Polythiol composition, polymerizable composition, resin, molded body, optical material, and lens

Abstract

Provided is a polythiol composition including a polythiol compound (A) and a compound represented by the following formula (1), wherein, in a high performance liquid chromatography measurement, the peak area of the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of all compounds contained in the polythiol composition. In formula (1), X represents a carbon atom or a sulfur atom.

Description

Technical Field

[0001] This disclosure relates to polythiol compositions, polymeric compositions, resins, molded articles, optical materials, and lenses. Background Technology

[0002] Plastic lenses are lighter and less prone to breakage than inorganic lenses, and they can also be stained. Therefore, in recent years, plastic lenses have rapidly gained popularity in optical components such as eyeglass lenses and camera lenses.

[0003] Resins for plastic lenses are required to have higher performance, including higher refractive index, higher Abbe number, lower specific gravity, and higher heat resistance. To date, various resin materials for lenses have been developed and used.

[0004] For example, Patent Document 1 describes a thiol compound represented by a specific structural formula.

[0005] For example, Patent Document 2 describes a method for manufacturing a polythiol compound, including: reacting 2-mercaptoethanol with a specific epihaloalcohol compound represented by formula (1) at a temperature of 10 to 50°C to obtain a polyol compound represented by formula (2); reacting the obtained polyol compound represented by formula (2) with thiourea in the presence of hydrogen chloride to obtain an isothiourea onion salt; adding ammonia water to a reaction solution containing the obtained isothiourea onion salt within 80 minutes, while maintaining the temperature of the reaction solution at 15 to 60°C, to hydrolyze the isothiourea onion salt to obtain a polythiol compound represented by formula (5); and adding hydrochloric acid with a concentration of 25 to 36% to a solution containing the obtained polythiol compound, and washing the solution at a temperature of 10 to 50°C to purify the polythiol compound.

[0006] Patent Document 1: Japanese Patent Application Publication (JP-A) No. H02-270859 Patent Document 2: WO 2014-027427A Summary of the Invention

[0007] Technical issues For resins obtained by curing polymeric compositions containing polythiol compounds, it is sometimes required that they have a reduced yellowness index and devitrification.

[0008] In fact, polymeric compositions containing polythiol compounds usually contain other compounds besides polythiol compounds.

[0009] The inventors of this application have discovered that when the polymerizable composition contains compounds other than polythiols, there is a tendency for the yellowness index and devitrification of the resulting resin to be impaired.

[0010] The inventors of this application conducted various studies on the above trends and found that it is sometimes difficult to obtain resins with reduced yellowness index and devitrification.

[0011] One embodiment of this disclosure aims to provide a polythiol composition capable of producing a resin with a reduced yellowness index.

[0012] Solution to the problem The means to solve the above problems include the following implementation methods.

[0013] <1> A polythiol composition comprising: Polythiol compound (A), and The compound represented by the following formula (1), wherein, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of all compounds contained in the polythiol composition: In formula (1), X represents -CH2- or sulfur atom.

[0014] <2> according to <1> The polythiol composition wherein the polythiol compound (A) comprises a polythiol compound obtained from a raw material comprising 2-mercaptoethanol and thiourea.

[0015] <3> according to <1> or <2> The polythiol composition wherein the polythiol compound (A) comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane or a mixture comprising 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.

[0016] <4> according to <1> to <3> The polythiol composition described in any one of the following examples comprises: Polythiols containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (A); and The compound represented by the following formula (1), wherein, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of all compounds contained in the polythiol composition: In formula (1), X represents -CH2- or sulfur atom.

[0017] <5> according to <1> to <4> The polythiol composition according to any one of the following, wherein, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is greater than 0 with respect to the total peak area 100 of all compounds contained in the polythiol composition.

[0018] <6> Polymerizable composition comprising: according to <1> to <5> The polythiol composition described in any one of the following, and Polyisocyanate compounds.

[0019] <7> according to <6> The polymerizable composition wherein the polyisocyanate compound comprises at least one selected from pentamethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, isophorone diisocyanate, bis(isocyanate-methyl)cyclohexane, bis(isocyanate-cyclohexyl)methane, 2,5-bis(isocyanate-methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate-methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl diisocyanate.

[0020] <8> according to <6> The polymerizable composition, wherein the polymerizable composition comprises a polyisocyanate composition, the polyisocyanate composition comprising the polyisocyanate compound, The polyisocyanate composition comprises: phenylene diisocyanate, and at least one selected from the group consisting of compound (N1), compound (N2), and compound (N3): in: When the polyisocyanate composition contains compound (N1), the peak area of ​​said compound (N1) in gas chromatography is 0.20 ppm or more relative to the peak area 1 of phenylene diisocyanate. When the polyisocyanate composition contains compound (N2), in gas chromatography determination, the peak area of ​​said compound (N2) is 0.05 ppm or more relative to the peak area 1 of phenylene diisocyanate, and When the polyisocyanate composition contains compound (N3), the peak area of ​​said compound (N3) is 0.10 ppm or more relative to the peak area 1 of phenylene diisocyanate in gas chromatography determination.

[0021] <9> Resin, which contains according to <6> to <8> The cured product of the polymeric composition described in any one of the above statements.

[0022] <10> Molded body, comprising according to <9> The aforementioned resin.

[0023] <11> Optical materials, which contain according to <9> The aforementioned resin.

[0024] <12> Lens, which includes according to <9> The aforementioned resin.

[0025] Beneficial effects of the invention According to one embodiment of this disclosure, a polythiol composition capable of producing a resin with a reduced yellowness index can be provided. Detailed Implementation

[0026] In this disclosure, the use of “to” to indicate a range of numbers represents the range of minimum and maximum values, respectively including the numbers recorded before and after “to”.

[0027] Regarding the numerical ranges for each stage recorded herein, the upper or lower limit of a certain numerical range may be replaced with the upper or lower limit of other numerical ranges for each stage, or may be replaced with the values ​​shown in the embodiments.

[0028] Here, when a material contains more than one substance corresponding to each component, unless otherwise stated, the amount of each component in the material refers to the total amount of the various substances present in the material.

[0029] In this article, "isocyanate" refers to isocyanate or isothiocyanate.

[0030] <<Polythiol Compositions>> The polythiol composition disclosed herein comprises a polythiol compound (A) and a compound represented by the following formula (1), wherein, in a high-performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of the compounds contained in the polythiol composition: In formula (1), X represents -CH2- or sulfur atom.

[0031] Since the polythiol composition of this disclosure contains the above-described components, it is possible to manufacture a resin having a reduced yellowness index.

[0032] The polythiol compound (A) preferably comprises a polythiol compound obtained from 2-mercaptoethanol and thiourea as raw materials.

[0033] Examples of polythiols obtained from 2-mercaptoethanol and thiourea as raw materials include mixtures of 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, and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0034] The polythiol compound (A) preferably comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or a mixture comprising 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.

[0035] (Other compounds) The polythiol compositions disclosed herein may further comprise compound (XB), which is obtained by replacing at least one of the three or more thiol groups of a polythiol compound (XA) containing three or more thiol groups with a group represented by the following formula (N1).

[0036] [Compound (XB)] Compound (XB) is a compound obtained by replacing at least one of the three or more thiol groups of a polythiol compound (XA) containing three or more thiol groups with a group represented by the following formula (N1).

[0037] The polythiol compound (XA) and the polythiol compound (A) mentioned above can be the same compound or different compounds, preferably the same compound.

[0038] In equation (N1), Indicates the bonding location.

[0039] Examples of compounds (XB) are shown below, but compounds (XB) are not limited to the examples shown below.

[0040] When the polythiol composition of the first embodiment described below further contains compound (XB), from the viewpoint of reducing the yellowness index and devitrification of the obtained resin, the ratio of the compound represented by formula (1) to compound (XB) (compound represented by formula (1) / compound (XB)) is preferably 0.5 to 18, more preferably 1 to 15, and even more preferably 2 to 12.

[0041] In the case where the polythiol composition of the second embodiment described below further comprises compound (XB), from the viewpoint of reducing the yellowness index and devitrification of the obtained resin and from the viewpoint of maintaining the pot life of the polymerizable composition of this disclosure well, the ratio of compound (1) to compound (XB) (compound (1) / compound (XB)) is preferably 0.1 to 9, more preferably 0.5 to 7, and even more preferably 0.9 to 5.

[0042] In the case of high performance liquid chromatography (HPLC) determination of polythiol compositions, the ratio of the peak area of ​​the compound represented by formula (1) to the peak area of ​​the compound (XB) is the ratio of the peak area of ​​the compound represented by formula (1) to the peak area of ​​the compound (XB). The HPLC determination conditions are as described later in <Determination of the peak area of ​​the compound represented by formula (1)>.

[0043] The polythiol compositions disclosed herein include those of the first and second embodiments described below.

[0044] <The polythiol composition of the first embodiment> The polythiol composition of the first embodiment comprises a polythiol compound (A) and a compound represented by the following formula (1), wherein the polythiol compound (A) contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, wherein, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of the compounds contained in the polythiol composition: In formula (1), X represents -CH2- or sulfur atom.

[0045] Since the polythiol composition of the first embodiment contains the above-described structure, when the polymerizable composition contains a combination of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a specific sulfur compound, it is possible to manufacture a resin with reduced yellowness index and devitrification.

[0046] <Compound represented by formula (1)> The polythiol composition of the first embodiment comprises a compound represented by the following formula (1): In formula (1), X represents -CH2- or sulfur atom.

[0047] Since the polythiol composition of the first embodiment contains a compound represented by the following formula (1), when the polymerizable composition contains a combination of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane and a specific sulfur compound, the yellowness index and devitrification of the resulting resin can be reduced. Since the polythiol composition of the first embodiment contains the above-described composition, a resin with reduced devitrification can be manufactured from this polythiol composition.

[0048] In the polythiol composition of the first embodiment, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0049] When the peak area of ​​the compound represented by formula (1) is below 9.0, the yellowness index and devitrification of the obtained resin can be reduced.

[0050] From the same point of view as described above, the peak area is preferably 7.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, and particularly preferably 3.0 or less, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0051] "The peak area of ​​the compound represented by formula (1) relative to the total peak area of ​​the compounds contained in the polythiol composition is 100" means that when the total peak area of ​​the compounds contained in the polythiol composition is 100, the peak area of ​​the compound represented by formula (1) is the relative value of the peak area of ​​the compound.

[0052] In high-performance liquid chromatography (HPLC) determination, from the viewpoint of reducing the workload of purifying and removing the compound represented by formula (1) from the polythiol composition, the peak area of ​​the compound represented by formula (1) is preferably greater than 0, more preferably 0.02 or more, even more preferably 0.05 or more, particularly preferably 0.1 or more, particularly preferably 0.2 or more, particularly preferably 0.3 or more, even more preferably 0.5 or more, and even more preferably 0.8 or more.

[0053] When the peak area of ​​the compound represented by Equation (1) meets the lower limit, the viscosity-increasing rate can be increased, thereby promoting polymerization.

[0054] There are no particular limitations on the method of adjusting the peak area of ​​the compound represented by formula (1) relative to the total peak area 100 of the compounds contained in the polythiol composition. For example, the peak area can be adjusted by column purification, washing, extraction, crystallization and other operations.

[0055] <Determination of peak area of ​​the compound represented by formula (1)> The peak area of ​​the compound represented by formula (1) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition can be determined by high performance liquid chromatography (HPLC) under the following conditions.

[0056] The content of the compound in the polythiol composition can be calculated as a percentage of the total peak area of ​​the compounds contained in the polythiol composition by determining the peak area of ​​the compound that appears during the retention time of 3.6 minutes to 4.8 minutes, as represented by formula (1).

[0057] (HPLC conditions) Column: YMC-PACK ODS-A A-312 (S5Φ6 mm×150 mm) Mobile phase: Acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Column temperature: 40℃ Flow rate: 1.0 ml / min Detector: UV detector, wavelength 230 nm Preparation of the assay solution: Dissolve and mix 160 mg of sample with 10 ml of acetonitrile.

[0058] Injection volume: 2 μL (Polythiol compound (A)) The polythiol composition of the first embodiment comprises a polythiol compound (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0059] 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is a compound represented by the following formula (2): The method for producing polythiol compound (A) is not particularly limited, and polythiol compound (A) can be produced by known methods. For example, it can be produced by the method described in WO 2014 / 027427A. Polythiol compound (A) is preferably a compound obtained, for example, by reacting 2-mercaptoethanol with an epihaloalcohol compound using a catalyst containing at least one of the group consisting of metal hydroxides such as sodium hydroxide and potassium hydroxide, and metal carbonates such as sodium carbonate and potassium carbonate.

[0060] The polythiol composition of the first embodiment may contain polythiol compound (A) and compounds other than those represented by formula (1).

[0061] For example, the polythiol composition may contain polythiol compound (A) and other polythiol compounds with thiol groups besides those represented by formula (1) (hereinafter also referred to as "other polythiol compounds").

[0062] Other examples of polythiols include: methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2-mercaptoethyl) sulfide, bis(2,3-dimercaptopropyl) sulfide, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,1 1-Dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiacyclohexane, 2,5-dimercapto-1,4-dithiacyclohexane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiacyclohexane, 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane.

[0063] <The Polythiol Composition of the Second Embodiment> The polythiol composition of the second embodiment comprises a polythiol compound (A) and a compound represented by the following formula (1), wherein the polythiol compound (A) contains a mixture of 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, wherein, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of the compounds contained in the polythiol composition: In formula (1), X represents -CH2- or sulfur atom.

[0064] Since the polythiol composition of the second embodiment contains the above-described components, it is possible to manufacture a resin with a reduced yellowness index from the polythiol composition.

[0065] In the polythiol composition of the second embodiment, in high performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is 9.0 or less relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0066] When the peak area of ​​the compound represented by formula (1) is below 9.0, the yellowness index of the obtained resin can be reduced.

[0067] From the same point of view as described above, the peak area is preferably 7.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, and particularly preferably 3.0 or less, relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0068] In high-performance liquid chromatography (HPLC) determination, from the viewpoint of reducing the workload of purifying and removing the compound represented by formula (1) from the polythiol composition, the peak area of ​​the compound represented by formula (1) is preferably greater than 0, more preferably 0.02 or more, even more preferably 0.05 or more, particularly preferably 0.1 or more, particularly preferably 0.2 or more, particularly preferably 0.3 or more, even more preferably 0.5 or more, and even more preferably 0.8 or more.

[0069] When the peak area of ​​the compound represented by Equation (1) meets the lower limit, the viscosity-increasing rate can be increased, thereby promoting polymerization.

[0070] The details of the specific and preferred manner of the compound represented by formula (1) in the second embodiment, the definition and measurement method of the peak area of ​​the compound represented by formula (1) relative to the total peak area 100 of the compounds contained in the polythiol composition, are the same as those of the specific and preferred manner of the compound represented by formula (1) and the definition and measurement method of the peak area of ​​the compound represented by formula (1) relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0071] The polythiol composition of the second embodiment may contain polythiol compound (A) and compounds other than those represented by formula (1).

[0072] The details of specific examples, preferred examples, etc. of other polythiol compounds in the second embodiment are the same as those in the first embodiment.

[0073] <<Polymerizable Compositions>> The polymerizable compositions disclosed herein comprise the polythiol compositions and polyisocyanate compounds disclosed herein.

[0074] (Polyisocyanate compounds) There are no particular limitations on the polyisocyanate compounds used, as long as they achieve the effects described herein; any previously known compound may be used. There are no particular limitations on any compound having at least two isocyanate groups in one molecule; specific examples include: Aliphatic polyisocyanate compounds, such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate and phenylene diisocyanate; Alicyclic polyisocyanate compounds, such as isophorone diisocyanate, bis(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, dicyclohexyl dimethylmethane diisocyanate, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanate methyl)tricyclodecane, 3,9-bis(isocyanate methyl)tricyclodecane, 4,8-bis(isocyanate methyl)tricyclodecane and 4,9-bis(isocyanate methyl)tricyclodecane; Aromatic polyisocyanate compounds, such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate and phenyl diisocyanate; Heterocyclic polyisocyanate compounds, such as 2,5-diisocyanate-thiophene, 2,5-bis(isocyanate-methyl)thiophene, 2,5-diisocyanate-tetrahydrothiophene, 2,5-bis(isocyanate-methyl)tetrahydrothiophene, 3,4-bis(isocyanate-methyl)tetrahydrothiophene, 2,5-diisocyanate-1,4-dithiocyclohexane, 2,5-bis(isocyanate-methyl)-1,4-dithiocyclohexane, 4,5-diisocyanate-1,3-dithiocyclopentane and 4,5-bis(isocyanate-methyl)-1,3-dithiocyclopentane; Aliphatic polyisothiocyanate compounds, such as hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate and phenyl diisothiocyanate. Alicyclic polyisothiocyanate compounds, such as isophorone diisothiocyanate, bis(isothiocyanate methyl)cyclohexane, bis(isothiocyanate cyclohexyl)methane, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5-bis(isothiocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isothiocyanate methyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isothiocyanate methyl)tricyclodecane, 3,9-bis(isothiocyanate methyl)tricyclodecane, 4,8-bis(isothiocyanate methyl)tricyclodecane and 4,9-bis(isothiocyanate methyl)tricyclodecane; Aromatic polyisothiocyanate compounds, such as toluene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyl disulfide-4,4-diisothiocyanate; and Sulfur-containing heterocyclic polyisothiocyanate compounds, such as 2,5-diisothiocyanate-thiophene, 2,5-bis(isothiocyanate-methyl)thiophene, 2,5-isothiocyanate-tetrahydrothiophene, 2,5-bis(isothiocyanate-methyl)tetrahydrothiophene, 3,4-bis(isothiocyanate-methyl)tetrahydrothiophene, 2,5-diisothiocyanate-1,4-dithiacyclohexane, 2,5-bis(isothiocyanate-methyl)-1,4-dithiacyclohexane, 4,5-diisothiocyanate-1,3-dithiacyclopentane, and 4,5-bis(isothiocyanate-methyl)-1,3-dithiacyclopentane. Polyisocyanate compounds may contain at least one selected from these compounds.

[0075] As a polyisocyanate compound, it can also be used with halogenated derivatives such as chlorinated or bromine-substituted derivatives, alkyl-substituted derivatives, alkoxy-substituted derivatives, nitro-substituted derivatives, prepolymer-type modifiers of polyols, carbodiimide modifiers, urea modifiers, biuret modifiers, or dimerization or trimerization reaction products.

[0076] The polyisocyanate compound is preferably a polyisocyanate compound, and Preferably, it comprises at least one selected from pentamethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl diisocyanate.

[0077] The mixing ratio of the polythiol composition to the polyisocyanate compound is not particularly limited. For example, the molar ratio (thiol group / isocyanate group) of the thiol group to the isocyanate group of the polyisocyanate compound in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3. When the mixing ratio is within the above range, there is a tendency to satisfy various performance characteristics such as refractive index and heat resistance required by plastic lenses in a well-balanced manner.

[0078] The polymerizable compositions disclosed herein may comprise polyisocyanate compositions containing polyisocyanate compounds.

[0079] Here, a polyisocyanate composition refers to a composition comprising at least one polyisocyanate compound.

[0080] Polyisocyanate compositions may contain components other than polyisocyanate compounds as impurities.

[0081] The polyisocyanate composition preferably contains at least one polyisocyanate compound as a major component.

[0082] The polyisocyanate composition preferably contains phenylene diisocyanate.

[0083] Hereinafter, polyisocyanate compositions containing phenylene diisocyanate will also be referred to as XDI compositions.

[0084] The XDI composition preferably contains phenylene diisocyanate as the main component.

[0085] The XDI composition preferably comprises at least one selected from the group consisting of the following compounds (N1), (N2), and (N3).

[0086] The following describes a preferred mode of XDI composition from the viewpoint of the stability of the polyisocyanate composition and the superior transparency of the resin formed using the polyisocyanate composition.

[0087] When the XDI composition contains compound (N1), in a gas chromatographic determination under the following GC conditions 1, the peak area of ​​compound (N1) is preferably 0.20 ppm or more relative to the peak area 1 of phenylene diisocyanate.

[0088] - GC Condition 1 - Filler material: DB-1 (film thickness) 1.5 μm Column: Inner diameter 0.53 mm × length 60 m (manufactured by Agilent Technologies, Inc.) Oven temperature: Increase from 130℃ to 220℃ at a rate of 3℃ / min, and then increase to 300℃ at a rate of 10℃ / min after reaching 220℃. Shunt ratio: Pulse shunt method Inlet temperature: 280℃ Detector temperature: 300℃ Carrier gas: N2 158 kPa, H2 55 kPa, air 45 kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2 μL Detection method: FID The peak area of ​​compound (N1) is more preferably 5.0 ppm or more, even more preferably 50 ppm or more, and even more preferably 100 ppm or more, relative to the peak area of ​​phthalic acid diisocyanate.

[0089] The peak area of ​​compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, relative to the peak area 1 of phenylene diisocyanate.

[0090] The peak area of ​​compound (N1) can be determined according to the method described in paragraph

[0377] of Japanese Patent No. 6373536.

[0091] When the XDI composition contains compound (N2), in the gas chromatographic determination under the following GC conditions 2, the peak area of ​​compound (N2) is preferably 0.05 ppm or more relative to the peak area 1 of phenylene diisocyanate.

[0092] - GC Condition 2 - Column: HP-50+, inner diameter 0.25 mm × length 30 m × film thickness 0.25 μm (manufactured by Hewlett-Packard Company) Oven temperature: Increase from 50℃ to 280℃ at a rate of 10℃ / min, and hold at 280℃ for 6 min. Shunt ratio: Pulse shunt method Inlet temperature: 200℃ Detector temperature: 280℃ Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume: 1.0 μL Detection method: SIM (monitoring ions: m / z 180, 215) (XDI content ratio) The peak area of ​​compound (N2) is more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and even more preferably 0.6 ppm or more, relative to the peak area of ​​phthalic acid diisocyanate.

[0093] The peak area of ​​compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and even more preferably 60 ppm or less, relative to the peak area of ​​phthalic acid diisocyanate.

[0094] The peak area of ​​compound (N2) can be determined according to the method described in paragraphs

[0375] and

[0376] of Japanese Patent No. 6373536.

[0095] When the XDI composition contains compound (N3), in the gas chromatographic determination under the above GC conditions 1, the peak area of ​​compound (N3) is preferably 0.10 ppm or more relative to the peak area 1 of phenylene diisocyanate.

[0096] The peak area of ​​compound (N3) is more preferably 0.1 ppm or more, more preferably 3.0 ppm or more, and more preferably 5.0 ppm or more, relative to the peak area of ​​phthalic acid diisocyanate.

[0097] The peak area of ​​compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, even more preferably 100 ppm or less, and even more preferably 75 ppm or less, relative to the peak area of ​​phthalic acid diisocyanate.

[0098] The peak area of ​​compound (N3) can be determined according to the method described in paragraph

[0377] of Japanese Patent No. 6373536.

[0099] The acid content in the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm.

[0100] There is no particular limit to the lower limit of acid content in XDI compositions; for example, the lower limit is 1 ppm.

[0101] The acid content in the XDI composition can be determined according to the method described in paragraph

[0091] of WO 2021 / 256417.

[0102] In addition, the XDI composition may contain a stabilizer.

[0103] The polymerizable compositions disclosed herein may contain components other than polythiols and polyisocyanates for purposes such as improving various physical properties and workability of the resin, polymerization reactivity of the polymerizable compositions, etc.

[0104] Examples of other components include polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, free radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, and blue colorants such as inorganic pigments.

[0105] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0106] Acidic phosphate esters can be used as internal release agents. Examples of acidic phosphate esters include monophosphate esters and diphosphate esters, which can be used alone or in mixtures of two or more.

[0107] Examples of resin modifiers include cyclic sulfur compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, and olefin compounds containing (meth)acrylate compounds.

[0108] The polymeric composition disclosed herein can be obtained by mixing the above-described components.

[0109] From the viewpoint of heat resistance, the glass transition temperature (Tg) of the polymeric composition of this disclosure when cured into a molded article is preferably 80°C or higher, more preferably 85°C or higher. This glass transition temperature (Tg) can be 130°C or lower, or 125°C or lower.

[0110] In this disclosure, the glass transition temperature Tg of the polymeric composition when molded into a molded body is a value measured using a plastic sheet molded according to <Manufacturing of Plastic Sheets> by the method described in the following examples.

[0111] <<Molded Body>> The molded body of this disclosure contains the resin of this disclosure.

[0112] The resin of this disclosure comprises a cured product of the polymeric composition of this disclosure.

[0113] The method for manufacturing the molded article disclosed herein is not particularly limited, but examples of preferred manufacturing methods include casting polymerization. First, the polymerizable composition is poured between molds held by gaskets, tapes, etc. At this time, depending on the desired physical properties of the plastic lens to be obtained, it is generally preferable to perform degassing under reduced pressure, filtration under pressure or reduced pressure, or other filtration processes as needed.

[0114] There are no limitations on polymerization conditions, as they vary considerably depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc. For example, polymerization can be carried out at temperatures ranging from -50°C to 150°C for 1 to 50 hours. In some cases, it is preferable to cure the composition within 1 to 48 hours while maintaining or gradually increasing the temperature within a range of 10°C to 150°C.

[0115] The molded body can be annealed or otherwise treated as needed. Annealing or other treatments are usually performed at 50°C to 150°C, preferably at 90°C to 140°C, and more preferably at 100°C to 130°C.

[0116] [use] The resin obtained from the polymerizable composition of this disclosure can be used as a material to manufacture molded bodies of various shapes by changing the type of mold during casting polymerization.

[0117] <<Optical Materials>> The optical material of this disclosure includes the resin of this disclosure.

[0118] A molded article obtained using the polymerizable composition of this disclosure can produce a material with a reduced yellowness index without compromising transparency. Furthermore, a molded article obtained using the polymerizable composition containing the polythiol composition of the first embodiment can also produce a material with excellent devitrification.

[0119] Therefore, such materials can be used in a variety of optical materials, such as plastic lenses.

[0120] <<Lens>> The lens of this disclosure contains the resin of this disclosure.

[0121] Lenses are particularly suitable as optical materials.

[0122] Examples of lenses include plastic eyeglass lenses and plastic polarizing lenses.

[0123] [Plastic eyeglass lenses] For plastic eyeglass lenses containing a lens substrate formed by the molding of this disclosure, a coating layer may be applied to one or both sides as needed.

[0124] The plastic eyeglass lens disclosed herein includes a lens substrate and a coating layer, the lens substrate comprising a cured product of the aforementioned polymeric composition.

[0125] Specific examples of coatings include primers, hard coats, anti-reflective coatings, anti-fog coatings, anti-fog coatings, and waterproofing coatings. These coatings can be used individually or in multiple layers. When applying a coating to both sides, the same coating or different coatings can be applied to each side.

[0126] Each of these coatings may incorporate known additives, such as infrared absorbers for the purpose of protecting the eyes from infrared damage, light stabilizers or antioxidants for the purpose of improving the weather resistance of the lens, photochromic compounds, dyes and pigments for the purpose of improving the style of the lens, and antistatic agents for the purpose of improving the performance of the lens, etc.

[0127] For layers coated by coating, various leveling agents can be used to improve coatability.

[0128] An anti-fog layer, an anti-pollution layer, or a waterproof layer can be formed on the anti-reflective layer as needed.

[0129] Although the embodiments of this disclosure have been described above, these are examples of this disclosure, and various other configurations besides those described above can be adopted without impairing the effect of this disclosure.

[0130] Example The polythiol compositions of this disclosure will now be described in detail with reference to the embodiments. The polythiol compositions of this disclosure are not limited in any way to the description of these embodiments. Unless otherwise stated, "parts" are based on weight.

[0131] <Evaluation Methods> In the embodiments, the evaluation methods for various properties of the plastic sheet are as follows. The results are shown in Table 1.

[0132] • Refractive index (ne), Abbe number (νe) Using a Shimadzu Pulfrich refractometer KPR-30, the refractive indices (ne, nF', and nC') were measured at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line), and the refractive index (ne) and Abbe number (νe) were calculated.

[0133] • Heat resistance Using a Shimadzu TMA-60 thermomechanical analyzer, the TMA penetration method was employed (load: 50 g, needle tip: 0.5 mm). (Heating rate: 10℃ / min) The glass transition temperature Tg was measured and used as an indicator of heat resistance.

[0134] • Yellowness Index (also known as YI) The resin was prepared into a circular plastic plate with a thickness of 9 mm and a diameter of 75 mm, and the YI value was determined using a KonicaMinolta, Inc. spectrophotometer CM-5.

[0135] There is a correlation between the YI value and the yellowness index: the smaller the YI value, the lower the yellowness index of the plastic sheet, and the larger the YI value, the higher the yellowness index.

[0136] • Devitrification A circular plastic plate with a thickness of 9 mm and a diameter of 75 mm was fabricated from resin, allowing light from a light source (LUMINAR ACE LA-150 A manufactured by HAYASHI-REPIC CO., LTD.) to pass through the side of the plate. An image of the light from the front of the plate was captured in an image processing device (manufactured by Ube Information Systems, Inc.), and the captured image underwent grayscale processing. The grayscale level of the processed image was quantified pixel by pixel, and the average value of the grayscale level of each pixel was obtained to determine the opacity of the plate.

[0137] The lower the devitrification, the less the transparency of the resin (in this case, the flat plate) is impaired (i.e., the resin has excellent transparency).

[0138] The polythiol composition of the first embodiment will now be described in detail with reference to the examples. The polythiol composition of the first embodiment is not limited in any way to the description of these examples.

[0139] <Synthesis of Polythiol Compound (A)> 124.6 parts by weight of 2-mercaptoethanol and 18.3 parts by weight of degassed water were added to the reactor. 101.5 parts by weight of a 32% sodium hydroxide aqueous solution were added dropwise over 40 minutes at 12°C to 35°C, followed by the dropwise addition of 73.6 parts by weight of epichlorohydrin over 4.5 hours at 29°C to 36°C, with stirring continued for 40 minutes. NMR data confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol.

[0140] Add 331.5 parts by weight (35.5% by weight) of hydrochloric acid, followed by 183.8 parts by weight of thiourea with a purity of 99.90%. The resulting mixture is refluxed and stirred at 110°C for 3 hours to induce the formation of thiourea onium salts. After cooling to 45°C, add 320.5 parts by weight of toluene. Cool the mixture to 31°C, and then add 243.1 parts by weight of a 25% by weight aqueous ammonia solution at 31°C to 41°C over 44 minutes. Stir the mixture at 54°C to 62°C for 3 hours to induce hydrolysis, yielding a toluene solution containing a polythiol as the main component, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. Add 162.8 parts by weight (35.5% by weight) of hydrochloric acid to this toluene solution, and wash the mixture with acid at 35°C to 43°C for 1 hour. Add 174.1 parts by weight of degassed water and wash the mixture twice at 35°C to 45°C for 30 minutes. Add 162.1 parts by weight of 0.1% ammonia water and wash the mixture for 30 minutes. Add 174.2 parts by weight of degassed water and wash the mixture twice at 35°C to 45°C for 30 minutes. Remove toluene and trace amounts of water under heating and reduced pressure, then filter the residue through a 1.2 μm PTFE membrane filter under reduced pressure to obtain 205.0 parts by weight of a polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as the polythiol compound (A).

[0141] [Example 1, Example 2, and Comparative Example 1] The polythiol composition (A) obtained above was mixed with γ-thiobutyrolactone (made by Sigma-Aldrich Co. LLC; the compound represented by formula (1)) to obtain the polythiol composition.

[0142] At this point, the mixing ratio is changed and the compounds are mixed such that the peak area of ​​the compound represented by formula (1) relative to the total peak area 100 of the compounds contained in the polythiol composition corresponds to the value recorded in Table 1.

[0143] <Determination of the proportion (area%) of γ-thiobutyrolactone> The proportion (area %) of γ-thiobutyrolactone based on HPLC was determined according to the method described in the section on <Determination of peak area of ​​compounds represented by formula (1)>.

[0144] The results are shown in Table 1.

[0145] <Manufacturing of Plastic Flat Sheets> [Manufacturing Example 1] 52 parts by weight of isophthalene diisocyanate, 0.01 parts by weight of dichlorodibutyltin as a curing catalyst, 0.10 parts by weight of ZELEC UN (trade name, Stepan product; acidic phosphate), and 1.5 parts by weight of VIOSORB 583 (Kyodo Chemical Co., Ltd.; ultraviolet absorber) were mixed and dissolved at 20°C. 48 parts by weight of the polythiol composition of Example 1 were added and mixed to obtain a homogeneous liquid. This homogeneous liquid was degassed at 600 Pa for 1 hour and filtered through a 1 μm TEFLON® filter. The filtrate was injected into a molding die consisting of a glass mold and adhesive tape. The molding die was placed in an oven and gradually heated from 10°C to 120°C for 38 hours for polymerization. After polymerization, the molding die was removed from the oven to obtain the resin by releasing it from the molding die. The obtained resin was further annealed at 120°C for 1 hour to obtain a plastic sheet. Each property was measured according to the aforementioned evaluation method for the physical properties of plastic sheets.

[0146] [Manufacturing Example 2] In Manufacturing Example 1, 48 parts by weight of the polythiol composition of Example 1 were replaced with 48 parts by weight of the polythiol composition of Example 2. Otherwise, the plastic sheet was manufactured using the same method as described in Manufacturing Example 1. Each property of the plastic sheet was measured according to the aforementioned evaluation method for each property.

[0147] [Manufacturing Example 3] In Manufacturing Example 1, 48 parts by weight of the polythiol composition of Example 1 were replaced with 48 parts by weight of the polythiol composition of Comparative Example 1. Otherwise, the plastic sheet was manufactured using the same method as described in Manufacturing Example 1. Each property of the plastic sheet was measured according to the aforementioned evaluation method for each property.

[0148] The physical properties of the plastic sheets manufactured in Examples 1 to 3 are shown in Table 1.

[0149] [Table 1]

[0150] As shown in Table 1, a resin with reduced yellowness index and devitrification can be produced from the polythiol composition according to the embodiments. This composition comprises a polythiol compound (A) (which contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane) and a compound represented by formula (1) below, and the peak area of ​​the compound represented by formula (1) in high-performance liquid chromatography is less than 9.0 relative to the total peak area 100 of the compounds contained in the polythiol composition. The polythiol composition according to the embodiments also exhibits excellent heat resistance.

[0151] On the other hand, the polythiol composition according to Comparative Example 1 cannot produce a resin with reduced yellowness index and devitrification, wherein the peak area of ​​the compound represented by formula (1) is greater than 9.0 relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0152] Hereinafter, the polythiol composition of the second embodiment will be described in detail with reference to the examples. The polythiol composition of the second embodiment is not limited in any way to the description of these examples.

[0153] <Synthesis of Polythiol Composition (A)> 51.2 parts by mass of 2-mercaptoethanol, 26.5 parts by mass of degassed water (dissolved oxygen concentration: 2 ppm), and 0.16 parts by mass of a 49% sodium hydroxide aqueous solution were added to the reactor. 61.99 parts by mass of epichlorohydrin were added dropwise over 6.5 hours at 9–11 °C, with stirring continued for 60 minutes. NMR data confirmed the formation of 1-chloro-3-(2-hydroxyethylthio)-2-propanol.

[0154] Next, 150.0 parts by weight of a 17.3% by weight aqueous solution of sodium sulfide was added dropwise over 5.5 hours at 7 to 37°C, and the mixture was stirred for 120 minutes. NMR data confirmed the formation of 1,5,9,13-tetrahydroxy-3,7,11-trithiatridecane. Then, 279.0 parts by weight of 35.5% by weight hydrochloric acid was added, followed by 125.8 parts by weight of thiourea with a purity of 99.90%. The resulting mixture was refluxed and stirred at 110°C for 3 hours to carry out the thiourea onium salt formation reaction. After cooling to 45°C, 214.0 parts by weight of toluene was added, the mixture was cooled to 26°C, and 206.2 parts by weight of a 25% by weight aqueous solution of ammonia was added over 30 minutes at 26°C to 50°C. The mixture was hydrolyzed by stirring at 50°C to 65°C for 1 hour to obtain a toluene solution of polythiols mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane. 59.4 parts by weight of 36% hydrochloric acid were added to this toluene solution, and the mixture was acid-washed twice at 34°C to 39°C for 30 minutes. Additionally, 118.7 parts by weight of degassed water (dissolved oxygen concentration: 2 ppm) were added, and the mixture was washed five times at 35°C to 45°C for 30 minutes. Toluene and trace amounts of moisture were removed under heating and reduced pressure. The residue was then filtered under reduced pressure through a 1.2 μm PTFE membrane filter to obtain 115.9 parts by weight of a polythiol composition (A) mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as the main components.

[0155] [Example 3, Example 4 and Comparative Example 2] The polythiol composition (A) obtained as described above was mixed with γ-thiobutyrolactone (made by Sigma-Aldrich Co. LLC; the compound represented by formula (1)) to obtain the polythiol composition.

[0156] At this point, the mixing ratio is changed and the compounds are mixed so that the peak area of ​​the compound represented by formula (1) relative to the total peak area 100 of the compounds contained in the polythiol composition corresponds to the value recorded in Table 2.

[0157] <Determination of the proportion (area%) of γ-thiobutyrolactone> The proportion (area %) of γ-thiobutyrolactone based on HPLC was determined according to the method described in the above-mentioned "<Determination of peak area of ​​compounds represented by formula (1)>".

[0158] The results are shown in Table 2.

[0159] <Manufacturing of Plastic Flat Sheets> [Manufacturing Example 4] 50.8 parts by weight of isophthalene diisocyanate, 0.01 parts by weight of dichlorodimethyltin as a curing catalyst, 0.10 parts by weight of ZELEC UN (a product of Stepan Corporation; acidic phosphate), 0.6 parts by weight of VIOSORB583 (manufactured by KYODO CHEMICAL CO., LTD.; ultraviolet absorber), and 0.6 parts by weight of SEESORB 706 (manufactured by ShiproKasei Kaisha, Ltd.; ultraviolet absorber) were mixed and dissolved at 20°C. 49.2 parts by weight of the polythiol composition of Example 3 were added and mixed to obtain a homogeneous liquid. This homogeneous liquid was degassed at 600 Pa for 1 hour and filtered through a 1 μm TEFLON® filter. The filtrate was then injected into a molding die consisting of a glass mold and adhesive tape. The molding die was placed in an oven and gradually heated from 20°C to 120°C for 30 hours for polymerization. After polymerization, the molding die was removed from the oven to obtain the resin by releasing it from the die. The obtained resin was further annealed at 120°C for 1 hour to obtain a plastic sheet. Each property of the plastic sheet was measured according to the aforementioned evaluation methods.

[0160] [Manufacturing Example 5] The polythiol composition of Example 3 was replaced with 49.2 parts by weight of the polythiol composition of Example 4, and the plastic sheet was otherwise manufactured using the same method as described in Manufacturing Example 4. Each property was measured according to the aforementioned evaluation method for the properties of the plastic sheet.

[0161] [Manufacturing Example 6] The polythiol composition of Example 3 (49.2 parts by weight) was replaced with the polythiol composition of Comparative Example 2 (49.2 parts by weight), and the plastic sheet was manufactured using the same method as described in Manufacturing Example 4. Each property of the plastic sheet was measured according to the aforementioned evaluation methods for each property.

[0162] The physical properties of the plastic sheets manufactured in Examples 4 to 6 are shown in Table 2.

[0163] [Table 2]

[0164] As shown in Table 2, a resin with a reduced yellowness index can be produced from the polythiol composition according to the embodiments. This composition comprises a polythiol compound (A) (which comprises a mixture of 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) and a compound represented by formula (1), wherein the peak area of ​​the compound represented by formula (1) in high-performance liquid chromatography is less than 9.0 relative to the total peak area 100 of the compounds contained in the polythiol composition. The polythiol composition according to the embodiments also exhibits excellent heat resistance.

[0165] On the other hand, the polythiol composition according to Comparative Example 2 cannot produce a resin with a reduced yellowness index, wherein the peak area of ​​the compound represented by formula (1) is greater than 9.0 relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0166] [Manufacturing Examples 1X to 6X] As for each of Manufacturing Examples IX to 6X, except for the following changes, when manufacturing plastic sheets by performing the same steps as each of Manufacturing Examples 1 to 6 (i.e., Example 1, Example 2, Comparative Example 1, Example 3, Example 4 and Comparative Example 2), the results obtained are basically the same as those in each of Manufacturing Examples 1 to 6 (Tables 1 and 2).

[0167] - Changes from Manufacturing Example 1 to Manufacturing Example 6 - In each of Manufacturing Examples 1 to 6, isophthalic acid diisocyanate (XDI) (52 parts by weight or 50.8 parts by weight) was used when manufacturing the plastic sheet. Meanwhile, in each of Manufacturing Examples IX to 6X, XDI (52 parts by weight or 50.8 parts by weight) was replaced with XDI composition X1 (in an amount equivalent to 52 parts by weight or 50.8 parts by weight of XDI) as the aforementioned XDI composition.

[0168] XDI composition X1 is prepared by adding trace amounts of compound (N1), compound (N2), and compound (N3) to XDI, which is the main component, and mixing them together.

[0169] When the XDI composition X1 is determined by gas chromatography under GC conditions 1 and 2 as described above: The peak area of ​​compound (N1) is greater than 0.20 ppm (e.g., 600 ppm) relative to the peak area of ​​XDI. The peak area of ​​compound (N2) is greater than 0.05 ppm (e.g., 18 ppm) relative to the peak area of ​​XDI, and The peak area of ​​compound (N3) is greater than 0.10 ppm (e.g., 100 ppm) relative to the peak area of ​​XDI.

[0170] The disclosure of Japanese Patent Application Publication (JP-A) No. 2020-189834, filed on November 13, 2020, is incorporated herein by reference in its entirety.

[0171] All documents, patent applications and technical standards described herein are incorporated herein by reference to the same extent as they are specifically and separately described herein.

Claims

1. A polymerizable composition comprising a polythiol composition and a polyisocyanate composition, The polythiol composition comprises: Polythiol compound (A); and The compound represented by the following formula (1), wherein, In high-performance liquid chromatography determination, the peak area of ​​the compound represented by formula (1) is greater than 0 and less than 9.0 relative to the total peak area 100 of all compounds contained in the polythiol composition: In formula (1), X represents -CH2- or a sulfur atom. The polythiol compound (A) comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane or a mixture comprising 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, and... The polyisocyanate composition comprises: phenylene diisocyanate, and at least one selected from the group consisting of compound (N1), compound (N2), and compound (N3): in: When the polyisocyanate composition contains compound (N1), the peak area of ​​said compound (N1) in gas chromatography is 0.20 ppm or more relative to the peak area 1 of phenylene diisocyanate. When the polyisocyanate composition contains compound (N2), in gas chromatography determination, the peak area of ​​said compound (N2) is 0.05 ppm or more relative to the peak area 1 of phenylene diisocyanate, and When the polyisocyanate composition contains compound (N3), the peak area of ​​said compound (N3) is 0.10 ppm or more relative to the peak area 1 of phenylene diisocyanate in gas chromatography determination.

2. The polymerizable composition according to claim 1, wherein, The polythiol compound (A) comprises a polythiol compound obtained from a starting material comprising epihaloalcohol, 2-mercaptoethanol and thiourea.

3. The polymerizable composition according to claim 1, wherein, The polythiol compound (A) comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

4. A resin comprising a cured product of the polymeric composition according to claim 1.

5. A molded article comprising the resin according to claim 4.

6. An optical material comprising the resin according to claim 4.

7. A lens comprising the resin according to claim 4.

Images