Isocyanate composition, method for storing same, and non-foamed polyurethane and optical lens comprising same

Abstract

The present invention relates to: an optical lens in which, in manufacturing the optical lens, a UV blocking agent for blocking blue light is not used or the amount used is greatly reduced; non-foamed polyurethane used in the manufacture of the optical lens; an isocyanate composition used in the synthesis of the non-foamed polyurethane; and a method for storing the isocyanate composition.

Description

Isocyanate composition, storage method thereof, non-foamed polyurethane and optical lens comprising the same

[0001] The present invention relates to an optical lens in which a UV blocking agent for blocking blue light is not used or the amount of the UV blocking agent used is greatly reduced during the manufacture of the optical lens, a non-foamed polyurethane used in the manufacture of the optical lens, an isocyanate composition used in the synthesis thereof, and a storage method for the isocyanate composition.

[0002] Isocyanate compounds are raw materials for polyurethane, widely used in coatings, adhesives, paints, foams, and optical materials. In fields requiring superior appearance properties, particularly optical applications requiring transparency, polyurethanes require minimal discoloration. To achieve this, it is crucial that not only does the polyurethane polymer resist discoloration during the polyurethane reaction, but also that the raw isocyanate compounds themselves, particularly those with higher than difunctionality, remain discoloration-free.

[0003] However, since isocyanate compounds are highly reactive, they are easily oxidized by oxygen in the air during the storage process, or they form self-polymers, causing deterioration or discoloration. There was also a problem of discoloration or clouding occurring in optical products such as urethane lenses that applied them.

[0004] To this end, various methods have been studied and proposed to suppress discoloration in isocyanate compounds and products manufactured using them, such as sealing with nitrogen gas to block air and storing in a refrigerator, or storing by adding additives such as ultraviolet absorbers.

[0005] However, in order to use an isocyanate compound, it must be moved from the storage location to the atmospheric environment. During this process, the isocyanate compound may discolor or become cloudy depending on changes in the moisture content or temperature of the atmosphere. If an isocyanate compound that has discolored or become cloudy is used to manufacture optical lenses, there is a problem that the clarity is reduced, resulting in a deterioration in quality.

[0006] Additionally, there are difficulties in ensuring long-term storage stability of isocyanate compounds.

[0007] In addition, when manufacturing optical lenses, UV blockers are used for the purpose of blocking blue light. However, there is a problem in that if UV blockers are used in the composition for manufacturing optical lenses, the defect rate of the optical lenses increases or the optical characteristics decrease.

[0008] The present invention has been conceived to overcome the above-described problems, and as a result of various studies and attempts to find a method for reducing or eliminating the amount of UV blocking agent that may cause a defect rate and / or deterioration of physical properties of optical lenses, it has been found that when an appropriate amount of a specific compound is included in an isocyanate compound composition used in the synthesis of non-foamed polyurethane used in the manufacture of optical lenses, an optical lens having an appropriate blue light blocking rate can be manufactured without causing adverse effects on the optical lens by reducing the amount of UV blocking agent used in the polyurethane used in the manufacture of optical lenses, or even without using the same. That is, the present invention seeks to provide an isocyanate composition, a non-foamed polyurethane containing the same, and an optical lens manufactured using the same.

[0009] In addition, it is intended to provide a method for storing the above isocyanate composition.

[0010] To solve the above-described problem, the isocyanate composition of the present invention comprises a diisocyanate compound; and a nitrile group-containing compound including at least one selected from a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.

[0011] As a preferred embodiment of the present invention, the additive may include a compound represented by the following chemical formula 1, a compound represented by the following chemical formula 2, and a compound represented by the following chemical formula 3.

[0012] [Chemical Formula 1]

[0013]

[0014] [Chemical Formula 2]

[0015]

[0016] In the above chemical formulas 1 and 2, R 1 and R 2 are each independently -CH2-, -CH2CH2- or -CH2CH2CH2-, and R 3 is a hydrogen atom, a straight-chain alkyl group of C1 to C3, a branched alkyl group of C3 to C5, or a metal salt, a is an integer from 0 to 3, b is an integer from 0 to 5, and n is 1 or 2.

[0017] As a preferred embodiment of the present invention, the nitrile group-containing compound may be included in an amount of 700 ppm or less based on the total weight of the isocyanate composition.

[0018] As a preferred embodiment of the present invention, the isocyanate composition of the present invention can satisfy the following equation 1.

[0019] [Equation 1]

[0020] 0.50 ≤ B / (A + B) ≤ 0.80

[0021] In Equation 1, A is the content (pppm) of the compound represented by Chemical Formula 1 with respect to the total weight of the isocyanate composition, and B is the content (ppm) of the compound represented by Chemical Formula 2 with respect to the total weight of the isocyanate composition.

[0022] As a preferred embodiment of the present invention, the isocyanate composition of the present invention may further include a metal element including 1 to 10 ppm of aluminum element (Al) and 1 to 20 ppm of calcium element (Ca) as measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES).

[0023] As a preferred embodiment of the present invention, the metal element may be included at 2.0 ppm or less, including at least one selected from tin (Sn), iron (Fe), titanium (Ti), chromium (Cr), nickel (Ni), manganese (Mn), and magnesium (Mg).

[0024] As a preferred embodiment of the present invention, the diisocyanate compound may include at least one selected from 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, methylenediphenyl diisocyanate, methylenedicyclohexyl isocyanate, toluene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and o-xylylene diisocyanate.

[0025] As a preferred embodiment of the present invention, the diisocyanate compound may include m-xylylene diisocyanate.

[0026] As a preferred embodiment of the present invention, in Chemical Formula 1 and / or Chemical Formula 2, R 1 and R 2 are each independently -CH2- or -CH2CH2, and R3 is a hydrogen atom or a metal salt, a is an integer from 0 to 2, b is an integer from 0 to 3, and n can be 1.

[0027] As a preferred embodiment of the present invention, the isocyanate composition of the present invention can satisfy the following condition (1).

[0028] (1) 0.001% ≤ H b - H a ≤ 4.0%

[0029] In the above condition (1), H a represents the haze value of the isocyanate composition, and H b It represents the haze value measured after storing the isocyanate composition under conditions of a temperature of 20°C or lower and a relative humidity of 1% or lower for 70 to 110 days.

[0030] Meanwhile, the method for storing the isocyanate composition of the present invention can store the isocyanate composition described above under conditions of a nitrogen-substituted atmosphere, a temperature of 20°C or lower, and a relative humidity of 1% or lower.

[0031] In addition, the polyurethane of the present invention is a non-foaming polyurethane as an optical resin, and is synthesized using the isocyanate composition described above.

[0032] Furthermore, the optical lens of the present invention may include the polyurethane.

[0033] As a preferred embodiment of the present invention, the optical lens of the present invention may have a yellowness (YI) of 5.0 or less.

[0034] As a preferred embodiment of the present invention, the optical lens of the present invention may have an absorbance of 0.30% or less, preferably 0.15 to 0.30%, for a wavelength of 415 nm, even though no UV blocking agent is additionally used.

[0035] The isocyanate composition of the present invention and the storage method of the isocyanate composition using the same can have excellent storage stability.

[0036] In addition, when manufacturing an optical lens with polyurethane using an isocyanate composition, the amount of UV blocking agent used can be greatly reduced or its use can be eliminated, thereby reducing the defect rate in manufacturing the optical lens, and a transparent optical material (e.g., an optical lens) having excellent optical properties with low absorbance for blue light and improved yellowness (YI) can be manufactured.

[0037] Hereinafter, the present invention will be described in more detail.

[0038] Various methods have been studied and proposed to suppress discoloration in existing isocyanate compounds and products manufactured using them, such as sealing with nitrogen gas to block air and storing in a refrigerator, or storing them using additives such as ultraviolet absorbers. However, in order to use isocyanate compounds, they must be moved from their storage location to the open air. During this process, the isocyanate compounds may discolor or become cloudy depending on changes in the moisture content or temperature of the air. If discolored or cloudy isocyanate compounds are used to manufacture optical lenses, there is a problem of reduced clarity and deterioration in quality. In addition, it is difficult to ensure long-term storage stability of isocyanate compounds.

[0039] Additionally, there was a problem that the defect rate of optical lenses increased and the optical characteristics deteriorated due to the use of UV blockers to block blue light during the manufacturing of optical lenses.

[0040] Accordingly, the present invention relates to an isocyanate composition comprising a diisocyanate compound; and a nitrile group-containing compound; wherein, when a specific compound, a nitrile group-containing compound, is included in the isocyanate composition used for polyurethane synthesis, the specific compound remains in the polyurethane, and the nitrile group-containing compound functions as a UV blocker, so that optical products such as optical lenses made of the polyurethane have an excellent blue light blocking effect. That is, by significantly reducing or eliminating the use of UV blockers in polyurethane, an increase in the defect rate and a deterioration in optical properties of optical products due to the use of UV blockers can be prevented.

[0041]

[0042] In the isocyanate composition of the present invention, the diisocyanate compound may include at least one selected from among 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, methylenediphenyl diisocyanate, methylenedicyclohexyl isocyanate, toluene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and o-xylylene diisocyanate, and preferably, m-xylylene diisocyanate.

[0043] And, in the isocyanate composition of the present invention, the nitrile group-containing compound includes at least one selected from a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.

[0044] [Chemical Formula 1]

[0045]

[0046] [Chemical Formula 2]

[0047]

[0048] In the above chemical formulas 1 and 2, R 1 and R 2 are each independently -CH2-, -CH2CH2- or -CH2CH2CH2-, preferably -CH2- or -CH2CH2, and more preferably -CH2-.

[0049] Also, the above R 3 is a hydrogen atom, a C1~C3 straight-chain alkyl group, a C3~C5 branched alkyl group or a metal salt, preferably a hydrogen atom or a metal salt, and more preferably a hydrogen atom. In this case, the metal salt is Na + , K + It is a monovalent cationic metal salt such as the following.

[0050] In addition, the above a is an integer from 0 to 3, preferably a is an integer from 0 to 2, and preferably a is 0 or 1. And, the above b is an integer from 0 to 5, preferably an integer from 0 to 3, and more preferably an integer from 0 to 2.

[0051] And, the above n is 1 or 2, and preferably 1.

[0052]

[0053] The above nitrile group-containing compound may be a by-product and / or compound generated in the process of synthesizing a diisocyanate compound, and is generally removed in the purification process during the process of synthesizing a diisocyanate compound. The present invention controls the amount of the nitrile group-containing compound removed in the purification process so that it is contained in the isocyanate compound within a specific content range. The content of the nitrile group-containing compound in the isocyanate composition for synthesizing a polyurethane using the above composition and improving optical properties while reducing the defect rate when manufacturing an optical lens with the synthesized polyurethane is 700 ppm or less, preferably 30 to 700 ppm, more preferably 50 to 500 ppm, even more preferably 60 to 480 ppm, and even more preferably 350 to 450 ppm, based on the total weight of the isocyanate composition. The purification process is performed so as to include the nitrile group-containing compound within this content range. If, after the purification process, the nitrile group-containing compound in the isocyanate composition is below the content range below, the isocyanate composition may be manufactured by optionally adding these compounds.

[0054] In addition, the nitrile group-containing compound may include only the nitrile group-containing compound represented by the above chemical formula 1 or the nitrile group-containing compound represented by the above chemical formula 2, and preferably, it is advantageous in terms of the UV blocking effect and low yellowness of the optical lens to include both the nitrile group-containing compound represented by the above chemical formula 1 and the nitrile group-containing compound represented by the above chemical formula 2, and more preferably, it is good to include the nitrile group-containing compound within a range satisfying the following Equation 1.

[0055] [Equation 1]

[0056] 0.50 ≤ B / (A + B) ≤ 0.80, preferably 0.55 ≤ B / (A + B) ≤ 0.80, more preferably 0.60 ≤ B / (A + B) ≤ 0.75

[0057] In Equation 1, A is the content (pppm) of the compound represented by Chemical Formula 1 with respect to the total weight of the isocyanate composition, and B is the content (ppm) of the compound represented by Chemical Formula 2 with respect to the total weight of the isocyanate composition.

[0058]

[0059] In addition, the isocyanate composition of the present invention may contain a metal element as a by-product generated during the synthetic process, and generally, the metal element in the isocyanate composition generally reduces the optical properties of the optical lens. However, a specific metal element may have a synergistic effect in terms of the UV blocking effect in the presence of a nitrile group-containing compound, and such metal elements include aluminum element (Al) and / or calcium element (Ca), and in terms of such effect, the isocyanate composition of the present invention may contain 1 to 15 ppm of aluminum element (Al) and 1 to 20 ppm of calcium element (Ca), preferably 1.2 to 10.0 ppm of aluminum element (Al) and 3.0 to 17.0 ppm of calcium element (Ca), and more preferably 1.2 to 6.0 ppm of aluminum element (Al) and 3.0 to 15.0 ppm of calcium element (Ca).

[0060] The composition of the present invention does not contain metal elements other than Al and Ca, which is advantageous in terms of preventing deterioration of the optical properties of polyurethane and optical lenses manufactured therefrom. Therefore, the isocyanate composition of the present invention may contain metal elements other than Al and Ca in an amount of 2.0 ppm or less, preferably 1.0 ppm or less, more preferably 0.5 ppm or less, or may not exist. In this case, the metal elements other than Al and Ca may include at least one selected from tin (Sn), iron (Fe), titanium (Ti), chromium (Cr), nickel (Ni), manganese (Mn), and magnesium (Mg).

[0061] The isocyanate composition of the present invention has excellent long-term storage stability and can satisfy the following condition (1).

[0062] (5) 0.001% ≤ H b - H a ≤ 4.0%, preferably 0.001% ≤ H b - H a ≤ 3.0%, more preferably 0.003% ≤ H b - H a ≤ 2.0%, more preferably 0.005% ≤ H b - H a ≤ 1.0%, more preferably 0.005% ≤ H b - H a ≤ 0.5%

[0063] In the above condition (1), H a represents the haze value of the isocyanate composition, and H b It represents the haze value measured after storing the isocyanate composition under conditions of a temperature of 20°C or lower and a relative humidity of 1% or lower for 70 to 110 days.

[0064]

[0065] Furthermore, it is preferable that the isocyanate composition of the present invention be stored under a nitrogen-substituted atmosphere at a temperature of 20°C or lower and a relative humidity of 1% or lower, preferably under a nitrogen-substituted atmosphere at a temperature of 0 to 20°C or lower and a relative humidity of 0.001 to 1%, and more preferably under a nitrogen-substituted atmosphere at a temperature of 5 to 15°C or lower and a relative humidity of 0.001 to 0.1%. At this time, if the storage temperature exceeds 20°C, not only may the storage stability deteriorate, but also haze may increase, causing a problem in that an optical lens manufactured using the composition may be opaque and / or in that an optical lens may not be manufactured using the composition. If the relative humidity exceeds 1%, not only may the storage stability deteriorate, but also haze may increase, causing a problem in that an optical lens manufactured using the composition may be opaque.

[0066] [Method for manufacturing composition]

[0067] The method for producing the isocyanate composition of the present invention described above is as follows.

[0068] The above isocyanate composition is synthesized by reacting an amine compound with phosgene in a solvent.

[0069] Solvents that can be used in the above phosgenation reaction include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; chlorinated aromatic hydrocarbon solvents such as monochlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. Two or more of these can be used in combination.

[0070] The amine compound used in the above phosgenation reaction may be, for example, an amine compound obtained by hydrogenating a nitro compound or a chloride thereof. Specifically, the amine compound may be at least one selected from the group consisting of 1,4-tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,3-cyclohexylene diamine, 1,4-cyclohexylene diamine, isophorone diamine, diamine, methylenediphenyl diamine, methylenedicyclohexyl diamine, toluene diamine, m-xylylene diamine, p-xylylene diamine, and o-xylylene diamine, and salts thereof, and preferably m-xylylene diamine, p-xylylene diamine, o-xylylene diamine, or a salt thereof.

[0071] The above amine compound may be included in an amount of 1 to 20 parts by weight per 100 parts by weight of the solvent. If the content of the amine compound exceeds 20 parts by weight, there is a risk of precipitation of a large amount of the amine compound. Preferably, the content may be included in an amount of 1 to 15 parts by weight or 3 to 10 parts by weight.

[0072] Specifically, the phosgenation reaction can be carried out by a direct phosgenation method (Method 1) in which an amine compound is directly reacted with phosgene; a method in which an amine compound is reacted with anhydrous hydrochloric acid to form an amine-hydrochloride compound and then the formed salt is reacted with phosgene (Method 2); or a method in which an amine compound is reacted with carbonic acid to form an aliphatic amine-carbonate compound and then the formed salt is reacted with phosgene (Method 3).

[0073] The direct phosgenation method of the above method 1 can be performed by reacting an amine compound and phosgene in the above organic solvent. At this time, the phosgene can be introduced all at once at the beginning of the reaction, or can be introduced in part at the beginning of the reaction and the remainder can be introduced in installments during the reaction.

[0074] Meanwhile, the above method 1 can be performed by a first step of dissolving a portion of phosgene in the solvent and then adding the amine compound; and a second step of adding the remaining phosgene after the addition of the amine compound is complete and causing a reaction. At this time, the first step is preferably performed at a temperature of -15°C to -10°C to prevent leakage of highly toxic phosgene and also to prevent rapid heat generation when the amine compound is added, and the phosgenation reaction in the second step can be controlled to 120°C to 140°C so that the reaction can occur at an appropriate reaction rate without concern for decomposition of the amine compound.

[0075] In the case of the above method 2, it can be carried out by a step of reacting an amine compound with hydrochloric acid in an organic solvent to form an amine-hydrochloride compound, and then introducing phosgene to cause the reaction. The formation of the amine-hydrochloride compound can be carried out at a temperature of 30°C or lower, preferably at a temperature of about 23±5°C, and the reaction after the introduction of phosgene can be controlled to 120°C to 140°C. When carried out under such temperature conditions, the solubility of the amine-hydrochloride compound can be increased, and thermal decomposition of the isocyanate can be prevented, thereby producing a high-purity isocyanate compound in high yield.

[0076] In the case of the above method 3, it can be carried out by a step of reacting an amine compound with carbonic acid in a solvent to form an amine-carbonate compound, and then introducing phosgene to cause the reaction. At this time, the formation of the amine-carbonate compound can be carried out at a temperature of 30°C or lower, preferably about 23±5°C, and the reaction after the introduction of phosgene can be controlled to 80°C to 180°C. Preferably, it can be in the range of 100°C or higher, or 120°C or higher, and 150°C or lower, or 140°C or lower. When carried out under such temperature conditions, the solubility of the amine-carbonate compound is increased, and thermal decomposition of the isocyanate is prevented, thereby producing a high-purity isocyanate compound in a high yield.

[0077] After the reaction with phosgene is completed according to each method, a removal process such as nitrogen bubbling for unreacted phosgene and hydrogen chloride gas and a solvent removal process such as distillation may be optionally further performed, and these processes may be performed according to a conventional method.

[0078] And, after completing the reaction with phosgene according to each method and / or performing the solvent removal process, a purification process is performed to remove inorganic impurities such as organic impurities and metal elements in the produced isocyanate compound, and preferably, the purification process is performed under specific conditions using a thin film distillation device (or system, TFE), so that the content of a specific nitrile group-containing compound and a specific metal element in the isocyanate compound can be controlled.

[0079] As a preferred example of the conditions for the purification process using the above TFE, the isocyanate compound feeding temperature is 75 to 150°C, the feeding rate is 8 to 35 ml / min, the TFE distillation temperature is 130 to 170°C, and the vacuum is 0.1 to 4.0 torr, and preferably, the process is performed under the conditions of the feeding temperature is 88 to 145°C, the feeding rate is 9 to 32 ml / min, the TFE temperature is 135 to 165°C, and the vacuum is 0.2 to 3.2 torr, and more preferably, the process is performed under the conditions of the feeding temperature is 90 to 142°C, the feeding rate is 9.5 to 31.0 ml / min, the TFE temperature is 138 to 162°C, and the vacuum is 0.3 to 3.0 torr. At this time, it is preferable to perform the purification process under the above conditions in terms of the effect of allowing the nitrile group-containing compound represented by Chemical Formula 1 and / or Chemical Formula 2 to remain in the synthesized isocyanate compound at a certain concentration without being completely removed, while allowing Al and Ca to remain within an appropriate range, and sufficiently removing other metal elements.

[0080]

[0081] The polyurethane of the present invention is a non-foaming polyurethane synthesized using the isocyanate composition described above.

[0082] In addition, the non-foamed polyurethane can be used for one or more purposes selected from automobiles, ships, coatings, adhesives, sealants, and elastomers.

[0083] In addition, the non-foamed polyurethane can be used as a transparent optical material, and when applied as a material for an optical lens, the amount of UV blocking agent used to provide a blue light blocking effect can be minimized or not used.

[0084] In addition, the optical lens may have a yellowness (YI) of 5.0 or less, preferably 0.1 to 4.5, and more preferably 0.5 to 4.0.

[0085] In addition, the optical lens of the present invention may have an absorbance of 0.30% or less, preferably 0.15 to 0.30%, for a wavelength of 415 nm, even though no UV blocking agent is additionally used.

[0086] Hereinafter, the present invention will be described in more detail through examples, but the following examples do not limit the scope of the present invention, and should be interpreted as helping to understand the present invention.

[0087] [Example]

[0088] Example 1-1: Preparation of isocyanate composition

[0089] A flask was filled with 471 g of 1,2-dichlorobenzene and 32.5 g of m-XDA (m-xylenediamine) with a purity of 99.4%, and anhydrous hydrochloric acid was injected at a rate of 20 g / hr while stirring at room temperature (23±5℃). The temperature rose to 50℃ as the anhydrous hydrochloric acid was injected.

[0090] After 4 hours of injection, the formed salt was cooled to room temperature, 43 ml of liquid phosgene was added to the reactor, and the reactor temperature was heated to 130°C. From the time of phosgene addition until the end of the reaction, a dry ice-acetone cooler was used to prevent phosgene from leaking to the outside. After the reactor temperature reached 130°C, the reactor temperature was maintained at 125-135°C for 2 hours to ensure that the reaction solution became transparent. After the solution became transparent, the inside of the reactor was cooled to 80°C and nitrogen was blown in to obtain a reaction solution from which phosgene was removed.

[0091] Next, the solvent was removed from the reaction solution from which phosgene had been removed through vacuum distillation, and the product was purified using a thin film distillation apparatus (TFE) to obtain an isocyanate composition containing m-XDI (m-xylene diisocyanate). At this time, the TFE purification conditions were a feeding temperature of 80°C, a TFE temperature of 160°C, a vacuum of 3 torr, and a feeding rate of 30 ml / min.

[0092] The above isocyanate composition contained 2 ppm of a nitrile group-containing compound represented by the following chemical formula 1-1 and 49 ppm of a nitrile group-containing compound represented by the following chemical formula 2-1.

[0093] [Chemical Formula 1-1]

[0094]

[0095] In the above chemical formula 1-1, R 1 is -CH2-, a is 1, b is 0, and n is 1.

[0096] [Chemical Formula 2-1]

[0097]

[0098] In the above chemical formula 2-1, R 2 is -CH2-, and R 3 is a hydrogen atom, a is 1, b is 0, and n is 1.

[0099]

[0100] Comparative Example 1-1

[0101] A reaction solution with phosgene removed was obtained using the same composition and method as in Example 1. Then, the solvent was removed through vacuum distillation, a conventional purification method, and the solution was decompressed at a bottom temperature of 148°C and a pressure of 0.6 mbar in a round flask to produce an isocyanate composition containing m-XDI (yield: 65%).

[0102]

[0103] Examples 1-2 to 1-5 and Comparative Examples 1-2 to 1-5

[0104] An isocyanate composition containing m-XDI was prepared using the same composition and method as in Example 1, but the purification process conditions were changed as shown in Table 1 below, and Examples 1-2 to 1-5 and Comparative Examples 1-2 to 1-5 were performed, respectively.

[0105] Classification Injection temperature TFE Temperature Vacuum degree Injection amount (speed) Example 1 - 180℃ 160℃ 3 torr 30ml / min Example 1 - 280℃ 140℃ 0.5 torr 10ml / min Example 1 - 3 1 10℃ 140℃ 1.5 torr 20ml / min Example 1 - 4 1 40℃ 150℃ 1.5 torr 20ml / min Example 1 - 5 80℃ 150℃ 3 torr 10ml / min Comparative Example 1 - 280℃ 127℃ 3 torr 30ml / min Comparative Example 1 - 3 80℃ 175℃ 3 torr 30ml / min Comparative Example 1 - 4 80℃ 160℃ 3 torr 36 ml / min

[0106]

[0107] Experimental Example 1: Measurement of Nitrile Compound and Metal Element Contents

[0108] The content of the nitrile compound represented by Chemical Formula 1-1 and / or Chemical Formula 2-1 and the content of the metal element of each of the isocyanate compositions manufactured in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 were measured, and the results are shown in Tables 2 and 3 below.

[0109] Content (ppm) of nitrile group-containing compound represented by Chemical Formula 1-1 Content (ppm) of nitrile group-containing compound represented by Chemical Formula 2-1 Example 1-1249 Example 1-2355 Example 1-3529 Example 1-43261 Example 1-5190112 Comparative Example 1-1320493 Comparative Example 1-2140213 Comparative Example 1-3173 Comparative Example 1-4228306

[0110] ClassificationAlSnFeTiCrNiMoMnNaCaMgExample 1-11.3ND<1NDNDNDNDND<13.8NDExample 1-24.5ND<1NDNDNDNDND<113<1Example 1-32.4ND<1NDNDNDNDND<113<1Example 1-42ND<1NDNDND<1ND<14.1NDExample 1-51.3ND<1NDNDNDNDND<19<1Comparative Example 1-129.6ND<1<1NDND3.2ND34.31.5<1Comparative Example 1-210.91.8<1NDNDND<1ND<121.72.7Comparative Example 1-37.2ND<1NDNDNDNDND2.223.36.7Comparative Example 1-427.42.2<1NDND<12.8<14.724.64.4

[0111] Looking at Tables 2 and 3 above, in the case of Comparative Example 1-1, which was manufactured by purification using a conventional purification process, the content of the nitrile group-containing compound was relatively very high compared to other examples, and in particular, the contents of Al and Na among the metal elements were high. In addition, Comparative Examples 1-2 and 1-3 had a Ca content exceeding 20 ppm, while the residual Mg was high, and Comparative Example 1-2 had residual Sn.

[0112] In addition, Comparative Examples 1-4 showed a relatively high content of nitrile-containing compounds compared to the examples, and showed high results not only in the Al content but also in the Ca content.

[0113]

[0114] Experimental Example 1: APHA Color and Haze Measurement

[0115] According to the method of ASTM E313, the APHA color and haze of each of the isocyanate compositions manufactured in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 were measured using Ultrascan Pro from HunterLab (light source: C / 2) and are shown in Table 4 below.

[0116] In addition, each of the isocyanate compositions manufactured in the examples and comparative examples was stored for 90 days under nitrogen-substituted atmosphere, temperature of 15°C, and humidity of 0.1% RH, and then the APHA color and haze of each of the stored isocyanate compositions were measured (light source: C / 2) and shown in Table 4 below.

[0117] The above APHA (Hazen color number) measurement was performed using a color difference analysis method under room temperature conditions according to ASTM D1003, and the Hazen color number was measured using a xenon lamp light source of Hunterlab's Ultrascane equipment.

[0118] Classification Haze (%) Haze (%) after 90 days of storage APHA color APHA color after 90 days of storage Example 1-10.30 0.36 4.4 2.6.4 3 Example 1-20.5 2.1.5 9 6.6 4 2.1.0 2 Example 1-30.39 2.6 5 5.38 16.88 Example 1-40.6 13.38 8.7 8 19.93 Example 1-50.2 3.5 0 9.10 2.1.3 0 Comparative Example 1-11.9 3.5 6 2.12.7 1 4 1.7 0 Comparative Example 1-20.28 3.0 7 9.38 36.34 Comparative Example 1-32.5 2.6 34 57.58 14 1.82 Comparative Example 1-42.035.9846.43109.91

[0119] As can be seen in Table 4, it was confirmed that the isocyanate compositions manufactured in Examples 1 to 4 had low haze values ​​and low APHA color values ​​even after 90 days of storage. In addition, it was confirmed that the isocyanate compositions manufactured in Examples 1-1 to 1-5 had increased haze values ​​and APHA color values ​​after 90 days of storage.

[0120] In contrast, the isocyanate compositions of Comparative Examples 1-1 to 1-4, which have a higher content of metal elements than the examples, had significantly higher APHA color values ​​that made them unusable as transparent optical materials, or showed relatively poor storage stability compared to the examples.

[0121]

[0122] Manufacturing Example 1: Manufacturing of an optical lens

[0123] Each of the isocyanate compositions manufactured in Example 1-1 was stirred and mixed at room temperature (23 to 25°C) for 20 minutes with 0.04 g of ZELEC UN (manufactured by Stepan) as an internal release agent and 0.04 g of Biosorb 583 (manufactured by Sakai Chemical industry Co., Ltd) as an ultraviolet absorbent, to prepare a mixture. 0.002 g of DBTC (dibutyltin dichloride) was added to the mixture and stirred for 10 minutes. 19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added, and then stirred for 1 hour while degassing under a pressure condition of 5 mbar to prepare a composition for polyisocyanate polymerization.

[0124] The prepared polyisocyanate polymerization composition was filtered using a 1 μm PTFE filter and then injected into a mold formed from a glass mold and tape, respectively. The mold was then placed in an oven and polymerization was performed for 20 hours while gradually increasing the temperature from 10°C to 120°C. After completion of the polymerization, the mold was taken out of the oven and released to obtain each plastic optical lens. The obtained optical lenses were annealed at 120°C for 6 hours to produce optical lenses having a thickness of 9 mm, respectively.

[0125]

[0126] Manufacturing Examples 2 to 6 and Comparative Manufacturing Examples 1 to 3

[0127] An optical lens was manufactured using the same composition and method as in Manufacturing Example 1, but instead of the isocyanate composition of Example 1-1, nitrile-containing compounds represented by Chemical Formula 1-1 and Chemical Formula 2-1 were additionally added to the isocyanate composition as shown in Table 5 below to increase the total amount of nitrile-containing compounds, and further, the content of nitrile-containing compounds was adjusted to satisfy Equation 1.

[0128] [Equation 1]

[0129] 0.50 ≤ B / (A + B) ≤ 0.80

[0130] In Equation 1, A is the content (pppm) of the compound represented by Chemical Formula 1-1 of Example 1-1 with respect to the total weight of the isocyanate composition, and B is the content (ppm) of the compound represented by Chemical Formula 1-2 of Example 1-1 with respect to the total weight of the isocyanate composition.

[0131] ClassificationIsocyanate compositionAdditional content in the pre-compositionAdditional content in the post-compositionB / (A+B)A content (ppm)B content (ppm)A content (ppm)B content (ppm)Manufacturing example 1Example 1-12492490.96Manufacturing example 2Example 1-12491302490.66Manufacturing example 3Example 1-23551482500.63Manufacturing example 4Example 1-35291223100.72Manufacturing example 5Example 1-432611052050.66Manufacturing example 6Example 1-51901122484060.62ComparativeManufacturing example 1Comparative example 1-13204933204930.61 Comparative Manufacturing Example 2 Example 1-1249703090.82 Comparative Manufacturing Example 3 Example 1-12491941860.49 A is the content (ppm) of a nitrile group-containing compound represented by Chemical Formula 1-1, and B is the content (ppm) of a nitrile group-containing compound represented by Chemical Formula 2-1.

[0132]

[0133] Experimental Example 2: Measurement of the physical properties of an optical lens

[0134] According to the method of ASTM D1209, the yellowness (YI) of each optical lens manufactured in Manufacturing Examples 1 to 5 and Comparative Manufacturing Examples 1 to 3 was measured using Ultrascan Pro from HunterLab, and the results are shown in Table 6.

[0135] In addition, transparency was evaluated by the degree of occurrence of white turbidity with the naked eye under various light source conditions according to the evaluation criteria below, and the evaluation was measured as follows, and the results are shown in Table 4 below.

[0136] <Transparency Evaluation Criteria>

[0137] C (Clear): Transparent under both fluorescent and zirconium lamps

[0138] SH (Slightly Lamp Haze): Transparent under fluorescent light, but some cloudiness observed under zirconium lamp

[0139] LH (Lamp Haze): Transparent under fluorescent light, but cloudiness observed under zirconium lamp

[0140] VH (Visual Haze): Cloudiness observed under both fluorescent and zirconium lamps

[0141] Additionally, according to the method of ASTM D1209, the absorbance for blue light (wavelength 415 nm) was calculated using the following equation 1 using Ultrascan Pro from HunterLab.

[0142] [Formula 1]

[0143] Absorbance (A) = 2-log (T)

[0144] T in Equation 1 represents the transmittance at a wavelength of 415 nm.

[0145] Yellowness (YI) Transparency 415nm wavelength Absorbance (%) Manufacturing example 12.30C 0.3108 Manufacturing example 22.32C 0.1797 Manufacturing example 33.43C 0.1860 Manufacturing example 44.02C 0.1885 Manufacturing example 54.85C 0.2004 Manufacturing example 64.46C 0.2004 Comparative manufacturing example 16.46S.H 0.1736 Comparative manufacturing example 24.07C 0.5900 Comparative manufacturing example 34.32C 1.2913

[0146] As shown in Table 6, the optical lenses of Manufacturing Examples 1 to 6 had excellent transparency while exhibiting particularly low yellowness, and particularly showed high blue light blocking rates even though no UV blocker was used during manufacturing, which is a result of low absorbance for blue light. However, Manufacturing Example 1, in which the content of the nitrile group-containing compound was approximately 51 ppm, showed a relatively slightly higher absorbance for blue light compared to Manufacturing Examples 2 to 6.

[0147] In addition, in the case of Comparative Manufacturing Example 1, which is an optical film manufactured with the isocyanate composition of Comparative Example 1-1 having a high metal element content and a nitrile group-containing compound content of 700 ppm or more, the absorbance for blue light was low, but the yellowness was relatively high and the transparency was poor.

[0148] In addition, in the case of Comparative Manufacturing Example 2 where the value of Equation 1 exceeded 0.75 and Comparative Manufacturing Example 3 where the value of Equation 1 was less than 0.50, the absorbance for blue light was low.

[0149]

[0150] The above illustrates and describes specific embodiments. However, the invention is not limited to the aforementioned embodiments, and those skilled in the art will readily appreciate that various modifications and implementations can be made without departing from the spirit and scope of the invention as set forth in the claims below.

Claims

1. Diisocyanate compounds; and An isocyanate composition comprising a nitrile group-containing compound comprising at least one selected from a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2. [Chemical Formula 1] [Chemical Formula 2] In the above chemical formulas 1 and 2, R 1 and R 2 are each independently -CH2-, -CH2CH2- or -CH2CH2CH2-, and R 3 is a hydrogen atom, a straight-chain alkyl group of C1 to C3, a branched alkyl group of C3 to C5, or a metal salt, a is an integer from 0 to 3, b is an integer from 0 to 5, and n is 1 or 2.

2. In paragraph 1, An isocyanate composition comprising the nitrile group-containing compound in an amount of 700 ppm or less based on the total weight of the isocyanate composition.

3. In paragraph 2, The above isocyanate composition is an isocyanate composition that satisfies the following equation 1. [Equation 1] 0.50 ≤ B / (A + B) ≤ 0.80 In Equation 1, A is the content (pppm) of the compound represented by Chemical Formula 1 with respect to the total weight of the isocyanate composition, and B is the content (ppm) of the compound represented by Chemical Formula 2 with respect to the total weight of the isocyanate composition.

4. An isocyanate composition comprising a metal element including 1 to 15 ppm of aluminum element (Al) and 1 to 20 ppm of calcium element (Ca) when measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) in the first paragraph.

5. An isocyanate composition having a content of at least one metal element selected from tin (Sn), iron (Fe), titanium (Ti), chromium (Cr), nickel (Ni), manganese (Mn), and magnesium (Mg) of 2.0 ppm or less in the first paragraph.

6. In paragraph 1, An isocyanate composition comprising at least one selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, methylenediphenyl diisocyanate, methylenedicyclohexyl isocyanate, toluene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, and o-xylylene diisocyanate.

7. In paragraph 1, An isocyanate composition wherein the above diisocyanate compound is m-xylylene diisocyanate.

8. In paragraph 1, R 1 and R 2 are each independently -CH2- or -CH2CH2, and R 3 An isocyanate composition wherein a is a hydrogen atom or a metal salt, a is an integer from 0 to 2, b is an integer from 0 to 3, and n is 1.

9. In paragraph 1, The above isocyanate composition is an isocyanate composition that satisfies the following condition (1). (1) 0.001% ≤ H b - H a ≤ 4.0% In the above condition (1), H a represents the haze value of the isocyanate composition, and H b It represents the haze value measured after storing the isocyanate composition under conditions of a temperature of 20°C or lower and a relative humidity of 1% or lower for 70 to 110 days.

10. A method for storing an isocyanate composition, wherein the isocyanate composition selected from any one of claims 1 to 9 is stored in a nitrogen-substituted atmosphere, at a temperature of 20°C or lower, and under conditions of relative humidity of 1% or lower.

11. A non-foaming polyurethane synthesized using an isocyanate composition selected from any one of claims 1 to 9.

12. An optical lens comprising the non-foamed polyurethane of Article 11.

13. An optical lens according to claim 11, characterized in that the yellowness (YI) is 5.0 or less.

14. An optical lens according to claim 11, characterized in that the absorbance for a wavelength of 415 nm is 0.15 to 0.30%.

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