Isocyanate composition

Abstract

The present invention relates to an isocyanate composition with improved storage stability, which suppress the generation of white turbidity.

Description

Isocyanate composition

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0110696, filed August 23, 2023, and Korean Patent Application No. 10-2024-0112100, filed August 21, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to an isocyanate composition having improved storage stability and suppressing discoloration and white clouding.

[0004]

[0005] Isocyanate compounds are highly valuable not only in the chemical and resin industries, but also as precision chemical products, including optical materials. Xylylene diisocyanate (XDI), a representative example of an isocyanate compound, is seeing increasing demand as a high-value-added chemical material used as a raw material for advanced optical lenses.

[0006] Isocyanate compounds are used as raw materials for polyurethane and are used in various ways, such as coatings, adhesives, paints, foams, and optical materials. However, since isocyanate compounds exhibit high reactivity, they are prone to discoloration or clouding by reacting with moisture in the air during storage.

[0007] When manufacturing a polyurethane lens using an isocyanate compound that causes discoloration or clouding in this way, there is a problem that workability is reduced due to a rapid increase in the molecular weight of the polymer solution, which causes a decrease in stirring power, an increase in filter time, and filter clogging, and also a decrease in transparency and discoloration of the manufactured lens.

[0008] To solve this problem, a method of manufacturing and storing the product by filling or sealing it with nitrogen gas to block it from air is being used, but there is still a risk of discoloration and clouding until the isocyanate compound is completely consumed.

[0009] Accordingly, a method of improving storage stability by prescribing a phenol-based stabilizer or adding a chlorine-based substance to an isocyanate-based compound has been proposed, but there was a problem that these additives caused coloration during subsequent product manufacturing or that it was difficult to secure stability sufficient to the desired level.

[0010] Typically, isocyanate compositions are stored and transported in containers made of metal. However, due to the high acidity of the isocyanate compound, metal ions in the container are easily eluted, thereby promoting self-polymerization to form oligomers greater than dimers, resulting in discoloration or clouding.

[0011] In order to solve this problem, Korean Patent Publication No. 10-2022-0054849 distinguishes containers according to acidity when storing isocyanate compositions in metal containers, and when the acidity is 15 ppm or higher, a separate resin layer is coated on the container for use. However, this method has the problem of low economic efficiency.

[0012] Accordingly, research is needed on the production of an isocyanate composition that can exhibit excellent transparency when manufacturing optical products such as lenses, and that does not cause discoloration or clouding even when stored for a long period of time in a metal container regardless of the acidity of the composition due to improved storage stability.

[0013]

[0014] The purpose of the present invention is to provide an isocyanate composition that has improved storage stability, suppresses discoloration or white clouding even when stored for a long period of time in a metal container, and thereby improves transparency when applied to a product.

[0015]

[0016] In order to solve the above problem, according to one embodiment of the present invention,

[0017] Isocyanate compounds;

[0018] An aromatic sulfonamide antioxidant represented by the following chemical formula 1; and

[0019] Containing a phenolic antioxidant;

[0020] Isocyanate composition:

[0021] [Chemical Formula 1]

[0022]

[0023] In the above chemical formula 1,

[0024] L is a direct bond or substituted or unsubstituted C 1-20 It is alkylene,

[0025] Ar is substituted or unsubstituted C 6-60 It's Aryl,

[0026] R is hydrogen, deuterium, substituted or unsubstituted C 1-60 Alkyl, substituted or unsubstituted C 1-60 Alkenyl, substituted or unsubstituted C 3-60 Cycloalkyl, substituted or unsubstituted C 6-60 Aryl, substituted or unsubstituted benzyl, substituted or unsubstituted C 1-60 Alkylcarbamoyl, or substituted or unsubstituted C 1-60 It is an alkoxycarbonyl.

[0027]

[0028] In addition, according to another embodiment of the invention,

[0029] A metal container for storing an isocyanate composition comprising the above-described isocyanate composition is provided.

[0030]

[0031] In addition, according to another embodiment of the invention,

[0032] A composition for polyisocyanate polymerization is provided, comprising the above-described isocyanate composition; and at least one multifunctional monomer compound selected from the group consisting of a multifunctional thiol compound, a multifunctional alcohol compound, and a multifunctional episulfide compound.

[0033]

[0034] In addition, according to another embodiment of the invention,

[0035] A polyisocyanate composition is provided, which comprises a polyisocyanate polymerized with the above-described isocyanate composition and a polyfunctional alcohol compound.

[0036]

[0037] In addition, according to another embodiment of the invention,

[0038] A polyisocyanate composition is provided, which includes a polyisocyanate polymerized with the above-described isocyanate composition and a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound.

[0039]

[0040] In addition, according to another embodiment of the invention,

[0041] An article is provided, comprising a polymer in which the above-described isocyanate composition and one or more multifunctional monomer compounds selected from the group consisting of a multifunctional thiol compound, a multifunctional alcohol compound, and a multifunctional episulfide compound are polymerized.

[0042]

[0043] The isocyanate composition according to the present invention has improved storage stability, and thus discoloration or clouding is suppressed even when stored for a long period of time in a metal container, and as a result, transparency can be improved (maintained) when applied to a product.

[0044] In addition, a polymer manufactured by polymerizing the above isocyanate composition with a multifunctional monomer exhibits excellent transparency, and is useful for manufacturing products such as optical adhesives, optical glues, optical coatings, and optical lenses.

[0045]

[0046] The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0047] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0048] Hereinafter, the present invention will be described in detail.

[0049]

[0050] Due to their high reactivity with moisture and alcohol, isocyanate compounds or their adducts are typically sealed and refrigerated after manufacturing, filled with nitrogen. However, upon opening for use, they react with atmospheric moisture, or discoloration or clouding occur depending on ambient temperature. Furthermore, upon opening and using sealed isocyanate compounds or their adducts, the oligomer content increases or yellowing occurs during the storage period until depletion.

[0051] In addition, it is usually stored for a long time in a metal storage container for ease of storage, but in this case, the high acidity of the isocyanate compound makes it easy for metal ions to be eluted, and accordingly, self-polymerization is promoted to form oligomers greater than dimers, which causes problems such as increased discoloration or cloudiness.

[0052] When manufacturing a polyurethane lens using such an isocyanate compound, the viscosity of the composition increases rapidly, which causes a decrease in stirring power, an increase in filter time, or clogging of the filter, resulting in a decrease in workability, a decrease in transparency of the manufactured lens, and discoloration.

[0053] Accordingly, the inventors of the present invention studied an isocyanate composition capable of improving the storage stability of a diisocyanate compound and suppressing viscosity increase and discoloration / whitening, and as a result, confirmed that by using an aromatic sulfonamide antioxidant and a phenol antioxidant of a specific structure together, the oligomerization reaction of the isocyanate compound can be suppressed, and the viscosity increase of the isocyanate composition caused by the oligomer can be suppressed. In particular, it was confirmed that discoloration and whitening can be suppressed even when stored for a long period of time in a metal container, and thus, it can be applied to a final product to realize excellent transparency, and thus the present invention was completed.

[0054]

[0055] Isocyanate composition

[0056] An isocyanate composition according to one embodiment of the invention comprises: an isocyanate compound; an aromatic sulfonamide antioxidant represented by chemical formula 1; and a phenol antioxidant.

[0057]

[0058] The above isocyanate composition includes an isocyanate compound, which means a compound including at least one isocyanate group (NCO group) in the molecule.

[0059] Specific examples of the above isocyanate compounds include aromatic diisocyanates such as paraphenylene diisocyanate, tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), and tolidine diisocyanate (TODI); aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), and octadecyl diisocyanate; Aliphatic cyclic diisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI); aryl aliphatic diisocyanates such as xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (HXDI), and tetramethylxylylene diisocyanate (TMXDI); or modified isocyanates of each of the above isocyanates. One of these may be used alone, or two or more may be used in combination.

[0060] Among these, aliphatic diisocyanates, more specifically, xylylene diisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate, and p-xylylene diisocyanate can be preferably used.

[0061]

[0062] The above isocyanate composition includes an aromatic sulfonamide antioxidant represented by chemical formula 1.

[0063] In general, discoloration and clouding in isocyanate compositions are caused by oligomerization of isocyanates, quinoidization of intramolecular benzene rings, or side products generated by side reactions due to oxygen, moisture, or high heat during the synthesis and purification processes.

[0064] The aromatic sulfonamide antioxidant of the above chemical formula 1 delays the oligomerization reaction rate of isocyanate, and when used in combination with the phenol antioxidant described below, suppresses the above-described side reactions through radical capture reaction, thereby preventing coloring, discoloration, and clouding of the isocyanate composition.

[0065] Below, the specific structure of chemical formula 1 is as follows:

[0066] [Chemical Formula 1]

[0067]

[0068] In the above chemical formula 1,

[0069] L is a direct bond or substituted or unsubstituted C 1-20 It is alkylene,

[0070] Ar is substituted or unsubstituted C 6-60 It's Aryl,

[0071] R is hydrogen, deuterium, substituted or unsubstituted C 1-60 Alkyl, substituted or unsubstituted C 1-60 Alkenyl, substituted or unsubstituted C 3-60 Cycloalkyl, substituted or unsubstituted C 6-60 Aryl, substituted or unsubstituted benzyl, substituted or unsubstituted C 1-60 Alkylcarbamoyl, or substituted or unsubstituted C 1-60 It is an alkoxycarbonyl.

[0072]

[0073] Here, the term "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkylthioxy group; arylthioxy group; alkylsulfoxy group; arylsulfoxy group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; alkylamine group; aralkylamine group; heteroarylamine group; arylamine group; arylphosphine group; acetyl group; acetamino group or a heterocyclic group containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the above-mentioned substituents connected.

[0074]

[0075] The above Ar is phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, diphenylfluorenyl or dimethylfluorenyl, and these are C 1-10 Substituted or unsubstituted with alkyl, acetyl, amino or acetamido.

[0076] The above L is a direct bond or C 1-10 Alkylene, preferably a direct bond or methylene.

[0077] The above R is hydrogen, deuterium, C 1-10 Alkyl, C 3-30 Cycloalkyl, C 1-10 Alkylcarbamoyl, C 1-10 Alkoxycarbonyl, benzyl or allyl, preferably hydrogen, methyl, ethyl, propyl, butyl, cyclohexyl, benzyl, allyl, tert-butoxycarbonyl or butylcarbamoyl.

[0078] Preferably, the aromatic sulfonamide-based antioxidant may include at least one selected from the group consisting of benzenesulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, N-methyl-p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-butyl-p-toluenesulfonamide, N-benzyl-p-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, N-allyl-p-toluenesulfonamide, N-(tert-butoxycarbonyl)-p-toluenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, 4-acetamidobenzenesulfonamide, benzylsulfonamide, 4-acetylbenzenesulfonamide, and 3-aminobenzenesulfonamide.

[0079] The above aromatic sulfonamide-based antioxidant may be included in an amount of 10 to 3,000 ppmw based on the total weight of the diisocyanate-based compound.

[0080] If the content of the aromatic sulfonamide antioxidant is too low, it is difficult to exhibit sufficient discoloration or whitening prevention effects. Conversely, if it is included in an excessive amount exceeding a certain level, the antioxidant itself may become discolored, reducing economic feasibility. Accordingly, by including the aromatic sulfonamide antioxidant within the above-described content range, an optimal synergistic effect with the phenol antioxidant described below can be realized, thereby realizing a more enhanced discoloration, discoloration, and whitening prevention effect.

[0081] Preferably, the aromatic sulfonamide-based antioxidant may be included in an amount of 30 ppmw or more, 50 ppmw or more, 80 ppmw or more, 100 ppmw or more, or 2,800 ppmw or less, 2,500 ppmw or less, or 2,300 ppmw or less, based on the total weight of the diisocyanate-based compound.

[0082]

[0083] The above isocyanate composition includes a phenol-based antioxidant.

[0084] The above phenol-based antioxidant delays the oligomerization reaction rate of isocyanate, and when used in combination with the above-described aromatic sulfonamide-based antioxidant, suppresses the above-described side reactions through radical capture reaction, thereby preventing coloring, discoloration, and clouding of the isocyanate composition.

[0085] Preferably, the phenolic antioxidant is selected from the group consisting of phenol, 4-methoxyphenol, dibutylhydroxytoluene (BHT), 2-tertbutyl-4-methoxyphenol, 3-tertbutyl-4-methoxyphenol, 4-tert-butylbenzene-1,2-diol, propyl-3,4,5-trihydroxybenzoate, 3,5-di-tert-butyl-4-hydroxyphenylpropionate, 2-tert-butylbenzene-1,4-diol, 2,5-di-tert-butylbenzene-1,4-diol, octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate and It may include at least one selected from the group consisting of 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine.

[0086] The above phenolic antioxidant may be included in an amount of 10 to 2,000 ppmw based on the total weight of the diisocyanate compound.

[0087] If the content of the above phenol-based antioxidant is too low, it is difficult to exhibit a sufficient whitening prevention effect, and conversely, if it is included in an excessive amount exceeding a certain level, the antioxidant itself may become a cause of discoloration and whitening. Accordingly, by including the above phenol-based antioxidant within the above content range, an optimal synergistic effect with the above-mentioned aromatic sulfonamide-based antioxidant can be realized, thereby realizing a more enhanced coloring, discoloration, and whitening prevention effect.

[0088] Preferably, the phenolic antioxidant may be included in an amount of 20 ppmw or more, 25 ppmw or more, or 30 ppmw or more, or 1,800 ppmw or less, 1,500 ppmw or less, 1,300 ppmw or less, or 1,000 ppmw or less, based on the total weight of the diisocyanate compound.

[0089]

[0090] Meanwhile, according to another embodiment of the invention, the isocyanate composition may use additional additives, etc., within a range that does not impair the effect intended by the invention. Additional additives may be used without particular limitation as long as they are commonly applied in the relevant field.

[0091]

[0092] The isocyanate composition of the present invention can effectively control the increase in viscosity, discoloration, and white turbidity of the isocyanate composition by suppressing the generation of oligomers or other by-products immediately after and after production through the use of an optimally combined antioxidant.

[0093] The APHA value measured after storing the above isocyanate composition in a metal container for 6 months may be 20 or less, preferably 19 or less, or 18 or less. The lower limit of the APHA value depends on the APHA value of the initial isocyanate composition before storage, and may preferably be 5 or more. The method for measuring the APHA value is in accordance with ASTM D1209, and will be described in more detail in the experimental examples described below.

[0094] The haze value measured after storing the above isocyanate composition in a metal container for 6 months may be 1 or less, preferably 0.9 or less, or 0.8 or less. The lower limit of the haze value depends on the haze value of the initial isocyanate composition before storage, and may preferably be 0.1 or more, or 0.2 or more. The haze value may be measured after the isocyanate composition is placed in a metal container, filled with nitrogen, and the temperature of the composition in the metal container is maintained at about 15°C, but is not limited thereto. The method for measuring the haze value is in accordance with ASTM D1003, and will be described in more detail in the experimental examples described below.

[0095] The oligomer content measured by gel permeation chromatography analysis after storing the above isocyanate composition in a metal container for 6 months may be 2% or less, preferably 1.8% or less, or 1.5% or less. The method for measuring the oligomer content will be described in more detail in the experimental examples described below.

[0096]

[0097] Metal container for storing isocyanate compositions

[0098] According to one embodiment of the invention, a metal container for storing the above-described isocyanate composition is provided. Specifically, a metal container comprising the above-described isocyanate composition is provided.

[0099] The type of the above metal container is not particularly limited, and examples thereof include, but are not limited to, aluminum containers, stainless steel containers, carbon steel containers, tin steel containers, tin-free chromium-plated containers, tin-free steel containers, etc.

[0100] The above metal container suppresses the generation of oligomers or other by-products of isocyanate compounds within the container even when stored for a long period of time due to the isocyanate composition containing an optimally combined antioxidant, and thus enables long-term storage without an increase in the viscosity of the isocyanate composition and without discoloration or white turbidity.

[0101]

[0102] Method for producing an isocyanate composition

[0103] The above-mentioned isocyanate composition can be prepared by mixing an isocyanate compound, an aromatic sulfonamide antioxidant, a phenol antioxidant, and additional additives as needed.

[0104] At this time, the order and method of adding the aromatic sulfonamide antioxidant and the phenol antioxidant are not particularly limited. The phenol antioxidant may be added to the isocyanate compound after the aromatic sulfonamide antioxidant has been added, or the aromatic sulfonamide antioxidant may be added after the phenol antioxidant has been added. Alternatively, the aromatic sulfonamide antioxidant and the phenol antioxidant may be mixed first and then added to the isocyanate compound.

[0105] The above mixing can be performed according to a conventional mixing method.

[0106]

[0107] Composition for polyisocyanate polymerization

[0108] According to one embodiment of the invention, a composition for polyisocyanate polymerization is provided, which comprises, together with the above-described isocyanate composition, at least one polyfunctional monomer compound selected from the group consisting of a polyfunctional alcohol compound, a polyfunctional thiol compound, and a polyfunctional episulfide compound.

[0109] Preferably, the polymerization composition may contain the isocyanate composition and the polyfunctional monomer compound in a mixed state, or may contain them in a separate state. That is, within the polymerization composition, the isocyanate composition and the polyfunctional monomer compound may be in a mixed state in contact with each other, or may be in a separated state so as not to contact each other.

[0110] The above polyfunctional alcohol compound is a compound containing two or more hydroxyl groups (-OH) per molecule, and specifically, may be a compound having two or more, or three or more, and eight or less, or four or less hydroxyl groups per 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, 1,2-hexanediol, polypropylene glycol, polytetramethylene ether glycol, ethylene oxide-propylene oxide block copolymer, polyalkylene carbonate diol, and polycaprolactone diol; trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); Examples thereof include tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; pentahydric alcohols such as L-arabinitol, 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 polyols, and any one of these or a mixture of two or more thereof may be used.

[0111] The above multifunctional thiol compound is a compound containing two or more thiol groups (-SH) in one molecule, and specifically, it may be a compound having two or more, or three or more, and eight or fewer, or five or fewer thiol groups in the molecule.

[0112] The above multifunctional thiol compound compounds include, for example, 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), 1,4-dithiane-2,5-diyldimethanethiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane 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 Pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate), 3,6,9,12-Tetrathiatetradecane-1,14-dithiol, 3,6,10,13-Tetrathiapentadecane-1,8,15-trithiolIt may be at least one selected from the group consisting of 15-trithiol.

[0113] Specifically, the above polyvalent thiol may be added in an amount such that the molar ratio of the thiol group in the polyvalent thiol is 0.8 or more, or 0.9 or more, and 1.1 or less, or 1.0, per 1 mole of the isocyanate group of the isocyanate compound. If the molar ratio of the thiol group to the isocyanate group is less than 0.8 outside the above molar ratio range, the viscosity of the polymer produced may decrease due to the excess isocyanate group, and thus, the processability may decrease. In addition, if the molar ratio of the thiol group to the isocyanate group exceeds 1.1, the discoloration prevention effect may decrease due to the excess thiol group.

[0114] The above multifunctional episulfide compound may be a compound containing two or more episulfides, i.e., thioepoxy groups, in the molecule, and may have an aliphatic, alicyclic, or aromatic skeleton. In one example, the above multifunctional episulfide compound is 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, 1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)butane, 1,5-bis(β-epithiopropylthio)pentane, 1-(β-Epithopropylthio)-4-(β-Epithopropylthiomethyl)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-epithiopropylthioethyl)thioethyl]thio]ethane, tetrakis(β-epithiopropylthiomethyl)methane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, 1,5-Bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane, 1,5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2-bis(β-epithiopropylthiomethyl)-4-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)-2,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,9-bis(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)-5-[(2-β-epithiopropylthioethyl)thiomethyl]-3,7-dithianonan, 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-trithiadecane, 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)-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, Bis[4-(β-epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, bis[4-(β-epithiopropylthio)cyclohexyl] sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, It may include at least one selected from 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.

[0115] The above polymerization composition may further include additives such as an internal release agent, an ultraviolet absorber, a urethane reaction catalyst, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, a filler, and a photosensitizer, as needed, within a range that does not impair the effect intended by the invention, and the content thereof may be appropriately determined within a range that does not impair the discoloration and discoloration inhibition properties of the composition.

[0116] The above polymerization composition can control the occurrence of white turbidity by delaying or inhibiting the reaction rate and oligomerization of isocyanate due to the combination of two types of antioxidants included in the isocyanate composition.

[0117]

[0118] polyisocyanate composition

[0119] According to one embodiment of the invention, a polyisocyanate composition is provided, which comprises the aforementioned isocyanate composition and a polyfunctional alcohol-based compound polymerized into a polyisocyanate. The polyisocyanate produced by the reaction with the polyhydric alcohol exhibits excellent transparency and excellent adhesion / adhesion properties. Accordingly, the polyisocyanate can be used in coatings, pressure-sensitive adhesives, adhesives, and the like, but is not limited thereto, and is useful in the production of optical pressure-sensitive adhesives, optical adhesives, or optical coatings.

[0120] Here, the description of the polyfunctional alcohol compound can be applied in the same manner as described above.

[0121]

[0122] According to another embodiment of the invention, a polyisocyanate composition is provided, which comprises a polyisocyanate polymerized with the above-described isocyanate composition and a polyfunctional thiol compound or a polyfunctional episulfide compound. The polyisocyanate composition can be used in optical materials, such as, but not limited to, optical lenses.

[0123] Here, the description of the multifunctional thiol compound and the multifunctional episulfide compound can be equally applied to the above.

[0124]

[0125] In the above polyisocyanate composition, the polymerization reaction of the isocyanate composition and the monomer compound (polyfunctional alcohol compound, polyfunctional thiol compound, polyfunctional episulfide compound) can be performed under atmospheric pressure and an inert gas atmosphere such as nitrogen or argon.

[0126] The above polymerization reaction can be carried out at a temperature range of -15°C or higher, or 0°C or higher, and 200°C or lower, or 170°C or lower. For example, when a polyfunctional alcohol-based compound is used as the monomer compound, it is preferably carried out at 60 to 80°C, and when a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound is used as the monomer compound, it is preferably carried out at 100 to 160°C.

[0127] When the polymerization reaction is performed in the above temperature range, the reaction rate can be easily controlled without concern for discoloration, and the reaction efficiency can also be increased, which is preferable.

[0128]

[0129] The above polymerization reaction may be carried out under non-catalytic conditions, or may be carried out in the presence of a catalyst that typically promotes urethane reactions, such as a tin-based or amine-based catalyst. When carried out in the presence of a catalyst, the catalyst may be added together with the monomer compound at the step of adding the isocyanate-based mixture.

[0130] The progress of the above polymerization reaction can be estimated by measuring the concentration of isocyanate groups in the polymerization reactant using the n-dibutylamine method using a transfer titration device, or by measuring the refractive index. In the present invention, the polymerization reaction can be performed until the concentration of isocyanate groups in the polymerization reactant reaches the calculated value of the isocyanate groups remaining after reacting with the monomer compound. As a result of the above polymerization reaction, a polyisocyanate is produced.

[0131]

[0132] The above polyisocyanate composition may further include additives such as an internal release agent, an ultraviolet absorber, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, a filler, a photosensitizer, etc., as needed, within a range that does not impair the effect intended by the invention, and the content thereof may be appropriately determined within a range that does not impair the discoloration and discoloration inhibition properties of the composition.

[0133]

[0134] article

[0135] According to another embodiment of the invention, an article is provided, which comprises a polymer obtained by polymerizing the above-described isocyanate composition and at least one polyfunctional monomer compound selected from the group consisting of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound. This may also be an article comprising a polymer obtained by polymerizing the above-described isocyanate composition and a polyfunctional monomer compound in the polymerization composition.

[0136] Polyisocyanate compositions exhibit excellent transparency and excellent adhesion properties, making them applicable to a wide range of fields. Specifically, they can be utilized in various ways, not only as coating agents, adhesives, and glues, but also as optical materials. More preferably, the product can be used as an optical adhesive, an optical adhesive, an optical coating, or an optical lens.

[0137]

[0138] The above article may be manufactured by performing a molding process after a polymerization reaction in the above composition, or may be manufactured through a molding process using the above polymerization composition. In the latter case, the polymerization reaction occurs simultaneously during the molding process.

[0139] Preferably, when used as an optical lens, the composition may be polymerized from an isocyanate composition and a polyfunctional thiol-based compound or a polyfunctional episulfide-based compound, and in this case, the polymerization composition including the isocyanate composition and the polyfunctional thiol-based compound or the polyfunctional episulfide-based compound may be injected into a lens mold, and then the temperature of the mold may be increased to perform a polymerization reaction between the isocyanate-based compound and the polyfunctional monomer compound. At this time, the mold is heated to a temperature range in which a urethane polymerization reaction occurs, and after the polymerization reaction is completed, the manufactured polymer, specifically, polythiourethane, may be separated from the mold to obtain an optical lens.

[0140]

[0141] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0142]

[0143] [Manufacturing Example: Manufacturing of Isocyanate Compounds]

[0144] Manufacturing Example 1

[0145] 471 g of 1,2-dichlorobenzene and 32.5 g of m-XDA with a purity of 99.4% were charged into a flask reactor, and anhydrous hydrochloric acid was injected at a rate of 20 g / hr at room temperature (23±5℃) while stirring. The temperature increased to 50℃ while injecting anhydrous hydrochloric acid. After 4 hours of injection, the formed salt was cooled to room temperature, and 118 g of phosgene was injected into the reactor, and the reactor temperature was heated to 130℃. From the time of phosgene injection until the end of the reaction, a dry ice-acetone cooler was used to prevent phosgene from leaking out. After the reactor temperature reached 130℃, the reactor temperature was maintained at 125-135℃ for 2 hours so that the reaction solution became transparent. After the solution became transparent, the inside of the reactor was cooled to 80℃ and nitrogen was blown in to cool it. The solvent was removed from the reaction solution from which phosgene had been removed through vacuum distillation, and the product was purified under reduced pressure at a high temperature of 160°C to obtain an isocyanate mixture containing m-XDI. The XDI obtained after the distillation process showed 99.8% in GC area %, and the GPC oligomer showed 0.18 area% APHA 10 and Haze 0.3%. Since the acidity (in terms of HCl) differed depending on the distillation process, the acidity of low-acidity XDI was adjusted to 150 ppm using anhydrous hydrochloric acid.

[0146] Here, GC Purity, GPC olimgomer content, APHA, and Haze are the same as those measured in the experimental example below.

[0147] For acidity, potentiometric titration was performed on the sample with a 0.01 N potassium hydroxide (KOH) methanol solution, and the obtained measurement value was used to calculate according to the following mathematical formula 1.

[0148] [Mathematical Formula 1]

[0149] Acidity (as HCl) (ppm) = [(AB) * N * f * 36.5 * 106] / (C * 103)

[0150] In the above mathematical formula 1,

[0151] A: Volume (ml) of KOH methanol solution consumed in titration of isocyanate composition sample

[0152] B: Volume (ml) of KOH methanol solution consumed in the blank titration

[0153] N: Normality of KOH methanol solution

[0154] f: When the normal concentration of the KOH methanol solution used for measurement changes, this is a correction factor to make it the same as the 0.01 N KOH methanol solution. It is measured according to ASTM D-1638 and TOLOCHIMIE 04-01-68. For a 0.01 N KOH methanol solution, the f value is 1.

[0155] C: Weight of isocyanate composition sample (g)

[0156]

[0157] [Example 1 and Comparative Example 1: Isocyanate Composition]

[0158] Example 1-1

[0159] To 100 g of the purified isocyanate mixture containing m-XDI prepared in the above Manufacturing Example 1, 0.05 g of p-TSA (500 ppmw relative to m-XDI) as an aromatic sulfonamide antioxidant and 0.005 g of BHT (50 ppmw relative to m-XDI) as a phenol antioxidant were added and mixed to prepare an isocyanate composition.

[0160]

[0161] Examples 1-2 to 1-7

[0162] In the above Manufacturing Example 1, an isocyanate composition was manufactured in the same manner as in Example 1-1, except that the compounds described in Table 1 below were added as antioxidants in the described amounts to the isocyanate mixture containing m-XDI.

[0163]

[0164] Comparative Example 1-1

[0165] The isocyanate mixture containing m-XDI prepared in Manufacturing Example 1 was used as is without adding a separate antioxidant.

[0166]

[0167] Comparative Examples 1-2 to 1-10

[0168] An isocyanate composition was prepared in the same manner as in Example 1-1, except that the compounds described in Table 1 below were added as antioxidants in the amounts described for the isocyanate mixture containing m-XDI prepared in Manufacturing Example 1.

[0169]

[0170] Classification Antioxidant type Antioxidant dosage (ppmw*) Example 1-1p-TSA / BHT500 / 50 Example 1-2p-TSA / IRGANOX 1076500 / 50 Example 1-3p-TSA / BHT2000 / 30 Example 1-4p-TSA / IRGANOX 10761000 / 30 Example 1-5Benzenesulfonamide / IRGANOX 107650 / 100 Example 1-6p-TSA / Phenol500 / 1000 Example 1-7p-TSA / Phenol / BHT250 / 500 / 30 Comparative Example 1-1--Comparative Example 1-2BHT50Comparative Example 1-3p-TSA500Comparative Example 1-4IRGANOX 107650Comparative Example 1-5Phenol500Comparative Example 1-6N,N-Dimethyl methanesulfonamide / IRGANOX 1076500 / 50Comparative Example 1-7Tributylphophite / IRGANOX 1076100 / 50Comparative Example 1-8Phenol / BHT500 / 50Comparative Example 1-9p-TSI1000Comparative Example 1-10p-TSI / BHT500 / 50*m=XDI content IRGANOX 1076 (manufactured by BASF): Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate BHT: Butylated Hydroxytolueneep-TSA: para toluene sulfonamidep-TSI: para toluenesulfonyl isocyanate

[0171]

[0172] [Experimental Example 1]

[0173] The isocyanate compositions manufactured in the above examples and comparative examples were placed in a metal container made of tin steel, filled with nitrogen, and stored for 6 months under conditions of 15°C. The samples were measured for white turbidity, purity, oligomer content, and acidity according to the following method, and the results are shown in Table 2 below.

[0174]

[0175] (1) Evaluation of white turbidity occurrence

[0176] For samples of the isocyanate compositions manufactured in the above examples and comparative examples stored in metal containers for 6 months, APHA was measured according to the ASTM D1209 method using HunterLab's Ultrascan Pro, and haze was measured according to ASTM D1003, and the results are shown in Table 2 below.

[0177] <APHA · Haze 분석 조건>

[0178] Colorimeter: Ultrascan Pro

[0179] Light source: C / 2

[0180] Cell: 10mm quartz

[0181] The initial Haze value of m-XDI is 0.3, which refers to the m-XDI manufactured in Manufacturing Example 1. The greater the change in the Haze value, the greater the degree of white turbidity that has occurred can be evaluated. In addition, the smaller the APHA value, the better the discoloration resistance.

[0182]

[0183] (2) Gel permeation chromatography (GPC) analysis

[0184] For samples of the isocyanate compositions manufactured in the above examples and comparative examples stored in metal containers for 6 months, the GPC Oligomer content was measured using gel permeation chromatography, and the results are shown in Table 2 below.

[0185] <GPC 분석 조건>

[0186] Device used: Agilent

[0187] Column: Agilent PL Mixed D, Agilent PLgel 100Å, Agilent PLgel

[0188] 50Å

[0189] Sample concentration: 1 wt / vol% in tetrahydrofuran (THF) Carrier: THF

[0190] Detection method: RI

[0191] Flow rate: 1.0 ml / min

[0192] Column temperature: 25 ℃

[0193] When preparing the calibration curve, polystyrene standard foams with molecular weights of 104 to 24,600 g / mol were used.

[0194]

[0195] [Example 2 and Comparative Example 2: Optical Lens]

[0196] Example 2-1

[0197] 20.8 g of the isocyanate composition manufactured in Example 1-1, 0.04 g of zelec UN (manufactured by Stepan), and 0.04 g of biosorb 583 (manufactured by Sakai Chemical industry Co., Ltd.) were mixed in a flask at room temperature with stirring for about 20 minutes to manufacture a polyisocyanate. After visually confirming that all components were well mixed in the polyisocyanate, 0.002 g of dibutyltin chloride was added and mixed with stirring for 10 minutes.

[0198] 19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol was added to the above mixture, and the mixture was degassed under 5 mbar conditions and stirred for 1 hour to prepare a polyisocyanate composition.

[0199] The above polyisocyanate composition was filtered through a 1 μm PTFE filter and then injected into a mold consisting of a glass mold and tape. The mold was placed in an oven and the temperature was gradually increased from 10°C to 120°C over 20 hours, and then maintained at 120°C for an additional 2 hours to perform a polymerization reaction. After polymerization was completed, the mold was removed from the oven and released to obtain a plastic lens. The obtained plastic lens was annealed at 120°C for 6 hours to produce a final optical lens sample.

[0200]

[0201] Examples 2-2 to 2-7 and Comparative Examples 2-1 to 2-8

[0202] An optical lens sample was manufactured in the same manner as in Example 2-1, except that the isocyanate compositions of Examples 1-2 to 1-7 and Comparative Examples 2-1 to 2-8 were used instead of the isocyanate composition manufactured in Example 1-1.

[0203]

[0204] [Experimental Example 2]

[0205] For the optical lenses manufactured in the above examples and comparative examples, YI was measured using Ultrascan Pro and HunterLab according to ASTM E313 using the following method, and the results are shown in Table 2 below.

[0206] <Method of measuring lens YI>

[0207] Equipment: Ultrascan Pro, HunterLab

[0208] Light source: D65 / 10

[0209] Isocyanate Composition APHAHaze(%) GPC Oligomer(area %) Optical Lens Lens YI Example 1-1 150.5 0.7 Example 2-1 1.8 Example 1-2 170.6 0.8 Example 2-2 1.8 Example 1-3 110.4 1.1 Example 2-3 1.6 Example 1-4 130.5 1.2 Example 2-4 1.8 Example 1-5 130.7 1.0 Example 2-5 1.7 Example 1-6 130.4 1.1 Example 2-6 1.6 Example 1-7 160.4 0.7 Example 2-7 1.7 Comparative Example 1-1 2546 X Comparative Example 2-1 X Comparative Example 1-2 323.5 1.2 Comparative Example 2-2XComparative Example 1-3301.32.8Comparative Example 2-31.8Comparative Example 1-42912XComparative Example 2-4XComparative Example 1-5232.73.1Comparative Example 2-51.8Comparative Example 1-6323.54.8Comparative Example 2-6XComparative Example 1-7229.9XComparative Example 2-7XComparative Example 1-8243.51.6Comparative Example 2-8XComparative Example 1-9386.52.3Comparative Example 2-9XComparative Example 1-104222XComparative Example 2-10X

[0210] As can be seen in Table 2 above, the isocyanate composition according to the present invention was confirmed to have high purity and low oligomer content, while preventing discoloration and clouding even when stored for a long period of time in a metal container by using an aromatic sulfonamide antioxidant and a phenol antioxidant of a specific structure together. In particular, it was confirmed that the examples had relatively low APHA values ​​and no significant change compared to the Haze value of the initial m-XDI composition.

[0211] Comparative Example 1 was prepared by using the isocyanate mixture containing m-XDI prepared in Manufacturing Example 1 without adding a separate antioxidant. The composition itself had a high acidity of 150 ppm, and accordingly, upon long-term storage, the APHA value was high and the Haze value was significantly increased, confirming that the storage stability was significantly reduced.

[0212] In addition, it was confirmed that in Comparative Examples 2 to 8, where only some of the two antioxidants of the present invention were used or in combination with other ingredients, the physical properties were significantly lower than those of the examples, and the problems of white turbidity and oligomer formation could not be solved at the same time.

[0213] Samples with Haze 3.0 or higher were not subjected to lens manufacturing as white turbidity was visible to the naked eye. Samples with Haze 9 or higher were not subjected to GPC measurement as white turbidity was very severe.

[0214] In addition, it was confirmed that the optical lens manufactured using the isocyanate composition according to the present invention had a relatively low value of YI and thus excellent transparency.

Claims

1. Isocyanate compounds; An aromatic sulfonamide antioxidant represented by the following chemical formula 1; and Containing a phenolic antioxidant; Isocyanate composition: [Chemical Formula 1] In the above chemical formula 1, L is a direct bond or substituted or unsubstituted C 1-20 It is alkylene, Ar is substituted or unsubstituted C 6-60 It's Aryl, R is hydrogen, deuterium, substituted or unsubstituted C 1-60 Alkyl, substituted or unsubstituted C 1-60 Alkenyl, substituted or unsubstituted C 3-60 Cycloalkyl, substituted or unsubstituted C 6-60 Aryl, substituted or unsubstituted benzyl, substituted or unsubstituted C 1-60 Alkylcarbamoyl, or substituted or unsubstituted C 1-60 It is an alkoxycarbonyl.

2. In paragraph 1, Ar is phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, diphenylfluorenyl or dimethylfluorenyl, These are C 1-10 Substituted or unsubstituted with alkyl, acetyl, amino or acetamido, Isocyanate composition.

3. In paragraph 1, L is a direct bond or C 1-10 alkylene, Isocyanate composition.

4. In paragraph 1, R is hydrogen, deuterium, C 1-10 Alkyl, C 3-30 Cycloalkyl, C 1-10 Alkylcarbamoyl, C 1-10 alkoxycarbonyl, benzyl or allyl, Isocyanate composition.

5. In paragraph 1, The above aromatic sulfonamide antioxidant comprises at least one selected from the group consisting of benzenesulfonamide, p-toluenesulfonamide, o-toluenesulfonamide, N-methyl-p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-butyl-p-toluenesulfonamide, N-benzyl-p-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, N-allyl-p-toluenesulfonamide, N-(tert-butoxycarbonyl)-p-toluenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, 4-acetamidobenzenesulfonamide, benzylsulfonamide, 4-acetylbenzenesulfonamide, and 3-aminobenzenesulfonamide. Isocyanate composition.

6. In paragraph 1, The above aromatic sulfonamide antioxidant is, Contains 10 to 3,000 ppmw based on the total weight of isocyanate compounds, Isocyanate composition.

7. In paragraph 1, The above phenolic antioxidants are phenol, 4-methoxyphenol, dibutylhydroxytoluene (BHT), 2-tertbutyl-4-methoxyphenol, 3-tertbutyl-4-methoxyphenol, 4-tert-butylbenzene-1,2-diol, propyl-3,4,5-trihydroxybenzoate, 3,5-di-tert-butyl-4-hydroxyphenylpropionate, 2-tert-butylbenzene-1,4-diol, 2,5-di-tert-butylbenzene-1,4-diol, octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate and Containing at least one selected from the group consisting of 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine, Isocyanate composition.

8. In paragraph 1, The above phenolic antioxidant is, Contains 10 to 2,000 ppmw based on the total weight of isocyanate compounds, Isocyanate composition.

9. In paragraph 1, The above isocyanate compound is, A composition comprising at least one selected from the group consisting of paraphenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tolidine diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, octadecyl diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, and modified isocyanates thereof. Isocyanate composition.

10. In paragraph 1, The above isocyanate compound is xylylene diisocyanate, Isocyanate composition.

11. In paragraph 1, The above isocyanate composition has a haze value of 0.9 or less measured after storage in a metal container for 6 months. Isocyanate composition.

12. A metal container for storing an isocyanate composition, comprising an isocyanate composition according to any one of claims 1 to 11.

13. An isocyanate composition according to any one of claims 1 to 11; and at least one polyfunctional monomer compound selected from the group consisting of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound; Composition for polyisocyanate polymerization.

14. A polyisocyanate comprising an isocyanate composition according to any one of claims 1 to 11 and a polyfunctional alcohol-based compound polymerized therewith. Polyisocyanate composition.

15. A polyisocyanate comprising an isocyanate composition according to any one of claims 1 to 11 and a polyfunctional thiol compound or a polyfunctional episulfide compound polymerized therewith. Polyisocyanate composition.

16. An article comprising a polymer obtained by polymerizing an isocyanate composition according to any one of claims 1 to 11 and at least one polyfunctional monomer compound selected from the group consisting of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

17. In paragraph 16, The above article is an optical adhesive, an optical glue, an optical coating or an optical lens.

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