KR20220001866A - Optical resin composition having high heat resistance and optical resin using it - Google Patents

Abstract

The present invention relates to a composition for an optical resin, containing diisocyanato methylcyclohexane. The optical resin obtained from the composition for an optical resin of the present invention is light with low specific gravity and has excellent various optical properties such as workability such as moldability and dyeability, UV protection properties, and transparency. In particular, the composition for an optical resin has excellent heat resistance, thereby solving the cracks of a multi-coating film at high temperatures.

Description

An optical resin composition having excellent heat resistance and an optical resin using the same

The present invention relates to a composition for an optical resin, and in particular, to an optical resin composition having high heat resistance and low specific gravity, which is light, and excellent in various optical properties such as moldability and dyeability, workability such as UV protection and transparency.

Optical resins prepared using isocyanate and polythiol or polyol compounds have excellent optical properties such as transparency and Abbe's number tensile strength, have a low specific gravity compared to glass, are light, and are easy to process. However, the existing urethane-based optical resin has a low thermal deformation temperature, so there is a problem that the center of the lens is deformed when hard-multi-coating on the lens surface after casting the optical resin. When exposed, thermal deformation of the urethane-based optical resin occurs, causing cracks in the multi-coating layer. When the multi-coating layer is cracked, a cloudy film is formed on the surface of the lens, so there is a problem that the transparency of the optical resin is rapidly lowered.

Korean Patent No. 10-1157497 suggests a method of using a prepolymer of isophorone diisocyanate or dicyclohexylmethane diisocyanate and a mercapto compound, and the thermal deformation temperature of a lens using the same is about 110°C. However, this resin composition for optical lenses has a problem in that an additional process for preparing a prepolymer is required.

The present inventors solve the problems of the conventional optical resin composition as described above, and provide a resin composition that maintains excellent optical properties while having superior heat resistance than any resin for urethane-based spectacle lenses of the mold injection method. have.

In order to solve the above problems, as a result of intensive studies, the present inventors studied heat resistance under various conditions using diisocyanatomethylcyclohexane of Formula (1) as a core raw material as a result of earnest examination to have superior heat resistance. As a result, a polythiourethane composition that has excellent heat resistance and has an adjustable refractive index from medium refractive index (1.55) to high refractive index (1.61) and whitening phenomenon is remarkably removed, and a polythiourethane composition that does not show yellowing was invented.

In one aspect, in order to achieve the above object, the present invention provides a composition for an optical resin comprising an isocyanate compound and a polyol or polythiol compound, wherein the isocyanate compound includes diisocyanatomethylcyclohexane represented by the following formula (1) It provides a composition for an optical resin, characterized in that:

.

.

In a further aspect, the diisocyanatomethylcyclohexane of the present invention is characterized in that it is a compound of Formula 2 or Formula 3:

.

.

In another aspect, the present invention provides a method for producing an optical resin by using the composition for an optical resin described above.

In another aspect, the present invention provides an optical resin obtained by using the composition for an optical resin described above. Here, the optical resin may be a spectacle lens.

The optically polymerizable composition according to the present invention generally contains at least one of one or more isocyanate compounds and polythiol compounds using diisocyanatomethylcyclohexane represented by the following formula (1) as a core raw material.

In the optically polymerizable composition of the present invention, the molar ratio between the functional group of the isocyanate (NCO) compound and the functional group of NCO/SH in the functional group of the polythiol (SH) is preferably in the range of 0.5 to 1.5, more preferably 0.9 to 1.1 range. Further, in the polyisocyanate compound, the content of the formula (1) is 10% or more, preferably 20% or more, more preferably 40% or more. On the other hand, another aspect of the present invention relates to a method for preparing an optical resin by polymerizing the above optically polymerizable composition. 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, particularly a lens, made of the above optical resin.

In the present invention, as the isocyanate compound other than diisocyanate methylhexane, an alkylene diisocyanate compound, an alicyclic diisocyanate compound, a heterocyclic diisocyanate compound, an aliphatic diisocyanate compound containing sulfur, etc. may be used.

The alkylene diisocyanate compound includes, for example, ethylene diisocyanate; trimethylene diisocyanate; tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; octamethylene diisocyanate; nonamethylene diisocyanate; 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexanediisocyanate; decamethylene diisocyanate; butenediisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 1,6,11-undecanetriisocyanate; 1,3,6-hexamethylene triisocyanate; 1,8-diisocyanato-4-isocyanatomethyloctane; 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane; bis(isocyanatoethyl)carbonate; bis(isocyanatoethyl)ether; 1,4-butylene glycol dipropyl ether-1,2-diisocyanate; 1,4-butylene glycol dipropyl ether-1,3-diisocyanate; 1,4-butylene glycol dipropyl ether-1,4-diisocyanate; 1,4-butylene glycol dipropyl ether-2,3-diisocyanate; 1,4-butylene glycol dipropyl ether-2,4-diisocyanate; methyllysine diisocyanate; lysine triisocyanate; 2-isocyanatoethyl-2,6-diisocyanatohexanoate; 2-isocyanatopropyl-2,6-diisocyanatohexanoate; mesitylene triisocyanate; 2,6-di(isocyanatomethyl)furan; and the like.

Examples of the alicyclic diisocyanate compound include isophorone diisocyanate; dicyclohexylmethane diisocyanate; 3,8-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 3,9-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 4,8-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 4,9-bis(isocyanatomethyl)tricyclo[5,2,1,0,6]decane; 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane; 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane; bis(isocyanatomethyl)cyclohexane; dicyclohexylmethane diisocyanate; cyclohexanediisocyanate; methylcyclohexanediisocyanate; dicyclohexyldimethylmethane diisocyanate; 2,2'-dimethyldicyclohexylmethane diisocyanate; bis(4-isocyanato-n-butylidene)pentaerythritol; dimer acid diisocyanate; 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethylbicyclo[2,2,1]-heptane; 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethylbicyclo[2,2,1]-heptane; 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane; 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane; 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2,2,1]-heptane; 1,3,5-tris(isocyanatomethyl)-cyclohexane; dicyclohexylmethane-4,4-diisocyanate (H12MDI);

Heterocyclic diisocyanate compounds include, for example, thiophene-2,5-diisocyanate; methyl thiophene-2,5-diisocyanate; 1,4-dithiane-2,5-diisocyanate; methyl 1,4-dithiane-2,5-diisocyanate; 1,3-dithiolane-4,5-diisocyanate; methyl 1,3-dithiolane-4,5-diisocyanate; methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate; ethyl 1,3-dithiolane-2,2-diisocyanate; tetrahydrothiophene-2,5-diisocyanate; methyltetrahydrothiophene-2,5-diisocyanate; ethyl tetrahydrothiophene-2,5-diisocyanate; methyl tetrahydrothiophene-3,4-diisocyanate; 1,2-diisothiocyanatoethane; 1,3-diisothiocyanatopropane; 1,4-diisothiocyanatobutane; 1,6-diisothiocyanatohexane; p-phenylenediisopropylidene diisothiocyanate; and cyclohexanediisothiocyanate.

Examples of the sulfur-containing aliphatic diisocyanate compound include 4-isocyanato-4'-isothiocyanatodiphenyl sulfide; 2-isocyanato-2'-isothiocyanatodiethyldisulfide; thiodiethyl diisocyanate; thiodipropyl diisocyanate; thiodihexyl diisocyanate; dimethyl sulfone diisocyanate; dithiodimethyl diisocyanate; dithiodiethyl diisocyanate; dithiodipropyl diisocyanate; dicyclohexylsulfur-4,4'-diisocyanate; 1-isocyanatomethylthia-2,3-bis(2-isocyanatoethylthia)propane;

The polythiol compound is a compound having at least one sulfur atom in the molecule. Preferably, 2-(2-mercaptoethylthio)propane-1,3-dithiol; 2,3-bis(2-mercaptoethylthio)propane-1-thiol; 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol; 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane; 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)-ethane; Bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 2-(2-mercaptoethylthio)-3-{2-mercapto-3-[3-mercapto-2 -(2-mercaptoethylthio)-propylthio]propylthio}-propane-1-thiol; 2,2-bis-(3-mercapto-propionyloxymethyl)-butyl ester; 2-(2-mercaptoethylthio)-3-(2-{2-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]ethylthio}ethylthio)propane-1-thiol Use one or two or more of them.

Alternatively, the mercapto compound includes a thiol ester compound. For example, a thiol ester compound is a trivalent thiol ester compound in which three thiol groups exist in one molecule. Trimethylolpropane tris(mercaptopropionate), trimethylolethane tris(mercaptopropionate), glycerol tris( Mercaptopropionate), trimethylolchlorotris(mercaptopropionate), trimethylolpropane tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), etc. As pentaerythritol tetrakis (mercaptopropionate) (PETMP), pentaerythritol tetrakis (mercaptoacetate) (PETMA), bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP) , bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA), bispentaerythritol hexa (2-mercaptoacetate) (BPEMA), bistrimethylolpropane tetrakis (3-mercaptopropio) nate) (BTMPMP), bistrimethylolpropanetetrakis(2-mercaptoacetate) (BTMPMA), etc. can be used alone or in mixture of two or more.

The polymerizable composition, in addition, if necessary, an internal mold release agent, an ultraviolet absorber, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a filler, a near-infrared absorber It further contains additives such as can do.

Examples of the internal mold release agent include: a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphoric acid ester group; a silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphoric acid ester group; alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; A component selected from acidic phosphoric acid esters may be used alone or in combination of two or more.

As the ultraviolet absorber, benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, cyanoacrylate-based, oxanilide-based and the like may be used.

As the polymerization initiator, amine-based, phosphorus-based, organotin-based, organic copper-based, organic gallium, organic zirconium, organic iron-based, organic zinc, organic aluminum, organic bismuth-based, and the like may be used.

As the heat stabilizer, one type or a mixture of two or more types of metal fatty acid salt-based, phosphorus-based, lead-based, organotin-based and the like can be used.

In addition, according to the present invention, there is provided a polythiourethane obtained from the above-described polymerizable composition. That is, the polythiourethane may be prepared by polymerization (and curing) of the isocyanate composition and thiol in the polymerizable composition. In the polymerization reaction, the molar ratio of SH group/NCO group may be 0.5 to 1.5, and more preferably 0.9 to 1.1.

Moreover, in order to adjust to a desired reaction rate, a reaction catalyst can be added suitably. As the catalyst preferably used, for example, as a urethanation catalyst, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, tetramethyldiacetoxydistanoxane, tetraethyldiacetoxydistanoxane Amine compounds, such as tin compounds, such as tetrapropyl diacetoxy distanoxane and tetrabutyl diacetoxy distanoxane, and a tertiary amine, can be used. It is also possible to use these independently, and to use 2 or more types together. As the amount of catalyst to be added, it is preferably used in the range of 0.001 to 1% by weight based on the total weight of the monomers in the composition. In the case of this range, it is preferable in terms of polymerizability as well as pot life during operation, 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 use, and although there is no particularly limited curing method, curing by heat is mainly used in general. Thereby, the resin of this invention is obtained. The resin of the present invention is obtained by mold polymerization, which is a conventional method, which is a mold injection method.

In addition, the resin composition for an optical lens of the present invention may further include a color correcting agent for correcting the initial color of the lens. An organic dye, an organic pigment, an inorganic pigment, etc. may be used as a color corrector. By adding 0.1 to 50,000 ppm, preferably 0.5 to 10,000 ppm of these organic dyes per 1 resin composition for optical lenses, it is possible to prevent the lens from being yellow due to the addition of an ultraviolet absorber, optical resin, and monomer.

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

The optical polymerization composition of the present invention is polymerized to obtain a resin composition, and then thermally cured to obtain an optical lens, particularly a spectacle lens. The process of manufacturing a 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 then stirring under reduced pressure is performed for 1 to 5 hours, stirring is stopped, and then degassed under reduced pressure and injected into the mold. do. In this case, preferably, a plastic gasket or a glass mold or a metal mold fixed with a polyester or polypropylene adhesive tape is used as the mold. Put the glass mold in which the mixture is injected into a forced circulation oven, slowly increase the temperature from room temperature to 120~130℃, keep it at 120~140℃ for 1~4 hours, cool it slowly to 60~80℃, and release the solid from the mold to obtain an optical lens. The optical lens thus obtained is annealed at a temperature of 120 to 140° C. for 1 to 4 hours to obtain a final target plastic spectacle lens (dough).

In addition, the optical lens obtained by the above method may be subjected to hard coating and multi-coating to improve optical properties. The formation of the hard coating layer is mainly composed of at least one silane compound having a functional group such as an epoxy group, an alkoxy group, a vinyl group, and at least one metal oxide colloid such as silicic acid, titanium oxide, antimony oxide, tin oxide, tungsten oxide, aluminum oxide, etc. After coating the optical lens surface with a thickness of 0.5 to 10 by impregnation or spin coating with a coating composition comprising

The multi-coating layer, that is, the anti-reflection coating layer, may be formed by vacuum deposition or sputtering of a metal oxide such as silicon oxide, magnesium fluoride, aluminum oxide, zirconium oxide, titanium oxide, tantalum oxide, and yttrium oxide. Most preferably, after vacuum deposition of silicon oxide and zirconium oxide films three or more times repeatedly on both sides of the hard coating film of the lens, the silicon oxide film is finally vacuum deposited. In addition, if necessary, a water film (fluororesin) layer may be provided last, or an ITO layer may be placed between the silicon oxide and zirconium oxide film.

The optical lens of the present invention may be used after being colored using a disperse dye or a photochromic dye, if necessary.

The resin composition for optical lenses of the present invention is not limited to plastic spectacle lenses and can be used in various optical products.

It is necessary to evaluate whether the optical lens manufactured by the present invention has suitable physical properties as a plastic spectacle lens, and each of the physical properties is (1) refractive index and Abbe's number (υE), (2) heat resistance (Tg), (3) yellowness , (4) Striae and cloudiness were evaluated by the following test methods.

(1) Refractive index (nD ²⁰ , nE ²⁰ ) and Abbe number (υE): Refractive index at 589 nm (D wavelength), 546 nm (E wavelength) and 546 nm using the ABBE refractometer, ATAGO’s DR-M4 model Abbe's number was measured at 20 degreeC.

(2) Heat resistance: The glass transition temperature (Tg) of the test piece was measured using a DSC N-650 thermal analyzer manufactured by SCINCO to determine the heat resistance.

(3) Yellowness: The Y.I value of the 2 mm test piece was measured using a UV-2600 spectrometer from SHIMADZU, and the yellowness was compared.

(4) Striae and cloudiness: Observe 100 lenses with the naked eye to determine the occurrence of streaks and whitening phenomena more than 10: X, 5-9: △, 3-4: ○, 2 or less: ◎ did

[Example]

Example 1

2,3-bis(2-mercaptoethylthio)propane-1-thiol (GST) 30.8 g and pentaerythritoltetrakis(mercaptopropionate) (PETMP) 19.7 in 46.5 g of diisocyanatomethylcyclohexane g, dibutyltin dichloride (DBDC) 0.1 g, ZELEC UN 0.12 g, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole 1.5 g, stirred under a nitrogen stream for 10 minutes, 1 It was vacuum defoamed for 1 hour below torr, purged with nitrogen, and injected into a glass mold using nitrogen pressure. The glass mold in which the composition for optical resin was injected was slowly heated from 30°C to 125°C in a forced circulation oven, maintained at 125°C for 2 hours, cooled to 70°C, and the optical resin was demolded from the mold to have a center thickness of 1.3 mm got spectacle lenses. After processing the obtained spectacle lens to a width of 72 mm, it was immersed in an aqueous alkaline washing solution, washed with ultrasonic waves, and then annealed at 125° C. for 2 hours. Thereafter, after thermal curing by dip coating in a hard liquid, multi-coated spectacle lenses were obtained by vacuum deposition of metal oxide and fluorine resin.

Examples 2-12, Comparative Examples 1-2

An optical resin was prepared according to the composition shown in Table 1 in the same manner as in Example 1, and physical properties were evaluated, and the results are shown in Table 2. Table 1 below shows the composition compounds and the amount used according to each Example and Comparative Example. Here, the horizontal axis represents Examples and Comparative Examples, and the weight unit of the compound on the vertical axis is (g).

One 2 3 4 5 6 7 8 9 10 11 12 Comparative Example 1 Comparative Example 2 Diisocyanatomethylcyclohexane 46.5 46.5 46.5 46.5 30 40 46.5 46.5 23 46.5 23 23 1,6-hexamethylene diisocyanate 20 10 1,3-bis(isocyanatomethyl)cyclohexane 60 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane 30 GST 30.8 38.1 44.84 15.2 BET 31.55 34.89 34.41 23.41 26.21 PETMP 19.7 29.33 21.03 23.26 22.94 9.51 26.21 31.20 14.2 PETMA 27.66 33.10 CET 27.66 29.33 27.12 33.10 internal release agent 0.12 0.06 0.12 0.06 0.06 0.2 0.06 catalyst 0.1 0.05 0.1 0.05 0.09 0.03

Abbreviations in Table 1 above are as follows:

DIMC: diisocyanatomethylcyclohexane

HDI: 1,6-hexamethylene diisocyanate

BIC: 1,3-bis(isocyanatomethyl)cyclohexane

BIBH: 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane

GST: 2,3-bis (2-mercaptoethylthio) propane-1-thiol

BET: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

PETMP: pentaerythritol tetrakis (mercaptopropionate)

PETMA: pentaerythritol tetrakis (mercaptoacetate)

CET: 1,4-dithiane-2,5-dimethanol

Table 2 below shows the physical property table according to each Example and Comparative Example.

nD ²⁰ nE ²⁰ vE ²⁰ Heat resistance (Tg) McLee cloudiness yellowness Example 1 1.5920 1.5956 39.5 139.86 ◎ ○ Good Example 2 1.5906 1.5921 38.8 150.99 ◎ △ Good Example 3 1.5859 1.5880 39.9 145.57 ◎ ○ Good Example 4 1.5937 1.5955 41.2 149.51 ◎ ○ Good Example 5 1.5944 1.5981 39.6 108.07 ◎ ○ Good Example 6 1.5938 1.5973 39.0 130.54 ◎ ○ Good Example 7 1.5970 1.5996 37.9 132.06 ◎ ○ Good Example 8 1.6118 1.6159 37.1 132.04 ◎ △ Good Example 9 1.6172 1.6211 37.2 152.51 ◎ ◎ Good Example 10 1.5849 1.5900 39.6 146.15 ◎ ○ Good Example 11 1.5558 1.5586 42.6 125.06 ○ Ⅹ Good Example 12 1.6155 1.6193 37.8 150.20 Good Comparative Example 1 1.5928 1.5965 39.8 108.69 ○ ○ fine yellowing Comparative Example 2 1.5949 1.5984 40.2 112.84 ◎ ◎ Good

Claims (5)

A composition for an optical resin composed of an isocyanate compound and a polyol or polythiol compound, wherein the isocyanate compound comprises diisocyanatomethylcyclohexane represented by the following Chemical Formula 1, the composition for an optical resin:

. The composition for an optical resin according to claim 1, wherein the diisocyanatomethylcyclohexane is a compound of Formula 2 or Formula 3 below:

. The method of manufacturing an optical resin using the composition for optical resins of Claim 1 or 2. An optical resin obtained by using the composition for optical resins according to claim 1 or 2. The optical resin according to claim 4, wherein the optical resin is a spectacle lens.