Isocyanate composition

Abstract

The present invention provides an isocyanate composition that contains an isocyanate compound and a phosphonate compound having a specific structure, thereby improving storage stability and suppressing discoloration and cloudiness, and also exhibiting improved workability such as a shortened filtering time, and improving discoloration resistance when used in products.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority rights based on Korean Patent Application No. 10-2022-0139402 dated October 26, 2022, and Korean Patent Application No. 10-2023-0135186 dated October 11, 2023, and all content disclosed in the documents of said Korean Patent Applications is incorporated herein by reference.

[0002] The present invention relates to an isocyanate composition that exhibits improved storage stability, suppression of discoloration and turbidity, and improved workability, such as a reduction in filtering time. [Background technology]

[0003] Isocyanate compounds are highly valuable not only in the chemical and resin industries but also as precision chemical products, including optical materials. Xylylene diisocyanate (XDI), a representative example of an isocyanate compound, is a high-value-added chemical material used as a raw material for high-grade optical lenses, and demand for it is increasing.

[0004] However, isocyanate compounds are highly reactive and tend to discolor or become cloudy when they react with moisture in the air during storage. In addition, when isocyanate compounds are stored for a long period of time, they can discolor or become cloudy due to the formation of oligomers (dimers or larger) through self-polymerization.

[0005] Isocyanate compounds are raw materials for polyurethane, and are widely used in coatings, pressure-sensitive / adhesive agents, paints, foams, optical materials and other applications. When producing polyurethane lenses using isocyanate compounds that have undergone such discoloration or clouding, problems occur including decreased stirring performance, increased filtering time, and filter clogging caused by the rapid increase in the molecular weight of the polymerization solution, which reduces workability, and also causes decreased transparency and discoloration of the produced lenses.

[0006] To solve this problem, methods of producing and storing the compounds by filling or sealing them with nitrogen gas to isolate them from air are commonly used, but there is still a risk of discoloration and clouding before the isocyanate compound is completely used up.

[0007] In addition, methods of adding stabilizers to isocyanate compounds have also been proposed, but the added stabilizer may cause coloring in subsequent product production, or reduce the stability of the isocyanate compound.

[0008] Accordingly, there is a need for research on the production of an isocyanate composition that eliminates the risk of discoloration or clouding even during long-term storage due to improved storage stability, and can exhibit improved workability during product production. Summary of the Invention Problems to be Solved by the Invention

[0009] An object of the present invention is to provide an isocyanate composition having improved storage stability and suppressed occurrence of discoloration and clouding, which as a result can improve transparency when applied to products, and can exhibit improved workability such as shortened filtering time. Means for Solving the Problems

[0010] According to the present invention, there is provided an isocyanate composition comprising an isocyanate compound and a phosphonate compound represented by the following chemical formula 1. [ka] In the aforementioned chemical formula 1, R a and R b Each of these independently represents a substitution or non-substitution of C. 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl group, substituted or unsubstituted C 7-30 Alkylaryl group, or substituted or unsubstituted C 7-30 It is an arylalkyl group.

[0011] Furthermore, the present invention provides a polymerization composition comprising the isocyanate composition and one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0012] Furthermore, the present invention provides an article comprising a polymer obtained by polymerizing the isocyanate composition with one or more of the polyfunctional thiol compounds, polyfunctional alcohol compounds, and polyfunctional episulfide compounds. [Effects of the Invention]

[0013] The isocyanate composition according to the present invention has improved storage stability and suppresses discoloration and clouding, and as a result, its transparency can be improved when applied to a product.

[0014] Furthermore, the isocyanate composition can exhibit improved workability, such as a reduction in filtering time.

[0015] Furthermore, polymerization compositions containing the isocyanate composition and a polyfunctional thiol compound, a polyfunctional alcohol compound, or a polyfunctional episulfide compound can be used in a wide range of fields due to their excellent physical properties, including paints for plastics, paints for automobiles, film coatings, various inks, various adhesives, sealants, various microcapsules, plastic lenses, artificial and synthetic leather, reaction injection molded (RIM) products, slush powders, elastic molded products (spandex), and urethane foams. Among these, the isocyanate composition is particularly useful as a material for optical articles such as optical adhesives, optical glues, spectacle lenses, camera lenses, and prisms due to its excellent adhesive properties and transparency. [Modes for carrying out the invention]

[0016] The terms used herein are used solely to describe exemplary embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “includes,” “equip,” or “have” are intended to specify the existence of implemented features, steps, components, or combinations thereof, and should not be understood to preemptively exclude the existence or possibility of adding one or more other features, steps, components, or combinations thereof.

[0017] In this specification, the term “substituted or unsubstituted” means a group that is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen groups; nitrile groups; nitro groups; hydroxyl groups; carbonyl groups; ester groups; imide groups; amino groups; phosphine oxide groups; alkoxy groups; aryloxy groups; alkylthiooxy groups; arylthiooxy groups; alkylsulfoxy groups; arylsulfoxy groups; silyl groups; boron groups; alkyl groups; cycloalkyl groups; alkenyl groups; aryl groups; aralkyl groups; aralkylkenyl groups; alkylaryl groups; alkylamine groups; aralkylamine groups; heteroarylamine groups; arylamine groups; arylphosphine groups; or heteroaryl groups containing one or more N, O, and S atoms, or a group that is substituted or unsubstituted with one or more substituents selected from the group consisting of substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent selected from one substituent

[0018] Unless otherwise specified herein, ordinary temperature means 23±5°C, which is the normal laboratory temperature, and atmospheric pressure means 1±0.05 atm, which is the normal laboratory pressure.

[0019] Furthermore, unless otherwise specified herein, a nitrogen atmosphere means that nitrogen is present in the atmospheric gas, specifically, the nitrogen concentration in the atmospheric gas is greater than 0% by volume and less than or equal to 100% by volume.

[0020] The present invention can be modified in various ways and may take many forms; therefore, specific embodiments are illustrated and described in detail below. However, this should not be understood as limiting the present invention to any particular form of disclosure, but rather as including any modifications, equivalents, or substitutions that fall within the spirit and technical scope of the present invention.

[0021] The present invention will be described in detail below.

[0022] Isocyanate compounds, due to their high reactivity with water or alcohol, are nitrogen-filled, completely sealed, and refrigerated after manufacturing. However, upon opening for use, they react with moisture in the air or discoloration or clouding occurs depending on the ambient temperature. Furthermore, when sealed isocyanate compounds are opened for use, the oligomer content increases or yellowing occurs during the storage period until they are used up. As a result, when polyurethane lenses are manufactured using such isocyanate compounds, a rapid increase in composition viscosity leads to a decrease in stirring power, an increase in filtering time, or filter clogging, resulting in reduced workability, and the transparency of the manufactured lenses decreases, causing discoloration.

[0023] Therefore, the present inventors have studied isocyanate compositions that can suppress the rate of increase of oligomers generated by the self-polymerization of isocyanate compounds during long-term storage, and that can exhibit improved workability during lens manufacturing. As a result, they have confirmed that when a phosphonate-based compound is used together with an isocyanate compound, the oligomerization rate of the isocyanate compound can be reduced, thereby suppressing discoloration and clouding caused by the oligomers, preventing lens color changes caused by various additives added to improve lens workability, and improving workability by shortening the filtering time during lens manufacturing. Thus, the present invention has been completed.

[0024] Specifically, the isocyanate composition according to the present invention comprises an isocyanate compound and a phosphonate compound represented by the following chemical formula 1. [ka] In the aforementioned chemical formula 1, R a and R beach independently represents a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-30 alkylaryl group, or a substituted or unsubstituted C 7-30 arylalkyl group.

[0025] Furthermore, when said R a and R b are substituted, specifically, they may be substituted with one or more substituents selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, arylalkyl groups, alkylaryl groups, hydroxy groups, alkoxy groups, alkoxyalkyl groups, aryloxy groups, and combined groups thereof.

[0026] Specifically, in said Chemical Formula 1, R a and R b each independently represent a substituted or unsubstituted C 1-18 alkyl group, a substituted or unsubstituted C 6-18 aryl group, a substituted or unsubstituted C 7-18 alkylaryl group, or a substituted or unsubstituted C 7-18 arylalkyl group, and when said R a and R b are substituted, each independently is substituted with C 1-12 alkyl group, C 3-12 cycloalkyl group, C 6-12 aryl group, C 7-18 arylalkyl group, C 7-18 alkylaryl group, hydroxy group, C 1-12 alkoxy group; C 2-18 alkoxyalkyl group, C 6-12 aryloxy group, and may be substituted with one or more substituents selected from the group consisting of combined groups thereof.

[0027] More specifically, in said Chemical Formula 1, R a and R b each independently represent C 1-8It may be an alkyl group, a phenyl group, or a benzyl group, in which case R a and R b Each is independent of C 1-6 It may be substituted with one or more substituents selected from the group consisting of alkyl groups, phenyl groups, hydroxyl groups, and combinations thereof, or it may be unsubstituted.

[0028] On the other hand, in the present invention, a combined group means a group to which two or more functional groups are bonded. For example, a combination of a hydroxyl group and a methyl group may be a methoxy group or a hydroxymethyl group, and a combination of a hydroxyl group and a phenyl group may be a phenoxy group or a hydroxyphenyl group. Another example is a combined group of a methyl group and a phenyl group which may be a benzyl group or a methylphenyl group.

[0029] More specifically, in the above chemical formula 1, R a and R b Each of these may independently be a methyl group, an ethyl group, a t-butyl group, a hexyl group, a 3,3-dimethylbutan-2-yl group, a 2-ethylhexyl group, a phenyl group, a hydroxybenzyl group, or a 3,5-di-tert-butyl-4-hydroxybenzyl group.

[0030] Specific examples of the phosphonate compounds include ethyl methylphosphonate (CAS NO. 1832-53-7), pinacolyl methylphosphonate, mono-2-ethylhexyl(2-ethylhexyl)phosphonate, or monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. One or more of these can be used as a mixture.

[0031] The higher the acidity of the isocyanate composition, the lower the reaction rate of the isocyanate, and as a result, the oligomerization of the isocyanate may be delayed or suppressed.

[0032] The phosphonate compound provides an acidic component that is released by reacting with alcohol during the production of the isocyanate composition. This increases the acidity of the isocyanate composition, thereby delaying or suppressing the reaction rate and oligomerization of the isocyanate, and also suppressing discoloration and turbidity caused by the oligomer.

[0033] Furthermore, the phosphonate compound prevents lens color changes caused by additives added to improve lens workability, and suppresses the increase in viscosity of the isocyanate composition, thereby shortening the filtering time during lens manufacturing.

[0034] Compared to phosphonic acid (HPO(OH)2) and phosphorous acid (P(OH)3), the phosphonate compounds exhibit superior storage stability due to differences in reactivity.

[0035] Phosphoric acid (H3PO4 (or PO(OH)3)) is excessively reactive, causing precipitates to form during the production of isocyanate compositions, which makes it difficult to produce polymerization compositions using it. However, the phosphonate compounds described above exhibit appropriate levels of reactivity and do not pose a risk of precipitate formation.

[0036] Furthermore, while phosphoric acid esters can partially increase the acidity of isocyanate compositions, they increase the viscosity of the polymerization composition, which can lead to filter clogging during lens manufacturing. In contrast, the phosphonate compounds mentioned above do not pose a risk of viscosity increase.

[0037] On the other hand, the acidity (as HCl) (ppm) of the isocyanate composition is a value expressed as the relative weight ratio of the amount of acidic component released by reaction with alcohol at room temperature (23±5℃) to the total weight of the isocyanate compound, after converting the amount of acidic component to HCl. The acidity of the isocyanate composition according to the present invention is determined by the acidic group content derived from the phosphonate compound. This allows the acidity to be adjusted by controlling the type and / or amount of phosphonate compound added, and the effect of using the phosphonate compound can be further enhanced by optimizing the acidity range.

[0038] Specifically, the isocyanate composition according to the present invention may have an acidity of 500 ppm or less.

[0039] The higher the acidity of the isocyanate composition, the lower the reaction rate of the isocyanate, which can delay or suppress the oligomerization of the isocyanate. However, if the acidity is excessively high, the reaction rate of the isocyanate may become excessively slow, making it difficult to form polymers and use them in the manufacture of products such as lenses. Furthermore, the use of an excessive amount of catalyst may be necessary to compensate for the delay in the isocyanate reaction rate caused by the use of an excessive amount of phosphonate compound. In this case, the excessive amount of catalyst may lead to a decrease in reaction efficiency, a deterioration in physical properties, and a decline in product quality due to discoloration and clouding of the isocyanate composition.

[0040] As a result, the phosphonate compound can be added in an amount such that the acidity of the isocyanate composition becomes 500 ppm or less, more specifically, it can be added so that the acidity becomes 500 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppm or less, or 130 ppm or less. On the other hand, in order to fully realize the effects such as the increase in acidity due to the addition of the phosphonate compound, the phosphonate compound can be added in an amount such that the acidity of the isocyanate composition becomes 100 ppm or more, 110 ppm or more, or 113 ppm or more.

[0041] In this invention, acidity was specifically determined by potentiometric titration of the isocyanate composition with a 0.01 N potassium hydroxide (KOH) methanol solution, and the resulting measured values ​​were calculated using the following formula 1. The measurement method and conditions are described in detail in the experimental example below.

[0042] [Formula 1] Acidity (as HCl) (ppm) = [(AB) × N × f × 36.5 × 10 6 ] / (C×10 3 ) In the above formula 1, A: Volume (ml) of KOH methanol solution consumed in the titration of the isocyanate composition sample. B: Volume (ml) of KOH methanol solution consumed in the titration of the joint test. N:Normal concentration of KOH methanol solution f: A coefficient used to correct the concentration of the KOH methanol solution used during measurement to the same value as a 0.01N KOH methanol solution, if the normal concentration differs from that of the KOH methanol solution used during measurement. This coefficient is measured according to ASTM D-1638 and TOLOCHIMIE 04-01-68. For a 0.01N KOH methanol solution, the f value is 1. C: Weight (g) of the isocyanate composition sample.

[0043] More specifically, in the isocyanate composition according to the present invention, the phosphonate compound may be included in an amount of 100 to 3,000 ppm relative to the total weight of the isocyanate compound, under conditions that satisfy the acidity range. When the content is within the above range, the isocyanate composition exhibits an acidity within the above range, and the effect of delaying the oligomerization rate can be achieved within the optimal range. More specifically, the phosphonate compound may be included in an amount of 100 ppm or more, or 200 ppm or more, or 300 ppm or more, or 350 ppm or more, or 380 ppm or more, or 600 ppm or more, or 900 ppm or more, and 3,000 ppm or less, or 2,000 ppm or less, or 1,500 ppm or less, or 1,200 ppm or less, or 1,100 ppm or less, relative to the total weight of the isocyanate compound.

[0044] On the other hand, in the isocyanate composition, the isocyanate compound is a monomer containing one or more, two or more, or two to four isocyanate groups in its molecule. More specifically, the isocyanate compound is a diisocyanate compound containing two isocyanate groups in its molecule.

[0045] Specific examples of the diisocyanate compounds include 1,5-pentamethylene diisocyanate, toluene diisocyanate, methylenediphenyl diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, or p-xylylene diisocyanate, and one or more of these can be used as a mixture.

[0046] Among the aforementioned compounds, the isocyanate compound can be o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, or a mixture thereof.

[0047] Furthermore, the isocyanate composition according to the present invention may further contain a phenolic stabilizer.

[0048] Generally, discoloration and turbidity in isocyanate compositions occur not only due to oligomerization of isocyanates, but also due to quinoidization of intramolecular benzene rings, or due to addition products generated by oxygen, moisture, or high heat during synthesis and purification processes. The phenolic stabilizer can prevent discoloration and turbidity of isocyanate compositions by suppressing these side reactions through radical scavenging reactions.

[0049] However, if the amount of the stabilizer is below a certain level, it is difficult to show sufficient discoloration or clouding prevention effect, and conversely, if it is included in an excessive amount exceeding a certain level, the phenolic stabilizer itself may become a cause of discoloration and clouding. For this reason, in the present invention, the phenolic stabilizer is included in an amount of 5 ppm to 1,000 ppm relative to the total weight of the isocyanate compound. More specifically, by including an amount of 5 ppm or more, or 8 ppm or more, or 10 ppm or more and 1,000 ppm or less, or 500 ppm or less, or 200 ppm or less, or 100 ppm or less, or 50 ppm or less, or 30 ppm or less, or 20 ppm or less, relative to the total weight of the isocyanate compound, a more enhanced discoloration and clouding suppression effect can be achieved.

[0050] Furthermore, by controlling the amount of the phosphonate compound and the phenolic stabilizer used, the rate of increase in oligomer content can be reduced, and the effect of suppressing discoloration and turbidity can be further enhanced. Specifically, the phosphonate compound and the phenolic stabilizer may be included in a weight ratio of 1.5:1 to 6:1. More specifically, the ratio may be 1.5:1 or more, or 1.9:1 or more, or 2:1 or more, or 3:1 or more and 6:1 or less, or 5.5:1 or less, or 4.5:1 or less. In this case, when stating the weight ratio, "or more" and "or less" refer to the amount of the phosphonate compound used.

[0051] The phenolic stabilizer is specifically a phenol or a derivative containing a phenolic structure in its molecule, and specific examples include phenol; or dibutylhydroxytoluene (BHT), t-butylhydroquinone (TBHQ), butylhydroxyanisole (BHA), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, manufactured by BASF), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1035, manufactured by BASF), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox Irganox 1076 (BASF), N,N'-Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (Irganox 1098, BASF), Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side-chain alkyl ester (Irganox 1135, BASF), 3,3',3'',5,5',5''-Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol (Irganox 1330, BASF), Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Irganox 245 (BASF), Hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259, BASF), or 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2-4-6(1H,3H,5H)-trione (Irganox 3114, BASF), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, Stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphate, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 4,4'-thiobis(6-te rt-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyrate] glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-secondary-butyl-6-tert-butylphenol), 1,1,3 -Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6(2-acryloyloxy-3- tert-butyl-5-methylbenzyl)phenol, 3,9-bis-1,1-dimethyl-2-[(3-tert-butyl-5-methylbenzyl)propionyloxy]ethyl-2,4,8,10-tetraoxaspiro[5,5]undecane or triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], or 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,Examples include sterically hindered phenols such as [2]dioxaphosphepin (6-[3-(3-tert-Butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin, SUMILIZER GP, Sumitomo), and one or more of these can be used.

[0052] Among these, phenol, dibutylhydroxytoluene, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepine, or mixtures thereof can be used in terms of their effect on improving transparency by preventing discoloration and clouding.

[0053] Furthermore, the isocyanate composition may further contain as a by-product an oligomer in which two or more isocyanate compounds are bonded together.

[0054] The oligomer of the isocyanate compound may be a dimer with two isocyanate compounds bonded together, a trimer with three bonded compounds, four or more bonded compounds, or four to ten bonded compounds. The oligomer may be produced by a side reaction during the synthesis of the isocyanate compound by the reaction of an amine compound and a phosgene compound, or it may form a polymer independently due to the high reactivity of the synthesized isocyanate compound. These oligomers cause problems not only with the transparency of the isocyanate composition itself, but also with discoloration and clouding of the polymerization composition using the isocyanate composition. Therefore, in the case of isocyanate compositions used in the optical field, it is necessary to reduce the content of the oligomers. However, it is difficult to control the oligomer content to an extreme degree in commercial processes from the viewpoint of process efficiency and cost. Thus, the isocyanate composition according to the present invention can further contain the oligomers that are inevitably generated, but by controlling the content through the manufacturing process and the use of phosphonic acid, the transparency and color characteristics of the product can be improved while maintaining processability.

[0055] Specifically, the isocyanate composition may contain oligomers at an area of ​​1 area or less immediately after manufacturing. In this case, the oligomer content is determined by calculating the ratio of the peak area corresponding to the oligomer to the total peak area in the molecular weight distribution curve obtained by gel permeation chromatography analysis of the isocyanate composition immediately after manufacturing, based on the total peak area. The peak area is calculated by integration. The method for measuring and calculating the oligomer content is as described in the experimental example below.

[0056] By including a phosphonate compound that delays the oligomerization reaction rate of the isocyanate in the isocyanate composition, as described above, the oligomer content and the rate of increase in oligomer content over time are lower compared to conventional methods.

[0057] Specifically, the isocyanate composition has an oligomer content increase rate of 600% or less, calculated by the following formula 2, more specifically, 100 to 600%, or 300 to 590%.

[0058] [Formula 2] Increase rate of oligomer content (%) = [(C f -Ci) / Ci]×100 In the above equation 2, Ci is the oligomer content (area%) in the isocyanate composition immediately after manufacturing, calculated by gel permeation chromatography analysis. C f This represents the oligomer content (area%) within the isocyanate composition after storage at 15°C under a nitrogen atmosphere for 8 weeks, as calculated by gel permeation chromatography analysis.

[0059] In this case, the aforementioned "under a nitrogen atmosphere" specifically refers to a condition where nitrogen is filled to 100% by volume, based on the total volume of the atmospheric atmosphere.

[0060] Specifically, the above Ci and C f This is the calculated value obtained by formula 3 below.

[0061] In this invention, nitrogen with a purity of 99.999% was used during the nitrogen filling process.

[0062] [Formula 3] Oligomer content (area%) = [E / D] × 100 In the above formula 3, D is the total area under the curve of the molecular weight distribution curve (GPC curve) obtained by gel permeation chromatography (GPC) analysis of the isocyanate composition. E is the area of ​​the peak corresponding to the oligomer in the molecular weight distribution curve for the isocyanate composition.

[0063] The gel permeation chromatography analysis conditions described above are based on the experimental examples shown later.

[0064] Furthermore, the total area under the GPC curve for the isocyanate composition and the area of ​​the fraction corresponding to the oligomer can be determined by integration. In this case, the oligomer refers to a polymer with a weight-average molecular weight (Mw) of 600 to 2,000 g / mol, and the fraction corresponding to the oligomer in the GPC curve is 19.42 ≤ log Mw ≤ 22.18.

[0065] More specifically, the isocyanate composition may have an oligomer content, i.e., a GPC oligomer area ratio, calculated by GPC analysis after being stored at 15°C for 8 weeks under a nitrogen atmosphere, specifically under conditions of 100% volume of atmospheric nitrogen by nitrogen filling, of 0.5 area or less, or 0.45 area or less. A lower oligomer content indicates better discoloration resistance, so the lower limit is not particularly limited, but it may exceed 0 area or be 0.1 area or more. In this invention, 99.999% pure nitrogen was used during the nitrogen filling.

[0066] On the other hand, in the present invention, the oligomer content (area%) in the isocyanate composition is obtained by GPC analysis, with the log value of the weight-average molecular weight (M) (log M) on the x-axis and the molecular weight distribution with respect to the log value (dwt / dlog M) on the y-axis. The GPC curve represents the percentage of the area ratio of the fraction corresponding to the oligomer within the total area of ​​the GPC curve, and can be calculated using the above formula 3. The specific GPC analysis method and conditions will be explained in detail in the experimental example below.

[0067] Thus, because the oligomer content increase rate and oligomer content remain low both immediately after and after the isocyanate composition is manufactured, discoloration and turbidity of the isocyanate composition can be effectively controlled.

[0068] Specifically, the isocyanate composition has an APHA value of 15 or less, measured by ASTM D1209 after being stored for 8 weeks at 15°C under a nitrogen atmosphere, specifically under a 100% volume nitrogen atmosphere filled with nitrogen. More specifically, it is 14.5 or less, or 14 or less. A lower APHA value indicates better discoloration resistance, so the lower limit is not limited, but as an example, it may be greater than 0 or greater than 1.

[0069] Furthermore, the isocyanate composition has a haze of 0.5% or less, measured by ASTM D1003 after being stored in a nitrogen atmosphere at 15°C for 8 weeks. More specifically, it is 0.45% or less, or 0.4% or less. A smaller haze value indicates lower turbidity and superior transparency, so there is no lower limit, but as an example, it may be greater than 0%, or 0.01% or more, or 0.1% or more.

[0070] Furthermore, the isocyanate composition does not exhibit turbidity even after being stored under a nitrogen atmosphere at 15°C for 12 weeks.

[0071] The isocyanate composition can be produced by mixing an isocyanate compound with a phosphonate compound represented by the above chemical formula 1.

[0072] More specifically, the isocyanate composition can be produced by a manufacturing method comprising the steps of: reacting an amine or a salt thereof with phosgene to produce an isocyanate compound; and mixing the isocyanate compound with a phosphonate compound represented by the chemical formula 1.

[0073] The amine is an aromatic, alicyclic, or aliphatic diamine containing two amine groups in its molecule.

[0074] More specifically, the amine may be 1,3-xylylenediamine (m-xylylenediamine, m-XDA), 1,4-xylylenediamine (p-xylylenediamine, p-XDA), 1,3-bis(aminomethyl)cyclohexane, or 1,4-bis(aminomethyl)cyclohexane, and depending on the structure of the desired diisocyanate, one or more of these can be used.

[0075] Furthermore, the salt of the amine refers to a salt produced by the reaction of the amine with an acid, and may be, for example, a hydrochloride salt produced by the reaction of an amine with hydrochloric anhydride, or a carbonate salt produced by the reaction of an amine with carbonic acid. While amines react rapidly with phosgene, using a solid salt can slow down the reaction rate.

[0076] Specifically, examples of the amine salts include 1,3-xylylenediamine hydrochloride, 1,4-xylylenediamine hydrochloride, 1,3-bis(aminomethyl)cyclohexane hydrochloride, 1,4-bis(aminomethyl)cyclohexane hydrochloride, 1,3-xylylenediamine carbonate, and 1,4-xylylenediamine carbonate, 1,3-bis(aminomethyl)cyclohexane carbonate, or 1,4-bis(aminomethyl)cyclohexane carbonate, and any one or a mixture of two or more of these can be used.

[0077] Furthermore, the production of amine salts by the reaction of amines with acids may be carried out in a solvent. In this case, the solvent can be an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or ethylbenzene; a chlorinated aromatic hydrocarbon solvent such as monochlorobenzene, 1,2-dichlorobenzene, or 1,4-dichlorobenzene; or a chlorinated hydrocarbon solvent such as dichloromethane, chloroform, or carbon tetrachloride. Two or more of these can also be used in mixture form. In addition, these solvents can also be used as solvents for phosgenation reactions. Therefore, after reacting amines with acids in the aforementioned solvents to obtain amine salts, phosgene may be added to carry out the phosgenation reaction without a separate purification process.

[0078] The amine salt production may be carried out at a temperature of 40°C or lower, more specifically, 5 to 30°C. Although the temperature may rise due to the heat of reaction during the reaction, it is preferable that the maximum temperature inside the reactor be maintained at 90°C or lower.

[0079] Next, the reaction between the amine or its salt and phosgene may be carried out at a temperature range of 80°C or higher, or 90°C or higher and 140°C or lower, or 130°C or lower. If the reaction temperature is too low, problems such as solid precipitation and clogging of pipes (plugging) may occur, and if the temperature is too high, side reaction problems such as phosgene decomposition may occur, so it is preferable to carry out the reaction within the above temperature range.

[0080] Furthermore, the reaction between the amine or its salt and phosgene may be carried out in an organic solvent.

[0081] The organic solvent may include at least one of aromatic hydrocarbon organic solvents and ester organic solvents.

[0082] The aforementioned aromatic hydrocarbon organic solvent may specifically be a halogenated aromatic hydrocarbon organic solvent such as monochlorobenzene, 1,2-dichlorobenzene, or 1,2,4-trichlorobenzene.

[0083] Furthermore, the ester-based organic solvent may specifically be fatty acid esters such as amyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, benzyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, ethyl acetate, butyl stearate, butyl lactate, or amyl lactate; and aromatic carboxylic acid esters such as metal salicylate, dimethyl phthalate, or methyl benzoate.

[0084] More specifically, the organic solvent may include at least one of the aromatic hydrocarbon organic solvents and ester organic solvents having a boiling point of 100°C or higher, or 100 to 200°C.

[0085] When the phosgenation reaction is carried out in an organic solvent in this manner, the amine or its salt can be used at a concentration of 20% by volume or less, for example, 1 to 20% by volume, or 5 to 20% by volume. If the concentration of the amine or its salt exceeds 20% by volume, there is a risk of a large amount of amine salt precipitation.

[0086] Furthermore, during the reaction between the amine or its salt and phosgene, a compound represented by the following chemical formula 2 may be optionally added. [ka]

[0087] In the aforementioned chemical formula 2, R1 through R4 are each independently of substitution or non-substitution of C. 1-12 Alkyl, substituted or unsubstituted C 3-12 Cycloalkyl groups, or substituted or unsubstituted C 6-12It is an aryl group, X is hydrogen, hydroxyl, or acetamide. Y is oxyl, substituted or unsubstituted C 1-12 Alkoxy, or substituted or unsubstituted C 6-12 It is an aryloxy.

[0088] The compound represented by chemical formula 2 above plays a role in suppressing the generation of monoisocyanates such as ethyl benzyl isocyanate (EBI) and chloromethyl benzyl isocyanate (CMBI) as by-products by removing hydrogen from the amine or the intermediate product carbamoyl chloride during the phosgenation reaction, thereby promoting the forward reaction and suppressing side reactions.

[0089] More specifically, the compound represented by the above chemical formula 2 is one in which R1 to R4 are each independently C 1-12 The compound may be an alkyl group in which X is hydrogen, a hydroxyl group, or an acetamide group, and Y is an oxyl (O·).

[0090] Specific examples include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hereinafter referred to as 4-hydroxyTEMPO), and 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl, and any one or a mixture of two or more of these can be used.

[0091] Furthermore, the compound represented by chemical formula 2 can be used in a ratio of 0.05 to 2 moles based on 100 moles of the amine or its salt. More specifically, it can be used in a ratio of 0.05 moles or more, or 0.1 moles or more, or 0.15 moles or more and 2 moles or less, or 1 mole or less, or 0.8 moles or less. When used within the above content range, the generation of diisocyanate oligomers is minimized, and diisocyanate can be synthesized with high purity and high yield, which is preferable.

[0092] The isocyanate formed as a result of the phosgenation reaction is obtained as a mixture in which the solvent, unreacted phosgene, and by-products are mixed with hydrogen chloride. For this reason, one or more of the following steps may be performed from the reaction mixture: a purification step to separate the isocyanate compound with high purity, a solvent removal step by distillation, and a removal step by nitrogen bubbling or the like for unreacted phosgene and hydrogen chloride gas.

[0093] The purification step may be carried out by conventional methods used for the purification of isocyanate compounds, for example, by vacuum distillation and / or thin-film distillation.

[0094] However, if the purification process of the isocyanate compound is carried out under excessively high temperatures or if the duration of the purification step is increased, the stability of the isocyanate compound may be significantly reduced. Conversely, if the process is carried out at excessively low temperatures, the process efficiency may decrease. For this reason, it is preferable that the purification step be carried out at a temperature of 100 to 170°C for 5 to 16 hours. If the maximum temperature of the purification step exceeds 170°C or the residence time of the purification step exceeds 16 hours, the produced isocyanate may absorb excessive heat, resulting in reduced stability.

[0095] Next, the obtained isocyanate compound is mixed with the phosphonate compound represented by the above chemical formula 1 to produce an isocyanate composition.

[0096] The mixing step may be carried out by conventional methods, and the type and amount of the phosphonate compound to be mixed are as described above.

[0097] Furthermore, additives used in the isocyanate composition may be added during the mixing process. For example, as mentioned above, a phenolic stabilizer may be added to improve the storage stability of the isocyanate composition. The type and amount of the phenolic stabilizer used are as described above.

[0098] The isocyanate composition produced by the manufacturing method of the present invention described above has excellent storage stability and high transparency, and can therefore be suitably used as a polymerization composition for manufacturing optical articles.

[0099] Accordingly, the present invention provides a polymerization composition comprising, together with the isocyanate composition, one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0100] The polymerization composition may contain the isocyanate composition and one or more of the polyfunctional thiol compound, polyfunctional alcohol compound, and polyfunctional episulfide compound in a mixed state, or in a separated state. In other words, within the polymerization composition, the isocyanate composition and the polyfunctional thiol compound, polyfunctional alcohol compound, or polyfunctional episulfide compound may be in contact with each other or in a separated state so as not to contact each other.

[0101] In the polymerization composition, the polyfunctional thiol compound is a compound containing two or more thiol groups (-SH) in one molecule, and specifically, it may be a compound having two or more, or three or more and eight or fewer, or five or fewer thiol groups in the molecule.

[0102] Examples of the polyfunctional thiol compounds include 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol, 1,9-dimercapto-3,7-dithianonane, 1,13-dimercapto-3,7,11-trithiatridecane, and glycol di(3-mercaptopropionate). di(3-mercaptopropionate), 1,4-Dithiane-2,5-diyldimethanethiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane (3-mercaptopropionate) tri(3-mercaptopropionate)), 4,8-di(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 5,9-di(mercaptoethyl)-1,12-dimercapto-3,7,10-trithiadodecane, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate) tetra(mercaptoacetate)), 3,6,9,12-Tetrathiatetradecane-1,14-dithiol, 3,6,10,13-Tetrathiapentadecane-1,8,15-trithiolIt may be one or more selected from the group consisting of 15-trithiol.

[0103] Furthermore, the polyfunctional alcohol compound is a compound containing two or more hydroxyl groups in one molecule, and specifically, it may be a compound having two or more, or three or more and eight or fewer, or four or fewer hydroxyl groups in the molecule. Specific examples include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, and 1,2-hexanediol; trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; pentahydric alcohols such as L-arabitol, ribitol, and xylitol; hexahydric alcohols such as D-glucitol, D-mannitol, and galactitol; heptahydric alcohols such as trehalose; octahydric alcohols such as sucrose and maltose; or low molecular weight polyols. Any one or a mixture of two or more of these can be used.

[0104] Furthermore, the polyfunctional episulfide compounds may be compounds containing two or more episulfide groups, i.e., thioepoxy groups, in their molecules, and may have an aliphatic, alicyclic, or aromatic skeleton. Specific examples include bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane, 1,2-bis(β-epithiopropylthio)propane, 1-(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)propane, 1,4-bis(β-epithiopropylthio)butane, 1,3-bis(β-epithiopropylthio)butane, and 1-(β-epithiopropylthio)-3-(β-epithiopropylthio Omethyl)butane, 1,5-bis(β-epithiopropylthio)pentane, 1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane, 1,6-bis(β-epithiopropylthio)hexane, 1-(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane, 1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthio Ethyl)thioethyl]thio]ethane, tetrakis(β-epithiopropylthiomethyl)methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, 1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane, 1,5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2-bis(β-epithiopropylthiomethyl)-4-thiahex Sun, 1,5,6-Tris(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3-thiahexane, 1,8-bis(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-Bis(β-epithiopropylthio)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-Bis(β-epithiopropylthio)-2,5-Bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,9-Bis(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)-5-[(2-β-epithiopropylthioethyl)thiomethyl]-3,7-dithianonane, 1,10-Bis(β-epithiopropylthio)-5,6-Bis[(2-β-epithiopropyl [(2-β-epithiopropylthioethyl)thio]-3,6,9-trithiadecane, 1,11-bis(β-epithiopropylthio)-4,8-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropyl Pyrthio)-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, bis[4 -(β-epithiopropylthio)cyclohexyl]sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,It may contain one or more selected from 2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfone, and 4,4'-bis(β-epithiopropylthio)biphenyl.

[0105] In the polymerization composition, the molar ratio of functional groups such as thiol groups, hydroxyl groups, or episulfide groups to isocyanate groups may be 0.5 to 1.5, 0.8 to 1.2, or 0.9 to 1.1, but the present invention is not necessarily limited to these.

[0106] Furthermore, the polymerization composition may optionally contain additives such as internal release agents, ultraviolet absorbers, urethane reaction catalysts, polymerization initiators, heat stabilizers, hue correctors, chain extenders, crosslinking agents, light stabilizers, fillers, and photosensitive agents, and their content can be appropriately determined within a range that does not impair the discoloration and discoloration suppression properties of the composition.

[0107] As an example, the polymerization composition may further contain an internal release agent to improve mold release during subsequent product molding.

[0108] Examples of the aforementioned internal release agent include phosphate ester-based release agents, alkyl phosphate ester-based release agents, and fatty acid ester-based release agents. One or more of these can be used. Among these, phosphate ester-based release agents are preferred.

[0109] The aforementioned phosphate ester-based release agent is ZELEC UN TM Products such as those manufactured by Stepan Company can also be commercially obtained and used.

[0110] The internal release agent may be included in an amount of 0.01% by weight or more, or 0.05% by weight or more and 10% by weight or less, or 5% by weight or less, relative to the total weight of the polymerization composition.

[0111] As another example, the polymerization composition may further contain an ultraviolet absorber. Specifically, the ultraviolet absorber may be a benzotriazole-based ultraviolet absorber, a formamidine-based ultraviolet absorber, or any one or a mixture of two or more of these. Among these, a formamidine-based ultraviolet absorber is preferably used.

[0112] As the formamidine-based ultraviolet absorber, commercially available products such as Zikasorb R, Zikasorb BS, ZIKA-FA02, ZIKA-FUA, ZIKA-FLS', ZIKA-UVS3, and ZIKA-UVS4 (manufactured by ZIKO Corporation); and Biosorb 583 (manufactured by SAKAI CHEMICAL INDUSTRY CO.,LTD.) can also be used.

[0113] The ultraviolet absorber may be included in an amount of 0.01% by weight or more, or 0.05% by weight or more and 0.1% by weight or less, or 0.08% by weight or less, based on the total weight of the polymerization composition.

[0114] Furthermore, examples of urethane reaction catalysts include dialkyltin halide compounds such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylate compounds such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate; dialkyltin dialkoxide compounds such as dibutyltin dibutoxide and dioctyltin dibutoxide; dialkyltin dithioalkoxide compounds such as dibutyltin di(thiobutoxide); dialkyltin oxide compounds such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin) oxide; or dialkyltin sulfide compounds. Any one or a mixture of two or more of these can be used.

[0115] The urethane reaction catalyst may be included in an amount of 0.001% by weight or more, or 0.002% by weight or more, or 0.004% by weight or more, and 0.1% by weight or less, or 0.05% by weight or less, or 0.01% by weight or less, or 0.008% increase or less, relative to the total weight of the polymerization composition.

[0116] The polymerization composition exhibits excellent colorfastness due to the phosphonate compound contained within the isocyanate composition, which delays or suppresses the reaction rate and oligomerization of the isocyanate. This prevents lens discoloration caused by various additives added to improve workability during lens manufacturing, and also allows for improved workability during product manufacturing, such as reduced filtering time, by suppressing the increase in viscosity of the polymerization composition.

[0117] Thus, the polymerization composition can be used in a wide range of fields due to its excellent physical properties, and is useful as a material for optical articles that require excellent external characteristics, especially transparency, such as optical adhesives, optical bonding agents, spectacle lenses, camera lenses, plastic lenses, and prisms.

[0118] According to the present invention, an article is provided which comprises a polymer obtained by polymerizing an isocyanate composition in the polymerization composition with one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide.

[0119] For example, if the polymerization composition contains a polyfunctional thiol compound, the polymerization reaction is carried out by a urethane reaction between the isocyanate group in the isocyanate compound and the thiol group in the polyfunctional thiol compound. Polyurethane produced by this reaction with a polyfunctional thiol compound exhibits excellent transparency and is therefore particularly useful in the manufacture of optical articles, especially optical lenses such as eyeglass lenses and camera lenses.

[0120] As another example, when the polymerization composition contains a polyfunctional alcohol compound, the polymerization reaction is carried out by a urethane reaction (or condensation polymerization reaction) between the isocyanate in the aromatic diisocyanate and the hydroxyl group in the polyfunctional alcohol. Polyurethane produced by this reaction with a polyfunctional alcohol compound exhibits excellent transparency and excellent tackiness / adhesion properties, making it useful as an optical adhesive or optical bonding agent.

[0121] Furthermore, the polymerization reaction may be carried out under atmospheric pressure and in an inert gas atmosphere such as nitrogen or argon.

[0122] Furthermore, it is preferable that the polymerization reaction be carried out at a temperature range of -15°C or higher, or 0°C or higher and 150°C or lower, or 120°C or lower, as this allows for easy control of the reaction rate without fear of discoloration and also increases the reaction efficiency.

[0123] The polymerization reaction may be carried out under catalyst-free conditions or in the presence of a urethane reaction catalyst as described above. When carried out in the presence of a catalyst, the catalyst can be added when mixing a polyfunctional thiol compound, a polyfunctional alcohol compound, or a polyfunctional episulfide compound with the isocyanate composition.

[0124] Furthermore, the degree of the polymerization reaction can be estimated by measuring the concentration of isocyanate groups in the polymerization product using the n-dibutylamine method with a potentiometric titrator, or by measuring the refractive index. In the present invention, the polymerization reaction can be carried out until the concentration of isocyanate groups in the polymerization product reaches the calculated value of the remaining isocyanate groups after reaction with the polyfunctional thiol compound.

[0125] As a result of the polymerization reaction described above, a polymer, specifically polythiourethane, is produced.

[0126] On the other hand, articles containing the polymer may specifically include paints such as paints for plastics or paints for automobiles; coatings such as film coatings; various inks; sealing materials; various microcapsules; artificial leathers such as artificial and synthetic leathers; reaction injection molded (RIM) products; slush powders; elastic molded products (spandex); urethane foam; or optical articles such as optical adhesives, optical glues, spectacle lenses, camera lenses, plastic lenses, and prisms. Considering the excellent transparency of the polymerization composition, it may also be an optical article, particularly an optical adhesive or optical glue, or an optical lens such as a spectacle lens or camera lens.

[0127] The article may be manufactured by performing a molding step after the polymerization reaction of the polymerization composition, or by a molding step using the polymerization composition. In the latter case, the polymerization reaction occurs simultaneously during the molding step.

[0128] As an example, in the case of an optical lens, the polymerization composition is injected into a lens molding mold, and then the temperature of the mold is increased to carry out a polymerization reaction between the isocyanate compound and the polyfunctional thiol compound or polyfunctional episulfide compound. At this time, the temperature of the mold is raised to the temperature range in which the urethane polymerization reaction occurs as described above. After the polymerization reaction is complete, the produced polymer, specifically polythiourethane, can be separated from the mold to obtain an optical lens.

[0129] Polymers produced from the polymerization composition according to the present invention, specifically polythiourethanes, exhibit excellent transparency and improved workability, making them particularly useful in the manufacture of optical articles, especially optical adhesives and optical lenses.

[0130] As an example, an optical lens containing a polymer produced from the polymerization composition according to the present invention exhibits a YI value of 1.6 or less, or 1.5 or less, when measured according to ASTM E313. A lower YI value indicates better discoloration resistance, so the lower limit is not particularly limited, but specifically, it may be greater than 0 or greater than 0.1.

[0131] The following examples illustrate the present invention, but these examples are merely illustrative, and it will be obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the technical concept, and that such changes and modifications will naturally fall within the scope of the appended claims. [Examples]

[0132] <Manufacturing of isocyanate compositions> Example 1-1 471 g of 1,2-dichlorobenzene, 32.5 g of m-XDA (99.4% purity), and 0.24 g of 4-hydroxy TEMPO were placed in a flask, and hydrochloric acid anhydrous was added at room temperature (23±5°C) at a rate of 20 g / hr while stirring. The temperature rose to 50°C after adding the hydrochloric acid anhydrous. After 4 hours of addition, the formed salt was cooled to room temperature, and 43 g of phosgene was added to the reactor. The reactor was then heated to a temperature of 130°C. From the time of phosgene addition until the end of the reaction, a dry ice-acetone condenser was used to prevent phosgene from escaping. After the reactor temperature reached 130°C, the reactor temperature was maintained at 125-135°C for 2 hours until the reaction solution became clear. After the solution became clear, the inside of the reactor was cooled to 80°C, and nitrogen was blown in to expel and remove the phosgene. The solvent was removed from the reaction solution from which phosgene had been removed by vacuum distillation, and the product was purified at a high temperature of 160°C under reduced pressure to obtain m-xylylene diisocyanate (m-XDI). An isocyanate composition was prepared by adding 380 ppm of ethyl methyl phosphonate (boiling point: 181°C) to the aforementioned m-XDI and mixing.

[0133] Examples 1-2 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 900 ppm of mono-2-ethylhexyl (2-ethylhexyl)phosphonate was added instead of ethylmethylphosphonate.

[0134] Examples 1-3 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 1,100 ppm of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate was added instead of ethylmethylphosphonate.

[0135] Examples 1-4 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 600 ppm of pinacolylmethylphosphonate was added instead of ethylmethylphosphonate.

[0136] Examples 1-5 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 200 ppm of phenol was added to m-XDI along with 380 ppm of ethyl methylphosphonate.

[0137] Examples 1-6 In Example 1-2, an isocyanate composition was prepared in the same manner as in Example 1-2, except that 200 ppm of phenol was added to m-XDI along with 900 ppm of mono-2-ethylhexyl (2-ethylhexyl)phosphonate.

[0138] Examples 1-7 In Examples 1-3, isocyanate compositions were prepared in the same manner as in Examples 1-3, except that 200 ppm of phenol was added to m-XDI along with 1,100 ppm of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

[0139] Examples 1-8 In Examples 1-4, isocyanate compositions were prepared in the same manner as in Examples 1-4, except that 200 ppm of phenol was added to m-XDI along with 600 ppm of pinacolylmethylphosphonate.

[0140] Comparative Example 1-1 An isocyanate composition was prepared in the same manner as in Example 1-1, except that ethylmethylphosphonate was not added.

[0141] Comparative Example 1-2 An isocyanate composition was prepared in the same manner as in Example 1-1, except that ethylmethylphosphonate was not added and 200 ppm of phenol was added.

[0142] Comparative Examples 1-3 In Example 1-1, instead of ethylmethylphosphonate, the phosphate ester compound ZELEC TM An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of UN (manufactured by Stepan Company) was added.

[0143] Comparative Example 1-4 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of bis(2-ethylhexyl) phosphate, a phosphate ester compound, was added instead of ethylmethylphosphonate.

[0144] Comparative Examples 1-5 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of phosphoric acid was added instead of ethyl methylphosphonate. However, precipitates formed in the manufactured isocyanate composition.

[0145] Comparative Examples 1-6 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of ethyl phosphate (a mixture of monoesters and diesters) (DEP) was added instead of ethyl methylphosphonate.

[0146] <Manufacturing of polymerization compositions and optical lenses> Example 2-1 20.8 g of the isocyanate composition prepared in Example 1-1, and ZELEC as an internal release agent. TM UN (manufactured by Stepan) 0.04g and Biosorb as a UV absorber. TM 0.04 g of 583 (manufactured by Sakai Chemical Industry Co., Ltd.) was mixed by stirring in a flask at room temperature for approximately 20 minutes.

[0147] To the resulting mixture, 0.002 g of dibutyltin dichloride was added and stirred for 10 minutes. Then, 19.2 g of 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol (based on 1 mole of isocyanate groups in the isocyanate compound, corresponding to a molar ratio of thiol groups in the polyfunctional thiol compound of 1.0) was added as a polyfunctional thiol compound. The mixture was degassed at 5 mbar and stirred for 1 hour to produce a polymerization composition.

[0148] Furthermore, the polymerization composition prepared as described above was filtered through a 1 μm PTFE filter and then poured into a mold consisting of a glass mold and tape. This mold was placed in an oven and the temperature was gradually increased from 10°C to 120°C for 20 hours to carry out the polymerization reaction. After polymerization was complete, the mold was removed from the oven and demolded to obtain a plastic lens. The obtained lens was annealed at 120°C for 6 hours.

[0149] Examples 2-2 to 2-8, and Comparative Examples 2-1 to 2-6 Polymerization compositions and lenses were produced in the same manner as in Example 2-1, except that the isocyanate compositions prepared in Examples 1-2 to 1-8 and Comparative Examples 1-1 to 1-6 were used. However, in Comparative Examples 1-3 and 1-4, filter clogging occurred during the filtration process after the production of the polymerization composition. Furthermore, the isocyanate compositions of Comparative Examples 1-5 were unsuitable for the manufacture of polymerization compositions due to the formation of precipitates, and therefore, the manufacture of polymerization compositions and lens manufacturing could not be carried out.

[0150] Experimental Example 1 The acidity of the isocyanate compositions prepared in the above examples and comparative examples was measured by the following method. <Acidity measurement method> 1. Equipment and Reagents 1.1 0.01N KOH standard solution (methanolic): 0.01 mol Potassium hydroxide methanolic standard solution (0.01N), DAEJUNG, S / T 1.2 n-Propyl Alcohol: Use a dilute hydrochloric acid solution, first adjusting the pH to 4-4.5. 1.3 300ml beaker 1.4 Potentiometric titrator with glass and calomel electrodes: Metrohm E 536

[0151] 2. Examination Procedures 2.1 Add 100 ml of n-Propyl Alcohol to a 300 ml beaker and stir. 2.2 Add 15 g of the isocyanate composition sample to the beaker containing the n-Propyl Alcohol, then cover with a watch glass and stir for 10 minutes. 2.3 After cooling the beaker, titrate it with a 0.01 N methanolic KOH standard solution using a potentiometric titrator to read the apparent acidity. Conditions: Mode; pH14, V0, titration rate 0.05ml increasement Apparent acidity occurs between pH 5.5 and 7.0. 2.4 A co-test is carried out in the same manner as described above, except that the isocyanate composition sample is not added in step 2.2.

[0152] 3.Calculation [Formula 1] Acidity (as HCl) (ppm) = [(AB) × N × f × 36.5 × 10 6 ] / (C×10 3 ) In the above formula 1, A: Volume (ml) of KOH methanol solution consumed in the titration of the isocyanate composition sample. B: Volume (ml) of KOH methanol solution consumed in the titration of the joint test. N:Normal concentration of KOH methanol solution f: This is a correction factor used to make the normal concentration of the KOH methanol solution used during measurement the same as that of a 0.01N KOH methanol solution, and is measured according to ASTM D-1638 and TOLOCHIMIE 04-01-68. For a 0.01N KOH methanol solution, the f value is 1. C: Weight (g) of the isocyanate composition sample.

[0153] [Table 1]

[0154] In Table 1 above, A, B, and C are as defined in Formula 1 above.

[0155] The experimental results showed that the isocyanate composition of Comparative Example 1-1, which did not contain any additives that could provide acidic components to be released by reacting with alcohol during its production, exhibited low acidity.

[0156] Furthermore, in Comparative Examples 1-3, where commercially available phosphate ester compounds were added to the isocyanate composition at the same level as in the Examples, low acidity was also observed.

[0157] Furthermore, in Comparative Examples 1-4 and 1-5, where a phosphate ester compound or phosphoric acid was added instead of the phosphonate compound of the present invention during the production of the isocyanate composition, the acidity was higher than that of Comparative Example 1-3, but slightly lower than that of the Examples.

[0158] Experimental Example 2 The isocyanate compositions prepared in the above examples and comparative examples were stored under a nitrogen atmosphere, specifically under conditions of 100% volume of atmospheric nitrogen by filling with 99.999% pure nitrogen, at a temperature of 15°C for 8 weeks. The increase in oligomer content in the isocyanate compositions over time was observed, and the storage stability was evaluated based on the results.

[0159] Specifically, the oligomer content (area%) in the isocyanate composition is obtained by subjecting the isocyanate composition to gel permeation chromatography (GPC) analysis under the following conditions to obtain a molecular weight distribution curve (GPC curve) for the isocyanate composition (X axis: log value of weight average molecular weight (M) (log M), Y axis: molecular weight distribution with respect to said log value (dwt / dlog M)), and the area of the fraction corresponding to the oligomer in the total area of the GPC curve is expressed as a percentage. Specifically, the oligomer content (area%) was calculated by the following mathematical formula 3.

[0160] [Mathematical Formula 3] Oligomer content (area%) = [E / D] × 100 In Mathematical Formula 3 above, D is the total area under the molecular weight distribution curve (GPC curve) obtained by gel permeation chromatography analysis of the isocyanate composition, E is the area of the peak corresponding to the oligomer in the molecular weight distribution curve of the isocyanate composition.

[0161] The total area of the GPC curve and the area of the fraction corresponding to the oligomer are each determined by integration. In this context, the oligomer refers to a polymer having a weight average molecular weight (Mw) of 600 to 2,000 g / mol, and the fraction corresponding to the oligomer on the GPC curve satisfies 19.42≦log Mw≦22.18.

[0162] <GPC Analysis Conditions> Equipment used: Agilent Columns: Agilent PL Mixed D, Agilent PLgel 100Å, Agilent PLgel 50Å Sample concentration: 1 wt / vol% in tetrahydrofuran (THF) Carrier: THF Detection method: RI Flow rate: 1.0 ml / min Column temperature: 25°C Detector: Agilent RI detector When creating the calibration curve, polystyrene standard foams with molecular weights ranging from 10⁴ to 24,600 g / mol were used.

[0163] Furthermore, based on the above measurement results, the oligomer content increase rate (%) was calculated using the following formula 2.

[0164] [Formula 2] Increase rate of oligomer content (%) = [(C f -Ci) / Ci]×100 In the above equation 2, Ci is the oligomer content (area%) in the isocyanate composition immediately after manufacturing. C f This is the oligomer content (area%) in the isocyanate composition when it is stored for 8 weeks at 15°C under a nitrogen atmosphere, specifically under a 100% volume nitrogen atmosphere achieved by filling with 99.999% pure nitrogen. The aforementioned Ci and C f These are the calculated values ​​using the aforementioned formula 3.

[0165] [Table 2]

[0166] In Table 2 above, a) shows the oligomer content in the isocyanate compositions immediately after production in the examples and comparative examples, measured by the same method as described above. b) In this case, accurate measurement of the oligomer content was difficult due to the formation of precipitates.

[0167] In the examples and comparative examples, the additives were added after the same m-XDI composition was manufactured, so the oligomer content in the isocyanate composition immediately after manufacturing was the same in all cases.

[0168] However, the oligomer content increased over time, and the rate of increase in oligomer content varied depending on the type of additive. Specifically, the rate of increase in oligomer content over time was lower in Examples than in Comparative Examples.

[0169] Experimental Example 3 (1) White turbidity phenomenon The isocyanate compositions produced in the above Examples and Comparative Examples were stored under refrigeration at a temperature of 15°C for 12 weeks under a nitrogen atmosphere, specifically an atmosphere of 100% by volume nitrogen obtained by charging nitrogen with a purity of 99.999%, after which the presence or absence of white turbidity was visually confirmed. The observation results were evaluated according to the following criteria and are shown in Table 3. <Evaluation Criteria> X: No white turbidity phenomenon O: White turbidity phenomenon occurred

[0170] (2) Haze (%) After the isocyanate compositions produced in the above Examples and Comparative Examples were stored under refrigeration at 15°C for 8 weeks under a nitrogen atmosphere, haze was measured in accordance with ASTM D1003. <Haze Measurement Conditions> Colorimeter: Ultrascan Pro Light source: C / 2 Cell: 10 mm quartz

[0171] (3) APHA After the isocyanate compositions produced in the above Examples and Comparative Examples were stored under refrigeration at 15°C for 8 weeks under a nitrogen atmosphere, APHA was measured using a HunterLab Ultrascan Pro in accordance with the method of ASTM D1209 under the following measurement conditions. The results are shown in Table 3 below. A smaller APHA value means superior discoloration resistance. <APHA Measurement Conditions> Colorimeter: Ultrascan Pro Light source: C / 2 Cell: 10 mm quartz

[0172]

Table 3

[0173] In Table 3 above, "-" indicates that accurate measurement was not possible.

[0174] The experimental results showed that the isocyanate composition in the example did not exhibit clouding and demonstrated improved discoloration resistance compared to the comparative example.

[0175] Experimental Example 4 For the polymerization compositions prepared in the above examples and comparative examples, the filtration time (min) was measured using a PTFE filter with a pore size of 1.0 μm (25 mm Diameter Syringe Filter, manufactured by Whatman), and the improvement in workability was evaluated from the results. Filtration time refers to the time from when 200g of polymerization composition passes through the filter until it has completed its passage.

[0176] [Table 4]

[0177] The experimental results showed that the polymerization composition of Comparative Example 2-1, which exhibited low acidity because it contained no additives that could provide acidic components to be released by reacting with alcohol during the production of the isocyanate composition, required a long filtration time.

[0178] In contrast, the polymerization composition of Example 2-1, in which a phosphonate compound of chemical formula 1 was added during the production of the isocyanate composition, showed a significantly shorter filtration time compared to the comparative example, confirming that it has improved workability.

[0179] On the other hand, the isocyanate compositions of Comparative Examples 1-3 had high viscosity, making it difficult to manufacture the polymerization compositions. As a result, the polymerization compositions of Comparative Examples 2-3 produced experienced filter clogging during the filtration process, making it impossible to measure the filtration time.

[0180] Further, in the case of Comparative Example 2-5, the generation of precipitates in the isocyanate composition of Comparative Example 1-5 made it unsuitable for the production of the polymerizable composition, and thus the production could not be carried out.

[0181] Experimental Example 5 For lenses produced using the polymerizable composition in the above Examples and Comparative Examples, YI (Yellowness Index) was measured by the method described below. However, the isocyanate composition of Comparative Example 1-3 had increased viscosity, which made it difficult to produce the polymerizable composition, and as a result, a lens could not be produced. Further, the isocyanate composition of Comparative Example 1-5 was unsuitable for producing the polymerizable composition due to the generation of precipitates, and thus lens production could not proceed. The results are shown in Table 5 below. <YI Measurement Method> Equipment: Ultrascan Pro, HunterLab Light source: D65 / 10 Measurement standard: ASTM E313

[0182] Further, the presence or absence of defects in the produced lenses was visually checked, and evaluation was performed according to the following criteria. <Defect Evaluation Criteria> X: No lens defect O: Lens defect present, a defective feature of white lines is observed in the lens

[0183]

Table 5

[0184] As a result of the experiment, it was confirmed that lenses produced using the polymerizable compositions of the Examples exhibited lower YI values compared to those of the Comparative Examples, and thus have a superior discoloration suppression effect.

[0185] On the other hand, the lenses of Comparative Examples 2-4 and 2-6, which used a phosphate compound during the production of the isocyanate composition, exhibited high YI, and in particular, defects occurred in the lens of Comparative Example 2-4 which used bis(2-ethylhexyl) phosphate.

[0186] Experimental Example 6 In the above examples and comparative examples, when manufacturing lenses using the RW polymerization composition, the degree of difficulty in manually separating the lenses from the lens mold was evaluated according to the following criteria, and the results are shown in Table 6. <Release properties evaluation criteria> ○: Good release properties. It can be easily released without applying force. △: Difficult to release from mold. Force must be applied, and it is not easily released. X: The mold breaks. Poor release properties.

[0187] [Table 6]

[0188] The experimental results showed that when lenses were manufactured using the polymerization composition of Comparative Example 2-4, it was difficult to release the lenses from the lens mold, and they could only be removed by applying force. From this, it was found that the polymerization composition of Comparative Example 2-4 had poor workability.

Claims

1. Isocyanate compounds, and It contains a phosphonate compound represented by the following chemical formula 1, Isocyanate compositions having an acidity of 100 to 500 ppm: 【Chemistry 1】 In the aforementioned chemical formula 1, R ａ and R ｂ Each of these independently represents a substitution or non-substitution of C. １－２０ Alkyl, substituted or unsubstituted C ６－２０ Aryl group, substituted or unsubstituted C ７－３０ Alkylaryl group, or substituted or unsubstituted C ７－３０ It is an arylalkyl group.

2. Said R ａ and R ｂ are each independently C １－８ alkyl group, phenyl group, or benzyl group, and said R ａ and R ｂ are each independently C １－６ substituted or unsubstituted with one or more substituents selected from the group consisting of alkyl groups, phenyl groups, hydroxy groups, and combination groups thereof, the isocyanate composition according to claim 1.

3. The isocyanate composition according to claim 1, wherein the phosphonate compound is ethylmethylphosphonate, pinacollylmethylphosphonate, mono-2-ethylhexyl(2-ethylhexyl)phosphonate, or monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

4. The isocyanate composition according to claim 1, wherein the phosphonate compound is contained in an amount of 100 to 3,000 ppm relative to the total weight of the isocyanate compound.

5. The isocyanate composition according to claim 1, wherein the isocyanate composition has an acidity of 110 to 150 ppm.

6. The isocyanate composition according to claim 1, wherein the isocyanate compound is a diisocyanate containing two isocyanate groups in its molecule.

7. The isocyanate composition according to claim 1, wherein the isocyanate compound is 1,5-pentamethylene diisocyanate, toluene diisocyanate, methylenediphenyl diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, or p-xylylene diisocyanate.

8. The isocyanate composition according to claim 1, further comprising a phenolic stabilizer.

9. The phenolic stabilizers mentioned above are phenol; dibutylhydroxytoluene; t-butylhydroquinone; butylhydroxyanisole; pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; N,N'-Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]; 3,5-bis(1,1-dimethylethyl)-4-hydroxyC7-C9 side-chain alkyl ester of benzenepropanoate; 3,3',3'',5,5',5''-Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol; Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]; Hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate; 2,6-di-tert-butyl-p-cresol; 2,6-diphenyl-4-octadecyloxyphenol; stearyl(3,5-di-tert-butyl-4-hydroxybenzyl) Roxyphenyl)propionate; distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphate; thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]; 4,4'-thiobis(6-tert-butyl-m-cresol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyrate] glycol ester; 4,4'-butylidenebis(6-tert-butyl-m-cresol); 2 ,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol); 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene; Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane; 2-tert-butyl-4-methyl-6(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol; 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]- The isocyanate composition according to claim 8, comprising 1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane; triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepine; or a mixture thereof.

10. The isocyanate composition according to claim 8, wherein the phenolic stabilizer is contained in an amount of 5 to 1,000 ppm relative to the total weight of the isocyanate compound.

11. The isocyanate composition according to claim 1, wherein the increase rate of oligomer content calculated by the following formula 2 is 600% or less: [Formula 2] Increase rate of oligomer content (%) = [(C ｆ -Ci) / Ci]×100 In the above formula 2, Ci is the oligomer content (area%) in the isocyanate composition immediately after manufacturing, calculated by gel permeation chromatography analysis. C ｆ This represents the oligomer content (area%) in the isocyanate composition after it has been stored in a nitrogen atmosphere at 15°C for 8 weeks, as calculated by gel permeation chromatography analysis.

12. The isocyanate composition according to claim 1, wherein, after being stored in a nitrogen atmosphere at 15°C for 8 weeks, the APHA value measured by ASTM D1209 is 15 or less, and the haze measured by ASTM D1003 is 0.5% or less.

13. An isocyanate composition according to any one of claims 1 to 12, One or more of the following: polyfunctional thiol compounds, polyfunctional alcohol compounds, and polyfunctional episulfide compounds A polymerization composition containing the following:

14. An isocyanate composition according to any one of claims 1 to 12, One or more of the following: polyfunctional thiol compounds, polyfunctional alcohol compounds, and polyfunctional episulfide compounds An article containing a polymer formed by polymerization.

15. The article according to claim 14, wherein the article is an optical adhesive, an optical bonding agent, or an optical lens.

16. The article according to claim 15, wherein the optical lens has a YI value of 2 or less when measured by ASTM E313.

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