Isocyanate composition, optical lens comprising it and method for storing isocyanate composition using it

Abstract

The present invention relates to isocyanate compositions, optical lenses comprising the isocyanate compositions and methods of storing isocyanate compositions using the isocyanate compositions.

Description

Technical Field

[0001] This invention relates to isocyanate compositions, optical lenses containing the isocyanate compositions, and methods for storing isocyanate compositions using the isocyanate compositions. Background Technology

[0002] Isocyanate compounds are raw materials for polyurethanes and are used in a wide variety of applications such as coatings, tackifiers / adhesives, paints, foams, and optical materials. In fields requiring excellent appearance properties, and especially in the case of polyurethanes used in optics where transparency is crucial, minimal discoloration is necessary. Therefore, it is important that not only does discoloration occur during the polyurethane forming reaction, but also that the isocyanate compound used as a raw material itself, particularly in the case of difunctional or more functional polyvalent isocyanate compounds, does not undergo discoloration.

[0003] However, due to the high reactivity of isocyanate compounds, they are easily oxidized by oxygen in the air or form self-polymers during storage, thus easily deteriorating or discoloring. There is also the problem that discoloration or clouding can occur in optical products that use them, such as urethane lenses.

[0004] In this regard, various methods have been studied and proposed as methods for suppressing discoloration in isocyanate compounds and products made using isocyanate compounds, such as sealing with nitrogen to prevent air from entering and storing under refrigeration, or storing after the introduction of additives such as ultraviolet absorbers.

[0005] However, in order to use isocyanate compounds, they need to be moved from their storage location to the atmospheric environment. During this process, the isocyanate compounds may change color or become cloudy, depending on the moisture content of the atmosphere or changes in atmospheric temperature. If optical lenses or similar products are made using isocyanate compounds that have already changed color or become cloudy, there will be problems with reduced clarity and thus deterioration in quality.

[0006] Furthermore, it is difficult to ensure the long-term storage stability of isocyanate compounds. Summary of the Invention

[0007] Technical issues The present invention was made to overcome the above-mentioned problems and aims to provide an isocyanate composition, an optical lens comprising the isocyanate composition, and a method for storing the isocyanate composition using the isocyanate composition, wherein the isocyanate composition has excellent storage stability even when the isocyanate composition is stored for a long time by containing a specific compound.

[0008] Furthermore, the present invention aims to provide an isocyanate composition with improved clarity, an optical lens comprising the isocyanate composition, and a method for storing the isocyanate composition using the isocyanate composition.

[0009] Furthermore, the present invention aims to provide an isocyanate composition capable of manufacturing a polyurethane resin with excellent thermal stability by using the isocyanate composition, an optical lens containing the isocyanate composition, and a method for storing the isocyanate composition using the isocyanate composition.

[0010] Furthermore, the present invention aims to provide isocyanate compositions that are not only unlikely to cause defect factors but also capable of producing transparent optical materials (e.g., optical lenses) with improved yellowness index (YI); optical lenses containing the isocyanate compositions; and methods for storing isocyanate compositions using the isocyanate compositions.

[0011] Furthermore, the present invention aims to provide an isocyanate composition having excellent impact resistance and strength, an optical lens comprising the isocyanate composition, and a method for storing the isocyanate composition using the isocyanate composition.

[0012] Technical solution To address the aforementioned problems, the isocyanate composition of the present invention may comprise: a diisocyanate compound; and a compound having a retention time of 10.5 to 12.5 minutes when measured under the following gas chromatography-mass spectrometry conditions: Measurement conditions for gas chromatography-mass spectrometry Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Oven temperature: Hold at 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

[0013] In a preferred embodiment of the invention, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes may have mass-to-charge ratios (m / z) of 148 to 150, 119 to 121, 106 to 108, 93 to 95, 76 to 78, and 64 to 66.

[0014] In a preferred embodiment of the invention, when measured under gas chromatography-mass spectrometry conditions, the compound having a retention time of 10.5 to 12.5 minutes can be a compound represented by the following chemical formula 1: [Chemical Formula 1]

[0015] In chemical formula 1, B1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and R1 is -H, a C1 to C12 straight-chain alkyl or a C3 to C12 branched alkyl.

[0016] In a preferred embodiment of the present invention, the isocyanate composition of the present invention can satisfy the following condition (1): (1)0.1 ppm ≤ A ≤ 60 ppm In condition (1), A represents the content (ppm) of the compound having a retention time of 10.5 to 12.5 minutes based on the total weight of the isocyanate composition when measured under the gas chromatography-mass spectrometry measurement conditions.

[0017] In a preferred embodiment of the present invention, the isocyanate composition of the present invention may further comprise a compound represented by the following chemical formula 2: [Chemical Formula 2]

[0018] In chemical formula 2, B2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2-.

[0019] In a preferred embodiment of the present invention, the isocyanate composition of the present invention can satisfy the following condition (2): (2)0.1 ppm ≤ B ≤ 100 ppm In condition (2), B represents the content (ppm) of the compound represented by chemical formula 2 based on the total weight of the isocyanate composition.

[0020] In a preferred embodiment of the invention, the isocyanate composition of the invention may comprise a compound represented by chemical formula 2 in a weight ratio of 1:0.05 to 0.6 and a compound having a retention time of 10.5 minutes to 12.5 minutes.

[0021] In a preferred embodiment of the present invention, the diisocyanate compound may include one or more 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, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophthalimethylene diisocyanate, terephthalimethylene diisocyanate, and orthophthalimethylene diisocyanate.

[0022] In a preferred embodiment of the present invention, the diisocyanate compound may be isophthalimide diisocyanate.

[0023] In a preferred embodiment of the present invention, the compound represented by chemical formula 1 may be a compound represented by the following chemical formulas 1-1.

[0024] [Chemical Formula 1-1]

[0025] In chemical formula 1-1, B1 is -CH2-, -CH2CH2-, or -CH2CH2CH2-, and R1 is a C1 to C12 straight-chain alkyl group.

[0026] In a preferred embodiment of the present invention, the compound represented by chemical formula 2 may be a compound represented by the following chemical formula 2-1.

[0027] [Chemical Formula 2-1]

[0028] In chemical formula 2-1, B2 is -CH2-, -CH2CH2-, or -CH2CH2CH2-.

[0029] In a preferred embodiment of the present invention, the isocyanate composition of the present invention can satisfy the following condition (3).

[0030] (3) 0% ≤ D – C ≤ 2.0% In condition (3), C represents the haze value of the isocyanate composition, and D represents the haze value measured after storing the isocyanate composition for 160 to 200 days at a temperature of 20°C or lower and a humidity of 1%RH or lower.

[0031] Meanwhile, the method for storing isocyanate compositions according to the present invention may include: a first step of preparing an isocyanate composition comprising a diisocyanate compound and a compound having a retention time of 10.5 to 12.5 minutes when measured under the following gas chromatography-mass spectrometry conditions; and a second step of storing the isocyanate composition under a nitrogen-purged atmosphere at a temperature of 20°C or lower and a humidity of 1% RH or lower.

[0032] Measurement conditions for gas chromatography-mass spectrometry Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Oven temperature: Hold at 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

[0033] In a preferred embodiment of the invention, when measured under the following gas chromatography-mass spectrometry conditions, a compound having a retention time of 10.5 to 12.5 minutes can be a compound represented by the following chemical formula 1.

[0034] [Chemical Formula 1]

[0035] In chemical formula 1, B1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and R1 is -H, a C1 to C12 straight-chain alkyl or a C3 to C12 branched alkyl.

[0036] In a preferred embodiment of the present invention, the isocyanate composition prepared in the first step can satisfy the following condition (1).

[0037] (1)0.1 ppm ≤ A ≤ 60 ppm In condition (1), A represents the content (ppm) of the compound having a retention time of 10.5 to 12.5 minutes when measured under the following gas chromatography-mass spectrometry measurement conditions, based on the total weight of the isocyanate composition.

[0038] In a preferred embodiment of the invention, the isocyanate composition prepared in the first step may further comprise a compound represented by the following chemical formula 2.

[0039] [Chemical Formula 2]

[0040] In chemical formula 2, B2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2-.

[0041] In a preferred embodiment of the present invention, the isocyanate composition prepared in the first step can satisfy the following condition (2).

[0042] (2)0.1 ppm ≤ B ≤ 100 ppm In condition (2), B represents the content (ppm) of the compound represented by chemical formula 2 based on the total weight of the isocyanate composition.

[0043] In a preferred embodiment of the invention, in the second step, the isocyanate composition can be stored in a nitrogen-substituted atmosphere at a temperature of 0°C to 20°C and a humidity of 0.0001%RH to 1%RH.

[0044] Furthermore, the optical lens of the present invention may contain the isocyanate composition of the present invention.

[0045] In a preferred embodiment of the invention, the optical lens may have a yellowness index (YI) of 2.5 or lower.

[0046] Meanwhile, the non-foamed resin of the present invention may contain the isocyanate composition of the present invention.

[0047] In a preferred embodiment of the invention, the non-foamed resin can be used in coatings, adhesives, sealants, or elastomers.

[0048] Beneficial effects The isocyanate composition of the present invention, the optical lens containing the isocyanate composition, and the method for storing the isocyanate composition using the isocyanate composition not only have excellent storage stability, but also have improved clarity and improved yellowness index (YI). Detailed Implementation

[0049] The invention will be described in more detail below.

[0050] Various methods have been studied and proposed to suppress discoloration in conventional isocyanate compounds and products manufactured using them, such as sealing with nitrogen to block air and storing under refrigeration, or storing after introducing additives such as ultraviolet absorbers. However, in order to use isocyanate compounds, they are moved from their storage location to the atmospheric environment. During this process, depending on changes in atmospheric moisture content or temperature, the isocyanate compounds may discolor or become cloudy. If optical lenses or similar products are manufactured using isocyanate compounds that have already discolored or become cloudy, there is a problem of reduced clarity and thus quality degradation. Furthermore, it is difficult to ensure the long-term storage stability of isocyanate compounds.

[0051] Therefore, by including specific compounds, the present invention not only has excellent storage stability, but also improved clarity and can improve the yellowness index (YI).

[0052] The isocyanate composition of the present invention may comprise: a diisocyanate compound; and a compound having a retention time of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, more preferably 11.4 to 11.6 minutes when measured under the following gas chromatography-mass spectrometry measurement conditions.

[0053] Measurement conditions for gas chromatography-mass spectrometry Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Oven temperature: Hold at 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

[0054] In this case, the diisocyanate compound of the present invention may include one or more selected from 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-cyclohexene diisocyanate, 1,4-cyclohexene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophthalimethylene diisocyanate, terephthalimethylene diisocyanate, and orthophthalimethylene diisocyanate, and may preferably include isophthalimethylene diisocyanate.

[0055] Furthermore, based on the total weight of the isocyanate composition, it may contain 98.00% to 99.99% by weight, preferably 99.00% to 99.99% by weight, more preferably 99.30% to 99.99% by weight, and even more preferably 99.60% to 99.95% by weight of a diisocyanate compound.

[0056] Meanwhile, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes can be byproducts and / or compounds generated during the production of diisocyanate compounds, and are typically removed during purification in the synthesis of diisocyanate compounds. In this invention, the amount of compound removed during purification is controlled such that the compound can be included in the isocyanate composition within a specific content range, and the compound can also be a compound additionally added to the diisocyanate compound.

[0057] Furthermore, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes can have a mass-to-charge ratio (m / z) of 148 to 150.

[0058] Furthermore, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes can have a mass-to-charge ratio (m / z) of 119 to 121.

[0059] Furthermore, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes can have a mass-to-charge ratio (m / z) of 10⁶ to 10⁸.

[0060] Furthermore, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes can have a mass-to-charge ratio (m / z) of 93 to 95.

[0061] Furthermore, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes may have a mass-to-charge ratio (m / z) of 76 to 78.

[0062] Furthermore, when measured under gas chromatography-mass spectrometry conditions, compounds having retention times of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes can have a mass-to-charge ratio (m / z) of 64 to 66.

[0063] Preferably, when measured under gas chromatography-mass spectrometry conditions, the compound having a retention time of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, more preferably 11.4 to 11.6 minutes, can be a compound represented by the following chemical formula 1.

[0064] [Chemical Formula 1]

[0065] In chemical formula 1, B1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and preferably -CH2-, -CH2CH2- or -CH2CH2CH2-.

[0066] In Formula 1, R1 is -H, a C1 to C12 straight-chain alkyl or a C3 to C12 branched alkyl, preferably a C1 to C12 straight-chain alkyl, and more preferably a C1 to C3 straight-chain alkyl.

[0067] Specifically, a compound represented by chemical formula 1 can be a compound represented by the following chemical formula 1-1.

[0068] [Chemical Formula 1-1]

[0069] In chemical formula 1-1, B1 is -CH2-, -CH2CH2- or -CH2CH2CH2-, and R1 is a C1 to C12 straight-chain alkyl group, preferably a C1 to C3 straight-chain alkyl group.

[0070] Meanwhile, the isocyanate composition of the present invention can satisfy the following condition (1).

[0071] (1) 0.1 ppm ≤ A ≤ 60 ppm, preferably 0.2 ppm ≤ A ≤ 40 ppm, more preferably 0.4 ppm ≤ A ≤ 20 ppm, and even more preferably 0.75 ppm ≤ A ≤ 10 ppm In condition (1), A represents the content (ppm) of the compound having a retention time of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, and more preferably 11.4 to 11.6 minutes, when measured under gas chromatography-mass spectrometry conditions based on the total weight of the isocyanate composition. If A in condition (1) is less than 0.1 ppm, there may be an increase in the yellowness index when manufacturing optical lenses using the isocyanate composition of the present invention; and if A in condition (1) is greater than 60 ppm, not only may the storage stability deteriorate, but there may also be an increase in the yellowness index when manufacturing optical lenses using the isocyanate composition of the present invention.

[0072] Furthermore, the isocyanate compositions of the present invention may also contain compounds represented by the following chemical formula 2.

[0073] [Chemical Formula 2]

[0074] In chemical formula 2, B2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and preferably -CH2-, -CH2CH2- or -CH2CH2CH2-.

[0075] The compound represented by Formula 2 may be a byproduct and / or compound generated during the production of the diisocyanate compound, and is typically removed during purification during the synthesis of the diisocyanate compound. In this invention, the amount of the compound removed during purification is controlled such that the compound can be included in the isocyanate composition within a specific content range, and the compound may also be a compound additionally added to the diisocyanate compound.

[0076] In addition, the isocyanate composition of the present invention can satisfy the following condition (2).

[0077] (2) 0.1 ppm ≤ B ≤ 100 ppm, preferably 0.5 ppm ≤ B ≤ 50 ppm, more preferably 1.0 ppm ≤ B ≤ 30 ppm, and even more preferably 2.0 ppm ≤ B ≤ 8.0 ppm In condition (2), B represents the content (ppm) of the compound represented by chemical formula 2 based on the total weight of the isocyanate composition. If B in condition (2) is less than 0.1 ppm, there may be problems with deterioration of storage stability, such as yellowing and / or turbidity; and if B in condition (2) is greater than 100 ppm, there may be problems with deformation when using the isocyanate composition of the present invention to manufacture optical lenses.

[0078] Furthermore, the isocyanate composition of the present invention may contain a compound represented by Formula 2 in a weight ratio of 1:0.05 to 0.6, preferably 1:0.08 to 0.5, more preferably 1:0.1 to 0.3, and a compound having a retention time of 10.5 minutes to 12.5 minutes, preferably 11.0 minutes to 12.0 minutes, more preferably 11.4 minutes to 11.6 minutes when measured under gas chromatography-mass spectrometry conditions. If the weight ratio is less than 1:0.05, when optical lenses are manufactured using the isocyanate composition of the present invention, not only may the yellowness index increase, but also distortion problems such as streaks may occur; and if the weight ratio is greater than 1:0.6, there may be problems with deteriorated storage stability, such as yellowing and / or turbidity, and when optical lenses are manufactured using the isocyanate composition of the present invention, the yellowness index may increase.

[0079] Meanwhile, the isocyanate composition of the present invention can satisfy the following condition (3).

[0080] (3) 0% ≤ D – C ≤ 2.0%, preferably 0% ≤ D – C ≤ 1.5%, more preferably 0% ≤ D – C ≤ 1.0%, even more preferably 0% ≤ D – C ≤ 0.5%, even more preferably 0.001% ≤ D – C ≤ 0.1%, and most preferably 0.001% ≤ D – C ≤ 0.05%. In condition (3), C represents the haze value of the isocyanate composition, and D represents the haze value measured after storing the isocyanate composition for 160 to 200 days, preferably 170 to 190 days, at a temperature of 20°C or lower (preferably 0°C to 20°C) and a humidity of 1%RH or lower (preferably 0.0001%RH to 1%RH).

[0081] Furthermore, the method for storing the isocyanate composition according to the present invention includes a first step and a second step.

[0082] First, in the first step of the method for storing the isocyanate composition according to the present invention, an isocyanate composition comprising: a diisocyanate compound; and a compound having a retention time of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, more preferably 11.4 to 11.6 minutes when measured under the following gas chromatography-mass spectrometry measurement conditions.

[0083] Measurement conditions for gas chromatography-mass spectrometry Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Oven temperature: 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

[0084] In addition, the isocyanate composition prepared in the first step can meet the following conditions (1).

[0085] (1) 0.1 ppm ≤ A ≤ 60 ppm, preferably 0.2 ppm ≤ A ≤ 40 ppm, more preferably 0.4 ppm ≤ A ≤ 20 ppm, and even more preferably 0.75 ppm ≤ A ≤ 10 ppm In condition (1), A represents the content (ppm) of a compound having a retention time of 10.5 to 12.5 minutes, preferably 11.0 to 12.0 minutes, more preferably 11.4 to 11.6 minutes, when measured under gas chromatography-mass spectrometry conditions based on the total weight of the isocyanate composition.

[0086] In addition, the isocyanate composition prepared in the first step may also contain a compound represented by the following chemical formula 2.

[0087] [Chemical Formula 2]

[0088] In chemical formula 2, B2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and preferably -CH2-, -CH2CH2- or -CH2CH2CH2-.

[0089] In addition, the isocyanate composition prepared in the first step can meet the following condition (2).

[0090] (2) 0.1 ppm ≤ B ≤ 100 ppm, preferably 0.5 ppm ≤ B ≤ 50 ppm, more preferably 1.0 ppm ≤ B ≤ 30 ppm, and even more preferably 2.0 ppm ≤ B ≤ 8.0 ppm In condition (2), B represents the content (ppm) of the compound represented by chemical formula 2 based on the total weight of the isocyanate composition.

[0091] Next, in the second step of the method for storing the isocyanate composition according to the present invention, the isocyanate composition prepared in the first step can be stored at a temperature of 20°C or lower, preferably 0°C to 20°C, more preferably 5°C to 15°C, and a humidity of 1%RH or lower, preferably 0.0001%RH to 1%RH, more preferably 0.001%RH to 0.1%RH. If the storage temperature in the second step is higher than 20°C, not only may the storage stability deteriorate, but there may also be problems such as increased haze causing the optical lenses made using the composition to become opaque and / or making it impossible to make optical lenses using the composition; and if the storage humidity in the second step is higher than 1%RH, not only may the storage stability deteriorate, but there may also be problems such as increased haze causing the optical lenses made using the composition to become opaque.

[0092] Meanwhile, the optical lens of the present invention may contain the isocyanate composition of the present invention and may have a yellowness index (YI) of 2.5 or lower, preferably 0.1 to 2.0, more preferably 0.5 to 1.5.

[0093] Furthermore, the non-foamed resin of the present invention may contain the isocyanate composition of the present invention.

[0094] The non-foamed resin of the present invention is a resin that does not have a foam shape and can be used in coatings, adhesives, sealants or elastomers, but is not limited thereto.

[0095] As a specific example, the non-foaming resin of the present invention can be a reaction product of the isocyanate composition of the present invention and a component containing active hydrogen groups. The component containing active hydrogen groups may include a polyol component (mainly comprising a polyol component having two or more hydroxyl groups), a polythiol component (mainly comprising a polythiol component having two or more thiol groups), a polyamine component (mainly comprising a polyamine compound having two or more amino groups), etc., and as a preferred example, it can be a raw material required for the production of polyurethane resin.

[0096] Meanwhile, the non-foamed resin of the present invention used in coatings, adhesives, sealants or elastomers can be, but is not limited to, a raw material for manufacturing automobiles, ships, flexible packaging, food packaging, construction, paints, inks, solar cells, microcapsules, adhesives for displays, optical materials and fuel cells.

[0097] Furthermore, the method for producing isocyanate compositions according to the present invention will be described below by way of examples.

[0098] Isocyanate compositions are synthesized by reacting amine compounds with phosgene in a solvent.

[0099] As solvents used in the phosgenation reaction, aromatic hydrocarbon solvents such as benzene, toluene, xylene, or ethylbenzene; chlorinated aromatic hydrocarbon solvents such as monochlorobenzene, 1,2-dichlorobenzene, or 1,4-dichlorobenzene; or chlorinated hydrocarbon solvents such as dichloromethane, chloroform, or carbon tetrachloride can be used, and two or more of these can be used in combination.

[0100] The amine compound used in the phosgenation reaction can be, for example, an amine compound obtained by hydrogenating a nitro compound or its hydrochloride salt. Specifically, the amine compound can be one or more selected from the group consisting of 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,3-cyclohexylenediamine, 1,4-cyclohexylenediamine, isophoronediamine, diamine, diphenylmethylenediamine, dicyclohexylmethylenediamine, toluenediamine, m-phenylenediamine, p-phenylenediamine, and o-phenylenediamine, and their salts, and preferably m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, or their salts.

[0101] Based on 100 parts by weight of solvent, the solvent may contain 1 to 20 parts by weight of amine compound. If the content of amine compound is greater than 20 parts by weight, there is a concern that a large amount of amine compound may precipitate. Preferably, the solvent may contain 1 to 15 parts by weight or 3 to 10 parts by weight of amine compound.

[0102] Specifically, the phosgenation reaction can be carried out by the following methods: a direct phosgenation method in which an amine compound reacts directly with phosgene (Method 1); a method in which an amine compound reacts with anhydrous hydrochloric acid to form an amine-hydrochloride compound, and then the formed salt reacts with phosgene (Method 2); or a method in which an amine compound reacts with carbonic acid to form an aliphatic amine-carbonate compound, and then the formed salt reacts with phosgene (Method 3).

[0103] Method 1, the direct phosgenation method, can be carried out by reacting an amine compound with phosgene in an organic solvent. In this case, the phosgene can be added all at once at the start of the reaction, or a portion of it can be added at the start of the reaction, with the remainder added in portions during the reaction.

[0104] Meanwhile, Method 1 can be carried out through the following steps: a first step, dissolving a portion of phosgene in a solvent, and then adding an amine compound; and a second step, after the addition of the amine compound, adding the remaining portion of phosgene and allowing the phosgene to react. In this case, the first step is preferably carried out at a temperature of -15°C to -10°C to prevent leakage of the highly toxic phosgene and also to prevent rapid heating during the addition of the amine compound. Furthermore, the phosgenation reaction in the second step can be controlled at 120°C to 140°C, allowing the reaction to proceed at an appropriate rate without concern about the decomposition of the amine compound.

[0105] In Method 2, the reaction can be carried out by reacting an amine compound with hydrochloric acid in an organic solvent to form an amine-hydrochloride compound, followed by the addition of phosgene to initiate the reaction. The formation of the amine-hydrochloride compound can be carried out at a temperature of 30°C or lower, preferably at about 23±5°C, and the reaction after the addition of phosgene can be controlled to 120°C to 140°C. When carried out at such temperature conditions, the solubility of the amine-hydrochloride compound increases, and thermal decomposition of the isocyanate is prevented, enabling the production of high-purity isocyanate compounds in high yields.

[0106] In method 3, the reaction can be carried out by reacting an amine compound with carbonic acid in a solvent to form an amine-carbonate compound, followed by the addition of phosgene to initiate the reaction. In this case, the formation of the amine-carbonate compound can be carried out at a temperature of 30°C or lower, preferably at about 23 ± 5°C, and the reaction after the addition of phosgene can be controlled to between 80°C and 180°C. Preferably, the reaction can be controlled to a 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 increases, and thermal decomposition of the isocyanate is prevented, enabling the production of high-purity isocyanate compounds in high yields.

[0107] After the reaction with phosgene is completed according to the various methods, optional further processes such as removal of unreacted phosgene and hydrogen chloride gas (e.g., nitrogen bubbling) and solvent removal processes such as distillation can be carried out, which can be performed according to conventional methods.

[0108] The invention will be described in more detail below by way of examples. However, the following examples do not limit the scope of the invention and should be construed as being provided to aid in understanding the invention.

[0109] Preparation Example 1: Preparation of Compounds (1) Prepare compounds that have a retention time of 11.5 minutes when measured using a gas chromatograph-mass spectrometer (GC-MSD) under the following measurement conditions.

[0110] Measurement conditions for gas chromatography-mass spectrometry Measuring instrument: Agilent 8890 5977C GC-MS Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Filter: 0.45 μm Teflon filter Injection concentration: 1.0% by mass, dichloromethane solution Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Carrier gas: He, 1 mL / min Detection method: Scanning method (30 m / z to 550 m / z) Oven temperature: Hold at 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

[0111] (2) It was confirmed that the prepared compound with a retention time of 11.5 minutes was a compound represented by the following chemical formulas 1-2 with mass-to-charge ratios (m / z) of 149, 120, 107, 94, 77 and 65.

[0112] [Chemical Formula 1-2]

[0113] In chemical formula 1-2, B1 is -CH2- and R1 is methyl.

[0114] Example 1: Preparation of isocyanate composition (1) 471 g of 1,2-dichlorobenzene and 32.5 g of m-xylenediamine (m-XDA) with a purity of 99.4% were added to the reactor, and anhydrous hydrochloric acid was injected at a rate of 20 g / h while stirring at room temperature (23±5℃). During the injection of anhydrous hydrochloric acid, the internal temperature of the reactor was raised to 50℃.

[0115] (2) Four hours after injecting anhydrous hydrochloric acid, the reactor was cooled until its internal temperature reached room temperature (23±5℃). Then, 43 mL of liquid phosgene was introduced into the reactor, and the reactor was heated until its internal temperature reached 130℃. From the time of phosgene introduction until the point of reaction completion confirmation (described later), a dry ice-acetone condenser was used to prevent phosgene leakage. After the internal temperature of the reactor reached 130℃, the internal temperature was maintained at 125℃ to 135℃ for 2 hours, allowing the solution contained in the reactor to become transparent. The fact that the solution contained in the reactor became transparent confirmed the completion of the reaction, thus confirming the formation of the phosgene-removed reaction product in the reactor.

[0116] (3) Subsequently, while blowing nitrogen into the reactor, the reactor is cooled until the internal temperature of the reactor reaches 80°C, and then the reaction products generated in the reactor are obtained.

[0117] (4) The solvent contained in the obtained reaction product was removed by vacuum distillation, followed by a purification process using a thin-film evaporator (TFE); then, an additional vacuum purification process was performed to remove the oligomers contained in the reaction product, thereby finally preparing the isocyanate composition. The purification using the thin-film evaporator (TFE) was carried out at a feed temperature of 150°C, a TFE temperature of 160°C, a vacuum degree of 0.5 Torr, and a feed rate of 20 ml / min; the vacuum purification was carried out at a pressure of 3.2 mbar and a temperature of 160°C.

[0118] Meanwhile, it was confirmed that the prepared isocyanate composition contained: 0.86 ppm of the compound prepared in Preparation Example 1 above, based on the total weight of the prepared isocyanate composition, and 3.60 ppm of the compound represented by the following chemical formula 2-2, based on the total weight of the prepared isocyanate composition.

[0119] [Chemical Formula 2-2]

[0120] In chemical formula 2-2, B2 is -CH2-.

[0121] Example 2: Preparation of isocyanate composition The isocyanate composition was prepared in the same manner as in Example 1. However, unlike in Example 1, purification using a thin-film evaporator (TFE) was carried out at a feed temperature of 150°C, a TFE temperature of 160°C, a vacuum of 0.8 Torr, and a feed rate of 20 mL / min; and vacuum purification was carried out at a pressure of 3.2 mbar and a temperature of 160°C.

[0122] Meanwhile, it was confirmed that the prepared isocyanate composition contained: 25.49 ppm of the compound prepared in Preparation Example 1 above, based on the total weight of the prepared isocyanate composition, and 46.10 ppm of the compound represented by the above chemical formula 2-2 above, based on the total weight of the prepared isocyanate composition.

[0123] Example 3: Preparation of isocyanate composition The isocyanate composition was prepared in the same manner as in Example 1. However, unlike in Example 1, purification using a thin-film evaporator (TFE) was carried out at a feed temperature of 150°C, a TFE temperature of 160°C, a vacuum of 1.0 Torr, and a feed rate of 20 ml / min; vacuum purification was carried out at a pressure of 3.2 mbar and a temperature of 160°C.

[0124] Meanwhile, it was confirmed that the prepared isocyanate composition contained: 0.73 ppm of the compound prepared in Preparation Example 1 above, based on the total weight of the prepared isocyanate composition; and 10.80 ppm of the compound represented by the above chemical formula 2-2, based on the total weight of the prepared isocyanate composition.

[0125] Example 4: Preparation of isocyanate composition (1) 471 g of 1,2-dichlorobenzene and 32.5 g of m-xylenediamine (m-XDA) with a purity of 99.4% were added to the reactor, and anhydrous hydrochloric acid was injected at a rate of 20 g / h while stirring at room temperature (23±5℃). During the injection of anhydrous hydrochloric acid, the internal temperature of the reactor was raised to 50℃.

[0126] (2) Four hours after injecting anhydrous hydrochloric acid, the reactor was cooled until its internal temperature reached room temperature (23±5℃). Then, 43 mL of liquid phosgene was introduced into the reactor, and the reactor was heated until its internal temperature reached 130℃. From the time of phosgene introduction until the point of reaction completion confirmation (described later), a dry ice-acetone condenser was used to prevent phosgene leakage. After the internal temperature of the reactor reached 130℃, the internal temperature was maintained at 125℃ to 135℃ for 2 hours, allowing the solution contained in the reactor to become transparent. The fact that the solution contained in the reactor became transparent confirmed the completion of the reaction, thus confirming the formation of the phosgene-removed reaction product in the reactor.

[0127] (3) Subsequently, while blowing nitrogen into the reactor, the reactor is cooled until the internal temperature of the reactor reaches 80°C, and then the reaction products generated in the reactor are obtained.

[0128] (4) The solvent contained in the obtained reaction product is removed by vacuum distillation, and a purification process using a thin-film evaporator (TFE) is carried out to remove the oligomers contained in the reaction product, thereby finally preparing the isocyanate composition. The purification using the thin-film evaporator (TFE) is carried out under the conditions of feed temperature of 80°C, TFE temperature of 150°C, vacuum degree of 0.5 Torr, and feed rate of 30 mL / min.

[0129] Meanwhile, it was confirmed that the prepared isocyanate composition contained: 39.90 ppm of the compound prepared in Preparation Example 1 above, based on the total weight of the prepared isocyanate composition, and 178.10 ppm of the compound represented by the above chemical formula 2-2 above, based on the total weight of the prepared isocyanate composition.

[0130] Comparative Example 1: Preparation of Isocyanate Compositions The isocyanate composition was prepared in the same manner as in Example 4. However, unlike in Example 4, purification using a thin-film evaporator (TFE) was carried out at a feed temperature of 150°C, a TFE temperature of 160°C, a vacuum of 0.01 Torr, and a feed rate of 2.6 mL / min.

[0131] Meanwhile, it was confirmed that the prepared isocyanate composition contained 1.90 ppm of the compound represented by the above chemical formula 2-2, based on the total weight of the prepared isocyanate composition.

[0132] Experimental Example 1: Measurement of APHA color and haze The APHA color and haze (light source: C / 2) of each isocyanate composition prepared in Examples 1 to 4 and Comparative Example 1 were measured using HunterLab's Ultrascan Pro according to ASTM E313, and the results are shown in Table 1 below.

[0133] [Table 1]

[0134] As can be confirmed in Table 1, the isocyanate compositions prepared in Example 3 and Comparative Example 1 have significantly high APHA color values, making them unsuitable for use as transparent optical materials.

[0135] Excluding the isocyanate compositions prepared in Example 3 and Comparative Example 1, each isocyanate composition prepared in Examples 1 to 2 and 4 was stored for 180 days at a temperature of 15°C and a humidity of 0.1%RH under a nitrogen-purified atmosphere. The APHA color and haze (light source: C / 2) of each isocyanate composition prepared in Examples 1 to 2 and 4 were then measured during storage. The results are shown in Table 2 below.

[0136] [Table 2]

[0137] As can be confirmed in Table 2, the isocyanate compositions prepared in Examples 1 and 2 still exhibit low haze and low APHA color values ​​even after 180 days of storage.

[0138] However, it was confirmed that the isocyanate composition prepared in Example 4 had a high haze value after 180 days of storage.

[0139] Manufacturing Examples 1 to 2 and 4: Manufacturing of Optical Lenses 20.8 g of each isocyanate composition prepared in Examples 1 to 2 and 4, 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 a UV absorber were stirred and mixed at room temperature (=23°C) for 20 minutes to prepare a mixture. 0.24 g of a dye solution containing 0.047 wt% Quinizarin Blue and 0.002 g of DBTC (dibutyltin dichloride) were added to the prepared mixture and stirred for 10 minutes. Then, 19.2 g of 2,3-bis(2-thioethylthio)propane-1-thiol was added, and the mixture was stirred while degassing at 5 mbar for 1 hour to prepare a composition for polyisocyanate polymerization.

[0140] The composition for polyisocyanate polymerization was prepared by filtering through a 1 μm PTFE filter and then injected into mold assemblies consisting of glass molds and tape. The mold assemblies were then placed in an oven, and polymerization was carried out for 20 hours while the temperature was gradually increased from 10°C to 120°C. After polymerization, the mold assemblies were removed from the oven and demolded to obtain the corresponding plastic optical lenses. The obtained optical lenses were annealed at 120°C for 6 hours to produce optical lenses with a thickness of 3 mm. Optical lenses manufactured using the isocyanate composition prepared in Example 1 are shown as Manufacturing Example 1 in Table 3 below; optical lenses manufactured using the isocyanate composition prepared in Example 2 are shown as Manufacturing Example 2 in Table 3 below; and optical lenses manufactured using the isocyanate composition prepared in Example 4 are shown as Manufacturing Example 4 in Table 3 below.

[0141] Experimental Example 2: Measurement of Color Difference The yellowness index (YI) of each optical lens manufactured in Examples 1 to 2 and 4 was measured using the Ultrascan Pro from HunterLab according to the method of ASTM D1209, and the results are shown in Table 3.

[0142] [Table 3]

[0143] As shown in Table 3, the optical lens of Manufacturing Example 1 was confirmed to exhibit a particularly low yellowness index.

[0144] The specific embodiments have been illustrated and described above. However, the present invention is not limited to the above embodiments, and those skilled in the art can make various modifications without departing from the spirit and intent of the invention as set forth in the appended claims.

Claims

1. An isocyanate composition comprising: Diisocyanate compounds; and Compounds with retention times of 10.5 to 12.5 minutes when measured under the following gas chromatography-mass spectrometry conditions: Measurement conditions for gas chromatography-mass spectrometry Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Oven temperature: Hold at 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

2. The isocyanate composition according to claim 1, wherein, The compounds having retention times of 10.5 to 12.5 minutes have mass-to-charge ratios (m / z) of 148 to 150, 119 to 121, 106 to 108, 93 to 95, 76 to 78, and 64 to 66.

3. The isocyanate composition according to claim 2, wherein, The compound having a retention time of 10.5 to 12.5 minutes is a compound represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, B1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and R1 is -H, a C1 to C12 straight-chain alkyl or a C3 to C12 branched alkyl.

4. The isocyanate composition according to claim 1, wherein, The isocyanate composition satisfies the following condition (1): (1)0.1 ppm ≤ A ≤ 60 ppm In condition (1), A represents the content (ppm) of the compound having a retention time of 10.5 to 12.5 minutes based on the total weight of the isocyanate composition.

5. The isocyanate composition according to claim 1, wherein, The isocyanate composition further comprises a compound represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, B2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2-.

6. The isocyanate composition according to claim 5, wherein, The isocyanate composition satisfies the following condition (2): (2)0.1 ppm ≤ B ≤ 100 ppm In condition (2), B represents the content (ppm) of the compound represented by chemical formula 2 based on the total weight of the isocyanate composition.

7. The isocyanate composition according to claim 5, wherein, The isocyanate composition comprises, by weight, a compound represented by chemical formula 2 and a compound having a retention time of 10.5 to 12.5 minutes.

8. The isocyanate composition according to claim 1, wherein, The diisocyanate compound includes one or more 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, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, isophthalimethylene diisocyanate, terephthalimethylene diisocyanate, and orthophthalimethylene diisocyanate.

9. The isocyanate composition according to claim 1, wherein, The diisocyanate compound is isophthalimide diisocyanate.

10. The isocyanate composition according to claim 3, wherein, Compounds represented by chemical formula 1 are compounds represented by the following chemical formula 1-1: [Chemical Formula 1-1] In chemical formula 1-1, B1 is -CH2-, -CH2CH2- or -CH2CH2CH2-, and R1 is a C1 to C12 straight-chain alkyl group.

11. The isocyanate composition according to claim 5, wherein, Compounds represented by chemical formula 2 are compounds represented by the following chemical formula 2-1: [Chemical Formula 2-1] In chemical formula 2-1, B2 is -CH2-, -CH2CH2-, or -CH2CH2CH2-.

12. The isocyanate composition according to claim 1, wherein, The isocyanate composition satisfies the following condition (3): (3)0% ≤ D – C ≤ 2.0% In condition (3), C represents the haze value of the isocyanate composition, and D represents the haze value measured after storing the isocyanate composition for 160 to 200 days at a temperature of 20°C or lower and a humidity of 1%RH or lower.

13. A method for storing an isocyanate composition, the method comprising: The first step is to prepare an isocyanate composition comprising: a diisocyanate compound, and a compound having a retention time of 10.5 to 12.5 minutes when measured under the following gas chromatography-mass spectrometry conditions; and The second step involves storing the isocyanate composition in a nitrogen-purified atmosphere at a temperature of 20°C or lower and a humidity of 1%RH or lower. Measurement conditions for gas chromatography-mass spectrometry Column: DB-17MS (inner diameter 0.25mm × length 30m, membrane 0.25μm) Injection volume: 1 μL, split ratio: 10:1 Injection temperature: 280℃ Oven temperature: Hold at 100℃ for 1 minute, increase from 100℃ to 165℃ at 10.0℃ / min, hold at 165℃ for 3 minutes, increase from 165℃ to 177℃ at 3.0℃ / min, increase from 177℃ to 300℃ at 20.0℃ / min, and hold at 300℃ for 15 minutes.

14. The method according to claim 13, wherein, The compound having a retention time of 10.5 to 12.5 minutes is a compound represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, B1 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, and R1 is -H, a C1 to C12 straight-chain alkyl or a C3 to C12 branched alkyl.

15. The method according to claim 13, wherein, The isocyanate composition prepared in the first step satisfies the following condition (1): (1)0.1 ppm ≤ A ≤ 60 ppm In condition (1), A represents the content (ppm) of the compound having a retention time of 10.5 to 12.5 minutes based on the total weight of the isocyanate composition.

16. The method according to claim 13, wherein, The isocyanate composition further comprises a compound represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, B2 is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, or -CH2CH2CH2CH2CH2-.

17. The method according to claim 16, wherein, The isocyanate composition prepared in the first step satisfies the following condition (2): (2)0.1 ppm ≤B ≤ 100 ppm In condition (2), B represents the content (ppm) of the compound represented by chemical formula 2 based on the total weight of the isocyanate composition.

18. The method according to claim 13, wherein, In the second step, the isocyanate composition is stored in a nitrogen-purified atmosphere at a temperature of 0°C to 20°C and a humidity of 0.0001%RH to 1%RH.

19. An optical lens comprising the isocyanate composition of claim 1.

20. The optical lens according to claim 19, wherein, The optical lens has a yellowness index (YI) of 2.5 or lower.

21. A non-foaming resin comprising the isocyanate composition of claim 1.

22. The non-foamed resin according to claim 21, wherein, The non-foamed resin is used in coatings, adhesives, sealants, or elastomers.

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