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

Abstract

This isocyanate composition contains: bis(isocyanatomethyl)bicyclo[2.2.1]heptane; and a specific compound having a molecular weight of 189, which is detected separately from bis(isocyanatomethyl)bicyclo[2.2.1]heptane by gas chromatography.

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 heat resistance is desired.

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

[0006] The present invention [1] includes an isocyanate composition comprising bis(isocyanatomethyl)bicyclo[2,2,1]heptane and a specific compound that is detected separately from bis(isocyanatomethyl)bicyclo[2,2,1]heptane by gas chromatography and has a molecular weight of 189.

[0007] The present invention [2] includes the isocyanate composition of [1] above, wherein, when a flame ionization detector is used in gas chromatography, the ratio of the peak area of ​​the specific compound to the peak area of ​​bis(isocyanatomethyl)bicyclo[2,2,1]heptane is 0.009000 or less.

[0008] The present invention [3] relates to a specific compound whose molecular formula is C １２ H １５ The present invention comprises the isocyanate composition of [1] or [2] above, which is NO.

[0009] The present invention [4] comprises any one of the isocyanate compositions [1] to [3] above, wherein the specific compound has an isocyanate group.

[0010] The present invention [5] includes any one of the isocyanate compositions of [1] to [4] above, in which the specific compound is represented by any one of the following structural formulas (1) to (4).

[0011] Structural formula (1):

[0012]

[0013] Structural formula (2):

[0014]

[0015] Structural formula (3):

[0016]

[0017] Structural formula (4):

[0018]

[0019] The present invention [6] includes a polymerizable composition containing any one of the isocyanate compositions of [1] to [5] above and an active hydrogen group-containing component.

[0020] The present invention [7] is a compound in which 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 The polymerizable composition [6] above contains at least one polythiol selected from the group consisting of (mercaptoethyl) 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).

[0021] The present invention [8] includes a resin which is a cured product of the polymerizable composition described in [6] above.

[0022] The present invention [9] includes a molded article made of the resin described in [8] above.

[0023] The present invention

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

[0024] The present invention

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

[10] above.

[0025] The present invention

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

[0026] The isocyanate composition and polymerizable composition of the present invention contain bis(isocyanatomethyl)bicyclo[2,2,1]heptane and the specified compound described above. Therefore, the resin produced from the isocyanate composition has excellent heat resistance.

[0027] Furthermore, the molded article, optical element, and lens of the present invention are made of the resin described above. Therefore, the molded article, optical element, and lens have excellent heat resistance.

[0028] 1. Isocyanate composition The isocyanate composition contains bis(isocyanatomethyl)bicyclo[2,2,1]heptane as its main component.

[0029] Examples of bis(isocyanatomethyl)bicyclo[2,2,1]heptanes include 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane. The isocyanate composition may contain both 2,5-bis(isocyanatomethyl)bicyclo[2,2,1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

[0030] 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 condition A. (Gas chromatography measurement condition A) Column: DB-5 (inner diameter: 0.53 mm, length: 60 m, film thickness: 1.5 μm) Oven temperature: Increased from 130°C to 190°C at 3°C / min, then increased to 280°C at 10°C / min after reaching 190°C. Held at 280°C for 15 minutes Inlet temperature: 280°C Detector temperature: 300°C Carrier flow rate: 25 mL / min Sample concentration: 150 mg of isocyanate composition / 5 ml of dichloromethane Injection method: Pulsed splitless method Injection volume: 1.0 μL Detector: Flame ionization detector (FID) In ​​gas chromatography under measurement condition A, the sum of the areas of all peaks detected from the isocyanate composition P ＳＵＭ The area of ​​the peak P for bis(isocyanatomethyl)bicyclo[2,2,1]heptane relative to the above. ＢＩＢＨ Ratio R ＢＩＢＨ It is calculated using the following formula (1).

[0031] Formula (1): R ＢＩＢＨ = (P ＢＩＢＨ / P ＳＵＭ ) × 100 Ratio RＢＩＢＨ 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.

[0032] 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%.

[0033] 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 99.60% 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.

[0034] The ratio (purity) of bis(isocyanatomethyl)bicyclo[2,2,1]heptane in the isocyanate composition may be 98. percentages by mass to 99.95% by mass, 99.00% by mass to 99.95% by mass, 99.30% by mass to 99.95% by mass, or 99.60% by mass to %.

[0035] The isocyanate composition contains a specific compound S as a subcomponent. The specific compound S is separated and detected from bis(isocyanatomethyl)bicyclo[2,2,1]heptane in gas chromatography. Specifically, the specific compound S is detected at a retention time of 11.0 minutes to 12.4 minutes in gas chromatography under the above measurement conditions A.

[0036] In gas chromatography under measurement conditions A, the total area P of all peaks detected from the isocyanate composition ＳＵＭ of the area P of the peak of the specific compound S Ｓ The ratio R Ｓ is calculated by the following formula (2).

[0037] Formula (2): R Ｓ = (P Ｓ / P ＳＵＭ ) × 100 The ratio RＳ For example, this could be greater than 0, 0.0010% or more, 0.0015% or more, 0.0020% or more, 0.0100% or more, 0.0200% or more, or 0.0300% or more. (Percentage R) Ｓ If the value is above the lower limit mentioned above, the heat resistance of the resulting resin can be improved.

[0038] Ratio R Ｓ For example, this could be 0.8000% or less, 0.5000% or less, 0.1000% or less, 0.0850% or less, or 0.0800% or less. (Percentage R) Ｓ If the value is above the lower limit mentioned above, the increase in the yellowness of the resulting resin can be suppressed.

[0039] Ratio R Ｓ This may be greater than 0.0000 and less than or equal to 0.8000%, between 0.0010% and 0.5000%, between 0.0015% and 0.1000%, between 0.0020% and 0.0850%, between 0.0100% and 0.0800%, between 0.0200% and 0.0800%, or between 0.0300% and 0.0800%.

[0040] In gas chromatography under measurement condition A (i.e., when a flame ionization detector is used in gas chromatography), the area P of the peak for bis(isocyanatomethyl)bicyclo[2,2,1]heptane ＢＩＢＨ The area P of the peak for the specific compound S against the given parameters. Ｓ The ratio (P Ｓ / P ＢＩＢＨ ) is, for example, 0.010000 or less, 0.009000 or less, or 0.005000 or less. Ratio (P Ｓ / P ＢＩＢＨ If the above upper limit is below this value, the increase in the yellowness of the resulting resin can be suppressed.

[0041] Ratio (P Ｓ / P ＢＩＢＨ ) are, for example, 0.000010 or more, 0.000020 or more, 0.000035 or more, 0.000800 or more, 0.001000 or more, or 0.004000 or more. Ratio (P Ｓ / P ＢＩＢＨ If the value is above the lower limit mentioned above, the heat resistance of the resulting resin can be improved.

[0042] Ratio (P Ｓ / P ＢＩＢＨ ) may be 0.000010 to 0.010000, 0.000020 to 0.009000, 0.000035 to 0.005000, 0.000800 to 0.005000, 0.001000 to 0.005000, or 0.004000 to 0.005000.

[0043] The molecular weight of specific compound S is 189. The molecular weight of specific compound S is measured by gas chromatography-mass spectrometry under the following measurement conditions B. (Measurement conditions B for gas chromatography-mass spectrometry) Column: J&W 122-5562 DB-5ms (Inner diameter: 0.25 mm, Length: 60 m, Film thickness: 0.25 μm) Oven temperature: Increased from 40°C to 330°C at 10°C / min, held at 330°C for 4 minutes after reaching 330°C Inlet temperature: 280°C Detector temperature: 330°C Quadrupole temperature: 150°C Ion source temperature: 230°C Detection method (Scan method): m / z: 19-500 Carrier gas: He Carrier flow rate: 1.5 mL / min Sample preparation: 100 mg isocyanate composition / 10 ml dichloromethane Injection method: Split method (100:1) Injection volume: 1.0 μL The molecular formula of specific compound S is C １２ H １５ The answer is NO. Specific compound S has an isocyanate group. Specifically, specific compound S is an isocyanate compound represented by the following structural formulas (1) to (4).

[0044] Structural formula (1):

[0045]

[0046] Structural formula (2):

[0047]

[0048] Structural formula (3):

[0049]

[0050] Structural formula (4):

[0051]

[0052] The isocyanate compound shown in structural formula (1) is 3-isocyanatomethyltricyclo[5.2.1.0 ２，６ It is deca-8-ene. The isocyanate compound shown in structural formula (2) is 4-isocyanatomethyltricyclo[5.2.1.0 ２，６ It is deca-8-ene. The isocyanate compound shown in structural formula (3) is 8-isocyanatomethyltricyclo[5.2.1.0 ２，６ It is deca-3-ene. The isocyanate compound shown in structural formula (4) is 9-isocyanatomethyltricyclo[5.2.1.0 ２，６ It's Deca-3-En.

[0053] 2. Method for producing isocyanate compositions A method for producing isocyanate compositions will be described.

[0054] A method for producing an isocyanate composition includes, for example, a synthesis step, a purification step, and a mixing step.

[0055] 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.

[0056] 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.

[0057] Examples of bis(aminomethyl)bicyclo[2.2.1]heptanes include mixtures of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] The reaction time for the isocyanation step is, for example, 4 to 25 hours, 6 to 20 hours, or 6 to 15 hours.

[0068] 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.

[0069] 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).

[0070] 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.

[0071] Next, the gaseous components, inert solvent, and tar components are removed from the reaction mass.

[0072] 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.

[0073] The inert solvent is removed from the reaction mass by distillation, for example, using a known distillation column.

[0074] The tar components are removed from the reaction mass, for example, using a known detarrifier.

[0075] 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.

[0076] Next, in the purification process, the reaction mass is purified. The purification process includes, for example, a deboiling step and a rectification step.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] The top reflux ratio of a low-boiling column is, for example, 1–80, 5–60, or 10–50.

[0083] 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.

[0084] 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.

[0085] Next, in the rectification process, the reaction mass after the low-boiling step is further distilled (rectified) using a rectification column.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] The top reflux ratio of a rectification column is, for example, 0.1–50, 0.2–20, or 0.3–10.

[0091] 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.

[0092] The rectification process yields a fraction containing bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

[0093] In the mixing step, the specific compound mentioned above is added to the fraction obtained in the rectification step and mixed.

[0094] This yields the isocyanate composition described above.

[0095] Furthermore, the specific compound to be added to the fraction obtained in the rectification process may be contained in the low-boiling point component removed from the reaction mass in the low-boiling point de-boiling step described above. In this case, the specific compound may be separated from the low-boiling point component and added to the fraction obtained in the rectification process.

[0096] Alternatively, the specific compound described above may be synthesized separately and added to the fraction obtained in the rectification process.

[0097] 3. Uses of the Isocyanate Composition The isocyanate composition described above is used as a raw material for resins. Resins are produced by reacting an isocyanate component containing the isocyanate composition with an active hydrogen group-containing component containing an active hydrogen group-containing compound.

[0098] 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.

[0099] Compounds containing active hydrogen groups can be used alone or in combination of two or more types.

[0100] 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.

[0101] 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.

[0102] The proportion of polythiols in a polythiol composition is measured, for example, by high-performance liquid chromatography.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] Examples of heterocyclic polythiols include 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, and bismuthiol.

[0107] Polythiols can be used alone or in combination of two or more types.

[0108] 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).

[0109] The polythiol composition may contain auxiliary components.

[0110] 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).

[0111] Chemical formula (1):

[0112]

[0113] 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.

[0114] 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%.

[0115] 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.

[0116] 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.

[0117] Chemical formula (2):

[0118]

[0119] (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 measured in high-performance liquid chromatography of the polythiol composition. ＳＵＭ The area P of the peak 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.

[0120] 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%.

[0121] 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.

[0122] 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.

[0123] Furthermore, known additives may be mixed into the polymerizable composition. Examples of additives include curing catalysts, stabilizers (acidic phosphate esters), and ultraviolet absorbers.

[0124] 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.

[0125] When the active hydrogen group-containing component contains polythiol, the resulting molded article exhibits excellent transparency.

[0126] Furthermore, because the isocyanate composition described above contains bis(isocyanatomethyl)bicyclo[2,2,1]heptane and the specified compound described above, the resulting molded article has low yellowness and excellent heat resistance.

[0127] 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.

[0128] The Y.I. value of the obtained molded article is, for example, 4.00 or less, 3.90 or less, or 3.80 or less. The Y.I. value of the obtained molded article is, for example, 3.00 or more. The Y.I. value of the obtained molded article may be 3.00 to 4.00, 3.00 to 3.90, or 3.00 to 3.80.

[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 bis(isocyanatomethyl)bicyclo[2,2,1]heptane and the specified compound described above. Therefore, the resin produced from the isocyanate composition has excellent heat resistance.

[0135] Furthermore, the molded article, optical element, and lens of the present invention are made of the resin described above. Therefore, the molded article, optical element, and lens have excellent heat resistance.

[0136] 5. Modifications (1) The method for synthesizing bis(isocyanatomethyl)bicyclo[2,2,1]heptane is not limited to the hydrochloride salt method described above. Examples of methods for synthesizing bis(isocyanatomethyl)bicyclo[2,2,1]heptane include a gas-phase method in which vaporized bis(aminomethyl)bicyclo[2.2.1]heptane is reacted with carbonyl dichloride, a one-step method in which bis(aminomethyl)bicyclo[2.2.1]heptane is reacted directly with carbonyl dichloride in one step, and a two-step cold-hot method in which bis(aminomethyl)bicyclo[2.2.1]heptane is reacted with carbonyl dichloride at a low temperature followed by a reaction at a high temperature. In these methods, bis(isocyanatomethyl)bicyclo[2,2,1]heptane is obtained by the reaction of bis(aminomethyl)bicyclo[2.2.1]heptane with carbonyl dichloride. Furthermore, as a method for synthesizing bis(isocyanatomethyl)bicyclo[2,2,1]heptane, one example is the non-dichloride carbonyl method, which involves thermal decomposition of xylylenedicarbamate to obtain bis(isocyanatomethyl)bicyclo[2,2,1]heptane.

[0137] (2) The production of the isocyanate composition does not have to be carried out continuously in the same plant. For example, a specific compound can be added to an isocyanate composition produced in the first plant at the second plant.

[0138] 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.

[0139] 1. Production of isocyanate compositions (1) Examples 1 to 5 (1-1) Production reactor for bis(isocyanatomethyl)bicyclo[2.2.1]heptane, with an internal volume of 2 m³ ３An autoclave was used. The reactor was equipped with a reflux condenser, a stirring blade, a thermometer, a hydrogen chloride gas inlet pipe, a carbonyl dichloride inlet pipe, a raw material tank, a raw material charging pump, and a pressure regulator.

[0140] 958 kg of o-dichlorobenzene was charged into the reactor. Additionally, 154.2 kg (1000 mol) of bis(aminomethyl)bicyclo[2.2.1]heptane and 702 kg of o-dichlorobenzene were charged into the raw material tank (total amine concentration 8.5% by mass).

[0141] Bis(aminomethyl)bicyclo[2.2.1]heptane is a mixture of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane.

[0142] Next, the temperature of the o-dichlorobenzene in the reactor was raised to 120°C. Then, the pressure in the reactor was adjusted to 0.01 MPa higher than atmospheric pressure.

[0143] Next, hydrogen chloride gas was introduced into the reactor at a rate of 43.8 kg / hr through a hydrogen chloride gas introduction pipe. Simultaneously, the entire mixture from the raw material tank was introduced into the reactor at a rate of 428.1 kg / hr using a raw material charging pump. In the reactor, bis(aminomethyl)bicyclo[2.2.1]heptane reacted with hydrogen chloride to obtain a slurry of bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride (salt production process).

[0144] Subsequently, hydrogen chloride gas was introduced into the reactor at a rate of 20 kg / hr while the slurry in the reactor was aged for 1 hour.

[0145] Next, the slurry in the reactor was heated to 160°C, and carbonyl dichloride was blown into the reactor at a rate of 100 kg / hr (1000 mol / hr) through a carbonyl dichloride introduction tube. The reaction between bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride and carbonyl dichloride was carried out for 8 hours while maintaining the temperature. As a result of the reaction between bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride and carbonyl dichloride, a reaction mass containing bis(isocyanatomethyl)bicyclo[2.2.1]heptane was obtained (isocyanation step).

[0146] After the isocyanation step, carbonyl dichloride and hydrogen chloride gas were removed from the reaction mass by introducing nitrogen into the reactor.

[0147] Next, the reaction mass was filtered to remove 0.5 kg (dry weight) of bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride.

[0148] Next, o-dichlorobenzene was removed from the obtained filtrate to obtain 206.9 kg of unpurified reaction mass.

[0149] In the gas chromatography under the "Measurement Condition A" described above, the ratio of the peak area of ​​bis(isocyanatomethyl)bicyclo[2.2.1]heptane to the total area of ​​all peaks detected from the unpurified reaction mass was 98.50%.

[0150] Next, the unpurified reaction mass was distilled under conditions of 20 stages and reflux ratio 20 to remove low-boiling point components from the reaction mass (de-boiling step).

[0151] In the gas chromatography under "Measurement Condition A" described above, the ratio of the peak area of ​​the specific compound to the total area of ​​all peaks detected from the low-boiling point components removed by distillation was 20.13%.

[0152] Next, the reaction mass after the deboiling step was further distilled under conditions of 20 stages and reflux ratio 5 to obtain fraction A containing bis(isocyanatomethyl)bicyclo[2.2.1]heptane.

[0153] In the gas chromatography under the "Measurement Condition A" described above, the ratio of the peak area of ​​bis(isocyanatomethyl)bicyclo[2.2.1]heptane to the total area of ​​all peaks detected in fraction A was 99.96%. Furthermore, the specific compound was not detected in fraction A.

[0154] (1-2) Production of the specific compound Low boiling point components removed during the production of bis(isocyanatomethyl)bicyclo[2.2.1]heptane were distilled under conditions of 12 stages and reflux ratio of 20 to obtain fraction B containing the specific compound.

[0155] In the gas chromatography under "Measurement Condition A" described above, the ratio of the peak area of ​​the specific compound to the total area of ​​all peaks detected in fraction B was 83.40%.

[0156] (1-3) Mixing step: Distillate A and Distillate B were mixed to prepare the isocyanate compositions of each example.

[0157] For each example of the isocyanate composition, the ratio of the peak area of ​​bis(isocyanatomethyl)bicyclo[2.2.1]heptane to the total area of ​​all peaks detected in gas chromatography under "Measurement Condition A" described above, the ratio of the peak area of ​​the specific compound to the total area of ​​all peaks detected in gas chromatography under "Measurement Condition A" described above, and the ratio of the peak area of ​​the specific compound to the peak area of ​​bis(isocyanatomethyl)bicyclo[2.2.1]heptane are shown in Table 1 below.

[0158] (2) The isocyanate composition of Comparative Example 1 was prepared in the same manner as in the above-described example, except that comparative example fraction B was not mixed with fraction A.

[0159] 2. Production of Molded Articles To obtain a polymerizable composition, 51 parts by mass of the isocyanate composition of each example and comparative example were uniformly mixed at room temperature (25°C) with dibutyltin dichloride as a polymerization catalyst (600 ppm by mass in the polymerizable composition), tinuvin 329 (manufactured by BASF Japan, 2-(2H-benzotriazole-2-yl)-4-tert-octylphenol, 500 ppm by mass in the polymerizable composition) as an ultraviolet absorber, zelec UN (manufactured by Stepan, acidic phosphate ester, 1000 ppm by mass in the polymerizable composition) as a mold release agent, 25 parts by mass of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a polythiol, and 24 parts by mass of pentaerythritol tetrakis(3-mercaptopropionate) as a polythiol.

[0160] Next, the polymerizable composition was filtered under reduced pressure using a polytetrafluoroethylene filter. Afterward, the polymerizable composition was degassed at 600 Pa.

[0161] Next, the degassed polymerizable composition was injected between a pair of glass molds secured with tape.

[0162] Next, the glass molds into which the polymerizable composition was injected were placed in an oven and heated from 10°C to 120°C over 17 hours to cure the polymerizable composition.

[0163] Subsequently, the glass mold was removed from the oven, and the cured polymerizable composition (resin) was released from the glass mold. This yielded the cured polymerizable composition (resin).

[0164] 3. 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.

[0165] Table 1 shows the glass transition temperature (Tg) of the resins prepared using the isocyanate compositions of each example and comparative example. (2) Yellowness (Y.I. value) A disc with a thickness of 9 mm and a diameter of 75 mm was prepared from the obtained resin, and the Y.I. value was determined using a Konica Minolta CR-400 spectrophotometer.

[0166] A smaller Y.I. value indicates a lower degree of yellowness in the resin, while a larger Y.I. value indicates a higher degree of yellowness in the resin.

[0167] Table 1 shows the Y.I. values ​​of the resins prepared using the isocyanate compositions of each example and comparative example.

[0168] 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.

[0169] 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. An isocyanate composition comprising bis(isocyanatomethyl)bicyclo[2,2,1]heptane and a specific compound that is detected separately from bis(isocyanatomethyl)bicyclo[2,2,1]heptane by gas chromatography and has a molecular weight of 189.

2. The isocyanate composition according to claim 1, wherein, when a flame ionization detector is used in gas chromatography, the ratio of the peak area of ​​the specific compound to the peak area of ​​bis(isocyanatomethyl)bicyclo[2,2,1]heptane is 0.009000 or less.

3. The molecular formula of the aforementioned specific compound is C １２ H １５ The isocyanate composition according to claim 1, wherein NO.

4. The isocyanate composition according to claim 1, wherein the specified compound has an isocyanate group.

5. The isocyanate composition according to claim 1, wherein the specified compound is represented by any one of the following structural formulas (1) to (4): Structural formula (1): Structural formula (2): Structural formula (3): Structural formula (4):

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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