JPH1045707A - Isocyanate derivative and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new isocyanate derivative containing sulfur atom, useful for plastic lens having an extremely high refractive index and an excellent heat resistance and surface hardness. SOLUTION: This diisocyanate derivative is represented by formula I [R is ethylene or propylene (carbon in the middle of propylene may be substituted by S); R' is methylthio or methylthiomethylthio; (n) is 1-3], e.g. 2,4- dithiapentane-1,3-diisocyanate of formula II. The compound of formula I, e.g. 2,4-dithiapentane-1,3-diisocyanate of formula II is obtained by subjecting a dihydrazide derivative obtained by reacting 2-methylthio-3-thiaglutaric acid dihydrazide with nitrous acid in an aqueous solution of hydrochloric acid to Curtius rearrangement. The new diisocyanate derivative of formula I and at least one kind of polythiol compound are included to provide a composition for optical resins having high refractive index. The composition is polymerized to produce a lens for various kinds of optical uses.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel diisocyanate derivative and its use. Specifically, the present invention relates to a novel diisocyanate derivative which is used for various optical lenses such as spectacle lenses and has an extremely high refractive index and is essential for producing a plastic lens having excellent heat resistance and surface hardness.

[0002]

2. Description of the Related Art Plastic lenses are lighter than inorganic lenses, are less likely to crack, can be dyed, and have good workability such as cutting and polishing properties. It is rapidly spreading in the field of devices. However, in order to be able to respond to needs with rich fashionability, it is necessary to reduce the center thickness, edge thickness, and curvature of the lens, and it is necessary for the lens to be thin as a whole. An increasingly higher refractive index is required. Polyurethane lenses have already been disclosed as monomers for high refractive index lenses. For example, Japanese Patent Application Laid-Open No. 63-46213 proposes a polyurethane lens made of a polymer of a xylylene diisocyanate compound and a polythiol compound, and is widely used in optical lenses such as eyeglass lenses.

As a polyurethane lens having a higher refractive index and higher heat resistance, a resin composition and a spectacle lens using a sulfur-containing isocyanate have been proposed (JP-A-2-270).
No. 859). Certainly, polyurethane resins using these sulfur-containing isocyanate compounds have extremely high heat resistance. However, if the temperature exceeds the high heat deformation temperature, the mechanical strength is slightly impaired, and attention must be paid to heat deformation in a high temperature range. There is no problem in ordinary applications such as eyeglass lenses, but special optical products that require higher processing temperatures can take advantage of the superior performance of polyurethane resins using sulfur-containing isocyanate compounds. In such a case, it is necessary to develop a polyurethane resin using a sulfur-containing isocyanate compound which has a high deformation temperature and a small deformation amount at a temperature higher than the deformation temperature.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyurethane resin comprising a polymer of a polyisocyanate compound and a polythiol compound, which has high heat resistance, low dispersion and high refractive index, and is subject to thermal deformation. It is to provide a hard resin.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a certain kind of material having high heat resistance, low dispersion and useful for improving the refractive index. The present inventors have found a diisocyanate derivative of the present invention and arrived at the present invention. That is, the present invention relates to a diisocyanate derivative represented by the general formula (1) (Formula 5).

[0006]

Embedded image (Wherein, R represents an ethylene group or a propylene group, a carbon atom at the center of the propylene group may be substituted with a sulfur atom, R ′ represents a methylthio group or a methylthiomethylthio group, and n represents 1 to 3 In addition, the present invention provides 2,4 represented by the formula (2) (Formula 6).
-Dithiapentane-1,3-diisocyanate, 2,4,6-trithiaheptane-3,5-diisocyanate represented by the formula (3) (formula 6), 2,4,7,9-tetrathiapentane-5,6-diisocyanate represented by any one of the above-mentioned, and a high-refractive-index optical resin containing at least one kind of polythiol compound. The present invention relates to a composition, and further relates to a lens obtained by polymerizing the composition for an optical resin having a high refractive index.

[0007]

Embedded image

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel diisocyanate derivative essential for producing a plastic lens having an extremely high refractive index and excellent heat resistance and surface hardness. A conventionally known sulfur-containing diisocyanate derivative in which a plurality of sulfur atoms have been introduced into a molecule for the purpose of improving the refractive index is a sulfur-containing diisocyanate derivative which has a polymerizable functional group on a main skeleton connecting two isocyanate groups. The molecule is designed with atoms. When such a diisocyanate derivative is polymerized with polythiol to form a resin, the distance between cross-linking points is increased, so that the degree of freedom for thermal motion is increased, and it is considered that the diisocyanate derivative is susceptible to thermal deformation. The sulfur-containing diisocyanate derivative of the present invention connects the isocyanate group, which is two polymerizable functional groups, with the shortest carbon chain, has as few sulfur atoms as possible on the main skeleton, and has a methylthio group and a methylthiomethylthio group. By introducing a sulfur atom into a side chain portion in a form, the refractive index is improved, and the refractive index is adjusted to a desired value by the number of sulfur atoms introduced into the side chain.

In the present invention, specific examples of the compound represented by the general formula (1) include 2,4-dithiapentane-1,3-diisocyanate and 2,4,6-trithiaheptane-3 , 5-Diisocyanate, 2,4,7,9-
Tetrathiapentane-5,6-diisocyanate, 2,
4,8,10-tetrathiaundecane-5,7-diisocyanate, 2,5,7-trithiaoctane-3,4-
Examples thereof include diisocyanate, 1,2-bis (methylthio) ethylene diisocyanate, and 1,2,3-tris (methylthio) propane-1,3-diisocyanate. Preferably, it is a compound represented by the formula (2), (3) or (4).

The diisocyanate derivative of the present invention can be synthesized as follows. For example, 2,4-dithiapentane-1,3-diisocyanate represented by the formula (2) is a dihydrazide derivative obtained by reacting 2-methylthio-3-thiaglutaric acid dihydrazide with nitrite in an aqueous hydrochloric acid solution. Curtius transfer. The Curtius transition may be performed in a solvent. As the solvent,
The solvent is not particularly limited as long as it does not react with the generated isocyanate derivative, but toluene is preferable. 2-Methylthio-3-thiaglutaric acid dihydrazide can be obtained by reacting 2-methylthio-3-thiaglutaric acid diester with hydrazine in a solvent. If hydroxylamine is used in place of hydrazine, a dicarbamic acid derivative is obtained, and the isocyanate derivative can also be obtained by subjecting it to Rosen transfer. 2
-Methylthio-3-thiaglutaric acid diester can be obtained by reacting thioglycolic acid ester with halomethylthioglycolic acid ester in the presence of a base. Thioglycolates are commercially available at low cost and widely. The halomethylthioglycolic acid ester derivative can be obtained by chlorinating a readily available methylthioglycolic acid ester with a method known in the literature, for example, with N-chlorosuccinimide or the like.

2,4,6-trithiaheptane-3,5-diisocyanate represented by the formula (3) and 2,4,7,9-tetrathiapentane represented by the formula (4) Similarly, -5,6-diisocyanate is 2-methylthio-3-thiaglutaric acid diester and 2,4,7,9-tetrathiapentane-5,6-dicarboxylic acid diester, respectively. Can be synthesized from 2-Methylthio-3-thiaglutaric acid diester can be easily synthesized by dimerizing a halomethylthioglycolic acid ester derivative with a sulfide. 2,
4,7,9-Tetrathiapentane-5,6-dicarboxylic acid diester can be synthesized by methylthiomethylating 2,3-dimercaptosuccinic acid diester by an ordinary method. To the sulfur-containing isocyanate thus produced, an appropriate amount of a stabilizer, an antioxidant, or the like can be added, if necessary, such as a storage form.

The composition for a high refractive index optical resin of the present invention is a monomer mixture containing at least one diisocyanate derivative represented by the above general formula (1) and at least one polythiol compound. is there. Any polythiol compound can be used as the polythiol as long as it has three or more functional groups. However, considering the refractive index of the obtained resin, 4- (2-mercaptomethyl) -3,6-dithiaoctane-1,8- Dithiol, 4,8-bis (2-mercaptomethyl) -3,6,9-trithiaundecane
Preferred are 1,11-dithiol, 1,2,4-tris (mercaptomethyl) benzene and the like. In addition, the composition for a high refractive index optical resin of the present invention includes a polyisocyanate compound other than the diisocyanate derivative represented by the general formula (1), a polyol, a polythiol having a hydroxyl group, and the like for improving physical properties. Can also be added.

Specific examples of the polyisocyanate compound other than the diisocyanate derivative represented by the general formula (1) include o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3,5-tris (isocyanatomethyl) benzene and their chlorinated products, bromides, methylated products or ethylated products [eg, 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) ) Etc.]. Some of these are commercially available.

In the composition for a high refractive index optical resin of the present invention, the use ratio of each component, that is, at least one kind of polythiol and a polyisocyanate containing a diisocyanate derivative represented by the general formula (1) are used. Is used in a ratio of NCO group / SH group in the range of 0.6 to 1.4, preferably 0.7 to 1.3, and most preferably 0.9.
~ 1.1. The amount of the diisocyanate derivative represented by the general formula (1) of the present invention varies depending on the heat resistance and the amount of thermal deformation required for the target resin. And it is preferably at least 85 mol%.

The lens of the present invention is obtained by polymerizing the composition for a high refractive index optical resin of the present invention. The production of a lens by polymerization is performed as follows. That is, if necessary, a monomer mixture containing at least one or more polyisocyanate compounds represented by the general formula (1) and at least one or more polythiol compounds may be
Additives are added for the purpose of accelerating mold release or absorbing ultraviolet light, and the mixture is mixed in a known casting polymerization method, that is, a mold combining a glass or metal mold and a resin gasket. And curing by heating. 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 the polymerization time in the casting polymerization vary depending on the composition of the monomer, the type and the amount of the additive, but generally, the temperature is raised from 5 to 20 ° C, and the temperature is increased from about 100 ° C to 130 ° C. The temperature rises in ~ 30 hours.

The lens obtained by the present invention may be improved in antireflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging property, or imparting 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 using the diisocyanate compound of the present invention has extremely low dispersion, high refractive index, excellent heat resistance, and is colorless, transparent and lightweight, and has excellent weather resistance and impact resistance. Further, it has a characteristic of low water absorption and excellent surface hardness, and is suitable not only for optical element materials such as spectacle lenses and camera lenses, but also for glazing materials, paints, and adhesives.

[0017]

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. The performance test of the obtained lens was evaluated by the following test methods. -Refractive index, Abbe number: 20 using a Pulfrich refractometer
Measured in ° C. The refractive index and Abbe number are n _d and ν _d measured using a d-line.・ Appearance: Observed visually.・ Heat resistance: Thermomechanical analyzer TAS300
10 g was applied to a test piece polished to a thickness of 2 mm using (manufactured by Rigaku Denki), heated at 5 ° C./min, and the thermal deformation onset temperature and the thermal deformation amount were measured by a penet method. Thermal deformation is T
It was determined by taking the difference in test piece length between the starting point of thermal deformation and the inflection point 2 on the MA curve (FIG. 1). Dyeability: ML-Yellow, ML-Red, which are disperse dyes for plastic lenses manufactured by Mitsui Toatsu Dye Co., Ltd.
Each of ML-Blue was prepared in an aqueous solution of 5 g / L, and immersed at 95 ° C. for 5 minutes in a dyeing tank to which a predetermined carrier was added to dye a flat plate having a thickness of 9 mm. After staining, Spectrophotometer, U-2000 (manufactured by Hitachi, Ltd.)
Was used to measure the transmittance at 400 to 700 nm. As an overall evaluation, a sample having good dyeability was rated as (）), and a sample having poor dyeability or not dyeable at all was rated as (x). -Water absorption: A test piece was prepared based on JIS-K-7209, immersed in water at room temperature for 48 hours, and the water absorption was measured from the weight change thereafter. Surface hardness: Pencil hardness was measured using a JIS-K-5401 pencil scratch tester for coating films.

Reference Example 1 Production of ethyl 2-chloro-2-methylthioacetate 22.8 g (0.17 mol) of ethyl methylthioacetate was dissolved in 85 ml of carbon tetrachloride, and N-chlorosuccinimide 22 was dissolved under vigorous stirring at room temperature. 0.8g (0.17m
ol) was added in three portions every 30 minutes. After the exotherm subsided, it was left at room temperature overnight. The precipitated white crystals were filtered and washed with a mixed solvent of chloroform-hexane 1: 1. The combined filtrate and washings were concentrated to give ethyl 2-chloro-2-methylthioacetate as a colorless oil. The product was almost pure by TLC analysis, and could be used for the next reaction as it was. ¹ H-NMR (CDCl ₃ ): δ = 1.29 (t, 3
H), 2.21 (s, 3H), 3.17 (s, 1H),
4.24 (q, 2H) ppm

Reference Example 2 Production of diethyl 2,3-dimercaptosuccinate 25 g of commercially available 2,3-dimercaptosuccinic acid was dissolved in 250 ml of ethanol and 250 ml of toluene, and 1 ml of concentrated sulfuric acid was added, followed by heating under reflux for 24 hours. Reacted down. During this time, water generated by the reaction was removed with a molecular sieve. After the reaction, ethanol was removed with an evaporator, and the mixture was washed with 5% sodium hydroxide, washed twice with water and concentrated as it was. This was almost pure by TLC analysis and could be used as it is in the next reaction.

Example 1 Preparation of diethyl 2-methylthio-3-thiglutarate 6.8 g (0.17 mol) of sodium hydroxide was added to 30 parts of water.
Then, 50 ml of methyl isobutyl ketone was added, and the mixture was cooled to 4 ° C. While stirring vigorously, 21.4 g (0.17 mol) of ethyl thiocholate was added dropwise over 30 minutes. After the addition, the mixture was further stirred at the same temperature for 30 minutes. Here, 30 ml of a methyl isobutyl ketone solution of ethyl 2-chloro-2-methylthioacetate synthesized in Reference Example 1
Was added dropwise and reacted at the same temperature for 4 hours and at room temperature for 8 hours. After the reaction, 100 ml of toluene was added, washed twice with a saturated saline solution, and dried over anhydrous magnesium sulfate. Concentrate with an evaporator, distill under reduced pressure, boiling point 130-132 ° C
A fraction (0.5 mmHg) was collected. Yield 21 g ¹ H-NMR (CDCl ₃ ): δ = 1.29 (t, 3
H), 1.31 (t, 3H), 2.27 (s, 3H),
3.42 (ABq, 2H), 4.22 (m, 4H),
4.63 (s, 1H) ppm

Example 2 Preparation of 2-methylthio-3-thiglutarate dihydrazide Diethyl 2-methylthio-3-thiaglutarate 23.5
g was dissolved in 80 ml of isopropanol and cooled to 6 ° C. 10.7g of hydrazine monohydrate over 1 hour
Was dissolved in 15 ml of an isopropanol solution.
The mixture was allowed to stand at the same temperature for 10 hours, and the precipitated white crystals were collected by filtration. The obtained crystals were washed with isopropanol and then with hexane to obtain 16.7 g. ¹ H-NMR (d ₆ -DMSO): δ = 2.11 (s,
3H), 3.21 (ABq, 2H), 3.99 (b, 4
H), 4.57 (s, 1H), 9.32 (b, 2H)
ppm

Example 3 2,4-dithiapentane-1,
Production of 3-diisocyanate 13.5 g was suspended in 70 ml of water, cooled to 6 ° C., 13.4 g of concentrated hydrochloric acid was added, and the mixture was stirred to obtain a colorless transparent homogeneous solution. An aqueous solution of 8.56 g of sodium nitrite 70 m here
1 was added dropwise. After dropping, 70 ml of toluene was added,
The mixture was further stirred at the same temperature for 3 hours. After the reaction, the toluene layer was separated and dried over anhydrous sodium sulfate. The toluene solution was kept at 65 ° C. for 2 hours and reacted until no more nitrogen gas was generated. This was concentrated under reduced pressure and distilled, and a fraction having a boiling point of 102 to 106 ° C (0.5 mmHg) was collected. Colorless transparent oil. Yield 4.8 g ¹ H-NMR (CDCl ₃ ): δ = 2.32 (s, 3
H), 4.49 (s, 2H), 5.59 (s, 1H)
ppm

Example 4 2,4-bis (methylthio)-
Production of diethyl 3-thiaglutarate 6.95 g of anhydrous sodium sulfide was added to 200 ml of ethanol.
And cooled to 10 ° C. 30 ml of an ethanol solution of ethyl 2-chloro-2-methylthioacetate produced in Comparative Example 1 was added dropwise thereto, and the mixture was vigorously stirred. After 8 hours, most of the ethanol was distilled off using a rotary evaporator, 200 ml of toluene was added, the mixture was washed twice with a saturated saline solution, and dried over anhydrous magnesium sulfate. Concentrate on an evaporator and distill under reduced pressure to a boiling point of 136 to 140 ° C.
A fraction (0.5 mmHg) was collected. Yield 15 g. A pale yellow oil was obtained. ¹ H-NMR (CDCl ₃ ): δ = 1.32 (t, 6
H), 2.21 (s, 3H), 2.24 (s, 3H),
4.24 (q, 4H), 4.61 (s, 2H) ppm

Example 5 2,4-bis (methylthio)-
Production of 3-thiaglutaric acid dihydrazide 14.6 g of diethyl 2,4-bis (methylthio) -3-thiaglutarate was dissolved in 45 ml of ethanol and cooled to 8 ° C. Here, hydrazine monohydrate 5.6 was taken for 1 hour.
g of ethanol solution in which g was dissolved was added dropwise. The mixture was allowed to stand at the same temperature for 10 hours, and the precipitated white crystals were collected by filtration. The obtained crystals were washed with isopropanol and then with hexane to obtain 7.7 g. ¹ H-NMR (d ₆ -DMSO): δ = 2.13 (b
s, 6H), 4.53 (s, 2H), 5.22 (b, 4
H), 9.22 (b, 2H) ppm

Example 6 Preparation of 2,4,6-trithiaheptane-3,5-diisocyanate 7.2 g of 2,4-bis (methylthio) -3-thiaglutaric acid dihydrazide was suspended in 50 ml of water and the suspension was heated at 6 ° C. Then, 5.5 g of concentrated hydrochloric acid was added thereto, followed by stirring to obtain a colorless transparent homogeneous solution. To this, 20 ml of an aqueous solution in which 3.95 g of sodium nitrite was dissolved was added dropwise. After completion of the dropwise addition, toluene 50
Then, the mixture was further stirred at the same temperature for 3 hours. After the reaction, the toluene layer was separated and dried over anhydrous sodium sulfate. The toluene solution was kept at 65 ° C. for 2 hours and reacted until no more nitrogen gas was generated. This was concentrated under reduced pressure and distilled, and a fraction having a boiling point of 145 to 150 ° C (0.2 mmHg) was collected. Colorless transparent oil. Yield 2.5 g ¹ H-NMR (CDCl ₃ ): δ = 2.32 (s, 6
H), 5.48 (s, 2H) ppm

Example 7 Preparation of diethyl 2,4,7,9-tetrathiapentane-5,6-dicarboxylate 3.35 g of sodium hydroxide was dissolved in a mixed solvent of 60 ml of water and 30 ml of methyl isobutyl ketone. After cooling to 10 ° C, 10 g of diethyl 2,3-dimercaptosuccinate prepared in Reference Example 2 was added, and the mixture was stirred vigorously and reacted for 30 minutes. To this, 8.1 g of chloromethylmethyl sulfide was added dropwise, and the mixture was further reacted at the same temperature for 5 hours. After the reaction, 100 ml of toluene was added, washed twice with a saturated saline solution, and dried over anhydrous magnesium sulfate. Concentrate with an evaporator and perform column chromatography (hexane: acetone = 4: 1)
Was purified. Yield 7.5 g ¹ H-NMR (CDCl ₃ ): δ = 1.31 (t, 6
H), 2.29 (s, 6H), 3.33 (bs, 2
H), 4.16 (q, 4H), 4.37 (s, 4H)
ppm

Example 8 Preparation of 2,4,7,9-tetrathiapentane-5,6-diisocyanate 7 g of diethyl 2,4,7,9-tetrathiapentane-5,6-dicarboxylate was added to 20 ml of ethanol. Dissolved in 7
5 ml of an ethanol solution in which 2.6 g of hydrazine monohydrate was dissolved was added dropwise at 1 ° C. over 1 hour. The resulting solution was allowed to stand at the same temperature for 10 hours, and the precipitated white crystals were collected by filtration. The obtained crystals were washed with diethyl ether and immediately dried in vacuo.
The white crystals were suspended as they were in 15 ml of water, cooled to 6 ° C., and 2.5 g of concentrated hydrochloric acid was added thereto, followed by stirring to obtain a colorless transparent uniform solution. To this, 8 ml of an aqueous solution in which 1.5 g of sodium nitrite was dissolved was added dropwise. After completion of the dropwise addition, toluene 50
Then, the mixture was further stirred at the same temperature for 3 hours. After the reaction, the toluene layer was separated and dried over anhydrous sodium sulfate. The toluene solution was kept at 65 ° C. for 2 hours and reacted until no more nitrogen gas was generated. This was concentrated under reduced pressure and distilled, and a fraction having a boiling point of 158 to 160 ° C (0.2 mmHg) was collected. Colorless transparent oil. Yield 2.8 g ¹ H-NMR (CDCl ₃ ): δ = 2.29 (s, 6
H), 4.17 (bs, 2H), 4.37 (s, 4H)
ppm

Example 9 2,4-dithiapentane-1,3-diisocyanate 3
0 g (0.158 mol), 5,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-
28.9 g (0.076 mol) of dithiol and 0.01% by weight (based on the total amount of the mixture) of dimethyltin dichloride were mixed to form a uniform liquid, which was sufficiently defoamed and then subjected to a mold release treatment. And a gasket. Then, the mixture was cured by heating for 24 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 polymer was taken out of the mold. The obtained resin is colorless and transparent, has a refractive index of 1.693,
Abbe number is 33.0, thermal deformation onset temperature is 128 ° C,
The deformation was 16μ. The resin was stained using 2% benzyl alcohol as a carrier. The transmittance after staining was 29% for ML-Yellow, 27% for ML-Red, and 34% for ML-Blue, and the overall evaluation of staining was (（). The water absorption after 48 hours is 0.01
% And the surface hardness was 2H.

Example 10 2,4-Dithiapentane-1,3-diisocyanate 3
4.1 g (0.179 mol), 25.9 g (0.12 mol) of 1,2,4-trismercaptomethylbenzene and 0.01% by weight of dimethyltin dichloride (based on the total amount of the mixture) were mixed. After making it a homogeneous liquid and thoroughly degassing,
It was injected into a mold composed of a glass mold and a gasket that had been subjected to a release treatment. Then, the mixture was cured by heating for 24 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 polymer was taken out of the mold. The obtained resin is colorless and transparent, and has a refractive index of 1.
696, Abbe number 29.1, thermal deformation onset temperature is 1
At 44 ° C., the deformation was 14 μ. The resin was stained using 2% benzyl alcohol as a carrier. The transmittance after staining was 31% for ML-Yellow and ML-Yellow.
It was 36% for Red and 44% for ML-Blue, and the overall evaluation of staining was (（). The water absorption after 48 hours was 0.01%, and the surface hardness was 2H.

Example 11 33.6 g (0.143 mol) of 2,4,6-trithiaheptane-3,5-diisocyanate, 5,7-bis (mercaptomethyl) -3,6,9-tri Thiaoundecan-
After mixing 1,11-dithiol 26.4 (0.072 mol) and dimethyltin dichloride 0.01% by weight (based on the total amount of the mixture) to make a uniform liquid, and sufficiently defoaming,
It was injected into a mold composed of a glass mold and a gasket that had been subjected to a release treatment. Then, the mixture was cured by heating for 24 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 polymer was taken out of the mold. The obtained resin is colorless and transparent, and has a refractive index of 1.
701, Abbe number 32.6, and thermal deformation onset temperature is 1.
At 19 ° C., the deformation was 17 μm. The resin was stained using 2% benzyl alcohol as a carrier.
The transmittance after staining was 15% for ML-Yellow and ML-Yellow.
-Red was 19%, ML-Blue was 21%, and the overall evaluation of staining was (O). The water absorption after 48 hours was 0.01%, and the surface hardness was 2H.

Example 12 37.1 g (0.159 mol) of 2,4,6-trithiaheptane-3,5-diisocyanate and 22.9 g (0.106 mol) of 1,2,4-trismercaptomethylbenzene Mol) and 0.01% by weight of dimethyltin dichloride (based on the total amount of the mixture) to make a uniform liquid, and after sufficient defoaming, pour into a mold made of a glass mold and a gasket that have been subjected to mold release treatment. did. Then from 30 ° C to 1
While gradually raising the temperature to 20 ° C., the mixture was cured by heating for 24 hours. After the completion of the polymerization, the mixture was gradually cooled, and the polymer was taken out of the mold. The obtained resin was colorless and transparent, had a refractive index of 1.712, an Abbe number of 28.7, a thermal deformation start temperature of 137 ° C., and a deformation amount of 13 μm. This resin,
Stained with 2% benzyl alcohol as carrier. The transmittance after staining was 30 in ML-Yellow.
%, ML-Red was 33%, and ML-Blue was 44%, and the overall evaluation of staining was (（). The water absorption after 48 hours was 0.01%, and the surface hardness was 2H.

Example 13 3,7.1 g (0.125 l) of 2,4,7,9-tetrathiapentane-5,6-diisocyanate, 5,7-bis (mercaptomethyl) -3,6,9 -22.9 g (0.062 mol) of trithiaundecane-1,11-dithiol and 0.01% by weight (based on the total amount of the mixture) of dimethyltin dichloride were mixed to form a homogeneous liquid, and after sufficient defoaming, Then, it was poured into a mold composed of a glass mold and a gasket subjected to a release treatment. Then from 30 ° C to 1
While gradually raising the temperature to 20 ° C., the mixture was cured by heating for 24 hours. After the completion of the polymerization, the mixture was gradually cooled, and the polymer was taken out of the mold. The obtained resin was colorless and transparent, had a refractive index of 1.692, an Abbe number of 33.4, a thermal deformation start temperature of 116 ° C., and a deformation amount of 19 μm. This resin,
Stained with 2% benzyl alcohol as carrier. The transmittance after staining was 20 in ML-Yellow.
%, 22% for ML-Red, and 27% for ML-Blue, 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 30.0 g (0.12 mol) of 1,2-bis (2-isocyanatoethylthio) ethane and 16.7 g (0.077 mol) of 1,2,4-tris (mercaptomethyl) benzene ), 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 mold for lenses comprising a glass mold and a gasket subjected to release treatment. Was injected. Then 4
While gradually raising the temperature from 0 ° C. to 120 ° C., the composition was cured by heating for 20 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 of 1.673 and an Abbe number of 31.0.
The thermal deformation start temperature was 115 ° C., and the deformation amount was 31 μm.
The lens was stained using 2% benzyl alcohol as a carrier. The transmittance after staining was ML-Yel
28% for low, 28% for ML-Red, ML-Blu
e was 35%, and the overall evaluation of dyeability was (（). The water absorption after 48 hours was 0.03%, and the surface hardness was H.

Comparing Example 10 with Comparative Example 1 in which a resin was produced using the same polythiol, the resin of Example 10 had a heat deformation starting temperature higher by 29 ° C. than the resin of Comparative Example 1, Is less than half. Nevertheless,
There is no great difference in the dyeability when using Carrier. That is,
The effect of the sulfur-containing isocyanate of the present invention is extremely remarkable.

[0035]

The sulfur-containing urethane resin obtained by polymerizing the optical resin composition containing the novel diisocyanate derivative containing a sulfur atom of the present invention has an extremely high refractive index, high heat resistance and thermal deformation. Less high refractive index optical resin.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a TMA curve used for measuring the amount of thermal deformation.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masao Imai 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Kenichi Fujii 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Inside the corporation

Claims (6)

[Claims] 1. A diisocyanate derivative represented by the following general formula (1). Embedded image (Wherein, R represents an ethylene group or a propylene group, a carbon atom at the center of the propylene group may be substituted with a sulfur atom, R ′ represents a methylthio group or a methylthiomethylthio group, and n represents 1 to 3 Represents an integer.) 2. A 2,4-dithiapentane-1,3-diisocyanate represented by the formula (2). Embedded image 3. 2,4,6 represented by the formula (3)
-Trithiaheptane-3,5-diisocyanate. Embedded image 4. The compound represented by the formula (4)
7,9-tetrathiapentane-5,6-diisocyanate. Embedded image 5. A composition for a high refractive index optical resin, comprising the isocyanate derivative according to claim 1 and at least one polythiol compound. 6. A lens obtained by polymerizing the resin composition for high refractive index optics according to claim 5.