Method for producing isocyanate compounds including non-chlorinated derivatives and compositions thereof

Abstract

To produce an isocyanate by simplifying a process by converting a chlorinated derivative produced in a general process into a non-chlorinated derivative through a simple reduction reaction without proceeding with a described complicated process for decreasing the chlorinated derivative.SOLUTION: The present invention relates to a method for preparing an isocyanate containing a non-chlorinated derivative obtained after converting a chlorinated derivative, which is generated in a process for preparing xylylene diisocyanate, into the non-chlorinated derivative by means of a reduction reaction. In particular, the present invention relates to an isocyanate composition comprising the non-chlorinated derivative obtained by the reduction reaction, and a polymerizable composition comprising the same.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing an isocyanate comprising converting a chlorinated derivative generated during the production of xylylene diisocyanate into a non-chlorinated derivative by a reduction reaction, and more particularly to an isocyanate composition comprising the non-chlorinated derivative, the non-chlorinated derivative being converted into a chlorinated derivative generated during the production of xylylene diisocyanate by a reduction reaction, together with a small amount of the chlorinated derivative, and a polymerizable composition comprising the non-chlorinated derivative. [Background technology]

[0002] Xylylene diisocyanate (hereinafter abbreviated as "XDI") is a highly useful compound in the chemical, resin, and paint industries as a raw material for polyurethane and polyisocyanate materials. It can be classified as ortho-, meta-, or para-xylylene diisocyanate depending on its structural isomer, with meta-xylylene diisocyanate (hereinafter abbreviated as "m-XDI" or "1,3-bis(isocyanatomethyl)benzene") accounting for the majority of the isocyanates. XDI is a specific diisocyanate with a methylene group in the benzene nucleus, and is an isocyanate that combines the characteristics of both aromatic and aliphatic isocyanates. Because it prevents the yellowing phenomenon that is a drawback of aromatic diisocyanates, it is used as a urethane raw material for non-yellowing paints, coatings, leather, adhesives, and other applications.

[0003] Various methods for producing XDI have been proposed in the past, but the most widely developed is the phosgenation method. The phosgenation method produces isocyanates by reacting organic primary amines with phosgene in an inert solvent. In this method, aromatic primary amines can be relatively easily converted into high-purity aromatic isocyanates by passing phosgene gas through a suspension of free aromatic amines, their carbonates, or hydrochlorides in a solvent.

[0004] However, although XDI contains an aromatic ring, it is classified as an aliphatic isocyanate. When xylylenediamine is reacted with phosgene to produce isocyanate, many side reactions occur during the reaction, and various chlorinated derivatives are generated as by-products.

[0005] Korean Patent Publication No. 1994-0001948 states that chlorinated derivatives formed during the production of typical aliphatic isocyanates are typically formed in amounts of 3-10% by weight, sometimes reaching up to 20% by weight. Therefore, when chlorinated derivatives are contained in XDI, they affect and inhibit the reaction between isocyanate groups and active hydrogen-containing compounds when producing polyurethane resin from XDI. They also promote gelation of the prepolymer, resulting in serious quality issues such as yellowing, opacity, and striae in optical lenses.

[0006] On the other hand, phosgenation methods can be divided into the direct method, in which phosgene is directly reacted with the raw material amine, and the hydrochloride method, in which the raw material amine is converted into a hydrochloride and then reacted with phosgene. The direct method is much simpler than the hydrochloride method, but since a considerable amount of chlorinated derivatives is produced, the direct method is not generally adopted. For this reason, when producing linear or cyclic aliphatic isocyanates, the hydrochloride method is used, in which the raw material amine is converted into a hydrochloride and then reacted with phosgene to produce the isocyanate. However, since a certain amount of chlorinated derivatives is produced even in the hydrochloride method, further methods have been developed to reduce the content of impurities produced and obtain high-purity XDI.

[0007] Korean Patent No. 10-0953019 discloses that in a method for producing isocyanates from linear or cyclic aliphatic amines, high pressure is applied during the salt formation reaction process (a process for obtaining a slurry containing amine hydrochloride) to suppress an increase in the particle size of the hydrochloride. Furthermore, the patent discloses that by miniaturizing the hydrochloride particles, the viscosity of the hydrochloride is reduced, improving fluidity and syneresis, and the conversion rate of the hydrochloride during phosgenation is increased, thereby reducing the yield and the production of chlorinated derivatives to 0.1-0.3% by weight.

[0008] Furthermore, Korean Patent Publication No. 2018-0104330 disclosed that resins for optical materials obtained from XDI compositions containing chlorinated derivatives of Chemical Formula 5 at concentrations of 0.2 ppm to less than 600 ppm exhibit excellent yellowing resistance and high production efficiency. Korean Patent Publication No. 2018-0127517 also disclosed that excellent discoloration resistance is achieved only when the chlorinated derivatives contain 60 ppm or less of Chemical Formula 7. However, these chlorinated derivatives, which are the main impurities produced in the isocyanate synthesis reaction, adversely affect the physical properties of optical lenses in polyurethane reactions. These impurities are believed to cause yellowing and have a negative impact on the product. Therefore, these chlorinated derivatives must either not be produced or, if produced, must be removed by purification or other means. These prior art technologies all have the drawback of requiring precise process control and the use of a high-plate distillation column for separation and purification, which increases equipment costs, reduces economic viability, and is deemed unlikely to be commercially viable. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Korean Patent No. 1994-0001948 [Patent Document 2] Korean Patent No. 0953019 [Patent Document 3] Korean Patent Publication No. 2018-0104330 [Patent Document 4] Korean Patent Publication No. 2018-0127517 Summary of the Invention [Problem to be solved by the invention]

[0010] In this invention, the chlorinated derivatives produced by the conventional process are converted into non-chlorinated derivatives through a simple reduction reaction, without undergoing the above-mentioned complicated process for reducing the chlorinated derivatives, thereby simplifying the process for producing isocyanates.

[0011] Therefore, the non-chlorinated derivatives formed by the reduction reaction, even if contained in some resins, have excellent yellowing resistance, can improve the physical properties of general resins, and have a boiling point 60-75°C lower than XDI, making them easier to separate and purify. Normally, to suppress the formation of chlorinated derivatives, it is necessary to convert the amine into hydrochloride, carry out a high-pressure reaction in the salt formation process, and then separate and purify them through precise control.

[0012] However, in the present invention, even in the direct process where it is difficult to control the chlorinated derivatives, the separation and purification can be simplified by a simple reduction reaction, which has economic benefits and is different from conventional processes.

[0013] Therefore, the present invention can bring economic benefits to industrialization by reducing process costs, increasing yields, and obtaining high-quality products. [Means for solving the problem]

[0014] In order to achieve the object of the present invention, in one aspect, the present invention provides a method for producing an isocyanate, characterized in that the non-chlorinated derivative obtained by reducing a chlorinated derivative represented by Chemical Formula 1 generated in the production process of xylylene diisocyanate is converted into a non-chlorinated derivative, and the resulting non-chlorinated derivative is: [ka] (wherein R1 is Cl or NCO, and R2 is H or Cl)

[0015] The xylylene diisocyanate of the present invention can be obtained by directly reacting an organic primary amine with a carbonylating agent in an inert solvent according to the following reaction scheme (Chemical Formula 8): [ka]

[0016] The xylylene diisocyanate of the present invention can also be obtained by a process comprising the following reaction scheme: a first step (chemical formula 9) of reacting an organic primary amine with hydrogen chloride gas; and a second step (chemical formula 10) of reacting the amine hydrochloride salt produced in the first step with a carbonylating agent: (First Stage) [ka] (Phase 2) [ka]

[0017] The carbonylating agent used in the present invention can be selected from phosgene, diphosgene, triphosgene, alkyl chloroformate, or a combination thereof. The chlorinated derivative can also be one or more of the chlorinated derivatives represented by the following formula: [ka] (wherein R1 is Cl or NCO and R2 is H or Cl)

[0018] Furthermore, the non-chlorinated derivatives may be one or more of the non-chlorinated derivatives represented by the following formula: [ka] (wherein R3 is H or NCO)

[0019] Meanwhile, the reduction reaction of the present invention can be carried out using a metal catalyst or reducing agent under a hydrogen (H) atmosphere. The metal catalyst used here can be one or more of palladium, platinum, and nickel, with palladium or platinum being preferred. The reducing agent used can be one or more selected from the following: Lithium aluminum hydride (LiAlH4), sodium amalgam (Na(Hg)), zinc amalgam (Zn(Hg)), diborane (B2H6), lithium borohydride (LiBH4), sodium borohydride (NaBH4), iron(II) sulfate (FeSO4), tin(II) chloride (SnCl2), sodium dithionite (Na2S2O6), sodium thiosulfate (Na2S2O3), ammonium thiosulfate ((NH4)2S2O3), diisobutylaluminum hydride (DI BAL-H), oxalic acid (C2H2O4), formic acid (HCOOH), dithiothreitol (DTT), tris-2-carboxyethylphosphine hydrochloride (TCEP), 2,2-diphenyl-1-picrylhydrazyl (DPPH), butylated hydroxytoluene (BHT), 2,6-di-tert-butyl-4-methylphenol, and 2,4-dimethyl-6-tert-butylphenol, metallic hydrides such as trialkyltin hydrides and tributyltin hydrides, and metals themselves such as zinc.

[0020] In order to achieve a further object of the present invention, in another aspect, the present invention provides an isocyanate composition comprising xylylene diisocyanate (XDI) as a main component, and further comprising methylbenzyl isocyanate represented by Chemical Formula 4 as a non-chlorinated derivative obtained by the above production method: [ka]

[0021] The isocyanate composition of the present invention may further contain a chlorinated derivative represented by Chemical Formula 1. The chlorinated derivative is a chlorinated derivative represented by Chemical Formula 2, and may further contain one or more of chloromethylbenzyl isocyanate, bis(chloromethyl)benzene, dichloromethylbenzyl isocyanate, and chloromethyldichloromethylbenzene: [ka] (wherein R1 is Cl or NCO, and R2 is H or Cl)

[0022] The isocyanate composition of the present invention may contain a non-chlorinated derivative in the range of 0.1 to 50,000 ppm, or may contain a chlorinated derivative in the range of more than 0 to 1,500 ppm. Furthermore, in the isocyanate composition of the present invention, when the isocyanate is xylylene diisocyanate (XDI), it is preferably contained in an amount of 99 mass% or more, taking into consideration various properties of optical lenses.

[0023] In order to achieve a further object of the present invention, in another aspect, the present invention provides a polymerizable composition comprising the above-mentioned isocyanate composition and a compound containing one or more isocyanate-reactive functional groups. Here, the compound containing one or more isocyanate-reactive functional groups used may be a polyol compound or a polythiol compound, and such a polymerizable composition may be used as a coating material.

[0024] In order to achieve a further object of the present invention, in another aspect, the present invention provides a resin obtained by reacting the above-mentioned polymerizable composition. Such a resin may be used as an optical material, including an optical lens.

[0025] On the other hand, in yet another aspect, the present invention can also provide an isocyanate composition containing, as a main component, xylylene diisocyanate, which is a non-chlorinated derivative obtained by separately synthesizing the non-chlorinated derivative, and further contains methylbenzyl isocyanate represented by Chemical Formula 4 above, rather than being obtained by a reduction reaction of the chlorinated derivative.

[0026] Such an isocyanate composition is a chlorinated derivative as described above, and may further contain one or more of the chlorinated derivatives represented by Chemical Formula 2 above.

[0027] Again, the isocyanate composition preferably contains non-chlorinated derivatives in the range of 0.1 ppm to 50,000 ppm, and preferably contains chlorinated derivatives in the range of more than 0 to 1,500 ppm. [Effects of the Invention]

[0028] The production method of the present invention can improve the production efficiency and quality of isocyanates, which are widely used in the chemical, resin, and paint industries, including the optical materials industry, and is therefore of great technological and industrial value.

[0029] The isocyanate composition containing a non-chlorinated derivative obtained through the reduction step of the present invention is economically advantageous and allows easy reduction of the chlorinated derivative, and can be used to produce high-quality optical resins and optical products with high economic efficiency. [Brief explanation of the drawings]

[0030] [Figure 1] 1 is a graph showing the results of gas chromatography (GC) of the product of Example 3 before (A) the reduction reaction and after (B) the reduction reaction of Preparation Example 3, before desolvation, in the process of converting the chlorinated derivative to a non-chlorinated derivative via a simple reduction reaction. DETAILED DESCRIPTION OF THE INVENTION

[0031] definition Unless otherwise defined, all technical and scientific terms used in the description of the present invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patent publications, published applications, and other publications cited by the prior art are incorporated by reference in their entirety.

[0032] The term "isocyanate" used in the description of the present invention refers to a substance used as a polyurethane-based material, and these materials are synthesized with different structures depending on the number and position of functional groups, etc. Here, "isocyanate" is used to include both monoisocyanates, diisocyanates, and polyisocyanates.

[0033] The term "chlorinated derivatives" refers to chlorine-containing impurities that are generated by side reactions when producing isocyanates by the direct method, the hydrochloride method, or the carbonate method.

[0034] In the present invention, chlorinated impurities include 3-chloromethylbenzyl isocyanate (Chemical Formula 5), ​​1,3-xylylene dichloride (Chemical Formula 6), 3-dichloromethylbenzyl isocyanate (Chemical Formula 7), etc. [ka] [ka] [ka]

[0035] The term "non-chlorinated derivatives" is used to mean substances obtained by removing the chlorine from the above "chlorinated derivatives" by a reduction reaction, replacing the chlorine with another atom or group of atoms.

[0036] In the present invention, non-chlorinated impurities include methylbenzyl isocyanate, xylene, and the like.

[0037] The term "isocyanate-reactive functional group" refers to an "active hydrogen group-containing component" that reacts with isocyanate, and examples thereof include polyol components (components mainly containing polyols having two or more hydroxy groups), polythiol components (components mainly containing polythiols having two or more mercapto groups), and polyamines (components mainly containing polyamines having two or more amino groups).

[0038] The term "carbonylation agents" refers to reagents that cause a carbonylation reaction, which is a reaction that introduces carbon monoxide into organic compounds, etc.

[0039] Carbonylation produces organic carbonyls, i.e., compounds containing a >C=O functional group, such as aldehydes, ketones, carboxylic acids, and esters. In particular, organic compounds containing carbonyl groups have a wide range of reactivity due to the presence of unsaturated bonds, and the reaction can be highly selective, making it a popular synthetic chemistry method.

[0040] Typical carbonylating agents that can be used in the present invention include phosgene, diphosgene, triphosgene, chloroformate compounds, and the like.

[0041] As used herein, the term "combination" is inclusive of blends, mixtures, reaction products, and the like.

[0042] Furthermore, specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. described in the present invention can be replaced with the upper limit (numerical value defined as "not more than" or "less than") or lower limit (numerical value defined as "not less than" or "greater than") of the base material for the corresponding blending ratio (content ratio), physical property values, parameters, etc. Meanwhile, "%" is based on mass unless otherwise specified.

[0043] As used in describing and claiming this invention, the tiered forms include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "isocyanate" includes mixtures of two or more monoisocyanates, diisocyanates, and polyisocyanates.

[0044] Each of the materials disclosed in this description is commercially available unless otherwise noted, and methods for their production are known to those skilled in the art. Also, unless otherwise noted to the contrary in this description, all testing standards are the most recent standards in effect at the time of this filing.

[0045] The method for producing an isocyanate and the composition of the present invention will be described in detail below.

[0046] First, the present invention aims to easily increase the purity of isocyanates without complex purification steps by converting chlorinated derivatives produced during the production of isocyanates into non-chlorinated derivatives through a reduction reaction according to the following reaction formula: [ka] (wherein R1 is Cl or NCO, and R2 is H or Cl) [ka] (wherein R3 is H or NCO)

[0047] As described above, the hydrochloride method, like the direct method, produces a certain amount of a chlorinated derivative known as the compound of formula 5, and may be used to obtain XDI, which constitutes the isocyanate composition of the present invention.

[0048] XDI includes the structural isomers 1,2-XDI (ortho-form), 1,3-XDI (meta-form), and 1,4-XDI (para-form), which can be used alone or in combination of two or more types. 1,3-XDI or 1,4-XDI is preferred, and 1,3-XDI is more preferred.

[0049] The isocyanate composition obtained by the production method of the present invention is used as a reactant to obtain a polymer compound such as polyurethane, and therefore the aliphatic amine used in the present invention is preferably a di- or higher functional chain or cyclic aliphatic amine.

[0050] The di- or higher functional chain or cyclic aliphatic amine preferably used in the present invention is not particularly limited, but reference may be made to those described in the above-mentioned prior art document, Korean Patent No. 10-0953019.

[0051] Representative examples thereof include chain aliphatic amines such as hexamethylenediamine, 2,2-dimethylpentanediamine, 2,2,4-trimethylhexanediamine, butenediamine, and xylylenediamine, and cyclic aliphatic amines such as bis(aminomethyl)cyclohexane, dicyclohexylmethanediamine, cyclohexanediamine, and bis(aminomethyl)norbornene.

[0052] The isocyanate obtained by reacting the above-mentioned linear or cyclic aliphatic diamine with phosgene is determined depending on the diamine to be reacted, and reference may be made to the above-mentioned prior art document, Korean Patent No. 10-0953019.

[0053] Representative examples thereof include chain aliphatic isocyanates such as hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, and xylylene diisocyanate, and cyclic aliphatic isocyanates such as bis(isocyanatemethyl)cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, and bis(isocyanatemethyl)norbornene.

[0054] Among the above-mentioned exemplary compounds obtainable by the production method of the present invention, compounds particularly preferred for use in various optical elements include xylylene diisocyanate, bis(isocyanatemethyl)norbornene, hexamethylene diisocyanate, and bis(isocyanatemethyl)cyclohexane.

[0055] Carbonylation agents that can be used in the production of XDI according to the present invention include phosgene, diphosgene, triphosgene and various chloroformate compounds, and can be used alone or in combination of two or more.

[0056] Phosgene gas, commonly known as carbonyl chloride or carbonyl dichloride (COCl), is a colorless gas at room temperature with a freezing point of 127.84°C and a boiling point of 7.84°C. It is typically produced by catalytically reacting anhydrous chlorine gas with high-purity carbon monoxide. Phosgene substitutes and / or precursors used in accordance with the present invention may include any phosgene equivalent, such as diphosgene, triphosgene, or any combination thereof. The phosgene used in the present invention may be provided by thermal decomposition of a carbamic acid derivative using chloroformate, diphenylcarbamate, or N,N'-carbonyldiimidazole.

[0057] Meanwhile, the isocyanate composition of the present invention can contain a small amount of non-chlorinated derivatives by converting the chlorinated derivative represented by Chemical Formula 1, which is generated in the production process of XDI, into a non-chlorinated derivative through a reduction reaction using a catalyst or a reducing agent, followed by filtration and purification: [ka] (wherein R1 is Cl or NCO, and R2 is H or Cl)

[0058] Here, the chlorinated derivatives contained in XDI include 3-chloromethylbenzyl isocyanate (chemical formula 5), ​​1,3-xylylene dichloride (chemical formula 6), 3-dichloromethylbenzyl isocyanate (chemical formula 7), etc., and may exist alone or in combination of two or more types.

[0059] On the other hand, the non-chlorinated derivatives would be methylbenzyl isocyanate (Formula 4) or xylene.

[0060] The compound of formula 4 of the present invention includes the structural isomers 1,2-methylbenzyl isocyanate, 1,3-methylbenzyl isocyanate, and 1,4-methylbenzyl isocyanate, as well as the structural isomers of XDI, and may exist alone or in combination of two or more kinds, preferably 1,3-methylbenzyl isocyanate and 1,4-methylbenzyl isocyanate, and more preferably 1,3-methylbenzyl isocyanate.

[0061] Xylene also includes structural isomers 1,2-xylene, 1,3-xylene, and 1,4-xylene, and may exist alone or in combination of two or more types, with 1,3-xylene and 1,4-xylene being preferred, and 1,3-xylene being more preferred.

[0062] The XDI composition of the present invention may contain methylbenzyl isocyanate. If the amount of methylbenzyl isocyanate exceeds 50,000 ppm relative to the total mass of the XDI composition, the physical properties of the lens, such as heat resistance, will be reduced, and therefore the amount is preferably 0.1 ppm or more and 50,000 ppm or less.

[0063] Furthermore, after conversion to methylbenzyl isocyanate, a small amount of chlorinated derivative may remain. If the chlorinated derivative exceeds 1,500 ppm in the presence of methylbenzyl isocyanate, the yellowness of the lens increases. Therefore, the content of the chlorinated derivative is preferably in the range of more than 0 to 1,500 ppm relative to the total mass of the XDI composition.

[0064] On the other hand, the reduction reaction of the present invention is a dechlorination reaction by hydrogenation, which can be divided into a reduction step using a metal catalyst under a hydrogen atmosphere and a reduction step using a reducing agent, and these steps can be carried out independently or in parallel. The reduction step using a noble metal catalyst under a hydrogen atmosphere is preferred.

[0065] The temperature of the reduction step is not particularly limited, but can be carried out at 0 to 180° C., preferably 10 to 150° C., and more preferably 20 to 50° C. Furthermore, the hydrogen pressure in the reduction step is not particularly limited, but is preferably 0.001 kgf / cm 2~200kgf / cm 2 It can proceed at 0.1 to 10 kgf / cm 2 and more preferably 1 to 5 kgf / cm 2 is preferred.

[0066] The catalyst used in the reduction step is not particularly limited, but may be a noble metal or transition metal catalyst, which may be used alone or in combination of two or more. Metal catalysts include Pd, Pt, Ru, Ni, etc., which may be used alone or in combination with activated carbon, SiO2, Al2O 3. The catalyst can be used by being supported on a metal oxide such as CeO2 or ZrO2, and metal ligands can be used alone or in combination of two or more.

[0067] The amount of catalyst in the reduction step is not particularly limited, but can proceed with 0.1% to 20% of the total mass of XDI, preferably 0.3 to 15%, and more preferably 0.5 to 5%.

[0068] Reducing agents include lithium aluminum hydride (LiAlH4), sodium amalgam (Na(Hg)), zinc amalgam (Zn(Hg)), diborane (B2H6), lithium borohydride (LiBH4), sodium borohydride (NaBH4), iron(II) sulfate (FeSO4), tin(II) chloride (SnCl2), sodium dithionite (Na2S2O6), sodium thiosulfate (Na2S2O3), ammonium thiosulfate ((NH4)2S2O3), and diisobutylaluminum hydride (DIBAL-H). The catalyst may be one or more selected from the group consisting of oxalic acid (C2H2O4), formic acid (HCOOH), dithiothreitol (DTT), tris-2-carboxyethylphosphine hydrochloride (TCEP), 2,2-diphenyl-1-picrylhydrazyl (DPPH), butylated hydroxytoluene (BHT), 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, metallic hydrides such as trialkyltin hydride and tributyltin hydride, and metals themselves such as zinc. A Pd / C catalyst is preferred.

[0069] The reduction step of the present invention is preferably carried out in a nitrogen or hydrogen atmosphere to exclude oxygen, and the reduction can be carried out in the presence of a solvent or after removing the solvent.

[0070] The solvent used in the present invention is not particularly limited. Examples of the inactivating solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane, halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene, nitrogen-containing compounds such as nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N'-dimethylimidazolidinone, and ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. Ethers such as ethers, for example, amyl formate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methyl isoamyl acetate, methoxybutyl acetate, 2-ethoxyethyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, ethyl acetate, butyl stearate, butyl lactate, and amyl lactate; and aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, and methyl benzoate, which may be used alone or in combination of two or more. Halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

[0071] In addition, after filtering the catalyst or reducing agent used in the reduction step of the present invention, the chlorinated and non-chlorinated derivatives can be prepared by simple distillation purification, etc. Of course, such a reduction step can also be applied after producing an isocyanate containing a chlorinated derivative together with XDI, removing the solvent, and purifying it.

[0072] Therefore, the products produced using the isocyanate composition obtained as described above can meet high optical properties, and therefore can be used in the production of optical materials, specifically plastic optical lenses.

[0073] According to the present invention, there is provided a polymerizable composition comprising the above-described isocyanate composition and a polyol / polythiol.

[0074] The polymerizable composition may contain the isocyanate composition and the polyol / polythiol in a mixed state or in a separate state. That is, within the polymerizable composition, the isocyanate composition and the polyol / polythiol may be in a blended state in contact with each other, or in a separate state so as not to contact each other.

[0075] The polyol component used in the polymerizable composition of the present invention may be, for example, a low molecular weight polyol or a high molecular weight polyol. The above polyols may be used alone or in combination of two or more.

[0076] The low-molecular-weight polyol is a compound having two or more hydroxyl groups and a number-average molecular weight of 60 or more but less than 400. Examples of the low-molecular-weight polyol include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propenediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentenediol, 1,6-hexenediol, diethylene glycol, triethylene glycol, dipropylene glycol, and mixtures thereof, 1,4-cyclohexenediol, hydrogenated bisphenol A, and bisphenol A; trihydric alcohols such as glycerin; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol); pentahydric alcohols such as xylitol; and hexahydric alcohols such as sorbitol, mannitol, allitol, and iditol.

[0077] The high-molecular-weight polyol is a compound having two or more hydroxyl groups and a number-average molecular weight of 400 or more, for example, 10,000 or less, preferably 5,000 or less. Examples of high-molecular-weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, silicone polyols, fluorine polyols, and vinyl monomer-modified polyols.

[0078] Examples of the polythiol component used in the polymerizable composition of the present invention include aliphatic polythiols, aromatic polythiols, heterocycle-containing polythiols, aliphatic polythiols containing sulfur atoms other than mercapto groups, aromatic polythiols containing sulfur atoms other than mercapto groups, heterocycle-containing polythiols containing sulfur atoms other than mercapto groups, etc. The above thiols may be thiol oligomers or polythiols, and one or more types may be used in combination.

[0079] Specific examples of the thiol include 3,3'-thiobis[(2-mercaptoethyl)thio]-1-propanethiol, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl)sulfide, tetrakis(mercaptomethyl)methane, 2-(2-mercaptoethylthio)propane- 1,3-Dithiol, 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercaptopropanyl) sulfide, bis(2,3-dimercaptopropanyl) disulfide, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)ethane, 2-(2-mercaptoethylthio)-3-2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propan Pan-1-thiol, 2,2-bis-(3-mercapto-propionyloxymethyl)-butyl ester, 2-(2-mercaptoethylthio)-3-(2-(2-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]ethylthio)ethylthio)propane-1-thiol, (4R,11S)-4,11-bis(mercaptomethyl)-3,6,9,12-tetrathiatetradecane-1,14-dithiol, (S)-3-((R-2,3-dimercaptopropyl)thio)propane-1,2-dithiol, (4R,14R)-4,14-bis(mercaptomethyl)-3,6,9,12-tetrathiatetradecane-1,14-dithiol (7R,11S)-7,11-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptane-1,17-dithiol, (S)-3-((R-3-mercapto-2-((2-mercaptoethyl)thio)propyl)thio)-2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2-dithiol), (7R,11S)-7,11-bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7,12-bis(mercaptomethyl)-3,6,9,10,13,16-Hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercapto acetate), bispentaerythritol ether hexakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane, etc.

[0080] The polymerizable composition may further contain additives such as an internal mold release agent, an ultraviolet absorber, a near-infrared absorber, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, and a filler, as necessary.

[0081] The internal mold release agent may be selected from the group consisting of a fluorine-based nonionic surfactant having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; a silicone-based nonionic surfactant having a dimethylpolysiloxane group, a hydroxyalkyl group, or a phosphate ester group; an alkyl quaternary ammonium salt, i.e., trimethylcetylammonium salt, trimethylstearyl, dimethylethylcetylammonium salt, triethyldodecylammonium salt, trioctylmethylammonium salt, and diethylcyclohexadodecylammonium salt; and an acidic phosphate ester, and may be used alone or in combination of two or more thereof.

[0082] As the ultraviolet absorber, benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, cyanoacrylate-based, oxanilide-based, etc. may be used.

[0083] Examples of near-infrared absorbents that can be used include azo-based, aminium-based, anthraquinone-based, cyanine-based, polymethine-based, diphenylmethane-based, triphenylmethane-based, quinone-based, diimonium-based, dithiol metal complex-based, squarylium-based, phthalocyanine-based, and naphthalocyanine-based absorbents. In particular, near-infrared absorbents with high near-infrared absorption, with a blocking rate of 30% or more in the 800-1000 nm range, can be used as electromagnetic wave absorbents. Such near-infrared absorbents are preferably mixtures of multiple phthalocyanine dyes with different structures, each of which has a minimum spectral transmittance of less than 80% in the following wavelength ranges: (i) 800-850 nm, (ii) 875-925 nm, and (iii) 950-1000 nm. For example, PANAX FND-83, PANAX FND-88, and PANAX FND-96 can be used.

[0084] As the polymerization initiator, amine-based, phosphorus-based, organotin-based, organocupper-based, organogallium-based, organozirconium-based, organoiron-based, organozinc-based, organoaluminum-based, organobismuth-based, etc. may be used.

[0085] As the heat stabilizer, metal fatty acid salts, phosphorus-based, lead-based, organotin-based, etc. can be used alone or in combination of two or more.

[0086] The present invention also provides a polythiourethane obtained from the polymerizable composition. Specifically, the polythiourethane can be produced by polymerizing (and curing) the isocyanate compound and thiol in the polymerizable composition. The polymerization reaction can be carried out so that the SH / NCO molar ratio is 0.5 to 3.0, more specifically, 0.8 to 1.3.

[0087] Furthermore, to control the reaction rate, a reaction catalyst commonly used in the production of polythiourethane may be added. As the curing catalyst (polymerization initiator), a tin-based catalyst such as dibutyltin dichloride, dibutyltin dilaurate, or dimethyltin dichloride may be used.

[0088] The following describes the identification of standard substances for various isocyanates and the methods for measuring their physical properties, including their content.

[0089] Analysis method (1) 1,3-xylylene diisocyanate (XDI) content XDI with a purity of 99% prepared in the formulation example described below was used as the standard substance and analyzed by gas chromatography under the conditions below. A calibration curve was created from the area values ​​of the resulting gas chromatogram and quantified. -Device: HP-6890(HP) - Column: DB-1 (inner diameter 0.53 mm x length 60 m x thickness 1.5 μm) -Inlet temperature; 180℃ -Detector temperature: 300℃

[0090] (2) 3-chloromethylbenzyl isocyanate (chemical formula 5) content The compound of formula 5 with a purity of 99% obtained by separating / purifying the XDI composition prepared in the formulation example by column distillation was used as a standard substance, and the content of the compound of formula 5 in the compositions of each example and comparative example was calculated in the same manner as in the XDI measurement method described above.

[0091] The obtained compound of formula 5 13 The product was analyzed by C-NMR (100 MHz, CDCl3), FT-IR, and MS.

[0092] 13 C-NMR(100MHz,CDCl3)δ46.5,54.6,125.6,127.9,128.8,130.5,139.9,139.1 FT-IR: 2260cm -1 MS: m / z = 181 (M + )

[0093] (3) Content of 1,3-xylylene dichloride (chemical formula 6) Using the compound of formula 6 (reagent, Sigma-Aldrich) with a purity of 98% as a standard substance, the content of the compound of formula 6 in the compositions of each example and comparative example was calculated in the same manner as in the above-mentioned XDI measurement method.

[0094] (4) Content of dichloromethylbenzene isocyanate (Chemical Formula 7) The compound of Chemical 7 with a purity of 99 mol% produced by the synthesis method disclosed in Korean Patent Publication No. 2018-0127517 was used as a standard substance and analyzed by gas chromatography under the following conditions. A calibration curve was created from the area value of the obtained gas chromatogram and quantified.

[0095] -Device: HP-6890(HP) -Column: HP-50 + (inner diameter 0.25mm x length 30m x thickness 0.25um) -Inlet temperature; 200℃ -Detector temperature: 280℃

[0096] The obtained compound of formula 7 13 The product was analyzed by C-NMR (100 MHz, CDCl3), FT-IR, and MS.

[0097] 13 C-NMR(100MHz,CDCl3)δ46.3,72.5,122.9,127.8,128.7,129.1,139.0,140.3 FT-IR: 2260cm -1 MS: m / z = 215 (M + )

[0098] (5) Content of 3-methylbenzyl isocyanate (compound of Chemical Formula 4) Using 98% pure methylbenzyl isocyanate (reagent, manufactured by Sigma-Aldrich) as a standard substance, the content of methylbenzyl isocyanate in the compositions of each example and comparative example was calculated in the same manner as in the above-mentioned XDI measurement method.

[0099] (6) Refractive index of optical lenses The refractive index of the optical lenses obtained from the compositions of the Examples and Comparative Examples described below was measured at 20°C using a refractometer DR-M4 model manufactured by ATAGO at a wavelength of 546.1 nm (mercury e-line) (n e ) was measured.

[0100] (7) Heat resistance evaluation of optical lenses The glass transition temperature (Tg) was measured using a thermomechanical analyzer DSC N-650. The glass transition temperature was used as an index of heat resistance.

[0101] (8) Yellow Index (YI) and Light Transmittance of Optical Lenses The yellowness of the optical lens was calculated using chromaticity coordinates x and y using UV-2600 240V EN (Shimadzu Corporation), and the yellowness was expressed by the formula (1).

[0102] Formula (1) YI=(234x+106y+106) / y

[0103] (9) Evaluation of dyeability (colorability) of optical lenses After preparing a Gray BPI #32000 (BPI dye) dye dispersion, a 2.0 mm thick resin was dyed by immersing it in the dispersion for 5 minutes in a 95°C water bath. The light transmittance (%) of the dyed resin was measured in a visible light wave field (380-780 nm). The dye absorbs light depending on the degree of dyeing, and the lower the light transmittance at each wavelength, the better the dyeing ability.

[0104] (10) Clouding of optical lenses The opacity of the optical lens was visually observed and evaluated according to the following criteria. Good: Transparent; Bad: Cloudy

[0105] (11) Striae of optical lenses The optical lenses were visually inspected under a mercury lamp, and if a heterogeneous phase was observed, they were classified as having striae.

[0106] The present invention will be illustrated by the following examples, but is not limited thereto. First, the process of producing XDI under various conditions will be examined by changing the reaction conditions in the production method of the present invention. [Example]

[0107] 1. Synthesis of 1,3-xylylene diisocyanate (XDI) and preparation of XDI compositions containing chlorinated derivatives

[0108] [Synthesis Example 1] In a 50 L reaction vessel equipped with a reflux condenser, 7.3 kg of bis(trichloromethyl)carbonate was dissolved in 36 kg of o-dichlorobenzene, and then a solution of 2 kg of m-xylylenediamine dissolved in 2 kg of o-dichlorobenzene was gradually added thereto at temperatures below 60°C. The temperature was raised to 160°C, and the reaction was carried out for 4 hours while controlling the release of hydrogen chloride gas. As the temperature increased, the solution of bis(trichloromethyl)carbonate dissolved in o-dichlorobenzene was gradually added to ensure smooth stirring. After the reaction was completed, nitrogen was purged from the reactor to remove unreacted phosgene and hydrogen chloride gas, and the resulting solution was filtered to obtain XDI containing chlorinated derivatives. The content of chlorinated derivatives in the XDI solution excluding o-dichlorobenzene was approximately 2.8%.

[0109] [Synthesis Example 2] The solution obtained in Synthesis Example 1 was desolvated and passed through a high vacuum distillation apparatus to obtain pure XDI free of chlorinated derivatives.

[0110] [Prescription Examples 1-3] The XDI produced in Synthesis Example 2 was mixed with chlorinated derivatives (compounds of formulas 5, 6, and 7 mixed at a fixed ratio) as the various isocyanate standard substances described above to obtain XDI containing chlorinated derivatives. These amounts are 500 ppm (Preparation Example 1), 1400 ppm (Preparation Example 2), and 5000 ppm (Preparation Example 3) relative to the total mass of the XDI solution.

[0111] 2. Preparation of XDI compositions containing non-chlorinated derivatives (methylbenzyl isocyanate) and / or chlorinated derivatives in the XDI compositions obtained in Preparation Examples 1 to 3 (2-1) Examples 1 to 3 100 g of o-dichlorobenzene was added to 900 g of XDI obtained in Preparation Examples 1 to 3, and 2 g of Pd / C was added. The mixture was then heated at 50°C and 2 kgf / cm 2 The mixture was stirred under a hydrogen atmosphere for 12 hours. After the reaction was completed, the mixture was filtered under reduced pressure, and then the solvent was removed and distilled to obtain an XDI composition containing methylbenzyl isocyanate.

[0112] (2-2) Examples 4 to 10 The XDI obtained in Synthesis Example 1 was mixed with methylbenzyl isocyanate and a chlorinated derivative in amounts relative to the total mass of XDI to obtain an XDI composition containing all of these.

[0113] (2-3) Example 11 0.2 g of Pd / C was added to 200 g of the XDI composition containing the actual chlorinated derivative obtained in Synthesis Example 1, and then the mixture was heated at 50°C and 2 kgf / cm 2 The mixture was stirred under a hydrogen atmosphere for 12 hours. After the reaction was completed, the mixture was filtered under reduced pressure and the solvent was removed to obtain XDI containing methyl benzyl isocyanate (2.7%) and chlorinated derivatives (0.06%). The resulting XDI solution was simply distilled under vacuum to obtain an XDI composition containing methyl benzyl isocyanate (0.5%) and chlorinated impurities (0.04%).

[0114] (2-4) Comparative Examples 1 and 2 An XDI composition containing only chlorinated derivatives of the XDI obtained in Synthesis Example 2 was obtained.

[0115] The contents of methylbenzyl isocyanate and chlorinated derivatives in the XDI compositions obtained by reduction reaction in Examples 1 to 3, XDI compositions containing methylbenzyl isocyanate or chlorinated derivatives in Examples 4 to 10, XDI compositions containing methylbenzyl isocyanate and chlorinated derivatives obtained by reducing XDI containing chlorinated derivatives produced by actual processes in Example 11, and XDI compositions containing only chlorinated derivatives in Comparative Examples 1 and 2 are shown in Table 1.

[0116] [Table 1]

[0117] 3. Evaluation of the conversion of chlorinated derivatives to non-chlorinated derivatives by reduction reactions In this conversion process, as shown in Figure 1, it was confirmed that the chlorinated derivative (A) before the reduction reaction can be easily converted to the non-chlorinated derivative (B) after the reduction reaction by a simple reduction process. Furthermore, the difference in boiling points between XDI and the chlorinated derivatives that are impurities of XDI is not large, making separation and purification difficult. However, it was confirmed that the present invention can simplify the separation and purification process by converting the chlorinated derivative into the non-chlorinated derivative with a large boiling point difference.

[0118] 4. Preparation and evaluation of optical lenses from XDI compositions (4-1) Manufacturing of optical lenses using the XDI compositions of Examples 1 to 11 and Comparative Examples 1 and 2 52 g of the XDI compositions prepared in Examples 1 to 11 and Comparative Examples 1 and 2, 0.015 g of dibutyltin dichloride, 0.12 g of Zelec UN (internal mold release agent, manufactured by Stepan), and 0.08 g of UV absorber were mixed and stirred at room temperature for 1 hour, and then 48 g of 2,3-bis(2-mercaptoethylthio)propane-1-thiol was added to prepare a polymerizable composition. The polymerizable composition was stirred under reduced pressure for 1 hour to remove air bubbles and then filtered through a 1 μm Teflon filter. The mixture was then poured into a mold consisting of a glass mold and tape, and the temperature was gradually raised to 120°C in an oven, where it was polymerized for 20 hours. The mold was removed from the oven and demolded to obtain a resin (plastic). The resulting resin was then annealed at 120°C for an additional 2 hours.

[0119] The physical properties of each manufactured optical lens were evaluated as follows and summarized in Table 2.

[0120] [Table 2] *The yellowness of the unprocessed lenses (3 mm flat plates) obtained by the methods of Examples 1 to 11 was measured. **The raw lenses obtained by the methods of Examples 1 to 11 were colored by the above-mentioned coloring degree measurement method, and the light transmittance was measured. ***Impact resistance tests were conducted in accordance with the Drop Test (16.3g x 127cm).

[0121] (4-2) Evaluation of physical properties of optical lenses manufactured using the XDI compositions of Examples 1 to 11 and Comparative Examples 1 and 2 (1) Lenses using XDI compositions containing up to 50,000 ppm of methyl methyl isocyanate have an ultra-high refractive index (n e It could be used as a lens with a focal length of 20:1.66 or more.

[0122] (2) When comparing Example 6 and Comparative Example 1, the yellowness index was 1.26 and 2.30, respectively, showing a significant difference. Compared to chlorinated derivatives, the lenses using the XDI composition containing methylbenzyl isocyanate, which is a reduced version of a chlorinated derivative, showed significantly better results in terms of yellowness index. The XDI composition reduced with methylbenzyl isocyanate was significantly superior in terms of yellowness index compared to the XDI composition containing chlorinated derivatives.

[0123] (3) As shown in Examples 8 and 9 and Comparative Example 2, the yellowness index tended to increase with an increase in the amount of chlorinated derivatives. While the amount of methylbenzyl isocyanate was the same at 50,000 ppm, the yellowness index was 1.38 when the amount of chlorinated derivatives was 1,500 ppm, 1.40 when the amount was 1,600 ppm, and 2.30 when the amount was 30,000 ppm. Therefore, when both methylbenzyl isocyanate and chlorinated derivatives are contained, the amount of chlorinated derivatives is preferably 1,500 ppm or less.

[0124] (4) As shown in Comparative Examples 1 and 2 and Examples 3 and 10, the coloring efficiency decreased and the light transmittance of the colored lens increased as the amount of chlorinated impurities increased, whereas the coloring efficiency increased and the light transmittance decreased as the amount of methylbenzyl isocyanate increased. Thus, unlike chlorinated derivatives, methylbenzyl isocyanate contributed to improving the coloring efficiency.

[0125] (5) As shown in Example 6 and Comparative Example 2, defects occurred in terms of opacity and striae at a chlorinated derivative concentration (30,000 ppm), but good results were observed in terms of opacity and striae at the same concentration of methylbenzyl isocyanate, making the film usable as an optical lens material.

Claims

1. In a method for producing a xylylene diisocyanate (XDI)-containing composition, a chlorinated derivative generated during the production process is converted into a non-chlorinated derivative by a simple reduction reaction, A method for producing a xylylene diisocyanate-containing composition, comprising the steps of: separating the non-chlorinated derivative in the XDI-containing composition by distillation after the simple reduction reaction;

2. The method for producing a xylylene diisocyanate-containing composition according to claim 1, wherein the chlorinated derivative is a compound represented by the following formula 1: 【Chemistry 1】 (where R １ is Cl or NCO, and R ２ is H or Cl)

3. The method for producing a xylylene diisocyanate-containing composition according to claim 1 or 2, wherein the non-chlorinated derivative is a compound represented by the following formula 3A: 【Chemistry 3A】 (where R ３ is H or NCO)

4. An isocyanate-containing composition comprising xylylene diisocyanate (XDI), a chlorinated derivative represented by the following Chemical Formula 1, and a non-chlorinated derivative comprising at least one selected from the group consisting of 1,2-xylene, 1,3-xylene, 1,4-xylene, 2-methylbenzyl isocyanate, and 4-methylbenzyl isocyanate, The isocyanate-containing composition, wherein the content of the chlorinated derivative (Chemical Formula 1) in the isocyanate-containing composition is in the range of more than 0 to 1,500 ppm. 【Chemistry 1】 (where R １ is Cl or NCO, and R ２ is H or Cl)

5. An isocyanate-containing composition comprising xylylene diisocyanate (XDI), a chlorinated derivative represented by the following formula 1, and 2-methylbenzyl isocyanate and / or 4-methylbenzyl isocyanate, The isocyanate-containing composition, wherein the total content of 2-methylbenzyl isocyanate and / or 4-methylbenzyl isocyanate in the isocyanate-containing composition is in the range of 0.1 to 50,000 ppm. 【Chemistry 1】 (where R １ is Cl or NCO, and R ２ is H or Cl)

6. An isocyanate-containing composition comprising xylylene diisocyanate (XDI), methylbenzyl isocyanate represented by the following formula 4A, and xylene represented by the following formula 3A: The isocyanate-containing composition has a content of methylbenzyl isocyanate (Chemical Formula 4A) in the isocyanate-containing composition in the range of 0.1 to 50,000 ppm. 【Chemistry 3A】 (where R ３ is H) [Chemistry 4A]

7. An isocyanate-containing composition comprising xylylene diisocyanate (XDI) and 2-methylbenzyl isocyanate and / or 4-methylbenzyl isocyanate, The isocyanate-containing composition, wherein the total content of 2-methylbenzyl isocyanate and / or 4-methylbenzyl isocyanate in the isocyanate-containing composition is in the range of more than 200 to 50,000 ppm.

8. A polymerizable composition comprising the isocyanate-containing composition of any one of claims 4 to 7 and a compound containing one or more isocyanate-reactive functional groups.

9. 9. The polymerizable composition of claim 8, wherein the compound containing one or more isocyanate-reactive functional groups is a polyol compound or a polythiol compound.

10. A resin obtained by reacting the polymerizable composition according to claim 9.

11. An optical material produced using the resin according to claim 10 as a raw material.

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