Polythiol compositions, polymerizable compositions, resins, molded articles, optical materials, and lenses

Abstract

To provide a polythiol composition capable of producing a resin with reduced yellowness, a polymerizable composition containing the polythiol composition, a resin, a molded article, an optical material, and a lens. [Solution] A polythiol composition comprising a polythiol compound (A) and at least one compound represented by formula (1) and formula (2), wherein, in high-performance liquid chromatography measurement, the total peak area of ​​the compounds represented by formula (1) and formula (2) is 1.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition. JPEG2026090346000013.jpg5767

Description

Technical Field

[0001] The present disclosure relates to a polythiol composition, a polymerizable composition, a resin, a molded body, an optical material, and a lens.

Background Art

[0002] Plastic lenses are lightweight, less likely to break, and can be dyed compared to inorganic lenses. In recent years, they have rapidly spread to optical elements such as spectacle lenses and camera lenses.

[0003] There has been an increasing demand for further improvement in performance of resins for plastic lenses, such as increasing the refractive index, increasing the Abbe number, reducing the specific gravity, and increasing the heat resistance. Various resin materials for lenses have been developed and used so far.

[0004] For example, Patent Document 1 describes a mercapto compound represented by a specific structural formula. For example, Patent Document 2 describes a process of reacting 2-mercaptoethanol with an epihalohydrin compound represented by a specific formula (1) at a temperature of 10 to 50°C to obtain a polyalcohol compound represented by a specific formula (2), a process of reacting the obtained polyalcohol compound represented by formula (2) with thiourea in the presence of hydrogen chloride to obtain an isothiouronium salt, a process of hydrolyzing the obtained isothiouronium salt by adding aqueous ammonia to the reaction solution within 80 minutes while maintaining the temperature of the reaction solution containing the isothiouronium salt at 15 to 60°C to obtain a polythiol compound represented by a specific formula (5), and a process of adding hydrochloric acid with a concentration of 25 to 36% to the solution containing the obtained polythiol compound and washing at a temperature of 10 to 50°C to purify the polythiol compound. A method for producing a polythiol compound is described.

[0005] Patent Document 1: Japanese Patent Laid-Open No. 2-270859 Patent Document 2: International Publication No. 2014-027427

Summary of the Invention

Problems to be Solved by the Invention

[0006] In some cases, it is desirable to reduce the degree of yellowness in resins obtained by curing polymerizable compositions containing polythiol compounds. In practice, polymerizable compositions containing polythiol compounds often also contain other compounds besides polythiol compounds. The inventors have found that when a polymerizable composition contains compounds other than polythiol compounds, the resulting resin tends to exhibit increased yellowness. After conducting various studies on the above trends, we found that it can sometimes be difficult to obtain resin with reduced yellowness.

[0007] One embodiment of this disclosure aims to solve the problem of providing a polythiol composition capable of producing a resin with reduced yellowness, a polymerizable composition containing the polythiol composition, a resin, a molded article, an optical material, and a lens. [Means for solving the problem]

[0008] The following embodiments are included as means for solving the above problems. <1> A polythiol composition comprising a polythiol compound (A) and at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), wherein, in high-performance liquid chromatography measurement, the total peak area of ​​the at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) is 1.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0009] [ka]

[0010] <2> The aforementioned polythiol compound (A) includes a polythiol compound obtained from 2-mercaptoethanol and thiourea as raw materials. <1> The polythiol composition described above. <3> The polythiol compound (A) contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 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. <1> or <2> A polythiol composition as described in any one of the following. <4> <1> ~ <3> A polymerizable composition comprising a polythiol composition described in any one of the above and a polyiso(thio)cyanate compound. <5> The polyiso(thio)cyanate compound includes at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene 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, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. <4> The polymerizable composition described above. <6> The polyiso(thio)cyanate composition comprises the aforementioned polyiso(thio)cyanate compound, The aforementioned polyiso(thio)cyanate composition Xylylene diisocyanate and At least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3), Includes, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate. When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate. If the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in gas chromatography measurement is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. <4> or <5> The polymerizable composition described above.

[0011] [ka]

[0012] <7> <4> ~ <6> A resin comprising a cured product of any one of the polymerizable compositions described in any one of the above. <8> <7> A molded article containing the resin described above. <9> <7> Optical materials containing the resin described above. <10> <7> Lenses containing the resin described above. [Effects of the Invention]

[0013] According to one embodiment of the present disclosure, it is possible to provide a polythiol composition capable of producing a resin with reduced yellowness, a polymerizable composition containing the polythiol composition, a resin, a molded article, an optical material, and a lens. [Modes for carrying out the invention]

[0014] In this disclosure, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages, or with the values ​​shown in the examples. In the present disclosure, the amount of each component in the material means the total amount of the plurality of substances present in the material, unless otherwise specified, when there are a plurality of substances corresponding to each component in the material. In the present disclosure, "iso(thio)cyanate" means isocyanate or isothiocyanate.

[0015] ≪Polythiol Composition≫ The present disclosure includes the following Embodiment A and Embodiment B. That is, the concept of the polythiol composition of the present disclosure encompasses the polythiol composition of Embodiment A and the polythiol composition of Embodiment B.

[0016] Embodiment A and Embodiment B may have overlapping parts. For example, the polythiol composition of Embodiment A may have the characteristics of Embodiment B described later. Here, the characteristics of Embodiment B, although details will be described later, include a polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by the following formula (3) and the compound represented by the following formula (4), and in high performance liquid chromatography measurement, the total peak area of at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) is 2.10 or less with respect to 100 of the total peak area of the compounds contained in the polythiol composition.

[0017] [Embodiment A] The polythiol composition of Embodiment A includes a polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by the following formula (1) and the compound represented by the following formula (2), and in high performance liquid chromatography measurement, the total peak area of at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) is 1.00 or less with respect to 100 of the total peak area of the compounds contained in the polythiol composition.

[0018] [Chemical Formula]

[0019] The polythiol composition of Embodiment A, by including the above-mentioned components, can produce a resin with reduced yellowness. Furthermore, the polythiol composition of Embodiment A can also be used to produce resins with reduced devitrification.

[0020] <Polythiol compound (A)> The polythiol composition of Embodiment A comprises a polythiol compound (A). The polythiol compound (A) in Embodiment A is not particularly limited.

[0021] The polythiol compound (A) preferably includes a polythiol compound obtained from 2-mercaptoethanol and thiourea as raw materials. Examples of polythiol compounds obtained from 2-mercaptoethanol and thiourea as raw materials include: At least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; These are some examples.

[0022] Polythiol compound (A) is Preferably, it contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane. It is more preferable to include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctan is a compound represented by the following formula (a-1).

[0023] [ka]

[0024] The method for producing the polythiol compound (A) is not particularly limited and can be produced by known methods. For example, the polythiol compound (A) can be produced by the method described in International Publication No. 2014 / 027427. Furthermore, it is preferable that the polythiol compound (A) is a compound obtained by using a catalyst that includes at least one selected from the group consisting of metal hydroxides such as sodium hydroxide and potassium hydroxide, and metal carbonates such as sodium carbonate and potassium carbonate, when reacting 2-mercaptoethanol with an epihalohydrin compound.

[0025] The polythiol composition of Embodiment A may contain compounds other than the polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2). For example, the compound may include polythiol compound (A) and other polythiol compounds having a mercapto group other than at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) (hereinafter also referred to as "other polythiol compounds").

[0026] Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2-mercaptoethyl)sulfide, bis(2,3-dimercaptopropyl)sulfide, 4,8-dimercaptomethyl-1,11-dimercapto- Examples include 3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0027] <Compound represented by formula (1), compound represented by formula (2)> The polythiol composition of Embodiment A comprises at least one compound selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2).

[0028] [ka]

[0029] The polythiol composition of Embodiment A contains at least one compound selected from the group consisting of compounds represented by formula (1) and compounds represented by formula (2), thereby reducing the yellowness and devitrification of the resulting resin when a combination of polythiol compound (A) and a specific sulfur compound is included in the polymerizable composition.

[0030] In high-performance liquid chromatography (HCM) chromatography, the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) in the polythiol composition of Embodiment A is 1.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0031] The yellowness and devitrification of the resulting resin can be reduced by ensuring that the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) is 1.00 or less. From the same viewpoint as described above, the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.90 or less, more preferably 0.70 or less, even more preferably 0.50 or less, and particularly preferably 0.30 or less, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0032] There is no particular limit to the lower limit of the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), relative to a total peak area of ​​100 of the compounds contained in the polythiol composition. However, the lower limit is, for example, 0.05, preferably 0.10.

[0033] "The total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition" means the relative value of the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), when the total peak area of ​​the compounds contained in the polythiol composition is set to 100. Furthermore, the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) means, for example, the total peak area of ​​the compound represented by formula (1) and the compound represented by formula (2) if the polythiol composition contains both the compound represented by formula (1) and the compound represented by formula (2), and the peak area of ​​the one of the compounds if the polythiol composition contains only one of the compounds represented by formula (1) and the compound represented by formula (2).

[0034] In high-performance liquid chromatography measurements, the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) is preferably greater than 0, more preferably 0.02 or greater, even more preferably 0.05 or greater, and particularly preferably 0.1 or greater, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition, from the viewpoint of reducing the burden of the work of purifying and removing at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) from the polythiol composition. Furthermore, polymerization can be promoted by increasing the viscosity rate if the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) satisfies the above lower limit range.

[0035] The method for adjusting the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is not particularly limited, but can be adjusted by operations such as column purification, washing, extraction, and crystallization.

[0036] <Measurement of peak areas of compounds represented by formula (1) and formula (2)> The total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), relative to a total peak area of ​​100 of the compounds contained in the polythiol composition, is determined by performing high-performance liquid chromatography (HPLC) measurement under the following conditions. The peak area that appears at a retention time of 7.5 to 8.0 minutes can be determined as the peak area of ​​the compound represented by formula (1) and the compound represented by formula (2), and the ratio of the total peak area of ​​the compounds contained in the polythiol composition to 100 can be calculated. (HPLC conditions) Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm) Mobile phase: Acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Column temperature: 40℃ Flow rate: 1.0ml / min Detector: UV detector, wavelength 230nm Preparation of the measurement solution: Dissolve and mix 160 mg of the polythiol composition in 10 ml of acetonitrile. Injection volume: 2μL

[0037] Under the HPLC conditions described above, the retention times of the compound represented by formula (1) and the compound represented by formula (2) are both, for example, 6.0 minutes to 8.0 minutes. The molecular weight of the compound represented by formula (1) and the molecular weight of the compound represented by formula (2) are both 166.

[0038] [Embodiment B] The polythiol composition of Embodiment B comprises a polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by the following formula (3) and the compound represented by the following formula (4). In high-performance liquid chromatography measurements, the total peak area of ​​the at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) is 2.10 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0039] [ka]

[0040] The polythiol composition of Embodiment B, by including the above-mentioned components, makes it possible to produce a resin with reduced yellowness. Furthermore, the polythiol composition of Embodiment B can also be used to produce resins with reduced yellowness.

[0041] The total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition (Embodiment B) is determined in the same manner as described above for the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition (Embodiment A) (i.e., by HPLC measurement under similar conditions).

[0042] There is no particular limit to the lower limit of the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) relative to a total peak area of ​​100 of the compounds contained in the polythiol composition, but the lower limit is, for example, 0.10, preferably 0.20, and more preferably 0.30.

[0043] Under the HPLC conditions described above, the retention times of the compound represented by formula (3) and the compound represented by formula (4) are both, for example, 9.0 minutes to 11.0 minutes. The molecular weight of the compound represented by formula (3) and the molecular weight of the compound represented by formula (4) are both 226.

[0044] <Polythiol compound (A)> The polythiol composition of Embodiment B contains polythiol compound (A). Details regarding the polythiol compound (A), such as specific examples, preferred examples, preferred embodiments, and manufacturing methods, are the same as those for the polythiol compound (A) in Embodiment A.

[0045] The polythiol composition of Embodiment B may contain compounds other than the polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4). For example, the compound may include polythiol compound (A) and at least one polythiol compound having a mercapto group other than the compound represented by formula (3) and the compound represented by formula (4) (hereinafter also referred to as "other polythiol compounds"). Details regarding specific examples of other polythiol compounds are the same as those for specific examples of other polythiol compounds in Embodiment A.

[0046] Other examples of polythiol compounds include at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), which are characteristic of Embodiment A. In other words, the polythiol composition of Embodiment B may have the characteristics of the polythiol composition of Embodiment A described above.

[0047] <Compound represented by formula (3), compound represented by formula (4)> The polythiol composition of Embodiment B comprises at least one compound selected from the group consisting of compounds represented by the following formula (3) and compounds represented by the following formula (4).

[0048] [ka]

[0049] The polythiol composition of Embodiment B contains at least one compound selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4), thereby reducing the yellowness and devitrification of the resulting resin when a combination of polythiol compound (A) and a specific sulfur compound is included in the polymerizable composition.

[0050] In high-performance liquid chromatography (HCM) chromatography, the total peak area of ​​at least one compound selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4) in the polythiol composition of Embodiment B is 2.10 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0051] The yellowness and devitrification of the resulting resin can be reduced by ensuring that the total peak area of ​​at least one compound selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4) is 2.10 or less. From the same viewpoint as described above, the total peak area of ​​at least one compound selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4) is preferably 2.05 or less, more preferably 1.90 or less, and even more preferably 1.50 or less, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0052] "The total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition" means the relative value of the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4), when the total peak area of ​​the compounds contained in the polythiol composition is set to 100. Furthermore, the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) means, for example, the total peak area of ​​the compound represented by formula (3) and the compound represented by formula (4) if the polythiol composition contains both the compound represented by formula (3) and the compound represented by formula (4), and the peak area of ​​the one of the compounds if the polythiol composition contains only one of the compounds represented by formula (3) and the compound represented by formula (4).

[0053] In high-performance liquid chromatography measurements, the total peak area of ​​at least one compound selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4) is preferably greater than 0, more preferably 0.10 or greater, and even more preferably 0.30 or greater, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition, from the viewpoint of reducing the burden of the work of purifying and removing at least one compound selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4) from the polythiol composition. Furthermore, polymerization can be promoted by increasing the viscosity rate if the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) satisfies the above lower limit range.

[0054] The method for adjusting the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is not particularly limited, but can be adjusted by operations such as column purification, washing, extraction, and crystallization.

[0055] <Measurement of peak areas of compounds represented by formula (3) and formula (4)> The total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is determined by performing high-performance liquid chromatography (HPLC) measurement under the following conditions. The peak areas that appear at retention times of 9.8 minutes to 11.2 minutes should be determined as the peak areas of the compound represented by formula (3) and the compound represented by formula (4), and the ratio of the total peak area of ​​the compounds contained in the polythiol composition to 100 should be calculated. (HPLC conditions) Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm) Mobile phase: Acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Column temperature: 40℃ Flow rate: 1.0ml / min Detector: UV detector, wavelength 230nm Preparation of the measurement solution: Dissolve and mix 160 mg of the polythiol composition in 10 ml of acetonitrile. Injection volume: 2μL

[0056] ≪Polymerizable composition≫ The polymerizable composition of this disclosure comprises the polythiol composition of this disclosure and a polyiso(thio)cyanate compound.

[0057] (Polyiso(thio)cyanate compounds) The polyiso(thio)cyanate compound is not particularly limited as long as it can exhibit the effects of the present disclosure, and conventionally known compounds can be used. It is not particularly limited as long as it has at least two or more iso(thio)cyanate groups in one molecule, and specifically, for example, 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 xylylene diisocyanate; Alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, dicyclohexyldimethylmethane diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, and 4,9-bis(isocyanatomethyl)tricyclodecane; Aromatic polyisocyanate compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate, and phenylene diisocyanate; Heterocyclic polyisocyanate compounds such as 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, and 4,5-bis(isocyanatomethyl)-1,3-dithiolane; Aliphatic polyisothiocyanate compounds such as hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, and xylylene diisothiocyanate; Alicyclic polyisothiocyanate compounds such as isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, bis(isothiocyanatocyclohexyl)methane, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isothiocyanatomethyl)tricyclodecane, 3,9-bis(isothiocyanatomethyl)tricyclodecane, 4,8-bis(isothiocyanatomethyl)tricyclodecane, and 4,9-bis(isothiocyanatomethyl)tricyclodecane; Aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, and diphenyl disulfide-4,4-diisothiocyanate; Examples include sulfur-containing heterocyclic polyisothiocyanate compounds such as 2,5-diisothiocyanatothiophene, 2,5-bis(isothiocyanatomethyl)thiophene, 2,5-isothiocyanatotetrahydrothiophene, 2,5-bis(isothiocyanatomethyl)tetrahydrothiophene, 3,4-bis(isothiocyanatomethyl)tetrahydrothiophene, 2,5-diisothiocyanato-1,4-dithiane, 2,5-bis(isothiocyanatomethyl)-1,4-dithiane, 4,5-diisothiocyanato-1,3-dithiolane, and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane. The polyiso(thio)cyanate compound may include at least one selected from these.

[0058] Furthermore, as polyiso(thio)cyanate compounds, halogen-substituted compounds such as chlorine-substituted and bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer-type modified compounds with polyhydric alcohols, carbodiimide-substituted compounds, urea-substituted compounds, biuret-substituted compounds, and dimerization or trimmerization reaction products can also be used.

[0059] The polyiso(thio)cyanate compound is preferably a polyisocyanate compound, and preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene 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, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0060] The mixing ratio of the polythiol composition and the polyiso(thio)cyanate compound is not particularly limited. For example, the molar ratio (mercapto group / iso(thio)cyanate group) of the mercapto group of the polythiol compound to the iso(thio)cyanate group of the polyiso(thio)cyanate 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, it tends to be possible to satisfy various properties such as refractive index and heat resistance required for plastic lenses, etc., in a well-balanced manner.

[0061] The polymerizable composition of this disclosure may include a polyiso(thio)cyanate composition containing the above-mentioned polyiso(thio)cyanate compound.

[0062] Here, a polyisocyanate composition means a composition containing at least one polyisocyanate compound.

[0063] The polyisocyanate composition may contain components other than the polyisocyanate compound as impurities. The polyisocyanate composition preferably contains at least one polyisocyanate compound as its main component. The meaning of "contains as a main component" is as explained above.

[0064] The polyisocyanate composition preferably contains xylylene diisocyanate.

[0065] Hereinafter, a polyisocyanate composition containing xylylene diisocyanate will also be referred to as an XDI composition. The XDI composition preferably contains xylylene diisocyanate as its main component.

[0066] The XDI composition preferably contains at least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3).

[0067] [ka]

[0068] The following describes preferred embodiments of the XDI composition from the viewpoint of superior stability of the polyiso(thio)cyanate composition and transparency of the resin formed using the polyiso(thio)cyanate composition.

[0069] If the XDI composition contains compound (N1), it is preferable that the peak area of ​​compound (N1) in gas chromatography measurement under GC condition 1 below is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate. -GC condition 1- Filler; DB-1 (film thickness) 1.5 μm Column; inner diameter 0.53 mm x length 60 m (manufactured by Agilent) Oven temperature: Increase temperature from 130°C to 220°C at a rate of 3°C / min, then increase to 300°C at a rate of 10°C / min. Split ratio; pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300℃ Carrier gas: N2 158kPa, H255kPa, Air 45kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method; FID

[0070] The peak area of ​​the above 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 ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above 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 of ​​xylylene diisocyanate. The peak area of ​​the above compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent Publication No. 6373536.

[0071] If the XDI composition contains compound (N2), it is preferable that the peak area of ​​compound (N2) in gas chromatography measurement under GC condition 2 below is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate. -GC condition 2- Column; HP-50+, inner diameter 0.25 mm x length 30 m x film thickness 0.25 μm (manufactured by Hewlett-Packard) Oven temperature: Increase from 50°C to 280°C at a rate of 10°C / min, hold for 6 minutes after reaching 280°C. Split ratio; pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas; He Carrier gas flow rate: 1.0 ml / min (constant flow control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method; SIM (Monitoring ions: m / z 180, 215) (Content ratio of xylylene diisocyanate (XDI))

[0072] The peak area of ​​the above 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 ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above 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 ​​xylylene diisocyanate. The peak area of ​​the above compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent Publication No. 6373536.

[0073] If the XDI composition contains compound (N3), it is preferable that the peak area of ​​compound (N3) in the gas chromatography measurement under the aforementioned GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the above compound (N3) is more preferably 0.1 ppm or more, even more preferably 3.0 ppm or more, and even more preferably 5.0 ppm or more, relative to the peak area of ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above 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 ​​xylylene diisocyanate. The peak area of ​​the above compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent Publication No. 6373536.

[0074] The acidity of 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. The lower limit of the acidity of the XDI composition is not particularly limited, but the lower limit is, for example, 1 ppm. The acidity of the XDI composition can be measured in accordance with the method described in paragraph 0091 of International Publication No. 2021 / 256417. Furthermore, the XDI composition may contain a stabilizer.

[0075] The polymerizable compositions of this disclosure may contain other components besides polythiol compounds and polyiso(thio)cyanate compounds for the purpose of improving the various physical properties of the resin, handling properties, polymerization reactivity of the polymerizable composition, etc. Other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion enhancers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and other blue ink agents.

[0076] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0077] As an internal release agent, an acidic phosphate ester can be used. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more types.

[0078] Examples of resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and their anhydrides, and olefin compounds including (meth)acrylate compounds. The polymerizable composition of this disclosure can be obtained by mixing the above components.

[0079] Molded body The molded articles of this disclosure include the resin of this disclosure. The resins of this disclosure include cured products of the polymerizable compositions of this disclosure. The method for manufacturing the molded articles of this disclosure is not particularly limited, and a preferred manufacturing method is casting polymerization. First, a polymerizable composition is injected between molds held together by a gasket or tape. At this time, depending on the physical properties required of the resulting plastic lens, it is often preferable to perform degassing treatment under reduced pressure, filtration treatment under pressure or reduced pressure, etc., as necessary.

[0080] Polymerization conditions are not limited to specific conditions, as they vary greatly depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc. For example, polymerization is carried out at a temperature of -50°C to 150°C for 1 to 50 hours. In some cases, it is preferable to maintain the temperature in the range of 10°C to 150°C or gradually increase the temperature and cure it for 1 to 48 hours.

[0081] The molded article may be subjected to treatments such as annealing, if necessary. Annealing is usually carried out at a temperature between 50°C and 150°C, preferably between 90°C and 140°C, and more preferably between 100°C and 130°C.

[0082] [Application] The resin obtained from the polymerizable composition of this disclosure can be used as a material for manufacturing molded articles of various shapes by changing the type of mold used during casting polymerization.

[0083] ≪Optical materials≫ The optical materials of this disclosure include the resins of this disclosure. Molded articles obtained from the polymerizable composition of this disclosure can be made of a material with reduced yellowness without impairing transparency. Furthermore, molded articles obtained from a polymerizable composition containing the polythiol composition of the first embodiment can also be made of a material with excellent devitrification. Therefore, it can be used in various optical materials such as plastic lenses.

[0084] ≪Lens≫ The lens of this disclosure includes the resin of this disclosure. Lenses are particularly suitable as optical materials. Examples of lenses include plastic eyeglass lenses and plastic polarized lenses.

[0085] [Plastic eyeglass lenses] A plastic spectacle lens using a lens substrate made from the molded body of this disclosure may have a coating layer applied to one or both sides, as needed. The plastic spectacle lens of this disclosure comprises a lens substrate containing a cured product of the polymerizable composition described above, and a coating layer.

[0086] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers can be used individually or in multiple layers. When applying coating layers to both surfaces, the same coating layer may be applied to each surface, or different coating layers may be applied to each surface.

[0087] These coating layers may each contain known additives such as infrared absorbers to protect the eyes from infrared rays, light stabilizers and antioxidants to improve the weather resistance of the lenses, photochromic compounds, dyes, and pigments to enhance the fashionability of the lenses, and antistatic agents to improve the performance of the lenses. For the layer to be coated by application, various leveling agents may be used to improve the applicability. Furthermore, an anti-fogging layer, an anti-staining layer, and a water-repellent layer may be formed on top of the anti-reflective layer, as needed.

[0088] The embodiments described above are examples of this disclosure, and various other configurations can be adopted as long as they do not impair the effects of this disclosure. [Examples]

[0089] The present disclosure will be described in detail below with reference to the examples. However, the present disclosure is not limited in any way to the descriptions of these examples. Unless otherwise specified, "parts" are based on mass.

[0090] <Evaluation Method> In this embodiment, the method for evaluating each physical property of the plastic lens is as follows.

[0091] • Yellowness (Yellow Index, also known as YI) The resin was fabricated as a circular plastic plate with a thickness of 9 mm and a diameter of 75 mm, and the YI value was determined using a Konica Minolta CM-5 spectrophotometer. Furthermore, there is a correlation between the YI value and the degree of yellowness of the plastic sheet; a smaller YI value corresponds to less yellowness, while a larger YI value corresponds to greater yellowness.

[0092] ·Device clarity A circular plastic plate with a thickness of 9 mm and a diameter of 75 mm was fabricated from resin. Light from a light source (Luminar Ace LA-150A, manufactured by Hayashi Repic) was transmitted through the side of the plate. An image of the light from the front of the plate was captured by an image processing device (manufactured by Ube Information Systems Co., Ltd.), and grayscale processing was performed on the captured image. The degree of grayscale in the processed image was quantified for each pixel, and the average value of the grayscale values ​​for each pixel was obtained to determine the degree of devitrification of the plate. The lower the degree of devitrification, the less the transparency of the resin (in this case, the flat sheet) is impaired (i.e., the resin has superior transparency).

[0093] <Preparation of Polythiol Composition (A)> 124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water were added to the reactor. At 12°C to 35°C, 101.5 parts by mass of a 32% by mass aqueous sodium hydroxide solution were added dropwise over 40 minutes, followed by the dropwise addition of 73.6 parts by mass of epichlorohydrin at 29°C to 36°C over 4.5 hours, with stirring continued for another 40 minutes. NMR data confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol. 331.5 parts by mass of 35.5% hydrochloric acid was added, followed by 183.8 parts by mass of 99.90% pure thiourea. The mixture was stirred at 110°C under reflux for 3 hours to carry out the thironium chloride reaction. After cooling to 45°C, 320.5 parts by mass of toluene was added, and the mixture was cooled to 31°C. 243.1 parts by mass of 25% aqueous ammonia solution were added over 44 minutes at 31°C to 41°C, and the hydrolysis reaction was carried out by stirring at 54°C to 62°C for 3 hours to obtain a toluene solution of polythiol mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. 162.8 parts by mass of 35.5% hydrochloric acid was added to this toluene solution, and the mixture was acid washed at 35°C to 43°C for 1 hour. 174.1 parts by mass of degassed water was added, and the mixture was washed twice at 35°C to 45°C for 30 minutes each. 162.1 parts by mass of 0.1% aqueous ammonia was added and washed for 30 minutes. 174.2 parts by mass of degassed water was added and washed twice at 35°C to 45°C for 30 minutes each. After removing toluene and trace amounts of water under heating and reduced pressure, the mixture was filtered under reduced pressure using a 1.2 μm PTFE type membrane filter to obtain 205.0 parts by mass of a polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is a polythiol compound (A).

[0094] <Preparation of a polythiol composition (A1) containing the compound represented by formula (1) and the compound represented by formula (2)> 200.0 parts by mass of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane were added to a reactor along with 4.0 parts by mass of diethylenetriamine, 400 ml of toluene, and 100 ml of water. The mixture was heated and stirred at 80-85°C for 5 hours. After standing and separation, the lower aqueous layer was drained, and 200 parts by mass of 35% hydrochloric acid was added to the upper layer (toluene layer) remaining in the reactor. Acid washing was performed twice at 35-40°C for 1 hour each. After standing and separation, the lower aqueous layer was drained, and 200.0 parts by mass of degassed water was added to the toluene layer and washed at 35-45°C for 30 minutes. After standing and separation, the aqueous layer was drained, and 200.0 parts by mass of 0.1% aqueous ammonia was added to the toluene layer and washed for 30 minutes. After standing separation, the lower aqueous layer was discharged, and 200.0 parts by mass of degassed water was added to the toluene layer. Washing was performed twice for 30 minutes each. After removing toluene and trace amounts of water under heating and reduced pressure, the mixture was filtered under reduced pressure using a 1.2 μm PTFE type membrane filter to obtain 188.7 parts by mass of a polythiol composition (A1) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, a polythiol compound. The obtained polythiol composition (A1) contained a total peak area of ​​100 for all compounds, with the compounds represented by formula (1) and formula (2) combined present at a ratio of 1.50.

[0095] <Preparation of a polythiol composition (A2) containing the compound represented by formula (3) and the compound represented by formula (4)> 152.19 parts by mass of 2-mercaptoethanol and 23.1 parts by mass of degassed water were added to the reactor. At 15-30°C, 128.32 parts by mass of a 30.3% by mass aqueous sodium hydroxide solution was added dropwise over 30 minutes, followed by the addition of 89.99 parts by mass of epichlorohydrin dropwise over 3 hours at 27-30°C, with stirring continuing for 1 hour. 405.1 parts by mass of 35% hydrochloric acid was added, followed by 224.3 parts by mass of 99.4% pure thiourea. The mixture was stirred at 110°C under reflux for 3 hours to carry out the thironium chloride reaction. After cooling to 40°C, 395.0 parts by mass of toluene was added, and the mixture was cooled to 34°C. 293.3 parts by mass of a 25.4% by mass aqueous ammonia solution was added over 25 minutes at 34-40°C, and the hydrolysis reaction was carried out by stirring at 60°C-62°C for 3 hours to obtain a toluene solution of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. To this toluene solution, 180.0 parts by mass of 35% hydrochloric acid was added, and acid washing was carried out twice at 75-80°C for 3 hours. 200.0 parts by mass of degassed water was added, and washing was performed at 35-45°C for 30 minutes. 200.0 parts by mass of 0.1% aqueous ammonia was added and the mixture was washed for 30 minutes. 200.0 parts by mass of degassed water was added and the mixture was washed for 30 minutes twice. After removing toluene and trace amounts of water under heating and reduced pressure, the mixture was filtered under reduced pressure through a 1.2 μm PTFE type membrane filter to obtain 247.1 parts by mass of a polythiol composition (A2) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is the polythiol compound (A). The obtained polythiol composition (A2) contained 1.31 units of the compound represented by formula (3) and 1.50 units of the compound represented by formula (4) per 100 units of the total peak area of ​​the compounds.

[0096] [Examples 1-3] A polythiol composition was obtained by mixing the polythiol composition (A) and polythiol composition (A1) obtained as described above. At that time, the mixing ratios were changed and the compounds were mixed such that the total peak area of ​​the compound represented by formula (1) and the compound represented by formula (2) relative to the total peak area of ​​100 of the compounds contained in the polythiol composition was as shown in Table 1.

[0097] [Comparative Example 1] Polythiol composition (A1) was used as the polythiol composition.

[0098] <Measurement of the ratio (area%) of the compound represented by formula (1) and the compound represented by formula (2)> The ratio (area%) of the compound represented by formula (1) and the compound represented by formula (2) by HPLC was measured by the method described in the section "<Measurement of peak area of ​​the compound represented by formula (1) and the compound represented by formula (2)>" above. The results are shown in Table 1.

[0099] <Manufacturing of plastic lenses> [Manufacturing Example 1] 52 parts by mass of m-xylylene diisocyanate, 0.01 parts by mass of dibutyltin dichloride as a curing catalyst, 0.10 parts by mass of Zerec UN (product of Stepan; acidic phosphate ester), and 1.5 parts by mass of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.; ultraviolet absorber) were mixed and dissolved at 20°C. 48 parts by mass of the polythiol composition from Example 1 were added and mixed to form a homogeneous solution. This homogeneous solution was degassed at 600 Pa for 1 hour, filtered through a 1 μm Teflon® filter, and then poured into a mold consisting of a glass mold and tape. This mold was placed in an oven and gradually heated from 10°C to 120°C for 38 hours to polymerize. After polymerization was complete, the mold was removed from the oven and demolded to obtain the resin. The obtained resin was further annealed at 120°C for 1 hour to produce a plastic lens. The properties of each plastic lens were determined based on the evaluation method described above.

[0100] [Manufacturing Example 2] In Production Example 1, a plastic lens was manufactured in the same manner as described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was replaced with 48 parts by mass of the polythiol composition of Example 2. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above.

[0101] [Manufacturing Example 3] In Production Example 1, a plastic lens was manufactured in the same manner as described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was replaced with 48 parts by mass of the polythiol composition of Example 3. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above.

[0102] [Manufacturing Example 4] In Production Example 1, a plastic lens was manufactured in the same manner as described in Production Example 1, except that 48 parts by mass of the polythiol composition of Example 1 was replaced with 48 parts by mass of the polythiol composition of Comparative Example 1. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above. Table 1 shows the physical properties of the plastic lenses from Manufacturing Examples 1 to 4 (i.e., Examples 1 to 3 and Comparative Example 1).

[0103] [Table 1]

[0104] As shown in Table 1, Examples 1 to 3, which include a polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), showed superior YI and devitrification in high-performance liquid chromatography measurements, with the total peak area of ​​the at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) being 1.00 or less relative to the total peak area of ​​the compounds contained in the polythiol composition (100). On the other hand, Comparative Example 1, in which the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) was not 1.00 or less, was inferior in YI and devitrification.

[0105] [Reference example 1~Reference example 3] A polythiol composition was obtained by mixing the polythiol composition (A) and polythiol composition (A2) obtained as described above. At that time, the mixing ratios were changed and the compounds were mixed such that the total peak area of ​​the compound represented by formula (3) and the compound represented by formula (4) relative to the total peak area of ​​the compounds contained in the polythiol composition (100) was as shown in Table 2.

[0106] [Comparative Example 2] Polythiol composition (A2) was used as the polythiol composition.

[0107] <Measurement of the ratio (area%) of the compound represented by formula (3) and the compound represented by formula (4)> The ratio (area%) of the compound represented by formula (3) and the compound represented by formula (4) by HPLC is determined from the above-mentioned measurement of the peak area of ​​the compound represented by formula (3) and the compound represented by formula (4). It was measured by the method described in the section. The results are shown in Table 2.

[0108] <Manufacturing of plastic lenses> [Manufacturing Example 5] 52 parts by mass of m-xylylene diisocyanate, 0.01 parts by mass of dibutyltin dichloride as a curing catalyst, 0.10 parts by mass of Zerec UN (product of Stepan; acidic phosphate ester), and 1.5 parts by mass of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.; ultraviolet absorber) were mixed and dissolved at 20°C. 48 parts by mass of the polythiol composition from Reference Example 1 were added and mixed to obtain a homogeneous solution. This homogeneous solution was degassed at 600 Pa for 1 hour, filtered through a 1 μm Teflon® filter, and then poured into a mold consisting of a glass mold and tape. This mold was placed in an oven and gradually heated from 10°C to 120°C for 38 hours to polymerize. After polymerization was complete, the mold was removed from the oven and demolded to obtain the resin. The obtained resin was further annealed at 120°C for 1 hour to produce a plastic lens. The physical properties of the plastic lens were determined based on the evaluation method for each physical property of the plastic lens described above.

[0109] [Manufacturing Example 6] In Production Example 5, a plastic lens was manufactured in the same manner as described in Production Example 1, except that 48 parts by mass of the polythiol composition of Reference Example 1 was replaced with 48 parts by mass of the polythiol composition of Reference Example 2. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above.

[0110] [Manufacturing Example 7] In Production Example 5, a plastic lens was manufactured in the same manner as described in Production Example 1, except that 48 parts by mass of the polythiol composition of Reference Example 1 was replaced with 48 parts by mass of the polythiol composition of Reference Example 3. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above.

[0111] [Manufacturing Example 8] In Production Example 5, a plastic lens was manufactured in the same manner as described in Production Example 1, except that 48 parts by mass of the polythiol composition of Reference Example 1 was replaced with 48 parts by mass of the polythiol composition of Comparative Example 2. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above. Table 2 shows the physical properties of the plastic lenses from Manufacturing Examples 5 to 8 (i.e., Reference Examples 1 to 3 and Comparative Example 2).

[0112] [Table 2]

[0113] As shown in Table 2, Reference Examples 1 to 3, which include a polythiol compound (A) and at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4), showed excellent YI in high-performance liquid chromatography measurements, with the total peak area of ​​the at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) being 2.10 or less relative to the total peak area of ​​the compounds contained in the polythiol composition (100). On the other hand, Comparative Example 2, in which the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (3) and the compound represented by formula (4) was not 2.10 or less, was inferior to YI.

[0114] [Example 1X, Example 2X, Example 3X, Reference Example 1X, Reference Example 2X, and Reference Example 3X] In each of Examples 1X, 2X, 3X, Reference Example 1X, Reference Example 2X, and Reference Example 3X, the same procedures as in Examples 1, 2, 3, Reference Example 1, Reference Example 2, and Reference Example 3 were followed, except that the manufacturing of the molded article was modified as follows. The results obtained were the same as those for Examples 1, 2, 3, Reference Example 1, Reference Example 2, and Reference Example 3 (Tables 1 and 2).

[0115] -Changes from each of the following: Example 1, Example 2, Example 3, Reference Example 1, Reference Example 2, and Reference Example 3- In each of Examples 1, 2, 3, Reference Example 1, Reference Example 2, and Reference Example 3, m-xylylene diisocyanate (52 parts by mass) was used in the production of the molded article. However, in Examples 1X, 2X, 3X, Reference Example 1X, Reference Example 2X, and Reference Example 3X, XDI (52 parts by mass) was changed to XDI composition X1 (an amount containing 52 parts by mass of m-xylylene diisocyanate) as described above. XDI composition X1 was prepared by adding trace amounts of compound (N1), compound (N2), and compound (N3) to the main component XDI, and then mixing them together.

[0116] In XDI composition X1, gas chromatography measurements were performed using GC condition 1 and GC condition 2 as described above, and the results were as follows: The peak area of ​​compound (N1) is 0.20 ppm or more (specifically 600 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N2) is 0.05 ppm or more (specifically 18 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) was 0.10 ppm or more (specifically 100 ppm) relative to the peak area of ​​xylylene diisocyanate.

[0117] The disclosure of Japanese Patent Application No. 2022-146425, filed on 14 September 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. Polythiol compound (A) and A compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), Includes, A polythiol composition in which, in high-performance liquid chromatography measurement, the total peak area of ​​at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) is 1.00 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition. 【Chemistry 1】

2. The polythiol composition according to claim 1, wherein the polythiol compound (A) comprises a polythiol compound obtained from 2-mercaptoethanol and thiourea as raw materials.

3. The polythiol composition according to claim 1 or claim 2, wherein the polythiol compound (A) comprises 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, or 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.

4. A polythiol composition according to claim 1 or claim 2, Polyiso(thio)cyanate compounds, A polymerizable composition containing the following:

5. The polymerizable composition according to claim 4, wherein the polyiso(thio)cyanate compound comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene 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, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

6. The polyiso(thio)cyanate composition comprises the aforementioned polyiso(thio)cyanate compound, The polyiso(thio)cyanate composition is Xylylene diisocyanate and At least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3), Includes, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate (1). When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate (1). If the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in gas chromatography measurement is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate (1). The polymerizable composition according to claim 4. 【Chemistry 2】

7. A resin comprising a cured product of the polymerizable composition described in claim 4.

8. A molded article comprising the resin described in claim 7.

9. An optical material comprising the resin described in claim 7.

10. A lens comprising the resin described in claim 7.

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