JP5204946B2 - Transparent resin composition and use - Google Patents

Description

  The present invention relates to a transparent resin composition containing a metal compound having an organic group containing a sulfur atom in the molecule and a metal atom in the molecule. Furthermore, it is related with the optical member which consists of this transparent resin composition.

  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-linkable 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 used 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 an episulfide group (Patent Documents 1 and 2) and metal-containing compounds such as Se are polymerized. Some proposals have been made such as resins obtained by making them (Patent Documents 3 and 4). Recently, optical resins having various properties necessary for a plastic lens (transparency, thermal properties, mechanical properties, etc.) and a refractive index (nd) exceeding 1.75 and higher refractive index. 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 1.70. It is in providing the transparent resin composition which gives a refractive index, and the optical member which consists of this resin composition.

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 transparent resin composition containing a metal compound having an organic group containing a sulfur atom in the molecule and a metal atom in the molecule.

More specifically,
Metal compound represented by formula (1-a)
(Wherein M represents a Sn, Si or Zr atom),
The above metal compound wherein M is Sn,
-Transparent resin composition containing the said metal compound.
Polymerizable monomer and a transparent resin composition obtained by polymerizing a composition containing the metal compound,
- the composition comprising a polymerizable monomer, after the homogeneous liquid by dissolving the metal compound, a transparent resin composition obtained by carrying out the polymerization,
-The transparent resin composition, wherein the polymerizable monomer comprises a polythiol compound and a poly (thio) isocyanate compound,
An optical material comprising the above transparent resin composition,
About.

  The transparent resin composition of the present invention has high transparency, good heat resistance and mechanical strength, and a high refractive index exceeding a refractive index (nd) of 1.70. It is useful as a resin used for optical members.

Hereinafter, the present invention will be described in detail.
The present invention relates to a transparent resin composition containing a metal compound having an organic group containing a sulfur atom in the molecule and a metal atom in the molecule.

  The transparent resin composition of the present invention is a resin composition containing such a metal compound as an additive in the resin, and has various properties required for transparent resins used for optical members and the like, and is particularly transparent. And high refractive index. The metal compound according to the present invention itself does not have a polymerizable group (for example, OH group, SH group, etc.) and is added to the resin to modify the physical properties of the resin. The effect is expressed.

  The resin used in the transparent resin composition of the present invention includes all known heat or photo-curing or thermoplastic transparent resins.

  Although the transparent resin composition of the present invention will be described in detail later, it is typically produced by the following method. That is, in the case of a thermosetting resin, for example, to the polymerizable composition containing a polymerizable monomer and a polymerization initiator, the metal compound is added and dissolved uniformly, and then the obtained polymerization is performed. For example, by performing cast polymerization, the functional composition can be obtained as a molded article made of the resin composition of the present invention.

  In the case of a thermoplastic resin, the resin composition is generally obtained by adding a desired amount of the metal compound to the resin and then performing operations such as kneading and pelletizing in the same manner as the method for producing a resin composition. It is obtained as a product. Thereafter, the resin composition is injection-molded to obtain a molded product such as an optical member.

Examples of the compound represented by the general formula (1- a ) include the following compounds.

As the metal compound represented by the general formula (1- a) used in the transparent resin composition of the present invention, one kind of the compound may be used alone, or two or more different kinds may be used in combination. There is no problem.

  The resin used in the transparent resin composition of the present invention includes all known transparent resins made of organic polymers such as heat or photo-curing resins or thermoplastic resins.

  The content of the metal compound relative to the total weight of the transparent resin in the transparent resin composition of the present invention is not particularly limited, but is usually 0.01 to 80% by weight, preferably 0.1 to 0.1% by weight. It is 70% by weight, more preferably 1 to 50% by weight or more, and further preferably 3 to 40% by weight.

  In order to further obtain the desired effect of the present invention, the content of the metal compound is particularly preferably 5 to 40% by weight.

  The transparent resin used in the transparent resin composition of the present invention includes heat, photo-curing or thermoplastic transparent resins in general.

  In the transparent resin composition of the present invention, when the transparent resin is a heat (or light) curable resin, for example, the metal compound is added to the polymerizable composition containing a polymerizable monomer and a polymerization initiator. And after making it melt | dissolve uniformly, the obtained polymeric composition is obtained as a molded article which consists of this resin composition by performing cast polymerization with a heat | fever or light.

  The transparent resin is not particularly limited, and a known heat or photocurable resin is used. Specifically, urethane resin, thiourethane resin, epoxy resin, thioepoxy resin, oxetane resin, thietane resin, acrylic resin, (meth) acrylic resin, diethylene glycol bisallyl carbonate resin, polyene / polythiol resin and the like can be mentioned. However, it is not limited to these.

  Considering mechanical properties such as optical properties and impact resistance, which are the desired objects of the present invention, among these transparent resins, urethane resins, thiourethane resins, epoxy resins, thioepoxy resins, and thietane resins are preferable.

  With respect to the casting polymerization method of these heat or photocurable resins, known methods such as JP-A No. 2001-342252, JP-A No. 10-63401, JP-A No. 2003-327583, JP-A No. 2003-2003 are disclosed. This is preferably carried out according to the methods described in Japanese Patent Application Laid-Open No. 160615, Japanese Patent Application Laid-Open No. 1-220349, and the like.

  A resin modifier may be added to the resin composition of the present invention in order to adjust various physical properties. That is, when performing cast polymerization, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an anti-coloring agent, blue, and the like, as long as the effects of the present invention are not impaired. Various substances such as an inking agent, a dye, a flow control agent, a filler, and an internal mold release agent may be added.

In the case of cast polymerization, a known reaction catalyst may be added as necessary for the purpose of adjusting the rate of the polymerization reaction. As such a reaction catalyst,
For example, in the case of (thio) urethanation reaction using a polythiol compound and a poly (thio) isocyanate compound, examples include tin compounds such as dibutyltin dilaurate, dibutyltin dichloride, and dimethyltin dichloride, and amine compounds such as tertiary amines. Is done.
In the case of a polymerization reaction of a thio (epoxy) compound, oxetane compound or thietane compound, an amine compound, a phosphine compound, a Lewis acid compound, a radical polymerization catalyst, a cationic polymerization catalyst and the like are exemplified. In the case of a polymerization reaction between an allyl group-containing compound such as a (meth) acrylic compound or diethylene glycol bisallyl carbonate or a compound having a carbon-carbon double bond in the molecule (polyene compound) and a polythiol compound, a radical polymerization catalyst, photosensitivity Examples are sensitizers and the like.

The production of the resin composition of the present invention is typically performed as follows, for example.
That is, to the above-described polymerizable compound, various additives are added as necessary to the mixed solution prepared by adding the polymerization catalyst and the metal compound according to the present invention, and then dissolved, and according to the present invention. A polymerizable composition containing a metal-containing compound is prepared. It is preferable that the polymerizable composition is sufficiently deaerated by an appropriate method. Furthermore, it is preferable to use it for superposition | polymerization, after removing insoluble matter, a foreign material, etc. by filtration before superposition | polymerization. Thereafter, the polymerizable composition is cast polymerized to produce the transparent resin composition of the present invention or an optical member comprising the transparent resin composition.

  Casting polymerization is carried out by injecting the polymerizable composition 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.

  As above-mentioned, the resinous composition of this invention can superpose | polymerize and manufacture by irradiating active energy rays, such as an electron beam, an ultraviolet-ray, and visible light. In the polymerization, a radical polymerization catalyst or a cationic polymerization catalyst that initiates polymerization by active energy rays 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.

  When the transparent resin is a thermoplastic resin, the transparent resin composition of the present invention is generally kneaded after adding a desired amount of the metal compound to the resin, for example, in the same manner as the method for producing a resin composition. It can be obtained as a resin composition by performing operations such as pelletization. Thereafter, the resin composition is subjected to, for example, injection molding to obtain a molded product such as an optical member.

  Such transparent resins include polycarbonate, polymethyl methacrylate, polycycloolefin, polystyrene, methyl methacrylate / styrene copolymer (MS resin), polymethylpentene, styrene / acrylonitrile copolymer (SAN), polyether sulfone, polysulfone, etc. However, it is not limited to these.

  The transparent resin composition of the present invention may contain an antioxidant for the purpose of improving thermal stability, weather resistance, light resistance and the like. As such an antioxidant, various compounds known as antioxidants are used. For example, phosphorus atom-containing compounds such as phosphate ester compounds and phosphites, phenol-based compounds, hindered phenol-based compounds, sulfur atom-containing compounds A compound or the like is used. One kind of antioxidant may be used alone, or two or more kinds may be used in combination.

  Further, as long as the desired effects of the present invention are not impaired, ultraviolet absorbers, mold release agents (for example, higher fatty acid esters of mono- or polyhydric alcohols), lubricants, flame retardants (for example, organic halogen compounds) In addition, various additives such as a dye, a fluidity improver, and a heat stabilizer (for example, a sulfur atom-containing compound) may be mixed and used.

  The method for producing the transparent resin composition of the present invention is not particularly limited as the method of blending such an antioxidant or additive, and is carried out by various known methods. That is, a metal compound represented by the general formula (1) is added to the resin after the polymerization reaction, and the antioxidant or additive is further added as necessary. Then, various known mixing devices ( For example, a tumbler mixer, a V-type blender, a Nauter mixer, a Henschel mixer, a ribbon blender, a super mixer, etc.) or, as described above, after being dispersed and mixed with various mixers, an extruder, a Banbury mixer, The method of melt-kneading with a roll etc. is mentioned. Also, these methods may be used in combination.

  The transparent resin composition is suitably molded in a molten state by various known molding methods such as injection molding, extrusion molding, blow molding, injection compression molding, and solution casting.

  The molding method for producing the optical member of the present invention is preferably injection molding, injection compression molding or extrusion molding, more preferably injection molding or injection compression molding.

  As the molding conditions for producing the optical member of the present invention, it can be performed under any conditions depending on the type of transparent resin to be used. Usually, the resin temperature is 100 to 400 ° C, and the mold temperature is 0 to 200 ° C. Yes, preferably in the range of a resin temperature of 120 to 350 ° C and a mold temperature of 25 to 200 ° C.

  When the optical member obtained by the above method is, for example, eyesight correction glasses, if necessary, antireflection, imparting high hardness, improving wear resistance, imparting chemical resistance, imparting antifogging or imparting fashionability, etc. In order to improve the above, various known physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, dyeing treatment, and light control treatment (for example, photochromic lens formation treatment) are performed. Can do. Also in the case of other optical members, various known physical or chemical treatments can be performed as necessary.

  The cured resin, transparent resin composition 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). It has a high refractive index exceeding 1.70.

  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.

  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 Formula (1-1) of the Present Invention]
A 300 ml reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was charged with 15.4 g (0.10 mol) of mercaptoethyl sulfide and 50 g of pure water, and 80 g of 10% NaOH aqueous solution (0. 20 mol) was added dropwise over 1 hour. Subsequently, 130.2 g (0.05 mol) of a 10% tin tetrachloride aqueous solution was added dropwise over 3 hours at the same temperature. The product formed as white crystals as the addition proceeded. After completion of dropping, the mixture was further stirred for 4 hours at the same temperature. The produced white crystals were separated by filtration, washed with 200 ml of pure water, and dried at 60 ° C., thereby obtaining 20.8 g of a compound represented by the formula (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.

  Under room temperature (25 ° C.), 7.0 g of the compound represented by the formula (1-1) produced in Example 1 in a glass beaker, 13.4 g of the polythiol represented by the formula (2-1) and m-xylylene diisocyanate 14.6 g was weighed, 0.035 g of dibutyltin dilaurate as a polymerization catalyst and 0.035 g of Zelec UN (manufactured by DuPont) as an internal mold release agent were 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 1.710.

  The molded article comprising the transparent resin composition of the present invention has high transparency, good heat resistance and mechanical strength, and has a high refractive index exceeding 1.70 (refractive index). It is useful as an optical member such as a plastic lens.

Claims (4)

A transparent resin composition for an optical material obtained by polymerizing a composition containing a polymerizable monomer and a metal compound , wherein the metal compound is a metal compound represented by the general formula (1-a) and polymerized A transparent resin composition for an optical material, wherein the polymerizable monomer is a polymerizable monomer that gives a transparent resin selected from urethane resin, thiourethane resin, epoxy resin, thioepoxy resin, and thietane resin by polymerization .
(In the formula, M represents a Sn atom ) A transparent resin composition for optical materials obtained by polymerizing a composition containing a polymerizable monomer after dissolving the metal compound to form a uniform liquid , wherein the metal compound is generally An optical compound which is a metal compound represented by the formula (1-a) and whose polymerizable monomer gives a transparent resin selected from urethane resin, thiourethane resin, epoxy resin, thioepoxy resin, and thietane resin by polymerization. Transparent resin composition for materials .
( Wherein M represents a Sn atom ). Polymerizable monomer, a polythiol compound and a polyiso (thio) cyanate compound is a claim 1 or 2 for optical material transparent resin composition according to. An optical material comprising the transparent resin composition for an optical material according to any one of claims 1 to 3 .