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 TO RELATED APPLICATIONS] This application claims the benefit of priority 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 contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to an isocyanate composition that has improved storage stability, is inhibited from discoloring and clouding, and exhibits improved workability, such as a shortened filtering time. [Background technology]

[0003] Isocyanate compounds are highly valuable compounds that are used not only in the chemical and resin industries but also as fine 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-quality optical lenses, and demand is increasing.

[0004] However, isocyanate compounds are highly reactive and easily discolor or become cloudy when they react with moisture in the air during storage. Furthermore, when isocyanate compounds are stored for a long period of time, they self-polymerize to form dimers and higher oligomers, which can cause discoloration or cloudiness.

[0005] Isocyanate compounds are raw materials for polyurethane and are widely used in coatings, adhesives, paints, foams, optical materials, and more. However, when polyurethane lenses are produced using isocyanate compounds that have undergone discoloration or clouding, the molecular weight of the polymerization solution increases rapidly, resulting in reduced stirring power, increased filtering time, and filter clogging, which reduces workability. In addition, the produced lenses can suffer from reduced transparency and discoloration.

[0006] To solve this problem, the isocyanate compound is produced and stored by filling or sealing it with nitrogen gas to block out air, but there is still a risk of discoloration and cloudiness until the isocyanate compound is used up.

[0007] In addition, a method of adding a stabilizer to an isocyanate compound has also been proposed, but there have been problems with the added stabilizer causing discoloration during subsequent product manufacturing or reducing the stability of the isocyanate compound.

[0008] Therefore, there is a need for research into the production of isocyanate compositions that have improved storage stability, are free from discoloration or cloudiness even during long-term storage, and can exhibit improved workability during product manufacturing. Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide an isocyanate composition that has improved storage stability and is suppressed from discoloring and becoming cloudy, thereby improving transparency when applied to products and exhibiting improved workability, such as a shortened filtering time. [Means for solving the problem]

[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 above formula 1, R a and R b are each independently a substituted or unsubstituted C 1-20 Alkyl groups, substituted or unsubstituted C 6-20 Aryl groups, substituted or unsubstituted C 7-30 alkylaryl groups, or substituted or unsubstituted C 7-30 It is an arylalkyl group.

[0011] The present invention also provides a polymerization composition containing the isocyanate composition and at least one of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0012] The present invention also provides an article comprising a polymer obtained by polymerizing the isocyanate composition and one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound. [Effects of the Invention]

[0013] The isocyanate composition according to the present invention has improved storage stability and is inhibited from discoloring and becoming cloudy, thereby improving the transparency of products when applied thereto.

[0014] Additionally, the isocyanate composition may exhibit improved workability, such as reduced filtering time.

[0015] Furthermore, a polymerization composition containing the isocyanate composition and a polyfunctional thiol compound, a polyfunctional alcohol compound, or a polyfunctional episulfide compound has excellent physical properties and can be used in a wide range of fields, such as plastic paints, automotive paints, film coating agents, various inks, various pressure-sensitive adhesives / adhesives, sealants, various microcapsules, plastic lenses, artificial and synthetic leather, reaction injection molded (RIM) products, slush powder, elastic molded products (spandex), and urethane foam. Among these, the excellent pressure-sensitive adhesive / adhesive properties and transparency of the isocyanate composition make it particularly useful as a material for optical articles such as optical pressure-sensitive adhesives, optical adhesives, eyeglass lenses, camera lenses, and prisms. DETAILED DESCRIPTION OF THE INVENTION

[0016] The terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the present invention. The singular expressions include the plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprise," "include," "comprise," "have," and the like are intended to specify the presence of implemented features, steps, components, or combinations thereof, and should be understood as not precluding the presence or additional possibility of one or more other features, steps, components, or combinations thereof.

[0017] As used herein, the term "substituted or unsubstituted" refers to a group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, nitrile, nitro, hydroxy, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, aryloxy, alkylthioxy, arylthioxy, alkylsulfoxy, arylsulfoxy, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamine, aralkylamine, heteroarylamine, arylamine, arylphosphine, or heteroaryl groups containing one or more N, O, and S atoms, or a group formed by combining these groups, specifically, a group formed by combining and linking two or more of the above-listed substituents. For example, a "substituent having two or more linked substituents" may be a biphenyl group. In other words, a biphenyl group may be interpreted as either an aryl group or a substituent formed by linking two phenyl groups.

[0018] Unless otherwise stated herein, ordinary temperature means ordinary laboratory temperature of 23±5° C., and ordinary pressure means ordinary laboratory pressure of 1±0.05 atm.

[0019] Unless otherwise specified in this specification, a nitrogen atmosphere means that nitrogen is present in the atmospheric gas, and specifically, the nitrogen concentration in the atmospheric gas is greater than 0% by volume and less than 100% by volume.

[0020] Since the present invention can be modified in various ways and can have various forms, specific examples are exemplified and described in detail below, but it is not intended to limit the present invention to the specific disclosed forms, and it should be understood that the present invention includes any modifications, equivalents, or alternatives falling within the spirit and technical scope of the present invention.

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

[0022] Due to their high reactivity with moisture or alcohol, isocyanate compounds are typically stored in a nitrogen-filled, sealed, and refrigerated container after preparation. However, upon opening, they can react with moisture in the air or become discolored or cloudy due to ambient temperature. Furthermore, when a sealed isocyanate compound is opened and used, the oligomer content increases or yellowing occurs over the storage time until the compound is used up. As a result, when polyurethane lenses are manufactured using such isocyanate compounds, the viscosity of the composition increases rapidly, resulting in a decrease in stirring force, an increase in filtering time, or filter clogging, reducing workability. Furthermore, the manufactured lenses lose transparency and discoloration.

[0023] Therefore, the present inventors conducted research into an isocyanate composition that can suppress the rate of increase in oligomers generated by the self-polymerization of an isocyanate compound during long-term storage and can also improve workability during lens manufacturing. As a result, they found that when a phosphonate-based compound is used together with an isocyanate compound, the rate of oligomerization of the isocyanate compound can be reduced, thereby suppressing discoloration and cloudiness caused by the oligomers. They also found that this can prevent lens color changes caused by various additives added to improve lens workability, and can also shorten the filtering time during lens manufacturing, improving workability, thereby completing the present invention.

[0024] Specifically, the isocyanate composition according to the present invention contains an isocyanate compound and a phosphonate compound represented by the following Chemical Formula 1. [ka] In the above formula 1, R a and R bare each independently a substituted or unsubstituted C 1-20 Alkyl groups, substituted or unsubstituted C 6-20 Aryl groups, substituted or unsubstituted C 7-30 alkylaryl groups, or substituted or unsubstituted C 7-30 It is an arylalkyl group.

[0025] In addition, the R a and R b When is substituted, specifically, it may be substituted with one or more substituents selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group, a hydroxy group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, and a combination thereof.

[0026] Specifically, in the above-mentioned chemical formula 1, R a and R b are each independently a substituted or unsubstituted C 1-18 Alkyl groups, substituted or unsubstituted C 6-18 Aryl groups, substituted or unsubstituted C 7-18 alkylaryl groups, or substituted or unsubstituted C 7-18 may be an arylalkyl group, a and R b are substituted, each independently, C 1-12 Alkyl group, C 3-12 Cycloalkyl groups, C 6-12 Aryl group, C 7-18 Arylalkyl groups, C 7-18 Alkylaryl group, hydroxy group, C 1-12 Alkoxy group; C 2-18 Alkoxyalkyl group, C 6-12 It may be substituted with one or more substituents selected from the group consisting of aryloxy groups and combinations thereof.

[0027] More specifically, in the above formula 1, R a and R b are each independently, C 1-8may be an alkyl group, a phenyl group, or a benzyl group, and in this case, a and R b are each independently, C 1-6 It may be unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl groups, phenyl groups, hydroxy groups, and combinations thereof.

[0028] Meanwhile, in the present invention, the term "combined group" refers to a group in which two or more functional groups are bonded. For example, a combination of a hydroxy group and a methyl group may be a methoxy group or a hydroxymethyl group, and a combination of a hydroxy group and a phenyl group may be a phenoxy group or a hydroxyphenyl group. As another example, a combination of a methyl group and a phenyl group may be a benzyl group or a methylphenyl group.

[0029] More specifically, in the above formula 1, R a and R b may each 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 compound include ethyl methylphosphonate (CAS No. 1832-53-7), pinacolyl methylphosphonate, mono-2-ethylhexyl(2-ethylhexyl)phosphonate, and monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and any one or a mixture of two or more of these may be used.

[0031] Higher acidity of the isocyanate composition can decrease the reaction rate of the isocyanate, and as a result, can slow or inhibit isocyanate oligomerization.

[0032] The phosphonate compound provides an acid component that is liberated by reacting with alcohol during the production of the isocyanate composition, thereby increasing the acidity of the isocyanate composition, thereby slowing or inhibiting the reaction rate and oligomerization of the isocyanate, and also suppressing discoloration and cloudiness caused by the oligomers.

[0033] In addition, the phosphonate-based compound can prevent lens color change caused by additives added to improve lens workability, and can also suppress an increase in viscosity of the isocyanate composition, thereby shortening the filtering time during lens manufacturing.

[0034] The phosphonate compounds can exhibit superior storage stability due to the difference in reactivity compared to phosphonic acid (HPO(OH)2) and phosphorous acid (P(OH)3).

[0035] Phosphoric acid (HPO (or PO(OH))) has excessively high reactivity, which causes precipitates during the preparation of an isocyanate composition, making it difficult to prepare a polymerization composition using it. However, the phosphonate-based compounds exhibit an appropriate level of reactivity and are free from the risk of precipitate formation.

[0036] In addition, while phosphoric acid esters can partially increase the acidity of isocyanate compositions, they also increase the viscosity of the polymerization composition, which can lead to filter clogging during lens production. In contrast, the phosphonate compounds do not increase viscosity.

[0037] Meanwhile, the acidity (as HCl) (ppm) of an isocyanate composition is the amount of acid released upon reaction with alcohol at room temperature (23±5°C), converted to HCl, and expressed as a relative weight ratio to the total weight of the isocyanate compound. The acidity of the isocyanate composition according to the present invention is determined by the content of acidic groups derived from the phosphonate compound. Therefore, the acidity can be adjusted by controlling the type and / or amount of the phosphonate compound, and the effects 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 slower the reaction rate of the isocyanate, which can delay or inhibit isocyanate oligomerization. However, if the acidity is too high, the isocyanate reaction rate may be too slow, making it difficult to form polymers and use in the manufacture of products such as lenses. Furthermore, to compensate for the slowdown in the isocyanate reaction rate caused by the use of an excess amount of phosphonate compound, an excess amount of catalyst must be used. In this case, the excess amount of catalyst can reduce reaction efficiency, deteriorate physical properties, and cause discoloration and clouding of the isocyanate composition, resulting in reduced product quality.

[0040] Thus, the phosphonate compound can be added in an amount that results in an acidity of the isocyanate composition of 500 ppm or less, more specifically, 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, to fully realize the effects of adding the phosphonate compound, such as increasing the acidity, the phosphonate compound can be added in an amount that results in an acidity of the isocyanate composition of 100 ppm or more, 110 ppm or more, or 113 ppm or more.

[0041] In the present invention, specifically, the acidity was calculated by potentiometric titration of the isocyanate composition with a 0.01N potassium hydroxide (KOH) methanol solution, and using the resulting measured value, the acidity was calculated according to the following mathematical formula 1. The measurement method and conditions will be explained in detail in the following experimental examples.

[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 titration of isocyanate composition sample B: Volume (ml) of KOH methanol solution consumed in the co-test titration N:Normal concentration of KOH in methanol f: If the concentration of the KOH methanol solution used during measurement is different from the normal concentration, this is a correction coefficient to make it the same as a 0.01N KOH methanol solution. It is measured according to ASTM D-1638, TOLOCHIMIE 04-01-68. In the case of 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 based on the total weight of the isocyanate compounds, provided that the acidity range is satisfied. When the content is within this range, the isocyanate composition exhibits an acidity within this range, thereby achieving an optimal oligomerization rate retardation effect. More specifically, the phosphonate compound may be included in an amount of 100 ppm or more, 200 ppm or more, 300 ppm or more, 350 ppm or more, 380 ppm or more, 600 ppm or more, or 900 ppm or more, and 3,000 ppm or less, 2,000 ppm or less, 1,500 ppm or less, 1,200 ppm or less, or 1,100 ppm or less based on the total weight of the isocyanate compounds.

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

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

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

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

[0048] Generally, discoloration and cloudiness of isocyanate compositions are caused by oligomerization of isocyanate, quinoid formation of benzene rings in the molecule, or addition products formed by oxygen, moisture, or high heat during the synthesis and purification process. The phenolic stabilizer can prevent discoloration and cloudiness of isocyanate compositions by suppressing these side reactions through a radical scavenging reaction.

[0049] However, if the stabilizer content is below a certain level, it is difficult to achieve sufficient discoloration or clouding prevention effects. 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. Therefore, in the present invention, the phenolic stabilizer is included in an amount of 5 ppm to 1,000 ppm based on the total weight of the isocyanate compounds. More specifically, by including the phenolic stabilizer in an amount of 5 ppm or more, 8 ppm or more, or 10 ppm or more and 1,000 ppm or less, 500 ppm or less, 200 ppm or less, 100 ppm or less, 50 ppm or less, 30 ppm or less, or 20 ppm or less based on the total weight of the isocyanate compounds, more enhanced discoloration and clouding prevention effects can be achieved.

[0050] Furthermore, controlling the amounts of the phosphonate compound and phenolic stabilizer used can further reduce the rate of increase in oligomer content and enhance the effect of suppressing coloration and cloudiness. Specifically, the phosphonate compound and 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 regard, when describing the weight ratio, "more than" and "less than" refer to the amount of the phosphonate compound used.

[0051] The phenolic stabilizer is specifically phenol or a derivative thereof containing a phenol structure in the molecule, and specific examples thereof include phenol; or dibutylhydroxytoluene (BHT), t-butylhydroquinone (TBHQ), butylhydroxyanisol (BHA), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, manufactured by BASF), thiodiethylenebis[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 1045, manufactured by BASF), and the like. 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), ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Irganox 245, BASF), hexamethylene bis[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)butyric acid] 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-bis1,1-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][1,3,2]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, manufactured by Sumitomo Co., Ltd.); and sterically hindered phenols such as dioxaphosphepin; and any one of these can be used alone or in combination.

[0052] Among these, from the viewpoint of the effect of improving transparency by preventing coloration and clouding, 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]dioxaphosphepine, or a mixture thereof can be used.

[0053] The isocyanate composition may further include an oligomer in which two or more of the isocyanate-based compounds are bonded as a by-product.

[0054] The oligomer of the isocyanate compound may be a dimer in which two isocyanate compounds are bonded, a trimer in which three isocyanate compounds are bonded, or a compound in which four or more isocyanate compounds are bonded, or a compound in which four to ten isocyanate compounds are bonded. The oligomer may be generated as a side reaction during the synthesis of an isocyanate compound by the reaction of an amine compound with a phosgene compound, or may be a polymer formed independently due to the high reactivity of the isocyanate compound after synthesis is complete. These oligomers can affect not only the transparency of the isocyanate composition itself but also cause discoloration and opacity in polymerization compositions containing the isocyanate composition. Therefore, the content of these oligomers must be reduced in isocyanate compositions used in optical applications. However, strict control of the oligomer content in commercial processes is difficult in terms of process efficiency and cost. Therefore, the isocyanate composition of the present invention may further contain the oligomers that are inevitably generated. However, controlling the content through the manufacturing process and the use of phosphonic acid can improve the transparency and color properties of the product while maintaining processability.

[0055] Specifically, the isocyanate composition may contain oligomers in an amount of 1 area % or less immediately after production. The oligomer content is determined by calculating the percentage of the peak area corresponding to the oligomer relative to the total peak area in a molecular weight distribution curve obtained by gel permeation chromatography analysis of the isocyanate composition immediately after production. The peak area is calculated by integration. The method for measuring and calculating the oligomer content is as described in the following experimental examples.

[0056] By including a phosphonate compound that retards the rate of oligomerization of isocyanate in the isocyanate composition, the content of oligomers and the rate of increase of the oligomer content over time are lower than in the prior art.

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

[0058] [Formula 2] Oligomer content increase rate (%) = [(C f -Ci) / Ci] x 100 In the above equation 2, C i is the oligomer content (area%) in the isocyanate composition immediately after production, calculated by gel permeation chromatography analysis; C f is the content (area %) of oligomers in the isocyanate composition after storing the isocyanate composition under a nitrogen atmosphere at 15°C for 8 weeks, calculated by gel permeation chromatography analysis.

[0059] In this case, the term "under a nitrogen atmosphere" specifically refers to a condition in which nitrogen is 100% by volume based on the total volume of the air atmosphere, as a result of nitrogen filling.

[0060] Specifically, the Ci and C f is a value calculated by the following Equation 3.

[0061] In the present invention, nitrogen with a purity of 99.999% was used when filling the nitrogen tank.

[0062] [Formula 3] Oligomer content (area%) = [E / D] x 100 In the above equation 3, D is the total area under 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 are the same as those in the experimental examples described below.

[0064] 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, respectively. Here, 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 in the GPC curve is 19.42≦log Mw≦22.18.

[0065] More specifically, the isocyanate composition may be stored at 15°C for 8 weeks under a nitrogen atmosphere, specifically, under conditions of 100% by volume nitrogen in the atmosphere by nitrogen filling, and then the oligomer content calculated by GPC analysis, i.e., the GPC oligomer area ratio, may be 0.5 area% or less, or 0.45 area% or less. Since a lower oligomer content indicates better discoloration resistance, the lower limit is not particularly limited, but may be more than 0 area% or 0.1 area% or more. In the present invention, nitrogen with a purity of 99.999% was used for the nitrogen filling.

[0066] Meanwhile, in the present invention, the content (area %) of oligomers in an isocyanate composition is determined by obtaining a molecular weight distribution curve (GPC curve) for the isocyanate composition by GPC analysis, where the logarithm of the weight average molecular weight (M) (log M) is the x-axis and the molecular weight distribution (dwt / dlog M) relative to the logarithm is the y-axis. The content (area %) of oligomers is the percentage of the area of ​​the fraction corresponding to oligomers in the total area of ​​the GPC curve, and can be calculated using Equation 3. Specific GPC analysis methods and conditions will be described in detail in the following experimental examples.

[0067] As described above, the rate of increase in the oligomer content and the oligomer content are low immediately after and after the production of the isocyanate composition, so that discoloration and clouding of the isocyanate composition can be effectively prevented.

[0068] Specifically, the isocyanate composition has an APHA value of 15 or less as measured according to ASTM D1209 after being stored for 8 weeks at 15°C in a nitrogen atmosphere, specifically in an atmosphere of 100% by volume of nitrogen filled with nitrogen. More specifically, the APHA value 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 may be, for example, more than 0 or 1 or more.

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

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

[0071] The isocyanate composition can be prepared by mixing an isocyanate compound and a phosphonate compound represented by Chemical Formula 1.

[0072] More specifically, the isocyanate composition can be prepared by a method including the steps of: reacting an amine or its salt with phosgene to prepare an isocyanate compound; and mixing the isocyanate compound with the phosphonate compound represented by Chemical Formula 1.

[0073] The amine is an aromatic, alicyclic, or aliphatic diamine containing two amine groups in the 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 any one or a mixture of two or more of these may be used depending on the structure of the desired diisocyanate.

[0075] The amine salt refers to a salt produced by the reaction of the amine with an acid, and may be, for example, a hydrochloride produced by the reaction of an amine with anhydrous hydrochloric acid, a carbonate produced by the reaction of an amine with carbonic acid, etc. Although amines react rapidly with phosgene, the reaction rate can be slowed down by switching to a solid salt.

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

[0077] The preparation of the amine salt by the reaction of the amine with the acid may be carried out in a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; chlorinated aromatic hydrocarbon solvents such as monochlorobenzene, 1,2-dichlorobenzene, and 1,4-dichlorobenzene; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. Mixtures of two or more of these solvents may also be used. Since these solvents can also be used as solvents for the phosgenation reaction, the amine salt may be prepared by reacting the amine with the acid in the solvent, and then phosgene may be added to carry out the phosgenation reaction without a separate purification process.

[0078] The amine salt preparation may be carried out at a temperature of 40° C. or less, 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 in the reactor is maintained at 90° C. or less.

[0079] The reaction of the amine or its salt with phosgene may be carried out at a temperature ranging from 80° C. or higher, or from 90° C. or higher, to 140° C. or lower, or from 130° C. If the reaction temperature is too low, problems such as pipe clogging due to the precipitation of solids may occur, whereas if the temperature is too high, problems such as side reactions such as phosgene decomposition may occur. Therefore, it is preferable to carry out the reaction within this temperature range.

[0080] The reaction of the amine or its salt with phosgene may also be carried out in an organic solvent.

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

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

[0083] In addition, the ester-based organic solvent may be specifically a fatty acid ester such as amyl formate, 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, methylcyclohexyl acetate, benzyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, ethyl acetate, butyl stearate, butyl lactate, or amyl lactate; or an aromatic carboxylic acid ester such as methyl 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, among the aromatic hydrocarbon organic solvents and ester organic solvents.

[0085] When the phosgenation reaction is carried out in an organic solvent, 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, a large amount of amine salt may precipitate.

[0086] In addition, during the reaction of the amine or its salt with phosgene, a compound represented by the following Chemical Formula 2 may be optionally added. [ka]

[0087] In the above formula 2, R1 to R4 are each independently a substituted or unsubstituted C 1-12 Alkyl groups, substituted or unsubstituted C 3-12 Cycloalkyl groups, or substituted or unsubstituted C 6-12is an aryl group, X is hydrogen, hydroxy or acetamido; Y is oxyl, substituted or unsubstituted C 1-12 Alkoxy, or substituted or unsubstituted C 6-12 It is aryloxy.

[0088] The compound represented by Chemical Formula 2 eliminates hydrogen from the amine or intermediate carbamoyl chloride during the phosgenation reaction, promoting the forward reaction and suppressing side reactions, thereby suppressing the generation of monoisocyanates such as ethylbenzyl isocyanate (EBI) and chloromethylbenzyl isocyanate (CMBI).

[0089] More specifically, the compound represented by the above Chemical Formula 2 is a compound represented by the above Chemical Formula 2, wherein R1 to R4 are each independently selected from the group consisting of C 1-12 The compound may be an alkyl group, X is hydrogen, a hydroxy group, or an acetamido group, and Y is oxyl (O·).

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

[0091] The compound represented by 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 this content range, it is preferable because the generation of diisocyanate oligomers is minimized and diisocyanate can be synthesized with high purity and high yield.

[0092] The isocyanate formed as a result of the phosgenation reaction is obtained in the form of a mixture of a solvent, unreacted phosgene, and by-products together with hydrogen chloride, and therefore one or more of a purification step for separating the isocyanate compound in high purity from the reaction mixture, a solvent removal step by distillation, and a removal step such as bubbling nitrogen through the unreacted phosgene and hydrogen chloride gas may be carried out.

[0093] The purification step may be carried out by a conventional method used for purifying isocyanate compounds, for example, by vacuum distillation and / or thin film distillation.

[0094] However, if the purification process of the isocyanate compound is performed under excessively high temperature conditions or if the purification step time is extended, the stability of the isocyanate compound may be significantly reduced, and if the purification step is performed under excessively low temperature conditions, the process efficiency may be reduced. Therefore, the purification step is preferably performed 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 and become unstable.

[0095] Next, the obtained isocyanate compound is mixed with the phosphonate compound represented by the above-mentioned Chemical Formula 1 to prepare an isocyanate composition.

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

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

[0098] The isocyanate composition produced by the production 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 producing optical articles.

[0099] Therefore, according to the present invention, there is provided a polymerization composition comprising the isocyanate composition and at least one 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 a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound in a mixed state or in a separated state. That is, in the polymerization composition, the isocyanate composition and the polyfunctional thiol compound, the polyfunctional alcohol compound, or the polyfunctional episulfide compound may be blended in contact with each other or separated 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, may be a compound having two or more, or three or more and eight or less, or five or less thiol groups in one molecule.

[0102] Examples of the polyfunctional thiol compound include 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol, 1,9-dimercapto-3,7-dithianonane, 1,13-dimercapto-3,7,11-trithiatridecane, glycol di(3-mercaptopropionate), and glycol di(3-mercaptopropionate). di(3-mercaptopropionate), 1,4-Dithiane-2,5-diyldimethanethiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane tri(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-trithiol15-trithiol).

[0103] The polyfunctional alcohol compound may be a compound containing two or more hydroxy groups in one molecule, specifically, a compound having two or more, or three or more and eight or less, or four or less hydroxy groups in one 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, and low-molecular-weight polyols, and any one or a mixture of two or more of these can be used.

[0104] The polyfunctional episulfide compound may be a compound containing two or more episulfide groups, i.e., thioepoxy groups, in the molecule, 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). (beta-epithiopropylthiomethyl)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 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-thiahexane San, 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-epithiopropylthioethyl)thiomethyl]-3,7-dithianonane 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-epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithiaundecane bis(4-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, ... -(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,The compound 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, or 0.8 to 1.2, or 0.9 to 1.1, but the present invention is not necessarily limited thereto.

[0106] The polymerization composition may further contain additives such as an internal mold release agent, an ultraviolet absorber, a urethane reaction catalyst, a polymerization initiator, a heat stabilizer, a hue corrector, a chain extender, a crosslinking agent, a light stabilizer, a filler, and a photosensitizer, as necessary, and the content thereof may be appropriately determined within a range that does not inhibit discoloration and discoloration-inhibiting properties of the composition.

[0107] For example, the polymerization composition may further include an internal mold release agent to improve mold release during subsequent product formation.

[0108] Specific examples of the internal release agent include phosphate-based release agents, alkyl phosphate-based release agents, and fatty acid ester-based release agents, and any one or a mixture of two or more of these can be used. Among these, phosphate-based release agents are preferred.

[0109] As the phosphate ester-based release agent, ZELEC UN TM Commercially available products such as those manufactured by Stepan Company can also be used.

[0110] The internal mold release agent may be present 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, based on the total weight of the polymerization composition.

[0111] As another example, the polymerization composition may further include an ultraviolet absorber. Specific examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers and formamidine-based ultraviolet absorbers. One or a mixture of two or more of these may be used. Among these, formamidine-based ultraviolet absorbers are preferred.

[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 contained 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] Examples of the urethane reaction catalyst 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; and dialkyltin sulfide compounds, and any one or a mixture of two or more of these can be used.

[0115] The urethane reaction catalyst may be contained 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% by weight or less, based on the total weight of the polymerization composition.

[0116] The polymerization composition can exhibit excellent discoloration resistance by delaying or inhibiting the reaction rate and oligomerization of isocyanate due to the phosphonate compound contained in the isocyanate composition, and can prevent lens discoloration caused by various additives added to improve workability during lens production. Furthermore, the polymerization composition can exhibit improved workability, such as shortened filtering time during product production, by inhibiting an increase in viscosity of the polymerization composition.

[0117] As described above, 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 properties, particularly transparency, such as optical pressure-sensitive adhesives, optical adhesives, eyeglass lenses, camera lenses, plastic lenses, and prisms.

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

[0119] For example, when the polymerization composition contains a polyfunctional thiol compound, the polymerization reaction is carried out by a urethane reaction between an isocyanate group in the isocyanate compound and a thiol group in the polyfunctional thiol compound. The polyurethane produced by the reaction with the polyfunctional thiol compound exhibits excellent transparency and is therefore particularly useful for producing optical articles, particularly 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 a urethane reaction (or a condensation polymerization reaction) between the isocyanate in the aromatic diisocyanate and the hydroxyl group in the polyfunctional alcohol. The polyurethane produced by the reaction with the polyfunctional alcohol compound exhibits excellent transparency and excellent adhesion / bonding properties, making it useful as an optical pressure-sensitive adhesive or optical adhesive.

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

[0122] In addition, 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, since this allows the reaction rate to be easily controlled without the risk of discoloration and also increases the reaction efficiency.

[0123] The polymerization reaction may be carried out in the absence of a catalyst or in the presence of a urethanization catalyst as described above. When the polymerization reaction is carried out in the presence of a catalyst, the catalyst may be added when the polyfunctional thiol compound, polyfunctional alcohol compound, or polyfunctional episulfide compound is mixed with the isocyanate composition.

[0124] The degree of progress of the polymerization reaction can be estimated by measuring the concentration of isocyanate groups in the polymerization reaction product by the n-dibutylamine method using 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 reaction product reaches the calculated value of the remaining isocyanate groups after the reaction with the polyfunctional thiol compound.

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

[0126] Meanwhile, the article containing the polymer may be specifically a paint such as a paint for plastics or an automobile paint; a coating agent such as a film coating agent; various inks; sealants; various microcapsules; artificial leather such as artificial and synthetic leather; reaction injection molded (RIM) products; slush powder; elastic molded products (spandex); urethane foam; or an optical article such as an optical pressure sensitive adhesive, an optical adhesive, a spectacle lens, a camera lens, a plastic lens, or a prism. Considering the excellent transparency of the polymerization composition, the article may be an optical article, particularly an optical pressure sensitive adhesive or an optical adhesive, or an optical lens such as a spectacle lens or a camera lens.

[0127] The article may be produced by carrying out a molding step after the polymerization reaction of the polymerization composition, or may be produced by a molding step using the polymerization composition, in which case the polymerization reaction occurs simultaneously during the molding step.

[0128] For example, in the case of an optical lens, the polymerization composition is injected into a lens mold, and the mold temperature is then increased to polymerize the isocyanate compound and the polyfunctional thiol compound or polyfunctional episulfide compound. The mold temperature is then increased to a temperature range where the urethane polymerization reaction occurs, as described above. After the polymerization reaction is complete, the resulting polymer, specifically, polythiourethane, can be separated from the mold to obtain the optical lens.

[0129] The polymer, specifically polythiourethane, produced from the polymerization composition according to the present invention exhibits excellent transparency and improved workability, and is therefore particularly useful for producing optical articles, particularly optical pressure-sensitive adhesives and optical lenses.

[0130] For 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 E 313. A lower YI value indicates better discoloration resistance, so the lower limit is not particularly limited, and specifically, the YI value may be more than 0 or 0.1 or more.

[0131] Preferred examples are presented below to aid in understanding the present invention. However, the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present invention. Naturally, such changes and modifications also fall within the scope of the appended claims. [Example]

[0132] <Production of isocyanate composition> Example 1-1 A flask was charged with 471 g of 1,2-dichlorobenzene, 32.5 g of m-XDA with a purity of 99.4%, and 0.24 g of 4-hydroxy TEMPO. Anhydrous hydrochloric acid was added at a rate of 20 g / hr at room temperature (23 ± 5°C) and stirred. The temperature rose to 50°C after adding anhydrous hydrochloric acid. After 4 hours of addition, the formed salt was cooled to room temperature, and 43 g of phosgene was added to the reactor, which was then heated to 130°C. A dry ice-acetone condenser was used to prevent phosgene from leaking out from the reactor until the end of the reaction. 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 reactor was cooled to 80°C, and nitrogen was blown in to 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 methylphosphonate (boiling point: 181° C.) to the m-XDI and mixing them.

[0133] Example 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 ethyl methyl phosphonate.

[0134] Examples 1-3 An isocyanate composition was produced 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 ethyl methylphosphonate.

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

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

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

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

[0139] Examples 1-8 An isocyanate composition was prepared in the same manner as in Examples 1-4, except that 200 ppm of phenol was added together with 600 ppm of pinacolyl methylphosphonate to m-XDI.

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

[0141] Comparative Example 1-2 An isocyanate composition was prepared in the same manner as in Example 1-1, except that 200 ppm of phenol was added instead of ethyl methylphosphonate.

[0142] Comparative Examples 1-3 In Example 1-1, ethyl methylphosphonate was replaced with ZELEC, a phosphate ester compound. TM An isocyanate composition was produced in the same manner as in Example 1-1, except that 250 ppm of UN (Stepan Company) was added.

[0143] Comparative Examples 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 ethyl methylphosphonate.

[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, the produced isocyanate composition produced precipitates.

[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 monoester and diester) (DEP) was added instead of ethyl methylphosphonate.

[0146] <Production of Polymerizable Composition and Optical Lens> Example 2-1 20.8 g of the isocyanate composition prepared in Example 1-1, ZELEC as an internal mold release agent, TM UN (Stepan) 0.04 g 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 about 20 minutes.

[0147] 0.002 g of dibutyltin dichloride was added to the resulting mixture, and the mixture was 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, an amount corresponding to a molar ratio of 1.0 of thiol groups in the multifunctional thiol compound) was added as a multifunctional thiol compound, and the mixture was degassed under 5 mbar conditions and stirred for 1 hour to prepare a polymerization composition.

[0148] The polymerization composition prepared 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, where the polymerization reaction was carried out for 20 hours. After polymerization was completed, 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 Polymerizable compositions and lenses were prepared 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 filtering process after the production of the polymerization composition. Furthermore, the isocyanate composition of Comparative Example 1-5 was not suitable for producing a polymerization composition due to the generation of precipitates, and therefore production of a polymerization composition and lens production 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): 0.01mol Potassium hydroxide methanolic standard solution (0.01N), DAEJUNG, S / T 1.2 n-Propyl Alcohol: First, adjust the pH to 4-4.5 with a dilute hydrochloric acid solution. 1.3 300ml beaker 1.4 Potentiometric titrator with glass and calomel electrodes: Metrohm E 536

[0151] 2. Examination Procedures 2.1 Add 100ml of n-Propyl Alcohol to a 300ml beaker and stir. 2.2 Add 15 g of the isocyanate composition sample to the beaker containing the n-propyl alcohol, cover with a watch glass and stir for 10 minutes. 2.3 After the beaker has cooled, read the apparent acidity by titrating with 0.01N methanolic KOH standard solution in a potentiometric titrator. Conditions: Mode; pH14, V0, titration rate 0.05ml increasement Apparent acidity occurs between pH 5.5 and 7.0. 2.4 A parallel test is carried out in the same manner as above, carrying out steps 2.1 to 2.3, except that no isocyanate composition sample is 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 titration of isocyanate composition sample B: Volume (ml) of KOH methanol solution consumed in the co-test titration N:Normal concentration of KOH in methanol f: A coefficient used to correct for a different normal concentration of the KOH methanol solution used in the measurement, so that the result is the same as that of a 0.01N KOH methanol solution. 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 Equation 1 above.

[0155] As a result of the experiment, the isocyanate composition of Comparative Example 1-1, which did not contain any additive capable of providing an acid component that reacts with alcohol to be liberated during the production of the isocyanate composition, showed low acidity.

[0156] Furthermore, in Comparative Examples 1-3, in which a commercially available phosphate ester compound was added at the same level as in the Examples during the preparation of the isocyanate composition, low acidity was also observed.

[0157] In addition, in Comparative Examples 1-4 and 1-5, in which a phosphate ester compound or phosphoric acid was used instead of the phosphonate compound of the present invention during the preparation 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 examples and comparative examples were stored in a nitrogen atmosphere, specifically, in a 100% by volume atmosphere filled with nitrogen of 99.999% purity, at a temperature of 15°C for 8 weeks in a refrigerator, and the increase in oligomer content in the isocyanate composition over time was confirmed, and the storage stability was evaluated from the results.

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

[0160] [Formula 3] Oligomer content (area%) = [E / D] × 100 In the above formula 3, D is the total area under the curve in 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 for 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. At this time, the oligomer means 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.

[0162] [[ID=第十九]] <GPC analysis conditions> Equipment used: Agilent Columns: Agilent PL Mixded 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 preparing the calibration curve, polystyrene standard foams with molecular weights of 104 to 24,600 g / mol were used.

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

[0164] [Formula 2] Oligomer content increase rate (%) = [(C f -Ci) / Ci] x 100 In the above equation 2, Ci is the oligomer content (area%) in the isocyanate composition immediately after production, C f is the content (area%) of oligomers in the isocyanate composition when the isocyanate composition is stored in a nitrogen atmosphere, specifically, in an atmosphere of 100% by volume of nitrogen filled with nitrogen of 99.999% purity, at 15°C for 8 weeks, The Ci and C f are the values ​​calculated by the above-mentioned Equation 3.

[0165] [Table 2]

[0166] In Table 2 above, a) indicates the oligomer content in the isocyanate composition of the examples and comparative examples immediately after production, which was measured by the same method as above. In b), it was difficult to accurately measure the oligomer content due to the occurrence of precipitates.

[0167] In the Examples and Comparative Examples, the same m-XDI composition was produced and then the additives were added later, so the oligomer content in the isocyanate composition immediately after production was the same.

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

[0169] Experimental Example 3 (1) Cloudiness phenomenon The isocyanate compositions produced in the above examples and comparative examples were placed in a nitrogen atmosphere. Specifically, after refrigerated storage at 15°C for 12 weeks in an atmosphere of 100% nitrogen by filling with nitrogen of 99.999% purity, the presence or absence of cloudiness was visually confirmed. The observation results were evaluated according to the following criteria and shown in Table 3. <Evaluation criteria> X: No cloudiness phenomenon O: Cloudiness phenomenon occurred

[0170] (2) Haze (%) After the isocyanate compositions produced in the above examples and comparative examples were refrigerated at 15°C for 8 weeks in a nitrogen atmosphere, the haze was measured according to ASTM D1003. <Haze measurement conditions> Color difference system: 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 refrigerated at 15°C for 8 weeks in a nitrogen atmosphere, APHA was measured using HunterLab's Ultrascan Pro under the following measurement conditions according to the method of ASTM D1209. The results are shown in Table 3 below. A smaller APHA value indicates better color fastness. <APHA measurement conditions> Color difference system: Ultrascan Pro Light source: C / 2 Cell: 10 mm quartz

[0172]

Table 3

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

[0174] As a result of the experiment, the isocyanate compositions of the examples did not become cloudy, and also showed improved effects in terms of discoloration resistance compared to the comparative examples.

[0175] Experimental Example 4 The polymerization compositions prepared in the examples and comparative examples were filtered using a PTFE filter having a pore size of 1.0 μm (25 mm Diameter Syringe Filter, manufactured by Whatman) to measure the time (min) required for filtration, and the improvement effect of workability was evaluated based on the results. The filtration time means the time from when 200 g of the polymerization composition passes through the filter to when it has completely passed through.

[0176] [Table 4]

[0177] As a result of the experiment, the polymerization composition of Comparative Example 2-1, which exhibited low acidity because it did not contain any additives capable of providing acid components that react with alcohol to be liberated during the production of the isocyanate composition, took a long time to filter.

[0178] In contrast, the polymerization composition of Example 2-1, in which the phosphonate compound of Formula 1 was added during the preparation of the isocyanate composition, exhibited a significantly shorter filtration time than the Comparative Example, demonstrating improved workability.

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

[0180] Also, in the case of Comparative Examples 2-5, due to the generation of precipitates in the isocyanate composition of Comparative Example 1-5, it was not suitable for the production of the polymerization composition and could not be produced.

[0181] Experimental Example 5 Regarding the lenses produced using the polymerization composition in the above Examples and Comparative Examples, the YI (Yellowness Index) was measured by the method described below. However, the isocyanate compositions of Comparative Examples 1-3 had high viscosities, making it difficult to produce the polymerization composition. As a result, lenses could not be produced. Also, the isocyanate composition of Comparative Example 1-5 was not suitable for the production of the polymerization composition due to the generation of precipitates, so lens production did not progress. The results are shown in Table 5 below. <YI Measurement Method> Equipment: Ultrascan Pro, HunterLab Light source: D65 / 10 Measurement standard: ASTM E313

[0182] Also, the produced lenses were visually inspected for defects and evaluated according to the following criteria. <Defect Evaluation Criteria> X No lens defects O Lens defects present, white line defect elements observed in the lens

[0183]

Table 5

[0184] As a result of the experiment, it was confirmed that the lenses produced using the polymerization composition of the Examples showed lower YI values compared to the Comparative Examples, indicating a better discoloration suppression effect.

[0185] On the other hand, the lenses of Comparative Examples 2-4 and 2-6 that used phosphate-based compounds during the production of the isocyanate composition showed high YI values, and defects occurred particularly in the lenses of Comparative Example 2-4 that used bis(2-ethylhexyl) phosphate.

[0186] Experimental Example 6 In the above Examples and Comparative Examples, when lenses were manufactured 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. <Releaseability evaluation criteria> ○: Good releasability. Easy to release without applying force. △: Demolding is difficult. Force must be applied and demolding is not easy. X: Mold breaks. Poor demolding properties.

[0187] [Table 6]

[0188] As a result of the experiment, when a lens was produced using the polymerization composition of Comparative Example 2-4, it was difficult to release the lens from the lens mold, and it became possible to peel it by applying force. This shows that the polymerization composition of Comparative Example 2-4 has poor workability.

Claims

1. isocyanate compounds, and An isocyanate composition comprising a phosphonate compound represented by the following chemical formula 1: 【Chemical 1】 In the above formula 1, R ａ and R ｂ are each independently substituted or unsubstituted C １－２０ alkyl group, 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. The R ａ and R ｂ are each independently １－８ is an alkyl group, a phenyl group, or a benzyl group, ａ and R ｂ are each independently １－６ 2. The isocyanate composition of claim 1, which is unsubstituted or substituted with one or more substituents selected from the group consisting of alkyl groups, phenyl groups, hydroxy groups, and combinations thereof.

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

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

5. The isocyanate composition according to claim 1, wherein the isocyanate composition has an acidity of 500 ppm or less.

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

7. The isocyanate composition according to claim 1, wherein the isocyanate compound is 1,5-pentamethylene diisocyanate, toluene diisocyanate, methylene diphenyl 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 of claim 1 , wherein the isocyanate composition further comprises a phenolic stabilizer.

9. The phenolic stabilizer may be selected from the group consisting of 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]; benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 side chain alkyl ester; 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol; ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]; hexamethylene bis[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) 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-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)butyric acid] 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]- 10. The isocyanate composition of claim 8, comprising {(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate}-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine; 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]dioxaphosphepine; or mixtures thereof.

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

11. The isocyanate composition according to claim 1, wherein the increase rate of the oligomer content calculated by the following Equation 2 is 600% or less: [Formula 2] Oligomer content increase rate (%) = [(C ｆ -Ci) / Ci]×100 In the above equation 2, Ci is the oligomer content (area%) in the isocyanate composition immediately after production, calculated by gel permeation chromatography analysis; C ｆ is the content (area %) of oligomers in the isocyanate composition after storing the isocyanate composition under a nitrogen atmosphere at 15°C for 8 weeks, calculated by gel permeation chromatography analysis.

12. 2. The isocyanate composition of claim 1, wherein the isocyanate composition has an APHA value of 15 or less as measured by ASTM D1209 and a haze of 0.5% or less as measured by ASTM D1003 after storage at 15°C for 8 weeks under a nitrogen atmosphere.

13. The isocyanate composition according to any one of claims 1 to 12; One or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound A polymerization composition comprising:

14. The isocyanate composition according to any one of claims 1 to 12; One or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound An article comprising a polymer obtained by polymerizing

15. The article of claim 14 , wherein the article is an optical pressure sensitive adhesive, an optical adhesive, or an optical lens.

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

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