Polythiol composition and its applications

Abstract

The present invention provides a polythiol composition which contains a polythiol compound, wherein: the composition contains a compound C2 that has a retention time of 16.0 minutes to 19.0 minutes as determined by high-speed liquid chromatography under specific measurement conditions A; and the peak area of the compound C2 as determined by the high-speed liquid chromatography is 1,000 or more relative to a total of 100 of the peak area of the compound C2 and the peak area of the main component of the polythiol composition.

Description

[Technical Field]

[0001] The present disclosure relates to polythiol compositions and applications thereof. [Background technology]

[0002] Plastic lenses, which are lenses containing resin, are lighter and less likely to break than inorganic lenses, and can be dyed, and so in recent years have rapidly become popular for use in eyeglass lenses, camera lenses, and the like. For example, various studies have been conducted on lenses containing thiourethane resins (see, for example, Patent Documents 1 to 3).

[0003] Patent document 1: Japanese Patent Application Laid-Open No. 63-46213 Patent document 2: Japanese Patent Application Laid-Open No. 2-270859 Patent Document 3: Japanese Patent Application Laid-Open No. 7-252207 Summary of the Invention [Problem to be solved by the invention]

[0004] The thiourethane resin is usually produced using a polythiol composition and a polyisocyanate compound as raw materials. There are cases where thiourethane resins are required to have improved dyeability.

[0005] An object of one embodiment of the present disclosure is to provide a polythiol composition that can produce a thiourethane resin with excellent dyeability, and applications thereof. [Means for solving the problem]

[0006] The means for solving the above problems include the following aspects. <1> A polythiol composition containing a polythiol compound, The compound C2 has a retention time of 16.0 minutes to 19.0 minutes in high performance liquid chromatography measurement under the following measurement condition A, the peak area of ​​the compound C2 measured by high performance liquid chromatography is 1.000 or more relative to the total peak area (100) of the peak area of ​​the compound C2 and the peak area of ​​the main component in the polythiol composition; Polythiol compositions. -Measurement Condition A- The column used was Mightysil (registered trademark) RP-18 GP (particle size S: 5 μm, column shape: Φ6 mm × 150 mm, product number: 25477-96) manufactured by Kanto Chemical Co., Ltd. The mobile phase used was a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol). A mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used as the measurement solution. The detector used was an ultraviolet detector with a measurement wavelength of 230 nm. The column temperature was set to 40°C. The flow rate was set to 1.0 mL / min. The injection volume was 2 μL. <2> The compound C2 is a polythiol compound having a molecular weight of 320. <1> or <2> The polythiol composition according to claim 1. <3> Further, the composition contains a compound C3 having a retention time of 32.0 minutes to 35.0 minutes in the high performance liquid chromatography measurement, the peak area of ​​the compound C3 measured by high performance liquid chromatography is 0.050 or more relative to 100, which is the total peak area of ​​the peak area of ​​the compound C3 and the peak area of ​​the main component in the polythiol composition; <1> or <2> The polythiol composition according to claim 1. <4> The compound C3 is a polythiol compound having a molecular weight of 426. <3> The polythiol composition according to claim 1. <5> Further, the compound C4 has a retention time of 21.5 minutes to 25.0 minutes in the high performance liquid chromatography measurement, the peak area of ​​the compound C4 measured by high performance liquid chromatography is 0.030 or more relative to 100, which is the total peak area of ​​the peak area of ​​the compound C4 and the peak area of ​​the main component in the polythiol composition; <1> ~ <4> The polythiol composition according to any one of the preceding claims. <6> The compound C4 is a polythiol compound having a molecular weight of 380. <5> The polythiol composition according to claim 1. <7> The main component is a polythiol compound (XA) containing three or more mercapto groups. <1> ~ <6> The polythiol composition according to any one of the preceding claims. <8> The polythiol compound (XA) is a polythiol component A1 which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; or the polythiol component A2 is at least one selected from the group consisting 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; <7> The polythiol composition according to claim 1. <9> The polythiol compound (XA) is a polythiol component A1 which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane. <7> The polythiol composition according to claim 1. <10> a polyiso(thio)cyanate compound; <1> ~ <9> The polythiol composition according to any one of the above items, A polymerizable composition for optical materials comprising: <11> 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. <10> The polymerizable composition for an optical material according to claim 1. <12> Contains a polyiso(thio)cyanate composition containing the polyiso(thio)cyanate compound, <10> or <11> The polymerizable composition for an optical material according to claim 1. <13> The polyiso(thio)cyanate composition is Xylylene diisocyanate, At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3): Including, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 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) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. <12> The polymerizable composition for an optical material according to claim 1. -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and 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 rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate content)

[0007] [ka]

[0008] <14> <10> ~ <13> 2. A resin which is a cured product of the polymerizable composition for an optical material according to claim 1. <15> <14> A molded article comprising the resin described in 1. <16> <14> An optical material comprising the resin described in 1. <17> <14> A lens comprising the resin described in 1.

[0009] <18> a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; <1> ~ <9> 10. A method for producing a polymerizable composition for an optical material, comprising: mixing the polythiol composition according to any one of the above items 1 to 9 with a polymerizable composition for an optical material. <19> The polyiso(thio)cyanate composition is Xylylene diisocyanate, At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3): Including, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 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) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. <18> 10. A method for producing the polymerizable composition for an optical material according to claim 9. -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and 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 rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate content)

[0010] [ka]

[0011] <20> A composition set used for producing a polymerizable composition for an optical material, comprising: a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; <1> ~ <9> The polythiol composition according to any one of the above items, A composition set comprising: <21> The polyiso(thio)cyanate composition is Xylylene diisocyanate, At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3): Including, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 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) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. <20> The composition set described in -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and 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 rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate (XDI) content)

[0012] [ka] [Effects of the Invention]

[0013] According to one aspect of the present disclosure, a polythiol composition capable of producing a thiourethane resin having excellent dyeability and an application thereof are provided. DETAILED DESCRIPTION OF THE INVENTION

[0014] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0015] [Polythiol composition] The polythiol composition of the present disclosure comprises: A polythiol composition containing a polythiol compound, The compound C2 has a retention time of 16.0 minutes to 19.0 minutes in high performance liquid chromatography measurement under the following measurement condition A (hereinafter also simply referred to as "high performance liquid chromatography measurement"); the peak area of ​​compound C2 measured by high performance liquid chromatography is 1.000 or more relative to the total peak area (100) of the peak area of ​​compound C2 and the peak area of ​​the main component in the polythiol composition; It is a polythiol composition.

[0016] (Measurement condition A) The column used was Mightysil (registered trademark) RP-18 GP (particle size S: 5 μm, column shape: Φ6 mm × 150 mm, product number: 25477-96) manufactured by Kanto Chemical Co., Ltd. The mobile phase was a mixture of acetonitrile and 0.01 mol potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol). A mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile was used as the measurement solution. The detector used was an ultraviolet detector with a measurement wavelength of 230 nm. The column temperature was set to 40°C. The flow rate was set to 1.0 mL / min. The injection volume was set to 2 μL.

[0017] By using the polythiol composition of the present disclosure as one of the raw materials for a thiourethane resin, a thiourethane resin with excellent dyeability can be produced.

[0018] (Polythiol composition) In this disclosure, a polythiol composition refers to a composition that contains at least one polythiol compound. In the present disclosure, the polythiol compound contained in the polythiol composition is also referred to as the "polythiol component." The polythiol composition may contain components other than the polythiol compound as impurities. The polythiol composition preferably contains at least one polythiol compound as a main component.

[0019] Here, "the polythiol composition contains at least one polythiol compound as a main component" means that the total content of the at least one polythiol compound relative to the total amount of the polythiol composition is 50% or more. The total content of the at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

[0020] Similarly, in the present disclosure, a composition "containing a certain component (hereinafter referred to as "component X") as a main component" means that the content of component X (when component X consists of two or more compounds, the total content of the two or more compounds) is 50% or more of the total amount of the composition. The content of the main component, component X, is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, based on the total amount of the composition.

[0021] The "%" in the explanation of the above phrase "contains as a main component" means the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) to the total area of ​​all peaks of the composition (e.g., a polythiol composition) determined by high performance liquid chromatography under the above measurement condition A.

[0022] The polythiol composition includes polythiol compositions containing known polythiol compounds. There are no particular limitations on the polythiol compound, as long as it is a compound containing two or more thiol groups (also known as mercapto groups). For the polythiol compound, reference can be made appropriately to the above-mentioned known documents (that is, JP-A Nos. 63-46213, 2-270859, 7-252207, WO 2008 / 047626, etc.).

[0023] (Compound C2) The polythiol composition of the present disclosure contains compound C2. Compound C2 is a compound whose retention time in high performance liquid chromatography measurement under measurement conditions A is 16.0 minutes to 19.0 minutes. The polythiol composition of the present disclosure may contain only one type of compound C2, or may contain two or more types. Compound C2 may or may not be a polythiol compound, but is preferably a polythiol compound.

[0024] Compound C2 is a component effective for improving the dyeability of a thiourethane resin produced using the polythiol composition. In the polythiol composition of the present disclosure, the peak area of ​​compound C2 (hereinafter also simply referred to as the "peak area of ​​compound C2") relative to the total peak area of ​​compound C2 and the peak area of ​​the main component in the polythiol composition (100) in high performance liquid chromatography measurement is 1.000 or more, thereby exhibiting the effect of improving the dyeability of the produced thiourethane resin.

[0025] From the viewpoint of further improving the dyeability of the produced thiourethane resin, the lower limit of the peak area of ​​compound C2 is preferably 1.250, more preferably 1.500, even more preferably 1.600, even more preferably 2.500, even more preferably 3.100, even more preferably 4.000, even more preferably 7.000, and even more preferably 8.000.

[0026] From the viewpoint of reducing the yellowness index (YI) of the produced thiourethane resin, the upper limit of the peak area of ​​compound C2 is preferably 20,000, more preferably 15,000, even more preferably 13,000, even more preferably 9,000, and even more preferably 6,000.

[0027] The molecular weight of compound C2 is, for example, 320. The molecular weight referred to here is a value measured by high performance liquid chromatography mass spectrometry under the measurement condition B below. (Measurement condition B) The column used was a YMC-Pack (registered trademark) C18RS (particle size S: 3 μm, column shape: Φ4.6 mm × 250 mm) manufactured by YMC Co., Ltd. The mobile phase used was a mixed solution of 10 mM ammonium acetate aqueous solution / acetonitrile = 30 / 70 (vol / vol). The detector used was an ultraviolet detector with a measurement wavelength of 230 nm. The column temperature was set to 40°C. The flow rate was set to 0.9 mL / min. The following conditions were applied as the mass analysis conditions. Ionization Mode:ESI+ Capillary Voltage: 3.0 kV Cone Voltage: 20 V Extractor: 4V Source Temp: 120℃ Desolvation Temp: 400℃ Cone Gas Flow: 50 L / Hr Desolvation Gas Flow: 800 L / Hr Mass: m / z 50-800

[0028] An example of compound C2 is a polythiol compound having a molecular weight of 320. As the compound C2, which is a polythiol compound having a molecular weight of 320, for example, 20 Examples include compounds represented by S6. Molecular formula C9H 20 An example of the compound C2, which is a compound represented by S6, is a compound represented by the following formula (C2-1).

[0029] [ka]

[0030] In formula (C2-1), each of l, m, and n is 0 or 1, and the sum of l, m, and n is 1.

[0031] The compound represented by formula (C2-1) may be a mixture of two or more compounds with different combinations of l, m, and n.

[0032] When compound C2 is a polythiol compound, it preferably contains at least one selected from the group consisting of the following compound (C2-1a), the following compound (C2-1b), and the following compound (C2-1c).

[0033] [ka]

[0034] Compound (C2-1a) is a compound represented by formula (C2-1), in which n is 1, and l and m are both 0. Compound (C2-1b) is a compound represented by formula (C2-1), in which l is 1, and n and m are both 0. The compound (C2-1b) is a compound represented by formula (C2-1), in which m is 1, and l and m are both 0.

[0035] (Compound C3) The polythiol composition of the present disclosure preferably further contains compound C3. This further improves the dyeability of the produced thiourethane resin. Compound C3 is a compound whose retention time in high performance liquid chromatography measurement under measurement conditions A is 32.0 minutes to 35.0 minutes. When the polythiol composition of the present disclosure contains compound C3, the compound C3 contained may be only one type, or two or more types. Compound C3 may or may not be a polythiol compound, but is preferably a polythiol compound.

[0036] In the high performance liquid chromatography measurement under the above measurement conditions A, the peak area of ​​compound C3 (hereinafter also simply referred to as "peak area of ​​compound C3") relative to the total peak area of ​​100, which is the peak area of ​​compound C3 and the peak area of ​​the main component in the polythiol composition, is preferably 0.050 or more. This further improves the dyeability of the produced thiourethane resin.

[0037] From the viewpoint of further improving the dyeability of the produced thiourethane resin, the lower limit of the peak area of ​​compound C3 is more preferably 0.100 or more, even more preferably 0.150 or more, even more preferably 0.600, even more preferably 1.000, even more preferably 1.500, and even more preferably 2.000.

[0038] From the viewpoint of reducing the yellowness index (YI) of the produced thiourethane resin, the upper limit of the peak area of ​​compound C3 is preferably 5,000, more preferably 4,000, even more preferably 3,500, even more preferably 2,500, even more preferably 2,000, and even more preferably 1,500.

[0039] The molecular weight of compound C3 is, for example, 426. The molecular weight referred to here is a value measured by high performance liquid chromatography mass spectrometry under the measurement condition B described above.

[0040] An example of compound C3 is a polythiol compound having a molecular weight of 426. As the compound C3, which is a polythiol compound having a molecular weight of 426, for example, 12 H 26 Examples include compounds represented by S8. Molecular formula C 12 H 26Examples of compound C3, which is a compound represented by S8, include at least one selected from the group consisting of compounds represented by the following formula (C3-1), (C3-2), or (C3-3):

[0041] [ka]

[0042] In formulas (C3-1) to (3-3), each of p, q, r, and s is 0 or 1, and the sum of p, q, r, and s is 1.

[0043] (Compound C4) The polythiol composition of the present disclosure preferably further contains compound C4. This further improves the dyeability of the produced thiourethane resin. Compound C4 is a compound whose retention time in high performance liquid chromatography measurement under measurement conditions A is 21.5 minutes to 25.0 minutes. When the polythiol composition of the present disclosure contains compound C4, the compound C4 contained may be only one type, or two or more types. Compound C4 may or may not be a polythiol compound, but is preferably a polythiol compound.

[0044] In the high performance liquid chromatography measurement under the above measurement condition A, the peak area of ​​compound C4 (hereinafter also simply referred to as "peak area of ​​compound C4") relative to the total peak area of ​​compound C4 and the peak area of ​​the main component in the polythiol composition, 100, is preferably 0.030 or more. This further improves the dyeability of the produced thiourethane resin.

[0045] From the viewpoint of further improving the dyeability of the produced thiourethane resin, the lower limit of the peak area of ​​compound C4 is preferably 0.040, more preferably 0.500, and even more preferably 0.600.

[0046] From the viewpoint of reducing the yellowness index (YI) of the produced thiourethane resin, the upper limit of the peak area of ​​compound C4 is preferably 1.300, more preferably 1.200, and even more preferably 1.100.

[0047] The molecular weight of compound C4 is, for example, 380. The molecular weight referred to here is a value measured by high performance liquid chromatography mass spectrometry under the measurement condition B described above.

[0048] Compound C4 is, for example, a polythiol compound having a molecular weight of 380. As the compound C4, which is a polythiol compound having a molecular weight of 380, for example, 11 H 24 Examples include compounds represented by S7. Molecular formula C 11 H 24 Examples of the compound C4, which is a compound represented by S7, include at least one selected from the group consisting of compounds represented by the following formula (C4-1).

[0049] [ka]

[0050] In formula (C4-1), each of l, m, and n is 0, 1, or 2, and the sum of l, m, and n is 2.

[0051] The compound represented by formula (C4-1) may be a mixture of two or more compounds with different combinations of l, m, and n.

[0052] (Polythiol compound (XA)) The main component in the polythiol composition of the present disclosure is preferably a polythiol compound, and is preferably a polythiol compound (XA) containing three or more mercapto groups. Here, polythiol compound (XA) is a polythiol compound containing three or more mercapto groups. However, if the aforementioned compound C2 is a "polythiol compound containing three or more mercapto groups," compound C2 is not included in the scope of polythiol compound (XA). Similarly, if the polythiol composition of the present disclosure contains compound C3, and the aforementioned compound C3 is a "polythiol compound containing three or more mercapto groups," compound C3 is not included in the scope of polythiol compound (XA).

[0053] Polythiol compound (XA) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 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 It is preferable.

[0054] Polythiol compound (XA) is a polythiol component A1 which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; or 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and Polythiol component A2 is at least one selected from the group consisting of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane. It is preferable that The polythiol component A1 is more preferred.

[0055] Here, the polythiol component A1 (that is, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane) is the following compound (A1).

[0056] [ka]

[0057] Under the above measurement conditions A, polythiol component A1 has a retention time between 12.0 minutes and 13.0 minutes, and polythiol component A2 has a retention time between 22.0 minutes and 26.0 minutes.

[0058] (Other ingredients) The polythiol composition of the present disclosure may contain at least one component other than the main component (for example, another polythiol compound, a component other than a polythiol compound, etc.). Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), bis(mercaptoethyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetra Examples include bis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0059] [Polymerizable composition for optical materials] The polymerizable composition for optical materials of the present disclosure (hereinafter also simply referred to as "polymerizable composition") is a polyiso(thio)cyanate compound; The polythiol composition of the present disclosure described above; Contains:

[0060] The polymerizable composition of the present disclosure contains the polythiol composition of the present disclosure described above, and therefore exhibits effects similar to those of the polythiol composition of the present disclosure.

[0061] (Polyiso(thio)cyanate compounds) The polyiso(thio)cyanate compound is not particularly limited as long as it has at least two iso(thio)cyanate groups in one molecule. Specific examples of polyiso(thio)cyanate compounds 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 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, diphenylsulfide-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 of sulfur-containing heterocyclic polyisothiocyanate compounds include 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 can include at least one selected from these.

[0062] Furthermore, the polyiso(thio)cyanate compound may also be a halogen-substituted product such as a chlorine-substituted product or a bromine-substituted product, an alkyl-substituted product, an alkoxy-substituted product, a nitro-substituted product, a prepolymer-type modified product with a polyhydric alcohol, a carbodiimide-modified product, a urea-modified product, a biuret-modified product, a dimerization or trimerization reaction product, or the like.

[0063] Polyiso(thio)cyanate compounds are It is preferable that the composition contains a polyisocyanate compound, It is preferable that the isocyanate-modifying agent contains at least one selected from 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.

[0064] The mixing ratio of the polythiol composition and the polyiso(thio)cyanate compound is not particularly limited, and for example, the molar ratio of mercapto groups of the polythiol compound contained in the polythiol composition to iso(thio)cyanate groups of the polyiso(thio)cyanate compound (mercapto groups / iso(thio)cyanate groups) 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 achieve a good balance of various performance characteristics required for plastic lenses, such as refractive index and heat resistance.

[0065] The polymerizable composition of the present disclosure may contain a polyiso(thio)cyanate composition comprising a polyiso(thio)cyanate compound. That is, the polymerizable composition of the present disclosure is a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; The polythiol composition of the present disclosure described above; It may also contain

[0066] When the polymerizable composition of the present disclosure contains a polyiso(thio)cyanate composition, the contained polyiso(thio)cyanate compound may be one type only, or two or more types.

[0067] When the polymerizable composition of the present disclosure contains a polyiso(thio)cyanate composition, the polyiso(thio)cyanate composition contained preferably contains xylylene diisocyanate. This improves the stability of the polyiso(thio)cyanate composition and the transparency of the resin formed using the polyiso(thio)cyanate composition (that is, clouding and / or yellowing is further suppressed).

[0068] Hereinafter, a polyiso(thio)cyanate composition containing xylylene diisocyanate will also be referred to as an XDI composition. The XDI composition preferably contains xylylene diisocyanate as a major component.

[0069] The XDI composition preferably contains at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).

[0070] [ka]

[0071] Below, preferred embodiments of the XDI composition will be described from the viewpoint of achieving excellent stability of the polyiso(thio)cyanate composition and transparency of a resin formed using the polyiso(thio)cyanate composition.

[0072] When the XDI composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is preferably 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate. -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: 0.53 mm inner diameter x 60 m length (Agilent) Oven temperature: Increase the temperature from 130°C to 220°C at 3°C / min, and then increase the temperature from 220°C to 300°C at 10°C / min. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H2 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID

[0073] The peak area of ​​the 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. The peak area of ​​the 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 compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0074] When the XDI composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area 1 of xylylene diisocyanate. -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at a rate of 10°C / min, and 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 rate control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (xylylene diisocyanate (XDI) content)

[0075] The peak area of ​​the 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. The peak area of ​​the 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 compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.

[0076] When the XDI composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the above-mentioned GC condition 1 is preferably 0.10 ppm or more relative to the peak area 1 of xylylene diisocyanate. The peak area of ​​the 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. The peak area of ​​the 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 compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0077] The acid content 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, even more preferably less than 15 ppm. The lower limit of the acid content of the XDI composition is not particularly limited, but the lower limit is, for example, 1 ppm. The acid content of the XDI composition can be measured in accordance with the method described in paragraph 0091 of WO 2021 / 256417.

[0078] The XDI composition may also include a stabilizer.

[0079] The polymerizable composition of the present disclosure may contain components other than the polythiol composition and the polyiso(thio)cyanate compound. Examples of other components include a polymerization catalyst, an internal mold release agent, a resin modifier, a chain extender, a crosslinking agent, a radical scavenger, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, an adhesion improver, an antibacterial agent, an antistatic agent, a dye, a fluorescent brightener, a fluorescent pigment, a blue ink agent such as an inorganic pigment, and the like.

[0080] Examples of the polymerization catalyst include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0081] The internal mold release agent may be an acidic phosphate ester, such as a monophosphate ester or a diphosphate ester, which may be used alone or in combination of two or more.

[0082] Examples of the resin modifier 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 the present disclosure can be obtained by mixing the above components.

[0083] The method for producing the polymerizable composition of the present disclosure is not particularly limited, and examples thereof include the following production method according to one embodiment. In addition, the following composition set according to one embodiment may be used to produce the polymerizable composition of the present disclosure.

[0084] [Method for producing polymerizable composition for optical material] A method for producing a polymerizable composition for an optical material according to one embodiment of the present disclosure includes a step of mixing a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound with the polythiol composition of the present disclosure. According to the method for producing a polymerizable composition for an optical material according to the embodiment, the polymerizable composition of the present disclosure can be easily produced.

[0085] In one embodiment of the method for producing a polymerizable composition for an optical material, The polyiso(thio)cyanate composition comprises: Xylylene diisocyanate, At least one selected from the group consisting of the compound (N1), the compound (N2), and the compound (N3), It is preferred that the compound contains: In this case, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the above-mentioned GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the above-mentioned GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the above-mentioned GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. It is more preferable that

[0086] The method for producing a polymerizable composition for an optical material according to the embodiment may include other steps in addition to the mixing step, if necessary. Other steps include a step of mixing the mixture obtained in the mixing step with other components in the polymerizable composition of the present disclosure other than the polythiol composition and the polyiso(thio)cyanate compound. These other ingredients may also be mixed with the polyiso(thio)cyanate composition and xylylene diisocyanate in the mixing step.

[0087] [Composition set] The composition set according to one embodiment of the present disclosure comprises: A composition set used for producing a polymerizable composition for an optical material, comprising: a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; The polythiol composition of the present disclosure described above; Includes. According to the composition set according to the one embodiment, the polymerizable composition of the present disclosure described above can be easily produced. For example, the composition set according to the embodiment can be used to carry out the mixing step in the method for producing a polymerizable composition for an optical material according to the embodiment.

[0088] In one embodiment, the composition set comprises: The polyiso(thio)cyanate composition comprises: Xylylene diisocyanate, At least one selected from the group consisting of the compound (N1), the compound (N2), and the compound (N3), It is preferred that the compound contains: In this case, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the above-mentioned GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the above-mentioned GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the above-mentioned GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. It is more preferable that

[0089] 〔resin〕 The resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure described above. The resin of the present disclosure can be obtained by curing the polymerizable composition of the present disclosure described above.

[0090] The polymerizable composition can be cured by polymerizing the monomers in the polymerizable composition (specifically, the polythiol composition and the polyiso(thio)cyanate compound; the same applies hereinafter). As a pretreatment for polymerization, the polymerizable composition may be subjected to treatments such as filtration and degassing. The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition are appropriately set in consideration of the composition of the composition, the type and amount of the monomers in the composition, the type and amount of the polymerization catalyst in the composition, and the properties of the mold when a mold described below is used. The polymerization temperature may be, for example, from -50°C to 150°C, or from 10°C to 150°C. The polymerization time may be, for example, 1 hour to 200 hours, or 1 hour to 80 hours.

[0091] When obtaining the resin of the present disclosure, a polymer obtained by polymerization of a monomer may be subjected to a treatment such as annealing to obtain the resin. The annealing temperature may be 50°C to 150°C, 90°C to 140°C, or 100°C to 130°C.

[0092] [Molded body] The molded article of the present disclosure contains the resin of the present disclosure. The molded article of the present disclosure can be obtained by curing the polymerizable composition of the present disclosure, similar to the resin of the present disclosure. The preferred conditions for curing the polymerizable composition, i.e., for polymerizing the monomers in the polymerizable composition, are as described above.

[0093] An example of a preferred method for producing the molded article of the present disclosure is cast polymerization. In cast polymerization, the polymerizable composition is first poured into a mold held by a gasket or tape, etc. At this time, degassing treatment, filtration treatment, etc. may be carried out as necessary. Next, the monomer in the polymerizable composition injected between the molds is polymerized to cure the composition between the molds, and the cured product is then removed from the molds to obtain a molded article containing the resin. The polymerization of the monomer may be carried out by heating the polymerizable composition, for example, using a heating device equipped with a mechanism for heating an object to be heated in an oven, water, or the like.

[0094] In cast polymerization, by changing the shape of the mold, it is possible to obtain molded articles of various shapes (for example, the optical materials described below).

[0095] [Optical materials] The optical material of the present disclosure includes the resin of the present disclosure. The optical material of the present disclosure can be obtained by curing the polymerizable composition of the present disclosure, similar to the resin of the present disclosure. The preferred conditions for curing the polymerizable composition, i.e., for polymerizing the monomers in the polymerizable composition, are as described above.

[0096] Examples of optical materials include lenses (for example, eyeglass lenses, camera lenses, and polarized lenses), light-emitting diodes (LEDs), and the like.

[0097] The optical material of the present disclosure may include a coating layer formed on one or both sides of the resin of the present disclosure (or a molded article containing the resin of the present disclosure). Specific examples of the coating layer include a primer layer, a hard coat layer, an anti-reflection layer, an anti-fogging coat layer, an anti-fouling layer, and a water-repellent layer. These coating layers may be formed individually or in a multi-layer structure of multiple coating layers. When coating layers are formed on both sides, the same coating layer may be formed on each side, or different coating layers may be formed on each side.

[0098] The components of the coating layer can be appropriately selected depending on the purpose. Examples of components of the coating layer include resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, and antistatic agents.

[0099] For details about eyeglass lenses and coating layers, reference can be made as appropriate to the descriptions in publicly known documents such as International Publication No. WO 2017 / 047745. [Example]

[0100] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.

[0101] <Production of Composition (A1-1) Containing Polythiol Component A1 as the Main Component> A composition (A1-1) containing polythiol component A1 as a main component was produced, as detailed below. A reactor was charged with 124.6 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water. 101.5 parts by mass of a 32% by mass aqueous sodium hydroxide solution was added dropwise over 40 minutes at 12 to 35°C, followed by 73.6 parts by mass of epichlorohydrin at 29 to 36°C over 4.5 hours, followed by stirring for 40 minutes. As a result, 1,3-bis(2-hydroxyethylthio)-2-propanol was produced in the reactor. This production was confirmed by NMR data. Next, 331.5 parts by weight of 35.5% by weight hydrochloric acid was added to the reactor, followed by 183.8 parts by weight of 99.90% by weight thiourea. The mixture was then stirred at 110°C under reflux for 3 hours to carry out a thiuronium chloride reaction. The liquid in the reactor was then cooled to 45°C, and 320.5 parts by weight of toluene was added. The resulting liquid was then cooled to 31°C. 243.1 parts by weight of 25% by weight aqueous ammonia solution was then added over 44 minutes at 31°C to 41°C, followed by stirring at 54°C to 62°C for 3 hours to carry out a hydrolysis reaction. This resulted in a toluene solution of a polythiol composition primarily composed of polythiol component A1 (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane). This toluene solution was then acid washed with 162.8 parts by weight of 35.5% by weight hydrochloric acid at 35°C to 43°C for 1 hour. The toluene solution after the acid wash was washed twice with 174.1 parts by mass of degassed water at 35°C to 45°C for 30 minutes. The toluene solution after the second wash with degassed water was washed with 162.1 parts by mass of 0.1% by mass ammonia water for 30 minutes. The toluene solution after the ammonia water wash was washed twice with 174.2 parts by mass of degassed water at 35°C to 45°C for 30 minutes. Next, the toluene and trace amounts of water were removed from this solution under heating and reduced pressure, followed by treatment with silica gel column chromatography and subsequent filtration under reduced pressure using a 1.2 μm PTFE-type membrane filter to obtain a composition (A1-1) (205.0 parts by mass) containing polythiol component A1 as the main component.

[0102] <Production of composition (A1-2) containing polythiol component A1 as the main component> A composition (A1-2) containing polythiol component A1 as the main component was produced. In the production of composition (A1-2), the amount of sodium hydroxide used in the step of producing 1,3-bis(2-hydroxyethylthio)-2-propanol was reduced compared to the production of composition (A1-1), thereby increasing the amount of residual 2-mercaptoethanol. As a result, in the production of composition (A1-2), conditions were set that made it easier to produce compound C2 (i.e., at least one selected from the group consisting of compound (C2-1a), compound (C2-1b), and compound (C2-1c) below), a reaction by-product of polythiol component A1 (i.e., compound (A1) below), the main reaction product, compared to the production of composition (A1-1).

[0103] [ka]

[0104] The production of the composition (A1-2) will be described in detail below. A reactor was charged with 124.8 parts by mass of 2-mercaptoethanol and 22.5 parts by mass of degassed water. 99.0 parts by mass of a 30.8% by mass aqueous sodium hydroxide solution was added dropwise over 40 minutes at 12°C to 35°C, followed by 74.0 parts by mass of epichlorohydrin added dropwise over 4.5 hours at 29°C to 36°C, followed by stirring for 40 minutes. As a result, 1,3-bis(2-hydroxyethylthio)-2-propanol was produced in the reactor. This production was confirmed by NMR data. Next, 331.7 parts by weight of 35.5% by weight hydrochloric acid was added to the reactor, followed by 182.7 parts by weight of 99.90% by weight thiourea. The mixture was then stirred at 110°C under reflux for 3 hours to carry out a thiuronium chloride reaction. The liquid in the reactor was then cooled to 45°C, and 355.0 parts by weight of toluene was added. The resulting liquid was then cooled to 31°C. 245.2 parts by weight of 25% by weight aqueous ammonia solution was then added over 44 minutes at 31°C to 41°C, followed by stirring at 54°C to 62°C for 3 hours to carry out a hydrolysis reaction. This resulted in a toluene solution of a polythiol composition primarily composed of polythiol component A1 (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane). This toluene solution was then acid washed with 147.8 parts by weight of 35.5% by weight hydrochloric acid at 35°C to 43°C for 1 hour. The toluene solution after the acid wash was washed twice with 147.8 parts by mass of degassed water at 35°C to 45°C for 30 minutes. The toluene solution after the second wash with degassed water was washed with 147.8 parts by mass of 0.1% by mass ammonia water for 30 minutes. The toluene solution after the ammonia water wash was washed twice with 147.8 parts by mass of degassed water at 35°C to 45°C for 30 minutes. Next, the toluene and trace amounts of water were removed from this solution under heating and reduced pressure, and the solution was filtered under reduced pressure using a 3.0 μm PTFE-type membrane filter to obtain a composition (A1-2) (199.7 parts by mass) containing polythiol component A1 as the main component.

[0105] [Examples 1 to 6] <Production of Polythiol Composition> The composition (A1-1) and the composition (A1-2) were mixed in a mixing mass ratio [composition (A1-1) / composition (A1-2)] of 99 / 1 to obtain the polythiol composition of Example 1, which contains polythiol component A1 as a main component and further contains compound C2 and compound C3 as reaction by-products.

[0106] The polythiol composition of Example 2 was obtained in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1) / composition (A1-2)] was changed to 75 / 25.

[0107] The polythiol composition of Example 3 was obtained in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1) / composition (A1-2)] was changed to 60 / 40.

[0108] The polythiol composition of Example 4 was obtained in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1) / composition (A1-2)] was changed to 40 / 60.

[0109] The polythiol composition of Example 5 was obtained in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1) / composition (A1-2)] was changed to 20 / 80.

[0110] The polythiol composition of Example 6 was obtained in the same manner as the polythiol composition of Example 1, except that the mixing mass ratio [composition (A1-1) / composition (A1-2)] was changed to 0 / 100.

[0111] <Measurement of Peak Areas of Compounds C2, C3, and C4> For each of the polythiol compositions of Examples 1 to 5, the peak area of ​​compound C2, the peak area of ​​compound C3, and the peak area of ​​compound C4 were determined by high performance liquid chromatography under the measurement conditions A described above. where: Compound C2 is a compound having a retention time of 16.0 minutes to 19.0 minutes in high performance liquid chromatography measurement under measurement condition A, Compound C3 is a compound having a retention time of 32.0 minutes to 35.0 minutes in high performance liquid chromatography measurement under measurement condition A, Compound C4 is a compound having a retention time of 21.5 minutes to 25.0 minutes in high performance liquid chromatography measurement under measurement condition A, The peak area of ​​compound C2 is the peak area of ​​compound C2 relative to the total peak area 1 of the peak area of ​​compound C2 and the peak area of ​​the main component in the polythiol composition (i.e., polythiol component A1), The peak area of ​​compound C3 is the peak area of ​​compound C3 relative to the total peak area 1 of the peak area of ​​compound C3 and the peak area of ​​the main component in the polythiol composition (ie, polythiol component A1). The peak area of ​​compound C4 is the peak area of ​​compound C4 relative to the total peak area 1 of the peak area of ​​compound C4 and the peak area of ​​the main component in the polythiol composition (ie, polythiol component A1). The results are shown in Table 1.

[0112] <Production of polymerizable composition and resin molded product> XDI composition X1 (52 parts by mass) as the XDI composition described above, which is one embodiment of the polyiso(thio)cyanate composition; Dibutyltin dichloride (0.01 parts by mass) as a curing catalyst; Zelec UN (trade name, manufactured by Stepan; acidic phosphate ester) (0.10 parts by mass) as a release agent, Biosorb 583 (Kyodo Pharmaceutical Co., Ltd.; ultraviolet absorber) (1.5 parts by mass) as an ultraviolet absorber, The mixture was mixed and dissolved at 20°C. The resulting mixture was mixed with 48 parts by mass of the polythiol composition of any one of Examples 1 to 5 to obtain a polymerizable composition that was a homogeneous mixture. Next, the polymerizable composition was degassed at 600 Pa for 1 hour. The degassed polymerizable composition was filtered through a 1 μm Teflon (registered trademark) filter, and the filtrate was poured between a pair of glass molds secured with tape. The pair of glass molds were then placed in an oven, and the temperature inside the oven was set to 10° C. Next, the temperature inside the oven was raised from 10° C. to 120° C. over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the polymerizable composition were polymerized, and a molded product containing the resin (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Subsequently, the inside of the oven was cooled, and after cooling, the pair of glass molds was removed from the oven, and then the molded body containing the resin (hereinafter referred to as the resin molded body) was removed from the pair of glass molds. As a result, a flat resin molded body having a thickness of 9 mm was obtained.

[0113] The XDI composition X1 was subjected to gas chromatography measurement under the above-mentioned GC conditions 1 and 2. As a result, the peak area of ​​the compound (N1) is 0.20 ppm or more (specifically, 600 ppm) relative to the peak area of ​​xylylene diisocyanate; the peak area of ​​the compound (N2) is 0.05 ppm or more (specifically, 18 ppm) relative to the peak area of ​​xylylene diisocyanate; The peak area of ​​the compound (N3) was 0.10 ppm or more (specifically, 100 ppm) relative to the peak area of ​​xylylene diisocyanate.

[0114] <Measurement and evaluation of resin molded products> The obtained resin molded product in the form of a flat plate having a thickness of 9 mm was subjected to measurement of yellowness index (YI) and evaluation of dyeability. The results are shown in Table 1.

[0115] (Yellowness (YI)) The yellowness index (YI) of a 9 mm thick flat resin molding was measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. The smaller the yellowness index (YI) of the resin molded product, the better the hue of the resin molded product.

[0116] (Stainability) A 9 mm thick flat resin molding was dyed, and the light transmittance of the dyed resin molding was measured to evaluate the dyeability of the resin molding. The lower the light transmittance of the dyed resin molding, the better the dyeability of the resin molding. Details are shown below.

[0117] 1985.5g of pure water, 1.5g of "FSP Red EA" (dye, manufactured by Futaba Sangyo Co., Ltd.) 1.0g of "FSP Yellow PE" (dye, manufactured by Futaba Sangyo Co., Ltd.) 4.0g of "FSP Blue AUL-S" (dye, manufactured by Futaba Sangyo Co., Ltd.) 4.0g of "Nikka Sunsalt #7000" (Nicca Chemical Co., Ltd., dye dispersant) "DK-CN" (dyeing auxiliary, manufactured by Yamato Chemical Industry Co., Ltd.) 4.0 g, were added and mixed to obtain a dye dispersion. A 9 mm thick plate-shaped resin molded body was immersed in the obtained dye dispersion at 90° C. for 30 minutes to dye the resin molded body. The light transmittance (%) of the dyed resin molded article was measured in the range of 350 nm to 800 nm, and the light transmittance (%) at 567 nm was calculated from the measurement results. The results are shown in Table 1. As mentioned above, the lower the light transmittance (%) at 567 nm, the better the dyeability of the resin molded body.

[0118] [Table 1]

[0119] As shown in Table 1, in Examples 1 to 6, which used polythiol compositions containing compound C2 having a retention time of 16.0 minutes to 19.0 minutes in high-performance liquid chromatography measurement under measurement condition A, and in which the peak area of ​​compound C2 in the high-performance liquid chromatography measurement was 1.000 or more relative to 100, the total peak area of ​​the peak area of ​​compound C2 and the peak area of ​​the main component in the polythiol composition, was obtained, resin molded articles with excellent dyeability.

[0120] The disclosure of Japanese Patent Application No. 2022-010749, filed on January 27, 2022, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A polythiol composition containing a polythiol compound, The compound C2 has a retention time of 16.0 minutes to 19.0 minutes in high performance liquid chromatography under the following measurement conditions A: the peak area of ​​the compound C2 measured by high performance liquid chromatography is 1.000 or more and 20,000 or less, relative to 100, which is the total peak area of ​​the peak area of ​​the compound C2 and the peak area of ​​a major component in the polythiol composition; The main component is polythiol component A1, which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; The compound C2 is at least one selected from the group consisting of the following compound (C2-1a), the following compound (C2-1b), and the following compound (C2-1c): Polythiol compositions. --Measurement Condition A-- The column used was Mightysil (registered trademark) RP-18 GP (particle size S: 5 μm, column shape: Φ6 mm × 150 mm, product number: 25477-96) manufactured by Kanto Chemical Co., Ltd. A mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used as the mobile phase. A mixed solution of 160 mg of a polythiol composition and 10 mL of acetonitrile was used as the measurement solution. As a detector, an ultraviolet detector with a measurement wavelength of 230 nm was used. The column temperature was set to 40°C. The flow rate was 1.0 mL / min. The injection volume was 2 μL. 【Chemical 1】

2. Further, the composition contains compound C3 having a retention time of 32.0 minutes to 35.0 minutes in the high performance liquid chromatography measurement, the peak area of ​​the compound C3 measured by high performance liquid chromatography is 0.050 or more relative to 100, which is the total peak area of ​​the peak area of ​​the compound C3 and the peak area of ​​the main component in the polythiol composition; The polythiol composition of claim 1 .

3. The polythiol composition of claim 2 , wherein compound C3 is a polythiol compound having a molecular weight of 426.

4. Further, the composition contains compound C4 having a retention time of 21.5 minutes to 25.0 minutes in the high performance liquid chromatography measurement, the peak area of ​​the compound C4 measured by high performance liquid chromatography is 0.030 or more relative to 100, which is the total peak area of ​​the peak area of ​​the compound C4 and the peak area of ​​the main component in the polythiol composition; The polythiol composition according to claim 1 or claim 2.

5. The polythiol composition of claim 4 , wherein compound C4 is a polythiol compound having a molecular weight of 380.

6. a polyiso(thio)cyanate compound; The polythiol composition according to claim 1 or claim 2; A polymerizable composition for optical materials comprising:

7. 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. The polymerizable composition for an optical material according to claim 6 .

8. The polymerizable composition for an optical material according to claim 6 , comprising a polyiso(thio)cyanate composition containing the polyiso(thio)cyanate compound.

9. The polyiso(thio)cyanate composition is Xylylene diisocyanate, at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); Including, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate: The polymerizable composition for an optical material according to claim 8 . -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm x length 60 m (Agilent) Oven temperature: Raise from 130°C to 220°C at 3°C / min, and after reaching 220°C, raise the temperature at 10°C / min to 300°C. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at 10°C / min, and 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 rate control) Sample concentration: 1.0 mass% dichloromethane solution Injection volume: 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (content of xylylene diisocyanate) 【Chemistry 2】

10. A resin which is a cured product of the polymerizable composition for optical materials according to claim 6.

11. A molded article comprising the resin according to claim 10.

12. An optical material comprising the resin according to claim 10.

13. A lens comprising the resin of claim 10.

14. a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; A method for producing a polymerizable composition for an optical material, comprising a step of mixing the polythiol composition according to claim 1 or 2 with a polymerizable composition for an optical material.

15. The polyiso(thio)cyanate composition is Xylylene diisocyanate, at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); Including, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate: The method for producing the polymerizable composition for an optical material according to claim 14 . -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm x length 60 m (Agilent) Oven temperature: Raise from 130°C to 220°C at 3°C / min, and after reaching 220°C, raise the temperature at 10°C / min to 300°C. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at 10°C / min, and 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 rate control) Sample concentration: 1.0 mass% dichloromethane solution Injection volume: 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (content of xylylene diisocyanate) 【Chemistry 3】

16. A composition set used for producing a polymerizable composition for an optical material, comprising: a polyiso(thio)cyanate composition containing a polyiso(thio)cyanate compound; The polythiol composition according to claim 1 or claim 2; A composition set comprising:

17. The polyiso(thio)cyanate composition is Xylylene diisocyanate, at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); Including, When the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography under the following GC condition 2 is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyiso(thio)cyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by gas chromatography under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate:

17. The set of compositions according to claim 16. -GC condition 1- Filler: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm x length 60 m (Agilent) Oven temperature: Raise from 130°C to 220°C at 3°C / min, and after reaching 220°C, raise the temperature at 10°C / min to 300°C. Split ratio: Pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55kPa, Air 45kPa (constant pressure control) Solvent: chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method: FID -GC condition 2- Column: HP-50+, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm (Hewlett-Packard) Oven temperature: Raise from 50°C to 280°C at 10°C / min, and 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 rate control) Sample concentration: 1.0 mass% dichloromethane solution Injection volume: 1.0μL Detection method: SIM (monitoring ions: m / z 180, 215) (content of xylylene diisocyanate (XDI)) 【Chemistry 4】

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