WO2014129788A1 - Polythiourethane-based polymerizable composition with remarkable impact resistance, and method for preparing optical resin by using same - Google Patents

Abstract

The present invention relates to a resin composition for a urethane-based optical lens, for which a problem of impact resistance, which is an advantage and a disadvantage of a conventional plastic optical lens, is remedied, and to an optical lens cured using same. The resin composition of the present invention comprises a polythiol compound and a polyisocyanate compound, and a urethane-based optical lens obtained by reacting the same is lightweight due to having a small specific gravity, has remarkable heat resistance, and has excellent workability such as formability, dyeing property and the like and various optical properties such as a UV screening property, transparency and the like. Particularly, the problem of the deterioration of impact resistance after hard multi-coating is solved.

Description

Polythiourethane-based polymerizable composition excellent in impact resistance and a manufacturing method of an optical resin using the same

The present invention relates to a polymerizable composition for polyurethane-based optical lenses excellent in impact resistance. Furthermore, the present invention relates to an optical article using such a composition, and a lens, spectacle lens, etc. made of such an optical component.

Since plastic optical materials are lighter, less brittle, and have considerably better dyeing properties than optical materials made of glass lenses, which are a kind of inorganic lenses, they have recently been widely used in optical materials such as spectacle lenses and camera lenses. Higher performance has been demanded for resin for optical materials. Specifically, high refractive index, high Abbe number, low specific gravity, high heat resistance, and the like have been demanded. According to such a request, various optical resins have been developed and used so far.

Especially, proposals regarding polyurethane resins have been actively made. Among the polyurethane resins, resins obtained by reacting a polythiol compound and a polyiso (thio) cyanate compound may be mentioned as the most typical resins. This resin is colorless and transparent, and has excellent properties such as high refractive index, high Abbe's number, impact resistance, dyeability and processability. Therefore, it is one of resin which has optimal conditions as optical materials, such as a plastic lens.

Glass lens, which has been widely used as an optical lens for a long time, has a low coefficient of thermal expansion, so that the lens is less deformed due to external temperature change, and there is less damage due to temperature change of the multi-layer treated on the surface to increase transmittance. However, glass lenses are weak in impact and heavy in weight, and are being replaced by plastic lenses that are light in weight and have excellent impact resistance and excellent processability such as dyeing.

Recently, as the demand for the transmittance and stability level of the plastic lens is increased, in most optical lenses, especially spectacle lenses, multi-coating (SiO2, ZrO2) is performed on both surfaces of the lens to increase the transmittance. There is a problem that the lens is easily broken by concentrating the impact from one place.

In particular, a copolymer of diaryl isophthalate, diaryl isophthalate added with dihydric alcohol, and diethylene glycol bisaryl carbonate known from Korean Unexamined Patent Publication No. 1992-0004464, Korean Unexamined Patent Publication No. 194-004010 Plastic glasses prepared using xylene diisocyanate, 1,2-bismercaptoethyl-3-mercaptopropane and polymethyl methacrylate copolymers known in the heading are also multi-coated to increase the transmittance. The problem of breaking easily occurs.

In addition, the injection molded polycarbonate optical lens has excellent impact strength after multi-coating but is severely deformed by heat during use as a thermoplastic resin, and more severely deformed at the center of thinner thickness than the edge of the thick lens. When wearing such spectacle lenses, eye dizziness is caused, and an important optical characteristic, Abbe's number, is lowered.

In order to solve the problem related to the thermal stability of the lens made of the thermoplastic resin, a resin for a heat crosslinkable plastic lens has been proposed as an alternative, and in Korean Patent Nos. 0638194 and 0688698, a modified polyol and a diisocyanate are mixed to provide an optical lens. Methods of preparing are known. However, although the impact resistance and heat resistance have been improved to some extent, the injection rate into the glass mold is very slow due to the high viscosity of the monomer composition to cast the lens, and it is difficult to remove the bubbles generated during the injection. Generated, and an injection mark remains in the lens. In addition, there is a problem that a lot of defects due to polymerization imbalance and the refractive index is as low as 1.523, so that the edge of the lens becomes thick.

In Korean Patent No. 472837, dihydric alcohol was added to diisocyanate, mixed with a tetravalent polythiol, and thermally cured to prepare an optical lens, thereby increasing the impact strength of the lens. However, the optical lens composition according to the patent was able to increase the impact strength in the state of the dough (non-processed plastic lens), but after the multi-coating, the impact resistance is poor FDA standards (127cm height, 16.3g) Did not satisfy. This optical lens composition is sufficient for making a frameless spectacle lens, but is insufficient as a spectacle lens which is safe for impact. In addition, there is also a problem that a lot of defects occur due to the high viscosity of the composition by preparing a monomer composition for an optical lens by adding a dihydric alcohol to diisocyanate in advance.

In Korean Patent No. 771176, an impact resistant optical lens was manufactured by reacting diisophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI) with a tetravalent polythiol. The manufactured optical lens passed the FDA impact resistance test (127 cm 16.3 g) as well as the state of the dough, even after multi-coating, but did not pass the industrial safety spectacle lens standard (ANS standard 127 cm, 67 g).

Korean Patent No. 10-0939451 discloses (a) trimethylolpropane tris (mercaptopropionate); Trimethylol ethane tris (mercaptopropionate); 38-68 wt% of one or more trivalent thiol ester compounds selected from glycerol tris (mercaptopropionate), and (b) hexamethylene diisocyanate (HDI); 4,4'-methylenebis (cyclohexyl isocyanate) (H12MDI); Heat resistance after multi-coating comprising 32-62% by weight of a diisocyanate compound obtained by mixing at least one compound selected from trimethyl 1,6-diisocyanatohexane in 7-30% by weight of isophorone diisocyanate (IPDI) There is disclosed a resin composition for impact resistant plastic spectacle lenses. However, such a composition has a disadvantage in that the refractive index is about 1.546 to 1.548 for the medium refractive index, the edge of which is thick in the case of a high number of lenses. In addition, the impact resistance of 120g * 127cm, 1.5J impact energy of sports goggles eyeglasses for extreme exercise, goggles for dangerous work is not yet suitable for use.

The polythiolurethane-based composition is described in Korean Patent Laid-Open Publication No. 2008-0000615, and also described in Korean Patent Laid-Open Publication No. 704314, Korean Patent Publication No. 2010-0094378, 2010-0120083, and the like.

In particular, although the prior art using the biuret (Biuret) of the formula (2) is described in Korean Patent Laid-Open Publication No. 2008-0000615, the dyeing properties and tensile strength of the resin is excellent, but there is no mention of impact resistance, It is different from the composition of the invention. Explaining the contents, (A) 2,5 (6) -bis (isocyanatemethyl) -bicyclo [2,2,1] heptane (NBDI) or 1,3-bis (isocyanatemethyl) which is an alicyclic isocyanate compound Cyclohexane (H-MXDI), (B) 1,6-hexamethylene diisocyanate (HDI) of formula (1), biuret of formula (2) HDI or trimer of HDI of formula (3) Trimer) 4-mercaptomethyl-1,8-, which is an isocyanate compound containing at least one selected from the group of compounds, and (C) a polythiol capable of having at least one (poly) sulfide bond in one molecule. At least one dimercapto-3,6-dithiaoctane (GST) or pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) compound, and (D) two or more hydroxyl groups in one molecule (Poly) hydroxy (poly) mercaptos having at least one polyhydroxy compound and / or at least one hydroxyl group and having at least one thiol group It describes about the polythiourethane-type resin obtained by superposing | polymerizing the polymerizable composition containing at least 1 sort (s) of a compound, ie, 2-mercaptoethanol.

(Formula (1)

OCN- (CH ₂ ) m-NCO

(Formula (2); Biuret Chemical Formula)

(Formula (3); Trimer Formula)

(In the above formula, m, p, and q each represent an integer of 2 or more and 10 or less.)

However, the conventional method is excellent in dyeing properties and excellent tensile strength, but since 2-mercaptoethanol is used, the odor is severe. The disadvantage is that there is a problem.

On the other hand, the patent publication of Korean Patent No. 0743314 discloses a mixture of a compound selected from the group consisting of (A) xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and the compound of formula (1), and (B) pentaeryet. An optical resin composition obtained by mixing and polymerizing a component selected from lititol tetrakismercapto propionate and pentaerythritol tetrakismercapto acetate with a sulfur-containing aliphatic diisocyanate, and (C) an ultraviolet absorber, a release agent, and a polymerization initiator. Is described.

Such an optical resin composition also has a problem in that the impact resistance in the raw material of the plastic plastic spectacle lens is weak to be used for industrial safety or sports, and in particular, the impact resistance after the multi-coating is weak.

The present inventors have solved the problems of the conventional optical composition as described above, to provide a resin composition that has a superior impact resistance than any of the resin for the urethane-based spectacle lens of the mold injection method, the impact resistance is maintained even after multi-coating. There is this.

In order to solve the above problems, as a result of earnest examination, the present inventors earnestly examined to maintain the impact resistance even after the multi-coating, using the biuret of the formula (2) as a key raw material, the impact resistance under various conditions As a result, the polythiourethane composition is excellent in impact resistance even after multi-coating in the dough, the lens and the whitening that can be adjusted from the medium refractive index (1.55) to the high refractive index (1.61) are remarkably removed, and the yellowing phenomenon does not appear. Invented.

The object of the present invention is

(A) an isocyanate compound (Biuret) represented by the following formula (2) and

[Formula (2)]

(2)

(Wherein p is an integer of 2 or more and 10 or less).

(B) a compound of 1,6-hexamethylene diisocyanate (HDI),

(C) a compound of isophorone diisocyanate (IPDI) or dicyclohexyl methane diisocyanate (H12MDI),

(D) at least one of polythiol compounds composed of 2,3-bis (2-mercaptoethylthio) -propane-1-thiol (GST) and pentaerythritol tetrakis (mercaptopropionate) (PEMP) It is achieved by the optically polymerizable composition containing these.

In the optically polymerizable composition of the present invention, the molar ratio of the functional group of NCO / SH in the functional group of polyisocyanate (NCO) and the functional group of polythiol (SH) composed of the above components (A), (B) and (C) is 0.5 to It is preferable to contain in 1.5 range, More preferably, it is the range of 0.9-1.1. Further, in the polyisocyanate compound composed of the components (A), (B) and (C), the content ratio (Biuret: HDI: IPDI) between them is further contained in a weight ratio of 30 to 40: 20 to 30: 30 to 40 desirable.

On the other hand, another aspect of this invention relates to the method of superposing | polymerizing said optically polymerizable composition and manufacturing resin for optics. Another aspect of the present invention relates to an optical resin by polymerizing the optically polymerizable composition. Furthermore, the present invention relates to an optical product made of the above optical resin, in particular a lens.

Moreover, this invention is a raw material of the said optical resin composition,

(A) an isocyanate compound (Biuret) represented by the following general formula (2),

[Formula (2)]

(2)

(Wherein p is an integer of 2 or more and 10 or less).

(B) a compound of 1,6-hexamethylene diisocyanate (HDI) or dicyclohexyl methane diisocyanate (H12MDI)

(C) It relates to the polyisocyanate composition for impact-resistant polyurethane resins containing the compound of isophorone diisocyanate (IPDI).

In such a polyurethane resin composition, the content ratio (Biuret: HDI: IPDI) between the components (A), (B) and (C) is preferably contained in a weight ratio of 30 to 40: 20 to 30: 30 to 40.

In the present invention, the isocyanate compound of the biuret type represented by the formula (2) used as the compound of component (A) is 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4- Butylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, 1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, etc. Include. However, in the present invention, 1,6-hexamethylene diisocyanate is essentially used as the compound of component (B), and therefore excluded from the compound of component (A). These components can be easily obtained as a specific raw material, the obtained compound may be purified and used, and raw material monomer itself may be mixed, and commercially available products such as Bayer's Desmodur N100 or Perstop's Tolonate HDB LV can be used. .

In the present invention, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as 'HDI') used as a compound of component (B) is a kind of alkylene diisocyanate compound and isophorone as a compound of component (C). Diisocyanate (hereinafter abbreviated as 'IPDI') and dicyclohexyl methane diisocyanate (hereinafter abbreviated as 'H12MDI') compounds will be said to belong to a class of alicyclic diisocyanate compounds. These diisocyanates may be synthesized and used, and commercially available compounds may be purchased.

(IPDI)

(HDI)

In addition, in this invention, as a polythiol compound used as a compound of component (D), 2, 3-bis (2-mercaptoethylthio) propane- 1- thiol and pentaerythritol tetrakis (mercaptopro) Cionate), and the structure of these compounds is as follows:

(GST)

(PEMP)

The polythiol compound includes the following compounds:

2,3- other than 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, trimethylolpropane tris (mercaptopropionate), and pentaerythritol tetrakis (mercaptopropionate) Bis (2-mercaptoethylthio) propane-1-thiol, 2- (2-mercaptoethylthio) -3- [2- (3-mercapto-2- (2-mercaptoethylthio) -propylthio ] Ethylthio-propane-1-thiol, 2- (2-mercaptoethylthio) -3- {2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio ] Propylthio} -propane-1-thiol, trimethylolpropane tris (mercaptopropionate, trimethylolethane tris (mercaptopropionate), glycerol tris (mercaptopropionate), trimethylolchloro tris (mer Captopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate, pentaerythritol tetrakis mercap Topropionate, pentaerythritol tetrakiscapcaptoacetate, [1,4] dithia-2-yl-methanethiol, 2- (2-mercapto-ethylsulfanyl) -propane-1,3-dithiol , 2-([1,4] dithiane-2ylmethylsulfanyl) -ethanethiol, 3- (3-mercapto-propionylsulfanyl) -propionic acid 2-hydroxymethyl-3- (3- Mercapto-propionyloxy) -2- (3-mercapto-propionyloxymethyl) -propyl ester, 3- (3-mercapto-propionylsulfanyl) -propionic acid 3- (3-mercapto- Propionyloxy) -2,2-bis- (3-mercapto-propionyloxymethyl) -propyl ester, (5-mercaptomethyl- [1,4] ditian-2-yl) -methanethiol One or two selected from the group consisting of polythiol compounds may be used, and in the present invention, 2,3-bis (2-mercaptoethylthio) -propane-1-thiol (GST) and Pentaerythritol tetrakis (mercaptopropione) (PEMP) is most preferred.

On the other hand, the present inventors have found that the burette compound used as component (A) in the present invention is very excellent in impact resistance, 1,6-hexamethylene diisocyanate (HDI) in the diisocyanate mixture used as component (B) Increasing the amount of) increases the impact strength of the lens, but the heat resistance is decreased, and when the amount of isophorone diisocyanate (IPDI) used as the component (C) increases, the heat resistance is improved but the impact strength gradually decreases. On the basis of this, the resin composition for an optical lens of the present invention is various in finding an optimal amount of isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI) in consideration of the heat resistance and impact strength of the final lens. An experiment was carried out, and based on this, the present invention was completed.

In particular, since the relationship between impact strength and heat resistance is in a trade off, it is difficult to satisfy both conditions at the same time. As a way to compensate for this, the isocyanate compound of [Formula (2)] is used to give the strong characteristics of the lens through the biuret and to have excellent durability and weather resistance. The present inventors guess that these components caused various uniform crosslinking in the optical product, resulting in an improvement in impact resistance.

The present inventors polymerized component (A), component (B) and component (C), and component (D) in this invention and manufactured the polythiourethane composition resin excellent in impact resistance preferentially. The method for producing a polythiourethane-based resin of the present invention and the polythiourethane-based resin obtained by the method have better impact resistance than conventional resins, do not have sufficient heat resistance and whitening, and have a specific gravity of 1.22 to 1.25, and have a yellowing resistance. Excellent.

On the other hand, the present inventors prepared a polythiourethane composition excellent in impact resistance as described above, and then analyzed the characteristics of the resin obtained from the composition to optimally suitable component (A), component (B), component (C) in the present invention. ) And the ratio of component (D) were found through trial and error to obtain an optically polymerizable composition of the present invention.

In consideration of the specification of the optical lens produced by the optical composition obtained in the present invention, the contents of the component (A), component (B), component (C) and component (D) used in the present invention were determined. In the present invention, the content of component (A) in the isocyanate mixture of components (A), (B) and (C) is in the range of 20-50 (wt%), preferably in the range of 30-40 (wt%), If it is out of this range, there is no problem in impact resistance, but it is difficult to inject into the mold due to the high viscosity of the mixture, the content of component (B) is in the range of 10 ~ 40 (wt%), preferably 20 ~ 30 (wt %) Range, if the content is less than this range, the impact resistance is weak, when the content is large, the impact resistance is excellent, but heat resistance and yellowing is a problem, and the content of component (C) is 20-50 (wt %) Range, preferably in the range of 30 to 40 (wt%), and outside this range, there is a problem in heat resistance.

In the present invention, the molar ratio of the functional group of polyisocyanate (NCO) and the functional group of NCO / SH in the functional group of polythiol (SH) is preferably used within the range of 0.5 to 1.5, preferably 0.9 to 1.1 mole ratio Preferably, more preferably, 1.0 mole ratio is more suitable for the physical properties of the optical lens. Polyisocyanate is preferably used in a content ratio (Biuret: HDI: IPDI) of 30 to 40: 20 to 30: 30 to 40 weight ratio between them, and in the case of polythiol, a resin having a high refractive index of 1.60 (nD) or more using only GST In the case where only PEMP is used, the refractive index is 1.55 (nD) or more, so that it can be used as a medium refractive lens. However, in order to prevent heat resistance, whitening, yellowing and the like, and to manufacture a high refractive lens having a high Abbe number (39 to 45) and a refractive index of 1.59 to 1.60 (nD), it is preferable to use a mixture of GST and PEMP. The use ratio is preferably in the range of 10 to 20 wt% of the content of PEMP in the polythiol, more preferably in the range of 14 to 18 wt%. If it is out of this range, the impact resistance tends to be slightly reduced, and in the case of 20 wt% or more, the refractive index is also decreased, and it is preferable to use it after adjusting appropriately.

Various additives may be used to obtain the necessary optical properties to be provided as a lens such as transparency, refractive index, specific gravity, impact resistance, heat resistance, viscosity of the polymerization composition, etc. of the resin obtained from the polymerization composition of the present invention. In addition, the composition of the present invention may be added a variety of materials such as a UV absorber, a light stabilizer, an antioxidant, a light yellowing agent (blueing agent) for the initial color correction of the light yellow.

Moreover, in order to adjust to a desired reaction rate, a reaction catalyst can be added suitably. As a catalyst which is preferably used, for example, as a urethanization catalyst, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, tetramethyldiacetoxydistanoxane, tetraethyldiacetoxydistanoxane And amine compounds such as tin compounds such as tetrapropyldiacetoxydistanoxane and tetrabutyldiacetoxydistanoxane, and tertiary amines. These can also be used independently and can also use two or more types together. As addition amount of a catalyst, it is preferable to use in 0.001 to 1 weight% with respect to the monomer total weight of a composition. In this range, it is preferable in view of the polymerizability, the pot life during operation, the transparency of the obtained resin, various optical properties or light resistance.

When the compositions of the present invention are cured by polymerization, there may be various molding methods depending on the application and there is no particularly limited curing method, but heat curing is mainly used. Thereby, resin of this invention is obtained. Resin of this invention is obtained by the casting polymerization which is a mold injection system which is a conventional method.

In addition, the resin composition for an optical lens of the present invention may further include a color corrector for correcting the initial color of the lens. As the color corrector, organic dyes, organic pigments, inorganic pigments, and the like may be used. By adding 0.1 to 50,000 ppm, preferably 0.5 to 10,000 ppm, of such organic dyes per resin composition for optical lenses, it is possible to prevent the lens from becoming yellow by the addition of an ultraviolet absorber, an optical resin, a monomer, or the like.

The resin composition for an optical lens of the present invention may further include a mold release agent and a polymerization initiator that are commonly used. As the release agent, a component selected from fluorine-based nonionic surfactants, silicone-based nonionic surfactants and alkyl quaternary ammonium salts may be used alone or in combination of two or more thereof. Preferably, phosphate ester is used. In addition, the polymerization initiator may be used alone or in combination of two or more amine-based or tin-based compounds.

The optical polymerization composition of the present invention is polymerized to obtain a resin composition, which is then thermally cured to obtain an optical lens, particularly an spectacle lens. The process of manufacturing the spectacle lens by thermosetting the resin composition of the present invention is as follows. First, after the polymerization initiator is finally added to the composition of the present invention, nitrogen is blown to remove air in the mixing vessel, and the mixture is stirred under reduced pressure for 2 to 5 hours, the stirring is stopped, and then degassed under reduced pressure and injected into the mold. do. The mold is preferably a glass mold or a metal mold fixed with a plastic gasket or polyester or polypropylene adhesive tape.

The glass mold injected with the mixture was placed in a forced circulation oven, maintained at 33 to 37 ° C. for 2 hours, heated to 38 to 42 ° C. for 3 hours, heated to 80 to 90 ° C. for 10 hours, and heated to 120 to 140 ° C. for 2 to 4 hours. After cooling at 120-140 degreeC for 2 hours, and cooling it for 60 hours at 60-80 degreeC, a solid material is released from a mold and an optical lens is obtained. The optical lens thus obtained is annealed at a temperature of 120 to 140 ° C. for 1 to 4 hours to obtain a final desired plastic spectacle lens (dough).

In addition, the optical lens obtained by the above method can be subjected to hard coating and multi-coating treatment in order to increase the optical characteristics. The hard coat layer may be formed of at least one silane compound having functional groups such as an epoxy group, an alkoxy group, a vinyl group, and at least one metal oxide colloid such as silicic acid oxide, titanium oxide, antimony oxide, tin oxide, tungsten oxide, and aluminum oxide. The coating composition is coated with a thickness of 0.5 to 10 on the surface of the optical lens by impregnation or spin coating, and then heated or UV cured to complete the coating film.

The multi-coating layer, that is, the anti-reflective coating layer may be formed by vacuum deposition or sputtering of metal oxides such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide and yttrium oxide. Most preferably, the silicon oxide film and the zirconium oxide film are vacuum-deposited three or more times on both surfaces of the lens and the silicon oxide film is finally vacuum deposited. If necessary, a water film (fluorine resin) layer may be provided last, or an ITO layer may be provided between the silicon oxide and the zirconium oxide film.

The optical lens of the present invention may be used after coloring treatment with a disperse dye or a photochromic dye, as necessary. The resin composition for an optical lens of the present invention is not limited to plastic spectacle lenses, and can be used for various optical products.

It is necessary to evaluate whether the optical lens produced by the present invention has suitable physical properties as a plastic spectacle lens, and each of the physical properties (1) refractive index (nD) and Abbe number (υ _d ), (2) impact resistance, (3) Heat resistance (Tg) and (4) specific gravity were evaluated by the following test method.

(1) The refractive index (nD) and Abbe number (υ _d): Using the ABBE refractometer 1T model ATAGO's was measured at 20 ℃.

(2) Impact resistance: The impact resistance is the weight which is destroyed by dropping light steel ball from heavy steel ball to heavy steel ball at 127cm height in order to test specimen made of flat plate of 80mm diameter and 1.9mm thickness at room temperature 20? Impact resistance was measured by potential energy.

-. Iron ball weight: Using a ball ball of 16g, 32g, 65g, 100g, 200g, and 300g, the ball dropping test for each height is used to calculate the potential energy at the time of failure.

Calculation Example 1) Potential energy (Ep) is 16g and 127cm

Ep = mgh = 0.016 * 9.8 * 1.27 = 0.2 (J)

Calculation example-2) When industrial safety standard 67g, 127cm standard

Ep = mgh = 0.067 * 9.8 * 1.27 = 0.83 (J)

(3) Heat resistance: The glass transition temperature (Tg) of the test piece was measured and made into heat resistance using the DSC N-650 thermal analyzer by SCINCO.

(4) Specific gravity: It measured by the Archimedes method.

The spectacle lens obtained from the composition for an optical lens manufactured according to the present invention is also excellent in heat resistance and FDA spectacle lens standard (ANS standard, 127 cm height 16.0 g falling ball test) and industrial safety (ANS standard, 127 cm height, 67 g falling ball test ) Has impact resistance to In the case of the lens manufactured by the present invention, it is possible to make a lens of sufficient strength without going through such a primer coating process. In particular, it can be said that the range of application is very high as lenses for industrial safety and sports goggles that can be used in industrial sites.

In the following, the invention will be described in more detail using examples which are not limiting the invention.

First, the inventors of the present invention, in order to find the optimum amount of isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI) in consideration of the heat resistance and impact strength of the lens produced in the present invention, Experiment 1 (Biuret) And experiments by ratio of HDI and GST), Experiment 2 (by ratio of HDI and IPDI and GST), and Experiment 3 (by ratio of Biuret and HDI and GST) respectively, and the results are shown in the table below. . Here 'Biuret' is to abbreviate the isocyanate compound of formula (2).

Representative Experiments and Examples

(1) Biuret (Tolonate HDB LV from Perstep), HDI and IPDI were mixed and dissolved according to the composition ratio (NCO / SH = 1.0 molar ratio) shown below, and 630 ppm of dibutyltin dichloride as a curing catalyst and SEESORB 709, an ultraviolet absorber (Japan Shipro Co., Ltd.) 15,000ppm, Zelec UN (Dupont) 1,200pppm is added as the internal releasing agent and the pressure is stirred for 40 minutes at room temperature to completely remove the bubble. After dissolving, polythiol PEMP and GST shown in the following table are mixed and degassed for 40 minutes, and then injected into a glass mold assembled with an adhesive tape.

(2) The glass mold into which the mixture is injected is charged into a forced circulation oven. Normal temperature-35 degrees Celsius 4 hours temperature rising, 35-50 degrees Celsius 5 hours temperature raising, 50-75 degrees Celsius 4.5 hours temperature raising, 75-90 degrees Celsius 5 hours raising temperature, 90 degrees Celsius 3 hours holding, 90-130 degrees Celsius 2 hours heating, 130 degrees Celsius 1.5 hours It is polymerized by cooling the fats and oils and 130-70 degreeC for 1 hour. After completion of the polymerization, the lens is separated from the mold to obtain a urethane optical lens. The lens obtained from this is annealed at 120 degreeC for 1 hour and 40 minutes. After annealing, the lens dough cured in the glass mold is released to obtain an optical lens having a center thickness of 1.2 mm.

(3) The optical lens obtained in (2) was processed to a diameter of 80 mm and then ultrasonically washed in an alkaline aqueous washing solution, followed by annealing treatment at 120 ° C. for 2 hours, and then the dough lens was coated on the silicon-based hard liquid by dipping. After the heat drying, and vacuum-deposited in the order of silicon oxide, zirconium oxide, silicon oxide, ITO, zirconium oxide, silicon oxide, zirconium oxide on both sides to obtain a hard coated and multi-coated optical lens.

(4) The optical lens obtained above was recorded by measuring physical properties such as refractive index, Abbe's number, Tg and impact energy.

(Experiment 1)

Except for the following matters, the experiment is performed according to the representative experiments and examples. The compounds of the isocyanate of the burette and HDI are mixed according to the ratio of the following Table 1), the polythiol is fixed with GST, the NCO / SH ratio is mixed in the equivalence ratio of 1.0, 1200ppm of Gelek UN (Dupont) as an internal release agent, 600 ppm of dibutyltin dichloride was added as a catalyst, sufficiently stirred, vacuum degassed, injected into a glass mold, thermally cured by a curing program, and then released in a glass mold, and then measured for various physical properties.

Table 1 Biuret (Proportion of Formula (2) and HDI) and the result of GST experiment

		Experimental example
		(1-1)	(1-2)	(1-3)	(1-4)	(1-5)
Monomer composition (g)	Biuret	0	25	50	75	100
	HDI	100	75	50	25	0
	GST	103.27	89.60	75.93	62.26	48.59
Lens property	Shockproof E (J)	5.34	4.74	5.63	4.15	4.15
	Tg (℃)	58	61	66	72	77
	Refractive index (liquid)	1.5338	1.5347	1.5368	1.5380	1.5405
	Refractive Index (High)	1.6141	1.6089	1.6011	1.5939	1.5883
	Abbe number (υ ｄ )	37.6	37.5	40.4	40.6	39.2
	colloquial Chinese	Very severe	Severe	has exist	none	none
	Yellowing (after secondary curing)	Obviously yellowish	yellowish	Very little	none	Almost none
	Other	Yellowing (dough)				McLee Bit

In the Biuret / HDI / GST system, the impact resistance was excellent at any ratio of burette and HDI, but the heat resistance was weak. In particular, the higher the HDI content, the weaker the heat resistance, and also the severe whitening and yellowing. The refractive index was high in the range of 1.58 ~ 1.61, and the Abbe number was in the range of 37 ~ 41.

Therefore, in order to improve heat resistance, IPDI was added to the following (Experiment 2).

(Experiment 2)

Except for the following matters, the experiment is performed according to the representative experiments and examples. Compounds of the isocyanate of HDI and IPDI were mixed and cured according to the ratio of the following Table 2), and then released in a glass mold to measure various physical properties.

TABLE 2 Percentage of HDI and IPDI and Results of GST Experiments

		Experimental example
		(2-1)	(2-2)	(2-3)	(2-4)	(2-5)
Monomer composition (g)	HDI (g)	0	25	50	75	100
	IPDI (g)	100	75	50	25	0
	GST (g)	78.14	84.42	90.70	96.99	103.27
Lens property	Shockproof E (J)	0.2 or less	0.35	5.93	5.93	5.34
	Tg (℃)	104	95	76	69	58
	Refractive index (liquid)	1.5407	1.5391	1.5371	1.5369	1.5338
	Refractive Index (High)	1.5945	1.6012	1.6063	1.6102	1.6141
	Abbe number (υ ｄ )	39.2	38.0	40.2	38.9	39.2
	colloquial Chinese	has exist	has exist	has exist	has exist	none
	Yellowing (after secondary curing)	has exist	has exist	has exist	has exist	Almost none
	Other					McLean

In the HDI / IPDI / GST system, the impact resistance is excellent when the content of HDI is 50% or more, but the heat resistance is weak. When the IPDI is 50% or more, the impact resistance is weak, but the heat resistance is excellent. At all ratios, bleaching and yellowing occurred, resulting in a significant drop in physical properties of the lens. Therefore, in order to reinforce the heat resistance and impact resistance, and to improve the whitening and yellowing phenomenon, the following experiment was performed by adding Biuret.

(Experiment 3)

Except for the following matters, the experiment is performed according to the representative experiments and examples. Compounds of the isocyanates of HDI and IPDI were mixed and cured according to the ratio of the following Table 3), and then released in a glass mold to measure various physical properties.

TABLE 3 Ratio of Buriret and IPDI and Results of GST Experiment

		Experimental example
		(3-1)	(3-2)	(3-3)	(3-4)	(3-5)
Monomer composition (g)	Biuret (g)	0	25	50	75	100
	IPDI (g)	100	75	50	25	0
	GST (g)	78.14	70.75	63.36	55.98	48.59
Lens property	Shockproof E (J)	0.2 or less	2.51	1.90	0.47	4.15
	Tg (℃)	104	100	92	85	77
	Refractive index (liquid)	1.5407	1.5407	1.5409	1.5399	1.5405
	Refractive Index (High)	1.5945	1.5930	1.5925	1.5863	1.5883
	Abbe number (υ ｄ )	39.2	38.1	40.9	43.8	39.2
	colloquial Chinese	Edge	Almost none	none	none	none
	Yellowing (after secondary curing)	has exist	Almost none	none	none	Almost none
	Other					McLean

Except for 100% Biuret, the IPDI / Biuret / GST system has a low impact resistance, but the heat resistance is excellent due to the IPDI effect, and the whitening and yellowing are much improved.

Experiment 4) to find the optimum conditions for the isocyanate component with Biuret / HDI / IPDI system and various isocyanate ratios in order to improve impact resistance, refractive index, Abbe's number, whitening and yellowing based on the results of Experiments 1 ~ 3) Was carried out and the results are shown in the following table.

(Experiment 4)

Except for the following matters, the experiment is performed according to the representative experiments and examples. Compounds of the isocyanate of HDI and IPDI were mixed and cured according to the ratio of the following Table 4), and then released in a glass mold to measure various physical properties.

Table 4 Physical property test according to type (change) of biuret / HDI / IPDI and various kinds of isocyanate (A liquid) and GST (B liquid)

		Experimental example
		(4-1)	(4-2)	(4-3)	(4-4)	(4-5)	(4-6)
Monomer composition (g)	Biuret	35.8	37.5		31.12
	HDI	32.9	25		28.68
	IPDI	31.3	37.5
	NBDI			100
	TCDI				40.21
	H-MXDI					100
	H12MDI						100
	GST	79.41	73.34	88.18	69.12	89.4	67.33
Lens property	Shockproof E (J)	6.97	5.63	0.35	4.78	1.49	0.59
	Tg (℃)	75	87	107	86	99	75
	Refractive index (liquid)	1.5402	1.5383	1.5566	1.5471	1.5483	1.5429
	Refractive Index (High)	1.6001	1.5979	1.6035	1.6028	1.6149	1.5948
	Abbe number (υ ｄ )	41	39.6	39.2	39.3	38.8	40.1
	colloquial Chinese	none	none	none	none	has exist	has exist
	Yellowing (after secondary curing)	none	none	none	has exist	none	none

-. NBDI: 2,5 (6) -bis (isocyanatemethyl) -bicyclo [2,2,1] heptane

-. TCDI: 3 (4), 8 (9) -diisocyanatomethyltricyclo- (5.2.1.0 ^2,6 ) decane

-. H-MXDI: 1,3-bis (isocyanatemethyl) cyclohexane

-. H12MDI: 4,4-methylenebis (cyclohexyl isocyanate)

In summary, the results of the experiments 1 to 4 showed that the yellowing resistance of the lens was in the order of Biuret> IPDI >> HDI, and if the HDI should be used to maintain the impact resistance, the yellowing resistance should be used around 25wt%. It was judged that it could be maintained.

The degree of whitening of the lens was not found in Biuret, but in HDI, bleaching was remarkable. This is presumed to correlate with the viscosity of the composition and the solubility of the composition with the pressure-sensitive adhesive of the tape.

In addition, the impact resistance of the various types of isocyanate was compared with NBDI, TCDI, and H12MDI itself, but the impact resistance was inferior, but in the case of TCDI, the combination of Biuret and HDI showed good impact resistance. In order to maintain impact resistance, Biuret and HDI are considered to be essential compositions, and I think that they can be used to reinforce heat resistance of IPDI, H12MDI and TCDI.

The experiment was performed to find the optimal amount of Biuret and IPDI by fixing the content of HDI to any value between 25 and 32.9 wt%.

The present invention was specifically implemented based on the above experiments 1 to 4. In Examples 1 and 2, in order to check the ratio of Biuret, IPDI, and H12MDI, HDI was fixed to 25 wt% in Example 1, and GST was used as the liquid B. In Example 3, an implementation was performed according to the change in the mass of HDI. In Example 4, according to the kind of the polythiol which is liquid B was carried out.

(Example 1)

The experiment was carried out according to the representative experiments and examples, and the ratio of the composition was carried out according to Table 5 below.

Table 5 Result table of Example by ratio of biuret (Biuret) and IPDI and H12MDI (HDI: fixed at 25wt%, liquid B: GST)

		Example
		(1-1)	(1-2)	(1-3)	(1-4)	(1-5)	(1-6)
Monomer composition (g)	Biuret	0	25	37.5	37.5	50	62
	HDI	25	25	25	25	25	25
	IPDI	75	50		37.5	25	13
	H12MDI			37.5
	GST	84.42	77.03	68.87	73.34	69.65	66.10
Lens property	Shock resistance E (J)	0.35	2.52	3.52	5.63	5.06	4.47
	Tg (℃)	95	88	78	87	80	75
	Refractive index (liquid)	1.5391	1.5384	1.5395	1.5383	1.5381	1.5381
	Refractive Index (High)	1.6012	1.5995	1.5975	1.5979	1.5970	1.5972
	Abbe number (υ ｄ )	38	39.4	39.6	39.6	40.1	40.2
	colloquial Chinese	a little	Severe	none	none	none	none
	Yellowing (after secondary curing)	none	none	Almost none	none	none	none
	Other

In the composition of the isocyanate, the HDI was fixed at 25wt%, and the results of experiments for each ratio showed that the ratio of Example (1-4) showed the best impact resistance, and the heat resistance also showed a suitable result of 87 ° C. By slightly increasing the content of 29wt% in the case of the ratio was shown.

(Example 2)

The experiment was carried out according to the representative experiments and examples, and the ratio of the composition was carried out according to Table 6 below.

Table 6 Example according to the ratio of the biuret (Biuret) and IPDI (HDI: fixed 29wt%, liquid B: GST)

		Example
		(2-1)	(2-2)	(2-3)
Monomer composition (g)	Biuret (g)	24	35.5	47
	HDI (g)	29	29	29
	IPDI (g)	47	35.5	24
	GST (g)	78.34	73.34	71.54
Lens property	Shock resistance E (J)	3.92	6.30	6.70
	Tg (℃)	87	83	78
	Refractive index (liquid)	1.5380	1.5380	1.5377
	Refractive Index (High)	1.5995	1.5988	1.5980
	Abbe number (υ ｄ )	39.1	38.3	42.8
	colloquial Chinese	none	none	none
	Yellowing (after secondary annealing)	none	none	none
	Other

In the results of Examples 1 and 2, both the HDI 25wt%, 29wt% of the content was almost no yellowing after the second annealing, 25wt% was a finer difference than 29wt%, but clearer, transparent. 29 wt% is more advantageous than 25 wt% in terms of impact resistance, but 25 wt% is more advantageous in terms of heat resistance. Therefore, the thermal resistance (Tg) of the lens having 25 wt%, which is excellent in heat resistance, was 87 ° C., which significantly reduced the multi-film cracking phenomenon.

Example 3

In order to further improve the heat resistance, the experiment was carried out as follows while the HDI content was further reduced. The experiment was carried out according to the representative experiments and examples, and the ratio of the composition was carried out according to Table 7 below.

In order to further improve the heat resistance, the experiment was carried out as follows while the HDI content was further reduced. The experiment was carried out according to the representative experiments and examples, and the ratio of the composition was carried out according to Table 7 below.

TABLE 7 Result Table of Example of Physical Properties (Biuret: IPDI = 1: 1, Liquid B: GST) According to Change of Component (HDI) Amount

		Example
		(3-1)	(3-2)	(3-3)
Monomer composition (g)	Biuret (g)	40	37.5	35.5
	HDI (g)	20	25	29
	IPDI (g)	40	37.5	35.5
	GST (g)	71.35	73.34	74.94
Lens property	Shock resistance E (J)	2.53	5.63	6.30
	Tg (℃)	87	87	83
	Refractive index (liquid)	1.5389	1.5383	1.5380
	Refractive Index (High)	1.5972	1.5979	1.5988
	Abbe number (υ ｄ )	40.0	39.6	39.3
	colloquial Chinese	none	none	none
	Yellowing (after secondary annealing)	No change	No change	No change

The HDI content of 20wt% was less than half the impact strength compared to 25wt%, unexpectedly without Tg improvement, and maintained at 87 ℃ as it is. Therefore, in the current Biuret / HDI / IPDI system, the optimal ratio is Biuret (37.5wt%), HDI (25wt%), IPDI (37.5wt%), and the whitening phenomenon, refractive index (1.60), yellowing phenomenon Excellent results were obtained.

Now, in order to see the results according to the change of the polythiol and the change of the kind in the optimized ratio of the isocyanate composition (Liquid A), it is shown in Table 8).

(Example 4)

The monomers were mixed at the composition ratios in the table below, and cured to measure physical properties. Representative Example 4-2) is shown below.

(1) 37.5 g of Biuret (Tolonate HDB LV from Perstep), 25 g of HDI, and 37.5 g of IPDI were mixed and dissolved. 1,200pppm of Zelec Un (Dupont) is added, and the mixture is subjected to reduced pressure stirring at room temperature for 40 minutes to completely remove bubbles. After dissolving, 12.84 g of PEMP and 64.21 g of GST are mixed and degassed for 40 minutes, and then injected into a glass mold assembled with an adhesive tape.

(2) The glass mold into which the mixture is injected is charged into a forced circulation oven. Normal temperature ~ 35 ℃ 4 hours, temperature 35 ~ 50 ℃ 5 hours, temperature 50 ~ 75 ℃ 4.5 hours temperature, 75 ~ 90 ℃ 5 hours temperature, 90 ℃ 3 hours maintenance, 90 ~ 130 ℃ 2 hours temperature, 130 ℃ 1.5 hours The oil is cooled at 130 to 70 ° C for 1 hour to polymerize. After completion of the polymerization, the lens is separated from the mold to obtain a urethane optical lens. The lens obtained from this is annealed at 120 degreeC for 1 hour and 40 minutes. After annealing, the lens dough cured in the glass mold is released to obtain an optical lens having a center thickness of 1.2 mm.

(3) The optical lens obtained in (2) was processed to a diameter of 80 mm and then ultrasonically washed in an alkaline aqueous washing solution, followed by annealing treatment at 120 ° C. for 2 hours, and then the dough lens was coated on the silicon-based hard liquid by dipping. After the heat drying, and vacuum-deposited in the order of silicon oxide, zirconium oxide, silicon oxide, ITO, zirconium oxide, silicon oxide, zirconium oxide on both sides to obtain a hard coated and multi-coated optical lens.

(4) The optical lens obtained above had the properties of refractive index 1.5932 (nD / 20 ° C), Abbe number 39.7, Tg 87 ° C, impact resistance 6.23 (J) (300g, 220cm break = 500g, 127cm break). Are recorded in Table 8).

Table 8 Result table of Example (Biuret: 37.5%, HDI: 25%, IPDI: 37.5% fixation) according to ratio of amount of B

		Example
		(4-1)	(4-2)	(4-3)	(4-4)	(4-5)	(4-6)
A liquid (g)	BIURET	37.5	37.5	37.5	37.5	37.5	37.5
	HDI	25	25	25	25	25	25
	IPDI	37.5	37.5	37.5	37.5	37.5	37.5
Liquid B (g)	PEMP	0 (0%)	12.84 (16.7%)	19.76 (25%)	42.86 (50%)	70.23 (75%)	103.16 (100%)
	GST	73.34 (100%)	64.21 (83.3%)	59.29 (75%)	42.86 (50%)	23.41 (25%)	0 (0%)
Lens property	Shock resistance E (J)	5.63	6.23	3.77	3.57	3.78	5.34
	Tg (℃)	87	86.6	88	86	85	83
	Refractive index (liquid)	1.5383	1.5339	1.5319	1.5246	1.5169	1.5069
	Refractive Index (High)	1.5979	1.5932	1.5899	1.5770	1.5645	1.5529
	Abbe number (υ ｄ )	39.6	39.7	41.2	42.4	43.8	45.2
	colloquial Chinese	none	none	none	none	none	none
	Yellowing (after secondary curing)	none	none	none	none	none	none

In Example 4-3, the impact energy was slightly decreased from about 20% of the PEMP content, and about 16% showed the maximum impact resistance (6.23J), so that the PEMP content in the polythiol was 10-20. It is thought that% (weight ratio) shows a good result for impact resistance.

The optimum proportion of isocyanate in Biuret / HDI / IPDI system is Biuret (37.5 wt%), HDI (25 wt%), IPDI (37.5 wt%), GST (83.3 wt%) and PEMP (16.7 wt%). In the case of optimum impact resistance and high refractive index (nD: 1.5932), Abbe's water (40), whitening or yellowing were not observed, which showed excellent physical properties as spectacle lenses.

(Example 5)

The monomers were mixed at the composition ratios in the table below, and cured to measure physical properties. Representative Example 5-3) is shown below.

(1) 37.5 g of Biuret (Tolonate HDB LV from Perstep), 25 g of HDI, and 37.5 g of IPDI were mixed and dissolved. 1,200pppm of Zelec Un (Dupont) is added, and the mixture is subjected to reduced pressure stirring at room temperature for 40 minutes to completely remove bubbles. After dissolving, 12.84 g of PEMP and 64.21 g of GST are mixed and degassed for 40 minutes, and then injected into a glass mold assembled with an adhesive tape.

The homogeneous solution obtained from the composition prepared above was agitated under reduced pressure for about 40 minutes, and poured into a mold fixed with a glass mold and an adhesive tape.

The glass mold type into which the mixed solution was injected was put into a forced circulation oven, and the temperature was raised to 35 ° C. for 5 hours, the temperature increased to 50 ° C. for 7 hours, the temperature increased to 90 ° C. for 7 hours, and the temperature increased to 130 ° C. for 4 hours, 130 It was hold | maintained at 2 degreeC for 2 hours, and it cooled at 80 degreeC over 1 hour, and formed primary molding. After completion of the polymerization, the mold was taken out of the oven and the lens was released to obtain an optical lens having a center thickness of 1.2 mm and a diameter of 80 mm. The obtained lens was further annealed at 130 ° C. for 1 hour.

The obtained lens was colorless and transparent, and an excellent optical lens with refractive index (nD) 1.6004, Abbe number 41, heat resistance (Tg) 85 ° C, and impact resistance (breakdown energy) 6.7 (J) was obtained. The dough thus obtained was impregnated into the hard coating solution, followed by heat curing after hard coating, followed by vacuum deposition to obtain a hard coated and multi-coated optical lens, and the impact resistance was 6.5 (J) to maintain excellent impact resistance.

Table 9 Example of polythiol type (Biuret: 37.5%, HDI: 25%, IPDI: 37.5% fixed) Result Table

		Example
		(5-1)	(5-2)	(5-3)	(5-4)	(5-5)	(5-6)
Monomer composition (g)	Biuret	37.5	37.5	37.5	37.5	37.5	37.5
	HDI	25	25	25	25	25	25
	IPDI	37.5	37.5	37.5	37.5	37.5	37.5
	GST	73.34		64.21			31.89
	PEMP			12.84	103.2
	GMT		56.42				31.89
	DMDDU					77.59
Lens property	Shock resistance E (J)	5.63	2.52	6.23	5.34	2.94	3.78
	Tg (℃)	87	99	87	83	95	94
	Refractive index (liquid)	1.5383	1.5290	1.5339	1.5069	1.5461	1.5332
	Refractive Index (High)	1.5979	1.5909	1.6004	1.5529	1.6009	1.5948
	Abbe number (υ ｄ )	39.6	40.6	41.0	45	40.5	42.5
	colloquial Chinese	none	has exist	none	none	none	has exist
	Yellowing (after secondary curing)	none	has exist	none	none	has exist	has exist

-. GMT: 2- (2-mercaptoethylthio) propane-1,3-dithiol

-. DMDDU: 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan

Under the amortization that the Biuret / HDI / IPDI ratio would be useful for impact resistant lenses in an optimized isocyanate system, the applicability of other polythiols was tested, and as shown in the table above, other polythiols such as PEMP, GMT and DMDDU were used. Even if it shows sufficient impact resistance, Abbe's number also shows excellent results in the range of 39 to 45, and yellowing or whitening is not observed, so it can be used as a spectacle lens. In the case of GMT and DMDDU, the heat resistance is more than 10 degrees higher than that of other polythiols. Therefore, Biuret / HDI / IPDI, an isocyanate composition applicable to various polythiols, is considered to be a combination of compounds useful for polyurethane.

After preparing such an optical lens, a table for comparing the physical properties of optical lenses of other companies is shown below. Comparative Example-1) refers to Comparative Example 1) of Korean Patent No. 10-0973858 of a high refractive index 1.60 lens of Mitsui Co., Ltd., which is the most representative example. In Comparative Example 2, a comparative example of 1.67, which is an ultra-high refractive lens, was described with reference to Korean Patent Publication No. 92-00578 of Mitsui Corporation.

Table 10 Comparison of lens properties of other companies

		Comparative Example-1) (Mitsui 1.60)	Comparative Example-2) (Mitsui 1.67)
Monomer composition (g)	MXDI (g)		100
	NBDI (g)	100
	PEMP (g)	47.23
	GST (g)	50.20	92.3
Lens property	Shockproof E (J)	0.8	0.2 or less
	Tg (℃)	113	84
	Refractive index (liquid)	1.5393	1.5865
	Refractive Index (High)	1.5942	1.6572
	Abbe number (υ ｄ )	41	32
	colloquial Chinese	none	none
	Yellowing (Secondary Annealing)	none	has exist

As shown in the comparative example, in the case of 1.60, which has a similar refractive index, the heat resistance or Abbe number is appropriate in Comparative Example-1, but in terms of impact resistance, a considerable difference is shown in comparison with Examples 1 to 5 in industrial safety or sports goggle lenses. The use was not appropriate. In the case of Comparative Example-2), the refractive index was 1.657, but the Abbe number was 32, and the impact resistance was 0.2J or less, which did not meet the FDA's basic impact resistance standard. After that, hard / multi-coated is used. Therefore, it is judged that the composition system of isocyanate developed in the present invention plays an excellent role in use as a core raw material of impact resistant lenses.

According to the present invention, an isocyanate composition and an optical lens composition for a urethane plastic optical lens having high refractive index and excellent impact resistance before and after hard / multi coating, excellent heat resistance and Abbe number, and low whitening and yellowing can be obtained. have. The optical lens according to the present invention can be particularly applied to the spectacle lens, and in addition to the spectacle lens, not only recording glasses substrates, coloring filters, ultraviolet absorbing filters used in industrial safety glasses, sports goggles, prisms, optical fibers, optical disks, magnetic disks, etc. It can be used for various optical products such as fluoroscopy.

Claims (8)

1. (A) an isocyanate compound (Biuret) represented by the following formula (2) and

   [Formula (2)]

   

   (2)

   (Wherein p is an integer of 2 or more and 10 or less).

   (B) a compound of 1,6-hexamethylene diisocyanate (HDI),

   (C) a compound of isophorone diisocyanate (IPDI) or dicyclohexyl methane diisocyanate (H12MDI),

   (D) at least one of polythiol compounds composed of 2,3-bis (2-mercaptoethylthio) -propane-1-thiol (GST) and pentaerythritol tetrakis (mercaptopropionate) (PEMP) Polymeric composition for optics containing these.
2. The molar ratio of the functional group of polyisocyanate (NCO) consisting of the components (A), (B) and (C) and the functional group of NCO / SH in the functional group of polythiol (SH) is contained within the range of 0.9 to 1.1. Impact resistant optically polymerizable composition.
3. The polyisocyanate compound of claim 2, wherein the content ratio (Biuret: HDI: IPDI) between them is 30 to 40: 20 to 30: 30 to 40 by weight Polymeric composition for optics containing.
4. A method for producing an optical resin by polymerizing the optically polymerizable composition according to any one of claims 1 to 3.
5. Optical resin obtained by superposing | polymerizing the optically polymerizable composition of any one of Claims 1-3.
6. The optical lens which consists of resin for optics of Claim 5.
7. As a raw material of the resin composition for optics of Claim 1,

   (A) an isocyanate compound (Biuret) represented by the following general formula (2),

   [Formula (2)]

   

   (2)

   (Wherein p is an integer of 2 or more and 10 or less).

   (B) a compound of 1,6-hexamethylene diisocyanate (HDI) or dicyclohexyl methane diisocyanate (H12MDI)

   (C) Polyisocyanate composition for impact resistant polyurethane resins containing a compound of isophorone diisocyanate (IPDI).
8. The polyisocyanate for polyurethane resin according to claim 7, wherein the content ratio (Biuret: HDI: IPDI) between the components (A), (B), and (C) is contained in a weight ratio of 30 to 40: 20 to 30: 30 to 40. Composition.