JP3238306B2 - 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.
Polyurethane lenses with poor heat resistance are usually 60 to 9
At the time of post-processing such as dyeing or surface coating of a lens that requires thermal processing at about 0 ° C., the lens is likely to be deformed, and there is a problem that the thermal processing temperature must be kept low.

[0003] With the widespread use of such high refractive index spectacle plastic lenses, in recent years it has become increasingly necessary for plastic lenses and compositions for producing such lenses to achieve both higher heat resistance and higher refractive index. It is increasingly being sought. For this purpose, improvement of the polythiol compound alone is not sufficient, and a polyisocyanate compound that achieves high heat resistance and a high refractive index is required. As an optical material having further excellent refractive index and heat resistance, Japanese Patent Application Laid-Open No. 6-65193 discloses an optical material obtained by polymerizing a mixture of a sulfur-containing triisocyanate derivative and a polythiol derivative. However, the isocyanate compound disclosed in the patent is 2-isocyanatomethyl-3-, which is the only production method disclosed in the patent.
The content of sulfur atoms realizing a high refractive index as represented by thiapentane-1,5-diisocyanate is low,
Further, since the methylene chain between the isocyanate groups is long, the refractive index is insufficient particularly.

[0004]

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 high heat resistance, a low water absorption, and a low surface absorption property. An object of the present invention is to provide a lens having excellent hardness.

[0005]

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 provides a component (a) containing tris (isocyanatomethylthio) methane,
2,2-bis (mercaptomethyl) -1,3-propanedithiol, 1,2,4-tris (mercaptomethyl)
Benzene, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, and 4,8-bis (mercaptomethyl) -3,6,9-trithia-1,1
Composition for high refractive index plastic lens containing two components of component (b) containing at least one selected from 1-undecanedithiol, high refractive index plastic lens obtained by polymerizing the composition, and Tris The present invention relates to a simple method for producing (isocyanatomethylthio) methane.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The component (a) contains tris (isocyanatomethylthio) methane, and may contain a polyisocyanate compound other than tris (isocyanatomethylthio) methane for the purpose of appropriately improving the physical properties of the optical material. . In that case, the amount of tris (isocyanatomethylthio) methane used is 50 mol% of the total polyisocyanate.
Or more, preferably 60 mol% or more, more preferably 70 mol% or more.

As polyisocyanate compounds other than tris (isocyanatomethylthio) methane, 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 nucleated chlorides, bromides, methylated or ethylated products thereof, and the like.

[0008] 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, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 2,4-dithiane
Bis (isocyanatomethyl) -1,3-dithiolane and the like can be mentioned. Some of these are commercially available.

Component (b) comprises 2,2-bis (mercaptomethyl) -1,3-propanedithiol, 1,2,4-
Tris (mercaptomethyl) benzene, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, and 4,8-bis (mercaptomethyl)-
It contains at least one member selected from 3,6,9-trithia-1,11-undecanedithiol,
Other polythiols may be included for the purpose of appropriately improving the physical properties of the optical material. In that case, 2,2-bis (mercaptomethyl) -1,3-propanedithiol,
1,2,4-tris (mercaptomethyl) benzene,
1,2-bis [(2-mercaptoethyl) thio] -3-
The amount of the polythiol selected from mercaptopropane and 4,8-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol is 50 mol% or more of the total polythiol, It is preferably at least 60 mol%, more preferably at least 70 mol%.

Examples of other polythiols that may be added include, for example, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, ,
2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, , 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-dimercapto Propyl methyl ether, 2,3-dimercaptopropyl methyl ether, 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 sulfide bis (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 polythiol 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.
These may be added alone or as a mixture of two or more.

In the composition for a high refractive index plastic lens of the present invention, tris (isocyanatomethylthio) methane suitable for the component (a) can be obtained from thioglycolic acid, which is widely marketed, inexpensive and easily available, by the following method. Can be manufactured. Commercially available thioglycolic acid and formic acid are replaced with Ho
Uben et al. (Ber. 45
2942, p. 1912) to tris (carboxymethylthio) methane. That is, thioglycolic acid and formic acid are allowed to react at room temperature, and the resulting tris (carboxymethylthio) methane is precipitated as crystals, which are collected by filtration.

The obtained tris (carboxymethylthio) methane is then reacted with a lower alcohol in the presence of a suitable acid catalyst to obtain the corresponding tris (alkoxycarbonylmethylthio) methane. 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,
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 below the boiling point of the solvent, but is preferably carried out under reflux.

The thus obtained tris (alkoxycarbonylmethylthio) methane derivative is reacted with hydrazine hydrate or a derivative thereof to obtain tris (hydrazinocarbonylmethyl) methane. At this time, as a reaction solvent, methanol, ethanol, propanol, butanol, THF, dioxane, water and the like can be used, but it is preferable to use a lower alcohol in which a 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 (hydrazinocarbonylmethyl) methane is reacted with nitrite in a dilute acid to convert it into an acid azide derivative. (Isocyanatomethylthio) methane 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. As the reaction temperature, the generated acid azide derivative is determined by Curtius.
There is no particular limitation as long as the reaction temperature does not cause a rearrangement reaction, but it 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 this case, an organic solvent which does not react with the isocyanate may be added and extracted. The extract can be used as it is for the next reaction. 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.
Toluene and the like are desirable. 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.

Reference Example 1 Production of tris (carboxymethylthio) methane (method disclosed by Houben et al., Ber. 45: 2942, 1912) 500 g of commercially available thioglycolic acid and 800 g of 99% formic acid
Was mixed at room temperature and left at room temperature for 1 week. About 5 ml of the reaction solution was added, 20 ml of ethyl ether was added, and the mixture was cooled and sludged to form crystals. After decanting the supernatant ether layer, the crystals were added to the original reaction solution and allowed to stand at room temperature for 2 days. The resulting crystals were collected by filtration, washed with about 20 ml of ice water, and air-dried at room temperature. Yield 255 g. Physical properties were in agreement with literature values.

Example 1 Production of tris (isocyanatomethylthio) methane [1] Production of tris (ethoxycarbonylmethylthio) methane 125 g of tris (carboxymethylthio) methane was suspended in a mixed solvent of 2000 ml of ethanol and 2500 ml of toluene, and concentrated sulfuric acid was added. After adding 15 ml and heating under reflux,
The reaction was performed for 20 hours while dehydrating with molecular sieves (4A). After cooling the reaction solution to room temperature, most of the ethanol was distilled off using an evaporator, and 600 ml of toluene was removed.
And then washed with 300 ml of ice water, twice with 250 ml of a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to give crude tris (ethoxycarbonylmethylthio) methane in colorless form. Obtained as an oil. Yield 122 g. ¹ H-NMR (CDCl ₃ ) δ: 5.41 (s, 1H), 4.23 (q, 6H),
3.46 (bs, 6H), 1.29 (t, 9H) pp
m.

[2] Production of tris (hydrazinocarbonylmethyl) methane Tris (ethoxycarbonylmethylthio) methane 121
g was dissolved in 650 ml of isopropanol, and 96 ml of hydrazine monohydrate was added dropwise while maintaining the temperature at 5 ° C. 5 ℃
, And the resulting white granular crystals of tris (hydrazinocarbonylmethyl) methane were collected by filtration. This was washed twice with 100 ml of cold ethanol and air-dried at room temperature.
Yield 103 g. ¹ H-NMR (D6-DMSO) δ: 9.15 (br, 3H), 5.34 (s, 1H),
4.22 (br, 6H), 3.28 (s, 6H)

[3] Production of tris (isocyanatomethylthio) methane 100 g of tris (hydrazinocarbonylmethyl) methane
Is dissolved in 1200 ml of water, cooled to 5 ° C., and concentrated hydrochloric acid 10
2 g were added dropwise. Further, while maintaining the same temperature, a solution in which 65 g of sodium nitrite was dissolved in 380 ml of water was added dropwise. After 30 minutes, 1200 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. A very small amount of phenylsulfonic acid amide was added to the obtained pale yellow oil, and the mixture was distilled under reduced pressure (122 to
126 ° C./0.3 mmHg) to obtain 67.5 g of tris (hydrazocarbonylmethyl) methane as a colorless liquid. ¹ H-NMR (CDCl ₃ ) δ: 5.40 (s, 1H), 4.55 (s, 6H) p
pm.

Example 2 Tris (isocyanatomethylthio) methane 25 parts (0.09 mol), 1,2,4-tris (mercaptomethyl) benzene 19.2 parts (0.089 mol), dibutyltin dilaurate 0.1 part The mixture was mixed in an amount of 01% by weight (based on the total amount of the mixture) to form 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 from 30 ° C to 12
While gradually raising the temperature to 0 ° 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 start temperature of 157 ° C. The lens was not deformed when dyed in a dye bath at 95 ° C. The transmittance after staining is ML
-37% for Yellow, 38% for ML-Red, ML
-Blue: 45%, and the overall evaluation of dyeability was (（).
Met. The water absorption after 48 hours was 0.01%, and the surface hardness was 2H.

Example 3 Tris (isocyanatomethylthio) methane 25 parts (0.09 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 23.5 parts (0.09 mol) ), Dibutyltin dilaurate 0.01
% By weight (based on the total amount of the mixture) was mixed to form a uniform liquid, sufficiently defoamed, and then poured into a lens mold including a glass mold and a gasket subjected to a mold 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 onset temperature of 124 ° C. The transmittance after staining is 26% in ML-Yellow,
It was 32% for ML-Red and 35% 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.

Example 4 Tris (isocyanatomethylthio) methane 25 parts (0.09 mol), 4,8-bis (mercaptomethyl)
24.8 parts (0.068 mol) of -3,6,9-trithia-1,11-undecanedithiol and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) were mixed to form a homogeneous liquid, After sufficient degassing, the mixture was poured into a lens mold composed of 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 is colorless and transparent, and has a refractive index n _d =
1.70, Abbe number ν _d = 31, and thermal deformation onset temperature was 141 ° C. The transmittance after staining was ML-Yel
31% for low, 33% for ML-Red, ML-Blu
e was 40%, and the overall evaluation of the dyeability was (（). The water absorption after 48 hours was 0.01%, and the surface hardness was 2H.

Example 5 46.1 parts (0.166 mol) of tris (isocyanatomethylthio) methane, 8.6 parts of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (0. 033 mol), 20.3 parts of 2,2-bis (mercaptomethyl) -1,3-propanedithiol (0.1
Mol) and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) to form a uniform liquid, and after sufficient defoaming, a mold for a lens comprising a glass mold and a gasket subjected to a release treatment. Injected into mold. Then
While gradually raising the temperature from 30 ° 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 = 1.70, an Abbe number ν _d = 31, and had a thermal deformation onset temperature of 145 ° C. The transmittance after staining was 37 for ML-Yellow.
%, ML-Red was 39%, and ML-Blue was 47%, and the overall evaluation of staining was (（). The water absorption after 48 hours was 0.01%, and the surface hardness was 2H.

Comparative Example 1 2-isocyanatomethyl-3-thiapentane-1,5
44 parts (0.16 mol) of diisocyanate, 1,2-
A mixture of 28 parts (0.107 mol) of bis [(2-mercaptoethyl) thio] -3-mercaptopropane to make a uniform liquid, and after sufficient defoaming, a glass mold and a gasket that have been subjected to a release treatment. It was injected into a lens mold. Then, the mixture was cured by heating for 20 hours while gradually raising the temperature from 40 ° 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. Refractive index n _d = 1.65,
Abbe number ν _d = 34 and thermal deformation onset temperature is 130 ° C.
Met. The transmittance after staining was 4 for ML-Yellow.
5%, ML-Red 58%, ML-Blue 58%
, And was not dyed, and the overall evaluation of the dyeability was (x). The transmittance after staining using 2% benzyl alcohol as a carrier was 28% for ML-Yellow,
-Red was 31%, ML-Blue was 35%, and the overall evaluation of the staining was (O). The water absorption after 48 hours was 0.04%, and the surface hardness was H.

[0034]

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.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C07C 323/57 G02B 1/04 G02C 7/02

Claims (5)

(57) [Claims] 1. A component (a) containing tris (isocyanatomethylthio) methane, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, 1,2,4
-Tris (mercaptomethyl) benzene, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, and 4,8-bis (mercaptomethyl)-
Component (b) containing at least one selected from 3,6,9-trithia-1,11-undecanedithiol,
A composition for a high refractive index plastic lens, comprising the two components: 2. A high refractive index plastic lens obtained by polymerizing the lens composition according to claim 1. 3. A process for producing tris (isocyanatomethylthio) methane, comprising subjecting tris (hydrazinocarbonylmethylthio) methane to a transfer reaction via an acid azide . 4. Tris (isocyanatomethylthio) me
Tan. 5. A compound obtained by subjecting an acid azide derivative to a rearrangement reaction.
Tris (isocyanatomethylthio) methane.