JP2006182910A - Metal-containing (meth)acrylic compound and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound usable as a material for high refractive index resins having >1.6 refractive index (nd), and to provide optical elements comprising the resin. <P>SOLUTION: The compound represented by formula (1), having one or two (meth)acryloyl and containing one selected from metal atoms is provided, and a polymerizable composition containing the compound, resins obtained by polymerizing the polymerizable composition and optical elements comprising the resin are provided. (Wherein, M is Sn, Si, Zr, Ti or Ge; R<SB>1</SB>is H or an alkyl; R<SB>2</SB>and R<SB>3</SB>are each independently a bivalent organic group; X<SB>1</SB>is S, O or NH; X<SB>2</SB>and X<SB>3</SB>are each independently S or O; Y is inorganic or organic residue; m is 0 or an integer of ≥1; n is an integer of 1 to p; and p is the atomic value of the metal atom M). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is useful as a raw material monomer for a transparent resin having a very high refractive index, having one or more (meth) acryloyl groups in the molecule, and a kind selected from metal atoms It relates to the compound to be contained.

  Furthermore, the present invention relates to a polymerizable composition containing the compound, a resin obtained by polymerizing the polymerizable composition, and an optical member made of the resin.

  Inorganic glass is used in a wide range of fields as a transparent material because it is excellent in transparency and has excellent physical properties such as low optical anisotropy. However, there are disadvantages such as being heavy and easily damaged, and having poor productivity when a product is obtained by molding, and transparent organic polymer materials (optical resins) are used as a material to replace inorganic glass. Optical members obtained from such optical resins include, for example, plastic lenses such as eyeglass lenses for correcting vision and lenses for photographing devices such as digital cameras, which have been put into practical use and are widely used. In particular, eyeglass lenses for correcting visual acuity are widely used taking advantage of features such as being lighter and harder to break than inorganic glass lenses, and capable of being dyed and rich in fashion.

  Conventionally, a cross-linked resin (commonly referred to as a DAC resin) obtained by casting polymerization of diethylene glycol bisallyl carbonate under heating has been put to practical use as an optical resin for use in spectacle lenses, and has good transparency and heat resistance. Because of its low chromatic aberration, it has been most frequently used in general-purpose vision correction plastic spectacle lens applications. However, since the refractive index is low (nd = 1.50), the center thickness and peripheral thickness (edge thickness) of the plastic lens are increased, and there are problems such as inferior wearing feeling and fashionability. A resin having a high refractive index that can be used has been demanded and developed.

  In that flow, polythiourethane containing sulfur atoms obtained by cast polymerization of diisocyanate compound and polythiol compound is excellent in transparency and impact resistance, and has a high refractive index (nd = 1.6 to 1.7) and has extremely excellent characteristics such as relatively low chromatic aberration, and has been used in the application of thin, lightweight, high-quality plastic eyeglass lenses for correcting vision.

On the other hand, in the pursuit of optical resins having a higher refractive index, transparent resins obtained by polymerizing compounds having episulfide groups (Patent Document 1, Patent Document 2) and Se-containing compounds such as Se Several proposals have been made on resins obtained by polymerization (Patent Document 3, Patent Document 4). Recently, there is a demand for optical resins having various properties necessary for a plastic lens (transparency, thermal properties, mechanical properties, etc.) and having a refractive index (nd) exceeding 1.6. Is being developed.
Japanese Patent Laid-Open No. 9-110979 JP 11-322930 A Japanese Patent Laid-Open No. 11-140046 JP 2001-296402 A

  An object of the present invention is to provide various properties necessary for an optical member such as a plastic lens (transparency, thermal properties, mechanical properties, etc.) and a high refractive index exceeding a refractive index (nd) of 1.6. It is an object of the present invention to provide a polymerizable compound that provides a resin, a resin obtained by polymerizing the compound, and an optical member made of the resin.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems.

  The present invention contains one or more (meth) acryloyl groups in a molecule useful as a raw material monomer for a transparent resin having a very high refractive index, and contains one kind selected from metal atoms It relates to a compound.

That is, the present invention
The present invention relates to a compound having one or more (meth) acryloyl groups in the molecule and containing one kind selected from metal atoms.
As a more specific embodiment, the metal atom is a Sn atom, a Si atom, a Zr atom, a Ti atom or a Ge atom,
Moreover, it is related with the compound represented by General formula (1).

(1)

[Wherein M represents a Sn atom, a Si atom, a Zr atom, a Ti atom or a Ge atom,
R ₁ represents a hydrogen atom or an alkyl group, R ₂ and R ₃ each independently represent a divalent organic group,
X ₁ represents a sulfur atom, an oxygen atom or a —NH— group, X ₂ and X ₃ each independently represent a sulfur atom or an oxygen atom,
Y represents an inorganic or organic residue,
m represents 0 or an integer of 1 or more, n represents an integer of 1 to p, and p represents the valence of the metal atom M]
Furthermore, the present invention relates to a polymerizable composition containing the compound, a resin obtained by polymerizing the polymerizable composition, and an optical member made of the resin.

  The resin obtained by polymerizing the compound of the present invention has a high refractive index exceeding a refractive index (nd) of 1.6 while having high transparency, good heat resistance and mechanical strength. It is useful as a resin used for optical members such as plastic lenses.

Hereinafter, the present invention will be described in detail.
The compound of the present invention is a compound having a chemical structure characterized by containing one or more (meth) acryloyl groups in the molecule and containing one kind selected from metal atoms.
Since the compound of the present invention has a polymerizable (meth) acryloyl group, it is useful as a polymerizable compound. As described in detail later, the resin obtained by polymerizing the compound is transparent and has a high refractive index. It has the characteristics.

In the compound of the present invention, the metal atom is not particularly limited as long as it exhibits a desired effect. For example, Sn, Si, Zr, Ge, Ti, Zn, Al, Fe, Cu, An atom of Pt, Au or Ag,
Preferably, it is an atom of Sn, Si, Zr, Ti or Ge.

  A preferred embodiment of the compound of the present invention is a compound represented by the general formula (1).

(1)

[Wherein M represents a Sn atom, a Si atom, a Zr atom, a Ti atom or a Ge atom,
R ₁ represents a hydrogen atom or an alkyl group, R ₂ and R ₃ each independently represent a divalent organic group,
X ₁ represents a sulfur atom, an oxygen atom or a —NH— group, X ₂ and X ₃ each independently represent a sulfur atom or an oxygen atom,
Y represents an inorganic or organic residue,
m represents 0 or an integer of 1 or more, n represents an integer of 1 to p, and p represents the valence of the metal atom M]

  In the general formula (1), M represents a Sn atom, a Si atom, a Zr atom, a Ti atom, or a Ge atom.

In the general formula (1), R ₁ represents a hydrogen atom or an alkyl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a cyclohexyl group.
The R group preferably represents a hydrogen atom or a methyl group, and more preferably represents a hydrogen atom.

In the general formula (1), R ₂ and R ₃ each independently represents a divalent organic group.

  Such a divalent organic group is a chain or cyclic aliphatic group, an aromatic group or an aromatic-aliphatic group, preferably a chain aliphatic group having 1 to 20 carbon atoms, They are 20 cyclic aliphatic groups, C5-C20 aromatic groups, and C6-C20 aromatic-aliphatic groups.

  Such a divalent organic group may contain a hetero atom other than a carbon atom and a hydrogen atom in the group. Such heteroatoms include oxygen atoms or sulfur atoms. In view of the desired effect of the present invention, a sulfur atom is preferable.

In the general formula (1), X ₁ represents a sulfur atom, an oxygen atom or a —NH— group.

In the general formula (1), X ₂ and X ₃ each independently represent a sulfur atom or an oxygen atom. In view of the high refractive index which is a desired effect of the present invention, it is more preferable that X ₂ and X ₃ are sulfur atoms.

In the general formula (1), m represents 0 or an integer of 1 or more.
As this m, Preferably, it is an integer of 0-4, More preferably, it is an integer of 0-2, More preferably, it is the integer 0 or 1.

In General formula (1), n represents the integer of 1-p.
Such n is preferably an integer p or p-1, and more preferably an integer p.

  In the general formula (1), p represents the valence of the metal M. That is, for example, when M is a Sn atom or a Ti atom, p = 2 or 4, and preferably represents the integer 4. When M is a Zr atom, Si atom, or Ge atom, p = 4.

In general formula (1), Y represents an inorganic or organic residue.
Examples of the residue include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkyloxy group, an alkylthio group, an aryloxy group, and an arylthio group.

Specific examples of the compound represented by the general formula (1) include:
Tetrakis (2-acryloylthioethylthio) tin,
Tetrakis (2-acryloylthioethylthio) silicon,
Tetrakis (2-acryloylthioethylthio) zirconium,
Tetrakis (2-acryloylthioethylthio) titanium,
Tetrakis (2-acryloylthioethylthio) germanium,

Tetrakis (2-acryloyloxyethylthio) tin,
Tetrakis (2-acryloyloxyethylthio) silicon,
Tetrakis (2-acryloyloxyethylthio) zirconium,
Tetrakis (2-acryloyloxyethylthio) titanium,
Tetrakis (2-acryloyloxyethylthio) germanium,

Tetrakis (2-acryloylaminoethylthio) tin,
Tetrakis (2-acryloylaminoethylthio) silicon,
Tetrakis (2-acryloylaminoethylthio) zirconium,
Tetrakis (2-acryloylaminoethylthio) titanium,
Tetrakis (2-acryloylaminoethylthio) germanium,

Tetrakis (3-acryloyloxypropylthio) tin,
Tetrakis (3-acryloyloxypropylthio) silicon,

Tris (2-acryloylthioethylthio) methyltin,
Tris (2-acryloylthioethylthio) butyltin,
Tris (2-acryloylthioethylthio) phenyltin,
Tris (2-acryloylthioethylthio) methyl silicon,

Tris (2-acryloyloxyethylthio) methyltin,
Tris (2-acryloyloxyethylthio) butyltin,
Tris (2-acryloyloxyethylthio) phenyltin,
Tris (2-acryloyloxyethylthio) methyl silicon,

Tris (2-acryloylaminoethylthio) methyltin,
Tris (2-acryloylaminoethylthio) butyltin,
Tris (2-acryloylaminoethylthio) phenyltin,
Tris (2-acryloylaminoethylthio) methyl silicon,

Bis (2-acryloylthioethylthio) dimethyltin,
Bis (2-acryloylthioethylthio) dimethylsilicon,
Bis (2-acryloyloxyethylthio) dimethylsilicon,
Bis (2-acryloyloxyethylthio) dimethyltin,
Bis (2-acryloylaminoethylthio) dimethylsilicon,

Tetrakis (2-methacryloylthioethylthio) tin,
Tetrakis (2-methacryloylthioethylthio) silicon,
Tetrakis (2-methacryloylthioethylthio) zirconium,
Tetrakis (2-methacryloylthioethylthio) titanium,
Tetrakis (2-methacryloylthioethylthio) germanium,
Tetrakis (2-methacryloyloxyethylthio) tin,
Tetrakis (2-methacryloyloxyethylthio) silicon,
Tetrakis (2-methacryloyloxyethylthio) zirconium,
Tetrakis (2-methacryloyloxyethylthio) titanium,
Tetrakis (2-methacryloyloxyethylthio) germanium,
Tetrakis (2-methacryloylaminoethylthio) tin,
Tetrakis (2-methacryloylaminoethylthio) silicon,
Tetrakis (2-methacryloylaminoethylthio) zirconium,
Tetrakis (2-methacryloylaminoethylthio) titanium,
Tetrakis (2-methacryloylaminoethylthio) germanium,
Tetrakis (3-methacryloyloxypropylthio) tin,
Tetrakis (3-methacryloyloxypropylthio) silicon,

Tris (2-methacryloylthioethylthio) methyltin,
Tris (2-methacryloylthioethylthio) butyltin,
Tris (2-methacryloylthioethylthio) phenyl tin,
Tris (2-methacryloylthioethylthio) methyl silicon,
Tris (2-methacryloyloxyethylthio) methyltin,
Tris (2-methacryloyloxyethylthio) butyltin,
Tris (2-methacryloyloxyethylthio) phenyltin,
Tris (2-methacryloylaminoethylthio) methyl silicon,
Tris (2-methacryloylaminoethylthio) methyltin,
Tris (2-methacryloylaminoethylthio) butyltin,
Tris (2-methacryloylaminoethylthio) phenyltin,
Tris (2-methacryloylaminoethylthio) methyl silicon,

Bis (2-methacryloylthioethylthio) dimethyltin,
Bis (2-methacryloylthioethylthio) dimethylsilicon,
Bis (2-methacryloyloxyethylthio) dimethylsilicon,
Bis (2-methacryloyloxyethylthio) dimethyltin,
Bis (2-methacryloylaminoethylthio) dimethylsilicon,
However, the present invention is not limited to these compounds.

The compound represented by the general formula (1) of the present invention typically includes, for example,
(I) A method of reacting a metal compound represented by the general formula (2) with a compound having a (meth) acryloyl group represented by the general formula (3), or (II) represented by the general formula (2) After obtaining the compound represented by the general formula (5) by the reaction of the metal compound represented by the general formula (4) with the chloropropionic acid compound represented by the general formula (4), the compound is removed by acting with the basic compound. Manufactured by a method of performing hydrogen chloride.

The reaction itself is described, for example, in Journal of Organometallic Chemistry. , 612 (2000) 133-140, Laboratory Chemistry (Edited by Chemical Society of Japan) Vol. 19, 471-482 (1957), Journal of Organic Chemistry., 45 , 5364 (1980), European Polymer Journal. , 19 , 39 (1983), Japanese Patent Application Laid-Open No. 10-67736, and the like.

(2)
(Wherein M, Y, n and p are the same as above, and Z represents a halogen atom.)

(3)

(4)

(5)

(In the above formula, R ₁ , R ₂ , R ₃ , X ₁ , X ₂ , X ₃ , Y, M, m, n, p and q are the same as above)

The compound represented by the general formula (2) is available as an industrial raw material or a reagent.
The compound represented by general formula (3) or general formula (4), which is the other raw material compound, is available as an industrial raw material or reagent for some compounds, or derived from these compounds as raw materials. It is manufactured by doing. Typically, it is produced according to a known method described in, for example, JP-A-10-67736.

  Hereinafter, the reaction between the metal compound represented by the general formula (2) and the compound represented by the general formula (3) or the general formula (4) will be described below.

  The reaction may be performed without a solvent, or may be performed in the presence of an organic solvent inert to the reaction. Such an organic solvent is not particularly limited as long as it is inert to the reaction, such as petroleum ether, hexane, benzene, toluene, xylene, mesitylene and other hydrocarbon solvents, diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, etc. Ether solvents of: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, chlorine-containing solvents such as methylene chloride, chloroform, chlorobenzene, dichlorobenzene, Examples include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, and dimethyl sulfoxide.

  The reaction temperature is not particularly limited, but is usually in the range of -78 ° C to 200 ° C, preferably -78 ° C to 100 ° C.

  The reaction time is affected by the reaction temperature, but is usually from a few minutes to 100 hours.

  Although the usage-amount of the compound represented by General formula (3) or General formula (4) with respect to the compound represented by General formula (2) in reaction is not specifically limited, Usually, General formula (2) The amount of the compound represented by the general formula (3) or the general formula (4) is 0.01 to 100 mol with respect to 1 mol of the compound represented by formula (3).

  Preferably, it is 0.1 mol-50 mol, More preferably, it is 0.5 mol-20 mol.

  Although the reaction may be carried out without a catalyst or in the presence of a catalyst, it is preferable to use a known basic compound in order to carry out the reaction efficiently. The basic compound is not particularly limited, and various known basic compounds are used. Examples of such compounds include organic basic compounds such as pyridine, triethylamine, dimethylaniline, diethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene, or sodium hydroxide, sodium carbonate, carbonate Inorganic basic compounds such as sodium hydrogen, potassium hydroxide, potassium carbonate, ammonia and the like can be mentioned.

  The polymerizable composition of the present invention contains, as a polymerizable compound, the compound of the present invention having one or more (meth) acryloyl groups in the molecule and containing a metal atom, and polymerization. It contains an initiator. In this case, the compound of the present invention represented by the compound represented by the general formula (1) may be used alone or a plurality of different compounds may be used in combination.

  The content of the compound of the present invention in the total weight of the polymerizable compound contained in the polymerizable composition of the present invention is not particularly limited, but is usually 10% by weight or more, preferably 30 % By weight or more, more preferably 50% by weight or more, and still more preferably 70% by weight or more.

  The polymerization catalyst used in the polymerizable composition of the present invention is not particularly limited. For example, a polymerization initiator (for example, thermal polymerization) used for radical polymerization of an ordinary (meth) acrylic acid ester compound. Various known compounds such as initiators and photopolymerization initiators can be used.

Examples of the polymerization initiator include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and tert-butyl peroxypivalate;
Thermal polymerization initiators such as azo compounds such as azobisisobutyronitrile,
Or, carbonyl compounds such as benzophenones and thioxatone, dicarbonyl compounds such as benzyls, inferred furquinone and 2-alkylanthraquinone;
Acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone;
Benzoin ether compounds such as benzoins and benzoin alkyl ethers;
Aryl phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Aminocarbonyl compounds such as 4-dialkylaminobenzoic acid alkyl esters, 4,4′-bisdimethylaminobenzophenone (Michler's ketone), 4,4′-bisdialkylaminobenzophenones;
Photopolymerization initiators such as halogen compounds such as 2,2,2-trichloro-1- (4′-tert-butylphenyl) ethane-1-one and 2,4,6-tris (trichloromethyl) triazine are used. Is done.

  The amount of the polymerization catalyst used is not particularly limited because it is affected by the composition of the polymerizable composition, the polymerization conditions, etc., but it is not limited to 100 parts by weight of all the polymerizable compounds contained in the polymerizable composition. On the other hand, it is 0.0001-10 weight part, Preferably, it is 0.001-5 weight part, More preferably, it is 0.005-3 weight part. A plurality of the polymerization catalysts may be used in combination.

  The polymerizable composition of the present invention is a compound of the present invention having one or more (meth) acryloyl groups in the molecule and containing a metal atom as long as the desired effect of the present invention is not impaired. Other polymerizable compounds other than those (more specifically, other than the compound represented by the general formula (1)) may be contained.

  Examples of the polymerizable compound include various known polymerizable monomers or oligomers. For example, other (meth) acrylic acid ester compounds other than the general formula (1), vinyl compounds, epoxy compounds, thiol compounds, episulfides Examples thereof include compounds, oxetane compounds, and thietane compounds.

  The content of these other polymerizable compounds in the total weight of the polymerizable compounds contained in the polymerizable composition of the present invention is not particularly limited, but is usually 90% by weight or less, preferably 80%. % By weight or less, more preferably 70% by weight or less, and further preferably 50% by weight or less.

  The polymerizable composition of the present invention has the purpose of adjusting various physical properties such as optical properties, impact resistance and specific gravity of the obtained resin, or adjusting the viscosity and handleability of the polymerizable composition. Thus, various resin modifiers may be added.

  Further, when producing the polymerizable composition of the present invention, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent are used as desired within the range not impairing the effects of the present invention. Various substances such as an inhibitor, a color pigment (for example, cyanine green, cyanine blue, etc.), a bluing agent, a dye, a flow control agent, a filler, and an internal release agent may be added.

  As a method for producing the polymerizable composition of the present invention, typically, the compound represented by the general formula (1) of the present invention is weighed, and various polymerizable compounds are used in combination as necessary. Then, after adding a polymerization catalyst and various additives as required to the prepared mixed solution, there may be mentioned a method of mixing and dissolving. The polymerizable composition is preferably sufficiently deaerated by an appropriate method such as under reduced pressure. Furthermore, it is preferable to use it for superposition | polymerization after removing insoluble matter, a foreign material, etc. by filtration before superposition | polymerization.

  The resin of the present invention and the optical member comprising the resin can be obtained by cast polymerization of the polymerizable composition as a representative method.

  That is, it is carried out by injecting the polymerizable composition of the present invention into a molding mold and performing polymerization by heating as necessary. The molding mold is usually composed of two glass plates held by a tape or a gasket.

  The polymerization conditions are not limited because they are affected by the type of polymerizable monomer used, the type and amount of polymerization catalyst, the shape of the molding mold, and the like. Usually, the polymerization temperature is −20 to 200 ° C. Preferably, it is -20-170 degreeC, More preferably, it is 0-150 degreeC. The polymerization time is affected by the polymerization temperature, but is usually 1 to 100 hours. Moreover, it is also possible to perform polymerization by combining several temperatures by raising or lowering the temperature as necessary.

  The polymerizable composition of the present invention can also be polymerized by irradiating an active energy ray such as an electron beam, ultraviolet ray or visible ray. In the polymerization, a radical polymerization catalyst that initiates polymerization by an active energy ray is used as necessary. In the case of photopolymerization, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a tungsten lamp, a fluorescent lamp, or sunlight is used as a light source. An optical member such as a lens obtained by polymerization may be annealed as necessary.

  The obtained optical lens is subjected to surface polishing in order to improve the antireflection, high hardness, wear resistance, chemical resistance, antifogging or fashionability, etc., if necessary, after curing. Various known physical or chemical treatments such as antistatic treatment, hard coat treatment, non-reflective coat treatment, dyeing treatment, and light control treatment (for example, photochromic lens formation treatment) can be applied.

  The cured resin and optical member obtained by polymerizing the polymerizable composition of the present invention have high transparency, good heat resistance and mechanical strength, and have a refractive index (nd) of 1.6. It has a high refractive index exceeding.

Examples of the optical member of the present invention include eyeglass lenses for correcting vision, lenses for imaging devices, Fresnel lenses for liquid crystal projectors, lenticular lenses, contact lenses and other plastic lenses, diffractive optical elements, and light emitting diode (LED) seals. Materials, optical waveguides, optical lenses, optical adhesives used for bonding optical waveguides, antireflection films used for optical lenses, etc., transparent coatings used for liquid crystal display device members (substrates, light guide plates, films, sheets, etc.) or transparent For example, a conductive substrate.
In addition, the polymerizable compound, polymerizable composition or resin of the present invention can be used for applications such as dental materials.

Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited to these examples.
<Production of compound represented by general formula (1) of the present invention>

[Production of Compound Represented by Formula (1-1) of the Present Invention]
β-chloropropionic acid (2-mercaptoethyl ester) 148.40 g (0.880 mol) and 396 g of pure water were weighed, and 352 g of 10% aqueous sodium hydroxide solution (sodium hydroxide 0 Sodium thiolate was prepared at 25 ° C. To this solution, tin tetrachloride aqueous solution prepared by dissolving 70.20 g (0.200 mol) of tin tetrachloride pentahydrate in 452 g of water was appropriately reduced at 30 ° C. for 4 hours. The reaction was further continued at the same temperature for 2 hours.

  After completion of the reaction, the product was extracted with 350 g of chloroform, and the organic layer was washed with water, separated and separated, and the solvent was distilled off from the organic layer under reduced pressure at 25 ° C. 126.28 g of tetrakis (β-chloropropionyloxyethylthio) tin was obtained.

To a solution obtained by dissolving 78.92 g (0.10 mol) of this compound in 100 g of acetone, triethylamine g (0.44 mol) was added dropwise at 5 ° C. over 1 hour. After completion of the dropwise addition, the mixture was further reacted by stirring at 5 ° C. for 2 hours, and then returned to room temperature (25 ° C.) after confirming that no raw material remained by HPLC. To the reaction mixture, 200 g of toluene and 200 g of pure water were added to extract the product. After adding 5% hydrochloric acid to the toluene solution of the organic layer at room temperature, washing with water and separation were repeated until no chlorine ions were detected, and then the solution was separated to take out the organic layer. After adding 62 mg of a polymerization inhibitor 4-methoxyphenol, toluene was distilled off under reduced pressure at 35 ° C. and concentrated to obtain a colorless transparent liquid crude product. The crude product was purified by silica gel column chromatography (developing solvent: toluene) to obtain 57.92 g (0.09 mol) of a compound represented by the formula (1-1) as a colorless transparent liquid.
Yield = 72% (calculated based on tin tetrachloride pentahydrate), purity (HPLC analysis) ≧ 95%

(1-1)

<Preparation of polymerizable composition of the present invention and production of cured resin by polymerization>
The physical properties of the resin or optical component (lens) produced in the examples were evaluated by the following methods.
Appearance: The presence of color, transparency, and optical distortion was confirmed by visual and microscopic observation.
Refractive index: Measured at 20 ° C. using a Purfrich refractometer.

  At room temperature (25 ° C.), 30 g of the compound represented by the formula (1-1) produced in Example 1 was weighed into a glass beaker, and 2-hydroxy-2-methyl-1-phenylpropane- was used as a polymerization initiator. 1-one (Darocur-1173, manufactured by Ciba Specialty Chemicals) 0.015 g was added, and the mixture was stirred and mixed well. The obtained mixed liquid was filtered through a Teflon (registered trademark) filter, and then sufficiently deaerated under a reduced pressure of 1.3 kPa or less until no foaming was observed. After inject | pouring this polymeric composition into the mold which consists of a glass mold and a tape, it put into heating oven and heated up gradually to 30-120 degreeC, and superposed | polymerized for 20 hours.

The obtained resin molded piece had good transparency and good appearance without distortion.
When the refractive index of the obtained resin was measured, the refractive index (nd) was 1.68.

  The resin obtained by polymerizing the polymerizable compound of the present invention has high transparency, good heat resistance and mechanical strength, and also has a high refractive index (nd) of 1.6 or more. It is useful as a resin used for optical members such as plastic lenses.

Claims (6)

  A compound having one or more (meth) acryloyl groups in the molecule and one kind selected from metal atoms.   The compound according to claim 1, wherein the metal atom is a Sn atom, a Si atom, a Zr atom, a Ti atom or a Ge atom. The compound of Claim 1 represented by General formula (1).
(1)

[Wherein M represents a Sn atom, a Si atom, a Zr atom, a Ti atom or a Ge atom,
R ₁ represents a hydrogen atom or an alkyl group, R ₂ and R ₃ each independently represent a divalent organic group,
X ₁ represents a sulfur atom, an oxygen atom or a —NH— group, X ₂ and X ₃ each independently represent a sulfur atom or an oxygen atom,
Y represents an inorganic or organic residue,
m represents 0 or an integer of 1 or more, n represents an integer of 1 to p, and p represents the valence of the metal atom M]   A polymerizable composition comprising the compound according to any one of claims 1 to 3.   A resin obtained by polymerizing the polymerizable composition according to claim 4.   An optical member made of the resin according to claim 5.