Benzidene dimethylene diisocyanate composition and optical polymerizable composition comprising the same

Abstract

A xylylene diisocyanate (XDI) composition according to an exemplary embodiment includes a xylylene diisocyanate and an acidity adjuster having a boiling point of 110°C or more, and the acidity of the composition is 100 ppm (inclusive) to 1,000 ppm (inclusive) based on the total weight of the xylylene diisocyanate (XDI). By controlling the polymerization rate by means of the acidity adjustment, an optical lens having high transmittance and improved optical uniformity can be manufactured.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority from Korean Patent Application No. 10-2020-0112405 filed on September 3, 2020, in the Korean Intellectual Property Office (KIPO), the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to a xylylene diisocyanate composition and an optical polymerizable composition ("polymerizable composition for optical materials") containing the same. More specifically, the present invention relates to a xylylene diisocyanate composition prepared by reacting an amine salt and a polymerizable composition for optical materials containing the same. Background Art

[0004] Diisocyanate compounds are widely used as raw materials, for example, for the production of polyurethane resins. For example, diisocyanate compounds are used to produce optical lenses using polyurethane resins. The physical properties of the diisocyanate compounds used as raw materials directly affect the optical properties of the optical lenses, such as transparency and refractive index.

[0005] For example, a polythiourethane resin prepared by reacting a polythiol compound and a diisocyanate compound may be used as a base material for an optical lens.

[0006] Among the diisocyanate compounds, xylylene diisocyanate (XDI) is widely used in consideration of chemical and optical properties such as reactivity and transparency.

[0007] For example, a polymerizable composition for an optical lens can be prepared by preparing a composition containing XDI and mixing it with a composition containing a polythiol compound. Considering the stability of XDI and its appropriate reactivity with the polythiol compound, it is necessary to design the physical properties and synthesis method of the XDI composition.

[0008] For example, Korean Patent Laid-Open Publication No. 2012-0076329 discloses a urethane-based optical material prepared using an isocyanate compound. However, the physical properties of the isocyanate composition itself are not considered. Summary of the Invention

[0009] An object according to an exemplary embodiment is to provide a xylylene diisocyanate composition having improved reaction stability and optical properties, and a preparation method thereof.

[0010] In addition, another object according to an exemplary embodiment is to provide a polymerizable composition for an optical material, which includes a xylylene diisocyanate composition having improved reaction stability and optical properties.

[0011] Furthermore, another object according to an exemplary embodiment is to provide an optical product prepared from the polymerizable composition for an optical material.

[0012] The xylylene diisocyanate composition according to the exemplary embodiment includes: xylylene diisocyanate (XDI); and an acidity regulator having a boiling point of 110° C. or higher, wherein the acidity of the xylylene diisocyanate composition is greater than 100 ppm and 1,000 ppm or less based on the total weight of the xylylene diisocyanate (XDI).

[0013] In some embodiments, the chlorine content of the composition may be less than 100 ppm.

[0014] In some embodiments, the chlorine content of the composition may be from 10 ppm to 95 ppm.

[0015] 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.

[0016] In some embodiments, the xylylene diisocyanate composition may have a transmittance of 99% or more to light with a wavelength of 380 nm after being stored in a dark room at 25° C. for 3 months.

[0017] In some embodiments, the acidity regulator may include at least one inorganic acid compound selected from the group consisting of hydrohalic acid, sulfuric acid, phosphoric acid, and phosphate-based compounds.

[0018] In some embodiments, the acidity regulator may include at least one organic acid compound selected from the group consisting of acetic acid, benzoic acid, trifluoroacetic acid (TFA), fatty acids, and aromatic carboxylic acid halides.

[0019] In some embodiments, the acidity regulator may include at least one solid acid selected from the group consisting of clay, silica-alumina, cation exchange resin, acid-impregnated silica gel, acid-impregnated alumina, aluminum oxide, and vanadium oxide.

[0020] In some embodiments, the acidity regulator may include a cyclic amine compound or a tertiary amine compound.

[0021] In some embodiments, the acidity regulator may be added in an amount ranging from 300 ppm to 4,000 ppm.

[0022] The polymerizable composition for an optical material according to the exemplary embodiment includes: a xylylene diisocyanate composition containing xylylene diisocyanate (XDI) and an acidity regulator having a boiling point of 110° C. or higher and having an acidity of greater than 100 ppm and less than 1,000 ppm based on the total weight of xylylene diisocyanate (XDI); and an additive.

[0023] In some embodiments, the chlorine content of the xylylene diisocyanate composition may be less than 100 ppm.

[0024] In some embodiments, the additive may include at least one selected from the group consisting of a release agent, a reaction catalyst, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

[0025] The method for preparing a xylylene diisocyanate composition according to an exemplary embodiment includes synthesizing xylylene diisocyanate from xylylenediamine to form a preliminary composition including xylylene diisocyanate; and adjusting the acidity of the preliminary composition to a range of greater than 100 ppm to 1000 ppm.

[0026] In some embodiments, in the step of adjusting the acidity of the preliminary composition, an acidic acidity regulator may be added if the acidity of the preliminary composition is 100 ppm or less, and an alkaline acidity regulator may be added if the acidity of the preliminary composition exceeds 1,000 ppm.

[0027] According to the above embodiment, the xylylene diisocyanate composition has an acidity of more than 100 ppm and 1,000 ppm or less, and can provide improved stability and a polymerization reaction rate with a polythiol-based compound within an appropriate range.

[0028] Therefore, an optical lens having high transmittance and improved optical uniformity in which white turbidity and unevenness ("stria") phenomena are substantially eliminated can be manufactured. DETAILED DESCRIPTION

[0029] Hereinafter, embodiments of the present application will be described in detail. In this regard, the present invention can be modified in various ways and has various embodiments, so that specific embodiments will be shown in the drawings and described in detail in this disclosure. However, the present invention is not limited to specific embodiments, and it will be understood by those skilled in the art that the present invention will cover all modifications, equivalents and alternatives that fall within the spirit and scope of the present invention.

[0030] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning consistent with their meaning in the context of the relevant art and, unless expressly defined herein, will not be interpreted in an idealized or overly formal sense.

[0031] According to one aspect of the present application, a composition including xylylene diisocyanate (hereinafter, abbreviated as XDI composition) is provided.

[0032] According to an exemplary embodiment, the XDI composition includes XDI, and the acidity thereof may be greater than 100 ppm and 1,000 ppm or less based on the total weight of XDI.

[0033] The term "acidity" used herein may be a value expressed as a ratio of the total weight of XDI calculated as the amount of free acid components by reacting with alcohol at room temperature, for example, HCl.

[0034] The XDI contained in the XDI composition can react with a polythiol-based 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 the XDI and its reactivity with the polythiol-based compound.

[0035] For example, excessively high acidity in the XDI composition can significantly reduce its polymerization reactivity with polythiol compounds. Consequently, this can reduce the yield of the polythiourethane resin used to manufacture optical lenses. Furthermore, this can lead to a white turbidity during the casting process used to mold lenses.

[0036] When the acidity of the XDI composition is excessively reduced, its polymerization reactivity with polythiol-based compounds may be excessively increased. Consequently, other byproducts, such as oligomers or polymers, may be produced in place of the desired polythiourethane resin, which in turn may cause lens streaks. Furthermore, the self-reactivity of XDI increases, which can lead to white turbidity during long-term storage. Consequently, as described below, the transmittance of the composition storage solution decreases when stored in a dark room at room temperature (25°C) for three months. Furthermore, during long-term storage, the desired target acidity may shift due to self-propagating reactions, thereby making it difficult to implement acidity control.

[0037] Taking the above into account, according to exemplary embodiments, the acidity of the XDI composition can be adjusted to greater than 100 ppm and less than 1,000 ppm. This maintains adequate reactivity with the polythiol compound, suppressing white turbidity during lens casting and preventing lens streaks. Furthermore, by ensuring the storage characteristics of the XDI composition, it is possible to suppress a decrease in the permeability of the XDI composition and changes in its acidity.

[0038] In one embodiment, the acidity of the XDI composition may be from 110 ppm to 800 ppm, and preferably from 110 ppm to 700 ppm.

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

[0040] In addition to adjusting the acidity of the XDI composition, the chlorine content can also be adjusted. When the chlorine content in the XDI composition increases, it may cause yellowing of the lens. In addition, the chloride ions contained in the composition can act as a variable acidity factor.

[0041] Therefore, when the chlorine content in the composition increases, as described above, the acidity of the composition adjusted to a predetermined range changes, and thus it may not be easy to achieve the desired target acidity range. In addition, when the composition is stored for a long time, the acidity may change due to chlorine, and the desired lens properties may not be achieved.

[0042] 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 less than 95 ppm.

[0043] In one embodiment, the chlorine content in the XDI composition can be maintained at a range of 10 ppm or more and less than 100 ppm. In this case, an excessive increase in process load during the distillation and purification of the XDI composition can be prevented, and the chlorine content can be stably maintained within a corresponding range. In one embodiment, the chlorine content in the XDI composition can be maintained in a range of 10 ppm to 95 ppm, 10 ppm to 80 ppm, preferably 30 ppm to 80 ppm, or 40 ppm to 80 ppm.

[0044] According to an exemplary embodiment, an acidity regulator for finely adjusting the acidity within the above range may be added to the XDI composition, and a compound having a boiling point of 110° C. or higher may be used as the acidity regulator.

[0045] By using an acidity regulator with a boiling point of 110°C or higher, changes in the acidity regulator content during the distillation process during the production of the XDI composition can be suppressed. Consequently, the acidity and chlorine content can be stably maintained within the aforementioned ranges. Furthermore, using an acidity regulator with a high boiling point can suppress side reactions caused by the acidity regulator, improve the long-term storage of the XDI composition, and maintain the desired acidity range for an extended period of time.

[0046] In some embodiments, the transmittance of the XDI composition to light with a wavelength of 380 nm after being stored in a dark room at 25° C. for 3 months may be greater than 99%.

[0047] The acidity regulator may include an inorganic acid compound, an organic acid compound, or a solid acid.

[0048] Examples of the inorganic acid compound may include hydrohalic acid such as hydrochloric acid, hydrobromic acid and iodic acid, sulfuric acid, phosphoric acid and phosphoric acid derivatives.

[0049] In one embodiment, the phosphoric acid derivative may include a phosphoric acid ester compound, such as a phosphoric acid ester compound or a phosphonate compound. For example, the phosphoric acid derivative may include a compound of Formula 1 below.

[0050] [Formula 1]

[0051]

[0052] In Formula 1, n is 1 or 2.

[0053] Examples of the organic acid compound may 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, isophthaloyl halide), and the like.

[0054] Examples of solid acids include acidic clays, silica-alumina, cation exchange resins, acid-leached silica gel, or solid acids such as alumina, aluminum oxide, or vanadium oxide.

[0055] In some embodiments, the acidity regulator may include a basic compound that is substantially non-reactive with XDI. For example, the acidity regulator may include a cyclic amine such as imidazole, tetrazole, or pyridine, or a tertiary amine such as N,N-dimethylaniline (PhNMe2).

[0056] In some embodiments, the addition amount or content of the acidity regulator may be adjusted in consideration of the above-mentioned acidity range and chlorine content, for example, 300 ppm to 4,000 ppm, preferably 400 ppm to 3,500 ppm, or 500 ppm to 3,000 ppm.

[0057] In one embodiment, the XDI content in the XDI composition may be 90 weight percent ("wt.%) or more, 95 wt.% or more, or 99 wt.% or more, and for example, 99 wt.% or more and less than 100 wt.%. In one embodiment, an acidity regulator may be added within a range capable of achieving an acidity within the above range.

[0058] According to an exemplary embodiment, a method for preparing an XDI composition is provided, which includes the following steps, processes or operations.

[0059] The method for preparing an XDI composition according to an exemplary embodiment may include at least one of the steps, processes, or operations described in S10 and S20 below. It should be understood that, for ease of description, the terms "S10" and "S20" below are used to distinguish between processes and are not intended to limit their order. For example, some or all of the processes in S10 and S20 below may be performed sequentially and / or in a different order depending on the processing conditions.

[0060] S10) obtaining a preliminary composition containing XDI through an XDI synthesis process.

[0061] S20) checking the acidity of the preliminary composition, and if the acidity of the composition is 100 ppm or less or greater than 1,000 ppm, adjusting the acidity to obtain an XDI composition having an acidity greater than 100 ppm and 1,000 ppm or less.

[0062] For example, xylylene diisocyanate (XDI) can be synthesized from xylylenediamine in step (S10).

[0063] In some embodiments, XDI can be synthesized from xylenediamine by phosgene. For example, xylenediamine can be reacted with concentrated hydrochloric acid in a solvent to produce an amine salt. XDI can be synthesized by reacting an amine salt with phosgene (COCl2) (see Scheme 1 below).

[0064] [Scheme 1]

[0065]

[0066] In some embodiments, XDI can be synthesized from xylene diamine by a non-phosgene process. For example, xylene diamine can react with concentrated hydrochloric acid to form an amine salt. The amine salt can react with a halogenated dialkyl carbonate to produce a biscarbamate. XDI can be synthesized by thermally degrading or degassing the biscarbamate in the presence of a catalyst (see Scheme 2 below).

[0067] [Scheme 2]

[0068]

[0069] As shown in Scheme 2, bis(trichloromethyl)carbonate (BTMC) can be used as an example of a halogenated dialkyl carbonate.

[0070] For example, a first solution in which an amine salt is dissolved in an inert solvent can be prepared, and a second solution in which a halogenated dialkyl carbonate is dissolved in an inert solvent can be prepared. The biscarbamate synthesis reaction can be carried out while the second solution is added dropwise to the first solution in the reactor. The temperature in the reactor can be maintained in the range of, for example, about 120° C. to 150° C.

[0071] Thereafter, a degassing treatment may be performed by supplying an inert gas to the reaction solution while maintaining the temperature within the above range. The reaction solution may then be cooled, followed by filtration and drying to obtain an XDI composition.

[0072] In some embodiments, a distillation process may be further performed to remove the inert solvent and take out the XDI. For example, a first distillation for removing the inert solvent and a second distillation for taking out the XDI may be performed sequentially.

[0073] The first distillation temperature can be appropriately adjusted according to the boiling point of the inert solvent.The second distillation can be performed at a second distillation temperature, for example, at a temperature greater than or equal to the boiling point of XDI.

[0074] In some embodiments, the first distillation temperature may be below 100° C., for example, in the range of 50° C. to 90° C., preferably 50° C. to 80° C. Meanwhile, the second distillation temperature may be above 115° C., for example, in the range of 120° C. to 150° C., preferably 120° C. to 140° C.

[0075] The first distillation and the second distillation can be performed under a pressure condition of 1 torr or less, and preferably under a pressure condition of 0.5 torr or less.

[0076] The inert solvent may include an organic solvent that is substantially unreactive with the amine salt, XDI, and halogenated dialkyl carbonate. In addition, an organic solvent having a boiling point lower than that of XDI may be used to carry out the above-mentioned distillation process.

[0077] In one embodiment, the inert solvent may include chlorinated aromatic hydrocarbons, such as monochlorobenzene, dichlorobenzene, trichlorobenzene, and chloroethylbenzene, among others.

[0078] According to an exemplary embodiment, the acidity of the preliminary composition including XDI prepared as described above in step S20 is measured, and if the acidity thereof is 100 ppm or less or greater than 1,000 ppm, the preliminary composition may be adjusted to have an acidity greater than 100 ppm and 1,000 ppm or less.

[0079] When the acidity of the preliminary composition is less than 100 ppm, an acidic acidity regulator may be added. The acidic acidity regulator may include the above-mentioned inorganic acid compound, organic acid compound or solid acid.

[0080] Preferably, a liquid organic acid compound may be used in view of fine acidity control.

[0081] When the acidity of the preliminary composition exceeds 1,000 ppm, the above-mentioned basic compound may be added.

[0082] In some embodiments, when the acidity of the preliminary composition is greater than 100 ppm and less than 1,000 ppm, the preliminary composition can be used as an XDI composition without adding an acidity regulator.

[0083] According to one aspect of the present application, a polymerizable composition for an optical material is provided, comprising the XDI composition prepared as described above.

[0084] The polymerizable composition for an optical material may include a polythiol-based compound and an XDI composition.

[0085] The polythiol-based compound may include a trifunctional polythiol compound and / or a tetrafunctional polythiol compound.

[0086] Non-limiting examples of the trifunctional polythiol compound may include a compound represented by Formula 1 below.

[0087] [Formula 1]

[0088]

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

[0090] After the polyol compound reacts with thiourea under acidic conditions to form a thiourea salt, the trifunctional polythiol compound can be prepared by hydrolysis under alkaline conditions.

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

[0092] [Formula 2-1]

[0093]

[0094] [Formula 2-2]

[0095]

[0096] [Formula 2-3]

[0097]

[0098] Tetrafunctional polythiol compounds can be synthesized by, for example, the polyol compound obtained by reacting with 2-mercaptoethanol and epihalohydrin.Polyol compound can react with metal sulfide to generate tetrafunctional polyol intermediate.After tetrafunctional polyol intermediate and thiourea react under acidic conditions to produce thiourea salt, tetrafunctional polythiol compounds can be prepared by hydrolysis under alkaline conditions.

[0099] The polymerizable composition for an optical material may further include additives such as a release agent, a reaction catalyst, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

[0100] Examples of the release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate group; silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group, or a phosphate group; alkyl quaternary ammonium salts such as trimethylhexadecyl ammonium salt, trimethylstearylammonium salt, dimethylethylhexadecylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, and diethylcyclohexyldodecylammonium salt; and acidic phosphates, etc. These can be used alone or in combination of two or more.

[0101] As the reaction catalyst, a catalyst used in the polymerization reaction of polythiourethane resin can be used. For example, dialkyl tin halide catalysts such as dibutyltin dichloride and dimethyltin dichloride; dialkyl tin dicarboxylate catalysts such as dimethyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate; dialkoxydialkyltin catalysts such as dibutoxydibutyltin alkane and dibutoxydioctyltin alkane; dithioalkoxydialkyltin catalysts such as di(thiobutoxy)dibutyltin; dialkyl tin oxide catalysts such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin) oxide; and dialkyl tin sulfide catalysts can be used. These can be used alone or in combination of two or more.

[0102] Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, and N,N'-oxanilide-based compounds. Examples of heat stabilizers include metal fatty acid-based, phosphorus-based, lead-based, and organotin-based compounds. These can be used alone or in combination of two or more.

[0103] A bluing agent may be included as a color control agent for an optical material prepared from a polythiourethane resin. For example, the bluing agent may have an absorption band having a wavelength band from orange to yellow in the visible light region.

[0104] Examples of bluing agents include dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments, and can be appropriately selected based on the physical properties or resin color required for manufacturing the optical product. 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, anthraquinone dyes can be used.

[0105] In some embodiments, based on the total weight of the polymerizable composition for an optical material, the polythiol-based compound may be included in an amount of about 40 wt.% to 60 wt.%, the isocyanate-based compound may be included in an amount of about 40 wt.% to 60 wt.%, and the additive may be included in an amount of about 0.01 wt.% to 1 wt.%.

[0106] The polythiourethane resin can be produced by a polymerization reaction of a polythiol-based compound contained in a polymerizable composition for an optical material and XDI.

[0107] As described above, by adjusting the acidity of the XDI composition used in the polymerizable composition for an optical material to greater than 100 ppm and less than 1,000 ppm, the reactivity with the polythiol compound and its reaction rate can be appropriately controlled. This suppresses white turbidity caused by the XDI composition itself and prevents white turbidity in optical lenses manufactured using the polymerizable composition for an optical material.

[0108] In some embodiments, the reaction rate of the polymerizable composition for an optical material involved in Formula 1 below can be maintained in the range of 0.17 to 0.30 by a reaction modifier. The reaction rate can be maintained in the range of 0.17 to 0.25, preferably 0.19 to 0.21.

[0109] Furthermore, through a stable polymerization reaction, an optical lens with a uniform refractive index and no fringing phenomenon can be produced.

[0110] According to one aspect of the present application, there is provided an optical product produced using the polymerizable composition for an optical material.

[0111] For example, after degassing the polymerizable composition for optical materials under reduced pressure, the resulting composition can be injected into a mold for forming an optical material. Mold injection can be performed at a temperature range of, for example, 10°C to 40°C, preferably 10°C to 30°C.

[0112] After mold injection, the temperature can be gradually increased to carry out polymerization of the polythiourethane resin. The polymerization temperature can be in the range of 20°C to 150°C, preferably 25°C to 125°C. For example, the maximum polymerization temperature can be in the range of 100°C to 150°C, preferably 110°C to 140°C, and more preferably 115°C to 130°C.

[0113] The polymerization time may be 1 to 10 hours, and preferably 1 to 5 hours.

[0114] For example, by appropriately controlling the reaction rate within the above-mentioned temperature range, a lens having uniform optical and mechanical properties can be easily obtained.

[0115] After the polymerization is completed, the polymerized polythiourethane resin can be separated from the mold to obtain an optical product. The optical product can be manufactured in the form of eyeglass lenses, camera lenses, light-emitting diodes, etc. according to the shape of the mold.

[0116] In one embodiment, after separation from the mold, a curing process may be further performed. The curing treatment may be performed at a temperature ranging from 100° C. to 150° C., preferably from 110° C. to 140° C., more preferably from 115° C. to 130° C., for about 1 to 10 hours, preferably from 1 to 3 hours.

[0117] The refractive index of the optical product can be adjusted by the type and / or content ratio of the polythiol compound and the isocyanate compound used in the polymerizable composition for an optical material. 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, and preferably within the range of 1.65 to 1.75, or 1.69 to 1.75.

[0118] The color index (yellowness index (YI)) of the optical product according to Formula 2 to be described below may be less than 30, preferably 28 or less, more preferably 22 or less, or 21 or less.

[0119] Optical products can be improved by further surface treatments such as antifouling, coloring, hard coating, surface polishing, and hardness enhancement.

[0120] Hereinafter, the embodiments provided in this application will be further described with reference to specific experimental examples. However, the following experimental examples are merely illustrative of the present invention and are not intended to limit the appended claims, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. Such changes and modifications are appropriately included in the appended claims.

[0121] Preparation Example

[0122] (1) Preparation of xylenediamine (XDA) hydrochloride

[0123] 1009.4 g (9.46 mol) of a 35% hydrochloric acid solution was introduced into the reactor, and the reactor was cooled while stirring to lower the internal temperature to 15 to 20° C. Then, while maintaining the reactor temperature in the range of 20 to 60° C., 600.0 g (4.4 mol) of m-xylenediamine (m-XDA) was slowly added.

[0124] After the completion of the m-XDA input, the reactor was cooled to reduce the internal temperature to a range of 10 to 20°C, and after stirring for 1 hour, 1,320.0 g of tetrahydrofuran was added. The reactor was then cooled again to reduce the internal temperature to a range of -5 to 0°C, and the reaction was allowed to proceed with further stirring for 1 hour.

[0125] After the reaction was completed, vacuum filtration was performed and then drying was performed at an external temperature outside the reactor in the range of 90 to 100° C. and a vacuum pump condition of 0.1 torr to remove residual solvent and moisture, thereby obtaining m-XDA hydrochloride.

[0126] (2) Preparation of xylylene diisocyanate composition

[0127] 800 g of the m-XDA hydrochloride prepared in 1) above and 3,550 g of o-dichlorobenzene (ODCB) were introduced into the reactor, and the reactor was heated while stirring to increase the internal temperature to about 125°C.

[0128] 950 g of bis(trichloromethyl)carbonate (BTMC) and 800 g of ODCB were dissolved while stirring at about 60° C., and then the reactor temperature was lowered to 125° C. over 24 hours to prevent precipitation. After the addition was complete, premixing was performed for 4 hours.

[0129] After the reaction was completed, N2 gas was supplied to the reaction solution at a temperature of 125° C., and then a degassing process was performed while bubbling. After the degassed reaction solution was cooled to 10° C., the remaining solid was filtered using Celite 545.

[0130] The filtered organic solvent and the synthesized crude XDI were purified by distillation under the following conditions.

[0131] 1) Removal of organic solvent (ODCB) (first distillation)

[0132] -Vacuum: less than 0.5torr

[0133] - Distillation column bottom temperature: 60℃

[0134] - Distillation time: 8 hours

[0135] 2) XDI distillation (second distillation)

[0136] -Vacuum: less than 0.5torr

[0137] - Distillation column bottom temperature: 120℃

[0138] - Distillation time: 10 hours

[0139] Each XDI composition according to the Examples and Comparative Examples was prepared by adding an acidity regulator to the XDI prepared as described above to measure the acidity shown in the following Table 1. Specifically, the acidity of the prepared preliminary composition containing XDI was first measured, and the acidity regulator was added to obtain the target acidity shown in Table 1, while the acidity was measured to obtain the XDI composition prepared as described above.

[0140] 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 the second distillation temperature of Comparative Example 3 was adjusted to 120°C.

[0141] Methods for measuring acidity

[0142] 20 g of the prepared XDI composition sample was quantified and introduced into a 200 ml beaker, 100 ml of a solvent (acetone and ethanol mixed at a weight ratio of 1:1) was added thereto, and heated on a hot plate to dissolve the sample, and then the solution was mixed at room temperature for 10 to 20 minutes.

[0143] Then, in accordance with JIS K4101, using an automatic measuring device (Hiranuma COM-500), the acidity was calculated according to the following formula, using a solution prepared by diluting 0.1 mol / L methanolic potassium hydroxide adjusted and expressed with methanol (N / 100 methanolic potassium hydroxide solution) to form a titration curve, and the rising point of the curve was used as the end point.

[0144] Acidity = 0.0365 × (AB) × f / S

[0145] A: The amount of N / 100 methanolic potassium hydroxide solution required to titrate the sample (ml)

[0146] B: The amount of N / 100 methanolic potassium hydroxide solution required for the blank test (ml)

[0147] F: Factor of N / 100 methanolic potassium hydroxide solution

[0148] S: sample weight (g)

[0149] 2) Preparation of polymerizable compositions for optical materials and lenses

[0150] 49.3 parts by weight ("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 xylylene diisocyanate synthesized according to the above preparation example, 0.01 parts by weight of dibutyltin chloride and 0.1 parts by weight of A phosphate release agent produced by UN Stepan was uniformly mixed, and then defoamed at 600 Pa for 1 hour to prepare a polymerizable composition for an optical material.

[0151] The resin composition, filtered through a 3μm Teflon filter, was injected into a mold consisting of a glass mold and adhesive tape. After the mold was maintained at 10 to 25°C for 8 hours, the temperature was slowly raised to 130°C at a constant rate for 8 hours, and polymerization was performed at 130°C for 2 hours. After polymerization was completed, the mold was separated and the product was further cured at 120°C for 2 hours to prepare a lens sample.

[0152] Experimental example

[0153] (1) Measurement of chlorine content

[0154] The chlorine content in each of the XDI compositions of Examples and Comparative Examples was measured using a sample combustion device (Analytech / AQF-2100H, Mitsubishi Chemical) and an ion chromatograph (881 Compact IC Pro, metrohm).

[0155] (2) Measurement of acidity changes

[0156] The acidity of each of the XDI compositions of Examples and Comparative Examples was measured by the above method after being stored in a dark room at 25° C. for 3 months. The change in acidity was calculated using the acidity measurement values ​​before and after storage in the dark.

[0157] (3) Evaluation of the turbidity of XDI composition

[0158] After each XDI composition of Examples and Comparative Examples was stored in a dark room at 25° C. for 3 months, the sample was placed in a 10 mm quartz cell and the transmittance was measured at a wavelength of 380 nm and 25° C. (transmittance measuring device: Lambda 365, PerkinElmer Co.).

[0159] (4) Evaluation of physical properties of polymerizable composition / lens

[0160] 1) Evaluation of stripes

[0161] As described above, lens samples with a diameter of 75 mm and a density of -8.00 D were prepared using the polymerizable compositions according to the Examples and Comparative Examples. Light from a mercury lamp was then transmitted through the prepared lens samples and projected onto a whiteboard to determine the presence or absence of streaks based on the presence or absence of contrast. The evaluation criteria were as follows.

[0162] ○: No streaks observed

[0163] △: Fine streaks are observed

[0164] X: Stripes can be clearly observed visually

[0165] 2) Evaluation of lens cloudiness

[0166] With respect to the lens samples of Examples and Comparative Examples prepared as described above, each sample was irradiated with a right beam from a projector in a dark room, and it was visually confirmed whether the lens had haze or opaque material.

[0167] The evaluation criteria are as follows.

[0168] ○: No haze

[0169] △: Some haze was observed

[0170] X: Haze is clearly observed overall

[0171] 3) Measurement of polymerization reaction rate (reactivity slope)

[0172] Using an EMS-1000 (KEM) non-contact viscometer, the standard viscosity (standard cps) was first determined using a viscosity standard solution (Brookfield, 1000 cps, 25°C). The viscosity of each of the polymerizable compositions according to Examples and Comparative Examples was then measured at 10°C for 24 hours. The measured values ​​were mathematically formulated ("mathematicalization") with time on the X-axis and viscosity on the Y-axis. The Y-axis was converted to a logarithmic scale as shown in the following formula 1, and the reaction rate was then derived from this.

[0173] [Formula 1]

[0174] Y = a × exp(b × X)

[0175] In Formula 1, the 'a' value represents the initial viscosity (cps), and the 'b' value represents the reaction rate, and the measured values ​​are expressed by rounding to two decimal places of the measured values.

[0176] 4) Measurement of color index (yellow index (YI))

[0177] The YI (Yellow Intensity Index) of the lens samples of the Examples and Comparative Examples was measured using a UV / VIS spectrometer (PerkinElmer, UV / VIS Lambda 365). Specifically, the chromaticity coordinates x and y were measured by transmitting light along the height of the plastic circumference (r (radius) x H (height) = 16 mm x 45 mm). The YI was calculated using the following equation 2 based on the measured x and y values.

[0178] [Formula 2]

[0179] YI=(234×x+106×y+106) / y

[0180] The measurement results and the evaluation results are shown together in Tables 1 and 2 below.

[0181] [Table 1]

[0182]

[0183] Specific compounds of the acidity regulators used in Table 1 are as follows.

[0184] A: Sulfonyl chloride

[0185] B: trimethylchlorosilane

[0186] C: Benzoyl chloride

[0187] D: Phenylacetyl chloride

[0188] E: Benzoic acid

[0189] F: Formic acid

[0190] G: Phosphoric acid

[0191] H: Acetic acid

[0192] I: Acetate phosphate

[0193] [Table 2]

[0194]

[0195] Referring to Tables 1 and 2, it was found that in Examples with an acidity of greater than 100 ppm and less than 1000 ppm, white turbidity in the composition and lens state was prevented, an appropriate polymerization reaction rate was achieved, and lens striae were suppressed. Furthermore, by adding a compound with a boiling point of 110°C or higher as an acidity regulator to suppress changes in acidity during long-term storage, the permeability of the composition was also improved.

[0196] Referring to Examples 1 to 8, the chlorine content in the composition is reduced to less than 100 ppm, thereby reducing yellowing of the lens and more effectively suppressing streaks caused by the increased reaction rate.

Claims

1. A xylylene diisocyanate composition comprising: Xylylene diisocyanate XDI; and an acidity regulator having a boiling point of 110°C or above, wherein the acidity of the xylylene diisocyanate composition is greater than 100 ppm and less than 1,000 ppm based on the total weight of the xylylene diisocyanate XDI, wherein the chlorine content in the xylylene diisocyanate composition is less than 100 ppm, and The amount of the acidity regulator added is in the range of 300 ppm to 4,000 ppm. 2 . The xylylene diisocyanate composition according to claim 1 , wherein the chlorine content in the xylylene diisocyanate composition is 10 ppm to 95 ppm.

3. The xylylene diisocyanate composition according to claim 1, wherein a change in acidity before and after storage in a dark room at 25°C for 3 months is 40 ppm or less.

4. The xylylenediisocyanate composition according to claim 1, wherein the transmittance to light of 380 nm wavelength is 99% or more after being stored in a dark room at 25°C for 3 months. 5 . The xylylene diisocyanate composition according to claim 1 , wherein the acidity regulator comprises at least one inorganic acid compound selected from the group consisting of sulfuric acid and phosphoric acid. 6 . The xylylene diisocyanate composition according to claim 1 , wherein the acidity regulator comprises at least one organic acid compound selected from the group consisting of benzoic acid, fatty acids, and aromatic carboxylic acid halides.

7. The xylylene diisocyanate composition according to claim 1, wherein the acidity regulator comprises at least one solid acid selected from the group consisting of clay, silica-alumina, cation exchange resin, acid-leached silica gel, acid-leached alumina, aluminum oxide, and vanadium oxide. 8 . The xylylene diisocyanate composition according to claim 1 , wherein the acidity regulator comprises a cyclic amine compound or a tertiary amine compound.

9. A polymerizable composition for an optical material, comprising: The xylylene diisocyanate composition according to claim 1, comprising xylylene diisocyanate XDI; Polythiol compounds; and additive. 10 . The polymerizable composition for an optical material according to claim 9 , wherein the additive comprises at least one selected from the group consisting of a release agent, a reaction catalyst, a heat stabilizer, an ultraviolet absorber, and a bluing agent.

11. A method for preparing a xylylene diisocyanate composition, the method comprising: synthesizing xylylenediisocyanate from xylylenediamine to form a preliminary composition comprising xylylenediisocyanate; and By adjusting the acidity of the preliminary composition to a range of greater than 100 ppm to 1,000 ppm using an acidity regulator having a boiling point of 110° C. or higher, wherein the xylylene diisocyanate composition is prepared to have a chlorine content of less than 100 ppm, and The amount of the acidity regulator added is in the range of 300 ppm to 4,000 ppm.

12. The method according to claim 11, wherein In the step of adjusting the acidity of the preliminary composition, an acidic acidity regulator is added when the acidity of the preliminary composition is 100 ppm or less, and an alkaline acidity regulator is added when the acidity of the preliminary composition exceeds 1,000 ppm.

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