Polythiol preparations, polymerizable preparations, resins, molded objects, optical materials, and lenses.

Abstract

The invention relates to a polythiol composition, which comprises: a polythiol component T, which is at least one compound selected from the group 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; and a component X, having a retention time between 30.0 min and 40.0 min in a specific high-performance liquid chromatography (HPLC) measurement; and component Y, with retention times ranging from 60.0 min to 70.0 min, where, in the specific high-performance liquid chromatography (HPLC) measurement, component X has a peak area less than or equal to 5.00 relative to a total peak area of ​​100, and component Y has a peak area less than or equal to 2.50 relative to a total peak area of ​​100.

Description

Polythiol composition and its applications

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

[0002] Plastic lenses, which are lenses containing resin, are lighter and less likely to break than inorganic lenses, and can be dyed, and therefore have rapidly become popular in recent years for use as eyeglass lenses, camera lenses, etc. For example, Patent Documents 1 and 2 disclose tetrafunctional thiols having specific structures as raw materials for plastic lenses.

[0003] Patent Document 1: JP-A-7-252207 Patent Document 2: WO 2014 / 027428

[0004] Examples of tetrafunctional thiols in Patent Documents 1 and 2 include three compounds: 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. However, there are cases where a resin produced using at least one compound selected from the group consisting of these three compounds (hereinafter also referred to as "polythiol component T") is required to have reduced yellowness and / or improved heat resistance.

[0005] The problem to be solved by the first and second embodiments of the present disclosure is to provide a polythiol composition capable of producing a resin having reduced yellowness and improved heat resistance, and applications thereof.

[0006] Means for solving the above problems include the following aspects. A polythiol composition according to a first embodiment of the present disclosure is the polythiol composition described in <1> below. A polythiol composition according to a second embodiment of the present disclosure is the method for producing a polythiol composition described in <5> below.

[0007] <1> A polythiol component T 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; a component X having a retention time of 30.0 minutes to 40.0 minutes in high performance liquid chromatography measurement under the following measurement condition A; and a component Y having the retention time of 60.0 minutes to 70.0 minutes, In the high performance liquid chromatography measurement, the peak area of ​​the polythiol component T relative to 100 of the total peak area of ​​compounds contained in the polythiol composition is 80.00 or more, the peak area of ​​the component X relative to 100 of the total peak area is 5.00 or less, and the peak area of ​​the component Y relative to 100 of the total peak area is 2.50 or less. - Measurement Condition A - A YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, column shape: Φ6 mm × 150 mm) manufactured by YMC Co., Ltd. was used as the column, 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 the 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 40°C, the flow rate was 1.0 mL / min, and the injection volume was 2 μL. <2> The polythiol composition according to <1>, wherein the component X is a polythiol compound having a molecular weight of 426, and the component Y is a polythiol compound having a molecular weight of 532. <3> The polythiol composition according to <1> or <2>, wherein the peak area of ​​the component X is 1.00 or more and the peak area of ​​the component Y is 1.00 or more. <4> The polythiol composition according to any one of <1> to <3>, wherein the ratio of the peak area of ​​the component Y to the peak area of ​​the component X is 0.40 to 0.90.<5> A polythiol component T which 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; a component W having a retention time of 8.7 minutes to 9.7 minutes in high performance liquid chromatography measurement under the following measurement condition A; and a component V having the retention time of 11.0 minutes to 13.5 minutes, In the high performance liquid chromatography measurement, the peak area of ​​the polythiol component T relative to 100 of the total peak area of ​​compounds contained in the polythiol composition is 75.00 or more, the peak area of ​​the component W relative to 100 of the total peak area is 3.50 or less, and the peak area of ​​the component V relative to 100 of the total peak area is 3.10 or less. -Measurement Condition A- A YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, column shape: Φ6 mm × 150 mm) manufactured by YMC Co., Ltd. was used as the column, 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 the 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 40°C, the flow rate was 1.0 mL / min, and the injection volume was 2 μL. <6> The polythiol composition according to <5>, wherein the component W is a polythiol compound having a molecular weight of 350, and the component V is a polythiol compound having a molecular weight of 260. <7> The polythiol composition according to <5> or <6>, wherein the peak area of ​​component W relative to the total peak area 100 is 1.30 or more, and the peak area of ​​component V relative to the total peak area 100 is 1.00 or more. <8> The polythiol composition according to any one of <5> to <7>, wherein the ratio of the peak area of ​​component V relative to the total peak area 100 to the peak area of ​​component W relative to the total peak area 100 is 0.10 to 2.80.<9> The polythiol composition according to any one of <5> to <8>, further comprising at least one of a component X having a retention time of 30.0 minutes to 40.0 minutes in high performance liquid chromatography measurement under the measurement condition A, and a component Y having the retention time of 60.0 minutes to 70.0 minutes. <10> A polymerizable composition comprising the polythiol composition according to any one of <1> to <9>, and a polyiso(thio)cyanate compound. <11> The polymerizable composition according to <10>, further comprising a thiol compound XS that is a thiol compound other than the polythiol compound contained in the polythiol composition. <12> The thiol compound XS is selected from the group consisting of 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, and bis(2-mercaptoethyl)sulfide. , 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.<13> The polymerizable composition according to any one of <10> to <12>, wherein 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. <14> The present invention relates to a polyiso(thio)cyanate composition comprising the polyiso(thio)cyanate compound, wherein the polyiso(thio)cyanate composition comprises 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), wherein, when the polyiso(thio)cyanate composition comprises the compound (N1), the peak area of ​​the compound (N1) measured by gas chromatography is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate, and when the polyiso(thio)cyanate composition comprises the compound (N2), the peak area of ​​the compound (N2) measured by gas chromatography is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, <10> to <13>. The polymerizable composition according to any one of <10> to <13>, wherein, when the polyiso(thio)cyanate composition contains the compound (N3), a peak area of ​​the compound (N3) measured by gas chromatography is 0.10 ppm or more relative to a peak area of ​​xylylene diisocyanate.

[0008]

[0009] <15> A resin comprising a cured product of the polymerizable composition according to any one of <10> to <14>. <16> A molded product comprising the resin according to <15>. <17> An optical material comprising the resin according to <15>. <18> A lens comprising the resin according to <15>.

[0010] According to the first and second embodiments of the present disclosure, it is possible to provide a polythiol composition capable of producing a resin with reduced yellowness and improved heat resistance, and applications thereof.

[0011] In this disclosure, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages, or may be replaced with a value shown in the examples. In this disclosure, when multiple substances corresponding to each component are present in the material, the amount of each component in the material means the total amount of multiple substances present in the material, unless otherwise specified. In this disclosure, "iso(thio)cyanate" means isocyanate or isothiocyanate.

[0012] Hereinafter, a first embodiment and a second embodiment of the present disclosure will be described. There may be an overlap between the first embodiment and the second embodiment. For example, the polythiol composition of the first embodiment may have the characteristics of the polythiol composition of the second embodiment. Hereinafter, preferred features of one embodiment can be appropriately referenced to preferred features of the other embodiment.

[0013] First Embodiment

[0014] <Polythiol Composition> The polythiol composition of a first embodiment contains: a polythiol component T that is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T1"), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T2"), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T3"); a component X that has a retention time of 30.0 minutes to 40.0 minutes in high performance liquid chromatography measurement under measurement condition A below; and a component Y that has the retention time of 60.0 minutes to 70.0 minutes, In the polythiol composition, the peak area of ​​the polythiol component T relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition is 80.00 or more, the peak area of ​​the component X relative to 100 of the total peak area is 5.00 or less, and the peak area of ​​the component Y relative to 100 of the total peak area is 2.50 or less, as measured by high performance liquid chromatography.

[0015] - Measurement Condition A - The following conditions were used: a YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, column shape: Φ6 mm × 150 mm) manufactured by YMC Co., Ltd. was used as the column; 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; an ultraviolet detector with a measurement wavelength of 230 nm was used as the detector; the column temperature was 40°C; the flow rate was 1.0 mL / min; and the injection volume was 2 μL.

[0016] The polythiol component T may be used as a polythiol component for forming a resin such as a plastic lens. In this case, the produced resin may be required to have reduced yellowness and / or improved heat resistance. According to the polythiol composition of the first embodiment, a resin having reduced yellowness and improved heat resistance can be produced, even though it is a polythiol composition containing polythiol component T. The reason why such an effect is achieved is unclear, but it is presumed to be because the amounts of component X and component Y are each reduced to the above-mentioned amounts or less.

[0017] The polythiol composition of the first embodiment and preferred aspects thereof will be described in more detail below.

[0018] <Polythiol Component T> The polythiol composition of the first embodiment contains polythiol component T. Polythiol component T is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., compound T1), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., compound T2), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., compound T3). The structures of compounds T1 to T3 are as follows:

[0019]

[0020] The polythiol component T does not necessarily have to be a mixture of the three compounds T1 to T3, but may be a mixture of two of the compounds T1 to T3, or may be any one compound of the compounds T1 to T3.

[0021] The three compounds T1 to T3 are isomers, and each of the compounds T1 to T3 has a molecular weight of 366.

[0022] When the total peak area of ​​polythiol component T measured by high performance liquid chromatography (hereinafter also referred to as "HPLC") under the above-described measurement condition A is taken as 100, the peak area of ​​compound T1 is preferably 80 or more, more preferably 80 to 90. When the total peak area of ​​the polythiol component T is taken as 100, the peak area of ​​compound T2 is preferably 20 or less, more preferably 2 to 20, even more preferably 5 to 20, and even more preferably 10 to 20. When the total peak area of ​​the polythiol component T is taken as 100, the peak area of ​​compound T3 is preferably 15 or less, more preferably 10 or less, even more preferably 5.0 or less, even more preferably 2.0 or less, even more preferably 1.0 or less, and even more preferably 0.1 to 1.0.

[0023] The peak area of ​​each of the compounds T1 to T3 and the peak area ratio between two or three of the compounds T1 to T3 can be adjusted by adjusting the production conditions (e.g., the reaction temperature and / or reaction time in the thiuronium chloride reaction using thiourea) when producing a polythiol composition containing the polythiol component T (e.g., see Example 1 described later).

[0024] In HPLC under the above-described measurement condition A, the peak area of ​​polythiol component T is 80.00 or more relative to the total peak area of ​​the compounds contained in the polythiol composition, which is 100. That is, polythiol component T is the main component in the polythiol composition of the first embodiment.

[0025] The peak area of ​​the polythiol component T is preferably 80.00 to 90.00.

[0026] <Component X> The polythiol composition of the first embodiment includes component X. Component X is a component having a retention time of 30.0 minutes to 40.0 minutes in HPLC under the above-described measurement condition A. Component X is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0027] In HPLC under the above-mentioned measurement condition A, the peak area of ​​component X is 5.00 or less. This reduces the yellowness of the produced resin and improves heat resistance. The peak area of ​​component X is preferably 4.50 or less, more preferably 4.00 or less. There is no particular restriction on the lower limit of the peak area of ​​component X, but examples of the lower limit include 0.10, 0.50, and 1.00.

[0028] Component X is preferably a polythiol compound having a molecular weight of 426. The molecular formula of component X in this embodiment is, for example, C １２ H ２６ S ８ is.

[0029] Component X, a polythiol compound with a molecular weight of 426, is a compound with a molecular weight 60 greater than that of each of compounds T1 to T3 (molecular weight 366). Component X, a polythiol compound with a molecular weight of 426, is, for example, a compound in which at least one of compounds T1 to T3 is substituted with a mercaptoethyl group (for example, compounds (X1) to (X3) below).

[0030] Examples of component X, which is a polythiol compound having a molecular weight of 426, include the following compound (X1), the following compound (X2), and the following compound (X3).

[0031]

[0032] In the compounds (X1) to (X3), each of p, q, r, and s is 0 or 1, and the sum of p, q, r, and s is 1.

[0033] <Component Y> The polythiol composition of the first embodiment includes component Y. Component Y is a component having a retention time of 60.0 minutes to 70.0 minutes in HPLC under the above-described measurement condition A. Component Y is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0034] In HPLC under the above-mentioned measurement condition A, the peak area of ​​component Y is 2.50 or less. This reduces the yellowness of the produced resin and improves its heat resistance. There is no particular restriction on the lower limit of the peak area of ​​component Y, but examples of the lower limit include 0.10, 0.50, and 1.00.

[0035] Component Y is preferably a polythiol compound having a molecular weight of 532. The molecular formula of component Y in this embodiment is, for example, C １５ H ３２ S １０ is.

[0036] Component Y, a polythiol compound with a molecular weight of 532, is a compound with a molecular weight 166 greater than that of each of compounds T1 to T3 (molecular weight 366).

[0037] Examples of component Y, which is a polythiol compound having a molecular weight of 532, include the following compound (Y1), the following compound (Y2), and the following compound (Y3).

[0038]

[0039] In the compounds (Y1) to (Y3), each of p, q, r, and s is 0 or 1, the sum of p, q, r, and s is 1, and L １ is a linking group (L1). In the linking group (L1), * indicates the bonding position to the sulfur atom, and ** indicates the bonding position to the hydrogen atom.

[0040] <Peak Area Ratio [Component Y / Component X]> In the polythiol composition of the first embodiment, the ratio of the peak area of ​​component Y to the peak area of ​​component X (also referred to as the "peak area ratio [component Y / component X]" in the first embodiment) is not particularly limited, but the peak area ratio [component Y / component X] is preferably 0.20 to 3.00, more preferably 0.30 to 2.00, even more preferably 0.30 to 1.10, even more preferably 0.30 to 1.00, even more preferably 0.40 to 1.00, even more preferably 0.40 to 0.90, and even more preferably 0.55 to 0.80.

[0041] <Other Components> The polythiol composition of the first embodiment may contain at least one other component (e.g., other polythiol compounds, components other than polythiol compounds, etc.) in addition to the components described above. Examples of other polythiol compounds include 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, tetrakis(3-mercaptopropyl ... methyl)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, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and the like.

[0042] Other components that can be contained in the polythiol composition of the first embodiment include component W, component V, compound (XB), compound (C1), and the like in the second embodiment described below.

[0043] <Method for producing polythiol composition> The polythiol composition of the first embodiment described above can be produced, for example, by adjusting the production conditions (for example, the reaction temperature and / or reaction time in the thiuronium chloride reaction using thiourea) when producing a polythiol composition containing polythiol component T, and adjusting the composition of the polythiol composition (particularly, the amount of component X and component Y) (see, for example, Example 1 described later). The polythiol composition of the first embodiment described above can also be produced by dissolving a polythiol composition containing polythiol component T in an organic solvent (for example, toluene), reacting the resulting solution with an alkaline substance (for example, sodium hydroxide, potassium hydroxide, etc.) to form a salt of the polythiol composition (hereinafter also referred to as salt formation), and then repeatedly extracting and separating with water to adjust the composition of the polythiol composition (particularly, the amount of component X and component Y).

[0044] <Polymerizable Composition> The polymerizable composition of the first embodiment contains the polythiol composition of the first embodiment and a polyiso(thio)cyanate compound.

[0045] (Polyiso(thio)cyanate Compound) The polyiso(thio)cyanate compound is not particularly limited as long as it can exhibit the effects of the first embodiment, and conventionally known compounds can be used. There is no particular limitation on the polyiso(thio)cyanate compound as long as it is a compound having at least two iso(thio)cyanate groups in one molecule, and specific examples include: aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, and 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; and the like. The polyiso(thio)cyanate compound may contain at least one selected from these compounds;

[0046] Furthermore, as the polyiso(thio)cyanate compound, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization reaction products, etc. can also be used.

[0047] The polyiso(thio)cyanate compound is preferably a polyisocyanate compound, and preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0048] 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 to iso(thio)cyanate groups of the polyiso(thio)cyanate compound contained in the polythiol composition (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, etc., such as refractive index and heat resistance.

[0049] The polymerizable composition of the first embodiment may contain a polyiso(thio)cyanate composition containing the polyiso(thio)cyanate compound.

[0050] Here, the polyisocyanate composition means a composition containing at least one polyisocyanate compound.

[0051] The polyisocyanate composition may contain components other than the polyisocyanate compound as impurities. The polyisocyanate composition preferably contains at least one polyisocyanate compound as a main component. The meaning of "containing as a main component" is as described above.

[0052] The polyisocyanate composition preferably contains xylylene diisocyanate.

[0053] Hereinafter, a polyisocyanate composition containing xylylene diisocyanate will also be referred to as an XDI composition. The XDI composition preferably contains xylylene diisocyanate as a main component.

[0054] 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).

[0055]

[0056] 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.

[0057] When the XDI composition contains compound (N1), it is preferable that the peak area of ​​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. -GC condition 1- Packing material: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm × length 60 m (manufactured by Agilent) Oven temperature: heating from 130°C to 220°C at 3°C / min, and after reaching 220°C, heating to 300°C at 10°C / min Split ratio: pulsed splitless method Injection port temperature: 280°C 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 mass% chloroform solution Injection amount: 2 μL Detection method: FID

[0058] 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 1. 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 1. The peak area of ​​the compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0059] When the XDI composition contains compound (N2), the peak area of ​​compound (N2) measured by gas chromatography under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1. -GC condition 2- Column: HP-50+, inner diameter 0.25 mm × length 30 m × film thickness 0.25 μm (manufactured by Hewlett-Packard Company) Oven temperature: temperature increased from 50°C to 280°C at a rate of 10°C / min, and held for 6 minutes after reaching 280°C. Split ratio: pulsed splitless method Injection port temperature: 200°C 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 amount: 1.0 μL Detection method: SIM (monitoring ions: m / z 180, 215) (content ratio of xylylene diisocyanate (XDI))

[0060] 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 1. 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 1. 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. 6,373,536.

[0061] When the XDI composition contains compound (N3), the peak area of ​​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 of ​​xylylene diisocyanate. The peak area of ​​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 ​​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 ​​compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0062] 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, and 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. The XDI composition may also contain a stabilizer.

[0063] The polymerizable composition of the first embodiment may further contain a thiol compound XS exemplified in the second embodiment described later.

[0064] The polymerizable composition of the first embodiment may contain components other than the polythiol compound and the polyiso(thio)cyanate compound for the purpose of improving various physical properties of the resin, operability, polymerization reactivity of the polymerizable composition, etc. Examples of such components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, and blue ink agents such as inorganic pigments.

[0065] Examples of the polymerization catalyst include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0066] The internal mold release agent may be an acidic phosphate ester. Examples of the acidic phosphate ester include a phosphate monoester and a phosphate diester, and these may be used alone or in combination of two or more.

[0067] Examples of the resin modifier include an episulfide compound, an alcohol compound, an amine compound, an epoxy compound, an organic acid and an anhydride thereof, an olefin compound including a (meth)acrylate compound, etc. The polymerizable composition of the first embodiment can be obtained by mixing the above components.

[0068] <<Molded Article>> The molded article of the first embodiment includes the resin of the first embodiment. The resin of the first embodiment includes a cured product of the polymerizable composition of the first embodiment. The method for producing the molded article of the first embodiment is not particularly limited, and a preferred production method is cast polymerization. First, the polymerizable composition is injected between a molding mold held by a gasket, tape, or the like. At this time, depending on the physical properties required of the resulting plastic lens, it is often preferable to perform a degassing treatment under reduced pressure, a filtration treatment under pressure, reduced pressure, or the like, as needed.

[0069] The polymerization conditions are not limited because they vary greatly depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., and are, for example, carried out for 1 to 50 hours at a temperature of −50° C. to 150° C. In some cases, it is preferable to maintain or gradually increase the temperature within a temperature range of 10° C. to 150° C. and cure for 1 to 48 hours.

[0070] The molded body may be subjected to a treatment such as annealing, if necessary. The treatment such as 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.

[0071] [Uses] The resin obtained from the polymerizable composition of the first embodiment can be used as a material for producing molded articles of various shapes by changing the type of mold used during cast polymerization.

[0072] <Optical Material> The optical material of the first embodiment includes the resin of the first embodiment. A molded article obtained from the polymerizable composition of the first embodiment can be obtained as a material with reduced yellowness without impairing transparency. Furthermore, a molded article obtained from the polymerizable composition containing the polythiol composition of the first embodiment can be obtained as a material with excellent devitrification. Therefore, it can be used for various optical materials such as plastic lenses.

[0073] Lens The lens of the first embodiment contains the resin of the first embodiment. Lenses are particularly suitable as optical materials. Examples of lenses include plastic eyeglass lenses and plastic polarized lenses.

[0074] [Plastic eyeglass lens] A plastic eyeglass lens using a lens substrate made of the molded article of the first embodiment may have a coating layer applied to one or both sides, as necessary. The plastic eyeglass lens of the first embodiment comprises a lens substrate containing a cured product of the polymerizable composition described above, and a coating layer.

[0075] Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water-repellent layer. These coating layers can be used alone or in combination with a plurality of coating layers. When coating layers are applied to both sides, the same coating layer or different coating layers may be applied to each side.

[0076] These coating layers may each contain known additives such as infrared absorbers to protect the eyes from infrared rays, light stabilizers, antioxidants, etc. to improve the weather resistance of the lens, photochromic compounds, dyes, pigments, etc. to enhance the fashionability of the lens, and antistatic agents, etc. to improve lens performance. Layers that are coated by application may contain various leveling agents to improve application properties. Furthermore, an antifogging layer, an antifouling layer, or a water-repellent layer may be formed on the antireflection layer, as needed.

[0077] Although the first embodiment has been described above, these are merely examples, and various other configurations can be adopted as long as the effects of the first embodiment are not impaired.

[0078] Second Embodiment

[0079] <Polythiol Composition> The polythiol composition of a second embodiment contains: a polythiol component T that is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T1"), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T2"), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T3"); a component W that has a retention time of 8.7 minutes to 9.7 minutes in high performance liquid chromatography measurement under measurement condition A below; and a component V that has the retention time of 11.0 minutes to 13.5 minutes, In the polythiol composition, the peak area of ​​the polythiol component T relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition is 75.00 or more, the peak area of ​​the component W relative to 100 of the total peak area is 3.50 or less, and the peak area of ​​the component V relative to 100 of the total peak area is 3.10 or less, as measured by high performance liquid chromatography.

[0080] - Measurement Condition A - A YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, column shape: Φ6 mm × 150 mm) manufactured by YMC Co., Ltd. was used as the column, 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 40°C, the flow rate was 1.0 mL / min, and the injection volume was 2 μL. Measurement Condition A in the second embodiment is the same as Measurement Condition A in the first embodiment described above.

[0081] The polythiol component T may be used as a polythiol component for forming a resin such as a plastic lens. In this case, the produced resin may be required to have reduced yellowness and / or improved heat resistance. According to the polythiol composition of the second embodiment, a resin having reduced yellowness and improved heat resistance can be produced, even though it is a polythiol composition containing polythiol component T. The reason why such an effect is achieved is unclear, but it is presumed to be because the amounts of component W and component V are each reduced to the above-mentioned amounts or less.

[0082] The polythiol composition of the second embodiment and preferred aspects thereof will be described in more detail below.

[0083] <Polythiol Component T> The polythiol composition of the second embodiment includes polythiol component T. The polythiol component T in the second embodiment is the same as the polythiol component T in the first embodiment described above. That is, the polythiol component T is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., compound T1), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., compound T2), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., compound T3). The structures of compounds T1 to T3 are as follows:

[0084]

[0085] The polythiol component T does not necessarily have to be a mixture of the three compounds T1 to T3, but may be a mixture of two of the compounds T1 to T3, or may be any one compound of the compounds T1 to T3.

[0086] The three compounds T1 to T3 are isomers, and each of the compounds T1 to T3 has a molecular weight of 366.

[0087] When the total peak area of ​​the polythiol component T measured by high performance liquid chromatography (hereinafter also referred to as "HPLC") under the above-mentioned measurement conditions A is taken as 100, the peak area of ​​compound T1 is preferably 77.00 or more, more preferably 80.00 or more, even more preferably 82.00 or more, and even more preferably 84.00 or more. The upper limit of the peak area of ​​compound T1 is preferably 90.00. When the total peak area of ​​the polythiol component T is taken as 100, the peak area of ​​compound T2 is preferably 21.00 or less, more preferably 19.00 or less, and even more preferably 17.00 or less. The lower limit of the peak area of ​​compound T2 is preferably 10.00. When the total peak area of ​​the polythiol component T is taken as 100, the peak area of ​​compound T3 is preferably 3.00 or less, more preferably 1.50 or less, and even more preferably 0.70 or less. The peak area of ​​compound T3 may be 0.00.

[0088] The peak area of ​​each of the compounds T1 to T3 and the peak area ratio of two or three of the compounds T1 to T3 can be adjusted by adjusting the production conditions (e.g., the reaction temperature and / or reaction time in the thiuronium chloride reaction using thiourea) when producing a polythiol composition containing the polythiol component T (e.g., see Example 101 described later).

[0089] In HPLC under the above-described measurement condition A, the peak area of ​​polythiol component T (hereinafter also simply referred to as the "peak area of ​​polythiol component T") is 75.00 or more relative to the total peak area of ​​the compounds contained in the polythiol composition, 100. That is, polythiol component T is the main component in the polythiol composition of the second embodiment.

[0090] The peak area of ​​the polythiol component T is preferably 80.00 or more, more preferably 84.00 or more, and even more preferably 85.00 or more. The peak area of ​​the polythiol component T may be 100.

[0091] <Component W> The polythiol composition of the second embodiment includes component W. Component W is a component having a retention time of 8.7 minutes to 9.7 minutes in HPLC under the above-described measurement condition A. Component W is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0092] In HPLC under the above-mentioned measurement conditions A, the peak area of ​​component W (hereinafter also simply referred to as "peak area of ​​component W") relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is 3.50 or less. This reduces the yellowness of the resin produced and improves heat resistance. The peak area of ​​component W is preferably 3.00 or less, more preferably 2.75 or less. The lower limit of the peak area of ​​component W is preferably 1.20, more preferably 1.30, even more preferably 1.50, and even more preferably 1.80. There is no particular restriction on the lower limit of the peak area of ​​component W, but examples of the lower limit include 1.20, 1.30, 1.50, and 1.80.

[0093] Component W is preferably a polythiol compound having a molecular weight of 350. The molecular formula of component W in this embodiment is, for example, C １０ H ２２ OS ６ is.

[0094] Component W, a polythiol compound with a molecular weight of 350, is a compound whose molecular weight is 16 smaller than that of each of compounds T1 to T3 (molecular weight 366). Component W, a polythiol compound with a molecular weight of 350, is, for example, a compound in which one of the SH groups in at least one of compounds T1 to T3 has been replaced with an OH group (for example, compounds (W1) to (W5) below).

[0095] Examples of component W, which is a polythiol compound having a molecular weight of 350, include the following compounds (W1) to (W5).

[0096]

[0097] <Component V> The polythiol composition of the second embodiment contains component V. Component V is a component having a retention time of 11.0 minutes to 13.5 minutes in HPLC under the above-described measurement condition A. Component V is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0098] In HPLC under the above-mentioned measurement condition A, the peak area of ​​component V (hereinafter also simply referred to as "peak area of ​​component V") relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is 3.10 or less. This reduces the yellowness of the produced resin and improves heat resistance. The peak area of ​​component V is preferably 3.00 or less, more preferably 2.90 or less. There is no particular restriction on the lower limit of the peak area of ​​component V, but examples of lower limits include 1.00, 1.30, and 1.60.

[0099] Component V is preferably a polythiol compound having a molecular weight of 260. The molecular formula of component V in this embodiment is, for example, C ７ H １６ S ５ is.

[0100] An example of component V, which is a polythiol compound having a molecular weight of 260, is the following compound (V1).

[0101]

[0102] A preferred combination of component W and component V is a combination in which component W is a polythiol compound having a molecular weight of 350, and component V is a polythiol compound having a molecular weight of 260.

[0103] A preferred combination of the peak area of ​​component W and the peak area of ​​component V is a combination in which the peak area of ​​component W is 1.30 or more and the peak area of ​​component V is 1.00 or more.

[0104] <Peak Area Ratio [Component V / Component W]> In the polythiol composition of the second embodiment, the ratio of the peak area of ​​component V (i.e., the peak area of ​​component W relative to the total peak area of ​​100 of the compounds contained in the polythiol composition) to the peak area of ​​component W (i.e., the peak area of ​​component V relative to the total peak area of ​​100 of the compounds contained in the polythiol composition) (also referred to as the "peak area ratio [component V / component W]" in the second embodiment) is preferably 2.80 or less, more preferably 2.40 or less, even more preferably 2.00 or less, and even more preferably 1.50 or less. There is no particular restriction on the lower limit of the peak area ratio [peak area ratio [component V / component W]], but examples of lower limits include 0.10 and 0.50. An example of a preferred range for the peak area ratio [peak area ratio [component V / component W]] is 0.10 to 2.80.

[0105] <Peak Area Ratio [Component V / Polythiol Component T]> In the polythiol composition of the second embodiment, the ratio of the peak area of ​​component V to the peak area of ​​polythiol component T (also referred to as the "peak area ratio [component V / polythiol component T]" in the second embodiment) is preferably 0.06 or less, more preferably 0.03 or less. There is no particular restriction on the lower limit of the peak area ratio [component V / polythiol component T], but an example of the lower limit is 0.01.

[0106] <Component U> The polythiol composition of the second embodiment may contain component U. Component U is a component having a retention time of 40.0 minutes to 49.0 minutes in HPLC under the above-described measurement condition A. Component U is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0107] In HPLC under the above-described measurement conditions A, the peak area of ​​component U (hereinafter also simply referred to as the "peak area of ​​component U") relative to the total peak area of ​​the compounds contained in the polythiol composition, 100, is preferably 1.70 or more, more preferably 2.10 or more, and even more preferably 2.50 or more. There is no particular restriction on the upper limit of the peak area of ​​component U, but examples of the upper limit include 5.00 and 4.00.

[0108] Component U is preferably a polythiol compound having a molecular weight of 472. The molecular formula of component U in this embodiment is, for example, C １３ H ２８ S ９ is.

[0109] Examples of component U, which is a polythiol compound having a molecular weight of 472, include the following compounds (U1) to (U4).

[0110]

[0111] <Component X and Component Y> The polythiol composition of the second embodiment may further contain at least one of a component X having a retention time of 30.0 minutes to 40.0 minutes in high performance liquid chromatography measurement under the above-described measurement condition A and a component Y having the retention time of 60.0 minutes to 70.0 minutes.

[0112] (Component X) The polythiol composition of the second embodiment may contain component X. Component X is a component having a retention time of 30.0 minutes to 40.0 minutes in HPLC under the above-described measurement condition A. Component X is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0113] In HPLC under the above-mentioned measurement condition A, the peak area of ​​component X (hereinafter also simply referred to as "peak area of ​​component X") relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is preferably 6.00 or less. This further reduces the yellowness of the produced resin and further improves heat resistance. The peak area of ​​component X is more preferably 5.00 or less, more preferably 3.00 or less. There is no particular restriction on the lower limit of the peak area of ​​component X, but examples of lower limits include 0.10 and 0.50.

[0114] Component X and preferred aspects thereof that can be contained in the polythiol composition of the second embodiment are the same as component X and preferred aspects thereof contained in the polythiol composition of the first embodiment described above.

[0115] (Component Y) The polythiol composition of the second embodiment may contain component Y. Component Y is a component having a retention time of 60.0 minutes to 70.0 minutes in HPLC under the above-described measurement condition A. Component Y is not limited to being one type of compound, and may be two or more types of compounds (for example, two or more types of compounds that are isomers).

[0116] In HPLC under the above-mentioned measurement condition A, the peak area of ​​component Y (hereinafter also simply referred to as "peak area of ​​component Y") relative to the total peak area of ​​100 of the compounds contained in the polythiol composition is preferably 3.00 or less. This further reduces the yellowness of the resin produced and further improves the heat resistance. The peak area of ​​component Y is more preferably 2.60 or less, and even more preferably 2.00 or less. There is no particular restriction on the lower limit of the peak area of ​​component Y, but examples of lower limits include 0.10 and 0.50.

[0117] Component Y and preferred aspects thereof that can be contained in the polythiol composition of the second embodiment are the same as component Y and preferred aspects thereof contained in the polythiol composition of the first embodiment described above.

[0118] (Peak Area Ratio [Component Y / Component X]) In the polythiol composition of the second embodiment, the ratio of the peak area of ​​component Y (i.e., the peak area of ​​component X relative to the total peak area 100 of the compounds contained in the polythiol composition) to the peak area of ​​component X (i.e., the peak area of ​​component Y relative to the total peak area 100 of the compounds contained in the polythiol composition) (also referred to as "peak area ratio [component Y / component X]" in the second embodiment) is not particularly limited, but the peak area ratio [component Y / component X] is preferably 0.40 or more, more preferably 0.60 or more, and even more preferably 0.65 or more. There is no particular limit to the upper limit of the peak area ratio [component Y / component X], but examples of the upper limit include 1.50 and 1.20.

[0119] <Compound (XB)> The polythiol composition of the second embodiment may contain the following compound (XB). Compound (XB) is a compound in which at least one of the mercapto groups in the above-described polythiol component T or component V is replaced with a group represented by the following formula (XB-1).

[0120]

[0121] In formula (XB-1), * represents a bonding position.

[0122] Examples of compound (XB) are shown below, but compound (XB) is not limited to these examples.

[0123]

[0124] <Compound (C1)> The polythiol composition of the second embodiment may contain the following compound (C1).

[0125]

[0126] In compound (C1), X is —CH ２ - or a sulfur atom.

[0127] <Other Components> The polythiol composition of the second embodiment may contain at least one other component (e.g., other thiol compounds, components other than thiol compounds, etc.) other than the above-described components. An example of the other thiol compound is the thiol compound XS that can be contained in the polymerizable composition described below.

[0128] <Method for producing polythiol composition> The polythiol composition of the second embodiment described above can be produced, for example, by adjusting the production conditions (for example, the reaction temperature and / or reaction time in the thiuronium chloride reaction using thiourea) when producing a polythiol composition containing polythiol component T, and adjusting the composition of the polythiol composition (particularly, the amount of component W and component V) (see, for example, Example 101 described later). In addition, the polythiol composition of the second embodiment described above can also be produced by dissolving a polythiol composition containing polythiol component T in an organic solvent (for example, toluene), reacting the resulting solution with an alkaline substance (for example, sodium hydroxide, potassium hydroxide, etc.) to form a salt of the polythiol composition (hereinafter also referred to as salt formation), and then repeatedly extracting and separating with water to adjust the composition of the polythiol composition (particularly, the amount of component W and component V).

[0129] <Polymerizable Composition> The polymerizable composition of the second embodiment contains the polythiol composition of the second embodiment and a polyiso(thio)cyanate compound.

[0130] <Polyiso(thio)cyanate Compound> The polyiso(thio)cyanate compound is not particularly limited as long as it can exhibit the effects of the second embodiment, and conventionally known compounds can be used. The polyiso(thio)cyanate compound is not particularly limited as long as it is a compound having at least two iso(thio)cyanate groups in one molecule. Specific examples of the polyiso(thio)cyanate compound in the second embodiment are the same as the specific examples of the polyiso(thio)cyanate compound in the first embodiment described above.

[0131] The polyiso(thio)cyanate compound is preferably a polyisocyanate compound, and preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0132] 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 to iso(thio)cyanate groups of the polyiso(thio)cyanate compound contained in the polythiol composition (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, etc., such as refractive index and heat resistance.

[0133] The polymerizable composition of the second embodiment may contain a polyiso(thio)cyanate composition containing the polyiso(thio)cyanate compound.

[0134] Here, the polyisocyanate composition means a composition containing at least one polyisocyanate compound.

[0135] The polyisocyanate composition may contain components other than the polyisocyanate compound as impurities. The polyisocyanate composition preferably contains at least one polyisocyanate compound as a main component. The meaning of "containing as a main component" is as described above.

[0136] The polyisocyanate composition preferably contains xylylene diisocyanate.

[0137] Hereinafter, a polyisocyanate composition containing xylylene diisocyanate will also be referred to as an XDI composition. The XDI composition preferably contains xylylene diisocyanate as a main component. The preferred aspects of the XDI composition in the second embodiment are the same as the preferred aspects of the XDI composition in the first embodiment. For example, like the XDI composition in the first embodiment, the XDI composition in the second embodiment preferably contains at least one selected from the group consisting of the aforementioned compound (N1), the aforementioned compound (N2), and the aforementioned compound (N3). In the second embodiment, the preferred ranges of peak areas in gas chromatography measurement for each of these compounds (N1), (N2), and (N3) are also the same as the preferred ranges of peak areas in gas chromatography measurement for each of the compounds (N1), (N2), and (N3) in the first embodiment.

[0138] <Thiol Compound XS> The polymerizable composition of the second embodiment may further contain a thiol compound XS, which is a thiol compound other than the polythiol compounds contained in the polythiol composition described above.

[0139] The thiol compound XS is preferably 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)sulfur The at least one selected from the group consisting of 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.

[0140] The polymerizable composition of the second embodiment may contain components other than the polythiol compound and the polyiso(thio)cyanate compound for the purpose of improving various physical properties of the resin, operability, polymerization reactivity of the polymerizable composition, etc. Examples of such components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, and blue ink agents such as inorganic pigments.

[0141] Examples of the polymerization catalyst include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0142] The internal mold release agent may be an acidic phosphate ester. Examples of the acidic phosphate ester include a phosphate monoester and a phosphate diester, and these may be used alone or in combination of two or more.

[0143] Examples of the resin modifier include an episulfide compound, an alcohol compound, an amine compound, an epoxy compound, an organic acid and an anhydride thereof, an olefin compound including a (meth)acrylate compound, etc. The polymerizable composition of the second embodiment can be obtained by mixing the above components.

[0144] <<Molded Article>> The molded article of the second embodiment includes the resin of the second embodiment. The resin of the second embodiment includes a cured product of the polymerizable composition of the second embodiment. The method for producing the molded article of the second embodiment is not particularly limited, and a preferred production method is cast polymerization. First, the polymerizable composition is injected between a molding mold held by a gasket, tape, or the like. At this time, depending on the physical properties required of the resulting plastic lens, it is often preferable to perform a degassing treatment under reduced pressure, a filtration treatment under pressure, reduced pressure, or the like, as needed.

[0145] The polymerization conditions are not limited because they vary greatly depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., and are, for example, carried out for 1 to 50 hours at a temperature of −50° C. to 150° C. In some cases, it is preferable to maintain or gradually increase the temperature within a temperature range of 10° C. to 150° C. and cure for 1 to 48 hours.

[0146] The molded body may be subjected to a treatment such as annealing, if necessary. The treatment such as 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.

[0147] [Uses] The resin obtained from the polymerizable composition of the second embodiment can be used as a material for producing molded articles of various shapes by changing the type of mold used during cast polymerization.

[0148] <Optical Material> The optical material of the second embodiment includes the resin of the second embodiment. A molded article obtained from the polymerizable composition of the second embodiment can be obtained as a material with reduced yellowness without impairing transparency. Furthermore, a molded article obtained from the polymerizable composition containing the polythiol composition of the second embodiment can also be obtained as a material with excellent devitrification. Therefore, it can be used for various optical materials such as plastic lenses.

[0149] Lens The lens of the second embodiment includes the resin of the second embodiment. Lenses are particularly suitable as the optical material. Examples of lenses include plastic eyeglass lenses and plastic polarized lenses.

[0150] [Plastic eyeglass lens] A plastic eyeglass lens using a lens substrate made of the molded article of the second embodiment may have a coating layer applied to one or both sides as needed. The plastic eyeglass lens of the second embodiment comprises a lens substrate containing a cured product of the polymerizable composition described above, and a coating layer.

[0151] Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water-repellent layer. These coating layers can be used alone or in combination with a plurality of coating layers. When coating layers are applied to both sides, the same coating layer or different coating layers may be applied to each side.

[0152] These coating layers may each contain known additives such as infrared absorbers to protect the eyes from infrared rays, light stabilizers, antioxidants, etc. to improve the weather resistance of the lens, photochromic compounds, dyes, pigments, etc. to enhance the fashionability of the lens, and antistatic agents, etc. to improve lens performance. Layers that are coated by application may contain various leveling agents to improve application properties. Furthermore, an antifogging layer, an antifouling layer, or a water-repellent layer may be formed on the antireflection layer, as needed.

[0153] The second embodiment has been described above, but these are merely examples of the second embodiment, and various configurations other than those described above can be adopted as long as they do not impair the effects of the second embodiment.

[0154] Hereinafter, examples of the first embodiment of the present disclosure will be first shown, but the first embodiment of the present disclosure is not limited to the following examples. Unless otherwise specified, "parts" are based on mass.

[0155] <Method of Evaluating Plastic Lenses> In each of the Examples and Comparative Examples described below, the plastic lenses used as resins were evaluated as follows. The results are shown in Table 1.

[0156] Yellowness Index (YI) The resin was prepared into a circular plastic plate having a thickness of 9 mm and a diameter of 75 mm, and the YI was determined using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. The measurement was carried out under transmission conditions. The smaller the YI, the smaller the yellowness of the plastic plate, and the larger the YI, the greater the yellowness.

[0157] Heat resistance: Resin test pieces measuring 10 mm in length, 10 mm in width, and 2.5 mm in thickness were prepared, and the glass transition temperature (Tg) was measured using a Shimadzu TMA-60 thermomechanical analyzer by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10°C / min) as an index of heat resistance. The higher the glass transition temperature (Tg), the better the heat resistance.

[0158] Example 1 Production of Polythiol Composition Compared to Example 1 of JP-A-7-252207, the conditions for the thiuronium chloride reaction using thiourea were changed from "9 hours at 110°C" to "6 hours at 100°C," and a polythiol composition was produced. Details are provided below. A reactor was charged with 89.3 parts by mass of 2-mercaptoethanol, 44.6 parts by mass of degassed water, and 0.58 parts by mass of a 31% by mass aqueous sodium hydroxide solution. 107.7 parts by mass of epichlorohydrin was added dropwise to the reactor at 9°C to 11°C over 4.5 hours, followed by stirring for 60 minutes. Next, 262.3 parts by mass of a 17.3% by mass aqueous sodium sulfide solution was added dropwise to the reactor at 25°C to 30°C over 1.0 hour, followed by stirring for 180 minutes. Next, 484.6 parts by mass of 35.0% by mass hydrochloric acid was added, followed by 214.0 parts by mass of thiourea with a purity of 99.30% by mass. The mixture was stirred at 100°C for 6 hours to carry out a thiuronium salt reaction, thereby obtaining a liquid containing thiuronium salt. The obtained liquid containing the thironium salt was cooled to 50°C, and then 373.0 parts by mass of toluene was added thereto and cooled to 35°C. Next, 347.2 parts by mass of a 25% by mass aqueous ammonia solution was added thereto at 35°C to 40°C over 30 minutes, and then the mixture was stirred at 60°C to 61°C for 1 hour to carry out a hydrolysis reaction, thereby obtaining a toluene solution containing, as a main component, polythiol component T, which is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T1"), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T2"), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T3"). The aqueous phase was removed from this toluene solution by a separation operation. Next, 250.0 parts by mass of 4% by mass hydrochloric acid was added to this toluene solution, followed by acid washing for 30 minutes at 35°C to 40°C, followed by adding 125.0 parts by mass of 35% by mass hydrochloric acid and acid washing for 30 minutes at 35°C to 40°C. This operation was repeated twice, and then 125.0 parts by mass of degassed water was added and washed for 15 minutes at 35°C to 45°C. This operation was repeated five times.Toluene and trace amounts of water were removed from the toluene solution after washing under heating and reduced pressure, and then the resulting solution was filtered under reduced pressure using a 3.0 μm PTFE-type membrane filter to obtain 196.7 parts by mass of a polythiol composition containing polythiol component T as a main component (hereinafter also referred to as the “polythiol composition of Example 1”).

[0159] <High Performance Liquid Chromatography (HPLC) Measurement of Polythiol Composition> The polythiol composition was subjected to high performance liquid chromatography (HPLC) measurement under the measurement condition A described above.

[0160] Table 1 shows the peak area ratio of polythiol component T1 (specifically, the ratio of the total peak area of ​​compounds T1, T2, and T3 to the total peak area of ​​the compounds contained in the polythiol composition), the peak area ratio of component X (specifically, the ratio of the peak area of ​​component X to the total peak area of ​​the compounds contained in the polythiol composition), and the peak area ratio of component Y (specifically, the ratio of the peak area of ​​component Y to the total peak area of ​​the compounds contained in the polythiol composition) in the above-mentioned HPLC of the polythiol composition. Table 1 also shows the peak area ratio [T1 / T2 / T3] of polythiol component T. The peak area ratio [T1 / T2 / T3] of polythiol component T means the ratio of the peak areas of compounds T1, T2, and T3, respectively, when the peak area of ​​polythiol component T (i.e., the total peak area of ​​compounds T1, T2, and T3) is taken as 100. Furthermore, Table 1 also shows the ratio [component Y (area %) / component X (area %)], that is, the ratio of the peak area of ​​component Y to the peak area of ​​component X.

[0161] Here, component X is a polythiol compound having a retention time of 30.0 minutes to 40.0 minutes and a molecular weight of 426. The molecular formula of component X is C １２ H ２６ S ８ Component Y is a polythiol compound with a molecular weight of 532 and a retention time of 60.0 to 70.0 minutes. The molecular formula of component Y is C １５ H ３２ S １０ It is estimated that...

[0162] <Production and Evaluation of Plastic Lenses> 51 parts by mass of m-xylylene diisocyanate, 0.015 parts by mass of dibutyltin dichloride as a curing catalyst, and 0.10 parts by mass of Zelec UN (trade name: acidic phosphate ester, manufactured by Stepan) as a mold release agent were mixed and dissolved at 20°C. Next, 49 parts by mass of the polythiol composition of Example 1 were added and mixed to obtain a polymerizable composition as a homogeneous liquid. The obtained polymerizable composition was degassed at 600 Pa for 1 hour and then filtered through a 1 μm Teflon (registered trademark) filter. The filtered polymerizable composition was poured between a pair of glass molds secured with tape, and then the pair of glass molds were placed in an oven, with the oven temperature set to 10°C. Next, the oven temperature was raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a plastic lens containing a thiourethane resin (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Subsequently, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven, and then the plastic lens was removed from the pair of glass molds. The obtained plastic lens was subjected to the above-mentioned evaluations. The results are shown in Table 1.

[0163] [Example 2] (Salt Formation 0.50 eq) The polythiol composition of Example 1 described above was salted with 0.50 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition to obtain the polythiol composition of Example 2. Details are provided below. 100.0 parts by mass of a polythiol composition primarily composed of the polythiol component T obtained in Example 1 and 250.0 parts by mass of toluene were charged into a reactor at 25°C to obtain a toluene solution. 70.6 parts by mass of a 30.9% by mass aqueous sodium hydroxide solution (specifically, an aqueous solution containing 0.50 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition) was added dropwise to the obtained toluene solution, followed by stirring at 37°C to 40°C for 15 minutes. 37.9 parts by mass of degassed water was added thereto, followed by stirring at 37°C to 40°C for 15 minutes, and components soluble in the aqueous layer were extracted. The solution was then filtered through 7 μm filter paper. The aqueous layer was separated from the obtained filtrate by a separation operation to obtain a toluene layer. 73.9 parts by mass of 35% by mass hydrochloric acid was added to the obtained toluene layer, and the mixture was stirred and washed at 37°C to 40°C. After stirring and washing, the aqueous layer was separated by a separation operation to obtain a toluene solution. This toluene solution was washed three times with 37.9 parts by mass of degassed water at 37°C to 40°C to obtain a toluene solution of a polythiol composition. Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling point components using a vacuum pump and filtration through a 3-micron PTFE membrane filter, in that order, to obtain 46.7 parts by mass of a polythiol composition composed mainly of polythiol component T (hereinafter also referred to as the "polythiol composition of Example 2").

[0164] <Production and Evaluation of Plastic Lens> The same operations as in "Production and Evaluation of Plastic Lens" in Example 1 were carried out, except that "49 parts by mass of the polythiol composition of Example 1" was changed to 49 parts by mass of the polythiol composition of Example 2. The results are shown in Table 1.

[0165] Example 3 (0.70 eq of salt formation) The polythiol composition of Example 1 described above was salted with 0.70 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition to obtain the polythiol composition of Example 3. Details are provided below. 200.0 parts by mass of a polythiol composition primarily composed of the polythiol component T obtained in Example 1 and 500.0 parts by mass of toluene were charged into a reactor at 25°C to obtain a toluene solution. 197.7 parts by mass of a 30.9% by mass aqueous sodium hydroxide solution (specifically, an aqueous solution containing 0.70 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition) was added dropwise to the obtained toluene solution, followed by stirring at 37°C to 40°C for 15 minutes. 106.1 parts by mass of degassed water was added thereto, followed by stirring at 37°C to 40°C for 15 minutes, and components soluble in the aqueous layer were extracted. The solution was then filtered through a 7 μm filter paper. The aqueous layer was separated from the obtained filtrate by a separation operation to obtain a toluene layer. 206.8 parts by mass of 35% by mass hydrochloric acid was added to the obtained toluene layer, and the mixture was stirred and washed at 37°C to 40°C. After stirring and washing, the aqueous layer was separated by a separation operation to obtain a toluene solution. This toluene solution was washed three times with 106.1 parts by mass of degassed water at 37°C to 40°C to obtain a toluene solution of a polythiol composition. Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling point components using a vacuum pump and filtration through a 3-micron PTFE membrane filter, in that order, to obtain 57.1 parts by mass of a polythiol composition composed mainly of polythiol component T (hereinafter also referred to as the "polythiol composition of Example 3").

[0166] <Production and Evaluation of Plastic Lens> The same operations as in "Production and Evaluation of Plastic Lens" in Example 1 were carried out, except that "49 parts by mass of the polythiol composition of Example 1" was changed to 49 parts by mass of the polythiol composition of Example 3. The results are shown in Table 1.

[0167]

[0168] As shown in Table 1, the yellowness index (YI) was reduced and the heat resistance (specifically, Tg) was improved in the plastic lenses (i.e., resins) of Examples 1 and 2, in which the peak area of ​​component X relative to the total peak area 100 of the compounds contained in the polythiol composition was 5.00 or less and the peak area of ​​component Y relative to the total peak area 100 was 2.50 or less. In contrast, the yellowness index (YI) was increased and the heat resistance (specifically, Tg) was reduced in the plastic lenses (i.e., resins) of Comparative Example 1, in which the peak area of ​​component X relative to the total peak area 100 of the compounds contained in the polythiol composition was more than 5.00 and the peak area of ​​component Y relative to the total peak area 100 was more than 2.50.

[0169] [Example 1X, Example 2X, and Comparative Example 1X] For each of Example 1X, Example 2X, and Comparative Example 1X, the same operations as for each of Example 1, Example 2, and Comparative Example 1 were carried out except that the production of the plastic lens was changed as follows, and results similar to the results for each of Example 1, Example 2, and Comparative Example 1 (Table 1) were obtained.

[0170] - Changes from Example 1, Example 2, and Comparative Example 1 - In each of Example 1, Example 2, and Comparative Example 1, m-xylylene diisocyanate (51 parts by mass) was used in the production of the plastic lens, but in each of Example 1X, Example 2X, and Comparative Example 1X, XDI (51 parts by mass) was changed to XDI composition X1 (an amount such that the amount of m-xylylene diisocyanate contained was 51 parts by mass) as the XDI composition described above. XDI composition X1 was produced by adding trace amounts of compound (N1), trace amounts of compound (N2), and trace amounts of compound (N3) to XDI, which is the main component, and mixing them.

[0171] 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) was 0.20 ppm or more (specifically, 600 ppm) relative to the peak area 1 of xylylene diisocyanate, the peak area of ​​the compound (N2) was 0.05 ppm or more (specifically, 18 ppm) relative to the peak area 1 of xylylene diisocyanate, and the peak area of ​​the compound (N3) was 0.10 ppm or more (specifically, 100 ppm) relative to the peak area 1 of xylylene diisocyanate.

[0172] Next, examples of the second embodiment of the present disclosure will be shown, but the second embodiment of the present disclosure is not limited to the following examples. Note that, unless otherwise specified, "parts" are based on mass.

[0173] <Method of Evaluating Plastic Lenses> In each of the Examples and Comparative Examples described below, the plastic lenses used as resins were evaluated as follows. The results are shown in Table 2.

[0174] Yellowness Index (YI) The resin was prepared into a circular plastic plate having a thickness of 9 mm and a diameter of 75 mm, and the YI was determined using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. The measurement was carried out under transmission conditions. The smaller the YI, the smaller the yellowness of the plastic plate, and the larger the YI, the greater the yellowness.

[0175] Heat resistance: Resin test pieces measuring 10 mm in length, 10 mm in width, and 2.5 mm in thickness were prepared, and the glass transition temperature (Tg) was measured using a Shimadzu TMA-60 thermomechanical analyzer by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10°C / min) as an index of heat resistance. The higher the glass transition temperature (Tg), the better the heat resistance.

[0176] Example 101 Production of Polythiol Composition Compared to Example 1 of JP-A-7-252207, the conditions for the thiuronium chloride reaction using thiourea were changed from "9 hours at 110°C" to "7 hours at 105°C," and a polythiol composition was produced. Details are provided below. A reactor was charged with 89.3 parts by mass of 2-mercaptoethanol, 44.6 parts by mass of degassed water, and 0.58 parts by mass of a 31% by mass aqueous sodium hydroxide solution. 107.7 parts by mass of epichlorohydrin was added dropwise to the reactor at 9°C to 11°C over 4.5 hours, followed by stirring for 60 minutes. Next, 262.3 parts by mass of a 17.3% by mass aqueous sodium sulfide solution was added dropwise to the reactor at 25°C to 30°C over 1.0 hour, followed by stirring for 180 minutes. Next, 484.6 parts by mass of 35.0% by mass hydrochloric acid was added, and then 214.0 parts by mass of thiourea with a purity of 99.30% by mass was added. The mixture was stirred at 105°C for 7 hours to carry out a thiuronium salt reaction, and a liquid containing thiuronium salt was obtained. The obtained liquid containing the thironium salt was cooled to 50°C, and then 373.0 parts by mass of toluene was added thereto and cooled to 35°C. Next, 347.2 parts by mass of a 25% by mass aqueous ammonia solution was added thereto at 35°C to 40°C over 30 minutes, and then the mixture was stirred at 60°C to 61°C for 1 hour to carry out a hydrolysis reaction, thereby obtaining a toluene solution containing, as a main component, polythiol component T, which is at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T1"), 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T2"), and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "compound T3"). The aqueous phase was removed from this toluene solution by a separation operation. Next, 250.0 parts by mass of 4% by mass hydrochloric acid was added to this toluene solution, followed by acid washing for 30 minutes at 35°C to 40°C, followed by adding 125.0 parts by mass of 35% by mass hydrochloric acid and acid washing for 30 minutes at 35°C to 40°C. This operation was repeated twice, and then 125.0 parts by mass of degassed water was added and washed for 15 minutes at 35°C to 45°C. This operation was repeated five times.Toluene and trace amounts of water were removed from the toluene solution after washing under heating and reduced pressure, and then the mixture was filtered under reduced pressure using a 3.0 μm PTFE-type membrane filter to obtain 196.7 parts by mass of a polythiol composition containing polythiol component T as a main component (hereinafter also referred to as the “polythiol composition of Example 101”).

[0177] <High Performance Liquid Chromatography (HPLC) Measurement of Polythiol Composition> The polythiol composition was subjected to high performance liquid chromatography (HPLC) measurement under the measurement condition A described above.

[0178] Table 2 shows the peak area ratio of polythiol component T (specifically, the total peak area (area %) of compounds T1, T2, and T3 relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition), the peak area ratio of component W (specifically, the peak area (area %) of component W relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition), the peak area ratio of component V (specifically, the peak area (area %) of component V relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition), the peak area ratio of component X (specifically, the peak area (area %) of component X relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition), the peak area ratio of component Y (specifically, the ratio of the peak area of ​​component Y relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition), and the peak area ratio of component U (specifically, the peak area (area %) of component U relative to 100 of the total peak area of ​​the compounds contained in the polythiol composition). Table 2 also shows the peak area ratio [T1 / T2 / T3] of polythiol component T. The peak area ratio [T1 / T2 / T3] of polythiol component T means the ratio of the peak areas of compounds T1, T2, and T3, respectively, when the peak area of ​​polythiol component T (i.e., the total peak area of ​​compounds T1, T2, and T3) is taken as 100. Table 2 also shows the ratio [component V / component W] (i.e., the ratio of the peak area of ​​component V to the peak area of ​​component W), the ratio [component V / polythiol component T] (i.e., the ratio of the peak area of ​​component V to the peak area of ​​polythiol component T), and the ratio [component X / component Y] (i.e., the ratio of the peak area of ​​component X to the peak area of ​​component Y).

[0179] Here, component W is a polythiol compound with a molecular weight of 350 and a retention time of 8.7 to 9.7 minutes. The molecular formula of component W is C １０ H ２２ OS ６ Component V is a polythiol compound with a molecular weight of 260, whose retention time is 11.0 minutes to 13.5 minutes. The molecular formula of component V is C ７ H １６ S５ Component X is a polythiol compound with a molecular weight of 426, whose retention time is 30.0 to 40.0 minutes. The molecular formula of component X is C １２ H ２６ S ８ Component Y is a polythiol compound with a molecular weight of 532 and a retention time of 60.0 to 70.0 minutes. The molecular formula of component Y is C １５ H ３２ S １０ Component U is a polythiol compound with a molecular weight of 472, whose retention time is 40.0 to 49.0 minutes. The molecular formula of component U is C １３ H ２８ S ９ It is estimated that...

[0180] <Production and Evaluation of Plastic Lenses> 51 parts by mass of m-xylylene diisocyanate, 0.015 parts by mass of dibutyltin dichloride as a curing catalyst, and 0.10 parts by mass of Zelec UN (trade name: acidic phosphate ester, manufactured by Stepan) as a mold release agent were mixed and dissolved at 20°C. Next, 49 parts by mass of the polythiol composition of Example 101 were added and mixed to obtain a polymerizable composition as a homogeneous liquid. The obtained polymerizable composition was degassed at 600 Pa for 1 hour and then filtered through a 1 μm Teflon (registered trademark) filter. The filtered polymerizable composition was poured between a pair of glass molds secured with tape, and the pair of glass molds were then placed in an oven, with the oven temperature set to 10°C. The oven temperature was then raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a plastic lens containing a thiourethane resin (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Subsequently, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven, and then the plastic lens was removed from the pair of glass molds. The obtained plastic lens was subjected to the above-mentioned evaluations. The results are shown in Table 2.

[0181] Example 102 Production of Polythiol Composition The polythiol composition of Example 101 described above was subjected to salt formation with 0.50 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition, yielding the polythiol composition of Example 102. Details are provided below. At 25°C, 150.0 parts by mass of a polythiol composition primarily composed of the polythiol component T obtained in Example 101 and 375.0 parts by mass of toluene were charged into a reactor to obtain a toluene solution. 106.6 parts by mass of a 30.7% by mass aqueous solution of sodium hydroxide (specifically, an aqueous solution containing 0.50 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition) was added dropwise to the resulting toluene solution, followed by stirring at 37°C to 40°C for 15 minutes. 57.2 parts by mass of degassed water was added thereto, followed by stirring at 37°C to 40°C for 15 minutes, and components soluble in the aqueous layer were extracted. The mixture was then filtered through a 7 μm filter paper. The toluene layer was separated from the obtained filtrate by a separation operation to obtain an aqueous layer. 150.0 parts by mass of toluene and 110.8 parts by mass of 35% by mass hydrochloric acid were added to the obtained aqueous layer, and the mixture was stirred and washed at 37°C to 40°C. After stirring and washing, the aqueous layer was separated by a separation operation to obtain a toluene solution. This toluene solution was washed three times with 57.2 parts by mass of degassed water at 37°C to 40°C to obtain a toluene solution of a polythiol composition. Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling point components using a vacuum pump and filtration through a 3-micron PTFE membrane filter, in that order, to obtain 71.1 parts by mass of a polythiol composition composed mainly of polythiol component T (hereinafter also referred to as the "polythiol composition of Example 102").

[0182] <Production and Evaluation of Plastic Lens> The same operations as in "Production and Evaluation of Plastic Lens" in Example 101 were carried out, except that "49 parts by mass of the polythiol composition of Example 101" was changed to 49 parts by mass of the polythiol composition of Example 102. The results are shown in Table 2.

[0183] Example 103 The polythiol composition of Example 101 described above was salted with 0.70 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition to obtain the polythiol composition of Example 103. Details are provided below. 150.0 parts by mass of a polythiol composition primarily composed of the polythiol component T obtained in Example 101 and 375.0 parts by mass of toluene were charged into a reactor at 25°C to obtain a toluene solution. 149.2 parts by mass of a 30.7% by mass aqueous sodium hydroxide solution (specifically, an aqueous solution containing 0.70 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition) was added dropwise to the obtained toluene solution and stirred at 37°C to 40°C for 15 minutes. 80.1 parts by mass of degassed water was added thereto and stirred at 37°C to 40°C for 15 minutes to extract components soluble in the aqueous layer. The mixture was then filtered through a 7 μm filter paper. The toluene layer was separated from the obtained filtrate by a separation operation to obtain an aqueous layer. 150.0 parts by mass of toluene and 155.1 parts by mass of 35% by mass hydrochloric acid were added to the obtained aqueous layer, and stirring and washing were carried out at 37°C to 40°C. After stirring and washing, the aqueous layer was separated by a separation operation to obtain a toluene solution. This toluene solution was washed three times with 80.1 parts by mass of degassed water at 37°C to 40°C to obtain a toluene solution of a polythiol composition. Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling point components using a vacuum pump and filtration through a 3-micron PTFE membrane filter, in that order, to obtain 99.4 parts by mass of a polythiol composition composed mainly of polythiol component T (hereinafter also referred to as the "polythiol composition of Example 103").

[0184] <Production and Evaluation of Plastic Lens> The same operations as in "Production and Evaluation of Plastic Lens" in Example 101 were carried out, except that "49 parts by mass of the polythiol composition of Example 101" was changed to 49 parts by mass of the polythiol composition of Example 103. The results are shown in Table 1.

[0185] Example 104 Production of Polythiol Composition The polythiol composition of Example 101 described above was salted with 0.50 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition to obtain the polythiol composition of Example 104. Details are provided below. 100.0 parts by mass of a polythiol composition primarily composed of the polythiol component T obtained in Example 101 and 250.0 parts by mass of toluene were charged into a reactor at 25°C to obtain a toluene solution. 70.6 parts by mass of a 30.9% by mass aqueous sodium hydroxide solution (specifically, an aqueous solution containing 0.50 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition) was added dropwise to the obtained toluene solution and stirred at 37°C to 40°C for 15 minutes. 37.9 parts by mass of degassed water was added thereto and stirred at 37°C to 40°C for 15 minutes to extract components soluble in the aqueous layer. The mixture was then filtered through a 7 μm filter paper. The aqueous layer was separated from the obtained filtrate by a separation operation to obtain a toluene layer. 73.9 parts by mass of 35% by mass hydrochloric acid was added to the obtained toluene layer, and the mixture was stirred and washed at 37°C to 40°C. After stirring and washing, the aqueous layer was separated by a separation operation to obtain a toluene solution. This toluene solution was washed three times with 37.9 parts by mass of degassed water at 37°C to 40°C to obtain a toluene solution of a polythiol composition. Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling point components using a vacuum pump and filtration through a 3-micron PTFE membrane filter, in that order, to obtain 46.7 parts by mass of a polythiol composition composed primarily of polythiol component T (hereinafter also referred to as the "polythiol composition of Example 104").

[0186] <Production and Evaluation of Plastic Lens> The same operations as in "Production and Evaluation of Plastic Lens" in Example 101 were carried out, except that "49 parts by mass of the polythiol composition of Example 101" was changed to 49 parts by mass of the polythiol composition of Example 104. The results are shown in Table 2.

[0187] Comparative Example 101 The polythiol composition of Example 101 described above was salted with 0.70 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition to obtain a polythiol composition of Comparative Example 101. Details are provided below. 200.0 parts by mass of a polythiol composition primarily composed of the polythiol component T obtained in Example 101 and 500.0 parts by mass of toluene were charged into a reactor at 25°C to obtain a toluene solution. 197.7 parts by mass of a 30.9% by mass aqueous sodium hydroxide solution (specifically, an aqueous solution containing 0.70 eq of sodium hydroxide relative to the SH functional groups in the polythiol composition) was added dropwise to the obtained toluene solution and stirred at 37°C to 40°C for 15 minutes. 106.1 parts by mass of degassed water was added thereto and stirred at 37°C to 40°C for 15 minutes to extract components soluble in the aqueous layer. The mixture was then filtered through a 7 μm filter paper. The aqueous layer was separated from the obtained filtrate by a separation operation to obtain a toluene layer. 206.8 parts by mass of 35% by mass hydrochloric acid was added to the obtained toluene layer, and the mixture was stirred and washed at 37°C to 40°C. After stirring and washing, the aqueous layer was separated by a separation operation to obtain a toluene solution. This toluene solution was washed three times with 106.1 parts by mass of degassed water at 37°C to 40°C to obtain a toluene solution of a polythiol composition. Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling point components using a vacuum pump and filtration through a 3-micron PTFE membrane filter, in that order, to obtain 57.1 parts by mass of a polythiol composition composed mainly of polythiol component T (hereinafter also referred to as the "polythiol composition of Comparative Example 101").

[0188] <Production and Evaluation of Plastic Lens> The same operations as in "Production and Evaluation of Plastic Lens" in Example 101 were carried out, except that "49 parts by mass of the polythiol composition of Example 101" was changed to 49 parts by mass of the polythiol composition of Comparative Example 101. The results are shown in Table 2.

[0189]

[0190] As shown in Table 2, the yellowness index (YI) was reduced and the heat resistance (more specifically, Tg) was improved in the plastic lenses (i.e., resins) of Examples 101 to 104, in which the peak area of ​​component W relative to the total peak area 100 of the compounds contained in the polythiol composition was 3.50 or less and the peak area of ​​component V relative to the total peak area 100 was 3.10 or less. In contrast, the yellowness index (YI) was increased and the heat resistance (more specifically, Tg) was reduced in the plastic lens (i.e., resin) of Comparative Example 101, in which the peak area of ​​component V relative to the total peak area 100 of the compounds contained in the polythiol composition was more than 3.10.

[0191] [Example 101X, Example 102X, Example 103X, Example 104X, and Comparative Example 101X] For each of Example 101X, Example 102X, Example 103X, Example 104X, and Comparative Example 101X, the same operations as for each of Examples 101, 102, Example 103, Example 104, and Comparative Example 101 were performed, except that the production of the plastic lens was changed as follows, and results similar to the results of each of Examples 101, 102, Example 103, Example 104, and Comparative Example 101 (Table 2) were obtained.

[0192] - Changes from Example 101, Example 102, Example 103, Example 104, and Comparative Example 101 - In each of Example 101, Example 102, Example 103, Example 104, and Comparative Example 101, m-xylylene diisocyanate (51 parts by mass) was used in the production of the plastic lens, but in each of Example 101X, Example 102X, Example 103X, Example 104X, and Comparative Example 101X, XDI (51 parts by mass) was changed to XDI composition X101 (an amount such that the amount of m-xylylene diisocyanate contained was 51 parts by mass) as the XDI composition described above. XDI composition X101 was produced by adding trace amounts of compound (N1), trace amounts of compound (N2), and trace amounts of compound (N3) to XDI, which is the main component, and mixing them.

[0193] The XDI composition X101 was subjected to gas chromatography measurement under the above-mentioned GC conditions 1 and GC conditions 2. As a result, the peak area of ​​the compound (N1) was 0.20 ppm or more (specifically, 600 ppm) relative to the peak area 1 of xylylene diisocyanate, the peak area of ​​the compound (N2) was 0.05 ppm or more (specifically, 18 ppm) relative to the peak area 1 of xylylene diisocyanate, and the peak area of ​​the compound (N3) was 0.10 ppm or more (specifically, 100 ppm) relative to the peak area 1 of xylylene diisocyanate.

[0194] The disclosures of Japanese Patent Application No. 2023-191755, filed on November 9, 2023, and Japanese Patent Application No. 2024-094653, filed on June 11, 2024, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A polythiol component T which 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; a component X which has a retention time of 30.0 minutes to 40.0 minutes in high performance liquid chromatography measurement under the following measurement condition A; and a component Y which has the retention time of 60.0 minutes to 70.0 minutes, In the high performance liquid chromatography measurement, the peak area of ​​the polythiol component T relative to a total peak area of ​​100 of compounds contained in the polythiol composition is 80.00 or more, the peak area of ​​the component X relative to the total peak area of ​​100 is 5.00 or less, and the peak area of ​​the component Y relative to the total peak area of ​​100 is 2.50 or less. - Measurement condition A - The following conditions were used: a YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, column shape: Φ6 mm × 150 mm) manufactured by YMC Corporation was used as the column; 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; an ultraviolet detector with a measurement wavelength of 230 nm was used as the detector; the column temperature was 40°C; the flow rate was 1.0 mL / min; and the injection amount was 2 μL.

2. The polythiol composition according to claim 1, wherein component X is a polythiol compound having a molecular weight of 426, and component Y is a polythiol compound having a molecular weight of 532.

3. The polythiol composition according to claim 1, wherein the peak area of ​​component X is 1.00 or more and the peak area of ​​component Y is 1.00 or more.

4. The polythiol composition according to claim 1, wherein the ratio of the peak area of ​​said component Y to the peak area of ​​said component X is 0.40 to 0.

90.

5. A polythiol component T which 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, a component W having a retention time of 8.7 minutes to 9.7 minutes in high performance liquid chromatography measurement under the following measurement condition A, and a component V having the retention time of 11.0 minutes to 13.5 minutes, a peak area of ​​the polythiol component T relative to a total peak area of ​​100 of compounds contained in the polythiol composition is 75.00 or more, a peak area of ​​the component W relative to the total peak area of ​​100 is 3.50 or less, and a peak area of ​​the component V relative to the total peak area of ​​100 is 3.10 or less, in the high performance liquid chromatography measurement. - Measurement condition A - The following conditions were used: a YMC-Pack (registered trademark) ODS-A (particle size S: 5 μm, column shape: Φ6 mm × 150 mm) manufactured by YMC Corporation was used as the column; 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; an ultraviolet detector with a measurement wavelength of 230 nm was used as the detector; the column temperature was 40°C; the flow rate was 1.0 mL / min; and the injection amount was 2 μL.

6. The polythiol composition according to claim 5, wherein component W is a polythiol compound having a molecular weight of 350, and component V is a polythiol compound having a molecular weight of 260.

7. The polythiol composition according to claim 5, wherein the peak area of ​​component W relative to the total peak area of ​​100 is 1.30 or more, and the peak area of ​​component V relative to the total peak area of ​​100 is 1.00 or more.

8. The polythiol composition according to claim 5, wherein the ratio of the peak area of ​​said component V to the total peak area of ​​100 relative to the peak area of ​​said component W to the total peak area of ​​100 is 0.10 to 2.

80.

9. The polythiol composition according to claim 5, further comprising at least one of a component X having a retention time of 30.0 to 40.0 minutes in high performance liquid chromatography measurement under the measurement conditions A, and a component Y having a retention time of 60.0 to 70.0 minutes.

10. A polymerizable composition comprising: the polythiol composition according to any one of claims 1 to 9; and a polyiso(thio)cyanate compound.

11. The polymerizable composition according to claim 10, further comprising a thiol compound XS which is a thiol compound other than the polythiol compound contained in the polythiol composition.

12. The thiol compound XS is 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, 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.

13. The polymerizable composition according to claim 10, wherein the polyiso(thio)cyanate compound comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

14. A polyiso(thio)cyanate composition comprising the polyiso(thio)cyanate compound, wherein the polyiso(thio)cyanate composition comprises 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), wherein when the polyiso(thio)cyanate composition comprises the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement is 0.20 ppm or more relative to the peak area of ​​the xylylene diisocyanate, and when the polyiso(thio)cyanate composition comprises the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement is 0.05 ppm or more relative to the peak area of ​​the xylylene diisocyanate, The polymerizable composition according to claim 10, wherein, when the polyiso(thio)cyanate composition contains the compound (N3), a peak area of ​​the compound (N3) measured by gas chromatography is 0.10 ppm or more relative to a peak area of ​​xylylene diisocyanate of 1.

15. A resin comprising a cured product of the polymerizable composition according to claim 10.

16. A molded article comprising the resin according to claim 15.

17. An optical material comprising the resin according to claim 15.

18. A lens comprising the resin of claim 15.