JP2000198818A - Optical material and optical product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an optical material having excellent optical characteristics such as high refractive index, low dispersion and excellent transparency and no optical distortion and excellent solvent resistance, impact resistance and weather resistance and an optical product comprising the optical material. SOLUTION: This optical material comprises a polymerized cured material obtained by prereacting a 1,4-dithian dithiol compound of the general formula (n and m are each an integer of 1-3) with a compound containing at least one isocyanate group and at least one (meth)acryloyl group in the molecule to give a polymerizable composition containing a radically polymerizable compound having a thiocarbamate bond and polymerizing the composition. This optical product comprises the optical material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material and an optical product using the same, and more particularly, to a high refractive index,
Optical materials such as low dispersion, excellent transparency, and excellent optical characteristics such as no optical distortion, as well as excellent solvent resistance, impact resistance, and weather resistance, and optical materials such as lenses made of this optical material The present invention relates to optical products such as lenses, prisms, optical fibers, substrates for recording media, filters, and glasses and vases.

[0002]

2. Description of the Related Art Compared with glass, plastics are lightweight, hard to break, and easy to dye, and have recently been used for optical parts such as various lenses. Practical optical plastic materials include polydiethylene glycol bisallyl carbonate (CR-39) and polymethyl methacrylate (PMMA). However,
Since these plastic materials have a refractive index of 1.5 or less, for example, when used as a lens material, as the power becomes stronger, the lens becomes thicker, and not only does the advantage of plastic being lighter is impaired, It was not desirable in terms of aesthetics. In particular, in the case of a concave lens, the thickness around the lens (edge thickness) is increased, and there is a problem that birefringence and chromatic aberration are likely to occur.

[0003] In order to make the thickness of the lens thinner by making use of the characteristics of plastic having a small specific gravity,
A plastic material having a high refractive index has been desired. As a material having such performance, for example, (1) a compound obtained by reacting a polymerizable unsaturated compound having an isocyanate group with a specific thiol compound is 10 to 90% by weight.
(2) a compound containing two or more (meth) acryloyl groups and two or more sulfur atoms in a molecule, a polyfunctional isocyanate compound, and a polyfunctional hydroxy or mercapto compound. Plastic lens containing a reaction product with a compound as a main component (JP-A-8-198)
No. 932) and (3) an optical material comprising an acrylic monomer having a bisphenol A skeleton and a carbonate structure in the molecule (Japanese Patent Application Laid-Open No. 9-208529).

However, the composition of the above (1) contains not only a compound obtained by reacting a polymerizable unsaturated compound having an isocyanate group with a specific thiol compound, but also contains other components. Therefore, the refractive index of the polymer obtained from the composition is greatly reduced by the influence of other components, or by introducing an aromatic ring or a halogen atom to improve the refractive index, the Abbe number or weather resistance is increased. There is a disadvantage that the properties are reduced. Also, as described in JP-A-4-80213, page 8, upper left column, line 13 to upper right column, line 8, there is a problem that synthesis of thiourethane acrylate takes time.

On the other hand, the plastic lens of the above (2) and the optical material of the above (3) have a higher refractive index, but the Abbe number and weather resistance are affected by the influence of the aromatic ring introduced to increase the refractive index. It has disadvantages such as inferiority,
Further, in the plastic lens (2), since different polymerization functional groups are simultaneously reacted, it is difficult to control the polymerization, and there is a problem that striae and optical distortion are likely to occur.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides excellent optical characteristics such as high refractive index, low dispersion, excellent transparency, and no optical distortion. It is an object of the present invention to provide an optical material having good resistance, impact resistance and weather resistance, and an optical product comprising the optical material.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to develop an optical material having the above-mentioned preferable properties, and as a result, have found that a specific polythiol compound and at least one isocyanate group in the molecule have An optical material comprising a cured product obtained by polymerizing a polymerizable composition containing at least a radical polymerizable compound obtained by preliminarily subjecting a compound having at least one (meth) acryloyl group to a urethane reaction, Have been found, and the present invention has been completed based on this finding.

That is, the present invention provides a compound represented by the general formula (I)

Embedded image (Wherein n and m each independently represent an integer of 1 to 3), and at least one isocyanate group and at least one ( An optical material comprising a polymerized cured product obtained by polymerizing a polymerizable composition containing a radical polymerizable compound having a thiocarbamate bond obtained by previously reacting a compound having a (meth) acryloyl group. Provide materials. The present invention also provides an optical product comprising the optical material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The optical material of the present invention comprises a cured polymer obtained by polymerizing a polymer composition containing a radical polymerizable compound having a thiocarbamate bond. The radical polymerizable compound is obtained by reacting a 1,4-dithiandithiol compound with a compound having at least one isocyanate group and at least one (meth) acryloyl group in a molecule. In addition, a (meth) acryloyl group means both an acryloyl group and a methacryloyl group.

A radical polymerizable compound having such a thiocarbamate bond is obtained by converting an alicyclic sulfide derived from a 1,4-dithiandithiol compound, which is one of the raw materials, to
Since the refractive index and the Abbe number are further increased by being included in the basic skeleton, when an optical material is manufactured using this, the refractive index and the Abbe number of the optical material are also increased. Furthermore, by including a thiocarbamate bond,
It is possible to impart excellent mechanical properties, such as high impact resistance, to an optical material manufactured using this. In addition, since it has two radical polymerizable groups and thus has self-crosslinking properties, when an optical material is manufactured using this, even if a crosslinking agent is not added as an auxiliary component, the optical material has high solvent resistance and High heat resistance can be provided.

The 1,4-dithiandithiol compound, which is one of the raw materials for the radically polymerizable compound having a thiocarbamate bond, has a general formula (I)

Embedded image It has a structure represented by This general formula (I)
N and m each represent an integer of 1 to 3,
They may be identical or different.

Examples of such compounds include 2,5-
Bis (mercaptomethyl) -1,4-dithiane, 2,5
-Bis (2-mercaptoethyl) -1,4-dithiane,
2,5-bis (3-mercaptopropyl) -1,4-dithiane, 2- (2-mercaptoethyl) -5-mercaptomethyl-1,4-dithiane, 2- (2-mercaptoethyl) -5- ( Examples thereof include 3-mercaptopropyl) -1,4-dithiane and 2-mercaptomethyl-5- (3-mercaptopropyl) -1,4-dithiane. From the viewpoint of easy availability, 2,5-bis (mercaptomethyl) -1,4-dithiane is preferred.

Examples of the compound having at least one isocyanate group and at least one (meth) acryloyl group in a molecule as another raw material include acryloyl isocyanate, methacryloyl isocyanate,
-Isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 2-isocyanatopropyl acrylate, 2-isocyanatopropyl methacrylate, and the like. Among them, particularly, the performance and availability of the obtained optical material, etc. In view of this, 2-isocyanatoethyl methacrylate is preferred. The number of isocyanate groups and (meth) acryloyl groups may each be two or more.

The radically polymerizable compound having a thiocarbamate bond includes the above 1,4-dithiandithiol compound and a compound having at least one isocyanate group and at least one (meth) acryloyl group in a molecule. Is usually 1.0: 0.-SH group / -NCO group ratio.
It is obtained by performing a urethane reaction at a ratio of 8 to 1.0: 1.2. The reaction method is not particularly limited, and a general urethane reaction method can be used.

In this reaction, a catalyst may be appropriately used, if desired. As this catalyst, an amine compound,
Organic metal compounds and the like are effective. Specifically, triethylenediamine, hexamethylenetetramine, N, N
-Dimethyloctylamine, N, N, N ', N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis (1-methylpiperidine), 1,8-diazabicyclo- (5,4 , 0) -7-undecene, dimethyltin dichloride, dimethyltin bis (isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinolate, dibutyltin bis (dodecyl mercaptide) , Dibutyltin bis (isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin bis (butylmaleate), dioctyltin dilaurate, dioctylus Diricinolate, dioctyltin dioleate, dioctyltin di (6-hydroxy) caproate, dioctyltin bis (isooctylthioglycolate), didodecyltin diricinolate, copper oleate, copper acetylacetonate, iron acetylacetonate, naphthenic acid Examples thereof include iron, iron lactate, iron citrate, iron gluconate, potassium octanoate, and 2-ethylhexyl titanate, and particularly preferably dibutyltin dichloride and dibutyltin dilaurate. These catalysts may be used alone or in combination of two or more.

The reaction temperature and the reaction time vary depending on the type of raw materials used and the presence or absence of a catalyst.
Generally, they are about -10 to 50 ° C and about 0.1 to 4 hours, respectively. That is, it can be synthesized in a shorter time than the method described in JP-A-4-80213.

In order to appropriately improve the physical properties of the optical material, the polymerizable composition has a radical polymerizable group in addition to the radical polymerizable compound having a thiocarbamate bond and is copolymerizable with the above compound. 1 radical polymerizable compound
Species or two or more species may be contained. Specific examples of the radical polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Ethylhexyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth)
Acrylate, phenoxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene diglycol di (meth) acrylate, polyethylene glycol di (meth) acrylate ,, neopentyl crychol di (meth) acrylate, ethylene glycol bisglycidyl (meth) acrylate, bisphenol A
Di (meth) acrylate, 2,2-bis (4- (meth)
(Acryloxydiethoxyphenyl) propane, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, styrene, chlorostyrene, methylstyrene, Bromostyrene, dibromostyrene, 2,5-bis (2-thia-3-butenyl) -1,4-dithiane, 2,
5-bis ((meth) acryloylthiomethyl) -1,4
-Dithiane, etc., and particularly preferably 2,5-
Bis (2-thia-3-butenyl) -1,4-dithiane is exemplified. The (meth) acrylate means both acrylate and methacrylate, and the (meth) acryloxy group means both acryloxy and methacryloxy groups.

The content of the radical polymerizable compound having a thiocarbamate bond in the polymerizable composition is preferably 30.
% By weight or more, more preferably 40% by weight or more, particularly preferably 50% by weight or more.

The optical material of the present invention contains an ultraviolet absorber, a dye or a pigment for improving the light absorption characteristics, and an antioxidant or a coloring inhibitor for improving the weather resistance. For improvement, a release agent or the like can be appropriately added as desired. Here, as the ultraviolet absorber, for example, benzotriazole type, benzophenone type, salicylic acid type and the like can be mentioned, and as the dye and pigment, for example, anthraquinone type and azo type can be mentioned. Examples of antioxidants and coloring inhibitors include, for example, monophenol-based, bisphenol-based, polymer-type phenol-based, sulfur-based, and phosphorus-based agents, and examples of the release agent include fluorine-based surfactants and silicone-based surfactants. , Acidic phosphate esters, higher fatty acids and the like.

As the polymerization method of the polymerizable composition for obtaining the polymerized cured product to be the optical material of the present invention, a known radical polymerization method using heat, ultraviolet rays, or the like can be used. From the viewpoint of optical uniformity and simplicity in production, a method using ultraviolet irradiation is particularly desirable.

At this time, a catalyst may be appropriately used for improving the polymerization reactivity, and a known sensitizer or the like is effective.
Specifically, benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexylphenyl ketone, isoamyl p-dimethylaminobenzoate,
-Methyl dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether,
Benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
ON, acylphosphine oxide and the like.
These catalysts may be used alone or in combination of two or more.

The conditions for the ultraviolet irradiation vary depending on whether or not a catalyst is used, the type of the catalyst, the type of the radical polymerizable compound to be used, and the like.
１００100 mW / cm ² , irradiation time is 5 seconds to 30 minutes.

As an example, a method for producing the optical material of the present invention will be described below. The above-mentioned radical polymerizable compound having a thiocarbamate bond, a homogeneous mixture containing the radical polymerizable compound copolymerizable with the compound and an additive or a catalyst, are prepared by a known casting polymerization method, that is, a glass or resin that transmits ultraviolet light. Is injected into a mold that combines a resin mold and a resin gasket, and is cured by irradiating ultraviolet rays. At this time, in order to facilitate removal of the resin after molding, the mold may be subjected to a mold release treatment in advance, or a mold release agent may be contained in a mixture containing a radical polymerizable compound having a thiocarbamate bond. Further, after completion of the irradiation with ultraviolet rays, heating is preferably performed in order to complete the polymerization or to relax the stress generated inside the material. The heating temperature and time vary depending on the amount of ultraviolet irradiation energy and the like.
° C, 0.2-24 hours. The optical material of the present invention thus obtained usually has a refractive index of 1.55 or more. Further, the optical material of the present invention uses a normal disperse dye, and can be easily dyed in water or an organic solvent.At this time, in order to further facilitate the dyeing, a carrier may be added or heated. .

The present invention also provides an optical product made of the optical material obtained in this manner. There is no particular limitation on the optical product, for example, an optical lens such as an eyeglass lens, a prism, and the like. , Optical fiber, recording medium substrate, filter, further glass, vase and the like, among these, optical lens,
In particular, spectacle lenses are suitable.

[0025]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the optical materials (polymerized cured products) obtained in the examples and comparative examples were evaluated as follows.

(1) Refractive index (nD) and Abbe number (νD) Measured at 20 ° C. using a precision refractometer KPR-200 manufactured by Calnew.

(2) Appearance Observed visually.

(3) Heat resistance Dynamic viscoelasticity was measured at a static tension of 100 g and a frequency of 10 kHz using a dynamic viscoelasticity measuring device manufactured by Toyo Seiki Seisaku-sho, and the elastic modulus obtained by heating at a rate of 2 ° C./min. Was evaluated by the temperature at the descent point of the chart.

(4) Weather Resistance A lens (an optical product using an optical material) was set on a weather meter equipped with a sunshine carbon arc lamp, and after 200 hours had elapsed, the lens was taken out. The lens and the hue before the test were compared. The weather resistance was evaluated according to the following criteria. ：: no change △: slight yellowing ×: yellowing

(5) Solvent Resistance A wiping test using acetone was performed, and the solvent resistance was evaluated based on the following criteria. ：: No change ×: Surface has swelling or swelling

(6) Optical Strain Visual observation was performed by the Schlieren method, and the optical strain was evaluated based on the following criteria. ：: no distortion is observed ×: distortion is observed

Example 1 (1) Preparation of radically polymerizable compound having thiocarbamate bond 31.8 g (0.15 mol) of 2,5-bis (mercaptomethyl) -1,4-dithiane and 2-isocyanatoethyl methacrylate In a mixture with 46.5 g (0.3 mol), 0.38 g of dibutyltin dilaurate was used as a catalyst.
Was added and stirred at 38 ° C. for 1.5 hours. After cooling, 78.3 g of a colorless, transparent, slightly viscous radically polymerizable compound having a thiocarbamate bond was obtained.

(2) Production of optical products 100 parts by weight of the radically polymerizable compound having a thiocarbamate bond obtained in the above (1) (indicated as TRM in Table 1) and 2,2-diethoxyacetophenone (Table 1) D in
EA) 0.2 parts by weight of the mixture was uniformly stirred, poured into two glass molds for lens molding, irradiated with ultraviolet light having an intensity of 8 mW / cm ² for 10 minutes, and then heated at 120 ° C. for 3 hours. By doing so, a plastic lens was obtained. Table 1 shows the physical properties of the obtained plastic lens. From Table 1, this plastic lens is colorless and transparent, has a high refractive index (nD) of 1.59, has a very high Abbe number (νD) of 44 (low dispersion), and has heat resistance (101).
° C), excellent weather resistance and solvent resistance, and no optical distortion.

Example 2 50 parts by weight of the TRM obtained in Example 1 and 2,5-bis (2-thia-3-butenyl) -1,4-dithiane (Table 1)
A mixture of 50 parts by weight and 0.2 parts by weight of DEA was uniformly stirred, poured into two glass molds for lens molding, and irradiated with ultraviolet light having an intensity of 8 mW / cm ² for 10 minutes. A plastic lens was obtained by heating at 120 ° C. for 3 hours. Table 1 shows the physical properties of the obtained plastic lens. From Table 1, this plastic lens is colorless and transparent, has a high refractive index (nD) of 1.61, and
The Abbe number (νD) is also very high (low dispersion) of 42, and is excellent in heat resistance (117 ° C.), weather resistance, and solvent resistance.
There was no optical distortion.

Examples 3 and 4 The procedure of Example 1 was repeated, except that the polymerizable composition shown in Table 1 was used, to obtain a plastic lens. Table 1 shows the physical properties of these plastic lenses together with the physical properties of the plastic lenses of Examples 1 and 2. From Table 1, the plastic lenses of Examples 3 and 4 are colorless and transparent.
The refractive index (nD) is as high as 1.56-1.59, the Abbe number (νD) is as very high as 44-46 (low dispersion), heat resistance (93-110 ° C.), weather resistance, and It had excellent solvent properties and had no optical distortion.

Comparative Example 1 Thiourethane methacrylate (shown as BBM in Table 1) obtained by equimolar reaction of 2,4,6-tribromobenzylthiol and 2-isocyanatoethyl methacrylate
A mixture of 2 parts by weight and 2 parts by weight of diisopropyl peroxycarbonate (indicated as IPPC in Table 1) was uniformly stirred and poured into two glass molds for lens molding.
A plastic lens was obtained by heating at 50 ° C. for 4 hours, at 70 ° C. for 3 hours, at 85 ° C. for 5 hours, and at 100 ° C. for 1 hour. Table 1 shows the physical properties of the obtained plastic lens. From Table 1, this plastic lens has a high refractive index of 1.64, excellent heat resistance (105 ° C.), and has no optical distortion, but has a low Abbe number of 29, is yellow, has weather resistance, The solvent resistance was poor.

Comparative Example 2 Thiol methacrylate of bis (2-mercaptoethylenethiomethylene) benzene (indicated as MBM in Table 1) 7
5 parts by weight of xylylene diisocyanate (XD in Table 1)
A mixture of 12 parts by weight of I), 13 parts by weight of pentaerythritol tetrathioglycolate (designated as PETG in Table 1) and 0.1 part by weight of IPPC was uniformly stirred,
A plastic lens was obtained by injecting into two glass molds for lens molding and heating at 80 ° C. for 6 hours and further at 115 ° C. for 10 hours. Table 1 shows the physical properties of the obtained plastic lens. As shown in Table 1, this plastic lens had a high refractive index of 1.63, was colorless and transparent, was excellent in heat resistance (100 ° C.) and solvent resistance, but had a low Abbe number of 30 and weather resistance. And optical distortion was observed.

[0038]

[Table 1]

[Note] TRM: Radical polymerizable compound having a thiocarbamate bond obtained in Example 1 TBD: 2,5-bis (2-thia-3-butenyl)-
1,4-dithiane, MMA: methyl methacrylate, TCDA: tricyclodecanyl methacrylate, DEA: 2,2-diethoxyacetophenone, BBM: 2,4,6-tribromobenzyl thiol and 2
Thiourethane methacrylate obtained by equimolar reaction of isocyanatoethyl methacrylate, MBM: bis (2-mercaptoethylenethiomethylene)
Thiol methacrylate of benzene, XDI: xylylene diisocyanate, PETG: pentaerythryl tetrathioglycolate, IPPC: diisopropyl peroxy carbonate,

[0040]

The novel optical material of the present invention has a 1,4-dithiane ring and a thiocarbamate bond in the basic skeleton, and therefore has a high refractive index and Abbe number, and is excellent in heat resistance, weather resistance and transparency. , Because there is no optical distortion, eyeglass lenses,
It is preferably used for lenses such as camera lenses, prisms, optical fibers, or optical products such as recording medium substrates and filters used for optical disks and magnetic disks. Furthermore, it is used for decorative articles such as glasses and vases that make use of the characteristic of high refractive index. Further, the optical material of the present invention can reduce the production time as compared with the production time of a conventional thiourethane acrylate lens.

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Claims (9)

[Claims] 1. A compound of the general formula (I) (Wherein n and m each independently represent an integer of 1 to 3), and at least one isocyanate group and at least one ( An optical material comprising a polymerized cured product obtained by polymerizing a polymerizable composition containing a radical polymerizable compound having a thiocarbamate bond obtained by previously reacting a compound having a (meth) acryloyl group. material. 2. The 1,4-dithiandithiol compound,
The optical material according to claim 1, which is 2,5-bis (mercaptomethyl) -1,4-dithiane. 3. The optical material according to claim 1, wherein the compound having at least one isocyanate group and at least one (meth) acryloyl group in a molecule is 2-isocyanatoethyl methacrylate. 4. The optical material according to claim 1, wherein the polymerizable composition contains a radical polymerizable compound having a thiocarbamate bond and a radical polymerizable compound copolymerizable therewith. 5. A copolymerizable radical polymerizable compound,
The optical material according to claim 4, which is 2,5-bis (2-thia-3-butenyl) -1,4-dithiane. 6. The optical material according to claim 1, which is optically transparent. 7. The optical material according to claim 1, which has a refractive index of 1.55 or more. 8. An optical product comprising the optical material according to claim 1. 9. The optical product according to claim 8, which is an eyeglass lens.