JP2017024994A - Monohydroxy-2-naphthyl(meth)acrylate compound, method for producing the same and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic (meth)acrylate compound that is free from an unpleasant odor peculiar to hetero atoms such as sulfur atoms, is environmentally friendly as it contains no halogen atom, has a high refractive index, and also has excellent adhesion.SOLUTION: The present invention provides a monohydroxy-2-naphthyl(meth)acrylate compound represented by formula (1) (Ris H or a methyl group; Ris H or a C1-8 alkyl group).SELECTED DRAWING: None

Description

The present invention relates to a monohydroxy-2-naphthyl (meth) acrylate compound, a production method thereof, a polymerizable composition containing the compound, a polymer, and a high refractive index material comprising the polymer.

In recent years, the demand for high refractive index materials has increased. The advancement of plastic materials with a high refractive index to optical articles is remarkable, such as liquid crystal display panels, color filters, spectacle lenses, Fresnel lenses, lenticular lenses, prism lens sheets for TFT, aspheric lenses, optical disks, optical fibers, and light. Studies on road waveguides are actively conducted.

The photopolymerizable composition can be classified into a photoradical polymerizable composition and a photocationic polymerizable composition depending on the difference in the species that initiates polymerization of the photopolymerizable compound. In general, the radical polymerization type has characteristics that the polymerization rate is high and the hardness of the coating film to be formed is high, but there are drawbacks in that the adhesion to the substrate is weak. In addition, it is easily affected by oxygen, and particularly in the production of a thin film, facilities such as nitrogen sealing are required. On the other hand, the cationic polymerization type is characterized by high adhesion to the substrate, excellent flexibility, and is hardly affected by oxygen. Therefore, a photocationically polymerizable composition is used in the field of electronic materials.

As a method for increasing the refractive index of an organic compound, it is already well known that it is useful to introduce a halogen atom or a sulfur compound into the molecular structure. For example, although a halogenated high refractive index polymer utilizing a high intrinsic refractive index of a halogen atom has been reported, there is a drawback that the light resistance is remarkably deteriorated due to halogenation and the specific gravity is high. (Patent Document 1). In addition to halogen, there is sulfur as an atom having a high intrinsic refractive index, and a monomer composition having this sulfur atom has been reported, although these have a high refractive index and excellent impact resistance, The obtained polymer had extremely poor light resistance, and there were drawbacks that caused unpleasant odor peculiar to sulfur (Patent Document 2).

Aromatic introduction is known as another method for increasing the refractive index of an organic compound. However, usually, when a high refractive index resin composition having a large number of aromatic rings is applied to a glass substrate or the like by a spin coating method or the like, the compatibility between the high refractive index resin composition and the substrate is poor, and the high refractive index resin composition However, there is a drawback that it is difficult to apply smoothly.

Ultraviolet LEDs are often used as a light source recently because they generate less heat and have a long lifetime. However, when aryliodonium salts or arylsulfonium salts are used as photopolymerization initiators, both emit long wavelengths emitted from light sources such as ultraviolet LEDs. However, it is common to add a photopolymerization sensitizer. Anthracene compounds and thioxanthone compounds are known as photopolymerization sensitizers, and anthracene compounds are often used (Patent Document 2).

JP 55-69543 A JP 2002-20433 A

Therefore, an object of the present invention is to provide an aromatic acrylate compound that does not have an unpleasant odor peculiar to a hetero atom such as a sulfur atom, is environmentally friendly because it does not contain a halogen atom, and has a high refractive index and excellent adhesion. Is to provide.

As a result of intensive studies on the structure and optical properties of the naphthalene compound, the present inventor has found that a monohydroxy-2-naphthyl (meth) acrylate compound in which the 2-position hydroxyl group of the naphthalene ring is (meth) acryloylated. Not only has a high refractive index, but also has excellent adhesion to films and the like, and the present invention has been completed.

That is, the gist of the present invention is the gist of the following. First, the first invention provides a monohydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In the second invention, there is provided a 3-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (2).

In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

The third invention provides a 7-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (3).

In the general formula (3), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

The fourth invention provides a 5-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (4).

In the general formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

The fifth invention provides a 6-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (5).

In the general formula (5), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In the sixth invention, a dihydroxynaphthalene compound represented by the following general formula (6) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound. A method for producing the represented monohydroxy-2-naphthyl (meth) acrylate compound is provided.

In the general formula (6), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same as or different from each other.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In the seventh invention, a 2,3-dihydroxynaphthalene compound represented by the following general formula (7) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound. A method for producing a 3-hydroxy-2-naphthyl (meth) acrylate compound represented by (2) is provided.

In the general formula (7), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, plurality of R ² may being the same or different.

In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In an eighth invention, the 2,7-dihydroxynaphthalene compound represented by the following general formula (8) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound. A method for producing a 7-hydroxy-2-naphthyl (meth) acrylate compound represented by (3) is provided.

In the general formula (8), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, plurality of R ² may being the same or different.

In the general formula (3), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In the ninth invention, a 2,5-dihydroxynaphthalene compound represented by the following general formula (9) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound. A method for producing a 5-hydroxy-2-naphthyl (meth) acrylate compound represented by (4) is provided.

In the general formula (9), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, plurality of R ² may being the same or different.

In the general formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In a tenth invention, a 2,6-dihydroxynaphthalene compound represented by the following general formula (10) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound. A method for producing a 6-hydroxy-2-naphthyl (meth) acrylate compound represented by (5) is provided.

In the general formula (10), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same as or different from each other.

In the general formula (5), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

The eleventh invention provides a polymerizable composition comprising the monohydroxy-2-naphthyl (meth) acrylate compound according to the first invention, a thermal polymerization initiator and / or a photopolymerization initiator. To do.

According to a twelfth aspect, there is provided a polymerizable composition comprising the 3-hydroxy-2-naphthyl (meth) acrylate compound according to the second aspect, a thermal polymerization initiator, and / or a photopolymerization initiator. provide.

According to a thirteenth invention, there is provided a polymerizable composition comprising the 7-hydroxy-2-naphthyl (meth) acrylate compound according to the third invention, a thermal polymerization initiator and / or a photopolymerization initiator. provide.

In the fourteenth invention, a polymerizable composition comprising the 5-hydroxy-2-naphthyl (meth) acrylate compound according to the fourth invention, a thermal polymerization initiator and / or a photopolymerization initiator, provide.

According to a fifteenth invention, there is provided a polymerizable composition comprising the 6-hydroxy-2-naphthyl (meth) acrylate compound according to the fifth invention, a thermal polymerization initiator and / or a photopolymerization initiator. provide.

In the sixteenth invention, the polymerizable composition according to any one of the eleventh invention to the fifteenth invention is further added to a copolymerizable monomer having an ethylenically unsaturated double bond (provided that the second invention 3-hydroxy-2-naphthyl (meth) acrylate compound described in the invention, 7-hydroxy-2-naphthyl (meth) acrylate compound described in the third invention, 5-hydroxy-2-naphthyl (meth) described in the fourth invention A polymerizable composition comprising an acrylate compound and a 6-hydroxy-2-naphthyl (meth) acrylate compound described in the fifth invention is incorporated.

The seventeenth invention provides a polymer obtained by thermal polymerization or photopolymerization of the polymerizable composition according to any of the eleventh invention to the sixteenth invention.

The eighteenth invention provides a high refractive index material containing the polymer according to the seventeenth invention.

Since the monohydroxy-2-naphthyl (meth) acrylate compound of the present invention does not have a hetero atom such as a sulfur atom, there is no unpleasant odor peculiar to a hetero atom, it does not contain a halogen atom, and it is environmentally friendly. It is a novel aromatic acrylate compound having a high refractive index and excellent adhesion, and is a useful compound. In the present invention, (meth) acrylate refers to acrylate or methacrylate, and (meth) acryloyl refers to acryloyl or methacryloyl. In the present invention, 3-hydroxy-2-naphthyl (meth) acrylate compound, 7-hydroxy-2-naphthyl (meth) acrylate compound, 5-hydroxy-2-naphthyl (meth) acrylate compound and 6-hydroxy-2 -A naphthyl (meth) acrylate compound is collectively called a monohydroxy-2-naphthyl (meth) acrylate compound.

(Compound)
Hereinafter, the present invention will be described in detail. The present invention is a monohydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

In the general formula (1), the alkyl group having 1 to 8 carbon atoms represented by ^{R 2,} a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, n- pentyl group , N-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

When the hydroxyl group in the general formula (1) is at the 3-position of the naphthalene ring, a 3-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (2) of the present invention is obtained.

In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

When the hydroxyl group in the general formula (1) is at the 7-position of the naphthalene ring, a 7-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (3) of the present invention is obtained.

In the general formula (3), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

When the hydroxyl group in the general formula (1) is at the 5-position of the naphthalene ring, a 5-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (4) of the present invention is obtained.

In the general formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

When the hydroxyl group in the general formula (1) is at the 6-position of the naphthalene ring, a 6-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (5) of the present invention is obtained.

In the general formula (5), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. Also good.

Examples of the 3-hydroxy-2-naphthyl (meth) acrylate compound represented by the general formula (2) include the following. That is, 3-hydroxy-2-naphthyl acrylate, 3-hydroxy-2-naphthyl methacrylate, 1-methyl-3-hydroxy-2-naphthyl acrylate, 1-methyl-3-hydroxy-2-naphthyl methacrylate, 4-methyl- 3-hydroxy-2-naphthyl acrylate, 4-methyl-3-hydroxy-2-naphthyl methacrylate, 5-methyl-3-hydroxy-2-naphthyl acrylate, 5-methyl-3-hydroxy-2-naphthyl methacrylate, 6- Methyl-3-hydroxy-2-naphthyl acrylate, 6-methyl-3-hydroxy-2-naphthyl methacrylate, 7-methyl-3-hydroxy-2-naphthyl acrylate, 7-methyl-3-hydroxy-2-naphthyl methacrylate, 8-methyl-3-hydride Xyl-2-naphthyl acrylate, 8-methyl-3-hydroxy-2-naphthyl methacrylate, 6,7-dimethyl-3-hydroxy-2-naphthyl acrylate, 6,7-dimethyl-3-hydroxy-2-naphthyl methacrylate, 5,8-dimethyl-3-hydroxy-2-naphthyl acrylate, 5,8-dimethyl-3-hydroxy-2-naphthyl acrylate, 1-ethyl-3-hydroxy-2-naphthyl acrylate, 1-ethyl-3-hydroxy 2-naphthyl methacrylate, 4-ethyl-3-hydroxy-2-naphthyl acrylate, 4-ethyl-3-hydroxy-2-naphthyl methacrylate, 5-ethyl-3-hydroxy-2-naphthyl acrylate, 5-ethyl-3 -Hydroxy-2-naphthyl methacrylate, 6- Til-3-hydroxy-2-naphthyl acrylate, 6-ethyl-3-hydroxy-2-naphthyl methacrylate, 7-ethyl-3-hydroxy-2-naphthyl acrylate, 7-ethyl-3-hydroxy-2-naphthyl methacrylate, 8-ethyl-3-hydroxy-2-naphthyl acrylate, 8-ethyl-3-hydroxy-2-naphthyl methacrylate, 6,7-diethyl-3-hydroxy-2-naphthyl acrylate, 6,7-diethyl-3-hydroxy Examples include 2-naphthyl methacrylate, 5,8-diethyl-3-hydroxy-2-naphthyl acrylate, and 5,8-diethyl-3-hydroxy-2-naphthyl methacrylate.

Moreover, as a 7-hydroxy-2- naphthyl (meth) acrylate compound represented by the said General formula (3), the following are mentioned, for example. 7-hydroxy-2-naphthyl acrylate, 7-hydroxy-2-naphthyl methacrylate, 1-methyl-7-hydroxy-2-naphthyl acrylate, 1-methyl-7-hydroxy-2-naphthyl methacrylate, 4-methyl- 7-hydroxy-2-naphthyl acrylate, 4-methyl-7-hydroxy-2-naphthyl methacrylate, 5-methyl-7-hydroxy-2-naphthyl acrylate, 5-methyl-7-hydroxy-2-naphthyl methacrylate, 6- Methyl-7-hydroxy-2-naphthyl acrylate, 6-methyl-7-hydroxy-2-naphthyl methacrylate, 8-methyl-7-hydroxy-2-naphthyl acrylate, 8-methyl-7-hydroxy-2-naphthyl methacrylate, 5,8-dimethyl-7 Hydroxy-2-naphthyl acrylate, 5,8-dimethyl-7-hydroxy-2-naphthyl acrylate, 1-ethyl-7-hydroxy-2-naphthyl acrylate, 1-ethyl-7-hydroxy-2-naphthyl methacrylate, 4- Ethyl-7-hydroxy-2-naphthyl acrylate, 4-ethyl-7-hydroxy-2-naphthyl methacrylate, 5-ethyl-7-hydroxy-2-naphthyl acrylate, 5-ethyl-7-hydroxy-2-naphthyl methacrylate, 6-ethyl-7-hydroxy-2-naphthyl acrylate, 6-ethyl-7-hydroxy-2-naphthyl methacrylate, 8-ethyl-7-hydroxy-2-naphthyl acrylate, 8-ethyl-7-hydroxy-2-naphthyl Methacrylate, 5,8-diethyl 7-hydroxy-2-naphthyl acrylate, 5,8-diethyl-7-hydroxy-2-naphthyl methacrylate, and the like.

Examples of the 5-hydroxy-2-naphthyl (meth) acrylate compound represented by the general formula (4) include the following. That is, 5-hydroxy-2-naphthyl acrylate, 5-hydroxy-2-naphthyl methacrylate, 1-methyl-5-hydroxy-2-naphthyl acrylate, 1-methyl-5-hydroxy-2-naphthyl methacrylate, 4-methyl- 5-hydroxy-2-naphthyl acrylate, 4-methyl-5-hydroxy-2-naphthyl methacrylate, 7-methyl-5-hydroxy-2-naphthyl acrylate, 7-methyl-5-hydroxy-2-naphthyl methacrylate, 6- Methyl-5-hydroxy-2-naphthyl acrylate, 6-methyl-5-hydroxy-2-naphthyl methacrylate, 8-methyl-5-hydroxy-2-naphthyl acrylate, 8-methyl-5-hydroxy-2-naphthyl methacrylate, 7,8-dimethyl-5 Hydroxy-2-naphthyl acrylate, 7,8-dimethyl-5-hydroxy-2-naphthyl acrylate, 1-ethyl-5-hydroxy-2-naphthyl acrylate, 1-ethyl-5-hydroxy-2-naphthyl methacrylate, 4- Ethyl-5-hydroxy-2-naphthyl acrylate, 4-ethyl-5-hydroxy-2-naphthyl methacrylate, 7-ethyl-5-hydroxy-2-naphthyl acrylate, 7-ethyl-5-hydroxy-2-naphthyl methacrylate, 6-ethyl-5-hydroxy-2-naphthyl acrylate, 6-ethyl-5-hydroxy-2-naphthyl methacrylate, 8-ethyl-5-hydroxy-2-naphthyl acrylate, 8-ethyl-5-hydroxy-2-naphthyl Methacrylate, 7,8-diethyl 5-hydroxy-2-naphthyl acrylate, 7,8-diethyl-5-hydroxy-2-naphthyl methacrylate, and the like.

Examples of the 6-hydroxy-2-naphthyl (meth) acrylate compound represented by the general formula (5) include the following. That is, 6-hydroxy-2-naphthyl acrylate, 6-hydroxy-2-naphthyl methacrylate, 1-methyl-6-hydroxy-2-naphthyl acrylate, 1-methyl-6-hydroxy-2-naphthyl methacrylate, 4-methyl- 6-hydroxy-2-naphthyl acrylate, 4-methyl-6-hydroxy-2-naphthyl methacrylate, 7-methyl-6-hydroxy-2-naphthyl acrylate, 7-methyl-6-hydroxy-2-naphthyl methacrylate, 5- Methyl-6-hydroxy-2-naphthyl acrylate, 5-methyl-6-hydroxy-2-naphthyl methacrylate, 8-methyl-6-hydroxy-2-naphthyl acrylate, 8-methyl-6-hydroxy-2-naphthyl methacrylate, 7,8-dimethyl-6 Hydroxy-2-naphthyl acrylate, 7,8-dimethyl-6-hydroxy-2-naphthyl acrylate, 1-ethyl-6-hydroxy-2-naphthyl acrylate, 1-ethyl-6-hydroxy-2-naphthyl methacrylate, 4- Ethyl-6-hydroxy-2-naphthyl acrylate, 4-ethyl-6-hydroxy-2-naphthyl methacrylate, 7-ethyl-6-hydroxy-2-naphthyl acrylate, 7-ethyl-6-hydroxy-2-naphthyl methacrylate, 5-ethyl-6-hydroxy-2-naphthyl acrylate, 5-ethyl-6-hydroxy-2-naphthyl methacrylate, 8-ethyl-6-hydroxy-2-naphthyl acrylate, 8-ethyl-6-hydroxy-2-naphthyl Methacrylate, 7,8-diethyl 6-hydroxy-2-naphthyl acrylate, 7,8-diethyl-6-hydroxy-2-naphthyl methacrylate, and the like.

Among these monohydroxy-2-naphthyl (meth) acrylate compounds, particularly high refractive index can be obtained, so that 3-hydroxy-2-naphthyl acrylate, 7-hydroxy-2-naphthyl acrylate, 5-hydroxy-2- Naphthyl methacrylate and the like are preferable.

(Production method)
Next, the manufacturing method of the monohydroxy-2-naphthyl (meth) acrylate compound of this invention is demonstrated. The monohydroxy-2-naphthyl (meth) acrylate compound of the present invention uses a dihydroxynaphthalene compound as a raw material, which is reacted with a halogenated (meth) acryloyl compound to give a monohydroxy-2-naphthyl (meth) acrylate compound. Can be obtained.

The method for producing a monohydroxy-2-naphthyl (meth) acrylate compound according to the present invention comprises reacting a dihydroxynaphthalene compound with a halogenated (meth) acryloyl compound in the presence of a basic compound as shown in the following (Reaction Formula 1). By making it.

In the above (Scheme 1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴ represents a chlorine atom or a bromine atom, and there are a plurality of them. R ² may be the same as or different from each other.

In the above (Reaction Formula 1), as the dihydroxynaphthalene compound used as a raw material, in the case of 2,3-hydroxynaphthalene compounds having hydroxyl groups at the 2-position and 3-position, 2,3-dihydroxynaphthalene, 1-methyl-2, 3-dihydroxynaphthalene, 4-methyl-2,3-dihydroxynaphthalene, 5-methyl-2,3-dihydroxynaphthalene, 6-methyl-2,3-dihydroxynaphthalene, 7-methyl-2,3-dihydroxynaphthalene, 8 -Methyl-2,3-dihydroxynaphthalene, 6,7-dimethyl-2,3-dihydroxynaphthalene, 5,8-dimethyl-2,3-dihydroxynaphthalene, 1-ethyl-2,3-dihydroxynaphthalene, 4-ethyl -2,3-dihydroxynaphthalene, 5-ethyl-2,3-dihydroxy Phthalene, 6-ethyl-2,3-dihydroxynaphthalene, 7-ethyl-2,3-dihydroxynaphthalene, 8-ethyl-2,3-dihydroxynaphthalene, 6,7-diethyl-2,3-dihydroxynaphthalene, 5, Examples include 8-diethyl-2,3-dihydroxynaphthalene.

As the dihydroxynaphthalene compound used as a raw material, in the case of 2,7-hydroxynaphthalene compounds having hydroxyl groups at the 2nd and 7th positions, 2,7-dihydroxynaphthalene, 1-methyl-2,7-dihydroxynaphthalene, 4-methyl -2,7-dihydroxynaphthalene, 5-methyl-2,7-dihydroxynaphthalene, 6-methyl-2,7-dihydroxynaphthalene, 3-methyl-2,7-dihydroxynaphthalene, 8-methyl-2,7-dihydroxy Naphthalene, 3,6-dimethyl-2,7-dihydroxynaphthalene, 5,8-dimethyl-2,7-dihydroxynaphthalene, 1-ethyl-2,7-dihydroxynaphthalene, 4-ethyl-2,7-dihydroxynaphthalene, 5-ethyl-2,7-dihydroxynaphthalene, 6-ethyl-2 7-dihydroxynaphthalene, 3-ethyl-2,7-dihydroxynaphthalene, 8-ethyl-2,7-dihydroxynaphthalene, 3,6-diethyl-2,7-dihydroxynaphthalene, 5,8-diethyl-2,7- And dihydroxynaphthalene.

As a dihydroxynaphthalene compound used as a raw material, in the case of a 2,5-hydroxynaphthalene compound having hydroxyl groups at the 2-position and 5-position, 2,5-dihydroxynaphthalene, 1-methyl-2,5-dihydroxynaphthalene, 4-methyl -2,5-dihydroxynaphthalene, 7-methyl-2,5-dihydroxynaphthalene, 6-methyl-2,5-dihydroxynaphthalene, 3-methyl-2,5-dihydroxynaphthalene, 8-methyl-2,5-dihydroxy Naphthalene, 3,6-dimethyl-2,5-dihydroxynaphthalene, 7,8-dimethyl-2,5-dihydroxynaphthalene, 1-ethyl-2,5-dihydroxynaphthalene, 4-ethyl-2,5-dihydroxynaphthalene, 7-ethyl-2,5-dihydroxynaphthalene, 6-ethyl-2 5-dihydroxynaphthalene, 3-ethyl-2,5-dihydroxynaphthalene, 8-ethyl-2,5-dihydroxynaphthalene, 3,6-diethyl-2,5-dihydroxynaphthalene, 7,8-diethyl-2,5- And dihydroxynaphthalene.

The dihydroxynaphthalene compound used as a raw material is 2,6-dihydroxynaphthalene, 1-methyl-2,6-dihydroxynaphthalene, 4-methyl in the case of 2,6-hydroxynaphthalene compounds having hydroxyl groups at the 2nd and 6th positions. -2,6-dihydroxynaphthalene, 7-methyl-2,6-dihydroxynaphthalene, 5-methyl-2,6-dihydroxynaphthalene, 3-methyl-2,6-dihydroxynaphthalene, 8-methyl-2,6-dihydroxy Naphthalene, 3,5-dimethyl-2,6-dihydroxynaphthalene, 7,8-dimethyl-2,6-dihydroxynaphthalene, 1-ethyl-2,6-dihydroxynaphthalene, 4-ethyl-2,6-dihydroxynaphthalene, 7-ethyl-2,6-dihydroxynaphthalene, 5-ethyl-2 6-dihydroxynaphthalene, 3-ethyl-2,6-dihydroxynaphthalene, 8-ethyl-2,6-dihydroxynaphthalene, 3,5-diethyl-2,6-dihydroxynaphthalene, 7,8-diethyl-2,6- And dihydroxynaphthalene.

Examples of the halogenated (meth) acryloyl compound used as a raw material in (Reaction Scheme 1) include acryloyl chloride, methacryloyl chloride, acryloyl bromide, and methacryloyl bromide.

In (Reaction Formula 1), as the basic compound to be used, inorganic bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; organic amine compounds such as trimethylamine, triethylamine, piperidine, and pyridine are used.

The usage-amount of a basic compound is 1.0 mol times or more and 1.5 mol times or less with respect to 1 mol of dihydroxy naphthalene compounds, More preferably, they are 1.1 mol times or more and 1.3 mol times or less. When the amount is less than 1.0 mol, the raw material dihydroxynaphthalene compound remains unreacted, and when it is used more than 1.5 mol, a by-product is produced as a by-product, and the purity of the target product is lowered. .

The amount of the halogenated (meth) acryloyl compound used is 1.0 mol times or more and 2.0 mol times or less, more preferably 1.1 mol times or more, 1.5 mol times based on 1 mol of the dihydroxynaphthalene compound as a raw material. It is less than mol times. If the amount is less than 1.0 mol, the amount of unreacted hydroxynaphthalene increases and treatment such as raw material recovery may be required.

As the solvent to be used, it is preferable to use a non-aqueous solvent that does not react with the halogenated (meth) acryloyl compound. Commonly used solvents are aromatic solvents such as toluene and xylene, and halogen solvents such as methylene chloride and dichloroethylene.

The reaction temperature is usually preferably from room temperature to 80 ° C. Since precipitation occurs as the reaction proceeds, a monohydroxy-2-naphthyl (meth) acrylate compound compound can be obtained by filtration and drying. If necessary, it can be recrystallized and purified.

(Polymerizable composition)
The monohydroxy-2-naphthyl (meth) acrylate compound of the present invention can be made into a polymerizable composition by containing a thermal polymerization initiator and / or a photopolymerization initiator. At this time, a copolymerizable monomer having an ethylenically unsaturated double bond (however, 3-hydroxy-2-naphthyl (meth) acrylate compound, 5-hydroxy-2-naphthyl (meth) acrylate compound, 7-hydroxy) 2-naphthyl (meth) acrylate compound and 6-hydroxy-2-naphthyl (meth) acrylate compound are excluded. A polymerizable composition containing a monohydroxy-2-naphthyl (meth) acrylate compound and a thermal polymerization initiator and / or a photopolymerization initiator, or a copolymerizable monomer having an ethylenically unsaturated double bond (however, 3-hydroxy-2-naphthyl (meth) acrylate compound, 5-hydroxy-2-naphthyl (meth) acrylate compound, 7-hydroxy-2-naphthyl (meth) acrylate compound and 6-hydroxy-2-naphthyl (meth) The polymerizable composition containing acrylate compound can be polymerized by heat or light. The resulting polymer is useful as a high refractive index material.

Copolymerizable monomer having an ethylenically unsaturated double bond (however, 3-hydroxy-2-naphthyl (meth) acrylate compound, 5-hydroxy-2-naphthyl (meth) acrylate compound, 7-hydroxy-2- Examples of naphthyl (meth) acrylate compounds and 6-hydroxy-2-naphthyl (meth) acrylate compounds) include side chain alkyl-substituted styrenes such as styrene and 瘁 | methylstyrene; and nuclear alkyl-substituted styrenes such as vinyltoluene. And halogenated styrene such as bromostyrene and chlorostyrene; divinylbenzene, vinylnaphthalene and the like. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile, and 瘁 | chloroacrylonitrile. (Meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate Cyclohexyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, and the like. The polyfunctional acrylate for coating includes trimethylolpropane triacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, epoxy acrylate , Urethane acrylate, polyester acrylate, polybutadiene acrylate, polyol acrylate, polyether acrylate, and the like.

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

Examples of the photopolymerization 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 oxide , 2-isopropylthioxanthone, 2-t-butylanthraquinone and the like. As industrial products that can be actually obtained, Irgacure 651 (“Irgacure” is a registered trademark of BSF, the same shall apply hereinafter), Irgacure 184, Darocur 1173 (“Darocur” is BAS Registered trademark of F Corporation, the same shall apply hereinafter), Irgacure 907, Irgacure 369, Darocur TPO, Irgacure 819 and the like.

The monohydroxy-2-naphthyl (meth) acrylate compound of the present invention and a copolymerizable monomer having an ethylenically unsaturated double bond (however, 3-hydroxy-2-naphthyl (meth) acrylate compound, 5-hydroxy- The composition ratio of 2-naphthyl (meth) acrylate compound, 7-hydroxy-2-naphthyl (meth) acrylate compound and 6-hydroxy-2-naphthyl (meth) acrylate compound) is from 100: 1 by weight. The ratio can be freely selected up to 1: 100, preferably 5: 1 to 1: 5, more preferably 2: 1 to 1: 4. Copolymerizable monomer having an ethylenically unsaturated double bond (however, 3-hydroxy-2-naphthyl (meth) acrylate compound, 5-hydroxy-2-naphthyl (meth) acrylate compound, 7-hydroxy-2- When the composition ratio of the naphthyl (meth) acrylate compound and 6-hydroxy-2-naphthyl (meth) acrylate compound is more than 4 times by weight with respect to the monohydroxy-2-naphthyl (meth) acrylate compound, The resulting polymer does not have a sufficiently high refractive index, while the monohydroxy-2-naphthyl (meth) acrylate compound is a monomer having an ethylenically unsaturated double bond (provided that 3-hydroxy- 2-naphthyl (meth) acrylate compound, 5-hydroxy-2-naphthyl (meth) acrylate compound, 7- If the weight ratio is more than twice that of loxy-2-naphthyl (meth) acrylate compound and 6-hydroxy-2-naphthyl (meth) acrylate compound), the coating property of the polymerizable composition is deteriorated, which is not preferable. .

The amount of polymerization initiator used is a monohydroxy-2-naphthyl (meth) acrylate compound and a copolymerizable monomer having an ethylenically unsaturated double bond (however, 3-hydroxy-2-naphthyl (meth) acrylate compound) , 5-hydroxy-2-naphthyl (meth) acrylate compound, 7-hydroxy-2-naphthyl (meth) acrylate compound and 6-hydroxy-2-naphthyl (meth) acrylate compound. Usually, it is 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight. If the amount of the polymerization initiator used is less than 0.1 parts by weight, it takes a long time for the polymerization reaction, and even if it is used in excess of 5 parts by weight, a large amount of the polymerization initiator remains in the produced polymer, resulting in physical properties. Unfavorable because it adversely affects.

The polymerization can be performed in the form of a film or in the form of a lump. In the case where the film is cured in the form of a film, for example, a photocurable composition is applied to a glass substrate using a bar coater and then irradiated with light. Examples of the lamp to be used include a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a xenon lamp, an ultraviolet LED, a blue LED, a white LED, an H bulb, a D bulb, and a V bulb manufactured by Fusion. The use of sunlight is also possible.

The light irradiation is desirably performed in the absence of oxygen. In the presence of oxygen, the surface of the film is hardly sticky due to oxygen inhibition, and it is necessary to increase the amount of polymerization initiator added. Examples of the curing method in the absence of oxygen include performing in an atmosphere such as nitrogen gas or helium gas. A method of photocuring with an oxygen-impermeable film is also effective. The film thus obtained exhibits a high refractive index.

The present invention is illustrated by the following examples which are not intended to limit the scope of the invention. Unless otherwise specified, all parts are parts by weight. The product was confirmed based on the measurement by the following equipment.

(1) Melting point: Melting point measuring device manufactured by Gelen Camp, model MFB-595 (conforms to JIS K0064)
(2) Infrared (IR) spectrophotometer: Model IR-810 manufactured by JASCO Corporation
(3) Nuclear magnetic resonance apparatus (NMR): manufactured by JEOL Ltd., model GSX FT NMR Spectrometer

(Synthesis Example 1) Synthesis of 3-hydroxy-2-naphthyl acrylate 1.60 g (10 mmol) of 2,3-dihydroxynaphthalene was well dispersed in 18 g of degassed water in a 100 ml three-necked flask equipped with a stirrer. Then, under a nitrogen atmosphere, a solution of 0.48 g (12 mmol) of sodium hydroxide in 2 g of water was added. 2,3-dihydroxynaphthalene quickly dissolved and became a colorless aqueous solution. Next, a 3.5 g toluene solution of 1.35 g (15 mmol) acryloyl chloride was added to the resulting aqueous solution. A white precipitate immediately formed. After stirring at room temperature for 20 minutes, the slurry was filtered with suction, washed with water, and further washed with toluene. The obtained powder was dried to obtain 1.53 g (7.1 mmol) of white powder of 3-hydroxy-2-naphthyl acrylate. The isolation yield with respect to the raw material 2,3-dihydroxynaphthalene was 71 mol%.

(1) Melting point: 144-145 ° C
(2) IR (KBr, cm ⁻¹ ): 3500, 3400, 3028, 1732, 1638, 1603, 1535, 1485, 1408, 1360, 1280, 1260, 1158, 1102, 1022, 986, 872, 810, 752, 604, 583, 486 cm ⁻¹ .
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 5.57 (s, 1H), 6.11 (d, J = 8 Hz, 1H), 6.42 (dd, J1 = 17 Hz, J2 = 8 Hz, 1H), 6.70 (d, J = 17 Hz, 1H), 7.19 (s, 1H), 7.28-7.40 (m, 2H), 7.63 (s, 1H), 7.65 (D, J = 7 Hz, 1H), 7.71 (d, J = 7 Hz, 1H).

(Comparative Comparative Example 1) 2-Naphthyl Acrylate Synthesis Thermometer A 100 ml three-necked flask equipped with a stirrer was charged with 1.44 g (10 mmol) of 2-hydroxynaphthalene and 1.08 g (12 mmol) of acryloyl chloride in 7 g of acetone. Then, a solution of 1.2 g (12 mmol) of triethylamine in 2 g of acetone was added at room temperature under a nitrogen atmosphere. A white precipitate immediately formed and was stirred at room temperature for 30 minutes. 6 g of water was added to dissolve the precipitate, the upper oil was dissolved in toluene, methanol was added, and the mixture was concentrated. Light brown crystals were precipitated, and suction filtration and drying were performed to obtain 1.32 g (6.6 mmol) of 2-naphthyl acrylate light brown crystals. The isolation yield with respect to the raw material 2-hydroxynaphthalene was 61 mol%.

(1) Melting point: 42-43 ° C
(2) IR (KBr, cm ⁻¹ ): 3050, 3020, 1733, 1623, 1598, 1508, 1398, 1254, 1237, 1207, 1155, 960, 847, 812, 755, 480, 471 cm ⁻¹ .
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 6.04 (d, J = 8 Hz, 1H), 6.40 (dd, J1 = 17 Hz, J2 = 8 Hz, 1H), 6.68 (d, J = 8 Hz, 1H), 7.27 (d, J = 7 Hz, 1H), 7.46-7.52 (m, 2H), 7.62 (s, 1H), 7.79-7.89 ( m, 2H), 7.90 (d, J = 7 Hz, 1H).

(Synthesis Example 2) Synthesis of 3-hydroxy-2-naphthyl methacrylate Thermometer, 1.60 g (10 mmol) of 2,3-dihydroxynaphthalene was well dispersed in 16 g of degassed water in a 100 ml three-necked flask equipped with a stirrer. Then, under a nitrogen atmosphere, a solution of 0.48 g (12 mmol) of sodium hydroxide in 2 g of water was added. 2,3-dihydroxynaphthalene dissolves quickly and becomes a colorless aqueous solution. Next, a solution of 1.56 g (15 mmol) of methacryloyl chloride in 5 g of toluene was added to the obtained aqueous solution. A white precipitate formed after a while. After stirring at room temperature for 20 minutes, the slurry was filtered with suction, washed with water, and further washed with toluene. The obtained powder was dried to obtain 1.18 g (5.5 mmol) of white powder of 3-hydroxy-2-naphthyl methacrylate. The isolation yield with respect to the raw material 2,3-dihydroxynaphthalene was 55 mol%.

(1) Melting point: 173-174 ° C
(2) IR (KBr, cm ⁻¹ ): 3390, 3025, 2986, 2973, 1730, 1632, 1530, 1402, 1308, 1253, 1208, 1162, 1096, 952, 902, 860, 750, 482 cm ⁻¹ .
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 2.12 (s, 3H), 5.55 (s, 1H), 5.86 (s, 1H), 6.46 (s, 1H), 7.30 (s, 1H), 7.31-7.41 (m, 2H), 7.61 (s, 1H), 7.65 (d, J = 7 Hz, 1H), 7.72 (d, J = 7 Hz, 1H).

(Synthesis Example 3) Synthesis thermometer of 7-hydroxy-2-naphthyl acrylate, 1.60 g (10 mmol) of 2,7-dihydroxynaphthalene was dispersed in 16 g of degassed water in a 100 ml three-necked flask equipped with a stirrer, Subsequently, 0.48 g (12 mmol) of sodium hydroxide in 2 g of water was added to obtain a light black solution. Next, when 1.35 g (15 mmol) of a toluene solution of acryloyl chloride was added, a light green solid was precipitated. After stirring at room temperature for 30 minutes, the reaction product was filtered with suction, washed with water, and washed with toluene. After drying, 1.41 g (6.6 mmol) of light green powder of 7-hydroxy-2-naphthyl acrylate was obtained. The isolation yield based on 2,7-dihydroxynaphthalene as a raw material was 66 mol%.

(1) Melting point: 135-136 ° C
(2) IR (KBr, cm ⁻¹ ): 3450, 1722, 1624, 1526, 1452, 1404, 1390, 1277, 1265, 1192, 1145, 1026, 968, 918, 840, 808, 604, 480 cm ⁻¹
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 5.16 (s, 1H), 6.05 (d, J = 8 Hz, 1H), 6.38 (dd, J ₁ = 17 Hz, J ₂ = 8 Hz, 1 H), 6.65 (d, J = 17 Hz, 1 H), 7.05 (d, J = 7 Hz, 1 H), 7.07 (s, 1 H), 7.10 (d, J = 7 Hz, 1H), 7.42 (d, J = 7 Hz, 1H), 7.71 (d, J = 7 Hz, 1H), 7.76 (d, J = 7 Hz, 1H).

(Synthesis Example 4) Synthesis thermometer of 7-hydroxy-2-naphthyl methacrylate, 1.60 g (10 mmol) of 2,7-dihydroxynaphthalene was dispersed in 16 g of degassed water in a 100 ml three-necked flask equipped with a stirrer, Subsequently, 0.48 g (12 mmol) of sodium hydroxide in 3 g of water was added to obtain a light black solution. Next, 1.46 g (14 mmol) of a toluene solution of methacryloyl chloride was added to precipitate a gray solid. After stirring at room temperature for 30 minutes, the reaction product was filtered with suction, washed with water, and washed with toluene. After drying, 1.89 g (8.3 mmol) of mauve powder of 7-hydroxy-2-naphthyl methacrylate was obtained. The isolation yield with respect to the raw material 2,7-dihydroxynaphthalene was 83 mol%.

(1) Melting point: 177-178 ° C
(2) IR (KBr, cm ⁻¹ ): 3430, 3028, 2970, 2940, 1728, 1718, 1640, 1612, 1522, 1450, 1390, 1332, 1308, 1220, 1204, 1160, 952, 902, 836 804, 617, 478 cm ⁻¹
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 2.09 (s, 3H), 5.27 (s, 1H), 6.40 (s, 1H), 7.05 (d, J = 7 Hz) , 1H), 7.07 (s, 1H), 7.10 (d, J = 7 Hz, 1H), 7.38 (s, 1H), 7.70 (d, J = 7 Hz, 1H)), 7 .77 (d, J = 7 Hz, 1H).

(Synthesis Example 5) 5-hydroxy-2-naphthyl methacrylate synthesis thermometer, 1.60 g (10 mmol) of 2,5-dihydroxynaphthalene was dispersed in 20 g of deaerated water in a 100 ml three-necked flask equipped with a stirrer. Subsequently, 0.48 g (12 mmol) of sodium hydroxide in 3 g of water was added to give a dark red solution. Next, when 1.56 g (15 mmol) of a toluene solution of methacryloyl chloride was added, a pale purple solid was precipitated. After stirring at room temperature for 30 minutes, the reaction product was filtered with suction, washed with water, and washed with toluene. After drying, 1.00 g (4.4 mmol) of gray powder of 5-hydroxy-2-naphthyl methacrylate was obtained. The isolated yield based on 2,5-dihydroxynaphthalene as a raw material was 44 mol%.

(1) Melting point: 125-127 ° C
(2) IR (KBr, cm ⁻¹ ): 3380, 1710, 1638, 1582, 1463, 1372, 1323, 1300, 1276, 1210, 1160, 1081, 1042, 953, 876, 843, 820, 780, 740, 637,426 cm ⁻¹
(3) ¹ H-NMR (CDCl ₃ , 400 MHz): δ 2.10 (s, 3H), 5.48 (s, 1H), 5.80 (s, 1H), 6.41 (s, 1H), 6.73 (d, J = 7 Hz, 1H), 7.18-7.30 (m, 2H), 7.53 (s, 1H), 8.16 (d, J = 7 Hz, 1H)).

The refractive indexes of the monohydroxy-2-naphthyl (meth) acrylate compound obtained in Synthesis Examples 1 to 5 and the 2-naphthyl acrylate compound obtained in Synthesis Comparative Example 1 were measured. The results are shown in Table 1.

(Evaluation Example 1) Copolymerization of trimethylolpropane triacrylate and 3-hydroxy-2-naphthylacrylate As a copolymerizable monomer having an ethylenically unsaturated double bond, 50 parts of trimethylolpropane triacrylate, As a hydroxy-2-naphthyl (meth) acrylate compound, add 1 part of Irgacure 819 (manufactured by BASF) as a photopolymerization initiator to 50 parts of 3-hydroxy-2-naphthyl acrylate, and heat-melt. Let it be a photopolymerizable composition. This was applied on a polyester film (Toray Co., Ltd. Lumirror, film thickness 100 μm) using a bar coater so as to have a film thickness of 12 μm. Next, an ultraviolet LED (with a central wavelength of light of 395 nm and an irradiation intensity of 3 mw / cm ² ) was irradiated for 30 minutes in a nitrogen atmosphere. As a result of the light irradiation, the polymerizable composition on the film hardened cleanly. The resulting film was streaked with a 1 cm drawing with a knife and covered with adhesive tape from above. Thereafter, the adhesive tape was peeled off, and the adhesion of the film was determined from the number of peeled off strokes. The evaluation results are summarized in Table 2.

(Evaluation Example 2) Copolymerization of trimethylolpropane triacrylate and 7-hydroxy-2-naphthyl acrylate Evaluation was made except that 7-hydroxy-2-naphthyl acrylate was used instead of 3-hydroxy-2-naphthyl acrylate A polymerizable composition was prepared in the same manner as in Example 1, and the polymerizable composition was coated on a polyester film in the same manner, and the polymerizable composition was irradiated with light in the same manner. The film adhesion was evaluated. The evaluation results are summarized in Table 2.

(Evaluation Example 3) Copolymerization of trimethylolpropane triacrylate and 5-hydroxy-2-naphthyl acrylate Evaluation was made except that 5-hydroxy-2-naphthyl acrylate was used instead of 3-hydroxy-2-naphthyl acrylate A polymerizable composition was prepared in the same manner as in Example 1, and the polymerizable composition was coated on a polyester film in the same manner, and the polymerizable composition was irradiated with light in the same manner. The film adhesion was evaluated. The evaluation results are summarized in Table 2.

(Evaluation Comparative Example 1) Copolymerization of trimethylolpropane triacrylate and 2-naphthyl acrylate In the same manner as in Evaluation Example 1, except that 2-naphthyl acrylate is used instead of 3-hydroxy-2-naphthyl acrylate. A polymerizable composition was prepared, the polymerizable composition was coated on a polyester film in the same manner, the polymerizable composition was irradiated with light in the same manner, and the adhesion of the film was evaluated in the same manner. . The evaluation results are summarized in Table 2.

(Evaluation Comparative Example 2) Trimethylolpropane triacrylate homopolymerization Evaluation Example 1 except that trimethylolpropane triacrylate is 100 parts and 3-hydroxy-2-naphthyl 3-hydroxy-2-naphthylacrylate is not used. A polymerizable composition is prepared in the same manner as described above, the polymerizable composition is applied onto a polyester film in the same manner, and the polymerizable composition is irradiated with light in the same manner. Adhesion was evaluated. The evaluation results are summarized in Table 2.

From the evaluation results in Tables 1 and 2, the following is clear. That is, in Table 1, it turns out that the monohydroxy-2- naphthyl (meth) acrylate compound of this invention has a high refractive index compared with well-known 2-naphthyl acrylate. In Table 2, the photopolymerizable composition obtained by using the monohydroxy-2-naphthyl acrylate compound of the present invention is rapidly photopolymerized and cured by light irradiation, and has excellent adhesion to the film. I understand that. Therefore, it can be said that the monohydroxy-2-naphthyl (meth) acrylate compound of the present invention is an industrially useful compound.

Claims (18)

A monohydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (1).

(In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) 3-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (2).

(In the above general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) 7-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (3).

(In the above general formula (3), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² are the same or different from each other. May be.) A 5-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (4).

(In the above general formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) 6-hydroxy-2-naphthyl (meth) acrylate compound represented by the following general formula (5).

(In the above general formula (5), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) A monohydroxy compound represented by the following general formula (1), wherein a dihydroxynaphthalene compound represented by the following general formula (6) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound. A process for producing a 2-naphthyl (meth) acrylate compound.

(In the general formula (6), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same as or different from each other.)

(In the above general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) A 2,3-dihydroxynaphthalene compound represented by the following general formula (7) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound, represented by the following general formula (2) For producing 3-hydroxy-2-naphthyl (meth) acrylate compound.

(In the general formula (7), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same as or different from each other.)

(In the above general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) A 2,7-dihydroxynaphthalene compound represented by the following general formula (8) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound, represented by the following general formula (3) For producing a 7-hydroxy-2-naphthyl (meth) acrylate compound.

(In the general formula (8), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other.)

(In the above general formula (3), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² are the same or different from each other. May be.) The 2,5-dihydroxynaphthalene compound represented by the following general formula (9) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound, and represented by the following general formula (4). For producing a 5-hydroxy-2-naphthyl (meth) acrylate compound.

(In the general formula (9), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same as or different from each other.)

(In the above general formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) A 2,6-dihydroxynaphthalene compound represented by the following general formula (10) is reacted with a halogenated (meth) acryloyl compound in the presence of a basic compound, and represented by the following general formula (5). For producing a 6-hydroxy-2-naphthyl (meth) acrylate compound.

(In the general formula (10), R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same as or different from each other.)

(In the above general formula (5), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a plurality of R ² may be the same or different from each other. May be.) A polymerizable composition comprising the monohydroxy-2-naphthyl (meth) acrylate compound according to claim 1 and a thermal polymerization initiator and / or a photopolymerization initiator. A polymerizable composition comprising the 3-hydroxy-2-naphthyl (meth) acrylate compound according to claim 2 and a thermal polymerization initiator and / or a photopolymerization initiator. A polymerizable composition comprising the 7-hydroxy-2-naphthyl (meth) acrylate compound according to claim 3 and a thermal polymerization initiator and / or a photopolymerization initiator. A polymerizable composition comprising the 5-hydroxy-2-naphthyl (meth) acrylate compound according to claim 4 and a thermal polymerization initiator and / or a photopolymerization initiator. A polymerizable composition comprising the 6-hydroxy-2-naphthyl (meth) acrylate compound according to claim 5 and a thermal polymerization initiator and / or a photopolymerization initiator. The polymerizable composition according to any one of claims 11 to 15, further comprising a copolymerizable monomer having an ethylenically unsaturated double bond (provided that 3-hydroxy-2-naphthyl according to claim 2 ( 6. A (meth) acrylate compound, a 7-hydroxy-2-naphthyl (meth) acrylate compound according to claim 3, a 5-hydroxy-2-naphthyl (meth) acrylate compound according to claim 4, and a 6 according to claim 5. -A polymeric composition characterized by mix | blending a hydroxy-2- naphthyl (meth) acrylate compound. A polymer obtained by thermal polymerization or photopolymerization of the polymerizable composition according to claim 11. A high refractive index material containing the polymer according to claim 17.