Isocyanate composition, polymerizable composition, resin, molded body, optical element, and lens

Abstract

This isocyanate composition contains five isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane. The five isomers are separated and detected when derivatized with N-methylethanolamine and analyzed by high performance liquid chromatography in a reverse-phase mode. When detection is performed at a detection wavelength of 220 nm using an absorbance detector, the ratio of the peak area of the N-methylethanolamine derivative of the fifth isomer (fifth detected isomer) to the total peak area of the N-methylethanolamine derivative (molecular weight: 356) of each isomer is 10.0-40.0%.

Description

Isocyanate compositions, polymerizable compositions, resins, molded articles, optical elements, and lenses

[0001] The present invention relates to isocyanate compositions, polymerizable compositions, resins, molded articles, optical elements, and lenses.

[0002] Conventionally, it is known that polythiourethane molded articles that can be used in optical elements such as lenses are produced by reacting bis(isocyanatomethyl)bicyclo[2,2,1]heptane with a polythiol (see Patent Document 1 below).

[0003] Japanese Patent Publication No. 2017-214488

[0004] In polythiourethane molded articles such as those described in Patent Document 1 above, improvement in dyeability is desired.

[0005] The present invention provides an isocyanate composition and a polymerizable composition capable of producing a resin with excellent dyeability, as well as a resin, a molded article, an optical element, and a lens with excellent dyeability.

[0006] The present invention [1] contains five isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane, and when these five isomers are derivatized with N-methylethanolamine and analyzed in reverse-phase mode by high-performance liquid chromatography, the following are detected: a first isomer N-methylethanolamine derivative, a second isomer N-methylethanolamine derivative detected later than the first isomer N-methylethanolamine derivative, a third isomer N-methylethanolamine derivative detected later than the second isomer N-methylethanolamine derivative, and the third isomer N-methylethanolamine derivative The isocyanate composition is detected separately as a fourth isomer of N-methylethanolamine derivative, which is detected later, and a fifth isomer of N-methylethanolamine derivative, which is detected later than the fourth isomer of N-methylethanolamine derivative, with each of the five isomers having a molecular weight of 356, and when detected at a detection wavelength of 220 nm using an absorbance detector, the ratio of the peak area of ​​the fifth isomer of N-methylethanolamine derivative to the total peak area of ​​each of the five isomers is between 10.0% and 40.0%.

[0007] The present invention [2] includes the isocyanate composition of [1] above, wherein the ratio of the peak area of ​​the fourth isomer N-methylethanolamine derivative to the total peak area of ​​each of the five isomer N-methylethanolamine derivatives is 0.1% or more and 5.0% or less.

[0008] The present invention [3] includes the isocyanate composition of [1] or [2] above, wherein the ratio of the peak area of ​​the first isomer of N-methylethanolamine derivative to the total peak area of ​​each of the five isomers of N-methylethanolamine derivative is 16.0% or more and 28.0% or less.

[0009] The present invention [4] includes any one of the isocyanate compositions [1] to [3] above, in which the ratio of the peak area of the N-methylethanolamine derivative of the second isomer to the total peak area of the N-methylethanolamine derivatives of each of the five isomers is 25.0% or more and 40.0% or less.

[0010] The present invention [5] includes any one of the isocyanate compositions [1] to [4] above, in which the ratio of the peak area of the N-methylethanolamine derivative of the third isomer to the total peak area of the N-methylethanolamine derivatives of each of the five isomers is 19.0% or more and 30.0% or less.

[0011] The present invention [6] includes a polymerizable composition containing any one of the isocyanate compositions [1] to [5] above and an active hydrogen group-containing component.

[0012] The present invention [7] includes the polymerizable composition [6] above, in which the active hydrogen group-containing component contains at least one polythiol selected from the group consisting of 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

[0013] The present invention [8] includes a resin which is a cured product of the polymerizable composition of [6] or [7] above.

[0014] The present invention [9] includes a molded article made of the resin described in [8] above.

[0015] The present invention

[10] includes an optical element which is a molded body as described in [9] above.

[0016] The present invention

[11] includes a lens, which is an optical element of the above

[10] .

[0017] The present invention

[12] comprises the use of any one of the isocyanate compositions [1] to [5] above for the manufacture of a lens.

[0018] The isocyanate composition and polymerizable composition of the present invention contain five isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in specific proportions. Therefore, it is possible to produce resins with excellent dyeability.

[0019] Furthermore, the molded articles, optical elements, and lenses of the present invention are made of the resin described above. Therefore, they exhibit excellent dyeability.

[0020] 1. Isocyanate composition The isocyanate composition contains bis(isocyanatomethyl)bicyclo[2,2,1]heptane as its main component.

[0021] Bis(isocyanatomethyl)bicyclo[2,2,1]heptane is detected at a retention time of 15.0 to 17.6 minutes in gas chromatography under the following measurement conditions.

[0022] <Measurement Conditions of Gas Chromatography> Column; DB-5 (inner diameter: 0.53 mm, length: 60 m, film thickness: 1.5 μm) Oven temperature; heated from 130 °C to 190 °C at 3 °C / min, then heated from 190 °C to 280 °C at 10 °C / min. Held at 280 °C for 15 minutes Injection port temperature; 280 °C Detector temperature; 300 °C Carrier gas flow rate; 25 mL / min Sample concentration; 150 mg of isocyanate composition in 5 ml of dichloromethane Injection method; pulsed splitless method Injection volume; 1.0 μL Detector; flame ionization detector (FID) In the gas chromatography under the above measurement conditions, the total area P of all peaks detected from the isocyanate composition ,

[0026] of the peak area P of bis(isocyanatomethyl)bicyclo[2,2,1]heptane relative to ＢＩＢＨ the ratio R ＢＩＢＨ is calculated by the following formula.

[0023] Formula: R ＢＩＢＨ = (P ＢＩＢＨ / P ＳＵＭ ) × 100 The ratio R ＢＩＢＨ is, for example, 98.00% or more, 99.00% or more, 99.30% or more, or 99.60% or more. The ratio R ＢＩＢＨ is, for example, 99.95% or less. [[ID=二十一]]

[0024] [[ID=二十二]] The ratio R ＢＩＢＨ may be 98.00% to 99.95%, 99.00% to 99.95%, 99.30% to 99.95%, or 99.60% to 99.95%.

[0025] The ratio (purity) of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in the isocyanate composition is, for example, 98.00% by mass or more, 99.00% by mass or more, 99.30% by mass or more, or 99.50% by mass or more. The ratio (purity) of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in the isocyanate composition is, for example, 99.95% by mass or less.

[0026] The proportion (purity) of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in the isocyanate composition may be 98.00% to 99.95% by mass, 99.00% to 99.95% by mass, 99.30% to 99.95% by mass, or 99.50% to 99.95% by mass.

[0027] Six isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane are listed. These six isomers are 2,5-diexo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane, 2-endo-5-exo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane, 2,5-diendo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane, 2,6-diexo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane, 2-endo-6-exo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane, and 2,6-diendo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

[0028] The isocyanate composition contains at least five of the six isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane described above.

[0029] When the five isomers are derivatized with N-methylethanolamine and analyzed in reverse-phase mode by high-performance liquid chromatography, they are separated and detected as the N-methylethanolamine derivative of the first isomer, the N-methylethanolamine derivative of the second isomer, the N-methylethanolamine derivative of the third isomer, the N-methylethanolamine derivative of the fourth isomer, and the N-methylethanolamine derivative of the fifth isomer.

[0030] In detail, first, N-methylmethanolamine is reacted with bis(isocyanatomethyl)bicyclo[2.2.1]heptane in an isocyanate composition using the method described in the examples below to obtain a sample containing the N-methylmethanolamine derivative of bis(isocyanatomethyl)bicyclo[2.2.1]heptane.

[0031] The N-methylethanolamine derivative of the second isomer is detected later than the N-methylethanolamine derivative of the first isomer. The N-methylethanolamine derivative of the third isomer is detected later than the N-methylethanolamine derivative of the second isomer. The N-methylethanolamine derivative of the fourth isomer is detected later than the N-methylethanolamine derivative of the third isomer. The N-methylethanolamine derivative of the fifth isomer is detected later than the N-methylethanolamine derivative of the fourth isomer.

[0032] For example, in high-performance liquid chromatography under the following measurement condition A, the first isomer of N-methylmethanolamine derivative is detected at retention times of 27.0 to 29.0 minutes, the second isomer of N-methylmethanolamine derivative is detected at retention times of 31.0 to 34.5 minutes, the third isomer of N-methylmethanolamine derivative is detected at retention times of 35.0 to 38.0 minutes, the fourth isomer of N-methylmethanolamine derivative is detected at retention times of 41.0 to 43.0 minutes, and the fifth isomer of N-methylmethanolamine derivative is detected at retention times of 42.0 to 46.0 minutes.

[0033] <Measurement conditions A for high-performance liquid chromatography> Column: ODS column (column size: inner diameter 4.6 mm x length 250 mm, particle size: 5 μm, pore size: 8 nm) Column temperature: 40°C Mobile phase: Mixture of methanol (A) and water (B) Elution method: Gradient elution (A:B = 15:85 from the start of analysis (0 min) to 15 min, changed to A:B = 30:70 for 5 minutes from 15 min to 20 min, A:B = 30:70 from 20 min to 50 min, changed to A:B = 90:10 for 10 minutes from 50 min to 60 min, A:B = 90:10 from 60 min to 70 min) Total flow rate: 0.8 mL / min Detector: Absorbance detector Detection wavelength: 220 nm Sample introduction method: 1 μL of sample filtered through a 0.45 μm filter was injected into the sample introduction section.

[0034] The molecular weight of each of the five isomers is 206, and the molecular weight of each of the N-methylmethanolamine derivatives of the five isomers is 356. The molecular weight of each N-methylmethanolamine derivative of each isomer is determined by high-performance liquid chromatography and mass spectrometry.

[0035] In high-performance liquid chromatography under measurement condition A (i.e., when detected at a detection wavelength of 220 nm using an absorbance detector), the total peak area P of each of the five isomers of N-methylmethanolamine derivatives was... １－５ Peak area P of the first isomer of N-methylmethanolamine derivative relative to １ Ratio R １ It is calculated using the following formula (1).

[0036] Formula (1): R １ = (P １ / P １－５ ) × 100 Ratio R １ For example, this is 16.0% or more, preferably 16.5% or more. １ For example, the ratio R is 28.0% or less, preferably 26.0% or less. １ This may be 16.0% to 28.0%, or 16.5% to 26.0%.

[0037] The proportion of the first isomer in the isocyanate composition is, for example, 16.0% by mass or more, preferably 16.5% by mass or more. The proportion of the first isomer in the isocyanate composition is, for example, 28.0% by mass or less, preferably 26.0% by mass or less. The proportion of the first isomer in the isocyanate composition may be 16.0% by mass to 28.0% by mass, or 16.5% by mass to 26.0% by mass.

[0038] Furthermore, the total peak area P of each of the five isomers of N-methylmethanolamine derivatives is also shown. １－５ Peak area P of the second isomer of N-methylmethanolamine derivative relative to ２ Ratio R ２ This is calculated using the following formula (2).

[0039] Formula (2): R ２ = (P ２ / P１－５ ) × 100 Ratio R ２ For example, this is 25.0% or more, preferably 27.0% or more. ２ For example, it is 40.0% or less, preferably 35.0% or less. Ratio R ２ This may be 25.0% to 40.0%, or 27.0% to 35.0%.

[0040] The proportion of the second isomer in the isocyanate composition is, for example, 25.0% by mass or more, preferably 27.0% by mass or more. The proportion of the second isomer in the isocyanate composition is, for example, 40.0% by mass or less, preferably 35.0% by mass or less. The proportion of the second isomer in the isocyanate composition may be 25.0% by mass to 40.0% by mass, or 27.0% by mass to 35.0% by mass.

[0041] Furthermore, the total peak area P of each of the five isomers of N-methylmethanolamine derivatives is also shown. １－５ Peak area P of the third isomer of N-methylmethanolamine derivative relative to ３ Ratio R ３ This is calculated using the following formula (3).

[0042] Formula (3): R ３ = (P ３ / P １－５ ) × 100 Ratio R ３ For example, this is 19.0% or more, preferably 20.0% or more. ３ For example, the percentage R is 30.0% or less, preferably 25.0% or less. ３ This may be 19.0% to 30.0%, or 20.0% to 25.0%.

[0043] The proportion of the third isomer in the isocyanate composition is, for example, 19.0% by mass or more, preferably 20.0% by mass or more. The proportion of the third isomer in the isocyanate composition is, for example, 30.0% by mass or less, preferably 25.0% by mass or less. The proportion of the third isomer in the isocyanate composition may be 19.0% by mass to 30.0% by mass, or 20.0% by mass to 25.0% by mass.

[0044] Furthermore, the total peak area P of each of the five isomers of N-methylmethanolamine derivatives is also shown. １－５ Peak area P of the fourth isomer of N-methylmethanolamine derivative relative to ４ Ratio R ４ This is calculated using the following formula (4).

[0045] Formula (4): R ４ = (P ４ / P １－５ ) × 100 Ratio R ４ For example, this is 0.1% or more, preferably 0.7% or more. Ratio R ４ For example, it is 5.0% or less, preferably 3.0% or less. Ratio R ４ This may be 0.1% to 5.0%, or 0.7% to 3.0%.

[0046] The proportion of the fourth isomer in the isocyanate composition is, for example, 0.1% by mass or more, preferably 0.7% by mass or more. The proportion of the fourth isomer in the isocyanate composition is, for example, 5.0% by mass or less, preferably 3.0% by mass or less. The proportion of the third isomer in the isocyanate composition may be 0.1% by mass to 5.0% by mass, or 0.7% by mass to 3.0% by mass.

[0047] Furthermore, the total peak area P of each of the five isomers of N-methylmethanolamine derivatives is also shown. １－５ Peak area P of the fifth isomer of N-methylmethanolamine derivative relative to ５ Ratio R ５ This is calculated using the following formula (5).

[0048] Formula (5): R ５ = (P ５ / P １－５ ) × 100 Ratio R ５ For example, the percentage is 10.0% or more, preferably 15.0% or more, and more preferably 20.0% or more. ５ For example, the percentage R is 40.0% or less, preferably 35.0% or less, and more preferably 30.0% or less. ５ This may be 10.0% to 40.0%, 15.0% to 35.0%, or 20.0% to 30.0%.

[0049] The proportion of the fifth isomer in the isocyanate composition is, for example, 10.0% by mass or more, preferably 15.0% by mass or more, and more preferably 20.0% by mass or more. The proportion of the fifth isomer in the isocyanate composition is, for example, 40.0% by mass or less, preferably 35.0% by mass or less, and more preferably 30.0% by mass. The proportion of the fifth isomer in the isocyanate composition may be 10.0% by mass to 40.0% by mass, 15.0% by mass to 35.0% by mass, or 20.0% by mass to 30.0% by mass.

[0050] The isocyanate composition preferably contains 2,5-diexo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane as a first isomer, 2-endo-5-exo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane as a second isomer, 2,6-diexo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane as a third isomer, 2,5-diendo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane as a fourth isomer, and 2-endo-6-exo-bis(isocyanatomethyl)bicyclo[2,2,1]heptane as a fifth isomer.

[0051] The chemical structure of each isomer can be determined based on the chemical structure of the N-methylmethanolamine derivative of each isomer. The chemical structure of the N-methylmethanolamine derivative of each isomer is determined by separating the N-methylmethanolamine derivative of each isomer after passing through the detector in the high-performance liquid chromatography described above, and then performing NMR analysis on the separated N-methylmethanolamine derivatives of each isomer.

[0052] 2. Method for producing isocyanate compositions A method for producing isocyanate compositions will be described.

[0053] A method for producing an isocyanate composition includes, for example, a synthesis step and a purification step.

[0054] In the synthesis process, bis(isocyanatomethyl)bicyclo[2,2,1]heptane is synthesized. The synthesis process is carried out, for example, by the hydrochloride salt method. When the hydrochloride salt method is used, the synthesis process includes a salt formation step and an isocyanation step.

[0055] In the salt production process, bis(aminomethyl)bicyclo[2.2.1]heptane and hydrogen chloride are mixed to produce bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride.

[0056] Bis(aminomethyl)bicyclo[2.2.1]heptane contains several isomers of bis(aminomethyl)bicyclo[2.2.1]heptane. Examples of isomers of bis(aminomethyl)bicyclo[2.2.1]heptane include 2,5-diexo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2-endo-5-exo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,5-diendo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6-diexo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2-endo-6-exo-bis(aminomethyl)bicyclo[2,2,1]heptane, and 2,6-diendo-bis(aminomethyl)bicyclo[2,2,1]heptane.

[0057] Bis(aminomethyl)bicyclo[2.2.1]heptane contains at least five of the six isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane described above.

[0058] Bis(aminomethyl)bicyclo[2.2.1]heptane preferably contains 2,5-diexo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2-endo-5-exo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,6-diexo-bis(aminomethyl)bicyclo[2,2,1]heptane, 2,5-diendo-bis(aminomethyl)bicyclo[2,2,1]heptane, and 2-endo-6-exo-bis(aminomethyl)bicyclo[2,2,1]heptane.

[0059] The method for producing bis(aminomethyl)bicyclo[2.2.1]heptane is not limited. For example, first, cyanobicyclo[2.2.1]heptene is added with carbon monoxide and hydrogen (hydroformylation reaction) to obtain cyanoformylbicyclo[2.2.1]heptane. Next, the obtained cyanoformylbicyclo[2.2.1]heptane is reacted with ammonia and hydrogen to obtain the above-mentioned bis(aminomethyl)bicyclo[2.2.1]heptane. Alternatively, for example, cyanobicyclo[2.2.1]heptene is reacted with hydrogen cyanide to obtain dicyanobicyclo[2.2.1]heptane. Next, the obtained dicyanoformylbicyclo[2.2.1]heptane is reacted with hydrogen to obtain the above-mentioned bis(aminomethyl)bicyclo[2.2.1]heptane. Cyanobicyclo[2.2.1]heptene can be obtained, for example, by the reaction of dicyclopentadiene with acrylonitrile.

[0060] In the salt production process, for example, bis(aminomethyl)bicyclo[2.2.1]heptane is reacted with hydrogen chloride in the presence of an inert solvent. Specifically, hydrogen chloride gas is mixed with a solution in which bis(aminomethyl)bicyclo[2.2.1]heptane is dissolved in an inert solvent to react bis(aminomethyl)bicyclo[2.2.1]heptane with hydrogen chloride.

[0061] Examples of inert solvents include those described in paragraph

[0059] of International Publication No. 2018 / 190290. Inert solvents can be used alone or in combination of two or more. Among the inert solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

[0062] The ratio of bis(aminomethyl)bicyclo[2.2.1]heptane to the total mass of bis(aminomethyl)bicyclo[2.2.1]heptane and the inert solvent (total amine concentration) is, for example, 3% to 30% by mass, 5% to 20% by mass, or 5% to 15% by mass.

[0063] The supply ratio of hydrogen chloride is, for example, 2 to 10 moles, 2 to 6 moles, or 2 to 4 moles per mole of bis(aminomethyl)bicyclo[2.2.1]heptane.

[0064] The reaction temperature in the salt production process is, for example, 30°C to 160°C, 50°C to 150°C, or 50°C to 140°C.

[0065] The reaction pressure (gauge pressure) in the salt production process is, for example, 0 MPaG (atmospheric pressure) to 1.0 MPaG, or 0.01 MPaG to 0.5 MPaG.

[0066] Bis(aminomethyl)bicyclo[2.2.1]heptane reacts with hydrogen chloride to produce bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride, and a slurry containing bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride is obtained.

[0067] Next, in the isocyanation step, bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride is reacted with carbonyl dichloride to produce a reaction mass containing bis(isocyanatomethyl)bicyclo[2,2,1]heptane. In the isocyanation step, carbonyl dichloride is mixed with a slurry containing bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride, and the bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride and carbonyl dichloride are reacted while removing the by-product hydrogen chloride gas. The reaction between bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride and carbonyl dichloride produces bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

[0068] The supply ratio of carbonyl dichloride is, for example, 4 to 50 moles, 5 to 40 moles, or 6 to 30 moles per mole of bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride.

[0069] The reaction time for the isocyanation step is, for example, 4 to 25 hours, 6 to 20 hours, or 6 to 15 hours.

[0070] The reaction temperature in the isocyanation step is, for example, 90°C to 190°C, 100°C to 180°C, or 110°C to 170°C.

[0071] The reaction pressure (gauge pressure) in the isocyanation step is, for example, 0 MPaG to 0.6 MPaG, 0.0005 MPaG to 0.4 MPaG, 0.001 MPaG to 0.2 MPaG, 0.003 MPaG to 0.2 MPaG, 0.01 MPaG to 0.2 MPaG, 0.02 MPaG to 0.2 MPaG, or 0.03 MPaG to 0.2 MPaG. The reaction pressure (gauge pressure) in the isocyanation step is preferably greater than 0 MPaG (atmospheric pressure).

[0072] The isocyanation process is preferably carried out in a continuous manner. That is, a slurry containing bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride is continuously supplied to a reaction vessel used for the isocyanation process, and while the bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride reacts with carbonyl dichloride in the reaction vessel, reaction masses are continuously withdrawn from the reaction vessel.

[0073] Next, the gaseous components, inert solvent, and tar components are removed from the reaction mass.

[0074] The gaseous components include carbonyl dichloride that remains in the reaction mass without reacting with bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride during the isocyanation process, and hydrogen chloride gas produced as a by-product during the isocyanation process. The gaseous components are removed from the reaction mass, for example, using a known degassing tower.

[0075] The inert solvent is removed from the reaction mass by distillation, for example, using a known distillation column.

[0076] The tar components are removed from the reaction mass, for example, using a known detarrifier.

[0077] The proportion of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in the unpurified reaction mass from which gaseous components, inert solvents, and tar components have been removed is, for example, 80.0% to 99.0% by mass, 90.0% to 99.0% by mass, or 95.0% to 99.0% by mass.

[0078] Next, in the purification process, the reaction mass is purified. The purification process includes, for example, a deboiling step and a rectification step.

[0079] In the low-boiling step, low-boiling components are removed from the reaction mass. These low-boiling components have a boiling point lower than that of bis(isocyanatomethyl)bicyclo[2,2,1]heptane. In the low-boiling step, for example, the reaction mass is distilled in a low-boiling column to remove the low-boiling components.

[0080] Examples of low-boiling-level columns include tray columns and packed columns, with packed columns being preferred. The theoretical number of stages in a low-boiling-level column is, for example, 3 to 40 stages, 5 to 20 stages, or 7 to 15 stages.

[0081] The bottom temperature of the de-boiling column is, for example, 130°C to 200°C, 140°C to 190°C, or 150°C to 180°C.

[0082] The top temperature of the de-boiling column is, for example, 90°C to 160°C, 100°C to 150°C, or 110°C to 140°C.

[0083] The top pressure of the de-boiling column is, for example, 0.05 kPa to 3.0 kPa, 0.1 kPa to 2.0 kPa, or 0.2 kPa to 1.0 kPa.

[0084] The top reflux ratio of a low-boiling column is, for example, 1–80, 5–60, or 10–50.

[0085] The residence time in the low-boiling column is, for example, 0.1 to 10 hours, 0.2 to 5 hours, or 0.3 to 3 hours.

[0086] By distillation using a low-boiling column, the reaction mass from which the low-boiling components have been removed is obtained as the bottom liquid.

[0087] Next, in the rectification process, the reaction mass after the low-boiling step is further distilled (rectified) using a rectification column.

[0088] Examples of rectification columns include tray columns and packed columns, with packed columns being preferred. The theoretical number of stages in the rectification column is, for example, 1 to 20 stages, 1 to 10 stages, or 1 to 5 stages.

[0089] The bottom temperature of the rectification column is, for example, 120°C to 190°C, 130°C to 180°C, or 140°C to 170°C.

[0090] The top temperature of the rectification column is, for example, 90°C to 180°C, 110°C to 170°C, or 130°C to 160°C.

[0091] The top pressure of the rectification column is, for example, 0.05 kPa to 3.0 kPa, 0.1 kPa to 2.0 kPa, or 0.2 kPa to 1.0 kPa.

[0092] The top reflux ratio of a rectification column is, for example, 0.1–50, 0.2–20, or 0.3–10.

[0093] The residence time in the rectification column is, for example, 0.2 hours to 20 hours, 0.5 hours to 10 hours, or 1.0 hour to 10 hours.

[0094] The rectification process yields a fraction containing bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

[0095] The above-described isocyanate composition is obtained.

[0096] Furthermore, the proportion of each isomer in the isocyanate composition can be adjusted by adjusting at least one of the conditions for the de-boiling step and the conditions for the rectification step described above.

[0097] Furthermore, the proportion of each isomer in an isocyanate composition can be adjusted by mixing multiple isocyanate compositions that have different proportions of each isomer.

[0098] 3. Uses of the Isocyanate Composition The isocyanate composition described above is used as a raw material for producing resins suitable as materials for optical elements. The resin is produced by reacting an isocyanate component containing the isocyanate composition with an active hydrogen group-containing component containing an active hydrogen group-containing compound.

[0099] Compounds containing active hydrogen groups contain active hydrogen groups. An active hydrogen group is a functional group capable of generating active hydrogen. Examples of active hydrogen groups include hydroxyl groups, mercapto groups, and amino groups. Examples of compounds containing active hydrogen groups include polyols, polythiols, and polyamines.

[0100] Compounds containing active hydrogen groups can be used alone or in combination of two or more types.

[0101] The active hydrogen group-containing compound is preferably a polythiol from the viewpoint of optical properties. The active hydrogen group-containing component is preferably a polythiol composition containing polythiol as the main component.

[0102] The proportion of polythiol in the polythiol composition is, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more.

[0103] The proportion of polythiols in a polythiol composition is measured, for example, by high-performance liquid chromatography.

[0104] Polythiols have multiple mercapto groups. Polythiols do not contain the minor components described later. Examples of polythiols include aliphatic polythiols, aromatic polythiols, and heterocyclic polythiols.

[0105] Examples of aliphatic polythiols include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis(2-mercaptoethyl) ether, tetrakis(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropanetris(2-mercaptoacetate) ), trimethylolpropanetris(3-mercaptopropionate), trimethylolethanetris(2-mercaptoacetate), trimethylolethanetris(3-mercaptopropionate), pentaerythritoltetrakis(2-mercaptoacetate), pentaerythritoltetrakis(3-mercaptopropionate), bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis (mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 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, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-Dimercapto-1,4-Dithiane, 2,5-Dimercaptomethyl-2,5-dimethyl-1,4-Dithiane, and esters thereof of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercapto Examples include propinates), bis(2-mercaptoethyl thiodiglycolate, bis(2-mercaptoethyl thiodipropionate), bis(2-mercaptoethyl dithiodiglycolate), bis(2-mercaptoethyl dithiodipropionate), bis(2-mercaptoethyl dithiodipropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and tris(mercaptoethylthio)methane.

[0106] Examples of aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,5-naphthalenedithiol, and 2,6-naphthalenedithiol.

[0107] Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, and bismuthiol.

[0108] Polythiols can be used alone or in combination of two or more types.

[0109] Furthermore, as polythiols, preferably, are 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptomethyl) At least one selected from the group consisting of captoethyl sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropionate).

[0110] The polythiol composition may contain auxiliary components.

[0111] As a minor component, for example, compound A is obtained in which at least one of the multiple mercapto groups of the polythiol described above is substituted with a functional group shown in the following chemical formula (1).

[0112] Chemical formula (1):

[0113]

[0114] When the polythiol composition contains compound A, the area P of the polythiol peak in high-performance liquid chromatography of the polythiol composition ｔｈｉｏｌ The area P of the peak of compound A relative to the given values. Ａ Ratio R ＡThis is calculated by the following formula (3). In this case, high-performance liquid chromatography is performed under the measurement conditions described in paragraph

[0041] of International Publication No. 2022 / 102625.

[0115] Formula (3): R Ａ = (P Ａ / P ｔｈｉｏｌ ) × 100 Ratio R Ａ For example, these ranges are 0.01% to 3.0%, 0.01% to 1.5%, or 0.01% to 0.5%.

[0116] Ratio R Ａ If the above range is maintained, the pot life of the polymerizable composition obtained from the polythiol composition and the polyisocyanate composition can be kept good, and further, by curing the polymerizable composition, a plastic lens made of polythiourethane resin with excellent quality in terms of hue, transparency, striations, etc. can be obtained.

[0117] Furthermore, if the polythiol composition contains at least one polythiol selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, the polythiol composition may also contain a compound represented by the following chemical formula (2) (hereinafter referred to as compound B) as a minor component.

[0118] Chemical formula (2):

[0119]

[0120] (In chemical formula (2), m and n each independently represent 0 or 1, and m + n = 1.) When the polythiol composition contains compound B, the sum of the areas of all detected peaks P is used in high-performance liquid chromatography measurement of the polythiol composition. ＳＵＭ The area of ​​the peak P of compound B relative to the given value. Ｂ Ratio R ＢThis is calculated using the following formula (4). In this case, the high-performance liquid chromatography measurement is performed under the measurement conditions described in paragraph

[0049] of International Publication No. 2022 / 138865.

[0121] Formula (4): R Ｂ = (P Ｂ / P ｓｕｍ ) × 100 Ratio R Ｂ For example, these ranges include: greater than 0 and 10.0% or less, 0.02% to 9.0%, 0.04% to 8.0%, 1.0% to 7.0%, 2.0% to 6.0%, 3.0% to 6.0%, or 4.0% to 6.0%.

[0122] Ratio R Ｂ If the above upper limit is below, the light resistance of the resin produced from the polythiol composition can be improved. Also, the ratio R Ｂ If the value is above the lower limit mentioned above, the dyeability of the resin produced from the polythiol composition can be improved.

[0123] The resin is manufactured, for example, by casting. In casting, first, an isocyanate component and an active hydrogen group-containing component are mixed in a ratio such that the isocyanate groups in the isocyanate component are 0.8 to 1.2 times the number of active hydrogen groups (amino groups, thiol groups, or hydroxyl groups) in the active hydrogen group-containing component. The resulting mixture is a polymerizable composition containing the isocyanate composition and the active hydrogen group-containing component.

[0124] Furthermore, known additives may be mixed into the polymerizable composition. Examples of additives include curing catalysts, stabilizers (acidic phosphate esters), and ultraviolet absorbers.

[0125] Next, the polymerizable composition is poured into a mold and then heat-cured. This yields a molded body made of resin. In other words, the resin is the cured product of the polymerizable composition.

[0126] When the active hydrogen group-containing component contains polythiol, the resulting molded article exhibits excellent transparency.

[0127] Furthermore, because the above-mentioned isocyanate composition contains five isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in specific proportions, the resulting molded articles exhibit excellent heat resistance and dyeability.

[0128] More specifically, the glass transition temperature (Tg) of the obtained molded article is, for example, 100.0°C or higher, 105.0°C or higher, or 110.0°C or higher. The glass transition temperature (Tg) of the obtained molded article is, for example, 120.0°C or lower. The glass transition temperature (Tg) of the obtained molded article may be between 100.0°C and 120.0°C, between 105.0°C and 120.0°C, or between 110.0°C and 120.0°C.

[0129] If the resulting molded body possesses the above-described physical properties, it is suitable as an optical element.

[0130] Examples of optical elements include lenses, sheets, and films, with lenses being preferred.

[0131] Examples of lenses include clear lenses, sunglass lenses, polarized lenses, eyeglass lenses, camera lenses, pickup lenses, and contact lenses.

[0132] The applications of isocyanate compositions are not limited to the optical materials described above. Examples of isocyanate compositions include inks, transfer foils, adhesives, binders, gels, elastomers, foams, adhesives, one-component curing sealants, RIM molded products, micro-foamed polyurethanes, various microcapsules, aqueous resins, thermosetting resins, active energy ray (e.g., electron beams, ultraviolet light) curable resins, artificial and synthetic leathers, slush powders, robot components, mobility components, healthcare materials, carbon fiber reinforced plastic (CFRP) base resins, transparent rubbers, and transparent rigid resins. Examples include waterproofing materials, films, sheets, tubes, blades, speakers, sensors, organic EL components, solar power generation components, humanoid robot components, wearable components, sports equipment, leisure goods, medical supplies, nursing care supplies, housing components, acoustic components, lighting components, chandeliers, streetlights, gaskets, vibration isolation / damping / seismic isolation components, soundproofing components, daily necessities, general merchandise, cushions, bedding, stress absorption materials, stress relaxation materials, automotive interior and exterior parts, transportation equipment components, office automation equipment components, general merchandise surface protection components, self-healing materials, and health equipment.

[0133] Preferred applications of the isocyanate composition include the optical materials, elastomers, foams, and one-component curing sealants mentioned above.

[0134] 4. Effects The isocyanate composition and polymerizable composition of the present invention contain five isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in specific proportions. Therefore, resins produced from the isocyanate composition exhibit excellent dyeability.

[0135] Furthermore, the molded articles, optical elements, and lenses of the present invention are made of the resin described above. Therefore, the molded articles, optical elements, and lenses have excellent dyeability.

[0136] The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Specific numerical values ​​such as blending ratios (content percentages), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than or equal to") of the blending ratios (content percentages), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above. Note that the "percentage" of each component is based on mass.

[0137] 1. Preparation of the isocyanate composition (1) Example 1 Using the "mixture of 2,5-bis(aminomethyl)bicyclo[2,2,1]heptane and 2,6-bis(aminomethyl)bicyclo[2,2,1]heptane" described in paragraph

[0085] (Example 2) of International Publication 2012 / 153509, a "mixture of 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane" with a purity of 99.0% by mass was obtained by the method described in paragraph

[0086] (Example 3) of International Publication 2012 / 153509.

[0138] (2) Example 2 An isocyanate composition was obtained in the same manner as in Example 1, except that the NBDA described in paragraph

[0032] of Japanese Patent Application Publication No. 2011-201786 was used instead of the "mixture of 2,5-bis(aminomethyl)bicyclo[2,2,1]heptane and 2,6-bis(aminomethyl)bicyclo[2,2,1]heptane" described in paragraph

[0085] (Example 2) of International Publication No. 2012 / 153509.

[0139] (3) Example 3 The isocyanate composition obtained in Example 1 and the isocyanate composition obtained in Example 2 were mixed to obtain an isocyanate composition.

[0140] (4) Comparative Example 1 An isocyanate composition was obtained by mixing 70 parts by mass of the isocyanate composition obtained in Example 3 with 30 parts by mass of an isocyanate composition containing 85.7% by mass of the fifth isomer.

[0141] The "isocyanate composition containing 85.7% by mass of the fifth isomer" is a portion of the fraction separated by distillation (20 theoretical plates, reflux ratio 20) in the production of the isocyanate composition of Comparative Example 3, which will be described later. The "isocyanate composition containing 85.7% by mass of the fifth isomer" further contains 2.6% by mass of the first isomer, 3.6% by mass of the second isomer, 7.8% by mass of the third isomer, and 0.2% by mass of the fourth isomer.

[0142] (5) Comparative Example 2 An isocyanate composition was obtained by mixing 50 parts by mass of the isocyanate composition obtained in Example 3 with 50 parts by mass of the above-mentioned "isocyanate composition containing 85.7% by mass of the fifth isomer".

[0143] (6) Comparative Example 3 An isocyanate composition was obtained in the same manner as in Example 1, except that a mixture of 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane was distilled under conditions of 20 theoretical plates and a top reflux ratio of 20.

[0144] 2. High-performance liquid chromatography The proportion of each isomer of bis(isocyanatomethyl)bicyclo[2.2.1]heptane in the isocyanate composition obtained in each example and comparative example was measured by the following method:

[0145] To a mixture of 100 mg (1.33 mmol) of N-methylmethanolamine and 5 ml of acetonitrile, 50 mg of an isocyanate composition (bis(isocyanatomethyl)bicyclo[2.2.1]heptane: 0.23 mmol) was added dropwise, the mixture was stirred for 1 hour, and then allowed to stand for 12 hours.

[0146] As a result, bis(isocyanatomethyl)bicyclo[2.2.1]heptane in the isocyanate composition was derivatized with N-methylmethanolamine, and a sample containing the N-methylmethanolamine derivative of bis(isocyanatomethyl)bicyclo[2.2.1]heptane was obtained.

[0147] The obtained samples were analyzed by high-performance liquid chromatography under the "Measurement Condition A" described above to determine the proportion of each isomer of bis(isocyanatomethyl)bicyclo[2.2.1]heptane in the isocyanate composition. The results are shown in Table 1.

[0148] 3. Manufacturing of molded articles 50.6 parts by mass of the isocyanate composition of each example and each comparative example, 0.035 parts by mass of dibutyltin dichloride as a polymerization catalyst, 0.10 parts by mass of an internal release agent for MR (manufactured by Mitsui Chemicals, Inc.), and 1.50 parts by mass of 2-(2-hydroxy-5-tert-butyl-octylphenyl)benzotriazole (manufactured by Kyodo Pharmaceutical Co., Ltd.) as an ultraviolet absorber were uniformly mixed to obtain a mixed solution.

[0149] To the resulting mixture, 25.5 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a polythiol and 23.9 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) as a polythiol were added and the mixture was uniformly mixed at room temperature (25°C) to obtain a polymerizable composition.

[0150] Next, the polymerizable composition was degassed at 400 Pa.

[0151] Next, the degassed polymerizable composition was passed through a filter with a pore size of 1 μm and injected into a molding mold.

[0152] Next, the molding mold into which the polymerizable composition was injected was placed in an oven and heated from 25°C to 120°C over 24 hours to cure the polymerizable composition.

[0153] Next, the molding mold was removed from the oven, and the cured polymerizable composition (resin) was released from the molding mold.

[0154] Subsequently, the cured product (resin) of the polymerizable composition was annealed at 120°C for 2 hours.

[0155] 4. Evaluation of Resin Properties (1) Heat Resistance Test specimens measuring 10 mm in length, 10 mm in width, and 2.5 mm in thickness were prepared from the obtained resin, and the glass transition temperature (Tg) was measured using the TMA penetration method (50 g load, 0.5 mm diameter pin tip, heating rate 10 °C / min) with a Shimadzu TMA-60 thermomechanical analyzer. A higher glass transition temperature (Tg) indicates better heat resistance.

[0156] Table 1 shows the glass transition temperature (Tg) of the resins prepared using the isocyanate compositions of each example and comparative example. (2) A flat plate-shaped test specimen with a thickness of 2.5 mm was prepared, and the light transmittance (%) of the test specimen at 461 nm (maximum absorption wavelength in the range of 400 nm to 800 nm) was measured using a UV-Vis spectrophotometer (UV-1800, manufactured by Shimadzu).

[0157] Next, the test specimens were immersed in a 50 ppm aqueous dispersion of "Brown S-3R" (a dye manufactured by Mitsui Chemicals, Inc.) at 85°C for 30 minutes. This stained the test specimens.

[0158] Next, the light transmittance (%) of the stained specimens at 461 nm was measured.

[0159] The difference between the light transmittance before staining and the light transmittance after staining (Δ-light transmittance) was used as an indicator of staining performance. A larger Δ-light transmittance value indicates better staining performance. The results are shown in Table 1.

[0160]

[0161] The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims below.

[0162] The isocyanate composition, polymerizable composition, resin, and molded articles of the present invention can be used, for example, in the manufacture of optical elements such as lenses.

Claims

1. It contains five isomers of bis(isocyanatomethyl)bicyclo[2,2,1]heptane, and when these five isomers are derivatized with N-methylethanolamine and analyzed by high-performance liquid chromatography in reverse-phase mode, they are separated and detected as a first isomer N-methylethanolamine derivative, a second isomer N-methylethanolamine derivative detected after the first isomer N-methylethanolamine derivative, a third isomer N-methylethanolamine derivative detected after the second isomer N-methylethanolamine derivative, a fourth isomer N-methylethanolamine derivative detected after the third isomer N-methylethanolamine derivative, and a fifth isomer N-methylethanolamine derivative detected after the fourth isomer N-methylethanolamine derivative, and the molecular weight of each of the five isomer N-methylethanolamine derivatives is 356. An isocyanate composition in which, when detected using an absorbance detector at a detection wavelength of 220 nm, the ratio of the peak area of ​​the fifth isomer of N-methylethanolamine derivative to the total peak area of ​​each of the five isomers of N-methylethanolamine derivative is 10.0% or more and 40.0% or less.

2. The isocyanate composition according to claim 1, wherein the ratio of the peak area of ​​the fourth isomer N-methylethanolamine derivative to the total peak area of ​​each of the five isomer N-methylethanolamine derivatives is 0.1% or more and 5.0% or less.

3. The isocyanate composition according to claim 1, wherein the ratio of the peak area of ​​the first isomer N-methylethanolamine derivative to the total peak area of ​​each of the five isomer N-methylethanolamine derivatives is 16.0% or more and 28.0% or less.

4. The isocyanate composition according to claim 1, wherein the ratio of the peak area of ​​the second isomer N-methylethanolamine derivative to the total peak area of ​​each of the five isomer N-methylethanolamine derivatives is 25.0% or more and 40.0% or less.

5. The isocyanate composition according to claim 1, wherein the ratio of the peak area of ​​the third isomer N-methylethanolamine derivative to the total peak area of ​​each of the five isomer N-methylethanolamine derivatives is 19.0% or more and 30.0% or less.

6. A polymerizable composition comprising the isocyanate composition according to any one of claims 1 to 5 and an active hydrogen group-containing component.

7. The active hydrogen group-containing component is 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, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptomethyl) The polymerizable composition according to claim 6, comprising at least one polythiol selected from the group consisting of captoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiethane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, tris(mercaptomethylthio)methane, and ethylene glycol bis(3-mercaptopropionate).

8. A resin which is a cured product of the polymerizable composition according to claim 6.

9. A molded article made of the resin described in claim 8.

10. An optical element which is a molded body according to claim 9.

11. A lens, which is an optical element according to claim 10.

12. Use of the isocyanate composition according to any one of claims 1 to 5 for the manufacture of a lens.

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