JP2006083313A - Polymerizable compound and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound with high transparency, heat resistance and mechanical strength required for optical materials such as a plastic lens, and a high refractivity over refractive index (nd) of 1.7 that can be used as a raw material of a resin and optical materials prepared from the resin. <P>SOLUTION: The compound has one or more oxetane group in the molecule and one selected from metal elements and preferably shown by general formula (1) (wherein M represents Sn, Si, Zr, Ti or Ge atom, R<SB>1</SB>represents a hydrogen atom or a univalent organic group, R<SB>2</SB>and R<SB>3</SB>represent bivalent organic groups, X<SB>1</SB>and X<SB>2</SB>each independently represents a sulfur atom or an oxygen atom, Y represents an inorganic or organic group, m represents 0 or an integer of 1 or over, n represents an integer of 1 to p, and p represents a valency of a metal atom M). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a compound useful as a raw material monomer for a transparent resin having a very high refractive index, having one or more oxetane groups in the molecule and containing one kind selected from metal atoms About.

  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 has been a demand for an optical resin having various properties necessary for a plastic lens (transparency, thermal properties, mechanical properties, etc.) and having a refractive index (nd) exceeding 1.7. 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

  The 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 very high refractive index (nd) exceeding 1.7. An object of the present invention is to provide a polymerizable compound that gives a refractive index, 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.
That is, the present invention relates to a compound having one or more oxetane groups in the molecule and one kind selected from metal atoms. As a more specific aspect, the present invention relates to the above compound in which the metal atom is a Sn atom, Si atom, Zr atom, Ti atom or Ge atom, and a compound represented by the general formula (1).

（１）

［式中、ＭはＳｎ原子、Ｓｉ原子、Ｚｒ原子、Ｔｉ原子またはＧｅ原子を表し、
Ｒ_１は水素原子または一価の有機基を表し、Ｒ_２およびＲ_３は二価の有機基を表し、
Ｘ_１およびＸ_２は各々独立に硫黄原子または酸素原子を表し、
Ｙは無機または有機残基を表し、
ｍは０または１以上の整数を表し、ｎは１〜ｐの整数を表し、ｐは金属原子Ｍの価数を表す］

(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 a monovalent organic group, R ₂ and R ₃ represent a divalent organic group,
X ₁ and X ₂ 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 the refractive index (nd) 1.7 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 having one or more oxetane groups in the molecule and containing one kind selected from metal atoms. Since the compound of the present invention has a polymerizable oxetane 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. Have.

  In the compound of the present invention, the metal atom is not particularly limited as long as it exhibits a desired effect, but is preferably an Sn atom, Si atom, Zr atom, Ti atom or Ge atom. .

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

（１）

［式中、ＭはＳｎ原子、Ｓｉ原子、Ｚｒ原子、Ｔｉ原子またはＧｅ原子を表し、
Ｒ_１は水素原子または一価の有機基を表し、Ｒ_２およびＲ_３は二価の有機基を表し、
Ｘ_１およびＸ_２は各々独立に硫黄原子または酸素原子を表し、
Ｙは無機または有機残基を表し、
ｍは０または１以上の整数を表し、ｎは１〜ｐの整数を表し、ｐは金属原子Ｍの価数を表す］

(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 a monovalent organic group, R ₂ and R ₃ represent a divalent organic group,
X ₁ and X ₂ 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), X ₁ and X ₂ 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, sulfur atoms are more preferable as X ₁ and X ₂ .

In the general formula (1), R ₁ represents a hydrogen atom or a monovalent organic group.
Such an organic group is a chain aliphatic group, a cycloaliphatic group, an aromatic group or an aromatic-aliphatic group, preferably a chain aliphatic group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. A cyclic aliphatic group, an aromatic group having 5 to 20 carbon atoms, and an aromatic-aliphatic group having 6 to 20 carbon atoms, more preferably a chain aliphatic group having 1 to 4 carbon atoms and a phenyl group. is there.

In the general formula (1), R ₂ and R ₃ each independently represent 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. Examples of such a hetero atom include an oxygen atom or a sulfur atom, but a sulfur atom is preferable in consideration of a desired effect of the present invention.

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, a thiol 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 (3-oxetanylthio) tin,
Tetrakis (3-oxetanylthio) zirconium,
Tetrakis (3-oxetanylthio) silicon,
Tetrakis (3-oxetanylthio) titanium,
Tetrakis (3-oxetanylthio) germanium,
Tetrakis (3-oxetanyloxy) tin,
Tetrakis (3-oxetanyloxy) zirconium,
Tetrakis (3-oxetanyloxy) silicon,
Tetrakis (3-oxetanyloxy) titanium,
Tetrakis (3-oxetanyloxy) germanium,

Tris (3-oxetanylthio) methyltin,
Tris (3-oxetanylthio) butyltin,
Tris (3-oxetanylthio) phenyltin,
Bis (3-oxetanylthio) dimethyltin,
Tetrakis (1-methyl-3-oxetanylthio) tin,
Tetrakis (1-ethyl-3-oxetanylthio) tin,
Tetrakis (1-ethyl-3-oxetanylthio) zirconium,
Tetrakis (1-ethyl-3-oxetanylthio) titanium

Tris (3-oxetanylthio) phenyloxytin,
Tris (3-oxetanylthio) phenylthiotin,
Tris (3-oxetanylthio) phenyloxyzirconium,
Examples include tris (2-oxetanylthio) phenylthiozirconium, but 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, a metal halide represented by the general formula (2-a) and / or (2-b), and the general formula (3). It is manufactured by reaction with the hydroxy compound which has an oxetane group represented by these, or a mercapto compound.

（２−ａ）

(2-a)

（２−ｂ）

（式中、Ｍ、Ｙ、ｎおよびｐは前記に同じであり、Ｚはハロゲン原子を表す）

(2-b)

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

（３）

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｘ_１、Ｘ_２およびｍは前記に同じ）

(3)

(Wherein R ₁ , R ₂ , R ₃ , X ₁ , X ₂ and m are the same as above)

  The compounds represented by the general formula (2-a) or (2-b) are available as industrial raw materials or reagents for some compounds.

  The compound represented by the general formula (3) is available as an industrial raw material or reagent for some compounds, and is produced by deriving from them as a raw material. Typically, for example, Journal of American Chemical Society. 79, 3455 (1957) and the like.

  The reaction may be performed without a solvent, or may be performed in the presence of an aqueous solvent or 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.

The amount of the compound represented by the general formula (2-a) and / or (2-b) and the compound represented by the general formula (3) in the reaction is not particularly limited. The usage-amount of the compound represented by General formula (3) is 0.01-100 mol with respect to 1 mol of compounds represented by Formula (2-a) and / or (2-b).
Preferably, it is 0.1 mol-50 mol, More preferably, it is 0.5 mol-20 mol.

  The reaction may be carried out without a catalyst or may be carried out in the presence of a catalyst, but it is preferable to use a base in order to carry out the reaction efficiently. Examples of such a base include pyridine, triethylamine, dimethylaniline, diethylaniline, 1,8-diazabicyclo [5,4,0] -7-undecene and the like.

  The polymerizable composition of the present invention contains, as a polymerizable compound, the compound of the present invention having one or more oxetane groups in the molecule and containing a metal atom, and a polymerization catalyst. Do it. 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, and various known polymerization catalysts such as a polymerization catalyst used for cationic polymerization of an oxetane compound can be used.

  Examples of the polymerization catalyst include inorganic acids, organic acids and derivatives thereof (salts, esters or acid anhydrides), quaternary ammonium salt compounds, quaternary phosphonium salt compounds, tertiary sulfonium salt compounds, secondary iodonium salts, and the like. Onium salt compounds, Lewis acid compounds, and other cationic polymerization catalysts other than those described above. In addition, radical polymerization catalysts, amine compounds, phosphine compounds, and the like may be used.

  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 is based on 100 parts by weight of all polymerizable compounds contained in the polymerizable composition. 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, and more preferably 0.005 to 3 parts by weight. A plurality of the polymerization catalysts may be used in combination.

  The polymerizable composition of the present invention has one or two or more oxetane groups in the molecule and does not impair the desired effect of the present invention, and other than the compound of the present invention containing a metal atom, You may contain another polymeric compound.

  Examples of the polymerizable compound include various known polymerizable monomers or polymerizable oligomers, and examples thereof include (meth) acrylic acid ester compounds, vinyl compounds, epoxy compounds, episulfide 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.

  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 used, and if desired, the above-mentioned various polymerizable compounds are used in combination, and further, Examples thereof include a method of mixing and dissolving after adding a polymerization catalyst. Furthermore, it is preferable that the polymerizable composition is sufficiently degassed (defoamed) under reduced pressure as necessary and used for polymerization after removing insoluble matters and foreign matters by filtration before polymerization.

  Further, when producing the polymerizable composition, an internal mold release agent, a light stabilizer, an ultraviolet absorber, an antioxidant, a color pigment (for example, cyanine) may be used as long as the effect of the present invention is not impaired. It is possible to add various known additives such as green, cyanine blue, etc.), dyes, flow regulators, fillers and the like.

The resin of the present invention and the optical member comprising the resin are obtained by polymerizing the polymerizable composition. Such a method is preferably carried out by various conventionally known methods used for producing plastic lenses, and typically includes cast polymerization.
That is, the polymerizable composition of the present invention produced by the above-described method, if necessary, after performing a detreatment process or filter filtration under reduced pressure, and then pouring the polymerizable composition into a molding mold, The polymerization is carried out by heating as necessary. In this case, it is preferable to polymerize by gradually heating from a low temperature to a high temperature.

  The mold for molding is composed of, for example, two molds that are mirror-polished through a gasket made of polyethylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, or the like. The mold is typically a combination of glass and glass, and other examples include a mold of a combination of glass and plastic plate, glass and metal plate, but are not limited thereto. The molding mold may be a mold in which two molds are fixed with a tape such as a polyester adhesive tape. As needed, you may perform well-known processing methods, such as a mold release process, with respect to a casting_mold | template.

  When performing cast polymerization, the polymerization temperature is affected by the polymerization conditions such as the type of polymerization initiator and is not limited, but is usually −50 to 200 ° C., preferably −20 to 170 ° C. More preferably, it is 0-150 degreeC.

  The polymerization time is influenced by the polymerization temperature, but is usually 0.01 to 100 hours, preferably 0.05 to 50 hours. Further, if necessary, polymerization can be carried out by combining several temperatures by lowering the temperature, raising the temperature, lowering the temperature, or the like.

  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 this case, a radical polymerization catalyst or a cationic polymerization catalyst that initiates polymerization by active energy rays is used as necessary.

  The obtained optical lens may be annealed as necessary after curing. If necessary, surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, dyeing treatment, dyeing treatment, antireflection, high hardness, wear resistance improvement, antifogging or fashionability. Various known physical or chemical treatments such as light treatment (for example, photochromic lens formation treatment) may be performed.

  Further, the cured resin and the 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 1.75. 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, sealing materials for light emitting diodes (LEDs), optical waveguides, and the like. , Optical adhesives used for bonding optical lenses and optical waveguides, antireflection films used for optical lenses, etc., transparent coatings or transparent substrates used for liquid crystal display members (substrates, light guide plates, films, sheets, etc.) Can be mentioned.

  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]
To a mixture obtained by weighing 39.67 g (0.440 mol) of 3-oxetanethiol and 198 g of pure water, 168 g of 10% aqueous sodium hydroxide solution (corresponding to 0.420 mol of sodium hydroxide) was added at 25 ° C. To prepare sodium thiolate. To this solution, a 10% aqueous solution of tin tetrachloride prepared by dissolving 35.10 g (0.100 mol) of tin tetrachloride pentahydrate in 226 g of water required 4 hours at 30 ° C. And further reacted at the same temperature for 2 hours. After completion of the reaction, the product was extracted with 200 g of chloroform, washed with water, separated and separated, and the solvent was distilled off from the organic layer under reduced pressure at 25 ° C. to obtain a slightly yellow transparent liquid crude product. The obtained crude product was purified by silica gel column chromatography to obtain 33.27 g (yield 70%) of tetrakis (3-oxetanylthio) tin of the following formula (1-1).

（１−１）

(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 according to the following methods.
Appearance: The presence of color, transparency, and optical distortion was confirmed by visual observation and microscopic observation.
-Refractive index: It measured at 20 degreeC using the Purfrich refractometer.

  At room temperature (25 ° C.), 30 g of the compound represented by the formula (1-1) produced in Example 1 was weighed in a glass beaker, and 0.015 g of trifluoromethanesulfonic acid was added as a polymerization catalyst, followed by stirring. And mixed well. The obtained mixed liquid was filtered through a Teflon filter, and then sufficiently deaerated until no foaming was observed under a reduced pressure of 1.3 kPa or less. 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 1.755.

  The resin obtained by polymerizing the polymerizable compound of the present invention has a high refractive index exceeding a refractive index (nd) of 1.7 while having high transparency, good heat resistance and mechanical strength. It is useful as a resin used for optical members such as plastic lenses.

Claims (6)

  A compound having one or more oxetane 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 a monovalent organic group, R ₂ and R ₃ represent a divalent organic group,
X ₁ and X ₂ 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 component made of the resin according to claim 5.