JPH07242722A - Composition for plastic lens with high refractive index and lens - Google Patents

Abstract

PURPOSE:To main a composition for use in producing a urethane resin lens excellent in heat resistance and surface hardness and having reduced water absorption and a high refractive index by polymerizing a monomer mixture comprising a specific polyisocyanate, a specific polythiol, and a specific polythiol compound. CONSTITUTION:A monomer mixture is polymerized which comprises a polyisocyanate represented by the formula (wherein X is H or methyl, R is a chlorine or bromine atom, methyl, or ethyl, m is 0-4, and n is 2-4), 1,2-bis[(2- mercaptoethyl)thio]-3mercaptopropane, and at least one member selected from an aromatic compound substituted with 5-6 mercaptomethyl groups, a cyclohexane derivative substituted with 3-4 mercaptomethyl groups 1-(2- mercaptoethyloxy)-2,4-bis(mercaptomethyl)benzene, and 2,6,2'',6''-tetrakis(mercaptomethyl)-1,1': 3',1''-terphenyl.

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 which is used for various optical lenses such as spectacle lenses and has excellent heat resistance, low water absorption and excellent surface hardness. It relates to a composition for producing the lens.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight than inorganic lenses, are less likely to be broken, and can be dyed, and thus have recently become rapidly popular in the field of optical elements such as spectacle lenses and camera lenses. At present, as a resin widely used for these purposes, D obtained by casting polymerization of diethylene glycol bisallyl carbonate (hereinafter abbreviated as DAC) is used.
There is AC resin. This DAC resin is lightweight,
It has features such as excellent dyeability, good machinability such as machinability and abrasivity, and the like, and can meet needs with rich fashionability. However, since the DAC resin has a lower refractive index than the inorganic lens, it is necessary to increase the center thickness, the edge thickness, and the curvature of the lens in order to obtain the optical characteristics equivalent to those of the glass lens. It is inevitable that it becomes thick. Therefore, a lens resin having a higher refractive index has been desired.

Polyurethane lenses are known as lenses having a higher refractive index than DAC resin lenses. The present inventors have proposed, for example, US Pat.
P-4775753 (JP-A-63-46213) proposes a polyurethane lens made of a polymer of a xylylene diisocyanate compound and a polythiol compound, and is widely used as an optical lens such as an eyeglass lens. ing. Further, as a polyurethane lens having a higher refractive index, for example, a polyurethane lens made of a polymer of a trithiol compound and a polyisocyanate compound described in USP-5191055 (JP-A-2-270859) is proposed. However, these polyurethane lenses are generally inferior in heat resistance to olefin radical-polymerization type resins, for example, DAC resins, and therefore, dyeing of lenses that require heat treatment at about 60 to 90 ° C. is usually performed. When post-processing such as surface coating, the lens is likely to be deformed, and the thermal processing temperature must be kept low.

On the other hand, as a method of improving the heat resistance of the polyurethane resin, JP-A-2-275901 and EP408459 (JP-A-3-56525).
No. gazette) is known. However, JP-A-2-
The polyurethane resin composed of a polymer of two kinds of aliphatic polythiol compounds and aromatic polyisocyanate compounds described in JP-A-275901 has a refractive index of 1.5.
It is as low as about 7 to 1.61, and the polyurethane resin obtained by this method has a high water absorption rate. Therefore, a lens having a thin center thickness may absorb water and cause deformation in the center part of the lens. Furthermore, the surface hardness of the obtained resin is low,
It has a drawback that the molded lens is easily scratched. Further, the polyurethane resin made of a polymer of a polythiol compound having three or more reactive groups and a polyisocyanate compound described in EP-408459 has too high heat resistance, and therefore a lens is dyed by an ordinary method. Difficult to do.

Further, 1- (2-mercaptoethyloxy) -2,4-bis (mercaptomethyl) benzene, 1,2,4- or 1,3,5-tris (mercaptomethyl) cyclohexane is used alone as a thiol component. When used in, it is preferable to use xylylene diisocyanate as the isocyanate component, from the viewpoint of poor dyeability due to too high heat resistance of the resulting polyurethane resin, low Abbe number and cloudiness. Absent. Furthermore, the thiol component used for the purpose of improving heat resistance may become solid. For example, pentakis (mercaptomethyl) benzene, hexakis (mercaptomethyl) benzene, or 2,6,2 ", 6" -tetrakis (mercaptomethyl) -1,1 ': 3', 1 "preferably used in the present invention. -Terphenyl has a high melting point,
Since it has poor solubility, when it is used alone as a thiol component, handling becomes very complicated in terms of molding operation of the lens and workability is poor.

[0006]

DISCLOSURE 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 provides flexibility in the selection of thermal conditions for post-processing such as dyeing and surface coating. In order to increase the heat resistance, a method of improving the heat resistance thereof is provided, and further, a lens having low water absorption and excellent surface hardness is provided.

[0007]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above-mentioned problems. That is, according to the present invention, as the component (a), at least one or more polyisocyanates represented by the general formula (1) (formula 6) and the component (b) represented by the formula (2) (formula 6) , 2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, an aromatic compound substituted with 5 or 6 mercaptomethyl groups as component (c), 3 or 4 mercaptomethyl groups A cyclohexane derivative substituted with 1- (2-mercaptoethyloxy) -2,4-bis (mercaptomethyl) benzene or 2,6,2 ", 6" -tetrakis (mercaptomethyl) -1,1 ': 3 A composition for a high refractive index plastic lens comprising a monomer mixture containing three components of at least one selected from the group consisting of ', 1 "-terphenyl, and a sulfur-containing ureta obtained by polymerizing the composition. The present invention relates to a high-refractive-index plastic lens made of resin.

[0008]

[Chemical 6] (In the above formula, X represents a hydrogen atom or a methyl group, R represents a chlorine atom, a bromine atom, a methyl group or an ethyl group, and m
Is an integer of 0 to 4 and n is an integer of 2 to 4)

The present invention also provides a novel compound suitable for the component (c) in the composition for a high refractive index plastic lens, that is, pentakis (mercaptomethyl) represented by the formula (3) ) Benzene, 1- (2-mercaptoethyloxy) -2,4 represented by the formula (4)
-Bis (mercaptomethyl) benzene and 1,3,5-tris (mercaptomethyl) cyclohexane represented by the formula (5) (formula 7).

[0010]

[Chemical 7]

The present invention will be described in detail below. The component (a) in the present invention is a compound represented by the general formula (1), and specifically, 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 nuclear chlorinated compounds, brominated compounds, methylated compounds or ethylated compounds, such as 4-chloro-m-xylylenediisocyanate, 4,5-dichloro-m- Examples thereof include xylylene diisocyanate, 2,3,5,6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, and 4-ethyl-m-xylylene diisocyanate. Some of these are commercially available. 1,2-represented by the formula (2) which is the component (b)
Bis [(2-mercaptoethyl) thio] -3-mercaptopropane can be prepared by the method described in JP-A-2-270859, that is, by reacting epihalohydrin with 2-mercaptoethanol and then reacting with thiourea. Easily manufactured.

Examples of the aromatic compound substituted with 5 or 6 mercaptomethyl groups as the component (c) include pentakis (mercaptomethyl) benzene and hexakis (mercaptomethyl) benzene. Hexakis (mercaptomethyl) benzene is a known compound described in the literature, and can be simply produced by a method described in the literature from an inexpensive and easily available compound. That is, HJ
Backer, Rec. Trav. Chim., 54, 745 (1935) converts hexamethylbenzene to hexakis (bromomethyl) benzene with bromine, and HJ Backer, Rec. T
As described in rav. Chim., 54, 905 (1935), it can be produced by reaction with thiourea and then hydrolysis in an aqueous alkaline solution. In addition, 2,6,2 ", 6" -tetrakis (mercaptomethyl) -1,1 ': 3', 1 "-terphenyl is also a known compound described in the literature, and from compounds that are inexpensive and easily available, , For example, T. Vinod, J. O.
It can be easily produced by the method described in rg. Chem., 55, 881 (1990). That is, 2,6-dimethylbromobenzene and 2,6-dichloroiodobenzene are condensed by a Grignard reaction, a methyl group is converted to a bromomethyl group with N-bromosuccinimide, and after reacting with thiourea, hydrolysis in an alkaline aqueous solution is performed. It can be manufactured by decomposition.

Cyclohexane derivatives substituted with 3 or 4 mercaptomethyl groups include, for example, 1,
2,3-tris (mercaptomethyl) cyclohexane,
1,2,4-Tris (mercaptomethyl) cyclohexane, 1,3,5-tris (mercaptomethyl) cyclohexane, 1,2,3,4-tetrakis (mercaptomethyl) cyclohexane, 1,2,4,5-tetrakis (Mercaptomethyl) cyclohexane etc. can be mentioned. Of these, 1,2,4-tris (mercaptomethyl) cyclohexane is a known compound described in the literature, and from compounds that are inexpensive and easily available, the literature, for example, A.
P. Kozikowsky, et al., J. Med. Chem., 36, 3035 (1993).
It can be easily produced by the method described in. That is, it can be produced by condensing tris (hydroxymethyl) cyclohexane and thioacetic acid with diisopropyl azodicarboxylate and triphenylphosphine to obtain a thioacetic acid ester derivative, which is reductively deesterified.

In the lens composition of the present invention, pentakis (mercaptomethyl) benzene, which is a novel compound suitable for the component (c), can be produced from pentakis (bromomethyl) benzene by the following method. That is, it can be obtained by reacting pentakis (bromomethyl) benzene with thiourea and then hydrolyzing it in an alkaline aqueous solution. Here, the reaction with thiourea can be carried out in a solvent such as tetrahydrofuran or lower alcohol, but ethanol or the like is preferable in view of solubility and the like. The reaction is
It can be carried out at room temperature or above and below the boiling point of the solvent, but heating under reflux is preferable. For hydrolysis in an alkaline aqueous solution, sodium hydroxide, potassium hydroxide, potassium carbonate or the like can be used as a base, but a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is preferable. The hydrolysis reaction can be carried out at room temperature or higher and the boiling point of the solvent or lower, but heating under reflux is preferable. The reaction time for both reactions is usually 3 to
10 hours. In addition, pentakis (bromomethylbenzene) is a commercially available pentamethylbenzene,
It can be obtained by reacting with N-bromosuccinimide or bromine. At this time, a solvent inert to the brominating agent can be used as the reaction solvent without any problem, but carbon tetrachloride or the like is preferable. The reaction can be carried out at room temperature or above and below the boiling point of the solvent, but heating under reflux is preferred. To accelerate the reaction, benzoyl peroxide or the like may be added or light irradiation may be performed.

1- (2-mercaptoethyloxy)-
2,4-bis (mercaptomethyl) benzene can be produced by the following method. That is, (2-hydroxyethyloxy) phthalic acid is produced by the reaction of hydroxyphthalic acid and 2-chloroethanol, and 1- (2-hydroxyethyloxy) -2,4 is produced by the reduction reaction.
-Converted to bis (hydroxymethyl) benzene and further reacted with a brominating agent to give 1- (2-bromoethyloxy)-
It can be obtained by converting it into 2,4-bis (bromomethyl) benzene, reacting with thiourea, and then hydrolyzing it in an alkaline aqueous solution. The reaction of hydroxyphthalic acid and 2-chloroethanol is carried out in the presence of a base. As the solvent, water, lower alcohol or the like can be used, but water is preferable. The reaction can be carried out above the freezing point and below the boiling point of the solvent, but room temperature is preferred. Although sodium hydroxide, potassium hydroxide, potassium carbonate, pyridine or the like can be used as the base, sodium hydroxide or potassium hydroxide is preferable.

For the reduction reaction of (2-hydroxyethyloxy) phthalic acid, borane / methyl sulfide complex, lithium aluminum hydride or the like can be used, but the borane / methyl sulfide complex is preferable. Tetrahydrofuran, diglyme, ether, dioxane, dichloromethane and the like can be used as the reaction solvent, but tetrahydrofuran is preferable. Hydrobromic acid, phosphorus tribromide, thionyl bromide, carbon tetrabromide and triphenylphosphine and the like can be used in the reaction with the brominating agent, but phosphorus tribromide is preferable. The reagent can be used in an amount of 1 equivalent or more with respect to the raw material, but a range of 1.5 to 2 equivalents is preferable. As the reaction solvent, ether, tetrahydrofuran,
Dichloromethane, dichloroethane and the like can be used, but dichloroethane is preferred. The reaction can be carried out under ice-cooling to below the boiling point of the reaction solvent, but room temperature is preferable. The reaction time is usually 2 to 24 hours. Here, the reaction with thiourea can be carried out in a solvent such as tetrahydrofuran or lower alcohol, but ethanol or the like is preferable in view of solubility and the like. The reaction can be carried out at room temperature or above and below the boiling point of the solvent, but heating under reflux is preferred. For hydrolysis in an alkaline aqueous solution, sodium hydroxide, potassium hydroxide, potassium carbonate or the like can be used as a base,
A sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution are preferable. The hydrolysis reaction can be carried out at room temperature or higher but below the boiling point of the solvent, but heating under reflux is preferable. The reaction time for both reactions is usually 3 to 10 hours.

1,3,5-tris (mercaptomethyl)
Cyclohexane can be manufactured by the following method.
That is, commercially available 1,3,5-cyclohexanetricarboxylic acid is reduced to give 1,3,5-cyclohexanetrimethanol, which is further reacted with a brominating agent to give 1,3,5-tris (bromomethyl) cyclohexane. Can be obtained by hydrolysis with an aqueous solution of alkali after conversion to thiourea. In the reduction reaction, lithium borohydride, sodium borohydride and Lewis acid, lithium aluminum hydride, etc. can be used,
Lithium aluminum hydride is preferred. As the reaction solvent, tetrahydrofuran, diglyme, ether, dioxane or the like can be used, but tetrahydrofuran is preferable. Hydrobromic acid, phosphorus tribromide, thionyl bromide, carbon tetrabromide and triphenylphosphine and the like can be used in the reaction with the brominating agent, but phosphorus tribromide is preferable. As the reaction solvent, ether, tetrahydrofuran, dichloromethane, dichloroethane or the like can be used, but dichloroethane is preferable. The reaction can be carried out under ice-cooling to below the boiling point of the reaction solvent, but room temperature is preferable. Here, the reaction with thiourea can be carried out in a solvent such as tetrahydrofuran or a lower alcohol,
Ethanol or the like is preferable in terms of solubility. The reaction can be carried out at room temperature or above and below the boiling point of the solvent, but heating under reflux is preferred. For hydrolysis in an alkaline aqueous solution, sodium hydroxide, potassium hydroxide, potassium carbonate or the like can be used as a base.
A potassium hydroxide aqueous solution is preferred. The hydrolysis reaction can be carried out at room temperature or higher but below the boiling point of the solvent, but heating under reflux is preferable.

The proportion of each component used in the present invention, that is,
The proportion of the polyisocyanate represented by the general formula (1) of the component (a) and the polythiol represented by the formula (2) of the component (b) and the polythiol compound of the component (c) is
The molar ratio of NCO group / SH group is in the range of 0.5 to 1.5, preferably 0.7 to 1.3, and most preferably 0.9.
The range is from 1.1 to 1.1. Moreover, the polythiol compound of the component (c) is 5 to 70 relative to the entire polythiol component.
It is in the range of wt%, preferably 8 to 60 wt%, and most preferably 10 to 50 wt%. This component (c)
The thiol compound of is, for the entire polythiol component,
If it is less than 5% by weight, it is difficult to obtain a sufficient improvement in heat resistance.
If it exceeds 70% by weight, the heat resistance becomes too high, so that it tends to be difficult to dye it easily by a usual method, or the operation tends to become difficult in view of the solubility of the component (c). The usage ratio of the thiol compound of the component (c) is appropriately determined depending on the compound of the component (a) and the compound of the component (c) used and various physical properties required for the obtained lens.

In the composition of the present invention, a polymerization catalyst for accelerating the polymerization reaction, a UV absorber for improving weather resistance, an antioxidant, an anti-coloring agent, a fluorescent dye, a light stabilizer, an oil-soluble dye, etc. You may add the additive of said suitably as needed. The lens of the present invention is produced by at least one of the polyisocyanates represented by the general formula (1) of the component (a), the polythiol represented by the formula (2) of the component (b), and the component (c ), A monomer mixture containing at least one or more polythiol compounds, and if necessary, additives are added, and a known cast polymerization method, that is, a glass or metal mold and a resin gasket are combined. It is carried out by injecting the mixed solution into the mold and heating and curing. At this time, the mold may be subjected to a known release treatment in order to facilitate the removal of the resin after molding. Further, in order to simplify the workability during the production of the lens, the compound of component (c) may be mixed with the compound of component (b) in advance. Particularly, when the component (c) is solid, it is preferably dissolved in the compound of the component (b) in advance. In this case, since the compound of component (b) is a low-viscosity liquid, the compound of component (c) can be easily dissolved.

The polymerization temperature and the polymerization time in the cast polymerization will vary depending on the composition of the monomer, the kind and the amount of the additive, but generally, the temperature rise is started from 5 to 20 ° C.
The temperature is raised to about 0 ° C to 130 ° C in 8 to 30 hours. The lens obtained in the present invention, if necessary, anti-reflection, imparting high hardness, improving wear resistance, improving chemical resistance, imparting anti-fog property, or imparting fashionability, etc., surface polishing, Physical or chemical treatments such as antistatic treatment, hard coat treatment, antireflection coat treatment, dyeing treatment, and light control treatment can be performed. Further, the lens obtained in the present invention can be easily dyed in water or a solvent by using an ordinary disperse dye. At the time of dyeing, a carrier which is a dyeing aid may be added to the dyeing bath to further facilitate dyeing. The sulfur-containing urethane resin of the present invention has extremely low dispersion, high refractive index, excellent heat resistance, is colorless and transparent, is lightweight, has excellent weather resistance and impact resistance, and further has low water absorption and a surface. It has excellent hardness, not only optical element materials such as eyeglass lenses and camera lenses, but also glazing materials,
It is also suitable as a material for paints and adhesives.

[0021]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. 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 Pulfrich refractometer
It was measured at ° C.・ Appearance: Visual observation. -Heat resistance: A thermomechanical analyzer TAS300 (manufactured by Rigaku Denki Co., Ltd.) was used to load 5 g on the test piece and heat it at 2.5 ° C / min to measure its thermal deformation start temperature. Dyeability: ML-Yellow, ML-Red, ML-Bl which are disperse dyes for plastic lenses manufactured by Mitsui Toatsu Dye Co., Ltd.
ue was immersed in a 5 g / L aqueous solution for 5 minutes at 95 ° C. to dye a flat plate having a thickness of 9 mm. After dyeing, the transmittance at 400 to 700 nm was measured using a spectrophotometer U-2000 (manufactured by Hitachi Ltd.). As a comprehensive evaluation, those having good dyeability were evaluated as (◯), and those having poor dyeability or being unable to be dyed at all were evaluated as (x). Dyeing heat resistance: After immersion in a dyeing bath at 95 ° C. for 5 minutes, it was visually observed whether or not the lens was deformed. Water absorption rate: A test piece was prepared based on JIS-K-7209, immersed in water at room temperature for 48 hours, and the water absorption rate was measured from the weight change thereafter. -Surface hardness: Pencil hardness was measured using the pencil scratch tester for coating film of JIS-K-5401.

Example 1 Production of pentakis (mercaptomethyl) benzene 7 g of pentamethylbenzene was dissolved in 500 ml of carbon tetrachloride, and N-bromosuccinimide 46.
2g was added in 5 portions every 2 hours. Each time N-bromosuccinimide was added, benzoyl peroxide 0.1
g was added. The reaction was carried out under direct sunlight and stirred under heating under reflux for a total of 24 hours. After standing to cool, it was filtered and the filtrate was concentrated under reduced pressure to give crude pentakis (bromomethyl) benzene 17.
9 g was obtained (about 87% pure by HPLC analysis). This was dissolved in 270 ml of ethanol as it was, and thiourea 13.
1 g was added, and the mixture was reacted under heating under reflux for 6 hours. Chill with ice,
The precipitated crystals were collected by filtration, dissolved in 250 ml of water containing 53 g of potassium hydroxide, and reacted again with heating under reflux for 6 hours. After the reaction, the mixture was cooled in an ice bath, acidified with 20% sulfuric acid, ice-cooled, and the precipitated crystals were collected by filtration and washed with water. The crystals were recrystallized from a large amount of ethanol to obtain 5.3 g of pale yellow powdery crystals of pentakis (mercaptomethyl) benzene.
Melting point 175-8 [deg.] C. NMR (D ₆ -DMSO): 7.34 ppm (s, 1
H) 3.8-4.4 ppm (m, 10H) 3.0-3.5 ppm (m, 5H) IR (KBr): 3350, 2930, 1450, 10
40 cm ^-1

Example 2 Preparation of 1- (2-mercaptoethyloxy) -2,4-bis (mercaptomethyl) benzene 15 g of hydroxyphthalic acid was added to 16.
Dissolve in 110 ml of water containing 5 g and stir at room temperature for 2
-16.5 ml of chloroethanol was added dropwise, the mixture was reacted overnight, neutralized with 10% sulfuric acid, and the precipitated (2-hydroxyethyloxy) phthalic acid was collected by filtration and dried (yield 1
5.1 g). This was dissolved in 300 ml of tetrahydrofuran, and 15 g of borane-dimethyl sulfide complex was added dropwise for reduction. After reacting for 24 hours at room temperature, it is poured into water, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate,
Concentrate to 1- (2-hydroxyethyloxy) -2,4
-Bis (hydroxymethyl) benzene was obtained as a colorless oil (yield 9.6g). This is the ether 3 as it is
After dissolving in 00 ml, 14.8 g of phosphorus tribromide was added, and the mixture was reacted overnight at room temperature. The reaction solution was washed with water three times, dried over anhydrous sodium sulfate, and then concentrated to give 1- (2-bromoethyloxy).
-2,4-Bis (bromomethyl) benzene was obtained as a pale yellow oil (yield 2.1 g). This is ethanol 50
Dissolve in 2.5 ml, react with 2.5 g of thiourea under heating under reflux for 16 hours, then concentrate to obtain a residue, which is hydrolyzed with 6% aqueous sodium hydroxide solution under heating under reflux for 6 hours to give 10% sulfuric acid. It was neutralized with and extracted with chloroform. Wash this with water,
The extract was dried over anhydrous sodium sulfate and then concentrated to obtain 1.75 g of 1- (2-mercaptoethyloxy) -2,4-bis (mercaptomethyl) benzene. NMR (D ₆ -DMSO): 7.1-7.44ppm
(M, 3H) 4. 1 ppm (m, 2H) 3.5-3.9 ppm (m, 6H) IR (KBr): 3300, 2850, 1660, 13
20,770 cm ^-1

Example 3 Preparation of 1,3,5-tris (mercaptomethyl) cyclohexane Commercially available 1,3,5-cyclohexanetricarboxylic acid 20
g was added to a suspension of 8 g of lithium aluminum hydride in tetrahydrofuran (200 ml), and the mixture was reacted with heating under reflux for 8 hours. After the reaction, water was added for treatment, filtration, and the filtrate was concentrated to obtain 11 g of 1,3,5-cyclohexanetrimethanol as a colorless oily substance. This was dissolved in 150 ml of dichloroethane and 15 ml of phosphorus tribromide was added dropwise. The reaction was carried out overnight at room temperature, the reaction solution was washed with water three times, dried over anhydrous sodium sulfate, and then concentrated to obtain 15 g of 1,3,5-tris (bromomethyl) cyclohexane as a pale yellow oil. This was dissolved in 150 ml of ethanol, 9.5 g of thiourea was added, and the mixture was reacted under heating under reflux for 14 hours. The reaction solution was concentrated as it was, and the obtained residue was dissolved in 330 ml of 6% aqueous sodium hydroxide solution, hydrolyzed under heating under reflux for 6 hours, neutralized with 10% sulfuric acid, and extracted 3 times with 100 ml of chloroform. . This was washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain 4.2 g of 1,3,5-tris (mercaptomethyl) cyclohexane. _{NMR (CDCl 3): 3.4-3.6ppm (} m, 3
H) 2.3-2.7 ppm (m, 6H) 1.2-1.9 ppm (m, 9H) IR (KBr): 3250, 1650, 1540, 13
70,1120,750 cm ^-1

Example 4 22.8 parts of m-xylylene diisocyanate (0.1
2 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 17.7 parts (0.06)
8 mol), pentakis (mercaptomethyl) benzene
A glass mold in which 2.0 parts (0.0076 mol) and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) were mixed to form a uniform liquid, which was sufficiently defoamed and then subjected to a mold release treatment. And a gasket. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin is colorless and transparent, has excellent impact resistance, and has a refractive index n _d =
1.66, Abbe number ν _d = 32, and thermal deformation start temperature was 106 ° C. The lens did not deform even when dyed in a dyeing bath at 95 ° C. The transmittance after dyeing is ML-Yel.
Low 30%, ML-Red 36%, ML-Blu
e was 45%, and the overall evaluation of the dyeability was (◯). The water absorption rate after 48 hours was 0.02%, and the surface hardness was H.

Example 5 18.3 parts of m-xylylene diisocyanate (0.1
0 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 13.5 parts (0.05
2 mol), 1- (2-mercaptoethyloxy) -2,
4-bis (mercaptomethyl) benzene 3.2 parts (0.013 mol), dibutyltin dilaurate 0.0
1% by weight (based on the total amount of the mixture) was mixed to form a uniform liquid, which was sufficiently defoamed, and then poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Then, while gradually raising the temperature from 40 ° C. to 120 ° C.,
It was heat-cured over time. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin is colorless and transparent, has excellent impact resistance, and has a refractive index n _d = 1.6.
6, Abbe number ν _d = 35, thermal deformation start temperature is 10
It was 7 ° C. The transmittance after dyeing is ML-Yellow.
31%, ML-Red 39%, ML-Blue 4
It was 3%, and the overall evaluation of dyeability was (◯). 48
The water absorption rate after time was 0.04%, and the surface hardness was H.

Example 6 43.8 parts of m-xylylene diisocyanate (0.2
3 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 33.1 parts (0.13
Mol), hexakis (mercaptomethyl) benzene
5.0 parts (0.014 mol) and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) were mixed to form a uniform liquid, which was sufficiently defoamed and then subjected to a mold release treatment. And a gasket. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin is colorless and transparent, has excellent impact resistance, and has a refractive index n _d =
1.66, Abbe number ν _d = 33, and thermal deformation start temperature was 109 ° C. The transmittance after dyeing is ML-Yel.
33% at low, 39% at ML-Red, ML-Blue
e was 45%, and the overall evaluation of the dyeability was (◯). The water absorption rate after 48 hours was 0.02%, and the surface hardness was H.

Example 7 m-xylylene diisocyanate 44.7 parts (0.2
4 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 33.0 parts (0.13
Mol), 1,2,4-tris (mercaptomethyl) cyclohexane 8.0 parts (0.037 mol), and 0.01 wt% of dibutyltin dilaurate (based on the total amount of the mixture) to form a uniform liquid, After sufficiently defoaming, the mixture was poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin was colorless and transparent, had excellent impact resistance, had a refractive index n _d = 1.65, an Abbe number ν _d = 33, and had a thermal deformation starting temperature of 107 ° C. The transmittance after dyeing is M
29% for L-Yellow, 33% for ML-Red, M
It was 45% in L-Blue, and the overall evaluation of dyeability was (◯). The water absorption rate after 48 hours was 0.04%, and the surface hardness was H.

Example 8 27.0 parts of m-xylylene diisocyanate (0.1
4 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 12.3 parts (0.04)
8 mol), 1,2,4-tris (mercaptomethyl) cyclohexane 12.0 parts (0.056 mol), and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) to form a uniform liquid. After sufficiently defoaming, the mixture was poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin was colorless and transparent, had excellent impact resistance, had a refractive index n _d = 1.65, an Abbe number ν _d = 34, and had a thermal deformation starting temperature of 116 ° C. The transmittance after dyeing is M
28% for L-Yellow, 31% for ML-Red, M
It was 38% in L-Blue, and the overall evaluation of dyeability was (◯). The water absorption after 48 hours was 0.05%, and the surface hardness was H.

Example 9 22.4 parts of m-xylylene diisocyanate (0.1
2 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 16.5 parts (0.07)
Mol), 1,3,5-tris (mercaptomethyl) cyclohexane 4.0 parts (0.018 mol), and 0.01% by weight of dibutyltin dilaurate (based on the total amount of the mixture) to form a uniform liquid. After sufficiently defoaming, the mixture was poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin was colorless and transparent, had excellent impact resistance, had a refractive index n _d = 1.65, an Abbe number ν _d = 33, and had a thermal deformation starting temperature of 111 ° C. The transmittance after dyeing is M
29% for L-Yellow, 35% for ML-Red, M
It was 44% in L-Blue, and the overall evaluation of dyeability was (◯). The water absorption after 48 hours was 0.05%, and the surface hardness was H.

Example 10 29.2 parts of m-xylylene diisocyanate (0.1
6 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 23.4 parts (0.09)
, 2,6,2 ", 6" -tetrakis (mercaptomethyl) -1,1 ': 3', 1 "-terphenyl 4.1 parts (0.
01 mol), dibutyltin dilaurate 0.01% by weight
(To the total amount of the mixture) was mixed to form a uniform liquid, which was sufficiently defoamed and then poured into a mold made of a glass mold and a gasket that had been subjected to a mold release treatment. Then, 40 ℃
From 20 to 120 ° C., the mixture was heated and cured for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin was colorless and transparent, had excellent impact resistance, had a refractive index n _d = 1.66, an Abbe number ν _d = 31, and had a thermal deformation starting temperature of 112 ° C. The transmittance after dyeing is 33% in ML-Yellow,
ML-Red was 39% and ML-Blue was 47%, and the overall evaluation of the dyeability was (◯). The water absorption after 48 hours was 0.05%, and the surface hardness was H.

Comparative Example 1 m-xylylene diisocyanate 17.9 parts (0.1
1 mol), 1,2,4-tris (mercaptomethyl) cyclohexane 16.0 parts (0.063 mol) were mixed to obtain a uniform liquid, which was sufficiently defoamed and then subjected to a mold release treatment, and a glass mold and a gasket. Was injected into the mold mold. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin was colored yellow and extremely brittle, and was not suitable for practical use. The refractive index n _d = 1.66, the Abbe number ν _d = 36, and the thermal deformation starting temperature was 132 ° C. The transmittance after dyeing is 68% for ML-Yellow and 7 for ML-Red.
5%, 78% with ML-Blue, and the overall evaluation of dyeability was (x). The water absorption rate after 48 hours was 0.2%, and the surface hardness was H.

Comparative Example 2 m-xylylene diisocyanate 20.1 parts (0.1
1 mol), 1- (2-mercaptoethyloxy) -2,
4-Bis (mercaptomethyl) benzene 17.5 parts (0.07 mol) was mixed to obtain a uniform liquid, which was sufficiently defoamed, and then poured into a mold made of a mold-treated glass mold and a gasket. . Then, from 40 ℃ to 12
While gradually raising the temperature to 0 ° C., it was heated and cured for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin was excellent in impact resistance, but was cloudy. The refractive index n _d = 1.66, the Abbe number ν _d = 33, and the thermal deformation starting temperature was 130 ° C. The transmittance after dyeing is 81% in ML-Yellow,
It was 78% for ML-Red and 84% for ML-Blue, was not dyed, and the overall evaluation of the dyeability was (x).
The water absorption rate after 48 hours was 0.2%, and the surface hardness was H.

Comparative Example 3 m-xylylene diisocyanate 64.1 parts (0.3
4 mol), pentakis (mercaptomethyl) benzene
After 36.0 parts (0.14 mol) were mixed and sufficiently defoamed, the mixture was poured into a mold made of a mold-treated glass mold and a gasket. Then, from 40 ℃ to 12
While gradually raising the temperature to 0 ° C., it was heated and cured for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. In the obtained resin, pentakis (mercaptomethyl) benzene was not completely dissolved, and it was non-uniform and clouded in a yellowish brown color, which was completely unsuitable for practical use.

Comparative Example 4 m-xylylene diisocyanate 65.4 parts (0.3
5 mol), 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 60.1 parts (0.23
Mol) and 0.1% by weight of dibutyltin dilaurate (relative to the total amount of the mixture) to form a uniform liquid, which is sufficiently defoamed and then poured into a mold made of a glass mold and a gasket that has been subjected to a mold release treatment. did. Then, from 40 ℃ to 1
While gradually raising the temperature to 20 ° C., it was heated and cured for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin is colorless and transparent, has excellent impact resistance, has a refractive index n _d = 1.66 and an Abbe number ν _d = 3.
3, and the thermal deformation starting temperature was 84 ° C. The lens was deformed when dyed in a dyeing bath at 95 ° C. The transmittance after dyeing is 24% for ML-Yellow and 31 for ML-Red.
%, 40% in ML-Blue, and the overall evaluation of dyeability was (◯).

Comparative Example 5 m-xylylene diisocyanate 17.9 parts (0.0
95 mol), 1,2-bis [(2-mercaptoethyl)
Thio] -3-mercaptopropane 15.7 parts (0.0
62 mol), 1,2,4-tris (mercaptomethyl)
Cyclohexane 0.60 parts (0.0024 mol) and dibutyltin dilaurate 0.01% by weight (based on the total amount of the mixture) are mixed to form a uniform liquid, which is sufficiently defoamed and then subjected to mold release treatment. It was poured into a mold composed of a mold and a gasket. Then, the temperature was gradually raised from 40 ° C. to 120 ° C., and heat curing was performed for 20 hours.
After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold. The obtained resin is colorless and transparent, and has a refractive index n _d =
The Abbe number v _{d was} 1.65, the thermal deformation start temperature was 88 ° C. The lens was deformed when dyed in a dyeing bath at 95 ° C. The transmittance after dyeing is 24% for ML-Yellow, 30% for ML-Red, and 34 for ML-Blue.
%, And the overall evaluation of the dyeability was (◯). The water absorption rate after 48 hours was 0.2%, and the surface hardness was H.

[0037]

The plastic lens made of the sulfur-containing urethane resin obtained by polymerizing the composition for a high refractive index plastic lens made of the monomer mixture containing the three components of the present invention is a polyisocyanate represented by the general formula (1). It is an extremely excellent high-refractive-index plastic lens that does not impair the physical properties of the plastic lens obtained by polymerizing the nato and the polythiol of the formula (2) and has improved heat resistance, which is a drawback thereof.

Claims (7)

[Claims] 1. A compound represented by the general formula (1) (formula 1) as the component (a):
At least one or more polyisocyanates represented by: (In the formula, X represents a hydrogen atom or a methyl group, R represents a chlorine atom, a bromine atom, a methyl group or an ethyl group, m represents 0 to 4, and n represents an integer of 2 to 4) Component (b) 1,2-represented by the formula (2)
Bis [(2-mercaptoethyl) thio] -3-mercaptopropane, Aromatic compounds substituted with 5 or 6 mercaptomethyl groups as component (c), cyclohexane derivatives substituted with 3 or 4 mercaptomethyl groups, 1-
Consists of (2-mercaptoethyloxy) -2,4-bis (mercaptomethyl) benzene or 2,6,2 ", 6" -tetrakis (mercaptomethyl) -1,1 ': 3', 1 "-terphenyl A composition for a high refractive index plastic lens, which comprises a monomer mixture containing three components of at least one selected from the group. 2. The component (a) is xylylene diisocyanate, and the component (c) is 1,3,5-tris (mercaptomethyl) cyclohexane or 1,2,4-tris (mercaptomethyl) cyclohexane. The composition for a high refractive index plastic lens according to claim 1, wherein 3. The NCO group and the SH group are 0.5 to 1.5 in terms of a molar ratio of NCO group / SH group, and the component (c) is 5 to 70% by weight of all the polythiol components. The composition for a high refractive index plastic lens according to claim 4 or 5. 4. A high-refractive-index plastic lens made of a sulfur-containing urethane resin obtained by polymerizing the lens composition according to any one of claims 1 to 3. 5. The high refractive index plastic lens composition according to claim 1, wherein the formula (3) is suitable for the component (c).
Pentakis (mercaptomethyl) benzene represented by Chemical formula 3. [Chemical 3] 6. The composition for a high refractive index plastic lens according to claim 1, wherein the formula (4) is suitable for the component (c).
1- (2-mercaptoethyloxy) -2,4-bis (mercaptomethyl) benzene represented by the formula (4). [Chemical 4] 7. The high refractive index plastic lens composition according to claim 1, wherein the formula (5) is suitable for the component (c).
1,3,5-tris (mercaptomethyl) cyclohexane represented by the formula (5). [Chemical 5]