Xylylene diisocyanate composition and polymerizable composition for optical use containing same

Abstract

To provide a xylylene diisocyanate composition capable of producing an optical lens having high transmittance and improved optical uniformity, and a polymerizable composition for optical use containing the same.SOLUTION: The xylylene diisocyanate (XDI) composition according to exemplary embodiments comprises a xylylene diisocyanate and an acid strength adjusting agent having a boiling point of 110 °C or more, and has an acid strength of more than 100ppm and 1, 000ppm or less based on the total weight of the xylylene diisocyanate (XDI). The polymerization reaction rate may be controlled by adjusting the acidity, and an optical lens having high transmittance and improved optical uniformity may be prepared.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a xylylene diisocyanate composition and an optical polymerizable composition containing the same. More specifically, the present invention relates to a xylylene diisocyanate composition prepared by the reaction of an amine salt and an optical polymerizable composition containing the same. [Background technology]

[0002] Diisocyanate compounds are widely used as raw materials for producing polyurethane resins, for example. For example, diisocyanate compounds are used in the production of optical lenses using polyurethane resins, and the physical properties of the diisocyanate compounds used as raw materials can directly affect the optical properties, such as transparency and refractive index, of the optical lenses.

[0003] For example, a polythiourethane resin produced by reacting a polythiol compound with a diisocyanate compound can be used as the base material of the optical lens.

[0004] Among the diisocyanate compounds, xylylene diisocyanate (XDI) is widely used from the viewpoint of chemical and optical properties such as reactivity and transparency.

[0005] For example, a polymerizable composition for optical lenses can be prepared by preparing a composition containing XDI and mixing it with a composition containing a polythiol compound. Therefore, the physical properties and synthesis process of the XDI composition must be designed taking into account the stability of XDI and the appropriate reactivity with the polythiol compound.

[0006] For example, Korean Patent Publication No. 2012-0076329 discloses a urethane-based optical material produced using an isocyanate compound, but does not consider the physical properties of the isocyanate composition itself. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the exemplary embodiments is to provide a xylylene diisocyanate composition and a method for producing the same that has improved reaction stability and optical properties.

[0008] An object of the exemplary embodiments is to provide an optical polymerizable composition including a xylylene diisocyanate composition having improved reaction stability and optical properties.

[0009] A problem according to an exemplary embodiment is to provide an optical article made from the optical polymerizable composition. [Means for solving the problem]

[0010] A xylylene diisocyanate composition according to an exemplary embodiment includes xylylene diisocyanate (XDI) and an acidity modifier having a boiling point of 110°C or higher, and has an acidity of more than 100 ppm and less than or equal to 1,000 ppm, based on the total weight of the xylylene diisocyanate (XDI).

[0011] In some embodiments, the chlorine content in the composition may be less than 100 ppm.

[0012] In some embodiments, the chlorine content in the composition may be between 10 ppm and 95 ppm.

[0013] In some embodiments, the change in acidity of the xylylene diisocyanate composition before and after storage in a dark room at 25°C for 3 months may be 40 ppm or less.

[0014] In some embodiments, the xylylene diisocyanate composition may have a transmittance of 99% or more for light with a wavelength of 380 nm after storage in a dark room at 25° C. for 3 months.

[0015] In some embodiments, the acidity adjuster can include at least one inorganic acid compound selected from the group consisting of halogen acids, sulfuric acid, phosphoric acid, and phosphate ester compounds.

[0016] In some embodiments, the acidity adjuster can comprise at least one organic acid compound selected from the group consisting of acetic acid, benzoic acid, trifluoroacetic acid (TFA), a fatty acid, and an aromatic carboxylic acid halide.

[0017] In some embodiments, the acidity adjuster can comprise at least one solid acid selected from the group consisting of clay, silica alumina, cation exchange resin, acid-attached silica gel, acid-attached alumina, aluminum oxide, and vanadium oxide.

[0018] In some embodiments, the acidity adjuster can include a cyclic amine compound or a tertiary amine compound.

[0019] In some embodiments, the amount of the acidity regulator added may be 300 ppm to 4,000 ppm.

[0020] An optical polymerizable composition according to an exemplary embodiment includes a xylylene diisocyanate composition that includes xylylene diisocyanate (XDI) and an acidity adjuster having a boiling point of 110°C or higher, and has an acidity of more than 100 ppm and not more than 1,000 ppm based on the total weight of the xylylene diisocyanate (XDI), a polythiol-based compound, and an additive.

[0021] In some embodiments, the chlorine content in the xylylene diisocyanate composition may be less than 100 ppm.

[0022] In some embodiments, the additives may include at least one selected from the group consisting of a mold release agent, a reaction catalyst, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

[0023] In an exemplary embodiment, a method for producing a xylylene diisocyanate composition includes synthesizing xylylene diisocyanate from xylylene diamine to form a preliminary composition containing xylylene diisocyanate, and adjusting the acidity of the preliminary composition to a range of greater than 100 ppm and 1,000 ppm.

[0024] In some embodiments, an acidic acidity adjuster can be added if the acidity of the preliminary composition is 100 ppm or less, and a basic acidity adjuster can be added if the acidity of the preliminary composition is greater than 1,000 ppm. [Effects of the Invention]

[0025] According to the above-described embodiment, the xylylene diisocyanate composition has an acidity of more than 100 ppm and not more than 1,000 ppm, and can provide improved stability and a suitable range of polymerization reaction rate with polythiol compounds.

[0026] This allows the production of optical lenses with high transmission and improved optical uniformity, with opacity and striae substantially eliminated. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, the present invention will be described in detail with reference to the preferred embodiments. However, since the present invention can be modified in various ways and can have various forms, specific embodiments will be illustrated in the drawings and described in detail herein. However, it should be understood that the present invention is not limited to the specific disclosed form, and that all modifications, equivalents, and alternatives within the spirit and technical scope of the present invention are included.

[0028] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which this invention pertains. Terms as defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning they have in the context of the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly defined in this application.

[0029] According to one aspect of the present application, there is provided a composition containing xylylene diisocyanate (XDI) (hereinafter sometimes abbreviated as "XDI composition").

[0030] According to an exemplary embodiment, the XDI composition comprises XDI and can have an acidity of greater than 100 ppm and less than or equal to 1,000 ppm, based on the total weight of the XDI.

[0031] The term "acidity" used in this application may be a value that represents the amount of acid components liberated by reaction with alcohol at room temperature, converted into, for example, HCl, and expressed as a percentage of the total weight of XDI.

[0032] The XDI contained in the XDI composition can be reacted with a polythiol compound, such as a trifunctional thiol compound and / or a tetrafunctional thiol compound, to obtain a polythiourethane resin. According to an exemplary embodiment, the acidity of the XDI composition can be adjusted as a factor affecting the stability of XDI and the reactivity with the polythiol compound.

[0033] For example, if the acidity of the XDI composition is too high, the polymerization reactivity with the polythiol compound may be too low. This may result in a decrease in the process yield of the polythiourethane resin for manufacturing optical lenses. Furthermore, cloudiness may occur during the casting process for molding lenses.

[0034] If the acidity of the XDI composition is too low, the polymerization reactivity with the polythiol-based compound may be excessive. As a result, instead of the desired polythiourethane resin, other by-products, such as oligomers or polymers, may increase, causing striae in the lens. Furthermore, the self-reactivity of XDI may increase, resulting in cloudiness during long-term storage. As a result, as described below, the transmittance of the undiluted composition may decrease after long-term storage in a dark room at room temperature (25°C) for 3 months. Furthermore, due to the self-reaction during long-term storage, the desired target acidity may fluctuate, making it impossible to control the acidity.

[0035] In consideration of the above aspects, according to an exemplary embodiment, the acidity of the XDI composition can be adjusted to more than 100 ppm and 1,000 ppm or less. This maintains appropriate reactivity with the polythiol compound, suppresses cloudiness during lens casting, and prevents striae on the lens. Furthermore, the storage properties of the XDI composition can be ensured, and the decrease in transmittance and change in acidity of the XDI composition can be suppressed.

[0036] In one embodiment, the acidity of the XDI composition may be greater than 100 ppm and less than or equal to 800 ppm, preferably 110 ppm to 800 ppm, more preferably 110 ppm to 700 ppm, or 110 ppm to 500 ppm. For example, the acidity of the XDI composition may be 110 ppm to 300 ppm, preferably 110 ppm to 250 ppm, more preferably 110 ppm to 200 ppm.

[0037] In one embodiment, the acidity of the XDI composition may be 300 ppm to 700 ppm, or may be 250 ppm to 500 ppm.

[0038] In some embodiments, the change in acidity of the XDI composition after 3 months of storage in a dark room at 25° C. may be 200 ppm or less. For example, the change in acidity of the XDI composition after 3 months of storage in a dark room at 25° C. may be 1 ppm to 200 ppm, 1 ppm to 150 ppm, or 1 ppm to 100 ppm.

[0039] Preferably, the change in acidity of the XDI composition after storage in a dark room at 25° C. for 3 months may be 40 ppm or less, more preferably 30 ppm or less, 20 ppm or less, or 15 ppm or less.

[0040] For example, the amount of change in acidity of the XDI composition may be 1 ppm to 40 ppm, 1 ppm to 35 ppm, or 1 ppm to 20 ppm, preferably 1 ppm to 15 ppm, and more preferably 1 ppm to 10 ppm.

[0041] The chlorine content can be adjusted along with the acidity of the XDI composition. Increasing the chlorine content in the XDI composition can lead to yellowing of the lenses. The chloride ions contained in the composition can also act as a variable factor for the acidity.

[0042] Therefore, if the chlorine content in the composition increases, the acidity of the composition, which has been adjusted to a predetermined range as described above, changes, and it may not be possible to easily achieve the desired target range of acidity. Furthermore, the acidity of the composition changes during long-term storage due to chlorine, and the desired, preferable physical properties of the lens may not be obtained.

[0043] In some embodiments, the chlorine content in the XDI composition may be less than 100 ppm. Preferably, the chlorine content in the XDI composition may be 95 ppm or less.

[0044] In one embodiment, the chlorine content in the XDI composition can be maintained at 10 ppm or more and less than 100 ppm. In this case, excessive increase in process load during the distillation and purification steps of the XDI composition can be prevented, and the chlorine content can be stably maintained within this range. In one embodiment, the chlorine content in the XDI composition can be maintained in the range of 10 ppm to 95 ppm, 10 ppm to 80 ppm, preferably 30 ppm to 80 ppm, or 40 ppm to 80 ppm.

[0045] According to an exemplary embodiment, an acidity adjuster may be added to the XDI composition to finely adjust the acidity within the above range. The acidity adjuster may be a compound having a boiling point of 110°C or higher.

[0046] By using an acidity regulator with a boiling point of 110°C or higher, it is possible to suppress changes in the acidity regulator content during the distillation process in the production process of the XDI composition. This makes it possible to stably maintain the acidity and chlorine content within the above ranges. Furthermore, by using an acidity regulator with a high boiling point, it is possible to suppress side reactions caused by the acidity regulator, improve the long-term storage stability of the XDI composition, and maintain the desired acidity range for a long period of time.

[0047] In one embodiment, the acidity regulator can be a compound having a boiling point of 110° C. to 500° C., 110° C. to 400° C., or 110° C. to 300° C. For example, the boiling point of the acidity regulator may be 110° C. to 250° C., or 110° C. to 200° C.

[0048] In some embodiments, the transmittance of the XDI composition to light with a wavelength of 380 nm after storage in a dark room at 25° C. for 3 months may be 99% or greater.

[0049] The acidity regulator may include an inorganic acid compound, an organic acid compound, or a solid acid.

[0050] Examples of the inorganic acid compound include halogen acids such as hydrochloric acid, bromic acid, and iodic acid, sulfuric acid, phosphoric acid, and phosphoric acid derivatives.

[0051] In one embodiment, the phosphoric acid derivative may include a phosphoric acid ester compound such as a phosphate compound, a phosphonate compound, etc. For example, the phosphoric acid derivative may include a compound of Formula 1:

[0052] JPEG2026012947000001.jpg2177

[0053] In formula 1, n is 1 or 2.

[0054] Examples of the organic acid compound include acetic acid, benzoic acid, formic acid, trifluoroacetic acid (TFA), fatty acids, and aromatic carboxylic acid halides (e.g., benzoyl halide, phenylacetyl halide, phthaloyl halide, terephthaloyl halide, and isophthaloyl halide).

[0055] Examples of the solid acid include acid clay, silica alumina, cation exchange resin, acid-attached silica gel or alumina, aluminum oxide, vanadium oxide, and other solid acids.

[0056] In some embodiments, the acidity adjuster can include a basic compound that is substantially unreactive with XDI. For example, the acidity adjuster can include a cyclic amine such as imidazole, tetrazole, or pyridine, or a tertiary amine such as N,N-dimethylaniline (PhNMe).

[0057] In some embodiments, the amount or content of the acidity adjuster can be adjusted taking into consideration the aforementioned acidity range and chlorine content, and may be, for example, 300 ppm to 4,000 ppm.

[0058] In one embodiment, the amount or content of the acidity regulator may be 300 ppm to 2,000 ppm, preferably 300 ppm to 1,000 ppm, more preferably 300 ppm to 700 ppm, or 300 ppm to 500 ppm.

[0059] In one embodiment, the amount or content of the acidity adjuster may be 500 ppm to 2,000 ppm, preferably 500 ppm to 1,000 ppm, or 700 ppm to 2,000 ppm, preferably 700 ppm to 1,000 ppm.

[0060] Preferably, it may be 400 ppm to 3,500 ppm, or 500 ppm to 3,000 ppm.

[0061] In one embodiment, the XDI content in the XDI composition may be 90% by weight or more, 95% by weight or more, or 99% by weight or more, for example, 99% by weight or more to less than 100% by weight. In one embodiment, the acidity regulator can be added in a range that provides an acidity within the above range.

[0062] According to an exemplary embodiment, there is provided a method for producing an XDI composition, comprising the following steps, processes or acts:

[0063] The method for producing an XDI composition according to an exemplary embodiment may include at least one of the steps, processes, or actions indicated as S10 and S20 below. It should be understood that the terms "S10" and "S20" below are used to distinguish between processes for the convenience of explanation and do not limit the order of the processes. For example, some or all of the following steps S10 and S20 may be performed sequentially, or may be performed with modifications depending on the process conditions.

[0064] S10) A preliminary composition containing XDI is obtained by the XDI synthesis step. S20) Check the acidity of the preliminary composition, and if it has an acidity of 100 ppm or less or more than 1,000 ppm, adjust the acidity to obtain an XDI composition having an acidity of more than 100 ppm and 1,000 ppm or less.

[0065] For example, in step S10), xylylene diisocyanate (XDI) can be synthesized from xylylene diamine.

[0066] In some embodiments, XDI can be synthesized from xylylenediamine by the phosgene method. For example, xylylenediamine can be reacted with concentrated hydrochloric acid in a solvent to produce an amine salt. The amine salt can then be reacted with phosgene (COCl) to synthesize XDI (see Reaction Scheme 1 below).

[0067] [Reaction Scheme 1] JPEG2026012947000002.jpg60123

[0068] In some embodiments, XDI can be synthesized from xylylenediamine using a non-phosgene method. For example, xylylenediamine can be reacted with concentrated hydrochloric acid to produce an amine salt. The amine salt can be reacted with a halodialkyl carbonate to produce a biscarbamate. The biscarbamate can be synthesized by, for example, thermal decomposition or degassing in the presence of a catalyst (see Reaction Scheme 2 below).

[0069] [Reaction Scheme 2] JPEG2026012947000003.jpg97132

[0070] As shown in Reaction Scheme 2, for example, bis(trichloromethyl)carbonate (BTMC) can be used as the halodialkyl carbonate.

[0071] For example, a first solution can be prepared by dissolving the amine salt in an inert solvent, and a second solution can be prepared by dissolving the halodialkyl carbonate in an inert solvent. The synthesis reaction of the biscarbamate can be carried out in a reactor while the second solution is added dropwise to the first solution. The temperature in the reactor can be maintained, for example, in the range of 120°C to 150°C.

[0072] Thereafter, the reaction solution may be degassed by supplying an inert gas while maintaining the temperature within the above range, and then the reaction solution may be cooled, filtered, and dried to obtain the XDI composition.

[0073] In some embodiments, further distillation steps can be performed to remove the inert solvent and recover the XDI, for example, a first distillation to remove the inert solvent and a second distillation to recover the XDI can be performed sequentially.

[0074] The temperature of the first distillation can be appropriately adjusted depending on the boiling point of the inert solvent, and the temperature of the second distillation may be a temperature equal to or higher than the boiling point of XDI.

[0075] In some embodiments, the temperature of the first distillation may be 100° C. or lower, for example, 50° C. to 90° C., preferably 50° C. to 80° C. The temperature of the second distillation may be 115° C. or higher, for example, 120° C. to 150° C., preferably 120° C. to 140° C.

[0076] The first distillation and the second distillation can be carried out under a pressure condition of 1 torr or less, preferably 0.5 torr or less.

[0077] The inert solvent can include an organic solvent that is substantially unreactive with the amine salt, XDI, and the halodialkyl carbonate. Alternatively, the distillation step can be carried out using an organic solvent having a boiling point lower than that of XDI.

[0078] In one embodiment, the inert solvent may include chlorinated aromatic hydrocarbons, such as monochlorobenzene, dichlorobenzene, trichlorobenzene, chloroethylbenzene, and the like.

[0079] According to an exemplary embodiment, in step S20, the acidity of the XDI-containing preliminary composition prepared as described above can be measured and adjusted. For example, if the preliminary composition has an acidity of 100 ppm or less or more than 1,000 ppm, the acidity can be adjusted to be more than 100 ppm and 1,000 ppm or less.

[0080] If the acidity of the pre-composition is 100 ppm or less, an acidic acidity adjuster can be added. The acidic acidity adjuster can include the inorganic acid compounds, organic acid compounds, or solid acids described above.

[0081] Preferably, a liquid organic acid compound can be used in consideration of fine adjustment of the acidity.

[0082] If the acidity of the preliminary composition exceeds 1,000 ppm, the aforementioned basic compound can be added.

[0083] In some embodiments, if the acidity of the preparatory composition is greater than 100 ppm and less than or equal to 1,000 ppm, the preparatory composition can be used as an XDI composition without the addition of an acidity adjuster.

[0084] According to one aspect of the present application, there is provided an optical polymerizable composition comprising the XDI composition prepared as described above.

[0085] The optical polymerizable composition may include a polythiol compound and the XDI composition.

[0086] The polythiol compound can include a trifunctional polythiol compound and / or a tetrafunctional polythiol compound.

[0087] Non-limiting examples of the trifunctional polythiol compound include compounds represented by the following Chemical Formula 1.

[0088] [Chemical formula 1] JPEG2026012947000004.jpg1546

[0089] The trifunctional polythiol compound can be synthesized from a polyol compound obtained by reacting, for example, 2-mercaptoethanol with epihalohydrin.

[0090] The polyol compound can be reacted with thiourea under acidic conditions to produce a thiuronium salt, which is then hydrolyzed under basic conditions to produce a trifunctional polythiol compound.

[0091] Non-limiting examples of the tetrafunctional polythiol compound include compounds represented by the following chemical formulas 2-1 to 2-3.

[0092] [Chemical formula 2-1] JPEG2026012947000005.jpg1566

[0093] [Chemical formula 2-2] JPEG2026012947000006.jpg2862

[0094] [Chemical formula 2-3] JPEG2026012947000007.jpg2560

[0095] The tetrafunctional polythiol compound can be synthesized from a polyol compound obtained by reacting 2-mercaptoethanol with epihalohydrin, for example. The polyol compound can be reacted with a metal sulfide to produce a tetrafunctional polyol intermediate. The tetrafunctional polyol intermediate can be reacted with thiourea under acidic conditions to produce a thiuronium salt, which can then be hydrolyzed under basic conditions to produce the tetrafunctional polythiol compound.

[0096] The optical polymerizable composition may further include additives such as a mold release agent, a reaction catalyst, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

[0097] Examples of the release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; silicon-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group, or a phosphate ester group; alkyl-based quaternary ammonium salts such as trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, and diethylcyclohexadodecylammonium salt; acidic phosphate esters, etc. These can be used alone or in combination of two or more.

[0098] The reaction catalyst may be a catalyst used in the polymerization reaction of the polythiourethane resin. For example, dialkyltin halide catalysts such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylate catalysts such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate; dialkyltin dialkoxide catalysts such as dibutyltin dibutoxide and dioctyltin dibutoxide; dialkyltin dithioalkoxide catalysts such as dibutyltin di(thiobutoxide); dialkyltin oxide catalysts such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin)oxide; and dialkyltin sulfide catalysts may be used. These may be used alone or in combination of two or more.

[0099] Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, and oxanilide-based compounds. Examples of the heat stabilizer include metal fatty acid salt-based, phosphorus-based, lead-based, and organotin-based compounds. These may be used alone or in combination of two or more.

[0100] The bluing agent may be included as a color adjuster in an optical material made from the polythiourethane resin. For example, the bluing agent may have an absorption band in the orange to yellow wavelength range in the visible light region.

[0101] Examples of the bluing agent include dyes, fluorescent brightening agents, fluorescent pigments, inorganic pigments, etc., and can be appropriately selected depending on the physical properties and resin color required for the optical product to be manufactured. When a dye is used as the bluing agent, for example, a dye having a maximum absorption wavelength of 520 nm to 600 nm, preferably 540 nm to 580 nm, can be used. Preferably, an anthraquinone dye can be used.

[0102] In some embodiments, the optical polymerizable composition may contain 40 wt % to 60 wt % of a polythiol compound, 40 wt % to 60 wt % of an isocyanate compound, and 0.01 wt % to 1 wt % of the additives, relative to the total weight of the optical polymerizable composition.

[0103] A polythiourethane resin can be produced by a polymerization reaction between the polythiol compound contained in the optical polymerizable composition and XDI.

[0104] As described above, the acidity of the XDI composition used in the optical polymerizable composition can be adjusted to more than 100 ppm and not more than 1,000 ppm, thereby appropriately controlling the reactivity or reaction rate with the polythiol compound, thereby suppressing the cloudiness caused by the XDI composition itself and also preventing the cloudiness in the optical lens manufactured from the optical polymerizable composition.

[0105] In some embodiments, the reaction rate of the optical polymerizable composition included in the formula 1 below can be maintained in the range of 0.17 to 0.30. In a preferred embodiment, the reaction rate can be maintained in the range of 0.17 to 0.25, more preferably 0.19 to 0.21.

[0106] Furthermore, the stable polymerization reaction allows the production of optical lenses with a uniform refractive index and no striae.

[0107] According to one aspect of the present application, an optical product can be provided that is manufactured from the optical polymerizable composition described above.

[0108] For example, the optical polymerizable composition can be degassed under reduced pressure and then poured into a mold for forming an optical material. The pouring into the mold can be carried out at a temperature ranging from 10°C to 40°C, preferably from 10°C to 30°C.

[0109] After injection into the mold, the temperature can be gradually increased to carry out the polymerization reaction of the polythiourethane resin. The polymerization temperature may be 20°C to 150°C, and preferably 25°C to 125°C. For example, the maximum polymerization temperature may be 100°C to 150°C, preferably 110°C to 140°C, and more preferably 115°C to 130°C.

[0110] The polymerization time may be 1 hour to 10 hours, preferably 1 hour to 5 hours.

[0111] For example, within the above temperature range, the reaction rate can be appropriately controlled, and lenses having uniform optical and mechanical properties can be easily obtained.

[0112] After the polymerization is completed, the polymerized polythiourethane resin is separated from the mold to obtain an optical product, which can be manufactured in the form of an eyeglass lens, a camera lens, a light-emitting diode, or the like, depending on the shape of the mold.

[0113] In one embodiment, after separation from the mold, a curing step can be further carried out at a temperature in the range of 100°C to 150°C, preferably 110°C to 140°C, and more preferably 115°C to 130°C, for example, for 1 hour to 10 hours, and preferably 1 hour to 3 hours.

[0114] The refractive index of the optical product can be adjusted by changing the type and / or content ratio of the polythiol compound and the isocyanate compound used in the optical polymerizable composition. For example, the refractive index of the optical product can be adjusted within the range of 1.56 to 1.78, 1.58 to 1.76, 1.60 to 1.78, or 1.60 to 1.76, preferably within the range of 1.65 to 1.75 or 1.69 to 1.75.

[0115] The color index (YI) of the optical product according to Equation 2 below may be less than 30, preferably 28 or less, more preferably 22 or less or 21 or less.

[0116] The optical products can also be improved by adding surface treatments such as anti-fouling, coloring, hard coating, surface polishing, and hardening.

[0117] Below, preferred examples are presented to help understand the present invention, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It is obvious to those skilled in the art that various changes and modifications can be made to these examples within the scope and technical spirit of the present invention, and it goes without saying that these changes and modifications also fall within the scope of the appended claims.

[0118] Manufacturing example (1) Production of xylylenediamine (XDA) hydrochloride 1,009.4 g (9.46 mol) of 35% hydrochloric acid solution was added to the reactor, and while stirring, the temperature inside the reactor was cooled to a temperature in the range of 15 to 20°C. Then, while maintaining the temperature of the reactor in the range of 20 to 60°C, 600.0 g (4.4 mol) of m-XDA (meta-xylylenediamine) was gradually added.

[0119] After the addition of m-XDA was completed, the temperature inside the reactor was cooled to a range of 10°C to 20°C and stirred for 1 hour, after which 1,320.0 g of tetrahydrofuran was added. The temperature inside the reactor was cooled again to a range of -5°C to 0°C and stirred for another 1 hour to allow the reaction to proceed.

[0120] After the reaction was completed, the reaction mixture was subjected to vacuum filtration, and the remaining solvent and water were removed by drying under the conditions of an external temperature of the reactor of 90°C to 100°C and a vacuum pump of 0.1 torr, to obtain m-XDA hydrochloride.

[0121] (2) Preparation of xylylene diisocyanate composition 800 g of the m-XDA hydrochloride prepared in (1) above and 3,550 g of ortho-dichlorobenzene (ODCB) were placed in a reactor, and the temperature inside the reactor was heated to about 125° C. with stirring.

[0122] 950 g of bis(trichloromethyl)carbonate (BTMC) and 800 g of ODCB were dissolved with stirring at approximately 60°C, and then the temperature of the reactor was adjusted to 125°C to prevent precipitation, and the mixture was added dropwise over 24 hours. After the dropwise addition was completed, pre-mixing was carried out for 4 hours.

[0123] After the reaction was completed, a degassing step was carried out by supplying N2 gas to the reaction solution and bubbling it at a temperature of 125° C. After the degassing, the reaction solution was cooled to 10° C., and the remaining solid content was filtered using Celite 545.

[0124] The filtered organic solvent and the synthesized crude XDI were purified by distillation under the following conditions. 1) Removal of organic solvent (ODCB) (first distillation) -Vacuum 0.5torr or less -Temperature at bottom of distillation column: 60℃ -Distillation time: 8 hours 2) XDI distillation (second distillation) -Vacuum 0.5torr or less -Temperature at bottom of distillation column: 120℃ -Distillation time: 10 hours

[0125] XDI compositions according to the examples and comparative examples were prepared by adding an acidity adjuster to the XDI prepared as described above so that the acidity was measured as shown in Table 1. Specifically, the acidity of the prepared preliminary composition containing XDI was first measured, and the acidity adjuster was added while measuring the acidity so that the target acidity shown in Table 1 was obtained, thereby preparing the XDI composition.

[0126] In Comparative Examples 2, 3, and 8, the acidity and chlorine content were changed by changing the second distillation temperature. In Comparative Examples 2 and 8, the second distillation temperature was changed to 180°C and 170°C, respectively, and in Comparative Example 3, the second distillation temperature was adjusted to 120°C.

[0127] How to measure acidity A 20 g sample of the prepared XDI composition was weighed and placed in a 200 ml beaker, and 100 ml of solvent (a mixture of acetone and ethanol in a 1:1 weight ratio) was added. The mixture was then heated on a hot plate to dissolve the sample, and then mixed at room temperature for 10 to 20 minutes.

[0128] Then, using an automatic titrator (COM-500, manufactured by Hiranuma Co., Ltd.), the acidity was calculated according to JIS K4101 using a solution prepared by diluting 0.1 mol / L methanolic potassium hydroxide adjusted and standardized with methanol by 10 times (N / 100 methanolic potassium hydroxide solution), with the rising point of the titration curve as the endpoint, using the following formula:

[0129] Acidity=0.0365×(AB)×f / S A: Amount (ml) of N / 100 methanolic potassium hydroxide solution required for titration of the sample B: Amount (ml) of N / 100 methanolic potassium hydroxide solution required for blank test f: Factor of N / 100 methanolic potassium hydroxide solution S: weight of sample (g)

[0130] 2) Preparation of optical polymerizable compositions and production of lenses 49.3 parts by weight of 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol as a polythiol compound, 50.7 parts by weight of the xylylene diisocyanate synthesized in the above Production Example, 0.01 parts by weight of dibutyltin chloride, and 0.1 parts by weight of a phosphate ester release agent manufactured by ZELEC (registered trademark) UN Stepan GmbH were uniformly mixed, and then a degassing process was carried out at 600 Pa for 1 hour to prepare an optical polymerizable composition.

[0131] The resin composition was filtered through a 3 μm Teflon filter and poured into a mold containing a glass mold and tape. The mold was maintained at 10 to 25°C for 8 hours, then slowly heated to 130°C at a constant rate for 8 hours, and polymerization was carried out at 130°C for 2 hours. After polymerization was complete, the mold was separated and the composition was further cured at 120°C for 2 hours to produce a lens sample.

[0132] Experimental example (1) Measurement of chlorine content The chlorine content in the XDI compositions of the examples and comparative examples was measured using a sample combustion device (Analytech / AQF-2100H, manufactured by Mitsubishi Chemical Corporation) and ion chromatography (881 Compact IC Pro, manufactured by Metrohm).

[0133] (2) Measurement of acidity change The XDI compositions of the Examples and Comparative Examples were stored in a dark room at 25° C. for 3 months, and then the acidity was measured by the above-mentioned method. The acidity values ​​measured before and after storage in the dark room were used to calculate the change in acidity.

[0134] (3) Evaluation of cloudiness of XDI composition The XDI compositions of the examples and comparative examples were stored in a dark room at 25°C for 3 months, and then the samples were placed in 10 mm quartz cells and the transmittance was measured at a wavelength of 380 nm and 25°C (transmittance measuring device: Lambda 365, manufactured by PerkinElmer).

[0135] (4) Evaluation of Polymerization Composition / Lens Properties 1) Evaluation of striae As described above, lens samples with a diameter of 75 mm and a diopter of -8.00D were manufactured using the polymerizable compositions of the Examples and Comparative Examples. A mercury lamp was passed through the manufactured lens samples, and the transmitted light was projected onto a white board to determine the presence or absence of striae based on the presence or absence of contrast. The evaluation criteria were as follows: ○: No striae observed △: Fine striae are partially observed ×: Striae are clearly observed with the naked eye

[0136] 2) Evaluation of lens opacity The lens samples of the examples and comparative examples manufactured as described above were irradiated with light from a projector in a dark room, and the presence or absence of haze and opaque substances in the lenses was visually confirmed. The evaluation criteria were as follows: ○: No haze occurs △: Partial haze observed ×: Haze is clearly observed throughout

[0137] 3) Measurement of polymerization reaction rate (Reactivity Slope) Using a non-contact viscometer EMS-1000 (manufactured by KEM), the standard viscosity (standard cps) was first determined using a viscosity standard solution (Brookfield, 1000 cps, 25°C). Then, the viscosity of the polymerizable compositions according to the Examples and Comparative Examples was measured at 10°C for 24 hours. Using the measured values, the X axis was plotted as time and the Y axis as viscosity, and the Y axis was converted into a logarithmic value, as shown in Equation 1 below, to calculate the reaction rate.

[0138] [Mathematical formula 1] Y = a × exp(b × X)

[0139] In Equation 1, the value of a represents the initial viscosity (cps), and the value of b represents the reaction rate, and the measured values ​​were rounded to three decimal places.

[0140] 4) Yellow Index (YI) measurement The YI of the lens samples of the examples and comparative examples was measured using a UV / VIS spectroscope (manufactured by PerkinElmer, model UV / VIS Lambda 365). Specifically, light was transmitted in the height direction of the plastic circumference (r (radius) × H (height) = 16 mm × 45 mm), and the chromaticity coordinates x and y were measured. Based on the measured values ​​of x and y, the YI was calculated using the following formula 2.

[0141] YI=(234×x+106×y+106) / y ...Formula 2

[0142] The measurement results and evaluation results are summarized in Tables 1 and 2 below.

[0143] [Table 1]

[0144] Specific compounds of the acidity regulators shown in Table 1 are as follows: A: Sulfuryl chloride B: Trimethylsilyl chloride C: Benzoyl chloride D: Phenylacetyl chloride E:benzoic acid F: Formic acid G:phosphoric acid H: acetic acid I: Ethyl acid phosphate

[0145] [Table 2]

[0146] Referring to Tables 1 and 2, in the examples where the acidity was in the range of more than 100 ppm and not more than 1,000 ppm, clouding of the composition and lens was prevented, an appropriate polymerization reaction rate was achieved, and striae in the lens were suppressed. Furthermore, by adding a compound with a boiling point of 110°C or higher as an acidity regulator, changes in acidity during long-term storage were suppressed and the transmittance of the composition was also improved.

[0147] With reference to Examples 1 to 8, the chlorine content in the composition was controlled to less than 100 ppm, which reduced yellowing of the lens and more effectively inhibited striae due to an increased reaction rate.

Claims

[Claim 1] Contains xylylene diisocyanate (XDI) and an acidity regulator having a boiling point of 110°C or higher, A xylylene diisocyanate composition having an acidity of greater than 100 ppm and less than or equal to 1,000 ppm, based on the total weight of the xylylene diisocyanate (XDI).

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