JP3328115B2 - Composition and lens for high refractive index plastic lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-refractive-index plastic lens having excellent heat resistance, low water absorption and excellent surface hardness, which is used for various optical lenses such as spectacle lenses. A composition for manufacturing.

[0002]

2. Description of the Related Art Plastic lenses are lighter than inorganic lenses, are less likely to break, can be dyed, and have good workability such as cutting and polishing. Is rapidly spreading. However, in order to be able to respond to needs with rich fashionability, it is necessary to reduce the center thickness, the edge thickness, and the curvature of the lens and make the lens as a whole thin. From this point, a resin material as an optical material has been required to have a high refractive index. Conventionally, a sulfur-containing polyurethane resin has been known as a resin for a plastic lens having a high refractive index. For example, Japanese Unexamined Patent Publication (Kokai) No. 2-153302 discloses an S-alkyl thiocabamate lens obtained by reacting a polyisocyanate derivative containing a sulfur atom with a polythiol derivative in order to realize a high refractive index. Is disclosed. However, the refractive index of the resin material disclosed in the patent is not always satisfactory, and its heat resistance is not considered much.
As an optical material further excellent in refractive index and heat resistance, Japanese Patent Application Laid-Open No. 5-105677 discloses an optical material obtained by polymerizing a mixture of a 1,3-dithiolane isocyanate derivative and a polythiol derivative. An optical material obtained by polymerizing a mixture of 1,3-dithiolane-4,5-diisocyanate and a polythiol derivative is also disclosed therein. However, these 1,3
For dithiolane-4,5-diisocyanate,
There is no disclosure of its production method, chemical and physical properties, and the like, and furthermore, 4,5-dihydroxy-1,3-dithiolane as a starting material is not known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyurethane lens comprising a polymer of a polyisocyanate compound and a polythiol compound, which has a low dispersion, a high refractive index, a low water absorption and an excellent surface hardness. Is to provide a lens.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have arrived at the present invention. That is, the present invention relates to a component (a) containing 1,3-dithiolane-4,5-diisocyanate.
And 1,2,4-tris (mercaptomethyl) benzene
And 1,2-bis [(2-mercaptoethyl) thio]-
High refractive index plastic lens composition containing two components with component (b) containing at least one of 3-mercaptopropane, high refractive index plastic lens obtained by polymerizing the composition, and 1 , 3-Dithiolane-4,5-diisocyanate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The component (a) contains 1,3-dithiolane-4,5-diisocyanate. For the purpose of appropriately improving the physical properties of the optical material, 1,3-dithiolane-4,5-diisocyanate is used.
It may contain a polyisocyanate compound other than diisocyanate. In that case, 1,3-dithiolane-4,
The amount of 5-diisocyanate used is 50 mol% or more, preferably 60 mol%, of the total polyisocyanate.
The content is more preferably 70 mol% or more.

Examples of polyisocyanate compounds other than 1,3-dithiolane-4,5-diisocyanate include, for example, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,
α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-
m-xylylene diisocyanate, 1,3,5-tris (isocyanatomethyl) benzene and their chlorinated, brominated, methylated or ethylated products.

More specifically, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2,3,5,6-tetrabromo-p
-Xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, norbornene diisocyanate, methylene bis (cyclohexyl isocyanate), bis (isocyanatomethylthio) methane, bis (isocyanatomethylthio) methylthiomethane, bis (2-isocyanatoethylthio) methane, bis (3-
Isocyanatopropylthio) methane, bis (4-isocyanatobutylthio) methane, isocyanatomethylthio (2-isocyanatoethylthio) methane, 2-isocyanatoethylthio (3-isocyanatopropylthio) methane, bis (isocyanate) Natomethylthio) phenylmethane, bis (2-isocyanatoethylthio) phenylmethane, bis (3-isocyanatopropylthio) phenylmethane, 1,2-bis (isocyanatomethylthio) ethane, 1,2-bis (2- Isocyanatoethylthio) ethane, 1,2-bis (3-isocyanatopropylthio) ethane, 1,2-bis (4-isocyanatobutylthio) ethane, 1-isocyanatomethylthio-2- (2-isocyanate) Ethyl) ethane, 1-
Isocyanatoethylthio-2- (3-isocyanatopropylthio) ethane, bis (isocyanatomethylthioethyl) sulfide, etc., and tetrakis (isocyanatomethylthio) methane, 1,1,2,2-tetrakis (isocyanatomethylthio) Ethane, 2,2,5,5
-Tetrakis (isocyanatomethylthio) -1,4-
Dithiane, 2,2,5,5-tetrakis (isocyanatomethylthio) -1,3-dithiane, tris (isocyanatomethylthio) methane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 2, 4-bis (isocyanatomethyl) -1,3-dithiolane and the like. Some of these are commercially available.

Component (b) is 1,2,4-tris (mel
Captomethyl) benzene and 1,2-bis [(2-mer
Captoethyl) thio] -3-mercaptopropane
It contains at least one of them, and may further contain other polythiol compounds for the purpose of appropriately improving the physical properties of the optical material. In that case, 1,2,4-to
Lis (mercaptomethyl) benzene and 1,2-bis
[(2-mercaptoethyl) thio] -3-mercaptopop
The amount of lopan used is at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, based on the total polythiol.

Examples of other polythiol compounds which may be added include, for example, methanedithiol, 1,2-
Ethanedithiol, 1,1-propanedithiol, 1,
2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1
-Cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol,
Bicyclo [2,2,1] pepta-exo-cis-2,
3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1
-Propanol (2-mercaptoacetate), 2, 3
-Dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-
Mercaptopropionate), 1,2-dimercaptopropylmethylether, 2,3-dimercaptopropylmethylether, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3 -Mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis (3-
Mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate)
Aliphatic polythiols, such as

1,2-dimercaptobenzene, 1,3-
Dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,
3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) ) Benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,2
4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris ( Mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4 -Tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1,2,4-
Tris (mercaptoethyleneoxy) benzene, 1,
3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,
2,3,5-tetramercaptobenzene, 1,2,4
5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,4,5
-Tetrakis (mercaptomethyl) benzene, 1,2,2
3,4-tetrakis (mercaptoethyl) benzene,
1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,2 3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,2
4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4 5-
Tetrakis (mercaptoethyleneoxy) benzene,
2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,
5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7
-Naphthalenedithiol, 2,4-dimethylbenzene-
1,3-dithiol, 4,5-dimethylbenzene-1,
3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di (p-methoxyphenyl) propane-
2,2-dithiol, 1,3-diphenylpropane-
Aromatic polythiols such as 2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di (p-mercaptophenyl) pentane;

2-methylamino-4,6-dithiol-
sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino-4,
6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym
-Triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-
Polythiol containing a heterocyclic ring such as 4,6-dithiol-sym-triazine;

1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene,
1,2-bis (mercaptoethylthio) benzene,
3-bis (mercaptoethylthio) benzene, 1,4-
Bis (mercaptoethylthio) benzene, 1,2,3-
Tris (mercaptomethylthio) benzene, 1,2,4
-Tris (mercaptomethylthio) benzene, 1,3,
5-tris (mercaptomethylthio) benzene, 1,
2,3-tris (mercaptoethylthio) benzene,
1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5 -Tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4
-Tetrakis (mercaptoethylthio) benzene, 1,
2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, etc., and aromatics containing a sulfur atom in addition to the mercapto group such as alkylated nuclei thereof Polythiol,

Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio)
Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2
-Mercaptoethylthio) ethane, 1,2-bis (3-
Mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3 -Tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3
-Tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) ) Sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide and the like, and thioesters of thioglycolic acid or mercaptopropionic acid;

Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfidebis (2-mercaptoacetate), hydroxyethyl sulfidebis (3-mercaptopropionate) , Hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfidebis (2-mercaptoacetate),
Hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-
Mercaptopropionate), 2-mercaptoethylether bis (2-mercaptoacetate), 2-mercaptoethyletherbis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-
Mercaptoacetate), 1,4-dithiane-2,5-
Diol bis (3-mercaptopropionate), 2,
5-bis (mercaptomethyl) -1,4-dithiane, bis (2-mercaptoethyl ester) thiodiglycolate, bis (2-mercaptoethyl ester) thiodipropionate, bis (2-mercaptoethyl ester) Mercaptoethyl ester), bis (2) dithiodiglycolate
-Mercaptoethyl ester), bis (2-mercaptoethyl ester) dithiodipropionate, bis (2-mercaptoethyl ester) 4,4-dithiodibutylate,
Bis (2,3-dimercaptopropyl ester) thiodiglycolate, bis (2,3-dimercaptopropyl ester) thiodipropionate, bis (2,3-dimercaptopropyl ester) dithioglycolate, dithiodipropion Aliphatic polythiols containing a sulfur atom in addition to a mercapto group such as bis (2,3-dimercaptopropyl ester) acid; 3,4-thiophenedithiol;
Examples thereof include a heterocyclic compound containing a sulfur atom in addition to a mercapto group such as 5-dimercapto-1,3,4-thiadiazole. Further, halogen-substituted products such as chlorine-substituted and bromine-substituted polythiols may be used.
Each of these may be added alone or two or more of them may be mixed and added.

In the composition for a high refractive index plastic lens of the present invention, 1,3-dithiolane-4,5-diisocyanate suitable for component (a) is widely commercially available and easily available. It can be produced from mercaptosuccinic acid by the following method. Commercially available 2,3-dimercaptosuccinic acid was prepared according to the method disclosed by Schaummann et al. (Tetrahedron Lett. 26:43 5).
265 (1985)) to dimethyl 1,3-dithiolane-4,5-dicarboxylate. That is, 2,3-dimercaptosuccinic acid is reacted with formaldehyde in the presence of a suitable acid catalyst to give 1,3-dithiolane-4,5-dicarboxylic acid, which is esterified as it is in methanol with sulfuric acid as a catalyst. , 1,3-dithiolane-4,5-dicarboxylate. At this time, the corresponding 1,3-dithiolane-4,5-dicarboxylic acid diester can be obtained similarly by using another lower alcohol instead of methanol.

Further, here, Hedblom (Ark. C)
hem. Vol. 31, No. 41, p. 489 (p. 1969), formalin and 2,3-dimercaptosuccinic acid as a raw material are suspended in ether, and sulfuric acid is added thereto to form 1,3-dithiolane-4. , 5-Dicarboxylic acid may be isolated and esterified by a conventional method. Also,
2,3-dimercaptosuccinic acid in the presence of a suitable acid catalyst,
After reacting with a lower alcohol to form the corresponding 2,3-dimercaptosuccinic acid diester, it may be cyclized by reacting with formaldehyde or a derivative thereof to give 1,3-dithiolane-4,5-dicarboxylic acid diester. In addition, since both the esterification and the cyclization can be performed using an acid as a catalyst, the intermediate is not isolated, and the two steps are continuously performed in one pot using a common acid catalyst, and the reaction is performed at once. 1,3-Dithiolane-4,5-dicarboxylic acid diester can also be obtained.

The esterification can be carried out by reacting the starting carboxylic acid with a suitable lower alcohol to convert it into an ester derivative. As the acid catalyst, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, boron trifluoride ether complex, metal salts such as titanium chloride and the like can be used, and sulfuric acid is preferred. Examples of the lower alcohol include methanol, ethanol, and propanol. The reaction may be carried out using the alcohol to be used as a solvent, or in a solvent such as toluene or benzene. Water generated by the reaction may be removed using a dehydrating agent such as anhydrous sodium sulfate or molecular sieve, or may be azeotropically dehydrated using a Dean-Stark apparatus with toluene or the like as a solvent. The reaction can be carried out at room temperature or higher and at a temperature lower than the boiling point of the solvent. However, it is preferable to carry out the reaction under reflux while dehydrating using a mixed solution of toluene and ethanol.

Next, the 1,3-dithiolane-4,5-dicarboxylic acid diester derivative is reacted with hydrazine hydrate or a derivative thereof to give 4,5-bis (hydrazinocarbonyl) -1,3-dicarboxylic acid. Dithiolane. At this time, as a reaction solvent, methanol, ethanol, propanol, butanol, THF, dioxane,
Although water or the like can be used, it is preferable to use a lower alcohol in which the diester derivative as a raw material is dissolved and a product is precipitated. The reaction can be carried out at a reaction temperature of 0 ° C. or higher and the boiling point of the solvent or lower, but preferably at room temperature or lower. It is desirable to use an excess of hydrazine hydrate or a derivative thereof in order to suppress a side reaction.

Next, the 4,5-bis (hydrazinocarbonyl) -1,3-dithiolane is reacted with nitrite in a dilute acid to convert it into an acid azide derivative. Then, transfer Curtius,
1,3-Dithiolane-4,5-diisocyanate can be obtained. In the step of producing the acid azide derivative, a dilute hydrochloric acid aqueous solution, a dilute sulfuric acid aqueous solution, or the like can be used as the dilute acid, and it can be used together with a solvent that does not hinder the reaction. The reaction temperature is not particularly limited as long as the generated acid azide derivative does not cause a Curtius rearrangement reaction, but is preferably in the range of 0 to 10 ° C. Here, since the intermediate acid azide derivative is hardly soluble in water, it may be released from the reaction solution, in which case an organic solvent that does not react with the isocyanate is added, and
Good to extract. The solvent used in the Curtius transfer step of the acid azide derivative is not particularly limited as long as it does not react with the product, but benzene, toluene and the like are preferable. The reaction can be carried out at any temperature between room temperature and the boiling point of the solvent, but a temperature in the range of 50 to 80 ° C is preferred because the reaction is quick and easy to control.

The proportion of each component used in the composition of the present invention, that is, the proportion of component (a) to component (b) is N
The ratio of CO group / SH group is in the range of 0.5 to 1.5, preferably 0.6 to 1.4, particularly preferably
It is in the range of 0.7 to 1.3. Further, the composition of the present invention includes a polymerization catalyst for accelerating the polymerization reaction, an ultraviolet absorber for improving weather resistance, an antioxidant, a coloring inhibitor, a fluorescent dye, a light stabilizer, and an oil-soluble dye. Additives may be added as needed. Further, an internal release agent may be added as required.

The lens of the present invention is prepared by adding a polymerization catalyst, an additive, and the like, if necessary, to the lens composition containing the component (a) and the component (b) and then sufficiently defoaming the mixture. In other words, it is obtained by injecting a mixed solution into a mold formed by combining a glass or metal mold and a resin gasket, heating, and curing. At this time, a known release treatment may be applied to the mold in order to facilitate removal of the resin after molding. The polymerization temperature and polymerization time during casting polymerization vary depending on the composition of the monomer, the type and amount of the additive,
Generally, the temperature is raised from 5 to 20 ° C.
The temperature is raised to about 130 ° C. in 8 to 30 hours.

The lens obtained by the present invention may be improved in antireflection, high hardness, high abrasion resistance, high chemical resistance, high antifogging property, or high fashionability, if necessary. Physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, light control treatment and the like can be performed. Further, the lens obtained in the present invention can be easily dyed in water or a solvent using a usual disperse dye. At the time of dyeing, a carrier as a dyeing assistant may be added to the dyeing bath to further facilitate the dyeing.

The sulfur-containing urethane resin obtained by curing the composition of the present invention has extremely low dispersion, high refractive index, excellent heat resistance, is colorless and transparent, lightweight, weather resistant, and impact resistant. It has excellent water-absorbing properties and excellent surface hardness, and is suitable not only for optical element materials such as eyeglass lenses and camera lenses, but also for glazing materials, paints, and adhesives. .

[0024]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In addition, the part shown in an Example shows a weight part.
The performance test of the obtained lens was evaluated by the following test methods. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measure in ° C.・ Appearance: Coloring and transparency are visually observed.・ Heat resistance: Thermomechanical analyzer, TAS30
Using 0 (manufactured by Rigaku Denki), 5 g of weight was applied to the test piece.
Heat at 5 ° C./min and measure its thermal deformation onset temperature. Dyeability: ML-Yellow, ML-Red, which are disperse dyes for plastic lenses manufactured by Mitsui Toatsu Dye Co., Ltd.
ML-Blue was immersed at 95 ° C. for 5 minutes in a dyeing tank prepared in an aqueous solution of 5 g / L each to dye a 9 mm-thick plate. After staining, Spectrophotometer, U
-2000 (manufactured by Hitachi, Ltd.).
Measure the transmittance in nm. As a comprehensive evaluation, a sample having good dyeability was evaluated as (○), and a sample having poor or no dyeability was evaluated as (x). Dyeing heat resistance: After immersion in a dyeing bath at 95 ° C. for 5 minutes, it is visually observed whether or not the lens is deformed. -Water absorption: A test piece is prepared based on JIS-K-7209, immersed in water at room temperature for 48 hours, and the water absorption is measured from the change in weight after that. Surface hardness: Pencil hardness is measured using a JIS-K-5401 pencil scratch tester for coating films.

Example 1 1,3-dithiolane-4,5-
Production of diisocyanate [1] Production of diethyl 1,3-dithiolan-4,5-dicarboxylate 25 g of commercially available 2,3-dimercaptosuccinic acid was added to 6.6 g of paraformaldehyde (70%) and ethyl ether 3
The suspension was suspended in 00 ml, and 3 ml of concentrated sulfuric acid was added dropwise. The mixture was stirred vigorously at room temperature for 1 day, ether was distilled off under reduced pressure by an evaporator, and 20 ml of 80% formic acid was added to the residue. The resulting white powdery crystals were collected by filtration and air-dried at room temperature (22 g). This powdery crystal is directly used in ethanol 20
0 ml, suspended in a mixed solvent of toluene 200 ml,
1 ml of concentrated sulfuric acid was added, and a reaction was carried out for 20 hours while heating and refluxing while dehydrating with molecular sieves (4A).
After cooling the reaction solution to room temperature, most of the ethanol was distilled off using an evaporator, 100 ml of toluene was added, and the mixture was washed twice with 50 ml of a saturated aqueous sodium hydrogen carbonate solution. After drying over anhydrous sodium sulfate, the solvent was concentrated under reduced pressure to obtain crude diethyl 1,3-dithiolane-4,5-dicarboxylate as a pale yellow oil (22 g). ¹ H-NMR (CDCl ₃ ) δ: 4.49 (bs, 2H), 3.16 (m, 4H),
1.27 (t, 3H)

[2] Production of 4,5-bis (hydrazinocarbonyl) -1,3-dithiolane 22 g of crude diethyl 1,3-dithiolane-4,5-dicarboxylate was dissolved in 50 ml of isopropanol and heated to 5 ° C. While maintaining, 14 g of hydrazine monohydrate was added dropwise. After 2 hours, the resulting white crystals of 4,5-bis (hydrazinocarbonylmethyl) -1,3-dithiolane were collected by filtration. This was washed twice with 10 ml of cold ethanol and air-dried at room temperature (24 g). ¹ H-NMR (D6-DMSO) δ: 9.46 (br, 2H), 4.87 (br, 4
H), 4.41 (s, 2H), 4.08 (s, 2H)

[3] Production of 1,3-dithiolane-4,5-diisocyanate 35.5 g of 4,5-bis (hydrazinocarbonyl) -1,3-dithiolane was dissolved in 120 ml of water, and the solution was heated to 5 ° C. After cooling, 26.6 ml of concentrated hydrochloric acid was added dropwise. Further, a solution in which 20 g of sodium nitrite was dissolved in 80 ml of water was added dropwise. After 30 minutes, 200 ml of toluene was added, and the mixture was heated to room temperature with vigorous stirring. The organic layer was separated, dried over anhydrous magnesium sulfate, and then slowly reacted at a rate in a range of 60 to 80 ° C. such that nitrogen was continuously generated. After the generation of nitrogen had ceased, the reaction was further continued at 90 ° C. for 2 hours, cooled to room temperature, insolubles were removed by filtration, and toluene was distilled off under reduced pressure. The resulting pale yellow oil was distilled under reduced pressure (8
8 to 91 ° C / 0.3 mmHg) to obtain 17.5 g of 1,3-dithiolane-4,5-diisocyanate as a colorless liquid. ¹ H-NMR (CDCl ₃ ) δ: 5.13 (s, 2H), 4.24 (s, 2H) p
pm.・ IR: 2240, 1420, 1340, 1270, 8
80 cm ^-1

Example 2 25 parts (0.133 mol) of 1,3-dithiolan-4,5-diisocyanate, 19.2 parts (0.089 mol) of 1,2,4-tris (mercaptomethyl) benzene , 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) was mixed to form a uniform liquid, and after sufficient defoaming, a mold mold for lenses consisting of a glass mold and a gasket subjected to mold release treatment was used. Injected. Then from 30 ° C to 1
While gradually raising the temperature to 20 ° C., the mixture was cured by heating for 23 hours. After the completion of the polymerization, the mixture was gradually cooled, and the lens was taken out of the mold. The obtained lens was colorless and transparent, had a refractive index n _d = 1.70, an Abbe number ν _d = 30, and had a thermal deformation initiation temperature of 152 ° C. The lens was not deformed when dyed in a dye bath at 95 ° C. The transmittance after staining is M
35% for L-Yellow, 38% for ML-Red, M
It was 49% for L-Blue, and the overall evaluation of staining was (（). The water absorption after 48 hours was 0.02%, and the surface hardness was 2H.

Example 3 25 parts (0.133 mol) of 1,3-dithiolane-4,5-diisocyanate, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 23.1 Parts (0.089 mol), dibutyltin dilaurate 0.0
1% by weight (based on the total amount of the mixture) was mixed to make a uniform liquid, sufficiently defoamed, and then poured into a lens mold comprising a glass mold and a gasket subjected to a release treatment. Then, the mixture was cured by heating for 23 hours while gradually raising the temperature from 30 ° C. to 120 ° C. After the completion of the polymerization, the mixture was gradually cooled, and the lens was taken out of the mold. The obtained lens was colorless and transparent, had a refractive index n _d = 1.69, an Abbe number ν _d = 33, and had a thermal deformation initiation temperature of 127 ° C. The transmittance after staining is 28% in ML-Yellow,
It was 33% for ML-Red and 39% for ML-Blue, and the overall evaluation of staining was (（). The water absorption after 48 hours was 0.02%, and the surface hardness was 2H.

Reference Example 1,3-Dithiolane-4,5-diisocyanate 47 parts (0.25 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 8.6 parts (0.
033 mol), 2,2-bis (mercaptomethyl)-
After mixing 20.3 parts (0.1 mol) of 1,3-propanedithiol and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) to make a uniform liquid, sufficiently degassing, and then releasing the mold. It was injected into a lens mold consisting of a treated glass mold and a gasket. Then 3
While gradually raising the temperature from 0 ° C. to 120 ° C., the composition was cured by heating for 23 hours. After the completion of the polymerization, the mixture was gradually cooled, and the lens was taken out of the mold. The obtained lens was colorless and transparent, had excellent impact resistance, had a refractive index n _d = 1.69, an Abbe number ν _d = 32, and had a thermal deformation onset temperature of 132 ° C. The transmittance after staining is 33% in ML-Yellow,
It was 33% for ML-Red and 42% for ML-Blue, and the overall evaluation of staining was (（). The water absorption after 48 hours was 0.02%, and the surface hardness was H.

Comparative Example 1 1,3-dithiolane-4,5-diisocyanate 25.
3 parts (0.134 mol) and 27.6 parts (0.13 mol) of 2,5-bis (mercaptomethyl) -1,4-dithiane were mixed to form a uniform liquid, and after sufficient defoaming, It was poured into a mold for lenses consisting of a glass mold and a gasket that had been subjected to release processing. Then from 40 ° C to 120
The mixture was cured by heating over 23 hours while gradually raising the temperature to ° C. After the completion of the polymerization, the mixture was gradually cooled, and the lens was taken out of the mold. The obtained lens was slightly cloudy and the refractive index could not be measured. This resin was extremely brittle and was unsuitable for lenses.

COMPARATIVE EXAMPLE 2 25 parts (0.133 mol) of 1,3-dithiolane-4,5-diisocyanate and 32.5 parts of pentaerythritol tetrakis (2-mercaptopropionate) (0.1%).
(067 mol) was mixed to form a uniform liquid, sufficiently degassed, and then poured into a lens mold comprising a glass mold and a gasket subjected to a release treatment. Then 30 ° C
While gradually increasing the temperature from 120 ° C. to 120 ° C., the mixture was cured by heating for 23 hours. After the completion of the polymerization, the mixture was gradually cooled, and the lens was taken out of the mold. The obtained lens was colorless and transparent. The refractive index n _{d was} 1.61, the Abbe number ν _{d was} 38, and the thermal deformation onset temperature was 113 ° C. The transmittance after staining was 27% for ML-Yellow, 33% for ML-Red, and 38% for ML-Blue, and the overall evaluation of staining was (（). The water absorption after 48 hours is 0.06
%, And the surface hardness was H.

[0033]

The plastic lens obtained by polymerizing the lens composition containing a diisocyanate containing a sulfur atom of the present invention is an excellent high refractive index plastic lens having an extremely high refractive index.

Continuation of front page (56) References JP-A-5-105677 (JP, A) JP-A-9-52931 (JP, A) JP-A-7-228659 (JP, A) JP-A-7-165859 (JP, A) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C07D 339/06 G02B 1/04 G02C 7/02 CA (STN)

Claims (5)

(57) [Claims] 1. A component (a) containing 1,3-dithiolane-4,5-diisocyanate, and 1,2,4-tris
(Mercaptomethyl) benzene and 1,2-bis [(2
-Mercaptoethyl) thio] -3-mercaptopropane
And a component (b) containing at least one of the above. 2. A high refractive index plastic lens obtained by polymerizing the lens composition according to claim 1. 3. A 4,5-bis (hydrazinocarbonyl)
1,3-dithiolane-4,5 , wherein a transfer reaction is carried out from -1,3-dithiolane via acid azide.
-A process for producing diisocyanates. 4. A 1,3-dithiolane-4,5-diisocyanate.
Anat. 5. A compound obtained by subjecting an acid azide derivative to a transfer reaction.
1,3-dithiolane-4,5-diisocyanate.