxy) ethoxy] -1, relative to the starting 9,10-bis [(2-hydroxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene The isolated yield of 2,3,4-tetrahydro-1,4-methanoanthracene was 55 mol%. The melting point of this product was determined by dispersing the obtained candy-like substance in methanol, solidifying it in a dry ice / acetone refrigerant, returning to room temperature, and having a temperature at which it melts in the middle.

(1) Melting point: -31 ° C., liquid at room temperature (2) Refractive index: n _D = 1.564
(3) IR: (neat, cm ⁻¹ ): 2970, 2880, 1723, 1641, 1458, 1380, 1350, 1322, 1300, 1170, 1092, 1044, 950, 772.
_{^{(4) 1 H-NMR (}} CDCl 3, 400MHz): δ = 1.32-1.39 (m, 2H), 1.60-1.66 (m, 1H), 1.76-1.82 ( m, 1H), 1.97 (s, 6H), 1.99-2.04 (m, 2H), 3.74 (s, 2H), 4.24-4.31 (m, 2H), 4 .32-4.41 (m, 2H), 4.46-4.58 (m, 4H), 5.61 (s, 2H), 6.16 (s, 2H), 7.35-7.45 (M, 2H), 8.05-8.11 (m, 2H).
(5) Viscosity: 800 mPa · s / 60 ° C

Example 3 Synthesis of 9,10-bis [(2-methacryloyloxy) butoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene In a 200 ml three-necked flask equipped with a stirrer and a thermometer 9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene 3.70 g (10 mmol) obtained in the same manner as in Synthesis Example 4 under a nitrogen atmosphere 20 g of methylene chloride and 2.60 g (25 mmol) of methacryloyl chloride were added. A solution of 2.02 g (20 mmol) of triethylamine in 5 g of methylene chloride in ice water was added to the resulting white slurry. Once dissolved, it immediately turned into a sol and stirred at room temperature for 3 hours. Thereafter, 14 g of water was added to form two layers, and the methylene chloride layer was further washed with 14 g of water. 60 g of methanol was added to the methylene chloride layer and passed through a silica gel column. The color of the effluent became light yellow. Concentration gave 3.6 g (7.1 mmol) of pale yellow candy. 9,10-bis [(2-methacryloyloxy) butoxy] -1,2,3 for 9,10-bis (2-hydroxybutoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene The isolated yield of 1,4-tetrahydro-1,4-methanoanthracene was 71 mol%. The melting point of this product was determined by dispersing the obtained candy-like substance in methanol, solidifying it in a dry ice / acetone refrigerant, returning to room temperature, and having a temperature at which it melts in the middle.

(1) Melting point: −44 ° C., room temperature liquid (2) Refractive index: n _D = 1.553
(3) IR (neat, cm ⁻¹ ): 2980, 2950, 2880, 1720, 1640, 1460, 1350, 1300, 1170, 1091, 1050, 770.
(4) ¹ H-NMR (CDCl ₃ , 400 MHz): δ = 1.03 (t, J = 8 Hz, 6H), 1.30-1.37 (m, 2H), 1.56-1.61 ( m, 1H), 1.74-1.79 (m, 1H). 1.91-2.05 (m, 7H), 3.69 (s, 2H), 4.07-4.26 (m, 4H), 5.21-5.32 (m, 2H), 5. 56 (s, 1H), 5.59 (s, 1H), 6.14 (s, 1H), 6.17 (s, 1H), 7.33-7.41 (m, 2H), 8.01 -8.10 (m, 2H).

From the results of Examples 1 to 3, the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention was obtained at room temperature. It can be seen that the compound is a low-viscosity liquid and has a high refractive index. In general, a highly refractive acrylate compound is often a solid at room temperature or a highly viscous rosin-like compound. A bifunctional (meth) acrylate having a fluorene skeleton known as a high refractive index compound has a viscosity of 100,000 to 1 million mPa · s. For example, as described in paragraph [0014] of Japanese Patent Application Laid-Open No. 2008-024637, the viscosity of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene is about several ten thousand at 50 ° C. mPa · s. On the other hand, as can be seen from Example 1, the compound of the present invention is a liquid having a fluidity of 710 mPa · s at 50 ° C. I can say that.

<Example of thermal polymerization>
"Example 4" 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene thermopolymerization thermometer, in a 200 ml three-necked flask equipped with a stirrer, nitrogen Under an atmosphere, 2.0 g of 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene obtained in the same manner as in Example 1 was charged, Next, 6 g of toluene was added, and 20 mg of azobisisobutyronitrile as a polymerization initiator was added. When the internal temperature was kept at 106 ° C. and heated, a large amount of white precipitate was formed after 5 minutes. The mixture was further heated for 5 minutes and cooled to obtain a white slurry. 50 ml of methanol was added, sufficiently stirred, suction filtered, and dried to obtain 1.60 g of a white powdery polymer. The isolation yield was 80 mol%. The monomer 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene is in a liquid state, but the powder obtained by thermal polymerization is 250 Heated to ° C but did not melt. Further, 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene well dissolved in toluene, acetone and dimethylacetamide did not dissolve at all. . Was measured IR, CO stretching vibration of 1730 cm ^-1 is moved to the longer wavelength side to 1738 cm ^-1, disappearance of the double bonds had been suggested.

"Example 5" 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene thermopolymerization thermometer, in a 200 ml three-necked flask equipped with a stirrer, nitrogen Under an atmosphere, 2.0 g of 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene obtained in the same manner as in Example 2 was charged, Next, 6 g of toluene was added, and 20 mg of azobisisobutyronitrile as a polymerization initiator was added. When the internal temperature was kept at 106 ° C. and heated, a large amount of white precipitate was formed after 5 minutes. The mixture was further heated for 5 minutes and cooled to obtain a white slurry. 50 ml of methanol was added, sufficiently stirred, suction filtered and dried to obtain 1.48 g of a white powdery polymer. The isolation yield was 74 mol%. The monomer 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene is liquid, but the powder obtained by thermal polymerization is 250. Heated to ° C but did not melt. Further, 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene well dissolved in toluene, acetone and dimethylacetamide did not dissolve at all. . When IR was measured, the CO stretching vibration at 1720 cm ⁻¹ shifted to the long wavelength side at 1730 cm ⁻¹ , suggesting the disappearance of the double bond.

<Example of photopolymerization>
"Example 6" 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene photopolymerizable monomer obtained in the same manner as in Example 2. In addition, 100 parts by weight of 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and 2-benzyl-2-dimethylamino-1 as an initiator 3 parts by weight of-(4-morpholinophenyl) butan-1-one (manufactured by BASF, trade name: Irgacure 369) was added to obtain a uniform radical photopolymerizable composition. This photo-radical polymerizable composition was applied to the surface of a polyester film (trade name: Lumirror, film thickness 100 microns) by a bar coater so as to have a film thickness of 200 microns. Subsequently, ultraviolet LED (wavelength: 365 nm, irradiation intensity: 550 mw / cm ² ) was irradiated under a nitrogen atmosphere. After 5 spectral irradiations, a smooth film in which 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene was polymerized was obtained.

Assuming the IR spectrum of the obtained film, the absorption at 1720 cm ⁻¹ due to the carbonyl group of the acryloyl group was shifted to 1730 cm ⁻¹ , suggesting the disappearance of the double bond. Furthermore, when the refractive index of this film was measured, it was 1.585 (n _D ), which was higher than the refractive index of the monomer, 1.564 (n _D ), and it was confirmed that the film was polymerized.

Example 7 Implementation as a photopolymerization monomer of 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and trimethylolpropane triacrylate Trimethylolpropane triacrylate was added to 50 parts by weight of 9,10-bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene obtained in the same manner as in Example 2. 50 parts by weight was further added, and further 3 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by BASF, trade name: Irgacure 369) was added as an initiator. A free radically polymerizable composition. This photo-radical polymerizable composition was applied to the surface of a polyester film (trade name: Lumirror, film thickness 100 microns) by a bar coater so as to have a film thickness of 200 microns. Subsequently, ultraviolet LED (wavelength: 365 nm, irradiation intensity: 550 mw / cm ² ) was irradiated under a nitrogen atmosphere. After 5 spectral irradiations, a smooth film in which the monomer mixture was polymerized was obtained.

When the refractive index of the obtained film was measured, it was 1.545 (n _D ), which was much higher than the refractive index 1.512 of the polymer of trimethylolpropane triacrylate, and 9,10 before light irradiation. The refractive index of a 1: 1 mixture of bis [(2-methacryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and trimethylolpropane triacrylate is higher than 1.518. It was confirmed that the polymerized.

"Example 8"
As a photopolymerization monomer of 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and trimethylolpropane triacrylate, the same manner as in Example 1 was performed. 54 parts by weight of trimethylolpropane triacrylate was added to 46 parts by weight of 9,10-bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene obtained in the above, Furthermore, 3-benzyl 2-dimethyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by BASF, trade name: Irgacure 369) was added as an initiator, and uniform radical photopolymerization was achieved. It was set as the composition. This photo-radical polymerizable composition was applied to the surface of a polyester film (trade name: Lumirror, film thickness 100 microns) by a bar coater so as to have a film thickness of 50 microns. Subsequently, ultraviolet LED (wavelength: 365 nm, irradiation intensity: 550 mw / cm ² ) was irradiated under a nitrogen atmosphere. After 5 spectral irradiations, a smooth film in which the monomer mixture was polymerized was obtained.

The refractive index of the obtained film was measured, 1.540 a _{(n D),} much higher than the refractive index 1.512 of the polymerization product of trimethylolpropane triacrylate, Also, before the light irradiation 9,10 A refractive index of a mixture of bis [(2-acryloyloxy) ethoxy] -1,2,3,4-tetrahydro-1,4-methanoanthracene and trimethylolpropane triacrylate is higher than 1.521; It was confirmed that it was polymerized.

As is apparent from Examples 4 to 8, the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound of the present invention is It can be radically polymerized by heat or light. In photoradical polymerization, it can be polymerized by a high-pressure mercury lamp, which is the most common light source, and the resulting polymer has a high refractive index and is industrially useful. It turns out that it is a compound. Further, a general polymerizable compound such as trimethylolpropane triacrylate and the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1, which is the present invention, are used. Since the refractive index of the polymer can be increased by copolymerizing the 4-methanoanthracene compound, the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3 of the present invention is used. , 4-tetrahydro-1,4-methanoanthracene compound is found to be an industrially useful compound.

Claims (5)

9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, R ⁷ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.) The method comprises (meth) acryloylating a 9,10-bis (2-hydroxyalkoxy) -1,2,3,4-tetrahydro-1,4-methanoanthracene compound represented by the general formula (2). A method for producing the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound according to 1.

(In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be the same or different from each other, and represent a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom, methyl A group or an ethyl group, and X represents a hydrogen atom, a halogen atom or an alkyl group.) Polymerization comprising the 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound according to claim 1 and a radical polymerization initiator. Composition. The 9,10-bis {[2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound according to claim 1, the 9,10-bis {[ 2- (meth) acryloyloxy] alkoxy} -1,2,3,4-tetrahydro-1,4-methanoanthracene compound other than the polymerizable composition and a polymerizable composition comprising a radical polymerization initiator. A polymer obtained by polymerizing the polymerizable composition according to claim 3 or 4.