Isocyanate composition

Abstract

The present invention provides an isocyanate composition in which, by including an antioxidant of a specific structure with respect to a diisocyanate compound, storage stability is improved, discoloration and clouding are suppressed, and transparency can be improved when applied to a product.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority rights under Korean Patent Application No. 10-2023-0039896 dated March 27, 2023, and Korean Patent Application No. 10-2024-0041057 dated March 26, 2024, and all content disclosed in the documents of said Korean patent applications is incorporated herein by reference.

[0002] The present invention relates to an isocyanate composition that offers improved storage stability, suppresses discoloration and clouding, and exhibits improved workability, such as reduced filtering time. [Background technology]

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

[0004] However, isocyanate compounds are highly reactive, so they are prone to discoloration or clouding during storage due to reactions with moisture in the air. Furthermore, when isocyanate compounds are stored for extended periods, they can undergo self-polymerization to form oligomers (dimers or larger), leading to discoloration or clouding.

[0005] Isocyanate compounds are raw materials for polyurethane and are widely used in coatings, adhesives, paints, foams, and optical materials. However, when polyurethane lenses are manufactured using isocyanate compounds that have discolored or become cloudy, the rapid increase in the molecular weight of the polymerization solution leads to a decrease in stirring power, an increase in filtering time, and filter clogging, resulting in reduced workability. Furthermore, there are problems with reduced transparency and discoloration of the manufactured lenses.

[0006] To address this, methods are used in which the product is manufactured and stored in a nitrogen-filled or sealed environment to isolate it from air. However, discoloration and clouding still occur until the isocyanate compounds are completely consumed.

[0007] Furthermore, methods have been proposed to improve storage stability by formulating phenolic stabilizers for isocyanate compounds or by adding chlorine-based substances. However, these additives have problems such as causing discoloration during subsequent product manufacturing or reducing the stability of the isocyanate compounds.

[0008] Furthermore, methods have been proposed to improve stability using various antioxidants. Among these antioxidants, BHT was mainly used, but BHT induces yellowing during long-term storage, and its use is gradually being restricted as an environmentally regulated substance.

[0009] Therefore, research is needed on the production of isocyanate compositions that can improve storage stability, eliminating the risk of discoloration or clouding during long-term storage, and that can exhibit excellent transparency during the manufacture of optical articles such as lenses. [Overview of the project] [Problems that the invention aims to solve]

[0010] The present invention aims to provide an isocyanate composition that has improved storage stability, suppresses discoloration and clouding, and as a result improves transparency when applied to a product. [Means for solving the problem]

[0011] Therefore, according to the present invention, One or more diisocyanate compounds among diisocyanates and their adducts; A phenolic antioxidant represented by the following chemical formula 1; A phosphorus-based antioxidant represented by the following chemical formula 2; An isocyanate composition is provided, which comprises: [Chemical formula] In the above Chemical formula 1, Ra is an alkylene group having 1 to 20 carbon atoms, m is an integer from 0 to 3, [Chemical formula] In the above Chemical formula 2, L is an alkylene group having 1 to 20 carbon atoms, R1 is hydrogen; an alkyl group having 1 to 20 carbon atoms; or an aryl group having 6 to 30 carbon atoms which is substituted with one or more substituents selected from a hydroxy group and an alkyl group having 1 to 20 carbon atoms, or unsubstituted, R2 and R3 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, or are linked to each other to form a heterocyclic structure, n is an integer of 0 or 1.

[0012] Further, according to the present invention, there is provided a polymerization composition comprising the isocyanate composition; and any one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0013] Furthermore, according to the present invention, there is provided an article comprising a polymer obtained by polymerizing the isocyanate composition; and any one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound, particularly, an optical adhesive, an optical bonding agent, or an optical lens. [Advantages of the Invention]

[0014] The isocyanate composition according to the present invention has improved stability, suppressed increase in viscosity, suppressed occurrence of discoloration or turbidity, and as a result, can improve transparency during product application.

[0015] In addition, a polymer produced by subjecting the isocyanate composition to a polymerization reaction with a polyfunctional thiol-based compound, a polyfunctional alcohol-based compound, or a polyfunctional episulfide-based compound also exhibits excellent transparency and is useful for the production of articles such as optical adhesives, optical bonding agents, and optical lenses.

Mode for Carrying Out the Invention

[0016] The terms used in this specification are merely used to explain exemplary embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprising," "including," or "having" are intended to specify the presence of implemented features, steps, components, or combinations thereof, and it should be understood that the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof is not precluded in advance.

[0017] Although the present invention can be modified in various ways and can have various forms, specific embodiments will be exemplified and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and it should be understood that all modifications, equivalents, or alternatives included in the spirit and technical scope of the present invention are included. Hereinafter, the present invention will be described in detail.

[0018] Diisocyanates and their adducts, due to their high reactivity with moisture or alcohol, are filled with nitrogen, completely sealed, and stored under refrigeration after production. However, upon opening for use, they react with moisture in the atmosphere, or discoloration or clouding occurs depending on the ambient temperature. Furthermore, when sealed diisocyanates or their adducts are opened for use, the oligomer content increases or yellowing occurs during the storage time until they are consumed. As a result, when polyurethane lenses are manufactured using such diisocyanate compounds, a rapid increase in the viscosity of the composition leads to a decrease in stirring power, an increase in filtering time, or filter clogging, resulting in reduced workability, and the transparency of the manufactured lenses decreases, and discoloration occurs.

[0019] Therefore, the present inventors have studied isocyanate compositions that can improve the storage stability of diisocyanate compounds and suppress the occurrence of viscosity increase and discoloration / clouding. As a result, they have confirmed that by using a phenolic antioxidant and a phosphorus-based antioxidant of a specific structure together, the oligomerization reaction of the isocyanate compound can be suppressed, and consequently, the viscosity increase of the isocyanate composition caused by the oligomer can be suppressed, as well as discoloration and clouding. Furthermore, it has been confirmed that changes in lens color caused by various additives added during the manufacture of optical articles, particularly optical lenses, can be prevented, thus completing the present invention.

[0020] Specifically, the isocyanate composition according to the present invention is (i) Diisocyanate compounds comprising one or more diisocyanates and their adducts; (ii) A phenolic primary antioxidant represented by the following chemical formula 1; and (iii) A phosphorus-based antioxidant represented by the following chemical formula 2; including: [ka] In the aforementioned chemical formula 1, Ra is an alkylene group from C1 to C20. m is an integer between 0 and 3. [ka] In the aforementioned chemical formula 2, L is an alkylene group from C1 to C20. R1 is hydrogen; a C1-C20 alkyl group; or a C6-C30 aryl group substituted with one or more substituents from a hydroxyl group and a C1-C20 alkyl group, or unsubstituted. R2 and R3 are either hydrogen or a C1-C6 alkyl group, or linked together to form a heterocyclic structure. n is an integer, either 0 or 1.

[0021] The components of the isocyanate composition according to the present invention will be described in detail below.

[0022] (i) Diisocyanate compounds In the isocyanate composition, the diisocyanate-based compound includes diisocyanates, their adducts, or mixtures thereof. Furthermore, the diisocyanate is not particularly limited as long as it contains two isocyanate groups (NCO groups) in its molecule.

[0023] Specific examples of the aforementioned diisocyanates include aromatic diisocyanates such as paraphenylenediisocyanate, tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), and tolidine diisocyanate (TODI); tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), and octade Examples include aliphatic diisocyanates that do not contain aromatic rings, such as sil diisocyanates; alicyclic diisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI); aliphatic diisocyanates that contain aromatic rings, such as xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (HXDI), and tetramethylxylylene diisocyanate (TMXDI); or modified isocyanates of each of the above, and any one or a mixture of two or more of these can be used.

[0024] In particular, aliphatic diisocyanates containing aromatic rings, more specifically xylylene diisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate, or p-xylylene diisocyanate, can be preferably used.

[0025] Furthermore, the adduct of the diisocyanate is a reaction product formed by a chemical reaction of the diisocyanate. Specifically, it may be a polyisocyanate formed by a polymerization reaction of the diisocyanate, or it may be an adduct formed by a reaction between the diisocyanate and trimethylolpropane or glycerin.

[0026] Specific examples of the aforementioned adducts include: polyisocyanate oligomers derived from diisocyanate; xylylene diisocyanate-trimethylolpropane adducts (XDI-TMP adducts), which are reaction products obtained by reacting xylylene diisocyanate (XDI) with trimethylolpropane (TMP); xylylene diisocyanate-glycerol adducts, which are reaction products of XDI and glycerin; tolylene diisocyanate-trimethylolpropane adducts, which are reaction products of tolylene diisocyanate (TDI) and TMP; tolylene diisocyanate-glycerol adducts, which are reaction products of TDI and glycerin; tetramethylxylylene diisocyanate-trimethylolpropane adducts, which are reaction products of tetramethylxylylene diisocyanate (TMXDI) and TMP; and tetramethylxylylene diisocyanate-glycerol adducts, which are reaction products of TMXDI and glycerin. Examples include serine adducts; hydrogenated xylylene diisocyanate-trimethylolpropane adduct, which is a reaction product of hydrogenated xylylene diisocyanate (HXDI) and TMP; hydrogenated xylylene diisocyanate-glycerol adduct, which is a reaction product of HXDI and glycerin; hexamethylene diisocyanate-trimethylolpropane adduct (HDI-TMP adduct), which is a reaction product of hexamethylene diisocyanate (HDI) and TMP; hexamethylene diisocyanate-glycerin adduct, which is a reaction product of HDI and glycerin; isophorone diisocyanate-trimethylolpropane adduct (IPDI-TMP adduct), which is a reaction product of isophorone diisocyanate (IPDI) and TMP; and isophorone diisocyanate-glycerin adduct, which is a reaction product of IPDI and glycerin. Any one or a mixture of two or more of these can be used.

[0027] (ii) Phenolic antioxidants The isocyanate composition according to the present invention contains a phenolic primary antioxidant represented by the following chemical formula 1: [ka] In the aforementioned chemical formula 1, Ra is an alkylene group of C1 to C20, more specifically, an alkylene group with C1 or more, or C5 or more, or C7 or more, and C20 or less, or C18 or less, or C17 or less. m is an integer between 0 and 3, more specifically, an integer of 0 or 3.

[0028] Specific examples of the phenol-based primary antioxidant include octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (CAS No. 2082-79-3); benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester (CAS No. 125643-61-0); or pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS No. 2082-79-3); Examples include No. 6683-19-8), and any one or more of these in combination may be used. Alternatively, commercially available products of IRGANOX1010 (BASF), IRGANOX1135 (BASF), IRGANOX1076 (BASF), or SONGNOX1076 (SONGWON) may be used.

[0029] Generally, discoloration and turbidity in isocyanate compositions occur due to oligomerization of isocyanates, quinoidization of benzene rings in the molecule, or addition products generated by side reactions involving oxygen, moisture, or high heat during synthesis and purification processes.

[0030] Among conventional phenolic antioxidants, the first phenolic antioxidant represented by chemical formula 1 can prevent discoloration and turbidity of the isocyanate composition by delaying the oligomerization reaction rate of isocyanates and suppressing the aforementioned side reactions through radical scavenging reactions.

[0031] Furthermore, since the phenol-based first antioxidant contains substituents that have greater steric hindrance than BHT, the resonance effect and electron-induced effect are maximized, resulting in a superior antioxidant effect. Consequently, it exhibits excellent improvement in the storage stability of the isocyanate composition.

[0032] Furthermore, when used in combination with the phosphorus-based secondary antioxidant described below, it is possible to prevent discoloration during lens manufacturing caused by the use of these phosphorus-based antioxidants. Moreover, because the phosphorus-based secondary antioxidant contains a t-butyl-substituted phenyl structure in its molecule, the phenol-based primary antioxidant exhibits excellent miscibility due to its high structural similarity, resulting in an enhanced antioxidant effect.

[0033] The phenol-based primary antioxidant may be present in an amount of 10 to 3000 ppm based on the total weight of the diisocyanate compound.

[0034] If the content of the phenol-based primary antioxidant is excessively low, it will be difficult to achieve sufficient discoloration or clouding prevention. Conversely, if it is present in excess above a certain level, the phenol-based primary antioxidant itself may become a cause of discoloration and clouding. Therefore, in the present invention, by including the phenol-based primary antioxidant within the aforementioned content range, a more enhanced discoloration and clouding suppression effect can be achieved. More specifically, the phenol-based primary antioxidant may be included in a content of 10 ppm or more, or 20 ppm or more, or 25 ppm or more and 3000 ppm or less, or 2000 ppm or less, or 1500 ppm or less, based on the total weight of the diisocyanate compound.

[0035] On the other hand, the phenol-based first antioxidant may further selectively contain one or more other phenol-based antioxidants that are commonly used in the production of isocyanate compositions, in addition to the compound represented by chemical formula 1.

[0036] Specific examples of the aforementioned other phenolic antioxidants include phenol; dibutylhydroxytoluene; t-butylhydroquinone; butylhydroxyanisole; pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]; and benzenepropanoic acid. 3,5-Bis(1,1-dimethylethyl)-4-hydroxyC7-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; Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]; Hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxyphenyl) (3,5-di-tert-pentylphenyl)-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; thiodiethyleneglyceride Colbis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]; 4,4'-thiobis(6-tert-butyl-m-cresol); 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol);Bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyrate] glycol ester; 4,4'-butylidenebis(6-tert-butyl-m-cresol); 2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol); 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6- It may be methylbenzene; 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; or 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]; or any one or more of these in mixtures may be used.

[0037] The aforementioned other phenolic antioxidants may be included in amounts that do not inhibit the effect of the isocyanate composition. Specifically, the aforementioned other phenolic antioxidants may be included in amounts of 5 to 1000 parts by weight, based on 100 parts by weight of the first phenolic antioxidant.

[0038] (iii) Phosphorus-based antioxidants Furthermore, the isocyanate composition contains a phosphorus-based antioxidant represented by the following chemical formula 2: [ka] In the aforementioned chemical formula 2, L is an alkylene group of C1 to C20, more specifically, an alkylene group of C1 or more, or C2 or more, and C20 or less, or C12 or less, or C6 or less, or C4 or less. R1 is hydrogen; a C1-C20 alkyl group; or a C6-C30 aryl group substituted with one or more substituents from a hydroxyl group and a C1-C20 alkyl group, or unsubstituted. R2 and R3 are either hydrogen or a C1-C6 alkyl group, or linked together to form a heterocyclic structure. n is an integer, either 0 or 1.

[0039] More specifically, in the above chemical formula 2, L may be an alkylene group of C1 or more, or C2 or more and C20 or less, or C12 or less, or C6 or less, or C4 or less.

[0040] Furthermore, R1 may more specifically be a hydrogen atom; a C1-C12 alkyl group; or an unsubstituted C6-C18 aryl group substituted with one or more substituents from a hydroxyl group and a C1-C6 alkyl group; and more specifically, R1 may be a phenyl group substituted with one or more substituents from a C3-C6 alkyl group.

[0041] More specifically, R2 and R3 can each be independently hydrogen or a C1-C4 alkyl group, or they can be linked together to form a heterocyclic structure.

[0042] More specifically, n is an integer equal to 0.

[0043] Specifically, the phosphorus-based antioxidant may be a compound represented by the following chemical formula 3 or chemical formula 4: [ka] In the aforementioned chemical formula 3, R 11is hydrogen; a C1 - C12 alkyl group; or a C6 - C18 aryl group which is substituted with one or more substituents selected from a hydroxy group and a C1 - C6 alkyl group, or is unsubstituted. More specifically, R 11 may be a phenyl group substituted with one or more substituents selected from C3 - C6 alkyl groups such as an isopropyl group, a t - butyl group, etc., R 12 and R 13 may each independently be hydrogen or a C1 - C6 alkyl group. More specifically, R 12 and R 13 may each independently be hydrogen or a C1 - C4 alkyl group. Even more specifically, R 12 and R 13 may each be hydrogen. [Chemical formula] In Chemical formula 4 above, L1 may be a C1 - C20 alkylene group. More specifically, L1 may be an alkylene group having 1 or more carbon atoms, or 2 or more carbon atoms, or 3 or more carbon atoms and 20 or fewer carbon atoms, or 12 or fewer carbon atoms, or 6 or fewer carbon atoms, or 4 or fewer carbon atoms. Even more specifically, it may be an ethylene, propylene, or butylene group, R 21 ~R 25 may each independently be hydrogen, a hydroxy group, or a C1 - C12 alkyl group. More specifically, R 21 and R 24 may each independently be a C1 - C6 alkyl group such as methyl, ethyl, t - butyl, R 25 is a hydroxy group, R 22 and R 23 may be hydrogen, ​​​​The phosphorus-based secondary antioxidant can improve processing stability through hydroperoxide decomposition of phosphite at high temperatures. As a result, when an isocyanate composition containing this antioxidant is used in the manufacturing and processing of optical products at high temperatures, it can exhibit excellent discoloration prevention properties.

[0045] More specifically, the phosphorus-based secondary antioxidants that can be used are tris(2,4-di-tert-butylphenyl)phosphite (CAS No. 31570-04-4), 2-(tert-butyl)-6-methyl-4-(3-((2,4,8,10-tetrakis(tert-butyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)propyl)phenol (CAS No. 203255-81-6), or mixtures thereof. Additionally, the following products can be used: IRGAFOS168 (BASF), ETHAPHOS368 (Albemarle Corp), ALKANOX240 (Great Lakes Chemical Corp. (Headquarters)), SONGNOX1680 (SONGWON Industrial), and SUMILIZER GP (Sumitomo).

[0046] The phosphorus-based antioxidant may be present in an amount of 10 to 3000 ppm based on the total weight of the diisocyanate compound.

[0047] If the content of the phosphorus-based antioxidant is excessively low, less than 10 ppm, it will be difficult to prevent discoloration or clouding. Conversely, if it is present in excess above a certain level, the phosphorus-based antioxidant itself may become a cause of discoloration and clouding. More specifically, the phosphorus-based antioxidant may be present in an amount of 10 ppm or more, or 20 ppm or more, or 25 ppm or more and 3000 ppm or less, or 2000 ppm or less, or 1500 ppm or less, based on the total weight of the diisocyanate compound.

[0048] Furthermore, the phosphorus-based secondary antioxidant may also selectively contain one or more other phosphorus-based antioxidants that are commonly used in the production of isocyanate compositions, in addition to the compound.

[0049] Specific examples of the aforementioned other phosphorus-based antioxidants include dioctyl phosphonate, tributyl phosphite, and triphenyl phosphite, and one or more of these can be used.

[0050] The aforementioned other phosphorus-based antioxidants may be included in an amount that does not inhibit the effect of the isocyanate composition, and specifically, the aforementioned other phosphorus-based antioxidants may be included in amounts of 5 to 50 parts by weight based on 100 parts by weight of the phosphorus-based second antioxidant.

[0051] Furthermore, in the isocyanate composition according to the present invention, the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant act complementaryly, and by optimizing their mixing ratio, the aforementioned effects can be further improved. Specifically, the isocyanate composition may contain the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant in a weight ratio of 1:1 to 5:1. More specifically, they may contain them in a weight ratio of 1:1 to 4:1 or 2:1 to 4:1.

[0052] Furthermore, the isocyanate composition may contain the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant in such a total weight of 20 to 4000 ppm, based on the total weight of the diisocyanate compounds. More specifically, it may contain 20 ppm or more, or 50 ppm or more and 4000 ppm or less, or 3000 ppm or less, or 1500 ppm or less.

[0053] As an example, the isocyanate composition according to the present invention may include, as a diisocyanate compound, xylylene diisocyanate; a phenol-based primary antioxidant represented by chemical formula 1; and a phosphorus-based secondary antioxidant represented by chemical formula 3. More specifically, the isocyanate composition may include, as a diisocyanate compound, xylylene diisocyanate; as a phenolic primary antioxidant, octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (e.g., IRGANOX1076, manufactured by BASF); benzenepropionic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester; or pentaerythritol tetrakis(3-3,5-di-tert-butyl-4-hydroxyphenyl)propionate (e.g., IRGANOX1010, manufactured by BASF); and as a phosphorus secondary antioxidant, tris(2,4-di-tert-butylphenyl) phosphite (IRGAFOS168, manufactured by BASF).

[0054] In this case, the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant may be present in amounts of 10 to 500 ppm, more specifically 10 to 100 ppm, or even more specifically 10 to 50 ppm, based on the total weight of the diisocyanate compound. When the above content range conditions are satisfied, the storage stability effect can be increased. Furthermore, the phenol-based primary antioxidant may be present in amounts of 10 to 50 ppm, more specifically 25 to 50 ppm, or 25 to 40 ppm, or 40 to 50 ppm, based on the total weight of the diisocyanate compound, and the phosphorus-based secondary antioxidant may be present in amounts of 10 to 50 ppm, more specifically 10 to 25 ppm, or 25 to 50 ppm, based on the total weight of the diisocyanate compound.

[0055] Furthermore, the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant may be included in a mixed weight ratio of 1:1 to 4:1.

[0056] As yet another example, the isocyanate composition according to the present invention may include, as a diisocyanate compound, xylylene diisocyanate-trimethylolpropane (XDI-TMP) adduct; a phenol-based primary antioxidant represented by chemical formula 1; and as a phosphorus-based secondary antioxidant, one of the compounds represented by chemical formula 3 and the compound represented by chemical formula 4. More specifically, the isocyanate composition may include, as a diisocyanate compound, xylylene diisocyanate-trimethylolpropane (XDI-TMP) adduct; as a phenolic primary antioxidant, octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate; and as a phosphorus secondary antioxidant, 2-(tert-butyl)-6-methyl-4-(3-((2,4,8,10)-tetrakis(tert-butyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl)oxy)propyl)phenol (e.g., SUMILIZER GP, manufactured by Sumitomo).

[0057] In this case, the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant may be present in amounts of 500 to 1500 ppm each, based on the total weight of the diisocyanate compound. More specifically, the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant may be present in amounts of 500 to 1000 ppm or 1000 to 1500 ppm each, based on the total weight of the diisocyanate compound. Furthermore, the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant may be present in a mixed weight ratio of 1:1 to 2:1.

[0058] The isocyanate composition can be produced by adding a phenol-based primary antioxidant and a phosphorus-based secondary antioxidant to a diisocyanate compound and mixing them.

[0059] At this time, the order in which the phenolic primary antioxidant and the phosphorus-based secondary antioxidant are added is not particularly limited. The phosphorus-based secondary antioxidant may be added after the phenolic primary antioxidant, or the phenolic primary antioxidant may be added after the phosphorus-based secondary antioxidant. Alternatively, the phenolic primary antioxidant and the phosphorus-based secondary antioxidant may be mixed first and then added to the diisocyanate compound.

[0060] Furthermore, the mixing may be carried out by a conventional mixing method.

[0061] The isocyanate composition of the present invention having the above configuration can effectively control the increase in viscosity and the occurrence of discoloration or turbidity of the isocyanate composition by suppressing the generation of oligomers immediately after and after manufacturing, through the use of optimally combined antioxidants.

[0062] Specifically, the isocyanate composition is stored in nitrogen at 25°C for one year, and then its APHA value, measured according to ASTM D1209, is 25 or less, more specifically 20 or less. A lower APHA value indicates better discoloration resistance, so the lower limit is not limited, but as an example, it may be greater than 0 or greater than 1.

[0063] Furthermore, the isocyanate composition may satisfy one or more, or all of, of the following conditions (i) and (ii): (i) After the isocyanate composition is filled with nitrogen and stored at 25°C for 7 days, the APHA value measured by ASTM D1209 is 10 or less, or 8 or less and greater than 0, or 1 or greater; (ii) The isocyanate composition is nitrogen-filled and stored at 25°C for 24 weeks, after which the APHA value measured by ASTM D1209 is 25 or less, or 20 or less, or 18 or less, or 15 or less and greater than 0, or greater than 1.

[0064] Furthermore, the isocyanate composition does not exhibit turbidity even after being stored for one year at 25°C in an air atmosphere.

[0065] More specifically, if the isocyanate composition contains diisocyanate, the following conditions (a1) and (a2) can be satisfied. (a1) In a graph obtained by analyzing an isocyanate composition after filling it with nitrogen and storing it at 25°C for one year using gel permeation chromatography (x axis: retention time (min), y axis: detector sensitivity (intensity)), the area of ​​the peak located in the retention time range of 15 to 17 minutes is 0.5 area % or less of the total peak area, more specifically 0.5 area % or less, 0.4 area % or less, or 0.36 area % or less and greater than 0 area %, or 0.01 area % or more, or 0.05 area % or more, or 0.08 area % or more. (a2) The isocyanate composition is filled with nitrogen and stored at a temperature of 25°C for one year, after which the APHA measured by the ASTM D1209 method is 20 or less, more specifically, 20 or less, or 18 or less, or 15 or less and greater than 0, or 1 or more. Furthermore, the isocyanate composition can further satisfy the conditions that (a3) ​​after being filled with nitrogen and stored at 25°C for 7 days, the APHA value measured by ASTM D1209 is 10 or less, more specifically, 10 or less, or 8 or less and greater than 0, or 1 or more.

[0066] Furthermore, if the isocyanate composition contains a diisocyanate adduct, the following conditions (b1) to (b4) can be satisfied: (b1) Viscosity measured after the isocyanate composition has been nitrogen-filled and stored at 25°C for 24 weeks: 500 to 1000 cps, more specifically, 500 cps or more, or 600 cps or more, or 650 cps or more and 1000 cps or less, or 850 cps or less, or 750 cps or less; (b2) APHA value measured by ASTM D1209 after the isocyanate composition has been nitrogen-filled and stored at 25°C for 24 weeks: 20 or less, more specifically, 20 or less, or 19 or less, or 18 or less and greater than 0, or greater than 1; (b3) After the isocyanate composition is filled with nitrogen and stored at 25°C for 24 weeks, the viscosity increase rate calculated by Formula 1 below must be 50% or less, more specifically, 50% or less, or 40% or less, or 36% or less, and 0% or more, or 5% or more, or 10% or more, or 18% or more; (b4) After nitrogen filling and storage at 25°C for 24 weeks, the APHA increase rate calculated by formula 2 below is 50% or less, more specifically, 50% or less, or 45% or less, or 43% or less, and 0% or more, or 5% or more, or 29% or more.

[0067] [Formula 1] Viscosity increase rate = [(Viscosity after 24 weeks - Initial viscosity) / Initial viscosity] x 100 (In the above formula 1, the initial viscosity is the viscosity of the diisocyanate compound used in the production of the isocyanate composition, measured under conditions of 25°C and a rotation speed of 5 rpm.) The viscosity after 24 weeks is the viscosity measured at 25°C and a rotation speed of 5 rpm after the isocyanate composition has been nitrogen-filled and stored at 25°C for 24 weeks.

[0068] [Formula 2] APHA growth rate = [(APHA after 24 weeks - initial APHA) / initial APHA] x 100 (In the above formula 2, the initial APHA is the APHA measured by ASTM D1209 for the diisocyanate compound used in the production of the isocyanate composition.) APHA after 24 weeks is the APHA of the isocyanate composition measured by ASTM D1209 after the composition was nitrogen-filled and stored at 25°C for 24 weeks.

[0069] As described above, the isocyanate composition according to the present invention has excellent stability and high transparency, making it suitable for use as a polymerization composition for manufacturing optical articles.

[0070] Therefore, according to the present invention, a polymerization composition is provided which, together with the isocyanate composition, comprises one or more of the following: a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

[0071] The polymerization composition may contain the isocyanate composition and one or more of the polyfunctional thiol compound, polyfunctional alcohol compound, and polyfunctional episulfide compound in a mixed state, or in a separated state. In other words, in the polymerization composition, the isocyanate composition and the polyfunctional thiol compound, polyfunctional alcohol compound, or polyfunctional episulfide compound may be blended in contact with each other, or in a separated state so as not to contact each other.

[0072] In the polymerization composition, the polyfunctional thiol compound is a compound containing two or more thiol groups (-SH) in one molecule, and specifically, it may be a compound having two or more, or three or more and eight or fewer, or five or fewer thiol groups in the molecule.

[0073] Examples of the polyfunctional thiol compounds include 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol, 1,9-dimercapto-3,7-dithianonane, 1,13-dimercapto-3,7,11-trithiatridecane, and glycol di(3-mercaptopropionate). di(3-mercaptopropionate), 1,4-Dithiane-2,5-diyldimethanethiol, 2-mercaptomethyl-1,5-dimercapto-3-thiapentane, trimethylolpropane (3-mercaptopropionate) tri(3-mercaptopropionate)), 4,8-di(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiaundecane, 5,9-di(mercaptoethyl)-1,12-dimercapto-3,7,10-trithiadodecane, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate) tetra(mercaptoacetate), 3,6,9,12-Tetrathiatetradecane-1,14-dithiol, or 3,6,10,13-Tetrathiapentadecane-1,8,15-trithiol.It may be 13-Tetrathiapentadecane-1,8,15-trithiol), or any one or more of these in a mixture of two or more can be used.

[0074] Furthermore, the polyfunctional alcohol compound is a compound containing two or more hydroxyl groups in one molecule, and specifically, it may be a compound having two or more, or three or more and eight or fewer, or four or fewer hydroxyl groups in the molecule. Specific examples include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, and 1,2-hexanediol; trihydric alcohols such as glycerol, trimethylolethane, and trimethylolpropane (TMP); tetrahydric alcohols such as diglycerin, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; pentahydric alcohols such as L-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; or low molecular weight polyols. Any one or a mixture of two or more of these can be used.

[0075] Furthermore, the polyfunctional episulfide compound may be a compound containing two or more episulfides, i.e., thioepoxy groups, in its molecule, and may have an aliphatic, alicyclic, or aromatic skeleton. For example, the polyfunctional episulfide compound may be 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-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane, 1,6-bis(β-epithiopropylthio)hexane, 1-(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane, 1-(β-epithiopropylthio)-2-[[2-(2 -β-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-epithiopropyl Thiomethyl)-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-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-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 S[4-(β-epithiopropylthio)cyclohexyl]sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β-epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,It may contain 2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β-epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfone, 4,4'-bis(β-epithiopropylthio)biphenyl, or mixtures thereof.

[0076] In the polymerization composition, the molar ratio of thiol groups to isocyanate groups may be about 0.5 to about 1.5, or about 0.8 to about 1.2, or about 0.9 to about 1.1, but the present invention is not necessarily limited thereto.

[0077] Furthermore, the polymerization composition may optionally contain additives such as internal release agents, ultraviolet absorbers, urethane reaction catalysts, polymerization initiators, heat stabilizers, color correctors, chain extenders, crosslinking agents, light stabilizers, fillers, and photosensitive agents, and their content can be appropriately determined within a range that does not impair the discoloration and discoloration suppression properties of the composition.

[0078] As an example, the polymerization composition may further contain an internal release agent to improve release properties from the mold during subsequent product molding.

[0079] Examples of the aforementioned internal mold release agent include phosphate ester-based mold release agents, alkyl phosphate ester-based mold release agents, and fatty acid ester-based mold release agents. One or more of these can be used. Among these, phosphate ester-based mold release agents are preferred.

[0080] The aforementioned phosphate ester-based release agent is ZELEC UN TM You may commercially obtain and use products such as those manufactured by Stepan Company.

[0081] The internal release agent may be included in an amount of 0.01% by weight or more, or 0.05% by weight or more and 10% by weight or less, or 5% by weight or less, relative to the total weight of the polymerization composition.

[0082] As yet another example, the polymerization composition may further contain an ultraviolet absorber. Specifically, the ultraviolet absorber may be a benzothiazole-based ultraviolet absorber, a formamidine-based ultraviolet absorber, or any one or a mixture of two or more of these. Among these, a formamidine-based ultraviolet absorber is preferably used.

[0083] 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.) may be used.

[0084] The ultraviolet absorber may be included in an amount of 0.01% by weight or more, or 0.05% by weight or more and 0.1% by weight or less, or 0.08% by weight or less, relative to the total weight of the polymerization composition.

[0085] Furthermore, examples of urethane reaction catalysts include dialkyltin halide compounds such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylate compounds such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate; dialkyltin dialkoxide compounds such as dibutyltin dibutoxide and dioctyltin dibutoxide; dialkyltin dithioalkoxide compounds such as dibutyltin di(thiobutoxide); dialkyltin oxide compounds such as di(2-ethylhexyl)tin oxide, dioctyltin oxide, and bis(butoxydibutyltin) oxide; or dialkyltin sulfide compounds, and any one or a mixture of two or more of these can be used.

[0086] The urethane reaction catalyst may be included in an amount of 0.001% by weight or more, or 0.002% by weight or more, or 0.004% by weight or more and 0.1% by weight or less, or 0.05% by weight or less, or 0.01% by weight or less, or 0.008% by weight or less, based on the total weight of the polymerization composition.

[0087] The polymerization composition exhibits excellent discoloration resistance because the phosphonate compound contained in the isocyanate composition delays or suppresses the reaction rate and oligomerization of the isocyanate, preventing discoloration of the lens color caused by various additives added to improve workability during lens manufacturing. Furthermore, the viscosity increase of the polymerization composition is suppressed, resulting in improved workability, such as a reduction in filtering time during product manufacturing.

[0088] Thus, the polymerization composition can be used in a wide range of fields due to its excellent physical properties, and can be used as an optical material that requires excellent appearance characteristics, especially transparency, such as eyeglass lenses, camera lenses, plastic lenses, and prisms.

[0089] According to the present invention, an optical article is provided which comprises a polymer obtained by polymerizing an isocyanate composition in the polymerization composition with one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide.

[0090] For example, if the polymerization composition contains a polyfunctional thiol compound, the polymerization reaction is carried out by a urethane reaction between the isocyanate group in the isocyanate compound and the thiol group in the polyfunctional thiol compound. Since polyurethane produced by this reaction with a polyfunctional thiol compound exhibits excellent transparency, it is particularly useful in the manufacture of optical articles, especially optical lenses such as eyeglass lenses and camera lenses.

[0091] As yet another example, if the polymerization composition contains a polyfunctional alcohol compound, the polymerization reaction is carried out by a urethane reaction (or condensation polymerization reaction) between the isocyanate in the aromatic diisocyanate and the hydroxyl group in the polyfunctional alcohol. Polyurethane produced in this way by reaction with a polyfunctional alcohol compound exhibits excellent transparency and excellent adhesive properties, and can therefore be useful as an optical adhesive or optical bonding agent.

[0092] Furthermore, the polymerization reaction may be carried out under atmospheric pressure and in an inert gas atmosphere such as nitrogen or argon.

[0093] Furthermore, it is preferable that the polymerization reaction be carried out at a temperature range of -15°C or higher, or 0°C or higher and 150°C or lower, or 120°C or lower, because this allows for easy control of the reaction rate without fear of discoloration and also increases the reaction efficiency.

[0094] The polymerization reaction may be carried out under catalyst-free conditions or in the presence of a urethane reaction catalyst as described above. When carried out in the presence of a catalyst, the catalyst can be added to the isocyanate composition at the time of mixing, such as a polyfunctional thiol compound, a polyfunctional alcohol compound, or a polyfunctional episulfide compound.

[0095] Furthermore, the degree of the polymerization reaction can be predicted by measuring the concentration of isocyanate groups in the polymerization product using the n-dibutylamine method with a potentiometric titrator, or by measuring the refractive index. In the present invention, the polymerization reaction can be carried out until the concentration of isocyanate groups in the polymerization product reaches the calculated value of the remaining isocyanate groups after reaction with the polyfunctional thiol compound.

[0096] As a result of such polymerization reactions, polymers, specifically polythiourethanes, are produced.

[0097] On the other hand, articles containing the polymer may specifically include paints such as paints for plastics or automotive paints; coatings such as film coatings; various inks; sealing materials; various microcapsules; artificial leathers such as artificial and synthetic leathers; reaction injection molded (RIM) articles; slush powders; elastic molded articles (spandex); urethane foams; or optical adhesives, optical glues, or optical articles such as optical lenses (eyeglass lenses, camera lenses, plastic lenses, prisms, etc.). When considering the excellent transparency of the polymerization composition, it may also be an optical article, in particular an optical lens such as an eyeglass lens or camera lens.

[0098] The article may be manufactured by performing a molding step after the polymerization reaction in the polymerization composition, or by a molding step using the polymerization composition. In the latter case, the polymerization reaction occurs simultaneously during the molding step.

[0099] As an example, in the case of an optical lens, the polymerization composition is injected into a lens molding mold, and then the temperature of the mold is increased to carry out a polymerization reaction between the isocyanate compound and the polyfunctional thiol compound or polyfunctional episulfide compound. At this time, the mold is heated to the temperature range in which the urethane polymerization reaction occurs, as described above. After the polymerization reaction is complete, the produced polymer, specifically polythiourethane, can be separated from the mold to obtain an optical lens.

[0100] Polymers produced from the polymerization composition according to the present invention, specifically polythiourethanes, exhibit excellent transparency and improved workability, making them particularly useful in the manufacture of optical articles, especially optical adhesives, optical bonding agents, or optical lenses.

[0101] As an example, an optical lens containing a polymer produced from the polymerization composition according to the present invention exhibits a YI value of 2 or less, or 1.8 or less, when measured according to ASTM E313. A lower YI value indicates better discoloration resistance, so the lower limit is not particularly limited, but specifically, it may be greater than 0, or 0.1 or greater.

[0102] The following examples illustrate the present invention, but these examples are merely illustrative, and it will be obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the technical concept, and it goes without saying that such changes and modifications fall within the scope of the attached claims. [Examples]

[0103] <Production of diisocyanate compounds> Manufacturing Example 1 471 g of 1,2-dichlorobenzene, 32.5 g of 99.4% pure m-XDA (m-Xylylenediamine), and 0.24 g of 4-hydroxy TEMPO (4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl) were placed in a flask, and hydrochloric acid anhydrous was added at a rate of 20 g / hr at room temperature (23 ± 5 °C) while stirring. After adding hydrochloric acid anhydrous, the temperature rose to 50 °C. After 4 hours of addition, the formed salt was cooled to room temperature, and 43 g of phosgene was added to the reactor, after which the reactor temperature was heated to 130 °C. From the time of phosgene addition until the end of the reaction, a dry ice-acetone condenser was used to prevent phosgene from escaping. After the reactor temperature reached 130 °C, the reactor temperature was maintained at 125-135 °C for 2 hours until the reaction solution became clear. After the solution became clear, the inside of the reactor was cooled to 80°C, and phosgene was removed by blowing in nitrogen. The solvent was removed from the reaction solution from which phosgene had been removed by vacuum distillation, and the product was purified under reduced pressure at a high temperature of 160°C to obtain m-XDI.

[0104] Manufacturing Example 2 Under a nitrogen atmosphere, 1500 g of m-XDI prepared in Production Example 1 was placed in a round flask and stirred. After raising the temperature of the flask to 70°C, 133 g of trimethylolpropane (TMP) was added dropwise while maintaining the temperature. After the addition was complete, the reaction temperature was maintained at 70°C until the concentration of isocyanate groups reached a calculated value of 33%. After the reaction was complete, the resulting reaction product was purified using a thin film evaporator (TFE) to separate the unreacted XDI and obtain the XDI-TMP adduct.

[0105] The resulting XDI-TMP adduct was diluted with ethyl acetate before use (solid content 75% by weight).

[0106] <Manufacturing of isocyanate compositions> Example 1-1 To the m-XDI produced in Production Example 1, IRGANOX1076 (manufactured by BASF) was added as a first antioxidant and IRGAFOS168 (manufactured by BASF) as a second antioxidant, and the mixture was prepared to produce an isocyanate composition. At this time, the first and second antioxidants were added in amounts of 25 ppm each, based on the total weight of m-XDI.

[0107] Examples 1-2 to 1-5 Isocyanate compositions were each prepared in the same manner as in Example 1-1, except that the compounds listed in Table 1 below were added as antioxidants to the m-XDI produced in Production Example 1 in the quantities specified.

[0108] Comparative Example 1-1 Without adding any antioxidants, the m-XDI produced in Production Example 1 was used as is.

[0109] Comparative Examples 1-2 to 1-17 Isocyanate compositions were each prepared in the same manner as in Example 1-1, except that the compounds listed in Table 1 below were added as antioxidants to the m-XDI produced in Production Example 1 in the quantities specified.

[0110] [Table 1]

[0111] The specific compound names of the substances used in Table 1 are as follows: IRGANOX1076 (BASF): Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate IRGANOX1010 (BASF): Pentaerythritol-tetrakis(3-3,5-di-tert-butyl-4-hydroxyphenyl)-propionate IRGANOX1135 (BASF): Isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate IRGAFOS168 (BASF): Tris(2,4-di-tert-butylphenyl) phosphite BHT: Butylated Hydroxytoluene LOWINOX TBM-6 (SI Group): Thiobis(2-t-butyl-5-methylphenol) TPP: Triphenyl phosphite IRGANOX OPH (BASF): Dioctyl phosphonate TBP: Tributyl phosphite

[0112] Example 2-1 To the XDI-TMP adduct produced in Production Example 2, IRGANOX1076 (manufactured by BASF) as a phenol-based primary antioxidant and SUMILIZER GP (manufactured by Sumitomo) as a phosphorus-based secondary antioxidant were added and mixed to produce an isocyanate composition. At this time, the primary and secondary antioxidants were added in amounts of 500 ppm each, based on the total weight of the XDI adduct.

[0113] Examples 2-2 to 2-4 Isocyanate compositions were prepared in the same manner as in Example 2-1, except that the compounds listed in Table 2 below were added as antioxidants in the quantities specified, to the XDI-TMP adduct prepared in Production Example 2.

[0114] Comparative Example 2-1 Without adding any antioxidants, the XDI-TMP adduct produced in Production Example 2 was used as is.

[0115] Comparative Examples 2-2 to 2-6 Isocyanate compositions were prepared in the same manner as in Example 2-1, except that the compounds listed in Table 2 below were added as antioxidants in the quantities specified, to the XDI-TMP adduct prepared in Production Example 2.

[0116] [Table 2]

[0117] The specific compound names of the substances used in Table 2 are as follows: IRGANOX1076 (BASF): Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate SUMILIZER GP (manufactured by Sumitomo): 2-(tert-butyl)-6-methyl-4-(3-((2,4,8,10)-tetrakis(tert-butyl)dibenzo[d,f][1,3,2]dioxaphosphine-6-yl)oxy)propyl)phenol BHT: Butylated Hydroxytoluene LOWINOX TBM-6 (SI Group): Thiobis(2-t-butyl-5-methylphenol)

[0118] Experimental Example 1 The isocyanate compositions prepared in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17 were subjected to turbidity and APHA values ​​measured by the following methods. Lenses were also prepared using the isocyanate compositions, and the Yellowness Index (YI) was measured. (1) Cloudy phenomenon In Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17, the isocyanate compositions were stored in an air atmosphere at a temperature of 25°C for one year, and the presence or absence of turbidity was visually confirmed.

[0119] The observation results were evaluated according to the following criteria and are shown in Table 3. <Evaluation Criteria> X: No turbidity phenomenon Δ: The turbidity phenomenon weakens O: The turbidity phenomenon becomes clear

[0120] (2) APHA For the isocyanate compositions produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17, after filling with nitrogen (nitrogen filling amount: 100%) and storing at a temperature of 25°C for 7 days, using HunterLab's Ultrascan Pro, APHA was measured under the following measurement conditions by the method of ASTM D1209.

[0121] Also, for the isocyanate compositions produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17, after filling with nitrogen (nitrogen filling amount: 100%) and storing at a temperature of 25°C for 1 year, APHA was measured in the same manner as above. The results are shown in Table 3 below. A smaller APHA value means better discoloration resistance.

[0122] <APHA Measurement Conditions> Color difference meter: Ultrascan Pro Light source: C / 2 Cell: 10mm quartz

[0123] (3) GPC Analysis The isocyanate compositions produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17 were filled with nitrogen (nitrogen filling amount: 100%) and stored at 25°C for 1 year, and then analyzed using a gel permeation chromatography UV detector under the following conditions.

[0124] <GPC Analysis Conditions> Equipment used: Agilent Columns: Agilent PL Mixded D, Agilent PLgel 100Å, Agilent PLgel 50Å Sample concentration: 1 wt / vol% in tetrahydrofuran (THF) Carrier: THF Detection method: UV detector, 254nm Outflow amount: 1.0ml / min Column temperature: 25℃ When creating the calibration curve, polystyrene standards with molecular weights ranging from 10⁴ to 24,600 g / mol were used.

[0125] As a result of the analysis of the GPC UV detector, a graph was obtained in which the X-axis represents retention time (RT(min)) and the Y-axis represents the detector's sensitivity (intensity). The graph shows that a peak corresponding to XDI appears at a retention time of 24.3 minutes, and peaks indicating high molecular weight (hereinafter referred to as "high molecular weight peaks") appear in the retention time range of 15 to 17 minutes. The retention time at the highest peak of the high molecular weight peaks was 16.3 minutes. Using the total peak area as a reference, the area ratio of high molecular weight peaks that appeared within a retention time range of 15 to 17 minutes was calculated and expressed as a percentage (area %). On the other hand, the peak area was calculated by integration.

[0126] (4) YI of the lens (4-1) Manufacturing of optical lenses 20.8 g of the isocyanate composition prepared in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17, and ZELEC as an internal release agent. TM UN (manufactured by Stepan) 0.04g and Biosorb as a UV absorber. TM 0.04 g of 583 (manufactured by Sakai Chemical Industry Co., Ltd.) was mixed by stirring in a flask at room temperature for approximately 20 minutes.

[0127] 0.002 g of dibutyltin dichloride was added to the resulting mixture, and the mixture was stirred for 10 minutes. After mixing, 19.2 g of 2,3-bis(2-sulfanyl ethyl sulfanyl)propane-1-thiol, as a polyfunctional thiol compound (the molar ratio of the thiol groups in the polyfunctional thiol compound corresponding to 1.0 based on 1 mol of the isocyanate groups in the isocyanate compound), was added. Then, it was defoamed under the condition of 5 mbar and stirred for 1 hour to produce a polymerization composition.

[0128] Further, the produced polymerization composition was filtered through a 1-μm PTFE filter and then injected into a mold formed of a glass mold and tape. This mold was put into an oven, and the temperature was gradually raised from 10°C to 120°C, and a polymerization reaction was carried out 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.

[0129] (4-2) YI of the lens For the lenses produced using the isocyanate compositions prepared in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-17, the YI (Yellowness Index) was measured by the method described below.

[0130] <YI measurement method> Apparatus: Ultrascan Pro, HunterLab Light source: D65 / 10 Measurement standard: ASTM E313

[0131]

Table 3

[0132] In Table 3 above, "-" means that accurate measurement was impossible or, when the APHA value was 20 or more after storage at 25°C for 7 days, it was judged not to be suitable and additional storage was not carried out.

[0133] The experimental results showed that the isocyanate compositions of Examples 1-1 to 1-5 did not exhibit turbidity or discoloration, and simultaneously, the area ratio of the 16-minute peak corresponding to high molecular weight was 0.5% or less. From this, it can be confirmed that the content of high molecular weight polymers that self-polymerize under 25°C conditions is low due to improved long-term storage stability. Furthermore, storage stability and lens YI also showed improved effects compared to Comparative Examples 1-1 to 1-17.

[0134] Experimental Example 2 The isocyanate compositions prepared in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-6 were filled with nitrogen (nitrogen filling amount: 100%), stored at 25°C for 24 weeks, and then their viscosity and APHA properties were evaluated by the following method.

[0135] (1) Viscosity and viscosity increase rate Viscosity was measured by placing 10 ml of the isocyanate composition to be measured into a viscometer (DV1 Viscometer, Brookfield) at 25°C and a rotation speed of 5 rpm. Furthermore, in manufacturing example 2, the viscosity of the XDI-TMP adduct was measured immediately after manufacturing using the same method as described above, and this was defined as the initial viscosity. The measurement result showed that the initial viscosity was 550 cps.

[0136] Using the viscosity measured after 24 weeks and the initial viscosity value, the viscosity increase rate was calculated using Equation 1 below. [Formula 1] Viscosity increase rate (%) = [(Viscosity after 24 weeks - Initial viscosity) / Initial viscosity] x 100 In the above formula 1, the initial viscosity is the viscosity of the diisocyanate compound used in the production of the isocyanate composition, measured under conditions of 25°C and a rotation speed of 5 rpm. The viscosity after 24 weeks is the viscosity measured at 25°C and a rotation speed of 5 rpm after the isocyanate composition was filled with nitrogen (100% nitrogen) and stored at 25°C for 24 weeks.

[0137] (2) APHA and APHA growth rate The APHA measurement was carried out using HunterLab's Ultrascan Pro by the method of ASTM D1209 under the following measurement conditions.

[0138] Specifically, for the containers containing the isocyanate compositions produced in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-6, after filling with nitrogen (nitrogen filling amount: 100%) and storing at a temperature of 25°C for 24 weeks, the APHA was measured by the method of ASTM D1209 under the following measurement conditions, and this was defined as the "APHA after 24 weeks".

[0139] <APHA Measurement Conditions> Color difference meter: Ultrascan Pro Light source: C / 2 Cell: 10 mm quartz

[0140] Also, in Production Example 2, immediately after the production of the XDI-TMP adduct, the APHA was measured in the same manner as above, and this was defined as the "initial APHA". As a result of the measurement, the initial APHA was 14.

[0141] Using the measured APHA after 24 weeks and the initial APHA value, the increase rate of APHA was calculated by the following Formula 2. [Formula 2] APHA increase rate (%) = [(APHA after 24 weeks - initial APHA) / initial APHA] x 100 (In Formula 2 above, the initial APHA is the APHA measured by ASTM D1209 for the diisocyanate-based compound used in the production of the isocyanate composition, and the APHA after 24 weeks is the APHA of the isocyanate composition measured by ASTM D1209 after filling the isocyanate composition with nitrogen (nitrogen filling amount 100%) and storing at 25°C for 24 weeks.)

[0142] The results are shown in Table 4 below. A smaller APHA value means better discoloration resistance, and a smaller APHA increase rate means better stability.

[0143] [Table 4]

[0144] The experimental results showed that the isocyanate compositions of Examples 2-1 to 2-4 exhibited lower viscosity and APHA increase rates compared to the comparative example, confirming their excellent stability.

Claims

1. One or more diisocyanate compounds among diisocyanates and their adducts; The first phenolic antioxidant represented by the following chemical formula 1; A phosphorus-based antioxidant represented by the following chemical formula 2; Isocyanate compositions containing: 【Chemistry 1】 In the aforementioned chemical formula 1, Ra is an alkylene group of C1 to C20, m is an integer between 0 and 3. 【Chemistry 2】 In the aforementioned chemical formula 2, L is an alkylene group of C1 to C20, R １ is a hydrogen atom; a C1-C20 alkyl group; or a C6-C30 aryl group substituted with one or more substituents from a hydroxyl group and a C1-C20 alkyl group, or unsubstituted. R ２ and R ３ Each of them is independently either hydrogen or a C1-C6 alkyl group, or linked together to form a heterocyclic structure. n is an integer, either 0 or 1.

2. The aforementioned phenol-based first antioxidant is present in an amount of 10 to 3000 ppm based on the total weight of the diisocyanate compound. The isocyanate composition according to claim 1.

3. The phenol-based first antioxidant includes octadecyl-3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate, benzenepropionic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl ester, pentaerythritol tetrakis(3-3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or a mixture thereof. The isocyanate composition according to claim 1.

4. The phosphorus-based antioxidant is present in an amount of 10 to 3000 ppm based on the total weight of the diisocyanate compound. The isocyanate composition according to claim 1.

5. The phosphorus-based secondary antioxidant is a compound represented by the following chemical formula 3 or chemical formula 4. The isocyanate composition according to claim 1. 【Transformation 3】 In the aforementioned chemical formula 3, R １１ is a hydrogen atom; a C1-C12 alkyl group; or an aryl group C6-C18 substituted with one or more substituents from a hydroxyl group and a C1-C6 alkyl group, or unsubstituted. R １２ and R １３ Each of these is independently hydrogen or a C1-C6 alkyl group. 【Chemistry 4】 In the aforementioned chemical formula 4, L １ These are alkylene groups of C1 to C20, R ２１ ~R ２５ each independently represents hydrogen, a hydroxy group, or an alkyl group having 1 to 12 carbon atoms, n １ is an integer, either 0 or 1.

6. The phosphorus-based secondary antioxidant includes tris(2,4-di-tert-butylphenyl) phosphite, 2-(tert-butyl)-6-methyl-4-(3-((2,4,8,10)-tetrakis(tert-butyl)dibenzo[d,f][1,3,2]dioxaphosphine-6-yl)oxy)propyl)phenol, or a mixture thereof. The isocyanate composition according to claim 1.

7. The phenol-based primary antioxidant and the phosphorus-based secondary antioxidant are present in a weight ratio of 1:1 to 5:

1. The isocyanate composition according to claim 1.

8. Based on the total weight of the diisocyanate compounds in the isocyanate composition, the total weight of the phenol-based primary antioxidant and the phosphorus-based secondary antioxidant is 20 to 4000 ppm. The isocyanate composition according to claim 1.

9. The diisocyanate is paraphenylenediisocyanate, 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, or modified isocyanates thereof. The isocyanate composition according to claim 1.

10. The diisocyanate adduct is a polyisocyanate oligomer, xylylene diisocyanate-trimethylolpropane adduct, xylylene diisocyanate-glycerin adduct, tolylene diisocyanate-trimethylolpropane adduct, tolylene diisocyanate-glycerin adduct, tetramethylxylylene diisocyanate-trimethylolpropane adduct, tetramethylxylylene diisocyanate-glycerin adduct, hydrogenated xylylene diisocyanate-trimethylolpropane adduct, hydrogenated xylylene isocyanate-glycerin adduct, hexamethylene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate-glycerin adduct, isophorone diisocyanate-trimethylolpropane adduct, or isophorone diisocyanate-glycerin adduct. The isocyanate composition according to claim 1.

11. The isocyanate composition is Examples of diisocyanate compounds include xylylene diisocyanate; A phenolic primary antioxidant represented by the aforementioned chemical formula 1; and The following contains a phosphorus-based antioxidant represented by chemical formula 3: The isocyanate composition according to claim 1: 【Transformation 5】 In the aforementioned chemical formula 3, R １１ is a hydrogen atom; a C1-C12 alkyl group; or an aryl group C6-C18 substituted with one or more substituents from a hydroxyl group and a C1-C6 alkyl group, or unsubstituted. R １２ and R １３ Each of these is independently either hydrogen or a C1-C6 alkyl group.

12. The phenol-based primary antioxidant and the phosphorus-based secondary antioxidant are each present in amounts of 10 to 500 ppm, based on the total weight of the diisocyanate compound. The isocyanate composition according to claim 11.

13. The isocyanate composition is Examples of diisocyanate compounds include xylylene diisocyanate-trimethylolpropane adduct; A phenolic primary antioxidant represented by the aforementioned chemical formula 1; and As a phosphorus-based antioxidant, it contains one or more compounds represented by the following chemical formula 3 and the following chemical formula 4. The isocyanate composition according to claim 1: 【Transformation 6】 In the aforementioned chemical formula 3, R １１ is a hydrogen atom; a C1-C12 alkyl group; or an aryl group C6-C18 substituted with one or more substituents from a hydroxyl group and a C1-C6 alkyl group, or unsubstituted. R １２ and R １３ Each of these is independently hydrogen or a C1-C6 alkyl group. 【Transformation 7】 In the aforementioned chemical formula 4, L １ These are alkylene groups of C1 to C20, R ２１ ~R ２５ Each of these is independently a hydrogen atom, a hydroxyl group, or a C1-C12 alkyl group. n １ is an integer, either 0 or 1.

14. The phenol-based primary antioxidant and the phosphorus-based secondary antioxidant are each present in amounts of 500 to 1500 ppm, based on the total weight of the diisocyanate compound. The isocyanate composition according to claim 13.

15. The isocyanate composition described in claim 1 satisfies one or more of the following conditions (i) and (ii): (i) The APHA value measured by ASTM D1209 after the isocyanate composition has been filled with nitrogen and stored at 25°C for 7 days: 10 or less; (ii) The isocyanate composition was filled with nitrogen and stored at 25°C for 24 weeks, after which the APHA value measured by ASTM D1209 was 25 or less.

16. The isocyanate composition according to claim 1, comprising diisocyanate as a diisocyanate compound and satisfying the following conditions (a1) and (a2): (a1) After the isocyanate composition was filled with nitrogen and stored at 25°C for one year, it was analyzed by gel permeation chromatography. In a graph with retention time (min) on the X axis and detector sensitivity on the Y axis, the area of ​​the peak located in the retention time range of 15 minutes to 17 minutes was 0.5 area % or less of the total peak area. (a2) The isocyanate composition is filled with nitrogen and stored at 25°C for one year, after which the APHA measured by the ASTM D1209 method is 20 or less.

17. The isocyanate composition is filled with nitrogen and stored at 25°C for 7 days, after which the APHA value measured by ASTM D1209 is 10 or less. The isocyanate composition according to claim 16.

18. The isocyanate composition comprises a diisocyanate adduct as a diisocyanate compound and satisfies the following conditions (b1) to (b4): The isocyanate composition according to claim 1: (b1) Viscosity measured after the isocyanate composition was filled with nitrogen and stored at 25°C for 24 weeks: 500-1000 cps (b2) The isocyanate composition was filled with nitrogen and stored at 25°C for 24 weeks, after which the APHA value measured by ASTM D1209 was 20 or less. (b3) After the isocyanate composition is filled with nitrogen and stored at 25°C for 24 weeks, the viscosity increase rate calculated by the following formula 1 is 50% or less. (b4) After the isocyanate composition is filled with nitrogen and stored at 25°C for 24 weeks, the APHA increase rate calculated by formula 2 below is 50% or less. [Formula 1] Viscosity increase rate = [(Viscosity after 24 weeks - Initial viscosity) / Initial viscosity] x 100 In the above formula 1, The initial viscosity is the viscosity of the diisocyanate compound measured under conditions of 25°C and a rotation speed of 5 rpm. The viscosity after 24 weeks is the viscosity of the isocyanate composition measured at 25°C and a rotation speed of 5 rpm after the isocyanate composition has been nitrogen-filled and stored at 25°C for 24 weeks; [Formula 2] APHA increase rate = [(APHA at 24 weeks - initial APHA) / initial APHA] x 100 In the above formula 2, The initial APHA is the APHA of diisocyanate compounds measured by ASTM D1209. APHA after 24 weeks is the APHA of the isocyanate composition measured by ASTM D1209 after the composition was nitrogen-filled and stored at 25°C for 24 weeks.

19. The isocyanate composition according to claim 1; and A compound comprising one or more of the following: a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound; Polymerization composition.

20. An article comprising the isocyanate composition according to claim 1; and a polymer obtained by polymerizing one or more of a polyfunctional thiol compound, a polyfunctional alcohol compound, and a polyfunctional episulfide compound.

21. The article according to claim 20, wherein the article is an optical adhesive, an optical bonding agent, or an optical lens.

22. The article according to claim 21, wherein the optical lens has a YI value of 2 or less when measured by ASTM E313.

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