Benzidene diisocyanate composition and photopolymerizable composition comprising the same

Abstract

The present invention relates to a xylylene diisocyanate composition and a photopolymerizable composition including the same. The xylylene diisocyanate composition according to an exemplary example includes a xylylene diisocyanate (XDI) and an acidity adjuster having a boiling point of 110°C or more, wherein the acidity of the composition is greater than 100 ppm and 1,000 ppm or less with respect to the total weight of the xylylene diisocyanate (XDI). The polymerization reaction rate is controlled by adjusting the acidity, so that an optical lens having high transmittance and improved optical uniformity can be manufactured.

Description

Technical Field

[0001] The present invention relates to phenylene diisocyanate compositions and photopolymerizable compositions comprising the same, and more particularly, to phenylene diisocyanate compositions prepared by reaction of amine salts and photopolymerizable compositions comprising the same. Background Technology

[0002] Diisocyanate compounds are widely used as raw materials, for example, in the preparation of polyurethane resins. For instance, diisocyanate compounds are used to manufacture optical lenses in which polyurethane resins are used, and the physical properties of the diisocyanate compounds used as raw materials directly affect the optical performance of the optical lenses, such as their transparency and refractive index.

[0003] For example, polythiourethane resins prepared by reacting polythiols and diisocyanates can be used as substrates for optical lenses.

[0004] Among diisocyanate compounds, phenylene diisocyanate (XDI) is widely used due to its chemical and optical properties, such as reactivity and transparency.

[0005] For example, polymeric compositions for optical lenses can be manufactured 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 of the XDI composition, its synthesis method, etc.

[0006] For example, Korean Patent Application Publication No. 2012-0076329 discloses urethane-based optical materials prepared using isocyanate compounds. However, the physical properties of the isocyanate composition itself are not considered in the aforementioned patent. Summary of the Invention

[0007] The purpose of the exemplary embodiments is to provide a phenylene diisocyanate composition and a method thereof with improved reaction stability and optical properties.

[0008] Another objective according to an exemplary embodiment is to provide a photopolymerizable composition comprising a phenylene diisocyanate composition having improved reaction stability and optical properties.

[0009] Furthermore, another objective of the exemplary embodiments is to provide an optical product manufactured from the above-described photopolymerizable composition.

[0010] To achieve the above objectives, according to one aspect of the present invention, a phenylene diisocyanate composition is provided, comprising phenylene diisocyanate (XDI) and an acidity modifier having a boiling point of 110°C or higher, wherein the acidity of the composition relative to the total weight of phenylene diisocyanate (XDI) is greater than 100 ppm and less than 1,000 ppm.

[0011] In an exemplary embodiment, the chlorine content of the composition may be less than 100 ppm.

[0012] In an exemplary embodiment, the chlorine content of the composition may be in the range of 10 ppm to 95 ppm.

[0013] In an exemplary embodiment, the acidity change before and after storage in a dark room at 25°C for 3 months can be less than 40 ppm.

[0014] In an exemplary embodiment, after being stored in a dark room at 25°C for 3 months, the transmittance to 380nm wavelength light can be above 99%.

[0015] In an exemplary embodiment, the acidity regulator may include at least one inorganic acid compound selected from the group consisting of hydrohalic acids, sulfuric acid, phosphoric acid, and phosphate ester compounds.

[0016] In an exemplary embodiment, 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.

[0017] In an exemplary embodiment, the acidity regulator may include at least one solid acid selected from the group consisting of clay, silica alumina, cation exchange resin, acid-attached silica gel, acid-attached alumina, alumina, and vanadium oxide.

[0018] In an exemplary embodiment, the acidity regulator may include a cyclic amine compound or a tertiary amine compound.

[0019] In an exemplary embodiment, the amount of acidity regulator added can be in the range of 300 ppm to 4,000 ppm.

[0020] In addition, according to another aspect of the present invention, a photopolymerizable composition is provided, comprising: a phenylene diisocyanate composition including phenylene diisocyanate (XDI) and an acidity regulator having a boiling point of 110°C or higher, wherein the acidity of the composition relative to the total weight of phenylene diisocyanate (XDI) is greater than 100 ppm and less than 1,000 ppm; a polythiol compound; and additives.

[0021] In an exemplary embodiment, the chlorine content of the phthalic acid diisocyanate composition may be less than 100 ppm.

[0022] In an exemplary embodiment, the additive may include at least one selected from the group consisting of release agents, reaction catalysts, heat stabilizers, ultraviolet absorbers, and bluing agents.

[0023] Furthermore, according to another aspect of the present invention, a method for preparing a phenylene diisocyanate composition is provided, comprising: synthesizing phenylene diisocyanate (XDI) from phenylene diamine to form a preliminary composition containing XDI; and adjusting the acidity of the preliminary composition to a range greater than 100 ppm and less than 1,000 ppm.

[0024] In an exemplary embodiment, the step of adjusting the acidity of the preliminary composition may include adding an acidic acidity regulator when the acidity of the preliminary composition is below 100 ppm, and adding an alkaline acidity regulator when the acidity of the preliminary composition is above 1,000 ppm.

[0025] According to the above embodiments, the phthalene diisocyanate composition has an acidity greater than 100 ppm and less than 1,000 ppm, and can provide improved stability and a suitable range of polymerization rates with polythiol compounds.

[0026] Therefore, it is possible to manufacture optical lenses with high transmittance and improved optical uniformity, which essentially eliminates clouding and streaking phenomena. Detailed Implementation

[0027] The embodiments of this application will now be described in detail. However, since the invention can include various forms and additional variations, specific embodiments are shown in the accompanying drawings and described in detail in the text. However, this is not intended to limit the invention to the specific forms disclosed above, but should be understood to include all modifications, equivalents, and substitutions within the spirit and scope of the invention.

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

[0029] According to one aspect of the present invention, a composition comprising ethylene diisocyanate (XDI) is provided (hereinafter, it may be abbreviated as XDI composition).

[0030] According to an exemplary embodiment, the XDI composition may include XDI, and the acidity of the XDI composition relative to the total weight of XDI may be greater than 100 ppm and less than 1,000 ppm.

[0031] The term “acidity” as used in this article can refer to the amount of acid that is released at room temperature by reaction with alcohol, expressed as a ratio of HCl to the total weight of XDI.

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

[0033] For example, when the acidity of the XDI composition increases excessively, its polymerization reactivity with polythiol compounds may decrease excessively. This can lead to a decrease in the process yield of the polythiourethane resin used to manufacture optical lenses. Furthermore, it may cause turbidity in the casting process used to shape the lenses.

[0034] When the acidity of the XDI composition is excessively reduced, its polymerization reactivity with polythiol compounds may increase excessively. Consequently, other byproducts, such as oligomers or polymers, may increase instead of the desired polythiourethane resin, which in turn may cause streaking in the lens. Furthermore, the self-reactivity of XDI is also increased, potentially causing turbidity during long-term storage. Therefore, as described below, the transmittance of the stock solution may decrease when stored in a dark room at room temperature (25°C) for a prolonged period of 3 months. Furthermore, during long-term storage, the desired target acidity may fluctuate due to its own reactions, making acidity control impossible.

[0035] Considering the above aspects, according to an exemplary embodiment, the acidity of the XDI composition can be adjusted to be greater than 100 ppm and less than 1,000 ppm. Therefore, appropriate reactivity with polythiol compounds can be maintained to suppress turbidity during lens casting while preventing lens streaks. Furthermore, by ensuring the storage properties of the XDI composition, the decrease in transmittance and changes in acidity of the XDI composition can be suppressed.

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

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

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

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

[0040] For example, the acidity of the XDI composition can vary in the range of 1ppm to 40ppm, 1ppm to 35ppm, or 1ppm to 20ppm, preferably 1ppm to 15ppm, and more preferably 1ppm to 10ppm.

[0041] The chlorine content can be adjusted along with the acidity of the XDI composition. An increase in the chlorine content of the XDI composition may cause the lens to yellow. Furthermore, the chloride ions contained in the composition can act as a variable factor for acidity.

[0042] Therefore, when the chlorine content in the composition increases, the acidity of the composition, adjusted to the predetermined range as described above, changes, and thus it becomes difficult to achieve the desired target acidity range. Furthermore, when the composition is stored for an extended period, the acidity may change due to chlorine, potentially preventing the attainment of the desired lens performance.

[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 less than 95 ppm.

[0044] In one embodiment, the chlorine content in the XDI composition can be maintained above 10 ppm 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 the corresponding range. In one embodiment, the chlorine content in the XDI composition can be maintained in the range of 10 ppm to 95 ppm, 10 to 80 ppm, and preferably 30 ppm to 80 ppm or 40 ppm to 80 ppm.

[0045] According to an exemplary embodiment, an acidity regulator that finely adjusts the acidity within the above range can be added to the XDI composition, and a compound with a boiling point of 110°C or higher can be used as the acidity regulator.

[0046] When an acidity regulator with a boiling point above 110°C is used, changes in the acidity regulator content during distillation in the XDI composition preparation process can be suppressed. Therefore, acidity and chlorine content can be stably maintained within the aforementioned range. 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.

[0047] In one embodiment, compounds with boiling points of 110°C to 500°C, 110°C to 400°C, or 110°C to 300°C can be used as acidity regulators. For example, the boiling point range of an acidity regulator can be 110°C to 250°C or 110°C to 200°C.

[0048] In some embodiments, after being stored in a dark room at 25°C for 3 months, the XDI composition can have a transmittance of more than 99% for light at a wavelength of 380 nm.

[0049] Acidity regulators may include inorganic acid compounds, organic acid compounds, or solid acids.

[0050] Examples of inorganic acid compounds may include hydrohalic 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 phosphate ester compounds such as phosphate ester compounds or phosphonate compounds. For example, the phosphoric acid derivative may include compounds of Formula 1.

[0052] [Formula 1]

[0053]

[0054] In Equation 1, n is 1 or 2.

[0055] Examples of organic acid compounds may include acetic acid, benzoic acid, formic acid, trifluoroacetic acid (TFA), fatty acids, and aromatic carboxylic acid halides (e.g., benzoyl halides, phenylacetyl halides, phthaloyl halides, terephthaloyl halides, isophthaloyl halide).

[0056] Examples of solid acids may include acidic clay, silica alumina, cation exchange resins, acid-attached silica gel, or solid acids such as acid-attached alumina, alumina, or vanadium oxide.

[0057] In some embodiments, the acidity regulator may comprise a basic compound that does not substantially react with XDI. For example, the acidity regulator may comprise cyclic amines such as imidazole, tetrazolium, and pyridine, or tertiary amines such as N,N-dimethylaniline (PhNMe2).

[0058] In some implementations, taking into account the above-mentioned acidity range and chlorine content, the amount or content of the acidity regulator can be adjusted, for example, in the range of 300 ppm to 4,000 ppm.

[0059] In one embodiment, the amount or content of the acidity regulator can range from 300 ppm to 2,000 ppm, preferably from 300 ppm to 1,000 ppm, and more preferably from 300 ppm to 700 ppm or from 300 ppm to 500 ppm.

[0060] In one embodiment, the amount or content of the acidity regulator can range from 500 ppm to 2,000 ppm, and preferably from 500 ppm to 1,000 ppm. Alternatively, the amount or content of the acidity regulator can range from 700 ppm to 2,000 ppm, and preferably from 700 ppm to 1,000 ppm.

[0061] In one embodiment, the amount or content of the acidity regulator can range from 400 ppm to 3,500 ppm, and preferably from 500 ppm to 3,000 ppm.

[0062] In one embodiment, the XDI content in the XDI composition may be 90 wt.% or more, 95 wt.% or more, or 99 wt.% or more, for example, 99 wt.% or more and less than 100 wt.%. In one embodiment, the acidity regulator may be added within the range of acidity that is within the above-mentioned range.

[0063] According to an exemplary embodiment, a method for preparing an XDI composition may be provided, the method comprising the following steps, processes, or actions.

[0064] The method for preparing the XDI composition according to the exemplary embodiments may include at least one of the steps, processes, or actions described below as S10 and S20. It should be understood that, for ease of description, the terms "S10" and "S20" are used to distinguish processes and are not intended to limit the order of processes. For example, some or all of the steps S10 and S20 below may be performed sequentially, and the order may be changed according to process conditions.

[0065] S10) Obtain a preliminary composition containing XDI through the XDI synthesis process;

[0066] S20) Confirm the acidity of the preliminary composition, and if its acidity is less than 100 ppm or greater than 1,000 ppm, adjust the acidity to obtain an XDI composition with an acidity greater than 100 ppm and less than 1,000 ppm.

[0067] For example, phenylene diisocyanate (XDI) can be synthesized from phenylene diamine in step S10.

[0068] In some embodiments, XDI can be synthesized from phenylene dimethylamine via a phosgene process. For example, phenylene dimethylamine can be reacted with concentrated hydrochloric acid in a solvent to form an amine salt. In this paper, XDI can be synthesized by reacting the amine salt with phosgene (COCl2) (see Scheme 1 below).

[0069] [Option 1]

[0070]

[0071] In some embodiments, XDI can be synthesized from phenylene dimethylamine via a phosgene process. For example, phenylene dimethylamine can be reacted with concentrated hydrochloric acid to form an amine salt. The amine salt can then be reacted with a halodialkyl carbonate to form a dicarboxylate. XDI can be synthesized by thermal decomposition or degassing of the dicarboxylate in the presence of a catalyst (see Scheme 2 below).

[0072] [Option 2]

[0073]

[0074] As shown in Scheme 2 above, bis(trichloromethyl) carbonate (BTMC) can be used as an example of halodialkyl carbonate.

[0075] For example, a first solution in which the amine salt is dissolved in an inert solvent can be prepared, and a second solution in which the halodialkyl carbonate is dissolved in an inert solvent can be prepared. The dicarboxylate synthesis reaction can be carried out simultaneously with the addition of the second solution to the first solution in the reactor. The temperature in the reactor can be maintained, for example, in the range of about 120°C to 150°C.

[0076] Subsequently, the degassing process can be carried out by supplying an inert gas to the reaction solution while maintaining the temperature within the aforementioned range. The reaction solution can then be cooled, followed by filtration and drying processes to obtain the XDI composition.

[0077] In some embodiments, a further distillation process can be performed to remove the inert solvent and extract XDI. For example, a first distillation for removing the inert solvent and a second distillation for extracting XDI can be performed sequentially.

[0078] The temperature of the first distillation can be adjusted appropriately based on the boiling point of the inert solvent. The temperature of the second distillation can be above the boiling point of XDI.

[0079] In some embodiments, the first distillation temperature can be below 100°C, for example, 50°C to 90°C, and preferably 50°C to 80°C. The second distillation temperature can be above 115°C, for example, 120°C to 150°C, and preferably 120°C to 140°C.

[0080] The first and second distillations can be carried out under pressure conditions below 1 Torr, and preferably under pressure conditions below 0.5 Torr.

[0081] Inert solvents may include organic solvents that are substantially non-reactive with amine salts, XDI, and halodialkyl carbonates. Furthermore, organic solvents with a boiling point lower than XDI may be used for the distillation process described above.

[0082] In one embodiment, the inert solvent may include chlorinated aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene, trichlorobenzene, and chloroethylbenzene.

[0083] According to an exemplary embodiment, the acidity of the XDI-containing preliminary composition prepared as described in step S20 above can be measured and adjusted. For example, when the acidity of the preliminary composition is less than 100 ppm or greater than 1,000 ppm, it can be adjusted to an acidity greater than 100 ppm and less than 1,000 ppm.

[0084] When the acidity of the initial composition is below 100 ppm, an acidity regulator may be added. The acidity regulator may include the aforementioned inorganic acid compounds, organic acid compounds, or solid acids.

[0085] Preferably, liquid organic acid compounds can be used to achieve precise acidity control.

[0086] When the acidity of the initial composition exceeds 1,000 ppm, the above-mentioned alkaline compound may be added.

[0087] 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 the addition of an acidity regulator.

[0088] According to one aspect of the present invention, a photopolymerizable composition is provided, comprising the XDI composition prepared as described above.

[0089] Photopolymerizable compositions may include polythiol compounds and XDI compositions.

[0090] Polythiol compounds can include trifunctional polythiol compounds and / or tetrafunctional polythiol compounds.

[0091] Non-limiting examples of trifunctional polythiol compounds may include compounds represented by the following formula 1.

[0092] [Formula 1]

[0093]

[0094] Trifunctional polythiols can be synthesized from polyols, for example, obtained by reacting with 2-mercaptoethanol and epihaloethanol.

[0095] After reacting polyol compounds with thiourea under acidic conditions to produce sulfonium urea salts, trifunctional polythiool compounds can be prepared by hydrolysis under alkaline conditions.

[0096] Non-limiting examples of tetrafunctional polythiols may include compounds represented by the following formulas 2-1 to 2-3.

[0097] [Equation 2-1]

[0098]

[0099] [Equation 2-2]

[0100]

[0101] [Equation 2-3]

[0102]

[0103] Tetrafunctional polythiols can be synthesized from polyols, for example, obtained by reacting with 2-mercaptoethanol and epihaloethanol. The polyols can be reacted with metal sulfides to produce tetrafunctional polyol intermediates. After reacting the tetrafunctional polyol intermediate with thiourea under acidic conditions to produce sulfonium urea salts, the tetrafunctional polythiols can be prepared by hydrolysis under alkaline conditions.

[0104] Photopolymerizable compositions may further include additives such as release agents, reaction catalysts, heat stabilizers, ultraviolet absorbers, and bluing agents.

[0105] Examples of release agents may include: fluorinated nonionic surfactants having perfluoroalkyl, hydroxyalkyl, or phosphate groups; organosilicon nonionic surfactants having dimethylpolysiloxane, hydroxyalkyl, or phosphate groups; alkyl quaternary ammonium salts, such as trimethylhexadecylammonium salt, trimethylstearylammonium salt, dimethylethylhexadecylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, and diethylcyclohexyldodecylammonium salt; or acidic phosphate esters, etc. These may be used alone or in combination of two or more thereof.

[0106] As reaction catalysts, catalysts used in the polymerization reaction of polysulfururethane resins can be used. Examples include dialkyltin halide catalysts, such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylic acid catalysts, such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate; dialkyltin diol oxide 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; or dialkyltin sulfide catalysts, etc. These can be used alone or in combination of two or more of them.

[0107] Examples of UV absorbers include benzophenone compounds, benzotriazole compounds, salicylate compounds, cyanoacrylate compounds, and oxaloaniline compounds. Examples of heat stabilizers include metal fatty acid salt compounds, phosphorus compounds, lead compounds, and organotin compounds. These can be used alone or in combination of two or more of them.

[0108] It may include a bluing agent as a color adjusting agent for optical materials made from polyurethane resin. For example, the bluing agent may have an absorption band in the wavelength range from orange to yellow in the visible light region.

[0109] Examples of bluing agents can include dyes, fluorescent whitening agents, fluorescent pigments, or inorganic pigments, and can be appropriately selected according to the physical properties or resin color required for the optical product to be manufactured. When using dyes as bluing agents, dyes with a maximum absorption wavelength of 520 nm to 600 nm, and preferably 540 nm to 580 nm, can be used. Anthraquinone dyes are preferred.

[0110] In some embodiments, the polythiol compound, the isocyanate compound, and the above-mentioned additives may be included in amounts of 40 wt.% to 60 wt.%, 40 wt.% to 60 wt.%, and 0.01 wt.% to 1 wt.%, respectively, relative to the total weight of the photopolymerizable composition.

[0111] Polyurethane resins can be manufactured by the polymerization reaction of polythiol compounds and XDI included in a photopolymerizable composition.

[0112] As described above, the acidity of the XDI composition used in the photopolymerizable composition is adjusted to be greater than 100 ppm and less than 1,000 ppm, so that the reactivity or reaction rate with the polythiol compounds can be appropriately controlled. Therefore, while suppressing turbidity originating from the XDI composition itself, turbidity in the optical lens prepared from the photopolymerizable composition can also be prevented.

[0113] In some embodiments, the reaction rate of the photopolymerizable composition comprising Equation 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, and preferably 0.19 to 0.21.

[0114] Furthermore, optical lenses with a uniform refractive index and no stripe phenomenon can be manufactured through a stable polymerization reaction.

[0115] According to one aspect of the present invention, optical products manufactured using the above-described photopolymerizable composition can be provided.

[0116] For example, after degassing the photopolymerizable composition under reduced pressure, it can be injected into a mold for forming optical materials. The mold injection can be carried out in a temperature range of, for example, 10°C to 40°C, and preferably 10°C to 30°C.

[0117] After injection molding, the temperature can be gradually increased to carry out the polymerization reaction of the polyurethane resin. The polymerization temperature range can be 20°C to 150°C, and preferably 25°C to 125°C. For example, the maximum polymerization temperature range can be 100°C to 150°C, preferably 110°C to 140°C, and more preferably 115°C to 130°C.

[0118] The polymerization time can be 1 to 10 hours, and preferably 1 to 5 hours.

[0119] For example, by appropriately controlling the reaction rate within the aforementioned temperature range, lenses with uniform optical and mechanical properties can be easily obtained.

[0120] After polymerization, the polymerized polyurethane resin can be separated from the mold to obtain optical products. These optical products can be manufactured in the form of eyeglass lenses, camera lenses, light-emitting diodes, etc., depending on the mold shape.

[0121] In one embodiment, after separation from the mold, a curing process can be further performed. The curing process can be carried out at a temperature in the range of 110°C to 150°C, preferably 110°C to 140°C, more preferably 115°C to 130°C, for 1 to 10 hours, and more preferably 1 to 3 hours.

[0122] The refractive index of an optical product can be adjusted according to the type and / or content ratio of polythiol compounds and isocyanate compounds used in the photopolymerizable composition. For example, the refractive index of an optical product can be adjusted in the range of 1.56–1.78, 1.58–1.76, 1.60–1.78, or 1.60–1.76, and preferably in the range of 1.65–1.75 or 1.69–1.75.

[0123] The yellowness index (YI) of the optical product according to Equation 2 described below can be less than 30, preferably less than 28, and more preferably less than 22 or less, or less than 21.

[0124] Optical products can be improved by additional surface treatments such as anti-fouling, coloring, hard coating, surface polishing, and hardening.

[0125] The embodiments provided in this application will be further described below with reference to specific experimental examples. The embodiments and comparative examples included in the experimental examples are merely illustrative of the invention and do not limit the appended claims. Furthermore, various changes and modifications to the embodiments are possible within the scope and spirit of the invention, which will be apparent to those skilled in the art. Furthermore, it should be understood that these changes and modifications fall within the scope of the appended claims.

[0126] Preparation Example

[0127] (1) Preparation of phenylenediamine diamine (XDA) hydrochloride

[0128] 1009.4 g (9.46 mol) of 35% hydrochloric acid solution was introduced into the reactor, and the temperature inside the reactor was cooled to the range of 15°C to 20°C while stirring. Then, 600.0 g (4.4 mol) of m-phenylenediamine (m-XDA) was slowly introduced, while the reactor temperature was maintained at 20°C to 60°C.

[0129] After the introduction of m-XDA, the temperature inside the reactor was cooled to the range of 10°C to 20°C, and after stirring for 1 hour, 1320.0 g of tetrahydrofuran was added. The temperature inside the reactor was then cooled again to the range of -5°C to 0°C, and the reaction was carried out while stirring for another 1 hour.

[0130] After the reaction was completed, the mixture was vacuum filtered and then dried in a vacuum pump at an external temperature of 90°C to 100°C under 0.1 Torr conditions to remove residual solvent and moisture, thereby obtaining m-XDA hydrochloride.

[0131] (2) Preparation of phenylene diisocyanate composition

[0132] 800g of m-XDA hydrochloride prepared in (1) above and 3,550g of o-dichlorobenzene (ODCB) were added to the reactor, and the internal temperature of the reactor was raised to about 125°C by heating while stirring.

[0133] Dissolve 950 g of bis(trichloromethyl) carbonate (BTMC) and 800 g of ODCB at approximately 60 °C with stirring, then add them dropwise over 24 hours to a reactor adjusted to 125 °C to prevent precipitation. Premix for 4 hours after the addition is complete.

[0134] After the reaction was complete, N2 gas was supplied to the reaction solution at 125°C, followed by bubbling and degassing. After degassing, the reaction solution was cooled to 10°C, and the remaining solids were filtered using a Celite 545 filter.

[0135] The filtered organic solvent and the synthesized crude XDI were purified by distillation under the following conditions.

[0136] 1) Removal of organic solvent (ODCB) (first distillation)

[0137] - Vacuum below 0.5 Torr

[0138] - Temperature at the bottom of the distillation column: 60℃

[0139] - Distillation time: 8 hours

[0140] 2) XDI distillation (second distillation)

[0141] - Vacuum below 0.5 Torr

[0142] - Temperature at the bottom of the distillation column: 120℃

[0143] - Distillation time: 10 hours

[0144] The XDI compositions according to the examples and comparative examples were prepared by adding an acidity control agent to XDI prepared as described above, and measuring the acidity as shown in Table 1 below. Specifically, the acidity of the prepared preliminary composition containing XDI was first measured, and an acidity regulator was added while measuring the acidity to obtain the target acidity as shown in Table 1, thereby preparing the XDI composition.

[0145] In Comparative Examples 2, 3, and 8, the acidity and chlorine content were changed by altering 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.

[0146] Acidity measurement methods

[0147] Quantitatively measure 20g of the prepared XDI composition sample and introduce it into a 200ml beaker, and add 100ml of solvent (acetone and ethanol mixed in a 1:1 weight ratio). Then heat on a hot plate to dissolve the sample, and then mix them at room temperature for 10-20 minutes.

[0148] Then, using an automatic measuring device (Hiranuma COM-500) and according to JIS K4101, a solution (N / 100 potassium hydroxide solution) was prepared by diluting 0.1 mol / L potassium hydroxide solution (adjusted with methanol) 10 times. The acidity was then calculated using the following formula, with the rising point of the titration curve prepared using the prepared solution as the endpoint.

[0149] Acidity = 0.0365 × (AB) × f / S

[0150] Where A represents the volume (ml) of N / 100 methanol-potassium hydroxide solution required for titrating the sample.

[0151] B represents the volume (ml) of N / 100 methanol-potassium hydroxide solution required for the blank test.

[0152] f represents the coefficient of N / 100 methanol-potassium hydroxide solution, and

[0153] S represents the weight of the sample (g).

[0154] 2) Preparation of photopolymerizable compositions and lenses

[0155] 49.3 parts by weight (“wt. parts”) of 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol as a polythiol compound, 50.7 wt. parts of phenylene diisocyanate synthesized according to the above preparation example, 0.01 wt. parts of dibutyltin chloride, and 0.1 wt. parts of UN Stepan's phosphate release agent is uniformly mixed and then defoamed at 600 Pa for 1 hour to prepare a photopolymerizable composition.

[0156] A resin composition filtered through a 3μm polytetrafluoroethylene (Teflon) filter was injected into a mold comprising a glass mold and tape. After holding the mold at 10°C–25°C for 8 hours, the temperature was slowly increased to 130°C over a constant rate over 8 hours, and polymerization was carried out at 130°C for 2 hours. After polymerization was complete, the mold was separated, and the product was further cured at 120°C for 2 hours to prepare a lens sample.

[0157] Experimental Example

[0158] (1) Measurement of chlorine content

[0159] The chlorine content in the XDI compositions of the above examples and comparative examples was measured using a sample combustion apparatus (Analytech / AQF-2100H, Mitsubishi Chemical) and an ion chromatograph (881Compact IC Pro, Metrohm Co.).

[0160] (2) Measurement of acidity change

[0161] After storing the XDI compositions of the above examples and comparative examples in a dark room at 25°C for 3 months, the acidity was measured using the method described above. The degree of change in acidity was calculated using the acidity values ​​measured before and after storage in the dark room.

[0162] (3) Turbidity evaluation of XDI compositions

[0163] After storing the XDI compositions of the above examples and comparative examples in a dark room at 25°C for 3 months, the samples were placed in a 10 mm quartz cell, and the transmittance was subsequently measured at a wavelength of 380 nm and at 25°C. (Transmittance measurement equipment: Lambda 365, Perkinelmer Co.)

[0164] (4) Evaluation of the physical properties of polymeric compositions / lenses

[0165] 1) Evaluation of stripes

[0166] As described above, a lens sample with a diameter of 75 mm and a diameter of -8.00 D was prepared using the polymerizable composition according to the above examples and comparative examples. Light from a mercury lamp light source was transmitted through the prepared lens sample, and the transmitted light was then projected onto a white board. The presence or absence of stripes was determined by the presence or absence of contrast. The evaluation criteria are as follows.

[0167] ○: No stripes observed

[0168] △: Some stripes were observed in detail.

[0169] ×: Clear stripes can be observed visually.

[0170] 2) Evaluation of lens opacity

[0171] The lens samples of the above-described embodiments and comparative examples prepared as described above were illuminated in a dark room with a projector, and the presence or absence of haze and whether opaque materials were observed through the lens were visually confirmed.

[0172] The evaluation criteria are as follows.

[0173] ○: No fog

[0174] △: Partial haze observed

[0175] ×: Overall, a clear haze was observed visually.

[0176] 3) Measurement of polymerization rate (reactivity slope)

[0177] Using a non-contact viscometer with an EMS-1000 (KEM), the standard viscosity (standard cps) was first confirmed using a viscosity standard solution (Brookfield, 1000 cps, 25°C). Subsequently, the viscosity of the polymerizable compositions according to the above examples and comparative examples was measured at 10°C for 24 hours. Using the measured values, the Y-axis was defined as logarithmically to form Equation 1 below, where the X-axis is time and the Y-axis is viscosity, from which the reaction rate was subsequently derived.

[0178] [Equation 1]

[0179] Y = a × exp(b × X)

[0180] In Equation 1, the value of "a" represents the initial viscosity (cps), the value of "b" represents the reaction rate, and the calculated value is rounded to three decimal places after the measured value.

[0181] 4) Measurement of Yellowness Index (YI)

[0182] For the lens samples of the above embodiments and comparative examples, chromaticity coordinates (YI) were measured using a UV / VIS spectrometer (PerkinElmer, model UV / VIS Lambda 365). Specifically, chromaticity coordinates x and y were measured by transmitting light along the height direction of the plastic circumference (r (radius) × H (height) = 16 mm × 45 mm). Based on the measured values ​​of x and y, YI was calculated using Equation 2 below.

[0183] [Equation 2]

[0184] YI=(234×x+106×y+106) / y

[0185] The measurement and evaluation results are presented together in Tables 1 and 2 below.

[0186] [Table 1]

[0187]

[0188] The specific compounds used as acidity regulators in Table 1 are as follows.

[0189] A: Thionyl chloride

[0190] B: Trimethylchlorosilane

[0191] C: Benzoyl chloride

[0192] D: Phenylacetyl chloride

[0193] E: Benzoic acid

[0194] F: Formic acid

[0195] G: Phosphoric acid

[0196] H: Acetic acid

[0197] I: Ethyl phosphate

[0198] [Table 2]

[0199]

[0200] Referring to Tables 1 and 2, turbidity in the compositions and lens states of the examples with acidity greater than 100 ppm and less than 1000 ppm was prevented, an appropriate polymerization rate was obtained, and lens streaks were suppressed. Furthermore, when a compound with a boiling point above 110°C was added as an acidity regulator and the composition was stored for a long time, acidity changes were suppressed while improving the transmittance of the composition.

[0201] Referring to Examples 1-8, the chlorine content in the composition was reduced to less than 100 ppm, resulting in less lens yellowing. Furthermore, streaking caused by increased reaction rate was more effectively suppressed.

Claims

1. A phenylene diisocyanate composition comprising phenylene diisocyanate XDI and an acidity modifier having a boiling point of 110°C or higher. The acidity of the phthalic acid diisocyanate composition is greater than 100 ppm and less than 1,000 ppm relative to the total weight of phthalic acid diisocyanate XDI. The acidity regulators mentioned above include inorganic acid compounds, organic acid compounds, solid acids, cyclic amine compounds, or tertiary amine compounds. The inorganic acid compound mentioned above includes at least one selected from the group consisting of sulfuric acid, phosphoric acid, and phosphate ester compounds. The organic acid compound mentioned above includes at least one selected from the group consisting of acetic acid and benzoic acid, and The solid acid mentioned herein includes at least one selected from the group consisting of clay, silica alumina, cation exchange resin, acid-attached silica gel, acid-attached alumina, alumina, and vanadium oxide.

2. The phenylene diisocyanate composition according to claim 1, wherein the chlorine content of the phenylene diisocyanate composition is less than 100 ppm.

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

4. The phenylene diisocyanate composition according to claim 1, wherein after being stored in a dark room at 25°C for 3 months, the transmittance to light at a wavelength of 380 nm is greater than 99%.

5. A photopolymerizable composition comprising: A phthalic acid diisocyanate composition comprising phthalic acid diisocyanate XDI and an acidity modifier having a boiling point of 110°C or higher, wherein the acidity of the phthalic acid diisocyanate composition is greater than 100 ppm and less than 1,000 ppm relative to the total weight of phthalic acid diisocyanate XDI. Polythiol compounds; and additive, The acidity regulators mentioned above include inorganic acid compounds, organic acid compounds, solid acids, cyclic amine compounds, or tertiary amine compounds. The inorganic acid compound mentioned above includes at least one selected from the group consisting of sulfuric acid, phosphoric acid, and phosphate ester compounds. The organic acid compound mentioned above includes at least one selected from the group consisting of acetic acid and benzoic acid, and The solid acid mentioned herein includes at least one selected from the group consisting of clay, silica alumina, cation exchange resin, acid-attached silica gel, acid-attached alumina, alumina, and vanadium oxide.

6. A method for preparing a phenylene diisocyanate composition, comprising: Benzene diisocyanate (XDI) was synthesized from phenylene dimethylamine to form a preliminary composition containing XDI; and The acidity of the preliminary composition is adjusted to a range greater than 100 ppm and less than 1,000 ppm by adding an acidity regulator. The acidity regulators mentioned above include inorganic acid compounds, organic acid compounds, solid acids, cyclic amine compounds, or tertiary amine compounds. The inorganic acid compound mentioned above includes at least one selected from the group consisting of sulfuric acid, phosphoric acid, and phosphate ester compounds. The organic acid compound mentioned above includes at least one selected from the group consisting of acetic acid and benzoic acid, and The solid acid mentioned herein includes at least one selected from the group consisting of clay, silica alumina, cation exchange resin, acid-attached silica gel, acid-attached alumina, alumina, and vanadium oxide.

7. The method for preparing the phenylene diisocyanate composition according to claim 6, wherein adjusting the acidity of the preliminary composition comprises adding an acidic acidity regulator when the acidity of the preliminary composition is below 100 ppm, and adding an alkaline acidity regulator when the acidity of the preliminary composition is above 1,000 ppm.

Images