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

Abstract

A polythiol composition containing polythiol compound A, which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and compound B1 which shows a retention time of 65-75 minutes in a high-performance liquid chromatography measurement under measurement condition A, wherein the peak area of compound B1 in the high-performance liquid chromatography measurement is 1.30 or less relative to the peak area of polythiol compound A of 100. Measurement condition A: Column: ODS-A. Mobile phase: a mixed solution of acetonitrile / aqueous 0.01 mol / L potassium dihydrogen phosphate solution = 60 / 40 (vol / vol). Measurement solution: a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile. Detector: a UV detector with a measurement wavelength of 230 nm. Column temperature: 40°C. Flow rate: 1.0 mL / min. Injection volume: 2 μL.

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 have rapidly spread in recent years as optical elements such as spectacle lenses and camera lenses because they are lighter and less likely to break than inorganic lenses and can be dyed.

[0003] There has been a demand for further performance improvement in resins for plastic lenses, and an increase in refractive index, an increase in Abbe number, a decrease in specific gravity, an increase in heat resistance, etc. have been required. 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, in Patent Document 2, 2-mercaptoethanol and an epihalohydrin compound represented by a specific formula (1) are reacted at a temperature of 10 to 50°C to obtain a polyalcohol compound represented by a specific formula (2), and the obtained polyalcohol compound represented by formula (2) and thiourea are reacted in the presence of hydrogen chloride to obtain an isothiouronium salt, and while maintaining the reaction solution containing the obtained isothiouronium salt at a temperature of 15 to 60°C, aqueous ammonia is added to the reaction solution within 80 minutes to hydrolyze the isothiouronium salt to obtain a polythiol compound represented by a specific formula (5), and 25 to 36% hydrochloric acid is added to the solution containing the obtained polythiol compound and washed at a temperature of 10 to 50°C to purify the polythiol compound. A method for producing a polythiol compound including these steps is described.

[0005] Patent Document 1: Japanese Patent Application 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] Examples of resins obtained using a polythiol composition include thiourethane resins. Thiourethane resins are typically manufactured using polythiol compositions and polyisocyanate compounds as raw materials. In some cases, it is necessary to further improve the heat resistance of thiourethane resin.

[0007] One embodiment of this disclosure aims to solve the problem of providing a polythiol composition and its applications that can produce a resin with excellent heat resistance. [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) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and a compound (B1) whose retention time in high-performance liquid chromatography measurement under the following measurement condition A is 65.0 minutes to 75.0 minutes, wherein the peak area of ​​compound (B1) in the high-performance liquid chromatography measurement is 1.30 or less relative to the peak area of ​​polythiol compound (A) which is 100. -Measurement Condition A- As the column, we used YMC-Pack(registered trademark) ODS-A manufactured by YMC Corporation (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm). 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 polythiol composition and 10 mL of acetonitrile was used as the measurement solution, an ultraviolet detector with a measurement wavelength of 230 nm was used as the detector, the column temperature was set to 40°C, the flow rate to 1.0 mL / min, and the injection volume to 2 μL. <2> The compound (B1) is a polythiol compound. <1> The polythiol composition described above. <3> The compound (B1) is at least two compounds selected from the group consisting of compounds represented by the following formulas (1) to (6). <1> or <2> The polythiol composition described above.

[0009] [ka]

[0010] <4> The peak area of ​​compound (B1) in the high-performance liquid chromatography measurement is 1.20 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition. <1> ~ <3> A polythiol composition as described in any one of the following. <5> The peak area of ​​the polythiol compound (A) in the high-performance liquid chromatography measurement is 91.50 or more relative to the total peak area of ​​the compounds contained in the polythiol composition (100). <1> ~ <4> A polythiol composition as described in any one of the following. <6> <1> ~ <5> A polymerizable composition comprising a polythiol composition described in any one of the above and a polyiso(thio)cyanate compound. <7> The polyiso(thio)cyanate compound comprises 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. <6> The polymerizable composition described above. <8> The polyiso(thio)cyanate composition comprises the aforementioned polyiso(thio)cyanate compound, The aforementioned polyiso(thio)cyanate composition Xylylene diisocyanate and At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3), comprising When the polyisothiocyanate composition contains the compound (N1), the peak area of the compound (N1) in gas chromatography measurement is the peak area of xylylene diisocyanate 1 is 0.20 ppm or more with respect to When the polyisothiocyanate composition contains the compound (N2), the peak area of the compound (N2) in gas chromatography measurement is the peak area of xylylene diisocyanate 1 is 0.05 ppm or more with respect to When the polyisothiocyanate composition contains the compound (N3), the peak area of the compound (N3) in gas chromatography measurement is the peak area of xylylene diisocyanate 1 is 0.10 ppm or more with respect to The polymerizable composition according to <6>.

[0011]

Chemical formula

[0012] <9> A resin containing a cured product of the polymerizable composition according to any one of <6> to <8>. <10> A molded article containing the resin according to <9>. <11> An optical material containing the resin according to <9>. <12> A lens containing the resin according to <9>.

Advantages of the Invention

[0013] According to one embodiment of the present disclosure, a polythiol composition capable of producing a resin having excellent heat resistance and its applications can be provided.

Modes for Carrying Out the Invention

[0014] In the present disclosure, a numerical range indicated using "~" indicates a range that includes the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described step by step in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other step-by-step descriptions, or may be replaced 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 when there are a plurality of substances corresponding to each component in the material, unless otherwise specified. In the present disclosure, "iso(thio)cyanate" means isocyanate or isothiocyanate.

[0015] ≪Polythiol Composition≫ The polythiol composition of the present disclosure includes a polythiol compound (A) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and a compound (B1) having a retention time of 65.0 minutes to 75.0 minutes in high performance liquid chromatography measurement under the following measurement condition A. The peak area of the compound (B1) in the high performance liquid chromatography measurement is 1.30 or less with respect to the peak area 100 of the polythiol compound (A). -Measurement Condition A- As the column, YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm) manufactured by WMC Co., Ltd. is used. As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) is used. As the measurement solution, a mixed solution of 160 mg of the polythiol composition and 10 mL of acetonitrile is used. As the detector, an ultraviolet detector with a measurement wavelength of 230 nm is used. The column temperature is set to 40°C. The flow rate is set to 1.0 mL / min. The injection volume is set to 2 μL.

[0016] The polythiol composition of this disclosure, by including the above-described composition, can be used to produce a resin with excellent heat resistance.

[0017] <Polythiol compound (A)> The polythiol composition of this disclosure comprises a polythiol compound (A) which is 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).

[0018] [ka]

[0019] 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.

[0020] The polythiol composition of this disclosure may contain compounds other than polythiol compound (A) and compound (B1). Specific examples of compounds other than polythiol compounds (A) and (B1) will be described later.

[0021] Preferably, the polythiol composition of this disclosure has a peak area of ​​91.50 or more of the total peak area of ​​the compounds contained in the polythiol composition, measured by high-performance liquid chromatography (i.e., high-performance liquid chromatography measurement under the measurement condition A below), relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition. -Measurement Condition A- As the column, we used YMC-Pack(registered trademark) ODS-A manufactured by YMC Corporation (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm). As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used. As the measurement solution, a mixed solution of 160 mg of polythiol composition and 10 mL of acetonitrile was used. As a detector, an ultraviolet detector with a measurement wavelength of 230 nm is used. The column temperature is set to 40°C. Set the flow rate to 1.0 mL / min. The injection volume should be 2 μL.

[0022] The peak area of ​​the above polythiol compound (A) is 91.50 or higher, which indicates excellent resin formation properties. From the above viewpoint, the peak area of ​​the polythiol compound (A) is preferably 91.60 or more, more preferably 91.70 or more, and even more preferably 91.80 or more, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0023] In high-performance liquid chromatography measurements, the peak area of ​​the polythiol compound (A) is preferably less than 100, more preferably 99.50 or less, even more preferably 99.00 or less, and still more preferably 95.00 or less, relative to the total peak area of ​​the compounds contained in the polythiol composition, from the viewpoint of producing a resin with excellent heat resistance.

[0024] <Measurement of peak area of ​​polythiol compound (A)> The peak area of ​​the polythiol compound (A) can be determined by performing high-performance liquid chromatography (HPLC) measurement under the following conditions. The peak area that appears between 11.5 and 13.5 minutes of retention is determined to be the peak area of ​​the polythiol compound (A), and the ratio of this area to the total peak area of ​​all compounds in the polythiol composition (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

[0025] <Compound (B1)> The polythiol composition of this disclosure includes compound (B1) having a retention time of 65.0 to 75.0 minutes in high-performance liquid chromatography measurement under the following measurement condition A. -Measurement Condition A- As the column, we used YMC-Pack(registered trademark) ODS-A manufactured by YMC Corporation (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm). As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used. As the measurement solution, a mixed solution of 160 mg of polythiol composition and 10 mL of acetonitrile was used. As a detector, an ultraviolet detector with a measurement wavelength of 230 nm is used. The column temperature is set to 40°C. Set the flow rate to 1.0 mL / min. The injection volume should be 2 μL.

[0026] Furthermore, for compound (B1) whose retention time in high-performance liquid chromatography measurement under measurement condition A is 65.0 to 75.0 minutes, LC-MS analysis performed under measurement condition B below confirms that its molecular weight is 518. -Measurement Condition B- The Waters LC-MS (ZQ) system was used as the apparatus. As the column, we used YMC-Pack(registered trademark) C18Rs manufactured by YMC Corporation (particle size S: 3 μm, pore size: 8 nm, column shape: Φ4.6 mm × 250 mm). As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L ammonium acetate aqueous solution = 70 / 30 (vol / vol) was used. As the measurement solution, a mixed solution of 10 μL of polythiol composition and 1 mL of acetonitrile was used. As a detector, an ultraviolet detector with a measurement wavelength of 230 nm is used. The column temperature is set to 40°C. The flow rate is set to 0.9 mL / min. The injection volume should be 10 μL. (MS conditions) Ionization Mode: ESI+ Capillary Voltage: 10V Cone Voltage: 10V Extractor Voltage: 4V Source Temp: 120℃ Desolvation Temp: 400℃ Cone Gas Flow: 50L / Hr Desolvation Gas Flow: 800 L / Hr Mass: 100~1000

[0027] Compound (B1) is preferably a polythiol compound.

[0028] More specifically, it is more preferable that compound (B1) is at least two compounds selected from the group consisting of compounds represented by the following formulas (1) to (6).

[0029] [ka]

[0030] The polythiol composition disclosed herein has a peak area of ​​compound (B1) of 1.30 or less relative to the peak area of ​​polythiol compound (A) of 100 in the high-performance liquid chromatography measurement (i.e., high-performance liquid chromatography measurement under measurement condition A). By having a peak area of ​​1.30 or less for the above compound (B1), a resin with excellent heat resistance can be produced. From the above viewpoint, the peak area of ​​compound (B1) is preferably 1.10 or less, more preferably 0.80 or less, and even more preferably 0.50 or less, relative to the peak area of ​​polythiol compound (A) of 100.

[0031] "The peak area of ​​compound (B1) relative to the peak area of ​​polythiol compound (A) (100)" means the relative value of the peak area of ​​compound (B1) when the peak area of ​​polythiol compound (A) is set to 100.

[0032] In high-performance liquid chromatography measurements, the peak area of ​​compound (B1) is preferably greater than 0, more preferably 0.01 or greater, even more preferably 0.10 or greater, and particularly preferably 0.20 or greater, relative to the peak area of ​​polythiol compound (A) (100), from the viewpoint of reducing the burden of the work required to purify and remove compound (B1) from the polythiol composition. Furthermore, by ensuring that the total peak area of ​​the above compound (B1) satisfies the above lower limit range, the viscosity can be increased, thereby promoting polymerization.

[0033] In the polythiol composition of this disclosure, it is preferable that the peak area of ​​compound (B1) in high-performance liquid chromatography measurement is 1.20 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition. By having a peak area of ​​1.20 or less for the above compound (B1), a resin with excellent heat resistance can be produced. From the above viewpoint, the peak area of ​​compound (B1) is preferably 1.00 or less, more preferably 0.80 or less, even more preferably 0.60 or less, and particularly preferably 0.40 or less, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

[0034] In high-performance liquid chromatography measurements, the peak area of ​​compound (B1) is preferably greater than 0, more preferably 0.01 or greater, even more preferably 0.10 or greater, and particularly preferably 0.20 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 required to purify and remove compound (B1) from the polythiol composition. Furthermore, by ensuring that the total peak area of ​​the above compound (B1) satisfies the above lower limit range, the viscosity can be increased, thereby promoting polymerization.

[0035] The method for adjusting the peak area of ​​compound (B1) relative to the peak area of ​​polythiol compound (A) (and the total peak area of ​​all compounds in the polythiol composition, which is 100) is not particularly limited, but can be adjusted by operations such as column purification, washing, extraction, and crystallization.

[0036] <Measurement of peak area of ​​compound (B1)> The peak area of ​​compound (B1) can be determined by performing high-performance liquid chromatography (HPLC) measurement under the following conditions. The peak area appearing between 65.0 and 75.0 minutes can be determined as the peak area of ​​compound (B1), and the ratio of the peak area of ​​polythiol compound (A) to 100, and the ratio of the total peak area of ​​all compounds 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] <Compounds other than polythiol compound (A) and compound (B1)> As stated above, the polythiol composition of this disclosure may contain compounds other than polythiol compound (A) and compound (B1).

[0038] Compounds other than polythiol compounds (A) and (B1) 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, and 4,8-dimercaptomethyl-1,11 Examples include -dimercapto-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.

[0039] (The compound represented by formula (X1)) Besides the polythiol compounds (A) and (B1), other compounds represented by the following formula (X1) can also be mentioned.

[0040] [ka]

[0041] In equation (X1), m and n each independently represent either 0 or 1, and m + n = 1.

[0042] The structure of the compound represented by formula (X1) is similar to the structure of the polythiol compound (A) in this disclosure (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; i.e., the compound represented by formula (a-1)). The structure of the compound represented by formula (X1) differs from the structure of the compound represented by formula (a-1), where both m and n are 1 (i.e., m+n=2), in that m and n each independently represent either 0 or 1, and m+n=1.

[0043] Examples of compounds represented by formula (X1) include the compound represented by formula (X1a) and the compound represented by formula (X1b).

[0044] [ka]

[0045] Furthermore, the polythiol composition of this disclosure may contain a plurality of compounds represented by formula (X1). For example, the polythiol composition of this disclosure may be a mixture of the compound represented by formula (X1a) and the compound represented by formula (X1b) as the compound represented by formula (X1). The compound represented by formula (X1) may be the compound represented by formula (X1a), the compound represented by formula (X1b), or a mixture of the compound represented by formula (X1a) and the compound represented by formula (X1b).

[0046] When the compound represented by formula (X1) contains the compound represented by formula (X1a) and the compound represented by formula (X1b), the content of the compound represented by formula (X1a) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total content of the compounds represented by formula (X1a) and formula (X1b).

[0047] (Compound (XB)) Other compounds besides the polythiol compounds (A) and (B1) include the following compound (XB). Compound (XB) also includes compounds obtained by replacing at least one of the three or more mercapto groups in a polythiol compound containing three or more mercapto groups (hereinafter also referred to as "polythiol compound (XA)") with a group represented by the following formula (XB-1). Here, the range of polythiol compounds containing three or more mercapto groups (i.e., polythiol compound (XA)) also includes polythiol compound (A) in this disclosure (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; i.e., the compound represented by formula (a-1)).

[0048] [ka]

[0049] In equation (XB-1), * represents a bond position.

[0050] Examples of compound (XB) are shown below, but compound (XB) is not limited to these examples.

[0051] [ka]

[0052] When the polythiol composition of this disclosure contains a compound represented by formula (X1) and compound (XB), the ratio of these compounds (compound represented by formula (X1) / compound (XB)) is preferably 1 to 30, more preferably 3 to 24, and even more preferably 5 to 18, from the viewpoint of reducing the yellowness and devitrification of the resulting resin and maintaining a good pot life of the polymerizable composition of this disclosure.

[0053] ≪Polymerizable composition≫ The polymerizable composition of this disclosure comprises the polythiol composition of this disclosure and a polyiso(thio)cyanate compound.

[0054] (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; 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; 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; These are some examples. The polyiso(thio)cyanate compound may include at least one selected from these.

[0055] 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.

[0056] As for the polyiso(thio)cyanate compound, polyisocyanate compounds are preferred. It is preferable to include 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.

[0057] 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.

[0058] The polymerizable composition of this disclosure may include a polyiso(thio)cyanate composition containing the above-mentioned polyiso(thio)cyanate compound.

[0059] Here, a polyiso(thio)cyanate composition means a composition containing at least one polyiso(thio)cyanate compound.

[0060] The polyiso(thio)cyanate composition may contain components other than the polyiso(thio)cyanate compound as impurities. The polyiso(thio)cyanate composition preferably contains at least one polyiso(thio)cyanate compound as its main component.

[0061] The polyiso(thio)cyanate composition preferably contains xylylene diisocyanate.

[0062] 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 its main component.

[0063] The XDI composition preferably contains at least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3).

[0064] [ka]

[0065] 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.

[0066] If the XDI composition contains compound (N1), it is preferable that the peak area of ​​compound (N1) in gas chromatography measurement under the following GC condition 1 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°C 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

[0067] 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.

[0068] 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))

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] [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.

[0080] ≪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.

[0081] ≪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.

[0082] [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.

[0083] 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.

[0084] 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.

[0085] 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]

[0086] 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.

[0087] <Evaluation Method> In this embodiment, the evaluation method for each physical property of the plastic lens is as follows. The results are shown in Table 1. ·Heat resistance Resin test specimens measuring 10 mm in length, 10 mm in width, and 2.5 mm in thickness were prepared. The glass transition temperature (Tg) was measured using the TMA penetration method (50 g load, 0.5 mm diameter pin tip, heating rate of 10 °C / min) with a Shimadzu TMA-60 thermomechanical analyzer, and this was used as an indicator of heat resistance. Furthermore, the higher the glass transition temperature (Tg), the better the heat resistance.

[0088] <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. 101.5 parts by mass of a 32% by mass aqueous sodium hydroxide solution was added dropwise over 40 minutes at 12°C to 35°C, followed by the dropwise addition of 73.6 parts by mass of epichlorohydrin over 4.5 hours at 29°C to 36°C, with stirring continued for another 40 minutes. NMR data of the resulting reaction solution confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol. Next, 331.5 parts by mass of hydrochloric acid with a concentration of 35.5% by mass was added to the reactor containing 1,3-bis(2-hydroxyethylthio)-2-propanol, followed by 183.8 parts by mass of thiourea with a purity of 99.90% by mass. The mixture was stirred at 110°C under reflux for 3 hours to carry out the thironium chloride reaction. After the reaction solution following the thironium chloride reaction was cooled to 45°C, 320.5 parts by mass of toluene were added, and the mixture was cooled to 31°C. 243.1 parts by mass of a 25% by mass 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. To this toluene solution, 162.8 parts by mass of hydrochloric acid with a concentration of 35.5% by mass was added, and the mixture was acid-washed at 35°C to 43°C for 1 hour. After acid washing, 174.1 parts by mass of degassed water was added to the toluene solution, and washing was performed twice at 35°C to 45°C for 30 minutes each. After washing with degassed water, 162.1 parts by mass of 0.1% by mass of aqueous ammonia was added to the toluene solution, and washing was performed for 30 minutes. After washing with aqueous ammonia, 174.2 parts by mass of degassed water was added to the toluene solution, and washing was performed twice at 35°C to 45°C for 30 minutes each. Next, after washing with degassed water, toluene and trace amounts of water were removed from the toluene solution under reduced pressure and heating. Then, 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).

[0089] <Preparation of a polythiol composition (B1) containing compound (B1)> 80.0 parts by mass of polythiol composition (A) and 80.0 parts by mass of a 25% by mass aqueous ammonia solution were placed in the reactor. The resulting solution was stirred at 60°C for 4 days while air was blown into it at a flow rate of 20 mL / min. The resulting reaction product was dissolved in 125.4 parts by mass of toluene and toluene extraction was performed. Then, 30.0 parts by mass of 35.5% by mass hydrochloric acid was added to the resulting toluene solution and the mixture was acid washed at 35°C to 43°C for 15 minutes. After acid washing, 30.0 parts by mass of degassed water was added to the toluene solution and the mixture was acid washed at 35°C to 45°C for 30 minutes. This procedure was repeated twice. After washing with degassed water, 30.0 parts by mass of 0.1% by mass aqueous ammonia was added to the toluene solution and the mixture was acid washed for 30 minutes. After washing with aqueous ammonia, 30.0 parts by mass of degassed water was added to the toluene solution and the mixture was acid washed at 35°C to 45°C for 30 minutes. This procedure was repeated twice. Next, after washing with degassed water, toluene and trace amounts of water were removed from the toluene solution under reduced pressure and heating. Then, the mixture was filtered under reduced pressure using a 3 μm PTFE type membrane filter to obtain 75.4 parts by mass of a polythiol composition (B1) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, which is the polythiol compound (A), and further containing compound (B1). The obtained polythiol composition (B1) contained a total peak area of ​​13.0 for every 100 total peak areas of the compounds (B1). In the HPLC analysis under the above measurement condition A, the area values ​​of the two peaks (i.e., isomers) at 65 min and 74 min were summed to calculate the area ratio (13.0) of compound (B1). LC-MS analysis of the two peaks under measurement condition B described above revealed that both peaks had a molecular weight of 518. The two peaks at 65 min and 74 min (i.e., isomers) were confirmed to be at least two compounds selected from the group consisting of compounds represented by formulas (1) to (6).

[0090] [Examples 1-4, Comparative Examples 1-2] A polythiol composition was obtained by mixing the polythiol composition (A) and polythiol composition (B1) obtained as described above. At that time, the mixing ratio was changed and each compound was mixed so that the total peak area of ​​compound (B1) relative to the total peak area of ​​the compounds in the polythiol composition (100) was the value shown in Table 1.

[0091] <Measurement of the ratio (area%) of polythiol compound (A) and compound (B1)> The ratio (area%) of polythiol compound (A) and compound (B1) by HPLC was measured using the methods described in the sections "<Measurement of peak area of ​​polythiol compound (A)>" and "<Measurement of peak area of ​​compound (B1)>" above. The results are shown in Table 1.

[0092] <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.

[0093] [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.

[0094] [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.

[0095] [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 Example 4. Each physical property of the plastic lens was determined based on the evaluation method for each physical property of the plastic lens described above.

[0096] [Manufacturing Example 5] 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.

[0097] [Manufacturing Example 6] 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 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.

[0098] Table 1 shows the physical properties of the plastic lenses from Manufacturing Examples 1 to 6 (i.e., Examples 1 to 4 and Comparative Examples 1 to 2).

[0099] [Table 1]

[0100] As shown in Table 1, each example using a polythiol composition comprising a polythiol compound (A) which is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and a compound (B1) whose retention time in high-performance liquid chromatography measurement under measurement condition A is 65.0 to 75.0 minutes, wherein the peak area of ​​compound (B1) in the high-performance liquid chromatography measurement is 1.30 or less relative to the peak area of ​​polythiol compound (A) which is 100, was able to produce a resin with a high Tg temperature and excellent heat resistance. On the other hand, in Comparative Examples 1 and 2, where the peak area of ​​compound (B1) was not 1.30 or less relative to the peak area of ​​polythiol compound (A) (100), the Tg temperature was low, and it was not possible to produce a resin with excellent heat resistance.

[0101] [Production Example 1X~Production Example 6X] For each of Manufacturing Examples 1X to 6X, the same operations as those for Manufacturing Examples 1 to 6 were performed, except that the manufacturing of the plastic lens was modified as follows. The results obtained were the same as those for Manufacturing Examples 1 to 6 (i.e., Examples 1 to 4, Comparative Examples 1 to 2) (Table 1).

[0102] -Changes from each of the manufacturing examples 1 to 6- In each of Production Examples 1 to 6, m-xylylene diisocyanate (XDI) (52 parts by mass) was used in the production of the plastic lens. However, in each of Production Examples 1X to 6X, the XDI (52 parts by mass) was replaced with XDI composition X1 (an amount containing 52 parts by mass) 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.

[0103] 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 ​​XDI. The peak area of ​​compound (N2) is 0.05 ppm or more (specifically 18 ppm) relative to the peak area of ​​XDI. The peak area of ​​compound (N3) was 0.10 ppm or more (specifically 100 ppm) relative to the peak area of ​​XDI.

[0104] The disclosure of Japanese Patent Application No. 2022-165812, filed on 14 October 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. A polythiol compound (A) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, Compound (B1) whose retention time in high-performance liquid chromatography measurement under the following measurement condition A is 65.0 minutes to 75.0 minutes, Includes, In the high-performance liquid chromatography measurement, the peak area of ​​compound (B1) is 1.30 or less and 0.10 or more relative to the peak area of ​​polythiol compound (A) which is 100. The compound (B1) is a polythiol composition in which at least two compounds are selected from the group consisting of compounds represented by the following formulas (1) to (6). -Measurement Condition A- The column used is YMC-Pack (registered trademark) ODS-A, manufactured by YMC Corporation. Using (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm), As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L-potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used. As the measurement solution, a mixed solution of 160 mg of polythiol composition and 10 mL of acetonitrile was used. As a detector, an ultraviolet detector with a measurement wavelength of 230 nm is used. The column temperature is set to 40°C. Set the flow rate to 1.0 mL / min. The injection volume should be 2 μL. 【Chemistry 1】

2. The polythiol composition according to claim 1, wherein the peak area of ​​compound (B1) in the high-performance liquid chromatography measurement is 1.20 or less relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

3. The polythiol composition according to claim 1, wherein the peak area of ​​the polythiol compound (A) in the high-performance liquid chromatography measurement is 91.50 or more relative to the total peak area of ​​100 of the compounds contained in the polythiol composition.

4. A polythiol composition according to any one of claims 1 to 3, 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 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. A polyiso(thio)cyanate composition comprising the aforementioned polyiso(thio)cyanate compound. fruit, 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, If the polyiso(thio)cyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement under the following GC condition 1 is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate, If the polyiso(thio)cyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement under the following GC condition 2 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 under the following GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. The polymerizable composition according to claim 4. 【Chemistry 2】 -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 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 once 220°C is reached. Split ratio; pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas; N ２ 158 kPa, H ２ 55 kPa, Air 45 kPa (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 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) (percentage of xylylene diisocyanate (XDI) content)

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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