Polythiol composition and its applications

Abstract

A polythiol composition that can improve the pot life of polymerizable compositions. [Solution] A polythiol composition comprising polythiol A2, which is at least one of the polythiols represented by formulas (6) to (8), as the main component, and containing 0.04 to 1.50% of compound (NA2) obtained by replacing at least one mercapto group in component A2 with formula (N1). JPEG2026090356000016.jpg70157

Description

Technical Field

[0001] The present disclosure relates to a polythiol composition and its applications.

Background Art

[0002] Plastic lenses, which are lenses containing resin, are lightweight, less likely to break, and can be dyed compared to inorganic lenses. In recent years, they have rapidly spread to applications such as glasses lenses and camera lenses.

[0003] As one of the resins for lenses, thiourethane resin is known. Patent Documents 1 and 2 disclose a method for producing a polythiol compound, which is one of the raw materials of thiourethane resin, and a polymerizable composition for optical materials (for example, a polymerizable composition for lenses) containing the polythiol compound. In addition, Patent Documents 3 and 4 disclose a polythiol composition containing a polythiol compound and having a reduced content of a nitrogen-containing compound as a polythiol composition capable of producing lenses with excellent quality. Patent Documents 3 and 4 also disclose a polymerizable composition for optical materials (for example, a polymerizable composition for lenses) containing the polythiol composition.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the manufacture of thiourethane resins, there is a need to further improve the pot life of polymerizable compositions containing polythiol compositions.

[0006] An object of one aspect of this disclosure is to provide a polythiol composition and its applications that can improve the pot life of a polymerizable composition containing a polythiol composition. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments. <1> A preparation step to prepare a crude polythiol composition, which is a polythiol composition before purification, A purification step to obtain a polythiol composition by purifying the crude polythiol composition with a solvent X containing alkylene glycol, including, A method for producing a polythiol composition. <2> The crude polythiol composition comprises a polythiol component A1, which is a polythiol compound represented by the following formula (5), and a compound (NA1) obtained by replacing at least one of the mercapto groups in the polythiol component A1 with a group represented by the following formula (N1). and, The crude polythiol composition comprises a polythiol component A2 which is at least one selected from the group consisting of a polythiol compound represented by the following formula (6), a polythiol compound represented by the following formula (7), and a polythiol compound represented by the following formula (8), and a compound (NA2) in which at least one of the mercapto groups in the polythiol component A2 is replaced with a group represented by the following formula (N1). Satisfying at least one of the following: <1> A method for producing the polythiol composition described above.

[0008] [ka]

[0009] In formula (N1), * represents the bonding position.

[0010] <3> The crude polythiol composition contains the thiol component A1 and the compound (NA1), The preparation step is reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following formula (1) to obtain a polyalcohol compound represented by the following formula (2); reacting the polyalcohol compound represented by the formula (2) with thiourea under acidic conditions to obtain a reaction solution containing an isothiouronium salt; adding a base compound to the reaction solution containing the isothiouronium salt to hydrolyze the isothiouronium salt and obtain the crude polythiol composition, and includes The method for producing a polythiol composition according to <2>.

[0011]

Chemical formula

[0012] In formula (1), X represents a halogen atom.

[0013] <4> The crude polythiol composition contains the thiol component A2 and the compound (NA2), The preparation step is reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following formula (1) to obtain a compound represented by the following formula (3); reacting the compound represented by the formula (3) with sodium sulfide to obtain a polyalcohol compound represented by the following formula (4); reacting the polyalcohol compound represented by the formula (4) with thiourea under acidic conditions to obtain a reaction solution containing an isothiouronium salt; adding a base compound to the reaction solution containing the isothiouronium salt to hydrolyze the isothiouronium salt and obtain the crude polythiol composition, comprising The method for producing a polythiol composition according to <2>.

[0014]

Chemical formula

[0015] In formula (1), X represents a halogen atom.

[0016] <5> The method for producing a polythiol composition according to any one of <1> to <4>, wherein the solvent X contains at least one selected from the group consisting of ethylene glycol and propylene glycol. <6> The preparation step prepares a toluene solution of the crude polythiol composition, The purification step purifies the crude polythiol composition in the toluene solution with the solvent X by mixing the toluene solution and the solvent X. The method for producing a polythiol composition according to any one of <1> to <5>. <7> The purification step obtains a polythiol composition by purifying the crude polythiol composition with the solvent X, pickles and cleans the obtained polythiol composition, comprising The method for producing a polythiol composition according to any one of <1> to <6>. <8> A step of producing a polythiol composition by the method for producing a polythiol composition according to any one of <1> to <7>, and a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate compound by mixing the polythiol composition and the polyisocyanate compound. A method for producing a polymerizable composition comprising.

[0017] <9> The step of obtaining the polymerizable composition is to mix the polythiol composition and the polyisocyanate composition containing the polyisocyanate compound to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate composition. The polyisocyanate composition is Xylylene diisocyanate and At least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3), Includes, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate. When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate. If the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in gas chromatography measurement is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. <8> A method for producing the polymerizable composition described above.

[0018] [ka]

[0019] <10> <8> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins.

[0020] <11> It contains as its main component a polythiol component A2 which is at least one selected from the group consisting of a polythiol compound represented by the following formula (6), a polythiol compound represented by the following formula (7), and a polythiol compound represented by the following formula (8), and The compound (NA2) contains a compound in which at least one of the mercapto groups in the aforementioned polythiol component A2 is replaced with a group represented by the following formula (N1), In high-performance liquid chromatography measurements, the peak area of ​​the compound (NA2) is 0.50 to 1.50 relative to the total peak area of ​​the compounds contained in the polythiol composition (100). Polythiol composition.

[0021] [ka]

[0022] In formula (N1), * represents the bonding position.

[0023] <12> <11> The polythiol composition described above, Polyisocyanate compounds and A polymerizable composition containing the following: <13> The polyisocyanate composition comprises the aforementioned polyisocyanate compound, The polyisocyanate composition is Xylylene diisocyanate and At least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3), Includes, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate. When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate. If the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in gas chromatography measurement is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. <12> The polymerizable composition described above.

[0024] [ka] [Effects of the Invention]

[0025] According to one aspect of this disclosure, a polythiol composition and its applications are provided that can improve the pot life of a polymerizable composition. [Modes for carrying out the invention]

[0026] In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved. In this disclosure, the amount of each component contained in the composition means the total amount of any multiple substances that constitute each component in the composition, unless otherwise specified. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. There may be overlaps between the multiple embodiments of this disclosure. That is, features of one embodiment may be present in another embodiment.

[0027] [Method for producing polythiol composition] The method for producing the polythiol composition disclosed herein is: A preparation step to prepare a crude polythiol composition, which is a polythiol composition before purification, A purification step to obtain a polythiol composition by purifying the crude polythiol composition with a solvent X containing alkylene glycol, Includes. The method for producing the polythiol composition of this disclosure may include other steps as necessary.

[0028] The method for producing a polythiol composition according to this disclosure makes it possible to produce a polythiol composition that can improve the pot life of a polymerizable composition containing the polythiol composition. The reason for this effect is presumed to be as follows:

[0029] In polymerizable compositions containing a polythiol composition, if unintended polymerization of polymerizable monomers (e.g., polythiol compounds in the polythiol composition and polyisocyanate compounds described later) occurs during storage, the viscosity of the polymerizable composition may increase during storage, i.e., the pot life of the polymerizable composition may decrease. Unintended polymerization of polymerizable monomers is thought to occur when impurities (for example, the compound (NA1) or compound (NA2) described below) that may be unintentionally included in the polymerizable composition act as a polymerization catalyst. In relation to this problem, the method for producing a polythiol composition of the present disclosure includes a purification step to obtain a polythiol composition by purifying a crude polythiol composition, which is a polythiol composition before purification, with a solvent X containing alkylene glycol (hereinafter also referred to as "purification with solvent X" or simply "purification"). This suggests that purification with solvent X removes at least some of the impurities from the crude polythiol composition, resulting in a polythiol composition with reduced impurity content. Consequently, it is believed that the increase in viscosity during storage is suppressed in the polymerizable composition containing the obtained polythiol composition (i.e., the pot life of the polymerizable composition is improved).

[0030] The purification method for producing the polythiol composition according to this disclosure suppresses the deterioration of the performance of the polythiol composition and the polymerizable composition and resin obtained using the polythiol composition, while achieving the above-mentioned effect (improvement of the pot life of the polymerizable composition). In other words, purification with solvent X is thought to be able to selectively remove impurities while reducing the impact on the polythiol compounds contained in the polythiol composition.

[0031] The following describes the steps that may be included in the method for producing the polythiol composition of this disclosure.

[0032] <Preparation process> The method for producing the polythiol composition of this disclosure includes a preparation step of preparing a crude polythiol composition, which is a polythiol composition before purification. The preparation step may simply involve preparing a pre-manufactured crude polythiol composition, or it may be a step in manufacturing the crude polythiol composition.

[0033] (Crude polythiol composition, polythiol composition) In this disclosure, the crude polythiol composition is the polythiol composition before purification.

[0034] In this disclosure, "polythiol composition" (including crude polythiol compositions; the same applies hereinafter) means a composition containing at least one polythiol compound. The polythiol compound can be any compound containing two or more thiol groups (also known as mercapto groups), and is not particularly limited in any other respect.

[0035] The polythiol composition may contain components other than the polythiol compound as impurities. The polythiol composition preferably contains at least one polythiol compound as its main component.

[0036] Here, "a polythiol composition contains at least one polythiol compound as its main component" means that the total content of at least one polythiol compound relative to the total amount of the polythiol composition is 50% or more. The total content of at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

[0037] Similarly, in this disclosure, "a composition contains a certain component (hereinafter referred to as "component X") as a main component" means that the content of component X (or, if component X consists of two or more compounds, the total content of the two or more compounds) is 50% or more of the total amount of the composition. The content of component X, which is the main component, is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, based on the total amount of the composition.

[0038] In the explanation of the phrase "contained as a main component" above, "%" refers to the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) to the total area of ​​all peaks of the composition (e.g., a polythiol composition), as determined by high-performance liquid chromatography.

[0039] In the following, the polythiol compounds contained in the polythiol composition will also be referred to as "polythiol components." Polythiol composition, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (3-mercaptopropionate), 2,5-Dimercaptomethyl-1,4-Dithiane, Bis(2-mercaptoethyl) sulfide, and Diethylene glycol bis(3-mercaptopropionate) It is preferable to include at least one selected from the group consisting of (hereinafter also referred to as "polythiol component A"). The polythiol composition more preferably contains polythiol component A as its main component. In this case, the polythiol composition may contain at least one other component besides polythiol component A (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0040] Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 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, and the like.

[0041] More specific embodiments of the polythiol composition as a raw material for thiourethane resin include, for example; An embodiment comprising 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A1") as the main component; An embodiment comprising 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 (hereinafter also referred to as "polythiol component A2") as the main component; An embodiment comprising pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as "polythiol component A3") as the main component; Embodiments comprising polythiol component A1 and polythiol component A3 as main components; Embodiments comprising polythiol component A2 and polythiol component A3 as main components; These are some examples. Each embodiment of the polythiol composition may contain at least one other component besides the main component (for example, other polythiol compounds, components other than polythiol compounds, etc.). Other components include, for example, the compounds (NA1) and (NA2) described later.

[0042] The preparation step may involve preparing a toluene solution of the crude polythiol composition. In this case, in the purification step described later, the crude polythiol composition in the toluene solution is purified with solvent X by mixing the toluene solution with solvent X (i.e., solvent X containing alkylene glycol). This can sometimes lead to a more effective purification process using solvent X. The toluene solution of the crude polythiol composition contains the crude polythiol composition and toluene, but may also contain other components as needed. Furthermore, it is also possible to purify the crude polythiol composition by directly mixing the crude polythiol composition and solvent X without first preparing the crude polythiol composition as a toluene solution.

[0043] <Purification process> The method for producing the polythiol composition of this disclosure includes a purification step to obtain the polythiol composition by purifying the crude polythiol composition with a solvent X containing alkylene glycol. Purification with solvent X removes impurities (e.g., compounds (NA1) and (NA2) described later) from the crude polythiol composition, resulting in a polythiol composition with reduced levels of these impurities. This provides a polythiol composition that can improve the pot life of the polymerizable composition.

[0044] (Purification with solvent X) As a specific example of the purification procedure using solvent X, one can apply the operation of washing a liquid composition with solvent X. The temperature of the mixture of the crude polythiol composition and solvent X during purification with solvent X is preferably 10°C to 60°C, more preferably 20°C to 60°C, and even more preferably 20°C to 50°C. The purification time with solvent X is preferably 1 minute to 120 minutes, more preferably 10 minutes to 90 minutes, and even more preferably 20 minutes to 60 minutes.

[0045] As mentioned above, solvent X contains alkylene glycol. From the viewpoint of removing impurities through purification, it is preferable that solvent X contains at least one of ethylene glycol and propylene glycol.

[0046] Solvent X may contain solvent components other than alkylene glycol. Other solvent components besides alkylene glycols include, for example, monoalcohols (such as methanol, ethanol, propanol, isopropanol, and other monoalcohols with 1 to 6 carbon atoms). The proportion of alkylene glycol in solvent X (for example, the total proportion of ethylene glycol and propylene glycol) is preferably 20% to 100% by mass, more preferably 50% to 100% by mass, even more preferably 50% to 100% by mass, and even more preferably 80% to 100% by mass.

[0047] (Acid cleaning) The refining process is, A polythiol composition is obtained by purifying a crude polythiol composition with solvent X. The obtained polythiol composition is acid-washed, It is preferable that it includes.

[0048] Hydrochloric acid is preferred as the acid used for acid cleaning. The temperature of the mixture of the polythiol composition and the acid during acid washing is preferably 10°C to 60°C, more preferably 20°C to 60°C, and even more preferably 20°C to 50°C. The acid washing time is preferably 1 minute to 120 minutes, more preferably 5 minutes to 90 minutes, and even more preferably 10 minutes to 70 minutes. The concentration of hydrochloric acid is preferably 25% to 36% by mass, more preferably 30% to 36% by mass.

[0049] The purification process may further include, in addition to acid washing of the polythiol composition, water washing and / or alkaline washing of the polythiol composition. Water washing and / or alkaline washing are preferably performed after acid washing. For water washing, it is preferable to use deaerated water with an oxygen concentration of 5 mg / L or less. Alkaline washing can be carried out by adding an alkaline aqueous solution and stirring it at a temperature of preferably 20°C to 50°C for preferably 10 minutes to 3 hours. Ammonia water is preferred as the alkaline aqueous solution. The concentration of aqueous ammonia is preferably 0.1% to 10% by mass, more preferably 0.1% to 1% by mass, and even more preferably 0.1% to 0.5% by mass.

[0050] <Other processes> The method for producing the polythiol composition of this disclosure may include other steps as necessary. Other processes include solvent removal, filtration, and distillation, which are performed after the purification process.

[0051] <First and Second Embodiments> The first and second embodiments of the method for producing the polythiol composition of this disclosure will be described below. The first and second embodiments may have overlapping portions. That is, one of the first and second embodiments may possess the features of the other.

[0052] The method for producing the polythiol composition of this disclosure preferably satisfies at least one of the following first embodiment and second embodiment. In the first embodiment, the crude polythiol composition is Polythiol component A1 is a polythiol compound represented by the following formula (5) (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane), Compound (NA1) obtained by replacing at least one of the mercapto groups in polythiol component A1 with a group represented by the following formula (N1), This is an embodiment that includes [the following]. In the second embodiment, the crude polythiol composition is Polythiol component A2 is at least one selected from the group consisting of a polythiol compound represented by the following formula (6) (i.e., 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), a polythiol compound represented by the following formula (7) (i.e., 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), and a polythiol compound represented by the following formula (8) (i.e., 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), A compound (NA2) obtained by replacing at least one of the mercapto groups in polythiol component A2 with a group represented by the following formula (N1), This is an embodiment that includes [the following].

[0053] [ka]

[0054] In formula (N1), * represents the bonding position.

[0055] (First Embodiment) The first embodiment is an embodiment in which the crude polythiol composition comprises polythiol component A1 and compound (NA1). The crude polythiol composition in the first embodiment preferably contains polythiol component A1 as the main component.

[0056] The compound (NA1) in the first embodiment is a compound in which at least one of the mercapto groups in the polythiol component A1 is replaced with a group represented by formula (N1). Compound (NA1) is a reaction by-product generated during the production of polythiol component A1, and is considered to be a compound that may be mixed in as an impurity in a crude polythiol composition mainly composed of polythiol component A1. Compound (NA1) is a compound whose retention time in HPLC (high-performance liquid chromatography) measurements, as shown in the "Examples" section below, is 4.3 to 4.8 minutes. Compound (NA1) is considered to be an impurity that has catalytic activity in polymerizable compositions, promoting the polymerization of monomers. For compound (NA1), refer to International Publication No. 2016 / 010065 (in particular, the description concerning "nitrogen-containing compounds (b)") and International Publication No. 2020 / 41183 (in particular, the description concerning "nitrogen-containing compounds (B)").

[0057] In the first embodiment, in the purification step described later, compound (NA1) is removed from the crude polythiol composition by purification with solvent X, and a polythiol composition with a reduced compound (NA1) content is obtained. This suppresses the increase in viscosity of polymerizable compounds containing polythiol compositions during storage.

[0058] In the HPLC measurement described above, the peak area of ​​compound (NA1) is preferably 0.01 to 0.30, and more preferably 0.01 to 0.20, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition obtained by the purification process.

[0059] The preparation step in the first embodiment is: The method involves reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following formula (1) to obtain a polyalcohol compound represented by the following formula (2), The polyalcohol compound represented by formula (2) and thiourea are reacted under acidic conditions to obtain a reaction solution containing an isothiouronium salt, A basic compound is added to a reaction solution containing an isothiouronium salt, and the isothiouronium salt is hydrolyzed to obtain a crude polythiol composition. It is preferable that it includes.

[0060] [ka]

[0061] In equation (1), X represents a halogen atom.

[0062] For the above preferred embodiments of the preparation steps in the first embodiment, refer to International Publication No. 2014 / 027427 (in particular, the description relating to a method for producing polythiol compounds).

[0063] The preferred embodiment of the preparation step in the first embodiment includes reacting 2-mercaptoethanol with an epihalohydrin compound represented by formula (1) to obtain a polyalcohol compound represented by the following formula (2).

[0064] In formula (1), X is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.

[0065] The reaction temperature between 2-mercaptoethanol and the epihalohydrin compound represented by formula (1) is preferably 10°C to 50°C, more preferably 15°C to 50°C, and even more preferably 25°C to 45°C.

[0066] The amount of 2-mercaptoethanol used is preferably 1.8 to 3 moles, more preferably 1.9 to 2.1 moles, per mole of the epihalohydrin compound represented by formula (1).

[0067] The reaction between 2-mercaptoethanol and the epihalohydrin compound represented by formula (1) below is preferably carried out in an aqueous solvent. Examples of aqueous solvents include water, or a mixed solvent of water and a lower alcohol (e.g., methanol or ethanol).

[0068] The reaction between 2-mercaptoethanol and the epihalohydrin compound represented by the following formula (1) is preferably carried out in the presence of a base. Examples of bases include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; and tertiary amines such as triethylamine and tributylamine. Among these, sodium hydroxide is particularly preferred. The amount of base used is preferably 0.5 to 2 moles, more preferably 0.9 to 1.1 moles, per mole of the epihalohydrin compound represented by formula (1) in the case of a monovalent base. In the case of a divalent base, half the amount used for a monovalent base is preferable.

[0069] The preferred embodiment of the preparation step in the first embodiment includes reacting a polyalcohol compound represented by formula (2) with thiourea under acidic conditions to obtain a reaction solution containing an isothiouronium salt. The amount of thiourea used is preferably 2.7 moles or more, more preferably 2.7 moles to 6.0 moles, and even more preferably 2.9 to 3.2 moles, per mole of the polyalcohol compound represented by formula (2). Under acidic conditions, the presence of hydrochloric acid is preferred. The amount of hydrochloric acid used is preferably 3 moles or more, more preferably 3 to 12 moles, and even more preferably 3 to 5 moles, per mole of the polyalcohol compound represented by formula (2). The reaction temperature between the polyalcohol compound represented by formula (2) and thiourea is preferably room temperature (25°C) to reflux temperature, more preferably 90°C to 120°C. The reaction time is preferably 1 to 10 hours.

[0070] The preferred embodiment of the preparation step in the first embodiment includes adding a base compound to a reaction solution containing an isothiouronium salt, hydrolyzing the isothiouronium salt, and obtaining a crude polythiol composition. The base compound is preferably ammonia. In this hydrolysis, an aqueous solution of a basic compound (e.g., aqueous ammonia) may be added to the reaction solution containing the isothiouronium salt. The reaction temperature for hydrolysis of isothiouronium salt is preferably 15°C to 60°C, more preferably 25°C to 55°C. The basic compound or an aqueous solution thereof is added to the reaction solution containing the isothiuronium salt over a period of time of preferably 80 minutes or less, more preferably 70 minutes or less, and even more preferably 20 to 60 minutes. After adding a basic compound or an aqueous solution thereof to a reaction solution containing an isothiuronium salt, the hydrolysis reaction is carried out preferably at room temperature to reflux temperature (more preferably 30°C to 80°C) for 1 to 8 hours.

[0071] In the process of obtaining a reaction solution containing an isothiouronium salt, when a polyalcohol compound represented by formula (2) and thiourea are reacted in the presence of hydrochloric acid, and ammonia is used as the base compound during the hydrolysis of the isothiouronium salt, the amount of ammonia used per mole of hydrochloric acid is preferably 1 mole or more, more preferably 1 to 3 moles.

[0072] It is preferable to add an organic solvent to the reaction solution containing the isothiuronium salt before adding the basic compound or an aqueous solution thereof. Examples of organic solvents include toluene, xylene, chlorobenzene, and dichlorobenzene. Among them, toluene is preferred. By adding toluene as an organic solvent, a toluene solution of the crude polythiol composition is obtained. As a result, the purification effect with solvent X is more effectively demonstrated, as described above.

[0073] <Second Embodiment> The second embodiment is an embodiment in which the crude polythiol composition comprises polythiol component A2 and compound (NA2). The crude polythiol composition in the second embodiment preferably contains polythiol component A2 as the main component.

[0074] The compound (NA2) in the second embodiment is a compound in which at least one of the mercapto groups in the polythiol component A2 is replaced with a group represented by formula (N1). Compound (NA2) is a reaction by-product generated during the production of polythiol component A2, and is considered to be a compound that may be mixed in as an impurity in a crude polythiol composition mainly composed of polythiol component A2. Compound (NA2) is a compound whose retention time in HPLC (High Performance Liquid Chromatography) measurements, as shown in the "Examples" section below, is 6.5 to 8.0 minutes. The compound (NA2) is considered to be an impurity that acts as a catalyst to promote the polymerization of monomers in polymerizable compositions.

[0075] In the second embodiment, in the purification step described later, compound (NA2) is removed from the crude polythiol composition by purification with solvent X, and a polythiol composition with a reduced compound (NA2) content is obtained. This suppresses the increase in viscosity of polymerizable compounds containing the polythiol composition during storage (i.e., improves the pot life of polymerizable compounds containing the polythiol composition).

[0076] In HPLC measurement, the peak area of ​​compound (NA2) is preferably 0.04 to 1.50, more preferably 0.50 to 1.50, and even more preferably 0.50 to 1.00, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition obtained by the purification step. When the peak area of ​​compound (NA2) is 0.04 or more (more preferably 0.50 or more) relative to the total peak area of ​​all compounds in the polythiol composition (100), the heat resistance (e.g., glass transition temperature (Tg)) of the resin produced using the polythiol composition is further improved. When the peak area of ​​compound (NA2) is 1.50 or less relative to the total peak area of ​​all compounds in the polythiol composition (100), the viscosity increase during storage of the polymerizable compound containing the polythiol composition is further suppressed (i.e., the pot life of the polymerizable compound containing the polythiol composition is further improved).

[0077] The preparation step in the second embodiment is: The method involves reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following formula (1) to obtain a compound represented by the following formula (3), The compound represented by formula (3) is reacted with sodium sulfide to obtain a polyalcohol compound represented by the following formula (4), The method involves reacting a polyalcohol compound represented by formula (4) with thiourea under acidic conditions to obtain a reaction solution containing an isothiouronium salt, A basic compound is added to a reaction solution containing an isothiouronium salt, and the isothiouronium salt is hydrolyzed to obtain a crude polythiol composition containing polythiol component A2. It is preferable that it includes.

[0078] [ka]

[0079] In equation (1), X represents a halogen atom.

[0080] For the above preferred embodiments of the preparation steps in the second embodiment, refer to International Publication No. 2014 / 027428 (in particular, the description relating to a method for producing polythiol compounds).

[0081] The preferred embodiment of the preparation step in the second embodiment includes reacting 2-mercaptoethanol with an epihalohydrin compound represented by formula (1) to obtain a compound represented by formula (3).

[0082] In formula (1), X is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom.

[0083] The reaction temperature between 2-mercaptoethanol and the epihalohydrin compound represented by formula (1) is preferably 2°C to 30°C, more preferably 5°C to 20°C, and even more preferably 5°C to 15°C. The reaction time is preferably 2 to 10 hours.

[0084] The amount of 2-mercaptoethanol used is preferably 0.5 to 3 moles, more preferably 0.7 to 2.0 moles, and even more preferably 0.9 to 1.1 moles, per mole of the epihalohydrin compound represented by formula (1).

[0085] The reaction between 2-mercaptoethanol and the epihalohydrin compound represented by formula (1) below is preferably carried out in an aqueous solvent. Examples of aqueous solvents include water, or a mixed solvent of water and a lower alcohol (e.g., methanol or ethanol).

[0086] The reaction between 2-mercaptoethanol and the epihalohydrin compound represented by the following formula (1) is preferably carried out in the presence of a base. Examples of bases include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; and tertiary amines such as triethylamine and tributylamine. Among these, sodium hydroxide is particularly preferred. The amount of base used is preferably 0.001 moles to 0.1 moles per mole of the epihalohydrin compound represented by formula (1) in the case of a monovalent base. In the case of a divalent base, half the amount used for a monovalent base is preferable.

[0087] The preferred embodiment of the preparation step in the second embodiment includes reacting a compound represented by formula (3) with sodium sulfide to obtain a polyalcohol compound represented by formula (4). The amount of sodium sulfide used is preferably 0.4 to 0.6 moles per mole of the polyalcohol compound represented by formula (3). The reaction temperature is preferably 10°C to 50°C, more preferably 20°C to 40°C. The reaction time is preferably 1 to 10 hours.

[0088] The preferred embodiment of the preparation step in the second embodiment includes reacting a polyalcohol compound represented by formula (4) with thiourea under acidic conditions to obtain a reaction solution containing an isothiouronium salt. The amount of thiourea used is preferably 3.0 moles or more, more preferably 3.0 moles to 6.0 moles, and even more preferably 4.6 to 5.0 moles, per mole of the polyalcohol compound represented by formula (4). Under acidic conditions, the presence of hydrochloric acid is preferred. The amount of hydrochloric acid used is preferably 3 moles or more, more preferably 3 to 12 moles, per mole of the polyalcohol compound represented by formula (4). The reaction temperature between the polyalcohol compound represented by formula (4) and thiourea is preferably room temperature (25°C) to reflux temperature, more preferably 90°C to 120°C. The reaction time is preferably 1 to 10 hours.

[0089] The preferred embodiment of the preparation step in the second embodiment includes adding a base compound to a reaction solution containing an isothiouronium salt, hydrolyzing the isothiouronium salt, and obtaining a crude polythiol composition. The base compound is preferably ammonia. In this hydrolysis, an aqueous solution of a basic compound (e.g., aqueous ammonia) may be added to the reaction solution containing the isothiouronium salt. The reaction temperature for hydrolysis of isothiouronium salt is preferably 20°C to 60°C, more preferably 25°C to 55°C. The basic compound or an aqueous solution thereof is added to the reaction solution containing the isothiuronium salt over a period of time of preferably 80 minutes or less, more preferably 70 minutes or less, and even more preferably 20 to 60 minutes. After adding a basic compound or an aqueous solution thereof to a reaction solution containing an isothiuronium salt, the hydrolysis reaction is carried out preferably at room temperature to reflux temperature (more preferably 30°C to 80°C) for 1 to 8 hours.

[0090] In the process of obtaining a reaction solution containing an isothiouronium salt, when a polyalcohol compound represented by formula (4) and thiourea are reacted in the presence of hydrochloric acid, and ammonia is used as the base compound during the hydrolysis of the isothiouronium salt, the amount of ammonia used per mole of hydrochloric acid is preferably 1 mole or more, more preferably 1 to 3 moles.

[0091] It is preferable to add an organic solvent to the reaction solution containing the isothiuronium salt before adding the basic compound or an aqueous solution thereof. Examples of organic solvents include toluene, xylene, chlorobenzene, and dichlorobenzene. Among them, toluene is preferred. By adding toluene as an organic solvent, a toluene solution of the crude polythiol composition is obtained. As a result, the purification effect with solvent X is more effectively demonstrated, as described above.

[0092] [Method for producing polymerizable compositions] The method for producing the polymerizable composition disclosed herein is: A step of producing a polythiol composition by the method for producing a polythiol composition described above in this disclosure, The process involves a step of obtaining a polymerizable composition containing the polythiol composition and a polyisocyanate compound by mixing at least the above-mentioned polythiol composition and a polyisocyanate compound, Includes. The method for producing the polymerizable composition of this disclosure may include other steps as necessary.

[0093] In the method for producing the polymerizable composition of this disclosure, the polythiol composition is produced by the method for producing the polythiol composition of this disclosure described above, and therefore the same effects as in the method for producing the polythiol composition of this disclosure are achieved. In other words, according to the method for producing the polymerizable composition of this disclosure, the polymerization reaction between the polythiol composition and the polyisocyanate compound during storage is suppressed, thereby suppressing the increase in viscosity during storage (i.e., suppressing the decrease in pot life).

[0094] <Process for manufacturing polythiol composition> For the steps involved in producing the polythiol composition in the method for producing the polymerizable composition of this disclosure, the method for producing the polythiol composition described above can be appropriately referenced.

[0095] <Steps to obtain a polymerizable composition> In the step of obtaining a polymerizable composition, a polymerizable composition containing the polythiol composition and the polyisocyanate compound is obtained by mixing at least the polythiol composition and the polyisocyanate compound.

[0096] The preferred embodiment of the polyisocyanate compound used in the process of obtaining the polymerizable composition is the same as the preferred embodiment of the "isocyanate compound as a raw material for thiourethane resin" described in the section on "Method for producing a polythiol composition".

[0097] In the process of obtaining a polymerizable composition, the mixing ratio of the polythiol composition and the polyisocyanate compound is not particularly limited. In the process of obtaining a polymerizable composition, the ratio of the mass of the polythiol composition to the mass of the polyisocyanate compound (i.e., mass [polythiol composition / polyisocyanate compound]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, even more preferably 0.50 to 1.50, and even more preferably 0.70 to 1.30. Furthermore, the molar ratio (mercapto group / isocyanato group) of the mercapto group of the polythiol compound and the isocyanate group of the polyisocyanate compound contained in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3.

[0098] In the process of obtaining a polymerizable composition, the total mass of the polythiol composition and the polyisocyanate compound charged is not particularly limited, but is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of polymerizable composition produced.

[0099] The step of obtaining a polymerizable composition may be a step of mixing a polythiol composition with a polyisocyanate composition containing a polyisocyanate compound to obtain a polymerizable composition containing a polythiol composition and a polyisocyanate composition.

[0100] Here, a polyisocyanate composition means a composition containing at least one polyisocyanate compound.

[0101] The polyisocyanate composition may contain components other than the polyisocyanate compound as impurities. The polyisocyanate composition preferably contains at least one polyisocyanate compound as its main component. The meaning of "contains as a main component" is as explained above.

[0102] The polyisocyanate composition preferably contains xylylene diisocyanate.

[0103] Hereinafter, a polyisocyanate composition containing xylylene diisocyanate will also be referred to as an XDI composition. The XDI composition preferably contains xylylene diisocyanate as its main component.

[0104] The XDI composition preferably contains at least one compound selected from the group consisting of the following compounds (N1), (N2), and (N3).

[0105] [ka]

[0106] The following describes preferred embodiments of the XDI composition from the viewpoint of superior stability of the polyisocyanate composition and transparency of the resin formed using the polyisocyanate composition.

[0107] If the XDI composition contains compound (N1), it is preferable that the peak area of ​​compound (N1) in gas chromatography measurement under GC condition 1 below is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate. -GC condition 1- Filler; DB-1 (film thickness) 1.5 μm Column; inner diameter 0.53 mm x length 60 m (manufactured by Agilent) Oven temperature: Increase temperature from 130°C to 220°C at a rate of 3°C / min, then increase to 300°C at a rate of 10°C / min. Split ratio; pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H255kPa, Air 45kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method; FID

[0108] The peak area of ​​the above compound (N1) is more preferably 5.0 ppm or more, even more preferably 50 ppm or more, and even more preferably 100 ppm or more, relative to the peak area of ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the above compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent Publication No. 6373536.

[0109] If the XDI composition contains compound (N2), it is preferable that the peak area of ​​compound (N2) in gas chromatography measurement under GC condition 2 below is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate. -GC condition 2- Column; HP-50+, inner diameter 0.25 mm x length 30 m x film thickness 0.25 μm (manufactured by Hewlett-Packard) Oven temperature: Increase from 50°C to 280°C at a rate of 10°C / min, hold for 6 minutes after reaching 280°C. Split ratio; pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas; He Carrier gas flow rate: 1.0 ml / min (constant flow control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method; SIM (Monitoring ions: m / z 180, 215) (Content ratio of xylylene diisocyanate (XDI))

[0110] The peak area of ​​the above compound (N2) is more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and even more preferably 0.6 ppm or more, relative to the peak area of ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and even more preferably 60 ppm or less, relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the above compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent Publication No. 6373536.

[0111] If the XDI composition contains compound (N3), it is preferable that the peak area of ​​compound (N3) in the gas chromatography measurement under the aforementioned GC condition 1 is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the above compound (N3) is more preferably 0.1 ppm or more, even more preferably 3.0 ppm or more, and even more preferably 5.0 ppm or more, relative to the peak area of ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, even more preferably 100 ppm or less, and even more preferably 75 ppm or less, relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the above compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent Publication No. 6373536.

[0112] The acidity of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm. The lower limit of the acidity of the XDI composition is not particularly limited, but the lower limit is, for example, 1 ppm. The acidity of the XDI composition can be measured in accordance with the method described in paragraph 0091 of International Publication No. 2021 / 256417. Furthermore, the XDI composition may contain a stabilizer.

[0113] In the process of obtaining a polymerizable composition, at least the polythiol composition and the polyisocyanate compound are mixed, but if necessary, the polythiol composition and the polyisocyanate compound may be mixed with other components. Furthermore, in the process of obtaining a polymerizable composition, at least the polythiol composition and the polyisocyanate compound may be mixed, and then other components may be added to the mixture. Other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion enhancers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and the like.

[0114] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0115] As an internal release agent, an acidic phosphate ester can be used. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more types.

[0116] Examples of resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, olefin compounds including (meth)acrylate compounds, etc. Here, (meth)acrylate compounds mean at least one of acrylate compounds and methacrylate compounds.

[0117] In the process of obtaining a polymerizable composition, the mixing of the above-mentioned components can be carried out according to conventional methods, and the method of mixing is not particularly limited.

[0118] [Method of manufacturing resin] The method for manufacturing the resin disclosed herein is: A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a resin by curing the above polymerizable composition, Includes. The resin manufacturing method of this disclosure may include other steps as necessary.

[0119] In the process of obtaining the resin, the polymerizable composition is cured to obtain the resin. The polymerizable composition described above can be cured by polymerizing the monomers in the polymerizable composition (specifically, the polythiol composition and the polyisocyanate compound; the same applies hereinafter). As a pretreatment for polymerization, the polymerizable composition may be subjected to treatments such as filtration and degassing. The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the above polymerizable composition are set appropriately, taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, and, if a mold described later is used, the properties of the mold. Examples of polymerization temperatures include -50°C to 150°C and 10°C to 150°C. Polymerization times can range from 1 hour to 200 hours, 1 hour to 80 hours, and so on.

[0120] The process of obtaining the resin may involve subjecting the polymer obtained by monomer polymerization to a treatment such as annealing. Typical annealing temperatures include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0121] [Method for manufacturing molded products] The method for manufacturing a molded article according to this disclosure is a method for manufacturing a molded article containing resin (hereinafter also referred to as "resin molded article"), A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing a molded article according to this disclosure may include other steps as necessary.

[0122] In the process of obtaining a molded article containing resin, the polymerizable composition is cured to obtain a molded article containing resin. Preferred conditions for curing the above polymerizable composition, that is, for polymerization of monomers in the above polymerizable composition, can be appropriately referred to in the section on "Method for Producing Resins".

[0123] One example of polymerization in this process is casting polymerization. In casting polymerization, the polymerizable composition is first injected between molds held together by gaskets or tape. Degassing and filtration may be performed as needed during this process. Next, the monomers in the polymerizable composition injected between the molding molds are polymerized, thereby curing the composition between the molding molds to obtain a cured product. Then, the cured product is removed from the molding molds to obtain a molded body containing resin. Polymerization of the above monomers may be carried out by heating the polymerizable composition. This heating can be performed, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, or the like.

[0124] [Manufacturing methods for optical materials, manufacturing methods for lenses] The method for manufacturing an optical material (e.g., a lens) according to this disclosure is a method for manufacturing an optical material (e.g., a lens) comprising a molded body containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing the optical material (e.g., a lens; the same applies hereinafter) described herein may include other steps as necessary.

[0125] The method for manufacturing optical materials of this disclosure is an application of the method for manufacturing molded articles of this disclosure. For example, in the method for manufacturing a molded article according to the present disclosure, by appropriately selecting the shape of the molding mold used in the aforementioned casting polymerization, a molded article applicable to optical materials (e.g., lenses) can be obtained.

[0126] Examples of optical materials include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses), light-emitting diodes (LEDs), and the like.

[0127] The method for manufacturing an optical material (e.g., a lens) according to this disclosure may include a step of forming a coating layer on one or both sides of a molded body containing a resin.

[0128] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers may be formed individually or in multiple layers. When coating layers are formed on both sides, similar coating layers may be formed on each side, or different coating layers may be formed on each side.

[0129] The components of the coating layer can be selected as appropriate depending on the purpose. Examples of components of the coating layer include resins (e.g., urethane resin, epoxy resin, polyester resin, melamine resin, polyvinyl acetal resin, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, and antistatic agents.

[0130] For eyeglass lenses and coating layers, you can refer to publicly available documents such as International Publication No. 2017 / 047745 as appropriate.

[0131] [Polymerizable composition] The polymerizable composition of this disclosure contains a polythiol composition obtained by the method for producing the polythiol composition of this disclosure described above, and a polyisocyanate compound.

[0132] The polymerizable composition of this disclosure may include a polyisocyanate composition containing the above-mentioned polyisocyanate compound. The polyisocyanate composition preferably contains xylylene diisocyanate (i.e., it is the aforementioned XDI composition). Preferred embodiments of the XDI composition (for example, including at least one selected from the group consisting of compound (N1), compound (N2), and compound (N3)) are as described in the section "<Step to obtain a polymerizable composition>" of the method for producing the polymerizable composition of the present disclosure described above.

[0133] The polymerizable composition of this disclosure can be produced by the method for producing the polymerizable composition of this disclosure described above. Preferred embodiments of the polymerizable composition of this disclosure can be appropriately referenced to the method for producing the polymerizable composition of this disclosure described above. However, the input mass [polythiol composition / polyisocyanate compound] shall be read as the content mass ratio [polythiol composition / polyisocyanate compound], and the total input mass of the polythiol composition and polyisocyanate compound shall be read as the total content mass of the polythiol composition and polyisocyanate compound.

[0134] [Resins, molded products, optical materials (e.g., lenses)] The resin of this disclosure is a cured product of the polymerizable composition of this disclosure described above. The molded article of this disclosure is a molded article comprising the resin of this disclosure as described above. The optical material (e.g., lens) of this disclosure is an optical material (e.g., lens) comprising the resin of this disclosure as described above.

[0135] The resins of the present disclosure, the molded articles of the present disclosure, and the optical materials (e.g., lenses) of the present disclosure can be manufactured by the methods described above for manufacturing the resins of the present disclosure, the molded articles of the present disclosure, and the optical materials (e.g., lenses), respectively. Preferred embodiments of the resins of the Disclosure, the molded articles of the Disclosure, and the optical materials (e.g., lenses) of the Disclosure can be referenced to preferred embodiments of the methods for manufacturing the resins of the Disclosure, the molded articles of the Disclosure, and the optical materials (e.g., lenses) of the Disclosure, respectively.

[0136] <Preferred performance of resin or molded article> The glass transition temperature Tg of the resin (or molded article) of this disclosure is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 85°C or higher, from the viewpoint of heat resistance. The above glass transition temperature Tg may be 130°C or lower, 120°C or lower, or 110°C or lower.

[0137] The refractive index (ne) of the resin (or molded article) of this disclosure is preferably 1.500 or higher, more preferably 1.540 or higher, and even more preferably 1.590 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the refractive index (ne) mentioned above, but a possible upper limit is 1.750.

[0138] The Abbe number of the resin (or molded article) of this disclosure is preferably 28 or higher, and more preferably 30 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the Abbe number mentioned above, but the upper limit is, for example, 50, and preferably 45.

[0139] The specific gravity d of the resin (or molded article) of this disclosure is preferably 1.10 or higher, and more preferably 1.20 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the specific gravity d mentioned above, but the upper limit is, for example, 1.50, and preferably 1.40.

[0140] A polythiol composition relating to an example of this disclosure, It contains as its main component a polythiol component A2 which is at least one selected from the group consisting of a polythiol compound represented by the following formula (6), a polythiol compound represented by the following formula (7), and a polythiol compound represented by the following formula (8), and The compound (XC) contains a compound in which at least one of the mercapto groups in polythiol component A2 is replaced with a group represented by the following formula (N1), In high-performance liquid chromatography measurements, the peak area of ​​compound (NA2) is 0.50 to 1.50 relative to the total peak area of ​​all compounds in the polythiol composition (100). It is a polythiol composition.

[0141] [ka]

[0142] In formula (N1), * represents the bonding position.

[0143] An example of a polythiol composition relating to this disclosure can be found by referring to the second embodiment described above. In HPLC measurement, the peak area of ​​compound (NA2) is preferably 0.04 to 1.50, more preferably 0.50 to 1.50, and even more preferably 0.50 to 1.00, relative to the total peak area of ​​100 of the compounds contained in the polythiol composition obtained by the purification step. When the peak area of ​​compound (NA2) is 0.04 or more (more preferably 0.50 or more) relative to the total peak area of ​​all compounds in the polythiol composition (100), the heat resistance (e.g., glass transition temperature (Tg)) of the resin produced using the polythiol composition is further improved.

[0144] An example of a polymerizable composition according to this disclosure contains the polythiol composition according to the above example and a polyisocyanate compound. A polymerizable composition according to one example of this disclosure may include the polythiol composition according to the above example and a polyisocyanate composition containing a polyisocyanate compound. The polyisocyanate composition preferably contains xylylene diisocyanate (i.e., it is the aforementioned XDI composition). Preferred embodiments of the XDI composition (for example, including at least one selected from the group consisting of compound (N1), compound (N2), and compound (N3)) are as described in the section "<Step to obtain a polymerizable composition>" of the method for producing the polymerizable composition of the present disclosure described above.

[0145] A polymerizable composition relating to an example of this disclosure can be manufactured by the method for manufacturing a polymerizable composition of this disclosure described above. Preferred embodiments of the polymerizable composition according to an example of this disclosure can be appropriately referenced to the method for producing the polymerizable composition of this disclosure described above. However, the input mass [polythiol composition / polyisocyanate compound] shall be read as the content mass ratio [polythiol composition / polyisocyanate compound], and the total input mass of the polythiol composition and polyisocyanate compound shall be read as the total content mass of the polythiol composition and polyisocyanate compound.

[0146] The resin relating to this example is a cured product of the polymerizable composition relating to this example described above. An example of a molded article relating to this disclosure is a molded article containing the resin relating to the example of this disclosure described above. An example of an optical material (e.g., a lens) relating to this disclosure is an optical material (e.g., a lens) containing the resin of this disclosure as described above. Preferred embodiments of the resin, molded article, and optical material relating to an example of the present disclosure are the same as the preferred embodiments of the resin, molded article, and optical material relating to the present disclosure described above. [Examples]

[0147] The following are examples of the embodiments of this disclosure, but this disclosure is not limited to the following embodiments. In the following, unless otherwise specified, "parts" refers to mass, and "room temperature" refers to 25°C.

[0148] [Comparative Example 1] <Preparation of crude polythiol composition (A1)> A toluene solution of a crude polythiol composition (A1) mainly composed of polythiol component A1 (i.e., the polythiol compound represented by formula (5) (4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane)) was obtained according to the manufacturing method in Example A-1 of International Publication No. 2014 / 027427. Details are provided below.

[0149] 125.4 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water were charged into the reactor. 99.8 parts by mass of a 32% by mass aqueous sodium hydroxide solution was added dropwise over 40 minutes at 12°C to 35°C. Then, 73.8 parts by mass of epichlorohydrin, the epihalohydrin compound represented by formula (1), was added dropwise over 4 hours at 29°C to 36°C, and the mixture was stirred for 30 minutes. As a result, NMR data confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol, the polyalcohol compound represented by formula (2). To the liquid in which the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed, 332.0 parts by mass of 36% by mass hydrochloric acid was added, followed by 183.8 parts by mass of 99.9% purity thiourea. The mixture was stirred under reflux at 110°C for 3 hours to carry out the thiuronium chloride reaction, and a reaction solution containing isothiouronium salt was obtained. After cooling the resulting reaction solution to 45°C, 355.0 parts by mass of toluene were added, and the mixture was cooled to 30°C. 244.6 parts by mass of a 25% by mass aqueous ammonia solution were then added over 44 minutes at 30°C to 40°C, and the hydrolysis reaction was carried out by stirring at 54°C to 62°C for 3 hours to obtain a toluene solution of a crude polythiol composition (A1) mainly composed of polythiol component A1.

[0150] <Purification of crude polythiol composition (A1)> The crude polythiol composition (A1) obtained above was subjected to acid washing with 147.8 parts by mass of 36% by mass hydrochloric acid at 35°C to 40°C for 1 hour using a toluene solution. The toluene solution after acid washing was subjected to a single washing cycle using 147.8 parts by mass of degassed water at 35°C to 40°C for 10 minutes. After one wash with degassed water, the toluene solution was washed for 10 minutes with 147.8 parts by mass of 0.1% by mass ammonia water. The toluene solution, after being washed with ammonia water, was washed twice with 147.8 parts by mass of degassed water at 35°C to 40°C for 10 minutes. Through the above procedure, the crude polythiol composition (A1) was purified, and this purification yielded a toluene solution of the purified crude polythiol composition (A1).

[0151] To the toluene solution of the polythiol composition (A1) obtained by the above purification, toluene and trace amounts of water were removed by heating under reduced pressure, and then 200.0 parts by mass of the polythiol composition (A1) was obtained by vacuum filtration using a 3.0 μm PTFE type membrane filter.

[0152] <Evaluation of Polythiol Composition (A1)> The following evaluation was performed on the polythiol composition (A1) obtained above. The results are shown in Table 1.

[0153] (External appearance check) The appearance of the polythiol composition (A1) was observed visually.

[0154] (Yellowness Index (YI)) The polythiol composition (A1) was packed into a 10 mm thick glass cell, and the degree of yellowness was determined by the transmittance. Transmittance was measured using a Konica Minolta CM-5 spectrophotometer.

[0155] (Thiol value) The thiol value [mmol / g] of polythiol composition (A1) was determined by redox titration using a 0.05 M iodine aqueous solution.

[0156] (Refractive index) The refractive index of the polythiol composition (A1) was measured using a liquid refractometer RA600 manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0157] (HPLC measurement) The polythiol composition (A1) obtained above was subjected to high-performance liquid chromatography (HPLC) measurement under the following HPLC measurement conditions. In this HPLC measurement, The main component is polythiol component A1, Compound (NA1) obtained by replacing at least one of the mercapto groups in polythiol component A1 with a group represented by the above formula (N1), The content of each compound (specifically, the area percentage (area%) relative to the total peak area of ​​the compounds contained in the polythiol composition (A1)) was determined. Compound (NA1) has a retention time of 4.3 to 4.8 minutes in this measurement.

[0158] -HPLC measurement conditions- As the column, we used Mightysil RP-18 GP (registered trademark) manufactured by Kanto Chemical Co., Ltd. (particle size S: 5 μm, column shape: Φ6 mm × 150 mm, product number: 25477-9). As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used. As the measurement solution, a mixed solution of 160 mg of polythiol composition and 10 mL of acetonitrile was used. As a detector, an ultraviolet detector with a measurement wavelength of 230 nm is used. The column temperature is set to 40°C. Set the flow rate to 1.0 mL / min. Condition: The injection volume is 2 μL.

[0159] <Preparation of polymerizable compositions> In a flask equipped with a stirring bar, The polymerization catalyst is dibutyltin dichloride (150 ppm by mass relative to the total amount of the polyisocyanate compound and polythiol composition (A)), Zelec-UN (manufactured by Stepan Co.; acidic phosphate ester) (1000 ppm by mass based on the total amount of the polyisocyanate compound and the polythiol composition (A)), and Tinuvin 329 (manufactured by BASF Japan Ltd., 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol), an ultraviolet absorber (0.05% by mass based on the total amount of the polyisocyanate compound and the polythiol composition (A)), and m-xylene diisocyanate (XDI), a polyisocyanate compound (52 parts by mass), and the above polythiol composition (A1) (48 parts by mass) were added and stirred and mixed at 20°C for 5 minutes to obtain a polymerizable composition.

[0160] <Viscosity change of the polymerizable composition> The viscosity (mPa·s) of the obtained polymerizable composition at 20°C was measured using a Brookfield B-type viscometer. The viscosity measurement was carried out immediately after 5 minutes of stirring and mixing (hereinafter referred to as "0 h"), after standing at 20°C for 1 hour after 5 minutes of stirring and mixing (hereinafter referred to as "1 h"), after standing at 20°C for 3 hours after 5 minutes of stirring and mixing (hereinafter referred to as "3 h"), after standing at 20°C for 5 hours after 5 minutes of stirring and mixing (hereinafter referred to as "5 h"), and after standing at 20°C for 7 hours after 5 minutes of stirring and mixing (hereinafter referred to as "7 h") at each of these timings, and thereby, the temporal change in viscosity was observed. The smaller the change in viscosity, the better the pot life of the polymerizable composition.

[0161] <Preparation and viscosity of the non-catalyst polymerizable composition> In a flask equipped with a stirrer, m-xylene diisocyanate (XDI), a polyisocyanate compound (52 parts by mass), and the above polythiol composition (A1) (48 parts by mass), The mixture was added and stirred at 30°C for 8 hours to obtain a catalyst-free polymerizable composition. The viscosity (mPa·s) of the obtained catalyst-free polymerizable composition at 30°C was measured using a Brookfield B-type viscometer. The results are shown in Table 1.

[0162] <Manufacturing of resin molded products> 52 parts by mass of m-xylylene diisocyanate, As a curing catalyst, 0.015 parts by mass of dibutyltin dichloride, Zerec UN (product of Stepan Corporation; acidic phosphate ester) 0.10 parts by mass, and Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.; ultraviolet absorber) 0.05 parts by mass These were mixed and dissolved at 20°C. 48 parts by mass of polythiol composition (A) were added and mixed to obtain a polymerizable composition for resin molded articles as a homogeneous liquid. The obtained polymerizable composition was degassed at 600 Pa for 1 hour, and then filtered through a 1 μm Teflon® filter. The filtered polymerizable composition was poured between a pair of glass molds fixed with tape, and then this pair of glass molds was 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 polymerizable composition were polymerized, and a resin molded article containing thiourethane resin (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. Then, the resin molded bodies were removed from the pair of glass molds to obtain flat resin molded bodies with a thickness of 9 mm. The resulting resin molded body was annealed at 120°C for 1 hour.

[0163] <Evaluation of resin molded products> The following evaluations were performed on the resin molded articles after the annealing described above. The results are shown in Table 1.

[0164] (External appearance check) The appearance of the resin molded product was observed visually.

[0165] (Yellow Index (YI), L*, a*, and b*) The yellowness (YI), L*, a*, and b* of the resin molded product were measured using a Konica Minolta CM-5 spectrophotometer.

[0166] (Refractive index (ne) and Abbe number (νe)) Using a Shimadzu KPR-30 Pulfrich refractometer, the refractive indices (ne, nF', nC') of the molded material were measured at 20°C at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line). Based on these measurement results, the refractive index (ne) and Abbe number (νe) of the molded material were determined.

[0167] (Heat resistance) Using a Shimadzu TMA-60 thermomechanical analyzer, the glass transition temperature (Tg) of the resin molded body was measured using the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10℃ / min) and used as an indicator of heat resistance.

[0168] (specific gravity d) The specific gravity d of the molded body was measured by the Archimedes method at 20°C.

[0169] [Example 1] In the "Purification of Crude Polythiol Composition (A1)," the procedure was the same as in Comparative Example 1, except that the following purification step with solvent X was added before acid washing with hydrochloric acid. The results are shown in Table 1.

[0170] -Purification with solvent X- The toluene solution of the crude polythiol composition (A1) obtained in "Preparation of Crude Polythiol Composition (A1)" was washed three times with 147.8 parts by mass of ethylene glycol as solvent X at 35-40°C for 15 minutes each.

[0171] [Example 2] The polythiol composition (A1) (50 parts by mass) obtained in Example 1 and the polythiol composition (A1) (50 parts by mass) obtained in Comparative Example 1 were blended to obtain the polythiol composition (A1) (100 parts by mass) in Example 2. The same operations as in Comparative Example 1 (specifically, the operations after "Evaluation of Polythiol Composition (A1)") were performed, except that the polythiol composition (A1) in Comparative Example 1 was changed to the polythiol composition (A1) in Example 2. The results are shown in Table 1.

[0172]

Table 1

[0173] As shown in Table 1, in the polythiol compositions (A1) of Examples 1 and 2 obtained by purifying the crude polythiol composition (A1) with solvent X, compared with the polythiol composition (A1) of Comparative Example 1 obtained without purifying the crude polythiol composition (A1) with solvent X, the effect of suppressing the viscosity change of the polymerizable composition containing the polythiol composition (A1) (that is, the effect of improving the pot life) was confirmed. It was confirmed that in the polythiol compositions (A1) of Examples 1 and 2, the content of the compound (NA1) which is an impurity was reduced compared with the polythiol composition (A1) of Comparative Example 1. From these results, in the polymerizable composition of Comparative Example 1, it is considered that the compound (NA1) which is an impurity functions as a polymerization catalyst, promoting the polymerization of the polythiol composition (A1) and the polyisocyanate compound, and this polymerization causes an increase in viscosity. In contrast, in Examples 1 and 2, the content of the compound (NA1) in the polythiol composition (A1) was reduced, suppressing the polymerization of the polythiol composition (A1) and the polyisocyanate compound, and as a result, it is considered that the increase in viscosity was reduced.

[0174] Furthermore, based on the evaluation results for each of the polythiol composition (A1) and the resin molded articles, it was confirmed that in Examples 1 and 2, the performance of both the polythiol composition (A1) and the resin molded articles was maintained at a similar level compared to Comparative Example 1.

[0175] As described above, in Examples 1 and 2, it was confirmed that the pot life of the polymerizable composition was improved while maintaining the same level of performance for both the polythiol composition (A1) and the resin molded article compared to Comparative Example 1.

[0176] [Example 1X] In Example 1X, the same procedure as in Example 1 was performed except for the following changes to the manufacturing process of the molded body, and the same results as in Example 1 (Table 1) were obtained.

[0177] -Changes from Example 1- In Example 1, m-xylylene diisocyanate (XDI) (52 parts by mass) was used in the production of the molded article. However, in Example 1X, this XDI (52 parts by mass) was replaced with XDI composition X1 (an amount containing 52 parts by mass), which is the aforementioned XDI composition. XDI composition X1 was prepared by adding trace amounts of compound (N1), compound (N2), and compound (N3) to the main component XDI, and then mixing them together. In XDI composition X1, gas chromatography measurements were performed using GC condition 1 and GC condition 2 as described above, and the results were as follows: The peak area of ​​compound (N1) is 0.20 ppm or more (specifically 600 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N2) is 0.05 ppm or more (specifically 18 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) was 0.10 ppm or more (specifically 100 ppm) relative to the peak area of ​​xylylene diisocyanate.

[0178] [Comparative Example 101] <Preparation of crude polythiol composition (A2)> A toluene solution of a crude polythiol composition (A2) mainly composed of polythiol component A2 was obtained according to the manufacturing method in Example C-1 of International Publication No. 2014 / 027428. Details are provided below.

[0179] Here, polythiol component A2 is, A polythiol compound represented by formula (6) (i.e., 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), A polythiol compound represented by formula (7) (i.e., 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), and It is at least one selected from the group consisting of polythiol compounds represented by formula (8) (i.e., 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane).

[0180] 89.25 parts by mass of 2-mercaptoethanol, 44.61 parts by mass of degassed water, and 0.58 parts by mass of a 30.7% by mass sodium hydroxide aqueous solution were added to the reactor and cooled to 10°C. Then, 107.68 parts by mass of epichlorohydrin, the epihalohydrin compound represented by formula (1), were added dropwise over 3.9 hours at 9°C to 11°C, and the mixture was stirred for 60 minutes to allow it to mature. As a result, the formation of the compound represented by formula (3) was confirmed from NMR data. Next, 262.09 parts by mass of a 17.3% by mass aqueous sodium sulfide solution were added dropwise at 28°C to 30°C over 1.0 hour, followed by stirring for 3.0 hours for maturation. As a result, the formation of the polyalcohol compound represented by formula (4) was confirmed from the NMR data. Next, 484.6 parts by mass of 36% by mass hydrochloric acid was added, followed by 214.0 parts by mass of 99.9% pure thiourea. The mixture was stirred under reflux at 110°C for 3 hours to carry out the thiuronium chloride reaction, obtaining a reaction solution containing isothiuronium salt. After cooling the resulting reaction solution to 45°C, 373.0 parts by mass of toluene were added, and the mixture was cooled to 32°C. 354.2 parts by mass of a 24.6% by mass aqueous ammonia solution were added over 25 minutes at 30°C to 38°C, and then the temperature was raised to 60°C. The mixture was stirred at 60°C for 1 hour to carry out the hydrolysis reaction, yielding a toluene solution of a crude polythiol composition (A2) mainly composed of polythiol component A2.

[0181] <Purification of crude polythiol composition (A2)> The crude polythiol composition (A2) obtained above was subjected to acid washing with 101.1 parts by mass of 4% hydrochloric acid at 35°C to 40°C for 15 minutes, and then to acid washing with 101.1 parts by mass of 35% hydrochloric acid at 35°C to 40°C for 30 minutes. The toluene solution, after acid washing with 35% hydrochloric acid, was subjected to five washes at 35°C to 40°C for 30 minutes each, using 101.1 parts by mass of degassed water. Through the above procedure, the crude polythiol composition (A2) was purified, and this purification yielded a toluene solution of the purified crude polythiol composition (A2).

[0182] To the toluene solution of the polythiol composition (A2) obtained by the above purification, toluene and trace amounts of water were removed by heating under reduced pressure, and then 200.0 parts by mass of the polythiol composition (A2) was obtained by vacuum filtration using a 3.0 μm PTFE type membrane filter.

[0183] <Evaluation of Polythiol Composition (A2)> The polythiol composition (A2) obtained above was evaluated in the same manner as the evaluation performed on polythiol composition (A1) in Comparative Example 1. The results are shown in Table 2.

[0184] In the HPLC measurement in Comparative Example 101, The main component is polythiol component A2, Compound (NA2) obtained by replacing at least one of the mercapto groups in polythiol component A2 with a group represented by the above formula (N1), The content of each compound (specifically, the area percentage (area%) relative to the total peak area of ​​the compounds contained in the polythiol composition (A2)) was determined. Compound (NA2) is a compound whose retention time in this HPLC measurement is between 6.5 and 8.0 minutes.

[0185] <Preparation of polymerizable compositions and viscosity changes> The same procedure as in Comparative Example 1 was followed, except that polythiol composition (A1) was changed to polythiol composition (A2). The results are shown in Table 2.

[0186] <Preparation and viscosity of catalyst-free polymerizable compositions> The same procedure as in Comparative Example 1 was followed, except that polythiol composition (A1) was changed to polythiol composition (A2). The results are shown in Table 2.

[0187] <Manufacturing and evaluation of resin molded products> The same procedure as in Comparative Example 1 was followed, except that polythiol composition (A1) was changed to polythiol composition (A2). The results are shown in Table 2.

[0188] [Example 101] In the "Purification of Crude Polythiol Composition (A2)," the procedure was the same as in Comparative Example 101, except that the following alcohol purification step was added before acid washing with 4% by mass hydrochloric acid. The results are shown in Table 2.

[0189] -Purification with solvent X- The crude polythiol composition (A2) obtained in "Preparation of Crude Polythiol Composition (A2)" was subjected to a toluene solution and washed three times with a mixed solvent of 75.8 parts by mass of ethylene glycol and 24.3 parts by mass of methanol at 35°C to 40°C for 15 minutes each time.

[0190] [Example 102] The polythiol composition (A2) (50 parts by mass) obtained in Example 101 and the polythiol composition (A2) (50 parts by mass) obtained in Comparative Example 101 were blended to obtain the polythiol composition (A2) (100 parts by mass) in Example 102. The procedure was the same as in Comparative Example 101, except that the polythiol composition (A2) in Comparative Example 101 was changed to the polythiol composition (A1) (blended product) in Example 102 (in detail, the procedure from "Evaluation of Polythiol Composition (A2)" onwards). The results are shown in Table 2.

[0191] [Example 103] The polythiol composition (A2) (70 parts by mass) obtained in Example 101 and the polythiol composition (A2) (30 parts by mass) obtained in Comparative Example 101 were blended to obtain the polythiol composition (A2) (100 parts by mass) in Example 103. The procedure was the same as in Comparative Example 101, except that the polythiol composition (A2) in Comparative Example 101 was changed to the polythiol composition (A1) (blended product) in Example 103 (in detail, the procedure from "Evaluation of Polythiol Composition (A2)" onwards). The results are shown in Table 2.

[0192] [Table 2]

[0193] As shown in Table 2, the polythiol compositions (A2) of Examples 101 to 103, obtained by purifying the crude polythiol composition (A2) with solvent X, showed an effect of suppressing viscosity changes in polymerizable compositions containing the polythiol composition (A2) (i.e., an effect of improving pot life) compared with the polythiol composition (A2) of Comparative Example 1, which was obtained without purifying the crude polythiol composition (A2) with solvent X. In the polythiol compositions (A2) of Examples 101 to 103, it was confirmed that the content of the impurity compound (NA2) was reduced compared to the polythiol composition (A2) of Comparative Example 101. These results suggest that in the polymerizable composition of Comparative Example 101, the impurity compound (NA2) functions as a polymerization catalyst, promoting polymerization between the polythiol composition (A2) and the polyisocyanate compound, and this polymerization causes an increase in viscosity. Compared to Comparative Example 101, in Examples 101 to 103, the content of compound (NA2) in the polythiol composition (A2) was reduced, which suppressed polymerization between the polythiol composition (A2) and the polyisocyanate compound, resulting in a reduction in viscosity increase.

[0194] Furthermore, from the evaluation results of each polythiol composition (A2) and each resin molded article, it was confirmed that in Examples 101 to 103, the deterioration of the performance of the polythiol composition (A2) and the performance of the resin molded article was suppressed compared to Comparative Example 101 (i.e., the pot life of the polymerizable composition was improved without causing deterioration of the performance of the polythiol composition (A2) and the performance of the resin molded article).

[0195] Among Examples 101 to 103, in HPLC measurements, the resin molded articles in Examples 102 and 103, where the peak area of ​​compound (NA2) was 0.50 to 1.50 relative to the total peak area of ​​all compounds in the polythiol composition (A2) (100), maintained a higher Tg and demonstrated superior heat resistance compared to the resin molded article in Example 101, where the peak area of ​​compound (NA2) was less than 0.50 relative to the total peak area of ​​all compounds in the polythiol composition (A2) (100).

[0196] [Example 101X] In Example 101X, the same procedure as in Example 101 was followed, except that the manufacturing of the molded body was modified as follows. The same results as in Example 101 (Table 2) were obtained.

[0197] -Changes from Example 101- In Example 101, m-xylylene diisocyanate (XDI) (52 parts by mass) was used in the production of the molded article. However, in Example 101X, this XDI (52 parts by mass) was replaced with XDI composition X1 (an amount containing 52 parts by mass), which is the aforementioned XDI composition. XDI composition X1 was prepared by adding trace amounts of compound (N1), compound (N2), and compound (N3) to the main component XDI, and then mixing them together. In XDI composition X1, gas chromatography measurements were performed using GC condition 1 and GC condition 2 as described above, and the results were as follows: The peak area of ​​compound (N1) is 0.20 ppm or more (specifically 600 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N2) is 0.05 ppm or more (specifically 18 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) was 0.10 ppm or more (specifically 100 ppm) relative to the peak area of ​​xylylene diisocyanate.

[0198] The disclosure of Japanese Patent Application No. 2022-153094, filed on 26 September 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. It contains as its main component a polythiol component A2 which is at least one selected from the group consisting of a polythiol compound represented by the following formula (6), a polythiol compound represented by the following formula (7), and a polythiol compound represented by the following formula (8), and The compound (NA2) contains a compound in which at least one of the mercapto groups in the polythiol component A2 is replaced with a group represented by the following formula (N1), In high-performance liquid chromatography measurements, the peak area of ​​the compound (NA2) is 0.50 to 1.50 relative to the total peak area of ​​100 of the compounds contained in the polythiol composition. Polythiol composition. 【Chemistry 1】 [In formula (N1), * indicates the bonding position.]

2. The polythiol composition according to claim 1, Polyisocyanate compounds and A polymerizable composition containing the following:

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

4. A resin which is a cured product of the polymerizable composition according to claim 2 or claim 3.

5. A molded article comprising the resin described in claim 4.

6. An optical material comprising the resin described in claim 4.

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