Isocyanate composition

Abstract

The present invention provides an isocyanate composition in which an isocyanate-based compound and a phosphonate-based compound having a specific structure are included, thereby suppressing the occurrence of discoloration and white turbidity by improving storage stability, exhibiting improved processability such as shortening filtration time, etc. And the discoloration resistance is improved when the product is applied.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority of Korean Patent Application Nos. 10-2022-0139402 and 10-2023-0135186, filed on October 26, 2022 and October 11, 2023, respectively, the disclosures of which are incorporated herein by reference in their entirety.

[0003] The present invention relates to an isocyanate composition having improved storage stability, thereby suppressing the occurrence of discoloration and white turbidity, and exhibiting improved processability, such as shortened filtration time, etc. Background Art

[0004] Isocyanate-based compounds are high-value compounds that can be used not only in the chemical and resin industries but also as fine chemicals including optical materials. A representative example of isocyanate-based compounds is xylene diisocyanate (hereinafter referred to as XDI), which is a raw material for advanced optical lenses and is in increasing demand as a high-value-added chemical material.

[0005] However, since isocyanate-based compounds exhibit high reactivity, they easily react with moisture in the air during storage, causing discoloration or white turbidity. In addition, isocyanate-based compounds will self-polymerize to form oligomers larger than dimers when stored for a long time, causing discoloration or white turbidity.

[0006] Isocyanate-based compounds are widely used as raw materials for polyurethanes, such as coatings, adhesives / adhesives, paints, foams, optical materials, etc. When using isocyanate-based compounds to manufacture polyurethane lenses, if the above-mentioned discoloration or turbidity occurs, the molecular weight of the polymer solution will increase sharply, resulting in a decrease in stirring force, an increase in filtration time, and filter clogging, which will reduce processability. In addition, the manufactured lenses also have problems such as decreased transparency and discoloration.

[0007] In order to solve these problems, although a method of isolating the product from the air by filling with nitrogen or sealing the product for production and storage is used, there are still problems of discoloration and white turbidity until the isocyanate-based compound is completely consumed.

[0008] In addition, a method of adding a stabilizer to an isocyanate-based compound has been proposed, but there is a problem in that the added stabilizer causes discoloration during subsequent product manufacturing or reduces the stability of the isocyanate-based compound.

[0009] Therefore, there is a need for research on preparing an isocyanate composition which has no concern about discoloration or turbidity even when stored for a long period of time due to improved storage stability and can show improved processability during product manufacturing. Summary of the invention

[0010] Technical issues

[0011] The present invention provides an isocyanate composition which has improved storage stability, thereby suppressing the occurrence of discoloration and white turbidity, and as a result, can improve transparency when applied to products and can show improved processability, such as shortening filtration time, etc.

[0012] Technical Solution

[0013] Therefore, the present invention provides an isocyanate composition including an isocyanate-based compound and a phosphonate-based compound represented by the following Chemical Formula 1:

[0014] [Chemical formula 1]

[0015]

[0016] In Chemical Formula 1,

[0017] R a and R b are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 7-30 Alkyl aryl, or substituted or unsubstituted C 7-30 Arylalkyl.

[0018] The present invention also provides a polymerizable composition comprising the above isocyanate composition; and any one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound.

[0019] The present invention also provides a product, which includes a polymer obtained by polymerizing the following components: an isocyanate composition; and one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound.

[0020] Beneficial Effects

[0021] The isocyanate composition according to the present invention has improved storage stability, thereby suppressing the occurrence of discoloration and white turbidity, and as a result, improving transparency when applied to a product.

[0022] In addition, the isocyanate composition may exhibit improved processability, such as shortened filtration time, and the like.

[0023] In addition, the polymerizable composition comprising the isocyanate composition and the polyfunctional thiol-based compound, the polyfunctional alcohol-based compound, or the polyfunctional episulfide-based compound can be used in a wide range of fields due to its excellent physical properties, such as paints for plastics, paints for automobiles, film coatings, various inks, various adhesives / adhesives, sealants, various microcapsules, plastic lenses, artificial and synthetic leathers, reaction injection molding (RIM) products, slush powders, elastic molded products (spandex), polyurethane foams, etc., among which the isocyanate composition is particularly suitable for use as a material for optical products, such as optical adhesives, optical adhesives, eyeglass lenses, camera lenses, prisms, etc., due to its excellent bonding / adhesive properties and transparency. DETAILED DESCRIPTION

[0024] The terms used in this specification are only used to explain the exemplary embodiments and are not intended to limit the present invention. Unless the context indicates otherwise, a singular expression may include a plural expression. It must be understood that the terms "including", "equipped with" or "having" in this specification are only used to specify the presence of implemented features, steps, components or combinations thereof, and do not exclude the presence or possibility of adding one or more different features, steps, components or combinations thereof in advance.

[0025] The term "substituted or unsubstituted" as used herein means unsubstituted or substituted by one or more substituents selected from the following: deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkylthiooxy group; arylthiooxy group; alkylsulfoxide group (alkylsulfoxy group); arylsulfoxide group (arylsulfoxy group); silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; alkylamino group; aralkylamino group; heteroarylamine group; arylamine group; arylphosphine group; or heteroaryl group containing one or more N, O, S atoms, or heteroaryl group unsubstituted or substituted by a combination thereof, wherein the combination is specifically a combination formed by connecting two or more substituents in the above-listed substituents. For example, "a substituent formed by connecting two or more substituents" can be a biphenyl group. In other words, the biphenyl group can be an aryl group, and can also be understood as a substituent formed by connecting two phenyl groups.

[0026] Unless otherwise specified in this specification, normal temperature refers to 23±5°C, i.e., common laboratory temperature, and normal pressure refers to 1±0.05 atmospheres, i.e., common laboratory pressure.

[0027] In addition, in this specification, unless otherwise specified, a nitrogen atmosphere means that the atmospheric gas contains nitrogen, and specifically, the nitrogen concentration in the atmospheric gas is 0 volume % or more and 100 volume % or less.

[0028] The present invention can be modified in various ways and has various forms, and specific exemplary embodiments are exemplified and explained in detail in the following description. However, this does not mean that the present invention is limited to specific exemplary embodiments, and it must be understood that the present invention includes all modifications, equivalents or replacements within the spirit and technical scope of the present invention.

[0029] The present invention is described in detail below.

[0030] Due to the high reactivity with moisture or alcohol, after preparation, isocyanate-based compounds are completely sealed by filling with nitrogen and stored in a refrigerator. However, when unsealed for use, they react with moisture in the air or become discolored or turbid depending on the atmospheric temperature. In addition, when an isocyanate-based compound that has been stored in a sealed state is unsealed for use, the oligomer content increases or yellowing occurs during storage until it is completely used. Therefore, when such isocyanate-based compounds are used to manufacture polyurethane lenses, due to the rapid increase in the viscosity of the composition, a decrease in stirring force, an increase in filtration time, filter clogging, etc. may occur, which reduces processability, and the transparency of the manufactured lenses may also decrease and discolor.

[0031] Therefore, the present inventors have studied an isocyanate composition that can suppress the increase rate of oligomers caused by self-polymerization of isocyanate-based compounds during long-term storage and can show improved processability during lens manufacturing. As a result, it was confirmed that when a phosphonate-based compound is used together with an isocyanate-based compound, the oligomerization rate of the isocyanate-based compound can be reduced, thereby suppressing discoloration and white turbidity caused by oligomers, preventing lens color changes caused by various additives added to improve lens processability, and shortening the filtration time during lens manufacturing to improve processability, thereby completing the present invention.

[0032] Specifically, the isocyanate composition according to the present invention includes an isocyanate-based compound and a phosphonate-based compound represented by the following Chemical Formula 1:

[0033] [Chemical formula 1]

[0034]

[0035] In Chemical Formula 1,

[0036] R a and R b are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 7-30Alkyl aryl, or substituted or unsubstituted C 7-30 Arylalkyl.

[0037] Furthermore, when R a and R b When substituted, they may specifically be substituted with one or more substituents selected from alkyl, cycloalkyl, aryl, arylalkyl, alkylaryl, hydroxy, alkoxy, alkoxyalkyl, aryloxy and combinations thereof.

[0038] Specifically, in Chemical Formula 1, R a and R b may be independently substituted or unsubstituted C 1-18 Alkyl, substituted or unsubstituted C 6-18 Aryl, substituted or unsubstituted C 7-18 Alkyl aryl or substituted or unsubstituted C 7-18 Arylalkyl, and when R a and R b When substituted, they may be independently selected from C 1-12 Alkyl, C 3-12 Cycloalkyl, C 6-12 Aryl, C 7-18 Arylalkyl, C 7-18 Alkyl aryl, hydroxyl, C 1-12 Alkoxy, C 2-18 Alkoxyalkyl, C 6-12 The aryloxy group and combinations thereof are substituted with one or more substituents.

[0039] More specifically, in Chemical Formula 1, R a and R b Can be independently C 1-8 Alkyl, phenyl or benzyl, where R a and R b can be independently selected from C 1-6 One or more substituents among the alkyl, phenyl, hydroxyl and combinations thereof may be substituted or unsubstituted.

[0040] Meanwhile, the term "combination" as used herein refers to two or more functional groups connected together. For example, the combination of hydroxyl and methyl can be methoxy or hydroxymethyl, and the combination of hydroxyl and phenyl can be phenoxy or hydroxyphenyl. For another example, the combination of methyl and phenyl can be benzyl or methylphenyl.

[0041] More specifically, in Chemical Formula 1, R a and R b Each independently may be methyl, ethyl, tert-butyl, hexyl, 3,3-dimethylbutan-2-yl, 2-ethylhexyl, phenyl, hydroxybenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.

[0042] Specific examples of phosphonate-based compounds may include ethyl methylphosphonate (CAS NO. 1832-53-7), pinacol methylphosphonate, mono-2-ethylhexyl (2-ethylhexyl) phosphonate, or monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and any one thereof or a mixture of two or more thereof may be used.

[0043] 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 inhibited.

[0044] When preparing an isocyanate composition, the phosphonate-based compound can provide an acidic component released by reacting with an alcohol, thereby increasing the acidity of the isocyanate composition, and as a result, can delay or inhibit the reaction rate and oligomerization of the isocyanate, and inhibit discoloration and white turbidity caused by oligomers.

[0045] Furthermore, the phosphonate-based compound can prevent the color change of the lens caused by the addition of an additive for improving the processability of the lens, and can also suppress the increase in the viscosity of the isocyanate composition, thereby shortening the filtration time during the manufacture of the lens.

[0046] Due to the difference in reactivity, phosphonate-based compounds can show better effects in terms of storage stability compared with phosphonic acid (HPO(OH)2) and phosphorous acid (P(OH)3).

[0047] Furthermore, phosphoric acid (H3PO4 (or PO(OH)3)) generates precipitation when preparing isocyanate compositions due to its excessively high reactivity, and as a result, it is difficult to use it to prepare polymerizable compositions. In contrast, phosphonate-based compounds exhibit an appropriate level of reactivity, so there is no concern about precipitation.

[0048] In addition, phosphate esters can show a certain effect of increasing the acidity of isocyanate compositions, but there is a problem in that the viscosity of the polymerizable composition increases, causing filter clogging during lens manufacturing. In contrast, phosphonate-based compounds do not have to worry about viscosity increase.

[0049] Meanwhile, the acidity (in terms of HCl) (ppm) of the isocyanate composition is a value expressed as a weight ratio of the amount of free acid components generated by reaction with alcohol at room temperature (23±5°C) relative to the total weight of the isocyanate compound, in terms of HCl. The acidity of the isocyanate composition according to the present invention depends on the acid group content derived from the phosphonate-based compound. Therefore, the acidity can be controlled by controlling the type and / or input amount of the phosphonate-based compound, and the effect of using the phosphonate-based compound can be further enhanced by optimizing the acidity range.

[0050] Specifically, the isocyanate composition according to the present invention may have an acidity of 500 ppm or less.

[0051] 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 inhibited. However, when the acidity is too high, the reaction rate of the isocyanate may become too slow, making it difficult to use for polymer formation and manufacturing products such as lenses. In addition, in order to compensate for the delay in the reaction rate of the isocyanate caused by using an excessive amount of phosphonate-based compounds, it is necessary to use an excessive amount of catalyst. In this case, the excessive catalyst may lead to a decrease in reaction efficiency, a deterioration in physical properties, and a decrease in product quality due to discoloration and turbidity of the isocyanate composition.

[0052] Therefore, the phosphonate-based compound should be introduced in such an amount that the acidity of the isocyanate composition is 500 ppm or less, more specifically, 500 ppm or less, or 300 ppm or less, or 200 ppm or less, or 150 ppm or less, or 130 ppm or less. Meanwhile, in order to fully achieve the effect of increasing the acidity by introducing the phosphonate-based compound, the phosphonate-based compound may be introduced so that the acidity of the isocyanate composition is 100 ppm or more, or 110 ppm or more, or 113 ppm or more.

[0053] In the present invention, the acidity is specifically calculated by potentiometric titration of the isocyanate composition using a 0.01N potassium hydroxide (KOH) methanol solution and using the obtained measured value according to the following formula 1. The conditions of the measurement method will be described in detail in the experimental examples below.

[0054] [Formula 1]

[0055] Acidity (in HCl) (ppm) = [(AB) × N × f × 36.5 × 10 6 ] / (C×10 3 )

[0056] In formula 1,

[0057] A: Volume of KOH methanol solution consumed in titrating the isocyanate composition sample (ml)

[0058] B: Volume of KOH methanol solution consumed in blank test (ml)

[0059] N: equivalent concentration of KOH methanol solution

[0060] f: A coefficient used to correct the change in the normality of the KOH methanol solution used in the measurement, measured according to ASTM D-1638, TOLOCHIMIE 04-01-68, to make it the same as the 0.01N KOH methanol solution. For a 0.01N KOH methanol solution, the f value is 1

[0061] C: Weight of isocyanate composition sample (g)

[0062] More specifically, in the isocyanate composition according to the present invention, under the condition of satisfying the above-mentioned acidity range, based on the total weight of the isocyanate-based compound, the phosphonate-based compound can be included in an amount of 100ppm to 3000ppm. Within the above-mentioned content range, the isocyanate composition can show an acidity within the above-mentioned range, thereby achieving the effect of delaying the oligomerization reaction rate within the optimal range. More specifically, based on the total weight of the isocyanate-based compound, the phosphonate-based compound can be included in an amount of 100ppm or more, or 200ppm or more, or 300ppm or more, or 350ppm or more, or 380ppm or more, or 600ppm or more, or 900ppm or more, and 3,000ppm or less, or 2000ppm or less, or 1500ppm or less, or 1200ppm or less, or 1100ppm.

[0063] Meanwhile, in the isocyanate composition, the isocyanate-based compound is a monomer compound containing one or more, or two or more, or two to four isocyanate groups in the molecule. More specifically, the isocyanate-based compound is a diisocyanate compound containing two isocyanate groups in the molecule.

[0064] Specific examples of the diisocyanate compound may include 1,5-pentamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate or p-xylene diisocyanate, and any one of them or a mixture of two or more thereof may be used.

[0065] Among the above compounds, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, or a mixture thereof may be used as the isocyanate-based compound.

[0066] In addition, the isocyanate composition according to the present invention may further include a phenolic stabilizer.

[0067] Generally speaking, discoloration and turbidity in isocyanate compositions are caused by oligomerization of isocyanate, quinone formation of benzene rings in the molecule, or byproducts generated by oxygen, moisture, or high heat during the synthesis and purification process. Phenolic stabilizers can inhibit the above side reactions through free radical capture reactions, thereby preventing discoloration and turbidity of isocyanate compositions.

[0068] However, when the content of stabilizer is lower than a predetermined level, it is difficult to fully show the effect of preventing discoloration or turbidity. On the contrary, when its content exceeds a predetermined level and is excessive, phenolic stabilizer itself may become a factor of discoloration and turbidity. Therefore, in the present invention, based on the gross weight of the compound of isocyanate as a benchmark, phenolic stabilizer is included in an amount of 5ppm to 1000ppm. More specifically, based on the gross weight of the compound of isocyanate as a benchmark, by comprising more than 5ppm, or more than 8ppm, or more than 10ppm, and less than 1000ppm, or less than 500ppm, or less than 200ppm, or less than 100ppm, or less than 50ppm, or less than 30ppm, or less than 20ppm of the phenolic stabilizer, more enhanced suppression of discoloration and turbidity can be achieved.

[0069] In addition, by controlling the usage of the above-mentioned phosphonate-based compound and phenolic stabilizer, the effect of reducing the increase rate of oligomer content and inhibiting discoloration and white turbidity can be further enhanced. Specifically, the weight ratio of 1.5:1 to 6:1 can be more specifically 1.5:1 or more than 1.9:1 or more than 2:1 or more than 3:1, and 6:1 or less than 5.5:1 or less than 4.5:1. In this case, when describing the weight ratio, "above" and "below" are based on the usage of the phosphonate-based compound.

[0070] The above-mentioned phenolic stabilizer is specifically phenol or its derivatives containing a phenol structure in the molecule, and specific examples thereof may include: phenol; or hindered phenols, such as butylated hydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, manufactured by BASF), diethylenethiobis[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 1076, manufactured by BASF), N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (Irganox 1098, manufactured by BASF), 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid C7-C9 side chain alkyl ester (Irganox 1135, manufactured by BASF), 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol (Irganox 1330, manufactured by BASF), ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (Irganox 245, manufactured by BASF), hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259, manufactured by 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, manufactured by 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-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], ,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 4,4'-thiobis(6-tert-butylm-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]ethylene glycol ester, 4,4'-butylenebis(6-tert-butylm-cresol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 2,2'-ethylenebis(4-2-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][1,3,2]dioxaphosphine (SUMILIZER GP, produced by Sumitomo Corporation), etc., and any one of them or a mixture of two or more thereof can be used. ,

[0071] Among them, from the perspective of preventing discoloration and turbidity to improve transparency, phenol, dibutylhydroxytoluene, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl ester, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine or a mixture thereof can be used.

[0072] In addition, the isocyanate composition may further include an oligomer formed by linking two or more isocyanate-based compounds as a by-product.

[0073] The oligomer of the compound based on isocyanate can be a dimer formed by connecting two isocyanate-based compounds, a trimer formed by connecting three thereof, a four or more thereof, or an oligomer formed by connecting four to ten thereof. The oligomer can be generated by the side reaction during the synthesis of the compound based on isocyanate by reacting an amine compound with a phosgene compound, or it can be a polymer formed by a highly reactive isocyanate compound after the synthesis is completed. Since these oligomers not only cause the transparency problem of the isocyanate composition itself, but also cause the problem of discoloration and turbidity of the polymerizable composition using the isocyanate composition, it is necessary to reduce the content of the oligomer when the isocyanate composition is used in the optical field. However, in the industrial process, from the perspective of process efficiency and cost, it is difficult to control the content of the oligomer as much as possible. Therefore, the isocyanate composition according to the present invention can further contain the oligomer that is inevitably generated. However, by controlling its content and using phosphonic acid in the preparation process, the transparency and color characteristics of the product can be improved while maintaining processability.

[0074] Specifically, the isocyanate composition contains less than 1 area % of oligomers immediately after preparation. In this regard, the content of oligomers is obtained by calculating the percentage obtained by the ratio of the peak area corresponding to the oligomer to the total peak area based on the molecular weight distribution curve obtained by analyzing the isocyanate composition by gel permeation chromatography immediately after preparation. In addition, the peak area is calculated by integration. The method of measuring and calculating the oligomer content is described in the following experimental example.

[0075] Furthermore, as described above, the isocyanate composition contains the phosphonate-based compound which can retard the oligomerization rate of the isocyanate, so that the content of oligomers and the rate of increase of the oligomer content are lower even over a period of time compared with conventionally used substances.

[0076] Specifically, according to the following formula 2, the increase rate of the oligomer content of the isocyanate composition is 600% or less, more specifically 100% to 600%, or 300% to 590%.

[0077] [Formula 2]

[0078] Increase rate of oligomer content (%) = [(C f -Ci) / Ci]×100

[0079] In formula 2,

[0080] Ci represents the oligomer content (area %) in the isocyanate composition just after preparation calculated by gel permeation chromatography analysis, and

[0081] C fThe oligomer content (area %) in the isocyanate composition after the isocyanate composition was stored in a nitrogen atmosphere at 15° C. for 8 weeks was calculated by gel permeation chromatography analysis.

[0082] The "nitrogen atmosphere" in this case specifically means a state in which 100 volume % of the total volume of the air atmosphere is nitrogen due to the filling of nitrogen.

[0083] Specifically, Ci and C f is a value calculated according to the following formula 3.

[0084] Meanwhile, in the present invention, during the nitrogen filling, nitrogen with a purity of 99.999% is used.

[0085] [Formula 3]

[0086] Oligomer content (area %) = [E / D] × 100

[0087] In formula 3,

[0088] D represents the sum of the areas under the curve in the molecular weight distribution curve (GPC curve) obtained by analyzing the isocyanate composition by gel permeation chromatography (GPC), and

[0089] E represents the area of ​​the peak corresponding to the oligomer in the molecular weight distribution curve of the isocyanate composition.

[0090] The conditions for gel permeation chromatography analysis refer to the following experimental examples.

[0091] In addition, the total area under the GPC curve of the isocyanate composition and the area of ​​the fraction corresponding to the oligomer can be obtained by integration, respectively. In this regard, the oligomer refers to a polymer having a weight average molecular weight (Mw) of 600 g / mol to 2000 g / mol, and the fraction corresponding to the oligomer in the GPC curve is 19.42≤logMw≤22.18.

[0092] More specifically, when the isocyanate composition is stored in a nitrogen atmosphere at 15° C. (specifically, by filling nitrogen, under the condition of an atmosphere of 100% by volume nitrogen) for 8 weeks, the oligomer content calculated by GPC analysis, that is, the area ratio of GPC oligomers can be 0.5 area% or less, or 0.45 area% or less. Since the lower the oligomer content, the better the color resistance, the lower limit is not particularly limited, but the oligomer content can be 0 area% or more, or 0.1 area% or more. In the present invention, nitrogen with a purity of 99.999% is used when filling nitrogen.

[0093] Meanwhile, in the present invention, the oligomer content (area %) in the isocyanate composition is expressed as the percentage of the area of ​​the fraction corresponding to the oligomer to the total area of ​​the GPC curve (molecular weight distribution curve), wherein the GPC curve of the isocyanate composition is obtained by plotting the logarithmic value (log M) of the weight average molecular weight (M) obtained by GPC analysis on the x-axis and the molecular weight distribution (dwt / dlog M) relative to the logarithmic value on the y-axis, and can be calculated according to Formula 3. The specific GPC analysis method and conditions will be described in detail in the following experimental examples.

[0094] Thus, even immediately after the preparation of the isocyanate composition and after the preparation, the increase rate of the oligomer content and the oligomer content are low, and thus the occurrence of discoloration and white turbidity of the isocyanate composition can be effectively suppressed.

[0095] Specifically, the isocyanate composition has an APHA value of 15 or less as measured according to ASTM D1209 after being stored in a nitrogen atmosphere at 15° C. (specifically, by filling nitrogen in an atmosphere of 100% by volume nitrogen) for 8 weeks. More specifically, the APHA value is 14.5 or less, or 14 or less. Since a lower APHA value indicates better discoloration resistance, the lower limit is not limited, but the APHA value may be, for example, greater than 0 or 1 or more.

[0096] In addition, the isocyanate composition has a haze of 0.5% or less measured according to ASTM D1003 after being stored in a nitrogen atmosphere at 15° C. for 8 weeks. More specifically, the haze is 0.45% or less, or 0.4% or less. Since a lower haze value indicates lower white turbidity and better transparency, there is no lower limit, but the haze may be, for example, greater than 0%, or 0.01% or more, or 0.1% or more.

[0097] Furthermore, the isocyanate composition did not show white turbidity even after being stored in a nitrogen atmosphere at 15° C. for 12 weeks.

[0098] The isocyanate composition may be prepared by mixing an isocyanate-based compound and a phosphonate-based compound represented by Chemical Formula 1.

[0099] More specifically, the isocyanate composition may be prepared by a preparation method including the steps of: preparing an isocyanate-based compound by reacting an amine or a salt thereof with phosgene; and mixing the isocyanate-based compound with a phosphonate-based compound represented by Chemical Formula 1.

[0100] The amine is an aromatic, alicyclic or aliphatic diamine containing two amine groups in the molecule.

[0101] More specifically, the amine can be 1,3-phenylenediamine (m-phenylenediamine, m-XDA), 1,4-phenylenediamine (p-phenylenediamine, p-XDA), 1,3-bis(aminomethyl)cyclohexane, or 1,4-bis(aminomethyl)cyclohexane, and the like, any one of which or a mixture of two or more thereof can be used depending on the structure of the desired diisocyanate.

[0102] In addition, the salt of an amine refers to a salt formed by the reaction of an amine with an acid, which may be, for example, a hydrochloride formed by the reaction of an amine with anhydrous hydrochloric acid, a carbonate formed by the reaction of an amine with carbonic acid, etc. Amines react rapidly with phosgene, but the reaction rate may slow down when converted into a solid salt for use.

[0103] Specifically, the salt of the amine may include 1,3-phenylenediamine hydrochloride, 1,4-phenylenediamine hydrochloride, 1,3-bis(aminomethyl)cyclohexane hydrochloride, 1,4-bis(aminomethyl)cyclohexane hydrochloride, 1,3-phenylenediamine carbonate, 1,4-phenylenediamine carbonate, 1,3-bis(aminomethyl)cyclohexane carbonate, 1,4-bis(aminomethyl)cyclohexane carbonate, etc., and any one of them or a mixture of two or more thereof can be used.

[0104] In addition, the reaction of amine and acid to form amine salt can be carried out in a solvent. At this time, the solvent can be an aromatic hydrocarbon solvent, such as benzene, toluene, xylene, ethylbenzene, etc.; a chlorinated aromatic hydrocarbon solvent, such as monochlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, etc.; a chlorinated hydrocarbon solvent, such as dichloromethane, chloroform, carbon tetrachloride, etc., and a mixture of two or more of the above can be used. In addition, these solvents can also be used as solvents for phosgenation reactions. Therefore, after the amine and acid react in the above solvents to obtain the amine salt, no separate purification process is required, and phosgene can be directly introduced for phosgenation reaction.

[0105] The preparation of the amine salt can be carried out at a temperature of 40° C. or less, specifically, at a temperature of 5° C. to 30° C. During the above reaction, the temperature may increase due to the heat of reaction, but the maximum temperature in the reactor is preferably maintained at 90° C. or less.

[0106] Secondly, the reaction of the amine or its salt with phosgene can be carried out in a temperature range of 80° C. or above, or 90° C. or above, and 140° C. or below, or 130° C. When the reaction temperature is too low, solids may precipitate, causing pipeline blockage, while when the temperature is too high, side reactions such as phosgene decomposition may occur, so it is preferred to carry out the reaction within the above temperature range.

[0107] Alternatively, the reaction of an amine or a salt thereof with phosgene may be carried out in an organic solvent.

[0108] The organic solvent may include at least one of an aromatic hydrocarbon-based organic solvent and an ester-based organic solvent.

[0109] The aromatic hydrocarbon-based organic solvent may specifically be a halogenated aromatic hydrocarbon-based organic solvent, such as monochlorobenzene, 1,2-dichlorobenzene, or 1,2,4-trichlorobenzene.

[0110] In addition, the ester-based organic solvent can specifically be a fatty acid ester, such as amyl formate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, secondary 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, etc.; and aromatic carboxylic acid esters, such as methyl salicylate, dimethyl phthalate, methyl benzoate, etc.

[0111] More specifically, the organic solvent may include at least one of the aromatic hydrocarbon-based organic solvent and the ester-based organic solvent having a boiling point of 100° C. or more or 100° C. to 200° C. among the above aromatic hydrocarbon-based organic solvent and the ester-based organic solvent.

[0112] As described above, when the phosgenation reaction is carried out in an organic solvent, the amine or its salt may be used at a concentration of 20% by volume or less, for example, 1% by volume to 20% by volume, or 5% by volume to 20% by volume. When the concentration of the amine or its salt exceeds 20% by volume, there is a concern that a large amount of amine salt may precipitate.

[0113] In addition, when the amine or the salt thereof is reacted with phosgene, a compound represented by the following Chemical Formula 2 may be optionally further introduced.

[0114] [Chemical formula 2]

[0115]

[0116] In chemical formula 2,

[0117] R1 to R4 are each independently substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 3-12 Cycloalkyl, or substituted or unsubstituted C 6-12 Aryl,

[0118] X is hydrogen, hydroxyl or acetamide,

[0119] Y is oxy, substituted or unsubstituted C 1-12 Alkoxy, or substituted or unsubstituted C 6-12 Aryloxy.

[0120] The compound represented by Chemical Formula 2 promotes the forward reaction and inhibits the side reaction by removing hydrogen from amine or intermediate carbamoyl chloride during the phosgenation reaction, thereby inhibiting the generation of monoisocyanates such as by-products ethylbenzyl isocyanate (EBI) and chloromethylbenzyl isocyanate (CMBI).

[0121] More specifically, the compound represented by Chemical Formula 2 may be wherein R1 to R4 in Chemical Formula 2 are each independently C 1-12 An alkyl group, a compound in which X is hydrogen, hydroxy or acetamido, and Y is oxy (O).

[0122] Specific examples may include 2,2,6,6-tetramethylpiperidine-1-oxide (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxide (hereinafter, referred to as 4-hydroxyTEMPO), and 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxide, and any one of them or a mixture of two or more thereof may be used.

[0123] In addition, based on 100mol of amine or its salt, the compound represented by Chemical Formula 2 can be used in a ratio of 0.05mol to 2mol. More specifically, the compound can be used in a ratio of 0.05mol or more, or 0.1mol or more, or 0.15mol or more, and 2mol or less, or 1mol or less, or 0.8mol or less. When used in the above content range, this is preferred because the generation of diisocyanate oligomers is minimized, and diisocyanates can be synthesized with high purity and high yield.

[0124] The isocyanate formed as a result of the above-mentioned phosgenation reaction is obtained in a mixed state in which the solvent, unreacted phosgene, and by-products are mixed together with hydrogen chloride. Therefore, one or more of a purification process for separating a high-purity isocyanate compound from the reaction mixture, a process for removing the solvent by distillation, and a process for removing unreacted phosgene and hydrogen chloride gas by nitrogen bubbling may be performed.

[0125] The purification step can be performed by a conventional method for purifying an isocyanate compound, and can be performed by, for example, reduced pressure distillation and / or thin film distillation.

[0126] However, when the purification process of the isocyanate compound is carried out under too high a temperature or the time of the purification step is increased, the stability of the isocyanate compound may be significantly reduced, and when the purification process is carried out at too low a temperature, the process efficiency may be reduced. Therefore, the purification step is preferably carried out at a temperature of 100° C. to 170° C. for 5 to 16 hours. When the maximum temperature of the purification step exceeds 170° C. or the residence time of the purification step exceeds 16 hours, the prepared isocyanate may absorb too much heat, resulting in reduced stability.

[0127] Next, the obtained isocyanate compound is mixed with a phosphonate-based compound represented by Chemical Formula 1 to prepare an isocyanate composition.

[0128] The mixing process may be performed according to a common method, and the kind and amount of the phosphonate-based compound to be mixed are as described above.

[0129] In addition, additives used in the isocyanate composition may be further introduced during the mixing process. For example, the above-mentioned phenolic stabilizer may be further introduced to improve the storage stability of the isocyanate composition. The type and amount of the phenolic stabilizer are as described above.

[0130] The isocyanate composition prepared by the preparation method of the present invention described above has excellent storage stability and high transparency, and thus is suitable for use as a polymerizable composition for producing optical products.

[0131] Therefore, according to the present invention, there is provided a polymerizable composition comprising the above isocyanate composition and any one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound and a polyfunctional episulfide-based compound.

[0132] The polymerizable composition may contain an isocyanate composition and any one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound, and these compounds may be in a mixed state or a separated state. In other words, in the polymerizable composition, the isocyanate composition and the polyfunctional thiol-based compound, the polyfunctional alcohol-based compound, or the polyfunctional episulfide-based compound may be in a mixed state in contact with each other, or may be in a separated state in which they are not in contact with each other.

[0133] In the polymerizable composition, the multifunctional thiol-based compound is a compound containing two or more thiol groups (—SH) in one molecule, specifically, a compound having two or more, or three or more and eight or less, or five or less thiol groups in one molecule.

[0134] The multifunctional thiol-based compound may be, for example, one or more selected from the group consisting of 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol, 1,9-dimercapto-3,7-dithianonane, 1,13-dimercapto-3,7,11-trithiatridecane, ethylene glycol di(3-mercaptopropionate), 1,4-dithiane-2,5-diyldimethylthiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane tris(1,2-dimercaptopropionate), and 1,4-dithiane-2,5-diyldimethylthiol. (3-mercaptopropionate), 4,8-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 5,9-bis(mercaptoethyl)-1,12-dimercapto-3,7,10-trithiadodecane, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), 3,6,9,12-tetrathiatetradecane-1,14-dithiol and 3,6,10,13-tetrathiapentadecane-1,8,15-trithiol.

[0135] The polyfunctional alcohol-based compound is a compound having two or more hydroxyl groups in one molecule, and specifically, a compound having two or more, or three or more, and eight or less, or four or less hydroxyl groups in one molecule. Specific examples may include diols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, etc.; triols, such as glycerol, trimethylolethane, trimethylolpropane (TMP), etc.; tetraols, such as diglycerol, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.; pentaols, such as L-arabinitol, ribitol, xylitol, etc.; hexaols, such as D-glucitol, D-mannitol, galactitol, etc.; heptaols, such as trehalose, etc.; octaols, such as sucrose, maltose, etc.; or low molecular weight polyols, etc., any one of which or a mixture of two or more thereof can be used.

[0136] In addition, the polyfunctional episulfide-based compound may be a compound containing two or more episulfide groups, ie, thioepoxy groups, in a molecule, and may have an aliphatic, alicyclic, or aromatic skeleton. Specific examples may include one or more selected from the following: bis(β-thiopropylthio)methane, 1,2-bis(β-thiopropylthio)ethane, 1,3-bis(β-thiopropylthio)propane, 1,2-bis(β-thiopropylthio)propane, 1-(β-thiopropylthio)-2-(β-thiopropylthiomethyl)propane, 1,4-bis(β-thiopropylthio)butane, 1,3-bis(β-thiopropylthio)butane, 1-(β-thiopropylthio)-3-(β-thiopropylthiomethyl)butane, 1,5-bis(β-thiopropylthio)pentane, 1-(β-thiopropylthio)-4-(β-thiopropylthiomethyl)pentane, 1,6-bis(β-thiopropylthio) hexane, 1-(β-thiopropylthio)-5-(β-thiopropylthiomethyl)hexane, 1-(β-thiopropylthio)-2-[(2-β-thiopropylthioethyl)thio]ethane, 1-(β-thiopropylthio)-2-[[2-(2-β-thiopropylthioethyl)thioethyl]thio]ethane, tetrakis(β-thiopropylthiomethyl)methane, 1,1,1-tris(β-thiopropylthiomethyl)propane, 1,5-bis(β-thiopropylthio)-2-(β-thiopropylthiomethyl)-3-thiopentane, 1,5-bis(β-thiopropylthio)-2,4-bis(β-thiopropylthiomethyl)-3-thiopentane, 1-(β-thiopropylthio)-2, 2-bis(β-epithiopropylthiomethyl)-4-thiahexane, 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)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-dithiaoctane, (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)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-thiopropylthio)-5,7-[(2-β-thiopropylthioethyl)thiomethyl]-3,6,9-trithiaundecane, 1,11-bis(β-thiopropylthio)-4,7-bis(β-thiopropylthiomethyl)-3,6,9-trithiaundecane, 1,3-bis(β-thiopropylthio)cyclohexane, 1,4-bis(β-thiopropylthio)cyclohexane, 1,3-bis(β-thiopropylthiomethyl)cyclohexane, 1,4-bis(β-thiopropylthiomethyl)cyclohexane, bis[4-(β-thiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-thiopropylthio)cyclohexyl]propane, bis[4-(β-thiopropylthio)cyclohexyl]propane 1,4-bis(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, 2,2-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.

[0137] In the polymerizable composition, a molar ratio of the functional group (eg, thiol group, hydroxyl group, or epithio group) to the isocyanate group 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.

[0138] In addition, the polymerizable composition may further contain additives as needed, such as internal mold release agents, ultraviolet absorbers, polyurethane reaction catalysts, polymerization initiators, heat stabilizers, color correction agents, chain extenders, crosslinking agents, light stabilizers, fillers, photosensitizers, etc., and their content can be appropriately determined within the range that does not inhibit the discoloration and discoloration inhibition properties of the composition.

[0139] For example, the polymerizable composition may further comprise an internal mold release agent to improve the release properties of the product from a mold during subsequent molding.

[0140] The internal mold release agent may specifically include a mold release agent based on phosphate ester, a mold release agent based on alkyl phosphate ester, a mold release agent based on fatty acid ester, etc., and any one of them or a mixture of two or more thereof may be used. Among them, a mold release agent based on phosphate ester may be preferably used.

[0141] Commercially available products such as ZELEC UN TM (manufactured by Stepan Corporation) as a phosphate ester-based mold release agent.

[0142] The internal mold release agent may be included in an amount of 0.01 wt % or more, or 0.05 wt % or more, and 10 wt % or less, or 5 wt % or less, based on the total weight of the polymerizable composition.

[0143] For another example, the polymerizable composition may further include an ultraviolet absorber. The ultraviolet absorber may specifically include an ultraviolet absorber based on benzotriazole, an ultraviolet absorber based on formamidine, and the like, and any one of them or a mixture of two or more thereof may be used. Among them, an ultraviolet absorber based on formamidine may be preferably used.

[0144] 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 be used.

[0145] The ultraviolet absorbent may be included in an amount of 0.01 wt % or more, or 0.05 wt % or more, and 0.1 wt % or less, or 0.08 wt % or less, based on the total weight of the polymerizable composition.

[0146] Further, the carbamate reaction catalyst may include compounds based on dialkyl tin halides, such as dibutyltin dichloride, dimethyltin dichloride, etc.; compounds based on dialkyl tin dicarboxylates, such as dimethyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, etc.; compounds based on dialkyl tin dialkoxides, such as dibutyltin dibutoxide, dioctyltin dibutoxide, etc.; compounds based on dialkyl tin dithioalkoxides, such as dibutyltin di(thiobutoxide), etc.; compounds based on dialkyl tin oxides, such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, bis(butoxydibutyltin) oxide, etc.; or compounds based on dialkyl tin sulfides, any one of which or a mixture of two or more thereof may be used.

[0147] The urethane reaction catalyst may be included in an amount of 0.001 wt % or more, or 0.002 wt % or more, or 0.004 wt % or more, and 0.1 wt % or less, or 0.05 wt % or less, or 0.01 wt % or less, or 0.008 wt % or less, based on the total weight of the polymerizable composition.

[0148] Due to the phosphonate-based compound included in the isocyanate composition, the polymerizable composition can exhibit excellent discoloration resistance by delaying or inhibiting the reaction rate and oligomerization of isocyanate, and can prevent lens color discoloration caused by various additives introduced during lens manufacturing to improve processability, and can exhibit improved processability by inhibiting the increase in viscosity of the polymerizable composition, such as shortening the filtration time during product manufacturing, etc.

[0149] As described above, the polymerizable composition can be used in a wide range of fields due to its excellent physical properties, and can be used as a material for optical products requiring excellent appearance properties, especially transparency, such as optical adhesives, optical adhesives, eyeglass lenses, camera lenses, plastic lenses, prisms, etc.

[0150] According to the present invention, there is provided an article comprising a polymer, wherein the polymer is obtained by polymerizing an isocyanate composition in a polymerizable composition with any one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound and a polyfunctional episulfide.

[0151] For example, when the polymerizable composition includes a multifunctional thiol-based compound, the polymerization reaction occurs through a urethane reaction between an isocyanate group in the isocyanate compound and a thiol group in the multifunctional thiol-based compound. Since the polyurethane generated by reacting with the multifunctional thiol-based compound as described above exhibits excellent transparency, it is particularly suitable for manufacturing optical products, particularly optical lenses, such as eyeglass lenses, camera lenses, etc.

[0152] For another example, when the polymerizable composition includes a polyfunctional alcohol-based compound, a polymerization reaction occurs through a urethane reaction (or polycondensation reaction) between the isocyanate in the aromatic diisocyanate and the hydroxyl in the polyfunctional alcohol. Since the polyurethane produced by reacting with the polyfunctional alcohol-based compound as described above exhibits excellent transparency and excellent bonding / adhesive properties, it can be used as an optical adhesive or an optical adhesive.

[0153] Furthermore, the polymerization reaction can be carried out under atmospheric pressure and in an inert gas atmosphere (eg, nitrogen, argon, etc.).

[0154] In addition, the polymerization reaction is preferably carried out within a temperature range of above -15°C, or above 0°C, and below 150°C, or below 120°C, because this makes it easy to control the reaction rate without worrying about discoloration and can also improve the reaction efficiency.

[0155] The polymerization reaction can be carried out without a catalyst or in the presence of a polyurethane reaction catalyst as described above. When carried out in the presence of a catalyst, the catalyst can be introduced when the isocyanate composition is mixed with a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound or a polyfunctional episulfide-based compound.

[0156] In addition, the degree of progress of the polymerization reaction can be predicted 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, and 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 isocyanate groups remaining after the reaction with the polyfunctional thiol-based compound.

[0157] As a result of the above-mentioned polymerization reaction, a polymer, specifically, polythiourethane is prepared.

[0158] Meanwhile, the article including the polymer may specifically be a paint, such as a paint for plastics or a paint for automobiles; a coating agent, such as a film coating agent; various inks; a sealant; various microcapsules; artificial leather, such as artificial and synthetic leather; a reaction injection molding (RIM) product; a coagulation powder; an elastic molded article (spandex); a polyurethane foam; or an optical article, such as an optical adhesive, an optical adhesive, a spectacle lens, a camera lens, a plastic lens, a prism, etc. In view of the excellent transparency of the polymerizable composition, the article may be an optical article, specifically an optical adhesive or an optical adhesive, or an optical lens, such as a spectacle lens, a camera lens, etc.

[0159] The article can be manufactured by molding after the polymerization reaction in the above-mentioned polymerizable composition, or can be manufactured by molding using the polymerizable composition. In the latter case, the polymerization reaction occurs simultaneously during the molding process.

[0160] For example, in the case of an optical lens, the polymerizable composition is injected into a lens mold, and then the temperature of the mold is increased to perform a polymerization reaction between an isocyanate-based compound and a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound. At this time, the mold is heated to a temperature range in which a urethane polymerization reaction occurs as described above. After the polymerization reaction is completed, the prepared polymer, specifically polythiocarbamate, can be separated from the mold to obtain an optical lens.

[0161] The polymer prepared from the polymerizable composition according to the present invention, in particular, polythiourethane, exhibits improved processability and excellent transparency, and is thus particularly suitable for use in the manufacture of optical articles, particularly optical bonding / adhesives or optical lenses.

[0162] For example, an optical lens comprising a polymer prepared from the polymerizable composition according to the present invention exhibits a YI value of 1.6 or less, or 1.5 or less measured in accordance with ASTM E313. Since a lower YI value indicates better anti-discoloration, the lower limit is not particularly limited, but the YI value may specifically be greater than 0 or 0.1 or more.

[0163] Below, in order to better understand the present invention, preferred exemplary embodiments will be provided. However, the following exemplary embodiments are only used to illustrate the present invention, and those skilled in the art will appreciate that various modifications and changes may be made thereto without departing from the scope and spirit of the present invention, and, obviously, these modifications and changes fall within the scope of the appended claims.

[0164] <Preparation of Isocyanate Composition>

[0165] Example 1-1

[0166] 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 were placed in a flask, and anhydrous hydrochloric acid was injected at a rate of 20 g / hr at room temperature (23±5°C) while stirring. The temperature was raised to 50°C while injecting anhydrous hydrochloric acid. After 4 hours of injection, the generated salt was cooled to room temperature, 43 g of phosgene was introduced into the reactor, and the reactor temperature was heated to 130°C. From the moment of phosgene injection to the end of the reaction, a dry ice-acetone cooler was used to prevent phosgene from leaking to the outside. After the reactor temperature reached 130°C, the reactor temperature was maintained at 125°C to 135°C for 2 hours to make the reaction solution transparent. After the solution became transparent, the reactor was cooled to 80°C, nitrogen was blown into it, and the phosgene was discharged and removed. The solvent was removed by vacuum distillation from the reaction solution from which phosgene was removed, and the product was purified under reduced pressure at a high temperature of 160° C. to obtain meta-xylylene diisocyanate (m-XDI).

[0167] 380 ppm of ethyl methylphosphonate (boiling point 181° C.) was added to m-XDI and mixed to prepare an isocyanate composition.

[0168] Example 1-2

[0169] 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 methylphosphonate.

[0170] Examples 1-3

[0171] An isocyanate composition was prepared in the same manner as in Example 1-1, except that 1100 ppm of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester was added instead of methylphosphonic acid ethyl ester.

[0172] Examples 1-4

[0173] An isocyanate composition was prepared in the same manner as in Example 1-1, except that 600 ppm of methylphosphonic acid pinacol was added instead of methylphosphonic acid ethyl ester.

[0174] Examples 1-5

[0175] An isocyanate composition was prepared in the same manner as in Example 1-1, except that 200 ppm of phenol was added to the m-XDI in Example 1-1 together with 380 ppm of ethyl methylphosphonate.

[0176] Examples 1-6

[0177] An isocyanate composition was prepared in the same manner as in Example 1-2, except that 200 ppm of phenol was added to the m-XDI in Example 1-2 together with 900 ppm of mono-2-ethylhexyl (2-ethylhexyl) phosphonate.

[0178] Examples 1-7

[0179] An isocyanate composition was prepared in the same manner as in Example 1-3, except that 200 ppm of phenol was added to m-XDI in Example 1-3 together with 1100 ppm of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

[0180] Examples 1-8

[0181] An isocyanate composition was prepared in the same manner as in Example 1-4, except that 200 ppm of phenol was added to the m-XDI in Example 1-4 together with 600 ppm of methylphosphonic acid pinacol.

[0182] Comparative Example 1-1

[0183] An isocyanate composition was prepared in the same manner as in Example 1-1, except that ethyl methylphosphonate in Example 1-1 was not added.

[0184] Comparative Example 1-2

[0185] An isocyanate composition was prepared in the same manner as in Example 1-1, except that 200 ppm of phenol was added instead of adding ethyl methylphosphonate in Example 1-1.

[0186] Comparative Examples 1-3

[0187] In addition to adding 250 ppm of the phosphate-based compound ZELEC TMAn isocyanate composition was prepared in the same manner as in Example 1-1, except that ethyl methylphosphonate was replaced with 1,4-dimethoxy- ...

[0188] Comparative Examples 1-4

[0189] An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of a phosphate-based compound, bis(2-ethylhexyl)phosphate, was added instead of ethyl methylphosphonate in Example 1-1.

[0190] Comparative Examples 1-5

[0191] 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 in Example 1-1.

[0192] However, the prepared isocyanate composition may cause precipitation.

[0193] Comparative Examples 1-6

[0194] An isocyanate composition was prepared in the same manner as in Example 1-1, except that 250 ppm of ethyl phosphate (monoester and diester mixture) (DEP) was added instead of ethyl methylphosphonate in Example 1-1.

[0195] <Preparation of polymerizable composition and optical lens>

[0196] Example 2-1

[0197] 20.8 g of the isocyanate composition prepared in Example 1-1 and 0.04 g of ZELEC TM UN (manufactured by Stepan), 0.04 g of Biosorb as a UV absorber TM 583 (manufactured by Sakai Chemical Industry Co., Ltd.) was stirred and mixed in a flask at room temperature for about 20 minutes.

[0198] To the resulting mixture, 0.002 g of dibutyltin dichloride was added, the mixture was stirred and mixed for 10 minutes, and then 19.2 g of 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol (the molar ratio of the thiol group in the polyfunctional thiol-based compound corresponded to 1.0 based on 1 mol of the isocyanate group in the isocyanate compound) was added as a polyfunctional thiol-based compound, and the mixture was stirred for 1 hour while degassing under 5 mbar to prepare a polymerizable composition.

[0199] In addition, the polymerizable composition prepared above was filtered through a 1 μm PTFE filter and then injected into a mold consisting of a glass mold and an adhesive tape. This mold was placed in an oven, and the temperature was gradually increased from 10° C. to 120° C. to perform polymerization for 20 hours. After the polymerization was completed, the mold was taken out of the oven and demolded to obtain a plastic lens. The obtained lens was annealed at 120° C. for 6 hours.

[0200] Examples 2-2 to 2-8 and Comparative Examples 2-1 to 2-6

[0201] 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, respectively.

[0202] However, in Comparative Examples 1-3 and 1-4, filter clogging occurred during filtration after the polymerizable composition was prepared.

[0203] In addition, the isocyanate compositions of Comparative Examples 1 to 5 were not suitable for preparing polymerizable compositions due to the generation of precipitates, and thus the preparation of polymerizable compositions and the manufacture of lenses were not performed.

[0204] Experimental Example 1

[0205] The acidity of the isocyanate compositions prepared in Examples and Comparative Examples was measured by the following method.

[0206] <Acidity measurement method>

[0207] 1. Instruments and Reagents

[0208] 1.1 0.01N KOH standard solution (methanol): 0.01mol potassium hydroxide methanol standard solution (0.01N), DAEJUNG, S / T

[0209] 1.2 n-Propanol: Use dilute hydrochloric acid solution to adjust the pH to 4 to 4.5 before use.

[0210] 1.3 300ml beaker

[0211] 1.4 Potentiometric titrator with glass electrode and calomel electrode: Metrohm E 536

[0212] 2. Test Procedure

[0213] 2.1 Add 100 ml of n-propanol into a 300 ml beaker and stir.

[0214] 2.2 Place 15 g of the isocyanate composition sample in a beaker containing n-propanol, cover with a watch glass, and stir for 10 minutes.

[0215] 2.3 After the beaker has cooled, titrate with 0.01N methanolic KOH standard solution in a potentiometric titrator and read the apparent acidity.

[0216] Conditions: Mode; pH 14, V 0, titration rate step 0.05 ml

[0217] Obvious acidity occurs between pH 5.5 and pH 7.0.

[0218] 2.4 Steps 2.1 to 2.3 were performed in the same manner as above, except that no isocyanate composition sample was added in step 2.2, to conduct a blank test.

[0219] 3. Calculation

[0220] [Formula 1]

[0221] Acidity (in HCl) (ppm) = [(AB) × N × f × 36.5 × 10 6 ] / (C×10 3 )

[0222] In formula 1,

[0223] A: Volume of KOH methanol solution consumed in titrating the isocyanate composition sample (ml)

[0224] B: Volume of KOH methanol solution consumed in blank test (ml)

[0225] N: equivalent concentration of KOH methanol solution

[0226] f: A coefficient used to correct the change in the normality of the KOH methanol solution used in the measurement, measured according to ASTM D-1638, TOLOCHIMIE 04-01-68, to make it the same as the 0.01N KOH methanol solution. For a 0.01N KOH methanol solution, the f value is 1

[0227] C: Weight of isocyanate composition sample (g) [Table 1]

[0228]

[0229] In Table 1, A, B, and C are defined as in Formula 1.

[0230] The experimental results show that the isocyanate composition of Comparative Example 1-1, in which no additive capable of providing a free acid component by reacting with an alcohol was introduced during the preparation of the isocyanate composition, exhibited low acidity.

[0231] In addition, Comparative Examples 1-3, in which a commercially available phosphate-based compound was introduced in an amount at the same level as that of Examples during the preparation of the isocyanate composition, also showed low acidity.

[0232] In addition, Comparative Examples 1-4 and 1-5 in which a phosphate-based compound or phosphoric acid is introduced during the preparation of the isocyanate composition in place of the phosphonate-based compound of the present invention show a higher acidity than Comparative Example 1-3, but show a slightly lower acidity than the Examples.

[0233] Experimental Example 2

[0234] For the isocyanate compositions prepared in the Examples and Comparative Examples, they were stored in a refrigerator at 15°C in a nitrogen atmosphere (specifically, under the condition of an atmosphere of 100% nitrogen by volume by charging nitrogen with a purity of 99.999%) for 8 weeks, and the increase in the oligomer content in the isocyanate composition over time was measured, and the storage stability was evaluated based on the results.

[0235] Specifically, for the oligomer content (area %) in the isocyanate composition, gel permeation chromatography (GPC) analysis of the isocyanate composition was performed under the following conditions to obtain the molecular weight distribution curve (GPC curve) of the isocyanate composition (x-axis: logarithm of the weight-average molecular weight (M) (log M), y-axis: molecular weight distribution relative to the logarithm (dwt / dlogM)), and the area corresponding to the fraction of the oligomer in the total area of the GPC curve was expressed as a percentage. Specifically, the oligomer content (area %) was calculated according to the following Formula 3.

[0236] [Formula 3]

[0237] Oligomer content (area %) = [E / D] × 100

[0238] In Formula 3,

[0239] D represents the total area under the curve in the molecular weight distribution curve (GPC curve) obtained by gel permeation chromatography analysis of the isocyanate composition, and

[0240] E represents the area of the peak corresponding to the oligomer in the molecular weight distribution curve of the isocyanate composition.

[0241] The total area of the GPC curve and the area of the fraction corresponding to the oligomer were obtained by integration respectively. Here, the oligomer refers to a polymer having a weight-average molecular weight (Mw) of 600 g / mol to 2000 g / mol, and the fraction corresponding to the oligomer in the GPC curve is 19.42 ≤ log Mw ≤ 22.18.

[0242] <GPC analysis conditions>

[0243] Instrument used: Agilent

[0244] Chromatographic columns: Agilent PL Mixed D, Agilent PLgel Agilent PLgel

[0245] Sample concentration: 1wt / vol% in tetrahydrofuran (THF)

[0246] Carrier: THF

[0247] Detection method: RI

[0248] Flow rate: 1.0ml / min

[0249] Column temperature: 25°C

[0250] Detector: Agilent RI detector

[0251] Polystyrene standards with molecular weights ranging from 104 g / mol to 24,600 g / mol were used to construct the calibration curve.

[0252] In addition, based on the above measurement results, the increase rate (%) of the oligomer content was calculated according to the following formula 2.

[0253] [Formula 2]

[0254] Oligomer content growth rate (%) = [(C f -Ci) / Ci]×100

[0255] In formula 2,

[0256] Ci represents the oligomer content (area %) in the isocyanate composition just after preparation, and

[0257] C f represents the oligomer content (area %) in the isocyanate composition after the isocyanate composition is stored in a nitrogen atmosphere at 15° C. (specifically, by filling with 99.999% pure nitrogen, 100% by volume nitrogen atmosphere) for 8 weeks, and

[0258] Ci and C f are the values ​​calculated according to Formula 3 respectively.

[0259]

Table 2

[0260]

[0261] In Table 2, a) the oligomer content in the isocyanate compositions of Examples and Comparative Examples immediately after preparation was measured using the same method as described above.

[0262] b) It is difficult to accurately measure the oligomer content due to the occurrence of precipitation.

[0263] In the examples and comparative examples, the same m-XDI composition was prepared and then additives were added. Therefore, the oligomer content in the isocyanate composition just after preparation was the same for all cases.

[0264] However, the oligomer content increased over time, and the rate of increase in the oligomer content showed different patterns depending on the type of additive. Specifically, over time, the examples showed a lower rate of increase in the oligomer content compared to the comparative examples.

[0265] Experimental Example 3

[0266] (1) Cloudiness

[0267] The isocyanate compositions prepared in the examples and comparative examples were stored in a refrigerator at 15 °C under a nitrogen atmosphere (specifically, by filling with nitrogen of 99.999% purity, in a 100% nitrogen atmosphere) for 12 weeks, and then visually inspected for cloudiness. The observation results were evaluated according to the following criteria, as shown in Table 3.

[0268] <Evaluation Criteria>

[0269] ×: No cloudiness occurred

[0270] O: Cloudiness occurred

[0271] (2) Haze (%)

[0272] The isocyanate compositions prepared in the examples and comparative examples were stored in a refrigerator at 15 °C under a nitrogen atmosphere for 8 weeks, and then the haze was measured according to ASTM D1003.

[0273] <Haze Measurement Conditions>

[0274] Colorimeter: Ultrascan Pro

[0275] Light source: C / 2

[0276] Cell: 10 mm quartz

[0277] (3) APHA

[0278] The isocyanate compositions prepared in the examples and comparative examples were stored in a refrigerator at 15 °C under a nitrogen atmosphere for 8 weeks, and then the APHA was measured using an Ultrascan Pro instrument from HunterLab according to the ASTM D1003 method under the following measurement conditions. The results are shown in Table 3 below. A smaller APHA value indicates better color fastness.

[0279] <APHA Measurement Conditions>

[0280] Colorimeter: Ultrascan Pro

[0281] Light source: C / 2

[0282] Battery: 10mm Quartz

[0283]

Table 3

[0284]

[0285] In Table 3, “-” indicates that accurate measurement cannot be performed.

[0286] The experimental results show that the isocyanate composition of the embodiment does not have a white turbidity phenomenon, and shows a better effect of color change resistance compared with the comparative example.

[0287] Experimental Example 4

[0288] For the polymerizable compositions prepared in Examples and Comparative Examples, the time (min) required for filtration using a PTFE filter having a pore size of 1.0 μm (25 mm diameter syringe filter, manufactured by Whatman) was measured, and the effect of improving processability was evaluated based on the results.

[0289] The filtration time refers to the time from the moment when 200 g of the polymerizable composition passes through the filter to the moment when the passing is completed.

[0290]

Table 4

[0291]

[0292] The experimental results show that the polymerizable composition of Comparative Example 2-1, which exhibits low acidity due to the fact that no additive capable of reacting with alcohol to provide a free acid component is introduced during the preparation of the isocyanate composition, has a long filtration time.

[0293] In contrast, the polymerizable composition of Example 2-1, in which the phosphonate-based compound of Chemical Formula 1 was introduced during the preparation of the isocyanate composition, showed a significantly shorter filtration time than the Comparative Example, confirming that it had improved processability.

[0294] In contrast, the isocyanate compositions of Comparative Examples 1-3 had high viscosity and were difficult to prepare polymerizable compositions, and the polymerizable compositions obtained in Comparative Examples 2-3 had filter clogging during filtration, so that the filtration time could not be measured.

[0295] In addition, since the isocyanate compositions of Comparative Examples 1-5 produced precipitates and were not suitable for preparing polymerizable compositions, Comparative Examples 2-5 were not considered.

[0296] Experimental Example 5

[0297] For the lenses manufactured from the polymerizable compositions of the Examples and Comparative Examples, the yellowness index (YI) was measured by the following method.

[0298] However, the isocyanate compositions of Comparative Examples 1-3 had high viscosities, making it difficult to prepare the polymerizable compositions, and as a result, lenses could not be manufactured. Additionally, the isocyanate compositions of Comparative Examples 1-5 were not suitable for preparing the polymerizable compositions due to the formation of precipitates, and thus lenses could not be manufactured.

[0299] The results are shown in Table 5 below.

[0300] <YI Measurement Method>

[0301] Instrument: Ultrascan Pro, HunterLab

[0302] Light source: D65 / 10

[0303] Measurement standard: ASTM E313

[0304] In addition, the defects of the manufactured lenses were visually inspected and evaluated according to the following criteria.

[0305] <Defect Evaluation Criteria>

[0306] X No lens defects

[0307] O Lens defects, with a defect element of a white line found on the lens

[0308]

Table 5

[0309]

[0310] The experimental results showed that the lenses manufactured using the polymerizable compositions of the Examples exhibited lower YI values compared to the Comparative Examples, confirming that they had a better effect of suppressing discoloration.

[0311] In contrast, the lenses of Comparative Examples 2-4 and 2-6, which used phosphate-based compounds in the preparation of the isocyanate compositions, showed high YI values, and in particular, defects occurred in the lenses of Comparative Example 2-4 that used bis(2-ethylhexyl) phosphate.

[0312] Experimental Example 6

[0313] When manufacturing lenses using the polymerizable compositions of the Examples and Comparative Examples, the mold release property was evaluated according to the following criteria based on the ease of removing the lens from the lens mold by hand, and the results are shown in Table 6.

[0314] <Mold Release Property Evaluation Criteria>

[0315] ○: Good mold release property. The lens can be easily demolded without applying force.

[0316] △: Difficult to demold. Force must be applied and demolding is not easy

[0317] ×: Mold damage. Poor demoulding properties

[0318]

Table 6

[0319]

[0320] The experimental results show that when the polymerizable compositions of Comparative Examples 2-4 are used to manufacture lenses, force needs to be applied to make the lenses difficult to release from the lens molds, indicating that the polymerizable compositions of Comparative Examples 2-4 have poor processability.

Claims

1. An isocyanate composition comprising: Isocyanate-based compounds, and A phosphonate-based compound represented by the following Chemical Formula 1: [Chemical formula 1] In Chemical Formula 1, R a and R b are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 7-30 Alkyl aryl, or substituted or unsubstituted C 7-30 Arylalkyl.

2. The isocyanate composition according to claim 1, wherein R a and R b Each independently is C 1-8 Alkyl, phenyl or benzyl, where R a and R b Each independently selected from C 1-6 One or more substituents among the alkyl, phenyl, hydroxyl and combinations thereof may be substituted or unsubstituted.

3. The isocyanate composition according to claim 1, wherein The phosphonate-based compound is ethyl methylphosphonate, pinacol methylphosphonate, 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-based compound is included in an amount of about 100 ppm to about 3000 ppm based on the total weight of the isocyanate-based 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-based compound is a diisocyanate containing two isocyanates in a molecule.

7. The isocyanate composition according to claim 1, wherein The isocyanate-based compound is 1,5-pentamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexene diisocyanate, isophorone diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate or p-xylene diisocyanate.

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

9. The isocyanate composition according to claim 8, wherein The phenolic stabilizer includes phenol; butylated hydroxytoluene; tert-butylhydroquinone; butylated hydroxyanisole; pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; diethylenethiobis[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-hydroxyphenylpropionic acid 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-hydroxyphenyl) 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'-butylenebis(6-tert-butyl-m-cresol); 2,2'-ethylenebis(4,6-di-tert-butylphenol); 2,2'-ethylenebis(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]-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-butyl dibenzo[d,f][1,3,2]dioxaphosphine; or a mixture thereof. ; 10. The isocyanate composition according to claim 8, wherein The phenolic stabilizer is included in an amount of 5 ppm to 1000 ppm based on the total weight of the isocyanate-based compound.

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

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

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

14. An article comprising a polymer, wherein: The polymer is obtained by polymerizing the isocyanate composition according to any one of claims 1 to 12 with any one or more of a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, and a polyfunctional episulfide-based compound.

15. The article of claim 14, wherein: The product is an optical adhesive, an optical bonding agent or an optical lens.

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

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