Phenylene dimethylene diisocyanate compositions and optical compositions comprising the same

Abstract

A xylylene diisocyanate (XDI) composition according to an exemplary embodiment includes a xylylene diisocyanate (XDI) and chloromethylbenzyl isocyanate (CBI), and can satisfy a predetermined relationship of CBI content and acidity. Accordingly, an optical lens having high transmittance and improved optical uniformity can be prepared as the polymerization reaction rate is controlled.

Description

Technical Field

[0001] This invention relates to phthalimide diisocyanate compositions and optical compositions comprising the same. More specifically, this invention relates to phthalimide diisocyanate compositions prepared by reaction of amine salts, and optical 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 using polyurethane resins, and the physical properties of the diisocyanate compounds used as raw materials directly affect the optical properties of the lenses, such as transparency and refractive index.

[0003] For example, polythiourethane resin, prepared by reacting polythiol compounds and diisocyanate compounds, can be used as a substrate for optical lenses.

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

[0005] For example, a polymeric composition for optical lenses can be prepared by preparing a composition comprising XDI and mixing it with a composition comprising 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 and the synthesis method, etc.

[0006] For example, Korean Patent 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. Summary of the Invention

[0007] One objective of the exemplary embodiments is to provide a phenylenediethylene diisocyanate composition having improved reaction stability and optical properties.

[0008] One object of the exemplary embodiments is to provide an optical composition comprising a phthalimide diisocyanate composition having improved reaction stability and optical properties.

[0009] According to one aspect of the present invention, a phthalimide diisocyanate composition comprising phthalimide diisocyanate (XDI) and chloromethyl benzyl isocyanate (CBI) and satisfying the following formula 1 is provided:

[0010] [Formula 1]

[0011]

[0012] In Formula 1, “A” represents the CBI content value in the XDI composition converted to ppm, and “B” represents the acidity value of the XDI composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

[0013] In some embodiments, the content of chloromethylbenzyl isocyanate can be in the range of 600 to 1,000 ppm based on the total weight of the composition.

[0014] In some embodiments, the phthalimide diisocyanate composition may include an acidity regulator.

[0015] In some embodiments, the acidity of the dimethyl phthalate composition can be in the range of 100 to 350 ppm.

[0016] According to another aspect of the present invention, an optical composition is provided, comprising: a phthalimide diisocyanate composition comprising phthalimide diisocyanate (XDI) and chloromethyl benzyl isocyanate (CBI) and satisfying the following formula 1; and a polythiol compound:

[0017] [Formula 1]

[0018]

[0019] In Formula 1, “A” represents the CBI content value in the XDI composition converted to ppm, and “B” represents the acidity value of the XDI composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

[0020] In some embodiments, the optical composition may further include additives, said additives comprising at least one selected from the group consisting of release agents, reaction catalysts, heat stabilizers, ultraviolet absorbers, and bluing agents.

[0021] According to another aspect of the present invention, an optical product is provided, comprising: a polysulfuric urethane resin prepared from the polymerizable composition.

[0022] According to another aspect of the present invention, a method for preparing a phenylenediamine diisocyanate composition is provided, comprising: synthesizing phenylenediamine diisocyanate from phenylenediamine to form a preliminary composition comprising phenylenediamine diisocyanate; and adjusting the content and acidity of chloromethylbenzyl isocyanate (CBI) in the preliminary composition by a distillation process at a temperature of 110 to 135°C.

[0023] In some embodiments, the step of adjusting the acidity in the preparative composition may include introducing imidazole in the range of 200 to 1,000 ppm during the distillation process.

[0024] In some embodiments, adjusting the content and acidity of chloromethyl benzyl isocyanate (CBI) in the preparative composition may include controlling the distillation process to satisfy the following formula 1:

[0025] [Formula 1]

[0026]

[0027] In Formula 1, “A” represents the CBI content value in the XDI composition converted to ppm, and “B” represents the acidity value of the XDI composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

[0028] According to the above embodiments, the phthalimide diisocyanate composition satisfies a predetermined relationship between acidity and the content of chloromethylbenzyl isocyanate (CBI) to provide improved stability and polymerization rate with polythiol compounds within an appropriate range.

[0029] Therefore, it is possible to manufacture optical lenses with high transmittance and improved optical uniformity that essentially eliminate turbidity and inhomogeneity (“stripes”). Detailed Implementation

[0030] The embodiments of this application will be described in detail below. In this respect, the invention can be modified in various ways and has various embodiments, such that particular embodiments are illustrated in the accompanying drawings and described in detail in this disclosure. However, the invention is not limited to the particular embodiments, and those skilled in the art will understand that the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

[0031] 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. It will be further understood that terms, such as those defined in commonly used dictionaries, shall be interpreted as having a meaning consistent with their meaning in the context of the relevant field, and shall not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0032] According to one aspect of the present invention, a composition comprising diphenylmethylene diisocyanate (XDI) is provided (hereinafter, it may be abbreviated as XDI composition).

[0033] According to an exemplary embodiment, the XDI composition may include XDI, and further include chloromethyl benzyl isocyanate (CBI).

[0034] CBI can be included in small amounts in XDI compositions to improve the stability of the compositions, and can also act as a compound for regulating reaction rates.

[0035] In some embodiments, the CBI content in the XDI composition can be in the range of about 600 to 1000 ppm. Within this range, streaking and cloudiness of the XDI composition or optical lenses made therefrom can be effectively suppressed, while excessive reduction in the reaction rate of the XDI composition can be prevented.

[0036] In a preferred embodiment, the CBI content in the XDI composition can be in the range of about 600 to 800 ppm. More preferably, the CBI content in the XDI composition can be in the range of 650 to 800 ppm, or 650 to 750 ppm.

[0037] CBI is produced together with the phthalimide diisocyanate compositions described below in the production or synthesis of XDI compositions, and may be included in the XDI compositions. As described below, in one embodiment, the content of CBI can be adjusted by temperature control during the distillation process.

[0038] For example, CBI may include o-chloromethylbenzyl isocyanate, m-chloromethylbenzyl isocyanate, and p-chloromethylbenzyl isocyanate. These may be included in the XDI composition alone or in combination of two or more thereof.

[0039] According to an exemplary embodiment, in addition to the CBI content of the XDI composition, acidity can also be controlled, such that, for example, the optical and chemical stability of the composition and its reactivity with polythiol compounds can be adjusted.

[0040] As used herein, the term "acidity" can be a value expressed as the proportion of the amount of acidic component (e.g., in the form of HCl) freed by reaction with an alcohol at room temperature to the total weight of XDI. For example, acidity can be expressed in ppm.

[0041] According to an exemplary embodiment, the XDI composition can satisfy the following formula 1:

[0042] [Formula 1]

[0043]

[0044] In Formula 1, “A” represents the CBI content in the XDI composition, and “B” represents the acidity of the XDI composition. The A and B in Formula 1 are used as numerical values ​​with units (ppm) omitted.

[0045] For example, when the acidity of the XDI composition is too low, its reactivity with polythiol compounds may be excessively increased. Therefore, instead of the desired polythiourethane resin, other byproducts in the form of oligomers or polymers may be added, potentially increasing the optical inhomogeneity of the lens and leading to streaking. Furthermore, the self-reactivity of XDI also increases, which can cause clouding during long-term storage.

[0046] When the acidity of the XDI composition increases excessively, its reactivity with polythiol compounds decreases. Consequently, the yield of the polysulfide-urethane resin used in the manufacture of optical lenses decreases. Furthermore, it can lead to clouding or yellowing in molded lenses.

[0047] According to an exemplary embodiment, the content of CBI can be considered as a buffer factor for acidity. For example, if the acidity of the XDI composition is excessively high, the content of CBI can be reduced. When the acidity of the XDI composition is too low, the content of CBI can be relatively increased.

[0048] Therefore, by balancing the acidity and CBI content, an appropriate reaction rate can be maintained within the range defined in Formula 1. Thus, optical products that simultaneously suppress the formation of byproducts such as oligomers and prevent streaks / cloudiness can be obtained. Furthermore, the long-term stability of the composition can be ensured.

[0049] According to an exemplary embodiment, the reactivity or reaction rate factor can be adjusted by weighting the CBI content, represented by A, and the acidity of the XDI composition, represented by B. For example, as shown in Formula 1, this can be achieved by giving a weight to acidity that is more sensitive to the physical properties of polymeric optical compositions or optical products such as lenses, compared to the CBI content.

[0050] Therefore, it is possible to achieve more effective and precise suppression of byproduct generation and control of reaction rate.

[0051] In a preferred embodiment, the value according to Formula 1 is greater than 400 and may be less than 600. More preferably, the value according to Formula 1 may be 410 to 580, or 430 to 580.

[0052] As described above, according to the exemplary embodiments, by taking both CBI content and acidity as reactivity / stability control factors for the XDI composition, the desired lens properties can be tuned more precisely and stably.

[0053] For example, even if the CBI content is in the range of about 600 to 1000 ppm as described above, it may deviate from the range defined in Formula 1 when the acidity is too high or too low.

[0054] Furthermore, in one instance, when the acidity is too high, the CBI content can be controlled to be low and adjusted to the range defined in Formula 1. In another instance, when the acidity is too low, the CBI content can be controlled to be high and adjusted to the range defined in Formula 1.

[0055] Therefore, when CBI content and acidity are mutually complementary and controlled together, the degradation of the physical properties of the optical lens caused by either CBI content or acidity can be suppressed.

[0056] In one embodiment, the acidity of the XDI composition can be adjusted in the range of about 100 to 350 ppm. Preferably, the acidity of the XDI composition can be in the range of 100 to 250 ppm, more preferably in the range of 110 to 230 ppm.

[0057] In some embodiments, an acidity regulator can be used to adjust the acidity of the XDI composition. For example, the acidity of the XDI composition can be adjusted to meet the range of Formula 1 by introducing an acidity regulator during the distillation process described below.

[0058] Acidity regulators may include inorganic acid compounds, organic acid compounds, or solid acids.

[0059] Examples of inorganic acid compounds may include, for example, halogen acids such as hydrochloric acid, hydrobromic acid, and iodic acid, sulfuric acid, phosphoric acid and phosphoric acid derivatives, or Lewis acids such as SOCl2 or SO2Cl2 that can release chloride ions.

[0060] In one embodiment, the phosphoric acid derivative may include, for example, a phosphate ester compound or a phosphonate compound. For example, the phosphoric acid derivative may include a compound of the following structural formula 1.

[0061] [Structure 1]

[0062]

[0063] In structure 1, n is 1 or 2.

[0064] Examples of organic acid compounds may include acetic acid, benzoic acid, formic acid, trifluoroacetic acid (TFA), fatty acids, aliphatic or alicyclic carboxylic acid halides (e.g., acetyl chloride, trichloroacetyl chloride, or N-chloroacetamide or N-bromosuccinimide); aromatic carboxylic acid halides (e.g., benzoyl chloride, phthaloyl chloride, terephthaloyl chloride, isophthaloyl chloride); aromatic, aliphatic or alicyclic carbamoyl chlorides (e.g., N-phenylcarbamoyl chloride, tert-butylcarbamoyl chloride); acidic chlorosilane compounds (e.g., trimethylsilyl chloride, trimethylsilyl trifluoromethanesulfonate); and sulfonyl halides (e.g., p-toluenesulfonyl chloride), etc.

[0065] Examples of solid acids may include acidic clay, silica-alumina, cation exchange resins, acid-impregnated silica gel, or solid acids such as alumina, aluminum oxide, or vanadium oxide.

[0066] In some embodiments, the acidity regulator may include a basic compound that does not substantially react with XDI. For example, the acidity regulator may include cyclic amines such as imidazole, tetrazolium, or pyridine, or tertiary amines such as N,N-dimethylaniline (PhNMe2), triethylamine, and trimethylamine.

[0067] In one embodiment, the XDI content in the XDI composition may be 90% by weight (“wt.%”) or more, 95% by weight or more, or 99% by weight or more, for example, 99% by weight or more and less than 100% by weight.

[0068] According to another aspect of the present invention, a method for preparing an XDI composition is provided.

[0069] For example, the phenylenediamine diisocyanate (XDI) included in the XDI composition can be synthesized from phenylenediamine.

[0070] In some embodiments, XDI can be synthesized from phenylenediamine via a phosgene process. For example, phenylenediamine can be reacted with concentrated hydrochloric acid in a solvent to generate an amine salt. XDI can then be synthesized by reacting the amine salt with phosgene (COCl2) (see Scheme 1 below).

[0071] [Option 1]

[0072]

[0073] In some embodiments, XDI can be synthesized from phenylenediamine via the biphosgene method. For example, phenylenediamine can react with concentrated hydrochloric acid to form an amine salt. The amine salt can then react with a halodialkyl carbonate to form a dicarboxylate. XDI can be synthesized by thermally decomposing or degassing the dicarboxylate in the presence of a catalyst (see Scheme 2 below).

[0074] [Option 2]

[0075]

[0076] As shown in Scheme 2, bis(trichloromethyl) carbonate (BTMC) can be used as an example of halodialkyl carbonate.

[0077] 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 biscarbamate 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, preferably 120°C to 140°C.

[0078] After the addition is complete, the reaction can proceed for approximately 1 to 8 hours, or 2 to 6 hours, preferably 3 to 5 hours, while the mixture is stirred.

[0079] Subsequently, degassing can be performed by supplying an inert gas to the reaction solution while maintaining the temperature within the aforementioned range. The reaction solution can then be cooled, and the prepared XDI composition can be obtained through filtration and drying.

[0080] For example, after degassing, the reaction solution can be cooled to about 5°C to 20°C, preferably about 10°C to 20°C, more preferably about 10°C to 15°C. Thereafter, a ceramic filter, such as a diatomaceous earth filter, can be used to filter the prepared XDI composition.

[0081] In some implementations, a further distillation process can be performed to remove the inert solvent and extract the XDI. For example, a first distillation for removing the inert solvent and a second distillation for extracting the XDI can be performed sequentially.

[0082] The first distillation temperature can be adjusted appropriately based on the boiling point of the inert solvent. The second distillation can be carried out at a second distillation temperature greater than or equal to the boiling point of XDI.

[0083] Inert solvents may include organic solvents that are substantially non-reactive with amine salts, XDI, and halodialkyl carbonates. Furthermore, organic solvents with boiling points lower than that of XDI can be used for the distillation process described above.

[0084] In one embodiment, the inert solvent may include chlorinated aromatic hydrocarbons, such as monochlorobenzene, dichlorobenzene, trichlorobenzene, and chloroethylbenzene.

[0085] For example, the first distillation temperature can be 40°C to 80°C, preferably 50°C to 70°C, and more preferably 55°C to 65°C.

[0086] In an exemplary embodiment, the CBI content in the XDI composition can be adjusted to the above-mentioned range by controlling the temperature of the distillation process.

[0087] In some embodiments, the second distillation temperature can be adjusted within the range of 110°C to 135°C. For example, XDI extraction or purification can be sufficiently carried out within the second distillation temperature range, and excessive increases in CBI content (e.g., greater than 1,000 ppm) can be prevented. Preferably, the second distillation temperature can be from 110°C to 130°C, more preferably from 110°C to 120°C.

[0088] According to an exemplary embodiment, the acidity regulator described above can be added during the distillation process. For example, if the acidity of the prepared XDI composition prepared as described above is measured and exceeds the range defined in Formula 1, the acidity regulator can be added during the second distillation process.

[0089] When the value of Formula 1 in the prepared XDI composition is less than 400, an acidic acidity regulator may be added. The acidity regulator may include the aforementioned inorganic acid compounds, organic acid compounds, or solid acids. Preferably, for fine acidity adjustment, a liquid organic acid compound may be used.

[0090] When the value of Formula 1 in the preparation of the XDI composition exceeds 750, the aforementioned basic compound, such as imidazole, may be added.

[0091] In a preferred embodiment, imidazole can be used as an acidity regulator. In some embodiments, the amount of imidazole introduced can be about 500 to 10,000 ppm of the prepared XDI composition.

[0092] Within the aforementioned range, the appropriate acidity and reactivity of the XDI composition can be easily maintained. Therefore, lens clouding due to excessively high acidity or streaking and chemical instability due to excessively low acidity can be suppressed.

[0093] Furthermore, according to another aspect of the present invention, an optical composition (e.g., an optically polymerizable composition) comprising the XDI composition prepared as described above is provided.

[0094] Polymerizable compositions may include polythiol compounds and XDI compositions.

[0095] Polythiol compounds can include trifunctional polythiol compounds and / or tetrafunctional polythiol compounds.

[0096] Non-limiting examples of trifunctional polythiol compounds may include compounds represented by the following chemical formula 1.

[0097] [Chemical Formula 1]

[0098]

[0099] Trifunctional polythiols can be synthesized from, for example, polyols obtained by reacting with 2-mercaptoethanol and epihaloethanol.

[0100] Under acidic conditions, polyol compounds react with thiourea to form thiourea salt, which can then be hydrolyzed under alkaline conditions to prepare trifunctional polythiool compounds.

[0101] Non-limiting examples of tetrafunctional polythiols may include compounds represented by formulas 2-1 to 2-3 below.

[0102] [Equation 2-1]

[0103]

[0104] [Equation 2-2]

[0105]

[0106] [Equation 2-3]

[0107]

[0108] Tetrafunctional polythiols can be synthesized, for example, from polyols obtained by reacting with 2-mercaptoethanol and epihaloethanol. The polyols can then react with metal sulfides to generate tetrafunctional polyol intermediates. Following the reaction of the tetrafunctional polyol intermediate with thiourea under acidic conditions to generate thiourea onium salts, the tetrafunctional polythiols can be prepared by hydrolysis under alkaline conditions.

[0109] The optical composition may further include additives such as mold release agents, reaction catalysts, heat stabilizers, ultraviolet absorbers, and bluing agents.

[0110] 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; and acidic phosphate esters. These may be used alone or in combination of two or more thereof.

[0111] As reaction catalysts, catalysts used in the polymerization reaction of polysulfururethane resins can be used. For example, dialkyltin halide catalysts such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylate catalysts such as dimethyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate; alkoxydialkyltin catalysts such as dibutoxydibutyltinane and dibutoxydioctyltinane; dithioalkoxydialkyltin catalysts such as di(thiobutoxy)dibutyltin; dialkyltin oxide catalysts such as di(2-ethylhexyl)tin oxide, dioctyltin oxide and bis(butoxydibutyltin) oxide; and dialkyltin sulfide catalysts, etc. These can be used alone or in combination of two or more.

[0112] Examples of UV absorbers include compounds based on benzophenone, benzotriazole, salicylates, cyanoacrylates, and N,N'-oxalyldiphenylamine. Examples of heat stabilizers include compounds based on metal fatty acid salts, phosphorus, lead, and organotin compounds. These can be used alone or in combination of two or more.

[0113] Bluing agents can be included as color control agents for optical materials prepared from polyurethane resins. For example, a bluing agent may have an absorption band in the visible light region ranging from orange to yellow wavelengths.

[0114] Examples of bluing agents can include dyes, fluorescent whitening agents, fluorescent pigments, and 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, for example, dyes with 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.

[0115] In some embodiments, based on the total weight of the optical composition, it may include a polythiol compound in an amount of about 40 wt.% to 60 wt.%, an isocyanate compound in an amount of about 40 wt.% to 60 wt.%, and additives in an amount of about 0.01 wt.% to 1 wt.%.

[0116] Polyurethane resins can be produced by the polymerization reaction of polythiol compounds included in an optical composition and XDI.

[0117] As described above, the XDI composition used in the optical composition can be adjusted to satisfy Formula 1, thereby appropriately controlling the reactivity or reaction rate with polythiol compounds. Therefore, while suppressing cloudiness originating from the XDI composition itself, cloudiness in optical lenses manufactured using the optical composition can also be prevented.

[0118] Furthermore, through a stable polymerization reaction, optical lenses with a uniform refractive index and no streaking phenomenon can be produced.

[0119] In some embodiments, the reaction rate of the optical composition included in Formula 1 below can be adjusted to 0.15 to 0.23, preferably to 0.18 to 0.23, more preferably to 0.20 to 0.23, or 0.21 to 0.23.

[0120] Furthermore, according to another aspect of the present invention, an optical product manufactured using the above-described optical composition can be provided.

[0121] For example, after degassing the optical composition under reduced pressure, the resulting product can be injected into a mold used to shape the optical material. Injection into the mold can be carried out in a temperature range, for example, from 20°C to 40°C.

[0122] After injection into the mold, the temperature can be gradually increased to carry out the polymerization reaction of the polyurethane resin. The polymerization temperature can be from 20°C to 150°C, preferably from 25°C to 130°C.

[0123] The polymerization temperature can be from 20°C to 150°C, preferably from 25°C to 130°C. For example, the maximum polymerization temperature can be in the range of 100°C to 150°C, preferably from 110°C to 140°C, and more preferably from 115°C to 130°C.

[0124] The heating rate can be 1 to 10°C / min, preferably 3 to 8°C / min, more preferably 4 to 7°C / min. The polymerization time can be 10 to 20 hours, preferably 15 to 20 hours.

[0125] After polymerization, the polymerized polyurethane resin can be separated from the mold to obtain an optical product. In one embodiment, after separation from the mold, a curing process can be further performed. The curing process can be carried out for about 1 to 10 hours, preferably 2 to 8 hours, and more preferably 2 to 6 hours, within the range of 100°C to 150°C, preferably 110°C to 140°C, more preferably 115°C to 130°C.

[0126] Optical products can be manufactured in the form of eyeglass lenses, camera lenses, light-emitting diodes, etc., depending on the shape of the mold.

[0127] 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 polymeric composition for optical materials. For example, the refractive index of an optical product can be adjusted in 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 in the range of 1.65 to 1.75 or 1.69 to 1.75.

[0128] Optical products can be improved by further surface treatments such as antifouling, coloring, hard coating, surface polishing, and hardening.

[0129] The embodiments provided in this application will be further described below with reference to specific experimental examples. However, the following experimental examples are merely illustrative of the invention and are not intended to limit the appended claims, and those skilled in the art will clearly understand that various changes and modifications are possible within the scope and spirit of the invention. Such changes and modifications are suitably included in the appended claims.

[0130] Example 1

[0131] (1) Preparation of phenylenediamine (XDA) hydrochloride

[0132] 1009.4 g (9.46 mol) of 35% hydrochloric acid solution was introduced into the reactor, and the reactor was cooled to reduce the internal temperature to the range of 15°C to 20°C while stirring. Then, while maintaining the reactor temperature in the range of 20°C to 60°C, 600.0 g (4.4 mol) of m-phenylenediamine (m-XDA) was slowly introduced.

[0133] After the introduction of m-XDA, the reactor was cooled to reduce the internal temperature to the range of 10°C to 20°C. 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 the range of -5°C to 0°C, and the reaction was carried out for 1 hour with further stirring.

[0134] After the reaction is complete, the mixture is vacuum filtered and then dried under external temperature conditions outside the reactor and 0.1 torr vacuum pump conditions in the range of 90°C to 100°C to remove residual solvent and moisture, thereby obtaining m-XDA hydrochloride.

[0135] (2) Preparation of phenyl dimethyl diisocyanate composition

[0136] 800g of m-XDA hydrochloride prepared in (1) above and 3,550g of o-dichlorobenzene (ODCB) were introduced into the reactor, and the reactor was heated while stirring to raise the internal temperature to about 125°C.

[0137] Dissolve 950g of bis(trichloromethyl) carbonate (BTMC) and 800g of ODCB while stirring at approximately 60°C. Then, reduce the reactor temperature to 125°C over 24 hours to prevent precipitation. After the addition is complete, premix for 4 hours.

[0138] After the reaction was complete, N2 gas was supplied to the reaction solution at 125°C, and degassing was carried out simultaneously with bubbling. After cooling the degassed reaction solution to 10°C, the remaining solids were filtered using a Celite 545 filter.

[0139] The filtered organic solvent and the synthesized crude XDI were purified by distillation under the following conditions. During the second distillation, 2,000 ppm of imidazole was introduced.

[0140] 1) Removal of organic solvent (ODCB) (first distillation)

[0141] - Vacuum: below 0.5 torr

[0142] - Distillation column bottom temperature: 60℃

[0143] - Distillation time: 8 hours

[0144] 2) XDI distillation (second distillation)

[0145] - Vacuum: below 0.5 torr

[0146] - Distillation column bottom temperature: 120℃

[0147] - Distillation time: 10 hours

[0148] (3) Preparation of polymeric compositions for optical materials and lenses

[0149] 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 phenylenediethylene diisocyanate synthesized according to the above, 0.01 wt. parts of dibutyltin chloride, and 0.1 wt. parts of... The phosphate release agent produced by UN Stepan is uniformly mixed and then defoamed at 600 Pa for 1 hour to prepare a polymeric composition for optical materials.

[0150] The resin composition, filtered through a 3μm Teflon filter, was injected into a mold comprising a glass mold and adhesive tape. The mold was held at 10°C to 25°C for 8 hours, then the temperature was slowly increased to 130°C at a constant rate over 8 hours, and polymerization was carried out at 130°C for 2 hours. After polymerization, the mold was removed, and the product was further cured at 120°C for 2 hours to prepare a lens sample.

[0151] Examples 2-8 and Comparative Examples

[0152] Except for the changes in the column bottom temperature and imidazole addition during the second distillation process as described in Table 1 below, the XDI composition and lens sample were prepared in the same manner as in Example 1.

[0153] Experimental Example

[0154] (1) Measurement of CBI content

[0155] The XDI composition prepared as described above was analyzed by gas chromatography (GC) under the following conditions to measure the molar number of chloromethylbenzyl isocyanate and the content of CBI was measured by its conversion.

[0156] GC measurement conditions

[0157] i) Device Name: Agilent 6890 / 7890

[0158] ii) Carrier gas: He

[0159] iii) Syringe: 250℃

[0160] iv) Oven temperature: 40℃ to 320℃

[0161] v) Column: HP-1, Wax, 30m

[0162] vi) Detector: FID, 300℃

[0163] (2) Measurement of acidity

[0164] Quantitatively measure 20g of the prepared XDI composition sample and introduce it into a 200ml beaker. Add 100ml of solvent (acetone and ethanol mixed in a 1:1 weight ratio) to the beaker and heat on a hot plate to dissolve the sample. Then, mix the solution at room temperature for 10 to 20 minutes.

[0165] Then, according to JIS K4101, using an automatic measuring device (Hiranuma COM-500), the acidity is calculated according to the following formula, thereby using a solution (N / 100 potassium hydroxide solution) prepared by diluting and expressing 0.1 mol / L potassium hydroxide in methanol to form a titration curve, and the rising point of the curve is used as the endpoint.

[0166] Acidity = 0.0365 × (AB) × f / S

[0167] A: The actual volume (ml) of 0.1 mol / L potassium hydroxide in the titration.

[0168] B: Volume (ml) of 0.1 mol / L potassium hydroxide in methanol used for titrating a control without sample measurement.

[0169] f: Correction factor for N / 100 methanol-potassium hydroxide solution

[0170] S: Weight of the sample introduced (g)

[0171] (3) Evaluation of the turbidity of the XDI composition

[0172] After storing the XDI compositions of the examples and comparative examples in a dark room at 25°C for 3 months, the stock solutions of the compositions were visually observed and evaluated as follows.

[0173] ○: Completely transparent

[0174] △: Partial fog was observed.

[0175] X: Complete fog clearly observed

[0176] (4) Evaluation of lens properties

[0177] 1) Evaluation of stripes

[0178] As described above, lens samples with a diameter of 75 mm and -4.00D were prepared using the polymerizable compositions according to the various embodiments and comparative examples. Light from a mercury lamp light source was transmitted through the prepared lens samples, and the transmitted light was projected onto a white board to determine the presence or absence of stripes based on the presence or absence of contrast. The evaluation criteria are as follows.

[0179] ○: No stripes observed

[0180] △: Fine partial stripes were observed.

[0181] X: Stripes are clearly visible to the naked eye.

[0182] 2) Evaluation of lens opacity

[0183] For the lens samples of the embodiments and comparative examples prepared as described above, each sample was illuminated in a dark room with a beam of light from a projector, and the presence of haze or opaque material in the lens was visually confirmed.

[0184] The evaluation criteria are as follows.

[0185] ○: No fog

[0186] △: Partial fog was observed.

[0187] X: The overall haze was clearly observed.

[0188] 3) Measurement of polymerization rate (reactivity slope)

[0189] Using an EMS-1000 (KEM) non-contact viscometer, 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 examples and comparative examples was measured at 10°C for 24 hours. The measured values ​​were mathematically formulated (“mathematicalized”) with time on the X-axis and viscosity on the Y-axis, while the Y-axis was converted to a logarithmic scale as shown in Equation 1 below, from which the reaction rate was derived.

[0190] [Mathematical Expression 1]

[0191] Y = a × exp(b × X)

[0192] In mathematical formula 1, the value of 'a' represents the initial viscosity (cps), while the value of 'b' represents the reaction rate. The measured values ​​are rounded to two decimal places.

[0193] 4) Measurement of color index (yellow index (YI))

[0194] For the lens samples of the embodiments and comparative examples manufactured in the form of a plastic cylinder (r (radius) × H (height) = 16 mm × 45 mm), YI was measured by transmitting light in the height direction of the plastic cylinder using a UV / VIS spectrometer (PerkinElmer, UV / VIS Lambda 365).

[0195] Specifically, YI is calculated based on the values ​​of x and y using the following equation (1).

[0196] [Equation (1)]

[0197] YI=(234×x+106×y) / y

[0198] The evaluation results are shown together in Table 1 and Table 2 below.

[0199] [Table 1]

[0200]

[0201] [Table 2]

[0202]

[0203] Referring to Tables 1 and 2, in the embodiments where the value of Formula 1 was adjusted to the range of 400 to 750 as described above, turbidity of the composition and lens state was prevented, and an appropriate polymerization rate was obtained.

[0204] On the other hand, in Comparative Examples 4 and 5, where the value of Formula 1 was less than 400, excessive reactivity resulted in cloudiness of the composition and lens streaks. Referring to Comparative Examples 1 to 3, when the value of Formula 1 exceeded 750, yellowing of the lens occurred. Referring to Comparative Examples 6 to 9, when the value of Formula 1 exceeded 1,000, cloudiness of the lens occurred. Furthermore, as the polymerization rate decreased excessively, the yield of the lens samples decreased.

Claims

1. A phthalimide diisocyanate composition comprising phthalimide diisocyanate (XDI) and chloromethyl benzyl isocyanate (CBI), and satisfying the following formula 1, The content of the chloromethyl benzyl isocyanate is based on a total weight of the composition ranging from 600 to 1,000 ppm, and The acidity of the phthalimide diisocyanate composition is in the range of 110 to 350 ppm. [Formula 1] In Formula 1, "A" represents the CBI content value in the phthalimide diisocyanate composition converted to ppm, and "B" represents the acidity value of the phthalimide diisocyanate composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

2. The phthalimide diisocyanate composition according to claim 1, further comprising an acidity regulator.

3. An optical composition comprising: A phenylene diisocyanate composition comprising phenylene diisocyanate (XDI) and chloromethyl benzyl isocyanate (CBI) and satisfying the following formula 1; and Polythiol compounds, The content of the chloromethyl benzyl isocyanate is based on a total weight of the composition ranging from 600 to 1,000 ppm, and The acidity of the phthalimide diisocyanate composition is in the range of 110 to 350 ppm. [Formula 1] In Formula 1, "A" represents the CBI content value in the phthalimide diisocyanate composition converted to ppm, and "B" represents the acidity value of the phthalimide diisocyanate composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

4. The optical composition according to claim 3, further comprising an additive, said additive comprising 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.

5. An optical product comprising: A copolymer of phthalimide diisocyanate composition and polythiol compound, The phthalimide diisocyanate composition comprises phthalimide diisocyanate (XDI) and chloromethyl benzyl isocyanate (CBI), and satisfies the following formula 1. The content of the chloromethyl benzyl isocyanate is based on a total weight of the composition ranging from 600 to 1,000 ppm, and The acidity of the phthalimide diisocyanate composition is in the range of 110 to 350 ppm. [Formula 1] In Formula 1, "A" represents the CBI content value in the phthalimide diisocyanate composition converted to ppm, and "B" represents the acidity value of the phthalimide diisocyanate composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

6. A method for preparing a phenylenediamine diisocyanate composition, comprising: Benzene diisocyanate (XDI) is synthesized from phenylenediamine to form a preliminary composition comprising phenylenediamine; and The content and acidity of chloromethyl benzyl isocyanate (CBI) in the prepared composition were adjusted by a distillation process at a temperature of 110°C to 135°C. The regulating step includes controlling the distillation process to satisfy the following formula 1. The content of the chloromethyl benzyl isocyanate is based on a total weight of the composition ranging from 600 to 1,000 ppm, and The acidity of the phthalimide diisocyanate composition is in the range of 110 to 350 ppm. [Formula 1] In Formula 1, "A" represents the CBI content value in the phthalimide diisocyanate composition converted to ppm, and "B" represents the acidity value of the phthalimide diisocyanate composition converted to ppm. A and B respectively represent values ​​with ppm units omitted.

7. The method of claim 6, wherein the step of adjusting the acidity in the preparative composition comprises introducing imidazole in the range of 500 to 10,000 ppm during the distillation process.

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