Patent Description:
This invention relates to a curable composition for forming high refractive index optical material, and optical material comprising the same.

General eyeglass lenses use glass having a high refractive index, but although glass may have high refractive index, light transmittance, flatness, strength and scratch prevention effect, it may give serious damage to the eyeball of a user, and it has high density and thus heavy weight, thus causing discomfort during extended-wear.

To the contrary, plastic lens is lighter than glass lens and thus is comfort to wear, is not easily damaged, and even if damaged, is relatively safer than glass lens, and enables realization of various colors. However, it is difficult for plastic lens to realize high refractive index and high Abbes' number, compared to glass lens, and due to low glass transition temperature, in case the lens is used in devices, thermal deformation may be generated.

<CIT>, <CIT>, <CIT>, <CIT> as well as <CIT> describe compositions for optical materials; <CIT>, <CIT> and <CIT> disclose a method for the production of a plastic lens, a resin composition for an optical member, and an optical product, respectively. <CIT> describes an optical film. The preparation of sulphur-rich nanoparticles is described by <NPL>) as well as by <NPL>.

It is an object of the invention to provide a curable composition for forming high refractive index optical material that is lighter than glass or tempered glass used in the existing lenses, and the like, has excellent strength and hardness, enables realization of various colors, enables realization of high refractive index, has low haze value and thus has excellent optical properties, and has high glass transition temperature and thus is less deformed, and optical material comprising the same.

According to the present disclosure, there is provided a curable composition for forming high refractive index optical material comprising: an episulfide compound; sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms; and a reducing agent. The sulfur-containing organic particles are as further described herein below and defined in the claims.

According to the present disclosure, there is also provided optical material comprising: an episulfide compound; sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms; and a reducing agent.

Hereinafter, a curable composition and optical material comprising the same according to specific embodiments of the invention will be explained in detail.

The terms used herein are only to explain specific embodiments, and are not intended to limit the present invention. A singular expression includes a plural expression thereof, unless it is expressly stated or obvious from the context that such is not intended.

As used herein, the terms "comprise" or "have", etc. are intended to designate the existence of practiced characteristic, number, step, constructional element or combinations thereof, and they are not intended to preclude the possibility of existence or addition of one or more other characteristics, numbers, steps, constructional elements or combinations thereof.

As used herein, an "episulfide compound" means a compound comprising one or more episulfides, wherein the episulfide means a compound in which the oxygen(O) atom of epoxide is substituted with a sulfur(S) atom.

As used herein, "sulfur-containing organic particles" mean organic particles which consist of carbon atoms, hydrogen atoms, oxygen atoms, and the like, and essentially comprises sulfur atoms.

As used herein, 'curing' means both thermal curing and photocuring, and a 'curable composition' means a thermally curable and/or photocurable composition.

As used herein, a high refractive index means a refractive index of about <NUM> or more at a wavelength region of <NUM> to <NUM> or at a wavelength of <NUM>.

According to one embodiment of the invention, there is provided a curable composition for forming high refractive index optical material comprising: an episulfide compound; sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms; and a reducing agent.

The inventors discovered that a composition comprising an episulfide compound; sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms; and a reducing agent, and optical material comprising the same, are lighter than glass or tempered glass used in the existing lenses, and the like, have excellent physical properties such as strength and hardness, and the like, have high transmittance and low haze and yellow index(Y. ) and thus have excellent optical properties, have high glass transition temperature and thus less thermal deformation, and therefore, can provide optical material capable of replacing previously used glass or plastic material, and completed the invention.

Thus, the curable composition and optical material comprising the same can replace the existing glass or optical glass, and be usefully applied as a display substrate, a display protection film, a touch panel, lens of wearable devices, and the like.

The episulfide compound included in the curable composition may be represented by the following Chemical Formula <NUM>:
<CHM>
<CHM>
in the Chemical Formula <NUM>,.

The episulfide compound, due to the above explained specific chemical structure, may comprise high content of sulfur(S) atoms having large atomic refraction in the molecule, and by such high sulfur atom content, may increase the refractive index of the cured product.

And, the episulfide compound may be cured by ring opening polymerization, and alkylene sulfide groups formed by the ring opening polymerization of episulfide groups may further increase the high refractive index of the cured product.

Meanwhile, in the Chemical Formula <NUM>, each of R<NUM> and R<NUM> may be independently, hydrogen or a methyl group, but is not limited thereto.

And, each of R<NUM> and R<NUM> may be independently, a single bond, methylene, ethylene, propylene, isopropylene, butylene, or isobutylene, but is not limited thereto.

And, each of a and b may be independently, <NUM> or <NUM>.

The a of the Chemical Formula <NUM> refers to the carbon number of an alkylene group included in a thioether repeat unit, and if a is too large, the length of a carbon chain in the molecule may lengthen, and thus, the glass transition temperature of the cured product may be lowered and heat resistance of the cured product may be deteriorated, and a relative sulfur content may decrease, and thus, the refractive index of the cured product may be lowered.

The b of the Chemical Formula <NUM> refers to the repeat number of a thioether repeat unit in which an alkylene group is linked by sulfur(S) atom, and if b is too large, the length of a carbon chain in the molecule may lengthen, and thus,the glass transition temperature of the cured product may be lowered and heat resistance of the cured product may be deteriorated.

And, the compound represented by the Chemical Formula <NUM> may be used alone, or in combination of two or more kinds.

The episulfide compound may comprise, for example, at least one selected from the group consisting of bis(β-epithiopropyl)sulfide, bis(β- epithiopropyl)disulfide, bis(β- epithiopropylthio)methane, <NUM>,<NUM>-bis(β- epithiopropylthio)ethane, <NUM>,<NUM>-bis(β-epithiopropylthio)propane, and <NUM>,<NUM>-bis(β- epithiopropylthio)butane, but is not limited thereto.

The episulfide compound may be included in the content of <NUM> to 99wt%, <NUM> to 95wt%, or <NUM> to 90wt%, based on 100wt% of the total curable composition. If the content of the episulfide compound is too large, yellowness of optical material such as a plastic substrate, and the like, manufactured after curing, may increase, and if it is too small, haze of optical material manufactured after curing may increase, and thus, transparency may decrease.

The curable composition may comprise sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms. The sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms may be used as a curing agent for curing the curable composition comprising an episulfide compound, and specifically, the reducing agent included in the curable composition may reduce the surface of each sulfur-containing organic particle to form <NUM> or more thiol groups, and such two or more thiol groups may react with the episulfide compound to newly form disulfide bonds, enabling the formation of a cured product.

Since the curable composition comprises the sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms, the cured product of the curable composition, namely optical material, may have excellent optical properties such as transmittance, haze and yellow index, the glass transition temperature may be increased to <NUM> or more, and it may exhibit a high refractive index of <NUM> or more.

The sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms comprise repeat units represented by the following Chemical Formula <NUM>:
<CHM>
in the Chemical Formula <NUM>,.

The sulfur-containing organic particles may comprise <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM> repeat units of the Chemical Formula <NUM>.

And, in one or more of the repeat units included in the sulfur-containing organic particles, n may be <NUM>, and in case n is <NUM>, it may correspond to a disulfide bond. And, n may be <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>.

The sulfur-containing organic particles may comprise sulfur atoms in the amount of <NUM> to 80wt%, <NUM> to 77wt%, or <NUM> to 74wt%. If the content of the sulfur atoms included in the sulfur-containing organic particles is too small, refractive index increasing effect may not be obtained but transmittance may be lowered, and if the content of the sulfur atoms is too large, although refractive index increasing effect may be obtained, yellow index may be increased.

The sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms may have particle diameters of <NUM> to <NUM>, <NUM> to <NUM>, or <NUM> to <NUM>. If the particle diameter of the sulfur-containing organic particles is too small, the organic particle may not maintain the shape of the particle during a reduction reaction by a reducing agent, and if the particle diameter is too large, the transmittance of a high refractive index plastic substrate may be lowered, and the haze may be increased.

The sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms may be prepared by the following method. Specifically, sodium sulfide nonahydrate (Na<NUM>S·<NUM><NUM>O) may be reacted with sulfur(S<NUM>) to prepare polysulfide(Na<NUM>Sa, a is an integer of <NUM> to <NUM>), and the polysulfide may be mixed with divinyl sulfone, a surfactant and a steric stabilizer to prepare the sulfur-containing organic particles.

Meanwhile, the content of the sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms may be <NUM> to 30wt%, <NUM> to 25wt%, or <NUM> to 20wt%, based on 100wt% of the total curable composition. If the content of the sulfur-containing organic particles is too large, the haze of optical material formed after curing may increase, and the yellow index may also increase, and if the content of the sulfur-containing organic particles is too small, the refractive index of optical material formed after curing may be lowered.

And, the weight ratio of the episulfide compound and the sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms may be <NUM>:<NUM> to <NUM>, <NUM>:<NUM> to <NUM>, or <NUM>:<NUM> to <NUM>. If the weight ratio of the episulfide compound and sulfur-containing organic particles is greater than <NUM>:<NUM>, the yellow index of optical material such as a plastic substrate, formed after curing, may increase, and if it is less than <NUM>:<NUM>, the refractive index of optical material formed after curing may be lowered.

The curable composition may comprise a reducing agent. The reducing agent may reduce the surface of each sulfur-containing organic particle comprising <NUM> to 80wt% of sulfur atoms to form <NUM> or more thiol groups. Thus, it can not only increase a reaction rate of the episulfide compound and the sulfur-containing organic particles, but also prevent production of unreacted compounds, thereby lowering haze and yellow index of the cured product to improve optical properties and increase glass transition temperature, while maintaining high refractive index and excellent mechanical properties.

The reducing agent may comprise, for example, at least one selected from the group consisting of triphenylphosphine(PPh<NUM>), tris(<NUM>-carboxylethyl)phosphine(TCEP), <NUM>,<NUM>-dimercaptobutane-<NUM>,<NUM>-diol(DTT), tris(<NUM>-hydroxypropyl)phosphine(THPP), beta-mercaptoethanol(BME) and dithiobutylamine(DTBA).

The content of the reducing agent may be <NUM> to15 wt%, <NUM> to 14wt%, or <NUM> to 13wt%, based on 100wt% of the total curable composition. If the content of the reducing agent is too large, glass transition temperature(Tg) of optical material formed after curing may be lowered, and if it is too small, haze of optical material may increase.

And, in the curable composition, the weight ratio of the reducing agent and sulfur-containing organic particles may be <NUM>: <NUM> to <NUM>, <NUM>: <NUM> to <NUM>, or <NUM>: <NUM> to <NUM>. If the weight ratio of the reducing agent and sulfur-containing organic particles is greater than <NUM>:<NUM>, glass transition temperature(Tg) of optical material formed after curing may be lowered, and if it is less than <NUM>:<NUM>, haze of optical material may increase.

The curable composition according to one embodiment may further comprise a catalyst. The catalyst is not specifically limited as long as it performs a function for accelerating the curing reaction of a curable composition, but for example, imidazole derivatives such as imidazole, <NUM>-methylimidazole, <NUM>-ethylimidazole, <NUM>-ethyl-<NUM>-methylimidazole, <NUM>-phenylimidazole, <NUM>-phenylimidazole, <NUM>-cyanoethyl-<NUM>-phenylimidazole, <NUM>-(<NUM>-cyanoethyl)-<NUM>-ethyl-<NUM>-methylimidazole, and the like; amine compounds such as dicyandiamide, benzyldimethylamine, <NUM>-(dimethylamino)-N,N-dimethyl benzylamine, <NUM>-methoxy-N,N-dimethyl benzylamine, <NUM>-methyl-N,N-dimethyl benzylamine, N,N-dicyclohexylmethylamine, and the like; hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, and the like; phosphorus compounds such as triphenylphosphine, and the like, may be mentioned. And, as commercially available catalysts, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ(product names of imidazole-based compounds) manufactured by Shikoku Kasei Kogyo Co. , U-CAT3503N, UCAT3502T(product names of block isocyanate of dimethylamine) manufactured by San-Apro Ltd. , DBU, DBN, U-CATSA102, U-CAT5002(bicyclic amidine compounds and salts thereof), and the like, may be mentioned.

The content of the catalyst may be0. <NUM> to 10wt%, <NUM> to 5wt%, or <NUM> to 1wt%, based on 100wt% of the total curable composition. If the content of the catalyst is too large, a curing speed may increase and thus storage stability of the composition may be deteriorated, and if it is too small, a curing speed may decrease and thus a thermal curing process may be lengthened.

Besides, the curable composition may further comprise other additives used to give specific functions to display substrates in the technical field to which the invention pertains, such as a UV absorber, a bluing agent, pigment, and the like.

According to another embodiment of the invention, there is provided optical material comprising: an episulfide compound; sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms; and a reducing agent.

For the episulfide compound, sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms, reducing agent, additives, and the like, included in the optical material, the above explanations regarding a photocurable composition are applied.

Such optical material may be prepared by curing the above explained curable composition. Specifically, the above explained curable composition or a homogeneous composition comprising the curable composition and various additives is prepared, and the composition may be injected into forms combining a mold made of glass, metal or polymer resin, and the like, and a resinous gasket, and heated and cured. Wherein, in order to facilitate taking out of the resin finally prepared after molding, the mold may be previously treated with a release agent, or a release agent may be further added to the above explained composition before use.

The curing temperature may vary according to the kind and content of compounds used, and the like, but it may be generally progressed at about <NUM> to about <NUM>, or about <NUM> to about <NUM>, and the curing time may be about <NUM> to about <NUM> hours, or about <NUM> to about <NUM> hours.

The curing reaction may be progressed by combining a process of maintaining a predetermined polymerization temperature as explained above for a certain time, a temperature increasing process, and a temperature decreasing process, and the like, and after the reaction is finished, post-treatment may be conducted at about <NUM> to about <NUM>, or about <NUM> to about <NUM> for about <NUM> minutes to about <NUM> hours, so as to prevent deformation.

The optical material released after polymerization may be equipped with various functionalities, through the subsequent processes of dyeing, coating, and the like.

The optical material according to another embodiment may have a refractive index of <NUM> or more, <NUM> to <NUM>, or <NUM> to <NUM>.

And, the optical material may have very high transmittance of <NUM>% or more, <NUM> to <NUM>%, or <NUM> to <NUM>%, specifically measured according to JIS K <NUM>, when the thickness is <NUM>.

And, the optical material may have very low haze value of <NUM>% or less, <NUM> to <NUM>%, or <NUM> to <NUM>%, specifically measured according to JIS K <NUM>, when the thickness is <NUM>.

And, the optical material may have glass transition temperature of <NUM> or more, <NUM> to <NUM>, or <NUM> to <NUM>.

The optical material according to another embodiment may be included in a wearable device, and specifically, it may be used for lens of wearable devices, instead of glass or tempered glass.

Namely, the optical material has a high refractive index equivalent to glass, is lighter than glass or tempered glass, has excellent optical properties as well as mechanical properties such as hardness and strength, and the like, and has high glass transition temperature, and thus, it may be used as lenses of wearable devices, such as augmented reality devices or virtual reality devices that may be heated.

According to the present disclosure, there are provided a curable composition for forming high refractive index optical material that is lighter than glass or tempered glass used in the existing lenses, and the like, has excellent strength and hardness, enables realization of various colors, enables realization of high refractive index, has low haze value and thus has excellent optical properties, and has high glass transition temperature and thus is less deformed, and optical material comprising the same.

Hereinafter, the actions and effects of the invention will be explained in more detail through specific examples. However, these examples are presented only as the illustrations of the invention.

Into a <NUM> round-bottom flask, <NUM> of triple distilled water was put, and degassed with argon(Ar) gas for <NUM> hours. And then, a <NUM> vial was closed with a septum and replaced with argon(Ar) gas, and oxygen(O<NUM>) gas included was removed by vacuum, which process was repeated three times. <NUM> of sodium sulfide nonahydrate(Na<NUM>S·<NUM><NUM>O) and <NUM> of sulfur(S<NUM>) were introduced and <NUM> of degassed distilled water was added, and the reaction solution was heated to <NUM> and stirred for <NUM> hours. After the reaction was finished, <NUM> of degassed distilled water was added to prepare a polysulfide(Na<NUM>S<NUM>) aqueous solution. Wherein, the reaction formula of preparing the polysulfide(Na<NUM>S<NUM>) aqueous solution is as follows, and <FIG> is a photograph of the prepared polysulfide aqueous solution, taken by scanning electron microscope.

And then, into a <NUM> vial, <NUM> of polyvinylpyrrolidone(PVP) and <NUM> of sodium dodecyl sulfate(SDS) were introduced, and a process of replacing with argon gas and removing oxygen gas in the vial by vacuum was repeated three times. And then, <NUM> of degassed triple distilled water was added, and the reaction solution was heated to <NUM> and stirred for <NUM> hours. And, <NUM> of divinyl sulfone(DVS) from which an inhibitor had been removed was introduced into the vial, and the reaction solution was stirred for <NUM> minutes. And then, <NUM> of the polysulfide(Na<NUM>S<NUM>) aqueous solution was slowly added for <NUM> seconds using a liquid injector, and then, reacted for <NUM> minutes. After confirming that a turbid yellow solution turned into turbid white, hydrochloric acid was added to adjust the pH of the solution to <NUM>. And then, a process of precipitating the product on triple distilled water using a centrifuge, and removing polyvinylpyrrolidone and sodium dodecyl sulfate was repeated <NUM> times, and by drying in a vacuum oven, sulfur-containing organic particles A were prepared.

Wherein, the reaction formula of preparing sulfur-containing organic particles is as shown in the following Reaction Formula <NUM>, wherein n denotes the number of sulfur atoms included in the polysulfide compound in aqueous solution state, and the polysulfide compound comprises <NUM> sulfur atoms. Meanwhile, m denotes the number of repeat units included in the prepared sulfur-containing organic particles. And, it was confirmed through element analysis of the prepared sulfur-containing organic particles, that the content of sulfur atoms is <NUM> wt%. And, <FIG> is a photograph of the prepared sulfur-containing organic particles, taken by scanning electron microscope, confirming that the particle diameter of each prepared sulfur-containing organic particles is <NUM>.

<NUM> of the following episulfide compound 70A, <NUM> of the sulfur-containing organic particles A prepared in the Preparation Example, <NUM> of a reducing agent triphenylphosphine(PPh<NUM>), and <NUM> of a dispersant cetyl trimethylammonium bromide(CTAB) were mixed, and then, the mixed solution was filtered using a glass filter having a pore size of <NUM>. And then, on each side of LCD Glass having a width of <NUM> and a height of <NUM>, slide glass having a thickness of <NUM> was placed, and about <NUM> of the above mixed solution was applied on the center of the LCD Glass, and then, covered with another LCD Glass, thus preparing a mold. It was put in an oven, and a curing reaction was progressed at about <NUM> for about <NUM> hours, and at about <NUM> for about <NUM> hours. After taking out from the oven, the LCD glasses were removed to obtain a plastic specimen, which is a flat optical member. The thickness of the plastic specimen was about <NUM>, when measured using a thickness gauge (Model: ID-C112XBS) manufactured by Mitutoyo corporation.

Curable compositions and the cured products thereof, plastic specimens, were prepared by the same method as Example <NUM>, except that the episulfide compounds, sulfur-containing organic particles A, reducing agents, dispersants and catalysts were used in the contents described in the following Table <NUM>. Meanwhile, 70B used in Comparative Example <NUM> is as follows.

For each of the above specimens, based on <NUM> standard thickness, in the thickness direction of the cured product, using NDH-<NUM> manufactured by Nippon Denshoku Industries Co. LTD, transmittance (JIS K <NUM>) and haze (JIS K <NUM>) were measured, and the results were shown in the following Table <NUM>.

And, for each specimen, using a colorimeter, yellow index was measured, and the results were shown in the following Table <NUM>.

For each specimens, using differential scanning calorimeter (DSC) manufactured by TA Instrument Inc. , glass transition temperature was measured, and the results were shown in the following Table <NUM>.

For each specimen, using spectroscopic ellipsometry manufactured by Ellipso Technology Co. , a refractive index value was measured at the wavelength of <NUM>, and the results were shown in the following Table <NUM>.

Claim 1:
A curable composition for forming high refractive index optical material comprising
an episulfide compound;
sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms; and
a reducing agent,
wherein the sulfur-containing organic particles comprising <NUM> to 80wt% of sulfur atoms comprise repeat units represented by the following Chemical Formula <NUM>:
<CHM>
in the Chemical Formula <NUM>,
n is an integer of <NUM> to <NUM>, and
m is an integer of <NUM> to <NUM>.