Manufacturing method and application of polythiol composition

Abstract

A method for producing a polythiol composition, said method comprising: a preparation step for preparing a crude polythiol composition, which is a polythiol composition before purification; and a purification step for obtaining a polythiol composition by purifying the crude polythiol composition with a solvent X containing an alkylene glycol.

Description

Technical Field

[0001] This disclosure relates to methods for manufacturing polythiol compositions and their applications. Background Art

[0002] Compared to inorganic lenses, plastic lenses, which contain resin, are lighter and less prone to breakage, and can be stained. As a result, they have become increasingly popular in recent years for applications such as eyeglass lenses and camera lenses.

[0003] Thioamino ester resin is known as one of the resins used for lenses.

[0004] Patent documents 1 and 2 disclose a method for manufacturing a polythiol compound, which is one of the raw materials for thiourethane resin, and a polymerizable composition for optical materials containing the polythiol compound (e.g., a polymerizable composition for lenses).

[0005] Furthermore, Patent Documents 3 and 4 disclose polythiol compositions containing polythiol compounds and with reduced nitrogen-containing compound content, which are capable of manufacturing lenses of excellent quality. Patent Documents 3 and 4 also disclose polymeric compositions for optical materials (e.g., polymeric compositions for lenses) comprising polythiol compositions.

[0006] Patent Document 1: International Publication No. 2014 / 027427

[0007] Patent Document 2: International Publication No. 2014 / 027428

[0008] Patent Document 3: International Publication No. 2016 / 010065

[0009] Patent Document 4: International Publication No. 2020 / 41183 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] However, there is sometimes a need to further improve the pot life of polymerizable compositions used to manufacture thiourethane resins and containing polythiols.

[0012] One aspect of this disclosure is to provide a method for manufacturing a polythiol composition and its application, said method being capable of producing a polythiol composition that can improve the pot life of a polymerizable composition comprising the polythiol composition.

[0013] Means for solving problems

[0014] The methods for solving the above problems include the following.

[0015] <1> A method for manufacturing a polythiol composition, comprising the following steps:

[0016] The preparation process for the crude polythiol composition, i.e., the preparation step for the polythiol composition before purification; and

[0017] The purification process involves purifying the aforementioned crude polythiol composition using a solvent X containing alkylene glycols to obtain the polythiol composition.

[0018] <2> like <1> The method for producing the polythiol composition satisfies at least one of the following conditions:

[0019] The aforementioned crude polythiol composition comprises a polythiol component A1, which is a polythiol compound represented by the following formula (5), and a compound (NA1) formed by replacing at least one of the thiol groups in the aforementioned polythiol component A1 with a group represented by the following formula (N1);

[0020] as well as,

[0021] The aforementioned crude polythiol composition comprises at least one polythiol component A2 selected from the group consisting of a polythiol compound represented by formula (6), a polythiol compound represented by formula (7), and a polythiol compound represented by formula (8), and a compound (NA2) formed by replacing at least one of the thiol groups in the aforementioned polythiol component A2 with a group represented by formula (N1).

[0022] [Chemical Formula 1]

[0023]

[0024] In equation (N1), * represents the bonding position.

[0025] <3> like <2> The method for manufacturing the aforementioned polythiol composition, wherein the crude polythiol composition comprises the aforementioned polythiol component A1 and the aforementioned compound (NA1),

[0026] The aforementioned preparation process includes the following steps:

[0027] The steps of reacting 2-mercaptoethanol with the epihalohydrin compound represented by formula (1) to obtain the polyol compound represented by formula (2);

[0028] The step of reacting the polyol compound represented by formula (2) with thiourea under acidic conditions to obtain a reaction solution containing isothiourea onium salt; and

[0029] The step of adding an alkaline compound to a reaction solution containing the aforementioned isothiourea onion salt to hydrolyze the aforementioned isothiourea onion salt to obtain the aforementioned crude polythiol composition.

[0030] [Chemical Formula 2]

[0031]

[0032] In equation (1), X represents a halogen atom.

[0033] <4> like <2> The method for manufacturing the aforementioned polythiol composition, wherein the crude polythiol composition comprises the aforementioned polythiol component A2 and the aforementioned compound (NA2),

[0034] The aforementioned preparation process includes the following steps:

[0035] The steps of reacting 2-mercaptoethanol with the epihalohydrin compound represented by formula (1) to obtain the compound represented by formula (3);

[0036] The step of reacting the compound represented by formula (3) above with sodium sulfide to obtain the polyol compound represented by formula (4) below;

[0037] The step of reacting the polyol compound represented by formula (4) with thiourea under acidic conditions to obtain a reaction solution containing isothiourea onium salt; and

[0038] The step of adding an alkaline compound to a reaction solution containing the aforementioned isothiourea onion salt to hydrolyze the aforementioned isothiourea onion salt to obtain the aforementioned crude polythiol composition.

[0039] [Chemical Formula 3]

[0040]

[0041] In equation (1), X represents a halogen atom.

[0042] <5> like <1> ~ <4> The method for producing the polythiol composition according to any one of the following, wherein the solvent X comprises at least one selected from the group consisting of ethylene glycol and propylene glycol.

[0043] <6> like <1> ~ <5> The method for producing the polythiol composition according to any one of the above methods, wherein the aforementioned preparation step prepares a toluene solution of the aforementioned crude polythiol composition,

[0044] The aforementioned purification process involves mixing the aforementioned toluene solution with the aforementioned solvent X, thereby using the aforementioned solvent X to purify the aforementioned crude polythiol composition in the aforementioned toluene solution.

[0045] <7> like <1> ~ <6> The method for producing the polythiol composition according to any one of the above methods, wherein the aforementioned purification step includes the following steps:

[0046] The step of purifying the aforementioned crude polythiol composition using the aforementioned solvent X to obtain the polythiol composition; and

[0047] The aforementioned polythiol composition is subjected to an acid cleaning step.

[0048] <8> A method for manufacturing a polymeric composition, comprising the following steps:

[0049] use <1> ~ <7> The method for manufacturing the polythiol composition according to any one of the above methods comprises the steps of manufacturing the polythiol composition; and

[0050] The process of obtaining a polymerizable composition containing the aforementioned polythiol composition and the aforementioned polyisocyanate compound by mixing the aforementioned polythiol composition with a polyisocyanate compound.

[0051] <9> like <8> The method for manufacturing the polymerizable composition, wherein the step of obtaining the polymerizable composition is a step of mixing the aforementioned polythiol composition with a polyisocyanate composition containing the aforementioned polyisocyanate compound to obtain a polymerizable composition containing the aforementioned polythiol composition and the aforementioned polyisocyanate composition.

[0052] The aforementioned polyisocyanate composition comprises:

[0053] phenylene diisocyanate, and

[0054] Choose at least one compound from the group consisting of the following compounds (N1), (N2), and (N3);

[0055] When the aforementioned polyisocyanate composition contains the aforementioned compound (N1), the peak area of ​​the aforementioned compound (N1) in high performance liquid chromatography is 0.20 ppm or more relative to the peak area 100 of phenylene diisocyanate.

[0056] When the aforementioned polyisocyanate composition contains the aforementioned compound (N2), the peak area of ​​the aforementioned compound (N2) in high performance liquid chromatography is 0.05 ppm or more relative to the peak area 100 of phenylene diisocyanate.

[0057] When the aforementioned polyisocyanate composition contains the aforementioned compound (N3), the peak area of ​​the aforementioned compound (N3) in high performance liquid chromatography is 0.10 ppm or more relative to the peak area 100 of phenylene diisocyanate.

[0058] [Chemical Formula 4]

[0059]

[0060] <10> A method for manufacturing resin, comprising the following steps:

[0061] use <8> The method for manufacturing the polymeric composition includes the steps involved in manufacturing the polymeric composition; and

[0062] The process of obtaining a resin by curing the aforementioned polymeric composition.

[0063] <11> A polythiol composition comprising a polythiol component A2 as a main component, wherein the polythiol component A2 is at least one selected from the group consisting of a polythiol compound represented by formula (6), a polythiol compound represented by formula (7), and a polythiol compound represented by formula (8), and,

[0064] The polythiol composition contains a compound (NA2) formed by replacing at least one of the thiol groups in the aforementioned polythiol component A2 with a group represented by the following formula (N1).

[0065] In high performance liquid chromatography determination, the peak area of ​​the aforementioned compound (NA2) is 0.50 to 1.50 relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0066] [Chemical Formula 5]

[0067]

[0068] In equation (N1), * represents the bonding position.

[0069] <12> Polymerizable composition comprising:

[0070] <11> The polythiol composition, and

[0071] Polyisocyanate compounds.

[0072] <13> like <12> The polymerizable composition comprises a polyisocyanate composition, wherein the polyisocyanate composition comprises the aforementioned polyisocyanate compound.

[0073] The aforementioned polyisocyanate composition comprises:

[0074] phenylene diisocyanate, and

[0075] Choose at least one compound from the group consisting of the following compounds (N1), (N2), and (N3);

[0076] When the aforementioned polyisocyanate composition contains the aforementioned compound (N1), the peak area of ​​the aforementioned compound (N1) in high performance liquid chromatography is 0.20 ppm or more relative to the peak area 100 of phenylene diisocyanate.

[0077] When the aforementioned polyisocyanate composition contains the aforementioned compound (N2), the peak area of ​​the aforementioned compound (N2) in high performance liquid chromatography is 0.05 ppm or more relative to the peak area 100 of phenylene diisocyanate.

[0078] When the aforementioned polyisocyanate composition contains the aforementioned compound (N3), the peak area of ​​the aforementioned compound (N3) in high performance liquid chromatography is 0.10 ppm or more relative to the peak area 100 of phenylene diisocyanate.

[0079] [Chemical Formula 6]

[0080]

[0081] Invention Effects

[0082] According to one aspect of this disclosure, a method for manufacturing a polythiol composition and its application are provided, the method for manufacturing a polythiol composition capable of improving the pot life of a polymerizable composition. Detailed Implementation

[0083] In this public document, the numerical range indicated by “~” refers to the range that includes the values ​​recorded before and after “~” as the lower and upper limits.

[0084] In this disclosure, the term "process" includes not only individual processes, but also processes that can be clearly distinguished from other processes, as long as the desired purpose of the process can be achieved.

[0085] In this disclosure, the amount of each component contained in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified.

[0086] In the numerical ranges described in this disclosure, the upper or lower limit of one numerical range can be replaced with the upper or lower limit of another numerical range described in other stages. Furthermore, the upper or lower limit of a numerical range described in this disclosure can be replaced with the values ​​shown in the embodiments.

[0087] There may be overlaps among the various embodiments described in this disclosure. That is, a feature in one embodiment may be included in other embodiments.

[0088] [Method for manufacturing polythiol compositions]

[0089] The method for manufacturing the polythiol composition disclosed herein includes the following steps:

[0090] The preparation process for the crude polythiol composition, i.e., the preparation step for the polythiol composition before purification; and

[0091] The purification process involves purifying the crude polythiol composition using a solvent X containing alkylene glycols to obtain the polythiol composition.

[0092] The method for manufacturing the polythiol composition disclosed herein may include other steps as needed.

[0093] According to the method for manufacturing the polythiol composition disclosed herein, a polythiol composition capable of improving the pot life of a polymerizable composition containing the polythiol composition can be manufactured.

[0094] The reasons for achieving the above effects are speculated as follows.

[0095] In polymerizable compositions containing polythiol compositions, if undesirable 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 shelf life of the polymerizable composition may decrease.

[0096] It is believed that unwanted polymerization of polymerizable monomers is caused by impurities (e.g., compounds (NA1) or (NA2) described later) sometimes unintentionally contained in the polymerizable composition acting as polymerization catalysts.

[0097] Regarding this issue, the method for manufacturing the polythiol composition disclosed herein includes a purification step of purifying the unpurified polythiol composition, i.e., the crude polythiol composition, using a solvent X containing an alkylene glycol (hereinafter also referred to as "solvent X-based purification" or simply "purification") to obtain the polythiol composition.

[0098] Therefore, it is believed that by purification based on solvent X, at least a portion of the impurities can be removed 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 (i.e., an increase in the shelf life of the polymerizable composition) can be suppressed in the obtained polymerizable composition containing the polythiol composition.

[0099] Purification in the method for manufacturing the polythiol composition according to this disclosure can suppress the deterioration of the properties of the polythiol composition, the polymerizable composition obtained using the polythiol composition, and the resin, and can achieve the above-mentioned effect (increased pot life of the polymerizable composition).

[0100] That is, it is believed that purification based on solvent X can selectively remove impurities while reducing the impact on polythiol compounds contained in the polythiol composition.

[0101] The following describes the steps that may be included in the method for manufacturing the polythiol composition of this disclosure.

[0102] <Preparation Process>

[0103] The method for manufacturing the polythiol composition disclosed herein includes a preparation step for preparing a crude polythiol composition before purification.

[0104] The preparation process can be either a simple process of preparing a pre-made crude polythiol composition or a process of manufacturing the crude polythiol composition.

[0105] (Crude polythiol composition, polythiol composition)

[0106] In this disclosure, the crude polythiol composition is the polythiol composition before purification.

[0107] In this disclosure, a polythiol composition (including crude polythiol compositions, hereinafter the same) refers to a composition containing at least one polythiol compound.

[0108] As a polythiol compound, it is acceptable as long as it contains two or more thiol groups (also known as mercapto groups), without any other special restrictions.

[0109] In polythiol compositions, components other than polythiol compounds may be present as impurities.

[0110] The polythiol composition preferably contains at least one polythiol compound as the main component.

[0111] Here, the phrase "a polythiol composition contains at least one polythiol compound as a main component" means that the total content of at least one polythiol compound is more than 50% relative to the total amount of the polythiol composition.

[0112] 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.

[0113] Similarly, in this disclosure, the statement that a composition “contains” a certain ingredient (hereinafter referred to as “Ingredient X”) “as a principal ingredient” means that the content of Ingredient X (or the total content of the two or more compounds if Ingredient X is formed from two or more compounds) is 50% or more relative to the total amount of the composition.

[0114] 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, relative to the total amount of the composition.

[0115] In the above description of the phrase "contains... as a main component", the "%" refers to the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) determined by high performance liquid chromatography to the total area of ​​all peaks of the composition (e.g., a polythiol composition).

[0116] Hereinafter, the polythiol compounds contained in the polythiol composition will also be referred to as "polythiol components".

[0117] The polythiol composition preferably comprises at least one selected from the group consisting of (hereinafter also referred to as "polythiol component A"), said group consisting of

[0118] 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,

[0119] 4,8-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0120] 4,7-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0121] 5,7-Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0122] Pentaerythritol tetra(2-mercaptoacetate),

[0123] Pentaerythritol tetra(3-mercaptopropionate),

[0124] 2,5-Dimercaptomethyl-1,4-dithionecyclohexane,

[0125] bis(2-mercaptoethyl) sulfide, and

[0126] Composed of diethylene glycol bis(3-mercaptopropionate).

[0127] The polythiol composition more preferably contains polythiol component A as the main component.

[0128] In this case, the polythiol composition may contain at least one of the following components other than polythiol component A (e.g., other polythiol compounds, components other than polythiol compounds, etc.).

[0129] Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiacyclohexane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiacyclohexane, 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane.

[0130] More specific examples of polythiol compositions used as raw materials for thiourethane resins include, for instance:

[0131] The method of containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A1") as the main component;

[0132] The method of including at least one of the following (hereinafter also referred to as "polythiol component A2") 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 as the main component;

[0133] It contains pentaerythritol tetra(3-mercaptopropionate) (hereinafter also known as "polythiol component A3") as a main ingredient;

[0134] The main components include polythiol A1 and polythiol A3;

[0135] It contains polythiol components A2 and A3 as the main components;

[0136] etc.

[0137] The polythiol compositions of various forms may contain at least one of the following components other than the main component (e.g., other polythiol compounds, components other than polythiol compounds, etc.).

[0138] Other components include, for example, compounds (NA1) and (NA2), which will be described later.

[0139] The preparation process can involve preparing a toluene solution of the crude polythiol composition.

[0140] In this case, in the purification process described later, the crude polythiol composition in the toluene solution is purified by mixing the toluene solution with solvent X (i.e., solvent X containing alkylene glycols).

[0141] Therefore, the purification effect of solvent X can sometimes be utilized more effectively.

[0142] The toluene solution of the crude polythiol composition contains the crude polythiol composition and toluene, and may also contain other components as needed.

[0143] Alternatively, the crude polythiol composition can be directly mixed with solvent X and purified without being made into a toluene solution.

[0144] <Purification Process>

[0145] The method for manufacturing the polythiol composition disclosed herein includes a purification step of purifying the crude polythiol composition by using a solvent X containing an alkylene glycol to obtain the polythiol composition.

[0146] Impurities (e.g., compounds (NA1) and (NA2) described later) in the crude polythiol composition can be removed by purification based on solvent X, resulting in a polythiol composition with reduced amounts of the aforementioned impurities. This leads to a polythiol composition capable of improving the pot life of the polymerizable composition.

[0147] (Purification based on solvent X)

[0148] As a specific operation for purification based on solvent X, for example, the operation of washing the liquid composition using solvent X can be applied.

[0149] The temperature of the crude polythiol composition and the mixture of solvent X during purification is preferably 10°C to 60°C, more preferably 20°C to 60°C, and even more preferably 20°C to 50°C.

[0150] The purification time based on 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.

[0151] As described above, solvent X contains alkylene glycols.

[0152] From the viewpoint of impurity removal based on purification, solvent X preferably includes at least one of ethylene glycol and propylene glycol.

[0153] Solvent X may also contain solvent components other than alkylene glycols.

[0154] Solvent components other than alkylene glycols include, for example, monools (e.g., methanol, ethanol, propanol, isopropanol, etc., which have 1 to 6 carbon atoms).

[0155] The proportion of alkylene glycols in solvent X (e.g., 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.

[0156] (Acid cleaning)

[0157] The purification process preferably includes the following steps:

[0158] The step of purifying the crude polythiol composition using solvent X to obtain the polythiol composition; and

[0159] The step of acid cleaning the obtained polythiol composition.

[0160] Hydrochloric acid is preferred as the acid used in acid cleaning.

[0161] The temperature of the mixture of polythiol composition and acid during acid cleaning is preferably 10°C to 60°C, more preferably 20°C to 60°C, and even more preferably 20°C to 50°C.

[0162] The acid cleaning time is preferably 1 minute to 120 minutes, more preferably 5 minutes to 90 minutes, and even more preferably 10 minutes to 70 minutes.

[0163] The concentration of hydrochloric acid is preferably 25% to 36% by mass, more preferably 30% to 36% by mass.

[0164] In addition to acid washing of the polythiol composition, the purification process may also include water washing and / or alkaline washing of the polythiol composition.

[0165] Water rinsing and / or alkaline rinsing are preferably performed after acid rinsing.

[0166] For water rinsing, degassed water with an oxygen concentration of less than 5 mg / L is preferred.

[0167] Alkaline cleaning can be carried out by adding an alkaline aqueous solution at a temperature preferably between 20°C and 50°C, and stirring for 10 minutes to 3 hours.

[0168] Ammonia water is preferred as an alkaline aqueous solution.

[0169] The concentration of ammonia water 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.

[0170] <Other processes>

[0171] The method for manufacturing the polythiol composition disclosed herein may include other steps as needed.

[0172] Other examples of processes include solvent removal, filtration, and distillation, which are performed after the purification process.

[0173] <First Embodiment and Second Embodiment>

[0174] Hereinafter, the first and second embodiments of the method for manufacturing the polythiol composition of this disclosure will be described.

[0175] The first and second embodiments may have overlapping parts. That is, one of the first and second embodiments may possess the features of the other.

[0176] The method for producing the polythiol composition disclosed herein preferably satisfies at least one of the following first embodiment and the following second embodiment.

[0177] The first embodiment is as follows, wherein the crude polythiol composition comprises:

[0178] Polythiol component A1, wherein polythiol component A1 is a polythiol compound represented by the following formula (5) (i.e., 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane); and

[0179] A compound (NA1) is formed by replacing at least one of the thiol groups in polythiol component A1 with a group represented by the following formula (N1).

[0180] The second embodiment is as follows, wherein the crude polythiol composition comprises:

[0181] Polythiol component A2, wherein polythiol component A2 is at least one selected from the group consisting of 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 a polythiol compound represented by formula (8) (i.e., 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane); and

[0182] The compound (NA2) is formed by replacing at least one of the thiol groups in polythiol component A2 with a group represented by the following formula (N1).

[0183] [Chemical Formula 7]

[0184]

[0185] In equation (N1), * represents the bonding position.

[0186] (First Embodiment)

[0187] The first embodiment is an embodiment in which the crude polythiol composition comprises polythiol component A1 and compound (NA1).

[0188] The crude polythiol composition in the first embodiment preferably contains polythiol component A1 as the main component.

[0189] The compound (NA1) in the first embodiment is a compound formed by replacing at least one of the thiol groups in the polythiol component A1 with a group represented by formula (N1).

[0190] Compound (NA1) is a reaction byproduct produced during the manufacture of polythiol component A1, and can be considered as a compound that may be mixed into crude polythiol compositions in which polythiol component A1 is the main component, as an impurity.

[0191] Compound (NA1) is the compound with a retention time of 4.3 min to 4.8 min as shown in the HPLC (high performance liquid chromatography) determination described in the "Examples" section below.

[0192] The compound (NA1) is considered to be an impurity that has a catalytic effect in polymerizable compositions, promoting the polymerization of monomers.

[0193] Regarding compound (NA1), see International Publication No. 2016 / 010065 (in particular the record of “Nitrogen-containing compound (b)”) and International Publication No. 2020 / 41183 (in particular the record of “Nitrogen-containing compound (B)”).

[0194] In the first embodiment, in the purification step described later, the compound (NA1) can be removed from the crude polythiol composition by purification based on solvent X, and a polythiol composition with a reduced content of compound (NA1) can be obtained.

[0195] This can suppress the increase in viscosity of polymeric compounds containing polythiol compositions during storage.

[0196] In the above HPLC determination, the peak area of ​​compound (NA1) is preferably 0.01 to 0.30, more preferably 0.01 to 0.20, relative to the total peak area 100 of the compounds contained in the polythiol composition obtained through the purification process.

[0197] The preparation process in the first embodiment preferably includes the following steps:

[0198] The steps of reacting 2-mercaptoethanol with the epihalohydrin compound represented by formula (1) to obtain the polyol compound represented by formula (2);

[0199] The step of reacting the polyol compound represented by formula (2) with thiourea under acidic conditions to obtain a reaction solution containing isothiourea onium salt; and

[0200] The step of adding an alkaline compound to a reaction solution containing isothiourea onion salt to hydrolyze the isothiourea onion salt to obtain a crude polythiol composition.

[0201] [Chemical Formula 8]

[0202]

[0203] In equation (1), X represents a halogen atom.

[0204] Regarding the preferred embodiment of the preparation process described above, reference can be made to International Publication No. 2014 / 027427 (in particular, a description of a method for manufacturing polythiol compounds).

[0205] The preferred embodiment of the preparation process described above includes the step of reacting 2-mercaptoethanol with the epihalool compound represented by formula (1) to obtain the polyol compound represented by formula (2).

[0206] 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.

[0207] The reaction temperature of 2-mercaptoethanol with 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.

[0208] The amount of 2-mercaptoethanol used is preferably 1.8 to 3 moles, more preferably 1.9 to 2.1 moles, relative to 1 mole of the epihaloethanol compound represented by formula (1).

[0209] The reaction of 2-mercaptoethanol with epihaloethanol compounds represented by the following formula (1) is preferably carried out in an aqueous solvent.

[0210] Examples of aqueous solvents include water, or mixtures of water and lower alcohols (e.g., methanol or ethanol).

[0211] The reaction of 2-mercaptoethanol with epihalohydrins represented by the following formula (1) is preferably carried out in the presence of a base.

[0212] Examples of bases include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and tributylamine; and so on.

[0213] Sodium hydroxide is particularly preferred.

[0214] Regarding the amount of alkali used, in the case of a monobasic alkali, it is preferably 0.5 to 2 moles, more preferably 0.9 to 1.1 moles, relative to 1 mole of the epihalohydrin compound represented by formula (1).

[0215] In the case of a binary alkali, it is preferable to use half the amount of a monobasic alkali.

[0216] The preferred embodiment of the preparation process described above includes the step of reacting the polyol compound represented by formula (2) with thiourea under acidic conditions to obtain a reaction solution containing isothiourea onion salt.

[0217] The amount of thiourea used is preferably 2.7 moles or more, more preferably 2.7 to 6.0 moles, and even more preferably 2.9 to 3.2 moles, relative to 1 mole of the polyol compound represented by formula (2).

[0218] As an acidic condition, the presence of hydrochloric acid is preferred.

[0219] 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, relative to 1 mole of the polyol compound represented by formula (2).

[0220] The reaction temperature of the polyol compound represented by formula (2) with thiourea is preferably room temperature (25°C) to reflux temperature, and more preferably 90°C to 120°C.

[0221] The preferred reaction time is 1 to 10 hours.

[0222] The preferred embodiment of the preparation process includes adding an alkaline compound to a reaction solution containing isothiourea onion salt, and hydrolyzing the isothiourea onion salt to obtain a crude polythiol composition.

[0223] Ammonia is preferred as an alkaline compound.

[0224] In this hydrolysis, an aqueous solution of an alkaline compound (e.g., ammonia) may also be added to the reaction solution containing isothiourea salt.

[0225] The preferred reaction temperature for hydrolyzing isothiourea onion salt is 15°C to 60°C, more preferably 25°C to 55°C.

[0226] An alkaline compound or its aqueous solution is added to a reaction solution containing isothiourea salt for a period of preferably 80 minutes or less, more preferably 70 minutes or less, and even more preferably 20 to 60 minutes.

[0227] After adding an alkaline compound or its aqueous solution to the reaction solution containing isothiourea onion salt, a hydrolysis reaction is carried out at a temperature preferably room temperature to reflux temperature (more preferably 30°C to 80°C) for 1 hour to 8 hours.

[0228] In the process of obtaining a reaction solution containing isothiourea onium salt, the polyol compound represented by formula (2) is reacted with thiourea in the presence of hydrochloric acid, and ammonia is used as the base compound when hydrolyzing the isothiourea onium salt. The amount of ammonia used is preferably 1 mole or more, more preferably 1 to 3 moles, relative to the amount of hydrochloric acid used (1 mole).

[0229] It is preferable to add the organic solvent before adding the alkali compound or its aqueous solution to the reaction solution containing isothiourea salt.

[0230] Examples of organic solvents include toluene, xylene, chlorobenzene, and dichlorobenzene.

[0231] Toluene is preferred.

[0232] By adding toluene as an organic solvent, a toluene solution of the crude polythiol composition can be obtained. Thus, as mentioned above, the purification effect based on solvent X can be more effectively achieved.

[0233] <Second embodiment>

[0234] The second embodiment is an embodiment in which the crude polythiol composition includes polythiol component A2 and compound (NA2).

[0235] The crude polythiol composition in the second embodiment preferably contains polythiol component A2 as the main component.

[0236] The compound (NA2) in the second embodiment is a compound formed by replacing at least one of the thiol groups in the polythiol component A2 with a group represented by formula (N1).

[0237] Compound (NA2) is a reaction byproduct produced during the manufacture of polythiol component A2, and can be considered as a compound that may be mixed into the crude polythiol composition in which polythiol component A2 is the main component, as an impurity.

[0238] Compound (NA2) is the compound with a retention time of 6.5 min to 8.0 min as shown in the HPLC (high performance liquid chromatography) determination section described later in the "Examples" section.

[0239] The compound (NA2) is considered to be an impurity that has a catalytic effect in polymerizable compositions, promoting the polymerization of monomers.

[0240] In the second embodiment, in the purification step described later, the compound (NA2) can be removed from the crude polythiol composition by purification based on solvent X, and a polythiol composition with a reduced content of compound (NA2) can be obtained.

[0241] This can suppress the increase in viscosity during storage of polymeric compounds containing polythiol compositions (i.e., increase the shelf life of polymeric compounds containing polythiol compositions).

[0242] In HPLC determination, 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 100 of the compounds contained in the polythiol composition obtained through the purification process.

[0243] When the peak area of ​​compound (NA2) is 0.04 or more (more preferably 0.50 or more) relative to the total peak area 100 of the compounds contained in the polythiol composition, the heat resistance (e.g., glass transition temperature (Tg)) of the resin manufactured using the polythiol composition is further improved.

[0244] When the peak area of ​​compound (NA2) is less than 1.50 relative to the total peak area of ​​100 of the compounds contained in the polythiol composition, the viscosity increase during storage of the polymerizable compound containing the polythiol composition can be further suppressed (i.e., the shelf life of the polymerizable compound containing the polythiol composition is further improved).

[0245] The preparation process in the second embodiment preferably includes the following steps:

[0246] The steps of reacting 2-mercaptoethanol with the epihalohydrin compound represented by formula (1) to obtain the compound represented by formula (3);

[0247] The steps of reacting the compound represented by formula (3) with sodium sulfide to obtain the polyol compound represented by formula (4) below;

[0248] The step of reacting the polyol compound represented by formula (4) with thiourea under acidic conditions to obtain a reaction solution containing isothiourea onium salt; and

[0249] The step of adding an alkaline compound to a reaction solution containing isothiourea onion salt to hydrolyze the isothiourea onion salt to obtain a crude polythiol composition containing polythiol component A2.

[0250] [Chemical Formula 9]

[0251]

[0252] In equation (1), X represents a halogen atom.

[0253] Regarding the preferred embodiment of the preparation process described above, reference can be made to International Publication No. 2014 / 027428 (in particular to a method for manufacturing polythiol compounds).

[0254] The preferred embodiment of the preparation process described above includes the step of reacting 2-mercaptoethanol with the epihalohydrin compound represented by formula (1) to obtain the compound represented by formula (3).

[0255] 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.

[0256] The reaction temperature of 2-mercaptoethanol with 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.

[0257] The preferred reaction time is 2 to 10 hours.

[0258] 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, relative to 1 mole of the epihalohydrin compound represented by formula (1).

[0259] The reaction of 2-mercaptoethanol with epihaloethanol compounds represented by the following formula (1) is preferably carried out in an aqueous solvent.

[0260] Examples of aqueous solvents include water, or mixtures of water and lower alcohols (e.g., methanol or ethanol).

[0261] The reaction of 2-mercaptoethanol with epihalohydrins represented by the following formula (1) is preferably carried out in the presence of a base.

[0262] Examples of bases include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; tertiary amines such as triethylamine and tributylamine; and so on.

[0263] Sodium hydroxide is particularly preferred.

[0264] Regarding the amount of alkali used, in the case of a monobasic alkali, it is preferably 0.001 to 0.1 moles relative to 1 mole of the epihalohydrin compound represented by formula (1).

[0265] In the case of a binary alkali, it is preferable to use half the amount of a monobasic alkali.

[0266] The preferred embodiment of the preparation process described above includes the step of reacting the compound represented by formula (3) with sodium sulfide to obtain the polyol compound represented by formula (4).

[0267] The amount of sodium sulfide used is preferably 0.4 to 0.6 moles relative to 1 mole of the polyol compound represented by formula (3).

[0268] The reaction temperature is preferably 10℃~50℃, more preferably 20℃~40℃.

[0269] The preferred reaction time is 1 to 10 hours.

[0270] The preferred embodiment of the preparation process described above includes the step of reacting the polyol compound represented by formula (4) with thiourea under acidic conditions to obtain a reaction solution containing isothiourea onion salt.

[0271] The amount of thiourea used is preferably 3.0 moles or more, more preferably 3.0 to 6.0 moles, and even more preferably 4.6 to 5.0 moles, relative to 1 mole of the polyol compound represented by formula (4).

[0272] As an acidic condition, the presence of hydrochloric acid is preferred.

[0273] The amount of hydrochloric acid used is preferably 3 moles or more, more preferably 3 to 12 moles, relative to 1 mole of the polyol compound represented by formula (4).

[0274] The reaction temperature of the polyol compound represented by formula (4) with thiourea is preferably room temperature (25°C) to reflux temperature, and more preferably 90°C to 120°C.

[0275] The preferred reaction time is 1 to 10 hours.

[0276] The preferred embodiment of the preparation process described above includes the steps of adding an alkaline compound to a reaction solution containing isothiourea onion salt, and hydrolyzing the isothiourea onion salt to obtain a crude polythiol composition.

[0277] Ammonia is preferred as an alkaline compound.

[0278] In this hydrolysis, an aqueous solution of an alkaline compound (e.g., ammonia) may also be added to the reaction solution containing isothiourea salt.

[0279] The preferred reaction temperature for hydrolyzing isothiourea salt is 20°C to 60°C, more preferably 25°C to 55°C.

[0280] An alkaline compound or its aqueous solution is added to a reaction solution containing isothiourea salt for a period of preferably 80 minutes or less, more preferably 70 minutes or less, and even more preferably 20 to 60 minutes.

[0281] After adding an alkaline compound or its aqueous solution to the reaction solution containing isothiourea onion salt, a hydrolysis reaction is carried out at a temperature preferably room temperature to reflux temperature (more preferably 30°C to 80°C) for 1 hour to 8 hours.

[0282] In the process of obtaining a reaction solution containing isothiourea onium salt, the polyol compound represented by formula (4) is reacted with thiourea in the presence of hydrochloric acid, and ammonia is used as the base compound when hydrolyzing the isothiourea onium salt. The amount of ammonia used is preferably 1 mole or more, more preferably 1 to 3 moles, relative to the amount of hydrochloric acid used (1 mole).

[0283] It is preferable to add the organic solvent before adding the alkali compound or its aqueous solution to the reaction solution containing isothiourea salt.

[0284] Examples of organic solvents include toluene, xylene, chlorobenzene, and dichlorobenzene.

[0285] Toluene is preferred.

[0286] By adding toluene as an organic solvent, a toluene solution of the crude polythiol composition can be obtained. Thus, as mentioned above, the purification effect based on solvent X can be more effectively achieved.

[0287] [Method for manufacturing polymeric compositions]

[0288] The method for manufacturing the polymeric composition disclosed herein includes the following steps:

[0289] The steps of manufacturing a polythiol composition using the aforementioned method of manufacturing a polythiol composition according to this disclosure; and

[0290] The process involves mixing the above-mentioned polythiol composition with a polyisocyanate compound to obtain a polymerizable composition containing the above-mentioned polythiol composition and the polyisocyanate compound.

[0291] The method for manufacturing the polymeric composition disclosed herein may include other steps as needed.

[0292] In the method for manufacturing the polymeric composition of this disclosure, the polythiol composition is manufactured using the aforementioned method for manufacturing the polythiol composition of this disclosure, and thus, the same effect as the method for manufacturing the polythiol composition of this disclosure can be achieved.

[0293] That is, according to the method of manufacturing the polymerizable composition of this disclosure, the polymerization reaction of the polythiol composition and the polyisocyanate compound during storage can be suppressed, thereby suppressing the increase in viscosity during storage (i.e., suppressing the reduction in shelf life).

[0294] <Process for manufacturing polythiol compositions>

[0295] The steps for manufacturing polythiol compositions in the method for manufacturing polymeric compositions of this disclosure may suitably refer to the aforementioned method for manufacturing polythiol compositions of this disclosure.

[0296] <Process for obtaining polymeric composition>

[0297] In the process of obtaining the polymerizable composition, the polymerizable composition containing the above-mentioned polythiol composition and the polyisocyanate compound is obtained by mixing the above-mentioned polythiol composition with at least the polyisocyanate compound.

[0298] The preferred method for using the polyisocyanate compound in the process of obtaining the polymerizable composition is the same as the preferred method for "isocyanate compound as a raw material for thiourethane resin" described in the section on "method for manufacturing polythiol composition".

[0299] In the process of obtaining the polymerizable composition, there is no particular limitation on the mixing ratio of the polythiol composition and the polyisocyanate compound.

[0300] In the process of obtaining the polymerizable composition, the ratio of the input mass of the polythiol composition to the input mass of the polyisocyanate compound (i.e., input 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.

[0301] Furthermore, the molar ratio (thiol group / isocyanate group) of the thiol compound to 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.

[0302] In the process of obtaining the polymerizable composition, the total mass of the polythiol composition and the polyisocyanate compound 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, relative to the total mass of the polymerizable composition produced.

[0303] The process of obtaining the polymerizable composition may also be the following process: by mixing the polythiol composition with a polyisocyanate composition containing a polyisocyanate compound, thereby obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition.

[0304] Here, the term "polyisocyanate composition" refers to a composition containing at least one polyisocyanate compound.

[0305] In polyisocyanate compositions, components other than polyisocyanate compounds may be contained as impurities.

[0306] The polyisocyanate composition preferably contains at least one polyisocyanate compound as the main component.

[0307] The meaning of "containing... as a main component" is as described above.

[0308] The polyisocyanate composition preferably contains phenylene diisocyanate.

[0309] Hereinafter, polyisocyanate compositions containing phenylene diisocyanate will also be referred to as XDI compositions.

[0310] The XDI composition preferably contains phenylene diisocyanate as the main component.

[0311] The XDI composition preferably comprises at least one compound selected from the group consisting of compound (N1), compound (N2), and compound (N3).

[0312] [Chemical Formula 10]

[0313]

[0314] The following shows a preferred embodiment of the XDI composition from the viewpoint of superior stability of the polyisocyanate composition and superior transparency of the resin formed using the polyisocyanate composition.

[0315] When the XDI composition contains compound (N1), it is preferable that the peak area of ​​compound (N1) in the gas chromatography determination under the following GC conditions 1 is 0.20 ppm or more relative to the peak area 1 of phenylene diisocyanate.

[0316] -GC Condition 1-

[0317] Filler: DB-1 (film thickness) 1.5μm

[0318] Column: Inner diameter 0.53mm × length 60m (manufactured by Agilent Technologies)

[0319] Column oven temperature: Increase from 130℃ to 220℃ at a rate of 3℃ / min, and then increase to 300℃ at a rate of 10℃ / min after reaching 220℃.

[0320] Shunt ratio: Pulse shunt method

[0321] Inlet temperature: 280℃

[0322] Detector temperature: 300℃

[0323] Carrier gas: N2 158kPa, H2 55kPa, air 45kPa (constant pressure control)

[0324] Solvent: Chloroform

[0325] Sample concentration: 2.0% by mass chloroform solution

[0326] Injection volume: 2μL

[0327] Detection method: FID

[0328] 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 1 of phthalic acid diisocyanate.

[0329] The peak area of ​​the above compound (N1) relative to the peak area 1 of phenylene diisocyanate 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.

[0330] The peak area of ​​the above compound (N1) can be determined according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0331] When the XDI composition contains compound (N2), it is preferable that the peak area of ​​compound (N2) in the gas chromatography determination under the following GC conditions 2 is 0.05 ppm or more relative to the peak area 1 of phenylene diisocyanate.

[0332] -GC Condition 2-

[0333] Column: HP-50+, inner diameter 0.25mm × length 30m × film thickness 0.25μm (manufactured by Hewlett-Packard).

[0334] Column oven temperature: Increase from 50℃ to 280℃ at a rate of 10℃ / min, and hold at 280℃ for 6 minutes.

[0335] Shunt ratio: Pulse shunt method

[0336] Inlet temperature: 200℃

[0337] Detector temperature: 280℃

[0338] Carrier gas: He

[0339] Carrier gas flow rate: 1.0 ml / min (constant flow control)

[0340] Sample concentration: 1.0% by mass dichloromethane solution

[0341] Injection volume: 1.0 μL

[0342] Detection method: SIM (monitoring ions: m / z 180, 215) (content of ethylene diisocyanate (XDI))

[0343] The peak area of ​​the above compound (N2) is more preferably 0.1 ppm or more, more preferably 0.3 ppm or more, and more preferably 0.6 ppm or more, relative to the peak area 1 of phenylene diisocyanate.

[0344] The peak area of ​​the above compound (N2) relative to the peak area 1 of phenylene diisocyanate 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.

[0345] The peak area of ​​the above compound (N2) can be determined according to the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.

[0346] When the XDI composition contains compound (N3), it is preferable that the peak area of ​​compound (N3) in the gas chromatography determination under the aforementioned GC conditions 1 is 0.10 ppm or more relative to the peak area 1 of phenylene diisocyanate.

[0347] The peak area of ​​the above compound (N3) is more preferably 0.1 ppm or more, more preferably 3.0 ppm or more, and more preferably 5.0 ppm or more, relative to the peak area 1 of phthalic acid diisocyanate.

[0348] The peak area of ​​the above compound (N3) relative to the peak area 1 of phenylene diisocyanate 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.

[0349] The peak area of ​​the above compound (N3) can be determined according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0350] The acid content of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm.

[0351] There is no particular limitation on the lower limit of acid content in XDI compositions, but the lower limit may be, for example, 1 ppm.

[0352] The acid content of the XDI composition can be determined according to the method described in paragraph 0091 of International Publication No. 2021 / 256417.

[0353] In addition, XDI compositions may also contain stabilizers.

[0354] In the process of obtaining the polymerizable composition, the above-mentioned polythiol composition is at least mixed with the polyisocyanate compound. If necessary, the above-mentioned polythiol composition and the polyisocyanate compound may also be mixed with other components.

[0355] Alternatively, in the process of obtaining the polymerizable composition, other components may be added to the mixture after at least the above-mentioned polythiol composition has been mixed with the polyisocyanate compound.

[0356] Other components include polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, free radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion enhancers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, and inorganic pigments.

[0357] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0358] Acidic phosphate esters can be used as internal mold release agents. Examples of acidic phosphate esters include monophosphate esters and diphosphate esters, which can be used alone or in combination of two or more.

[0359] Examples of resin modifiers include cyclic sulfur compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, and olefin compounds containing (meth)acrylate compounds. Here, (meth)acrylate compounds refer to at least one of acrylate compounds and methacrylate compounds.

[0360] In the process of obtaining the polymerizable composition, the mixing of the above-mentioned components can be carried out in accordance with conventional methods, and there are no particular restrictions on the mixing method.

[0361] [Resin Manufacturing Method]

[0362] The method for manufacturing the resin disclosed herein includes the following steps:

[0363] The process of manufacturing a polymeric composition using the method for manufacturing a polymeric composition described above in this disclosure; and

[0364] The process of obtaining a resin by curing the above-mentioned polymeric composition.

[0365] The method for manufacturing the resin described in this disclosure may include other steps as needed.

[0366] In the process of obtaining the resin, the resin is obtained by curing the above-mentioned polymeric composition.

[0367] The curing of the above-mentioned polymerizable composition can be achieved by polymerizing the monomers (specifically, the polythiol composition and the polyisocyanate compound, hereinafter the same) in the polymerizable composition. As a pretreatment for polymerization, the polymerizable composition can be subjected to treatments such as filtration and degassing.

[0368] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) used to polymerize the monomers in the above-described polymeric composition can be appropriately set taking into account the composition of the composition, the type and amount of monomers in the composition, the type and amount of polymerization catalyst in the composition, and the properties of the mold when using the mold described later.

[0369] Examples of polymerization temperatures include -50℃ to 150℃ and 10℃ to 150℃.

[0370] Examples of aggregation times include 1 hour to 200 hours, 1 hour to 80 hours, etc.

[0371] In the process of obtaining resin, the polymer obtained by polymerization of monomers can be subjected to treatments such as annealing to obtain resin.

[0372] Examples of annealing temperatures include 50℃~150℃, 90℃~140℃, and 100℃~130℃.

[0373] [Manufacturing method of molded body]

[0374] The method for manufacturing a molded body disclosed herein is a method for manufacturing a molded body containing resin (hereinafter also referred to as "resin molded body"), which includes the following steps:

[0375] The process of manufacturing a polymeric composition using the method for manufacturing a polymeric composition described above in this disclosure; and

[0376] The process of obtaining a molded body containing resin by curing the above polymeric composition.

[0377] The method for manufacturing the molded body disclosed herein may include other steps as needed.

[0378] In the process of obtaining a molded body containing resin, the above-mentioned polymeric composition is cured to obtain a molded body containing resin.

[0379] Preferred conditions for the curing of the above-mentioned polymeric composition, i.e. the polymerization of the monomers in the above-mentioned polymeric composition, may be suitably referred to the section on "method of manufacturing resin".

[0380] As an example of polymerization in this process, casting polymerization can be cited.

[0381] In the casting polymerization process, the polymeric composition described above is first injected into the mold space held by gaskets or tapes. At this time, degassing, filtration, and other treatments may be performed as needed.

[0382] Next, the monomers in the polymeric composition injected into the molding die are polymerized, thereby curing the composition in the molding die to obtain a cured product. Then, the cured product is removed from the molding die to obtain a molded body containing resin.

[0383] The polymerization of the aforementioned monomers can be carried out by heating the polymerizable composition. This heating can be carried out, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, or the like.

[0384] [Methods for manufacturing optical materials, methods for manufacturing lenses]

[0385] The method for manufacturing an optical material (e.g., a lens) disclosed herein is a method for manufacturing an optical material (e.g., a lens) comprising a molded body containing a resin, and the manufacturing method includes the following steps:

[0386] The process of manufacturing a polymeric composition using the method for manufacturing a polymeric composition described above in this disclosure; and

[0387] The process of obtaining a molded body containing resin by curing the above polymeric composition.

[0388] The manufacturing method of the optical materials (e.g., lenses, hereinafter the same) disclosed herein may include other steps as needed.

[0389] The method for manufacturing optical materials disclosed herein is an application of the method for manufacturing molded articles disclosed herein.

[0390] For example, in the method of manufacturing the molded body of this disclosure, the shape of the molding die used in the aforementioned casting polymerization is suitably selected, thereby enabling the obtaining of a molded body suitable for optical materials (e.g., lenses).

[0391] Examples of optical materials include lenses (e.g., spectacle lenses, camera lenses, polarizing lenses) and light-emitting diodes (LEDs).

[0392] The method of manufacturing optical materials (e.g., lenses) disclosed herein may include the following steps: forming a coating layer on one or both sides of a molded body containing resin.

[0393] As a coating layer, specific examples include primer layer, hard coating layer, anti-reflective layer, anti-fog coating, anti-pollution layer, and waterproof layer.

[0394] These coatings can be formed individually or in multiple layers. When coatings are formed on both sides, the same coating can be formed on each side, or different coatings can be formed.

[0395] The composition of the coating can be appropriately selected according to the purpose.

[0396] Examples of components that can be used as coatings include resins (e.g., polyurethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, etc.

[0397] Regarding eyeglass lenses and coatings, one may appropriately refer to known documents such as International Publication No. 2017 / 047745.

[0398] [Polymerizable Composition]

[0399] The polymeric compositions disclosed herein contain a polythiol composition obtained by the aforementioned method for manufacturing the polythiol compositions of this disclosure and a polyisocyanate compound.

[0400] The polymeric compositions disclosed herein may contain polyisocyanate compositions comprising the aforementioned polyisocyanate compounds.

[0401] The polyisocyanate composition preferably comprises phenylene diisocyanate (i.e., the aforementioned XDI composition).

[0402] The preferred mode of the XDI composition (e.g., including at least one selected from the group consisting of compound (N1), compound (N2) and compound (N3)) is shown in the "<Step of obtaining the polymeric composition>" section of the method for manufacturing the polymeric composition described in the foregoing text of this disclosure.

[0403] The polymeric compositions of this disclosure can be manufactured using the aforementioned methods for manufacturing polymeric compositions of this disclosure.

[0404] Preferred embodiments of the polymeric compositions of this disclosure may suitably refer to the foregoing methods for manufacturing the polymeric compositions of this disclosure.

[0405] Wherein, the input mass [polythiol composition / polyisocyanate compound] is replaced by the content mass ratio [polythiol composition / polyisocyanate compound], and the total input mass of polythiol composition and polyisocyanate compound is replaced by the total content mass of polythiol composition and polyisocyanate compound.

[0406] [Resin, molded body, optical materials (e.g., lenses)]

[0407] The resin in this disclosure is a cured product of the polymeric composition described above.

[0408] The molded body of this disclosure is a molded body of resin containing the above-described disclosure.

[0409] The optical material (e.g., lens) in this disclosure is an optical material (e.g., lens) containing the resin described above in this disclosure.

[0410] The resin, the molded body, and the optical material (e.g., lens) of this disclosure can be manufactured using the aforementioned methods for manufacturing the resin, the molded body, and the optical material (e.g., lens) of this disclosure.

[0411] The preferred embodiments of the resin, the molded body, and the optical material (e.g., lens) of this disclosure can be referred to the preferred embodiments of the resin manufacturing method, the molded body manufacturing method, and the optical material (e.g., lens) manufacturing method described above.

[0412] <Preferred properties of the resin or molded article>

[0413] From the viewpoint of heat resistance, 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.

[0414] The glass transition temperature Tg mentioned above can be below 130℃, below 120℃, or below 110℃.

[0415] From the viewpoint of suitability for optical materials, the refractive index (ne) of the resin (or molded body) of this disclosure is preferably 1.500 or more, more preferably 1.540 or more, and even more preferably 1.590 or more.

[0416] There is no particular upper limit to the refractive index (ne) mentioned above; for example, the upper limit is 1.750.

[0417] From the viewpoint of applicability to optical materials, the Abbe number of the resin (or molded article) of this disclosure is preferably 28 or more, and more preferably 30 or more.

[0418] There is no particular upper limit to the Abbe number mentioned above; for example, the upper limit is 50, and preferably 45.

[0419] From the viewpoint of applicability to optical materials, the specific gravity d of the resin (or molded body) in this disclosure is preferably 1.10 or more, and more preferably 1.20 or more.

[0420] There is no particular upper limit to the above-mentioned specific gravity d, but the upper limit is, for example, 1.50, preferably 1.40.

[0421] One example of the polythiol composition involved in this disclosure is the following polythiol composition,

[0422] It contains polythiol component A2 as a main component, wherein polythiol component A2 is at least one selected from the group consisting of polythiol compounds represented by formula (6), polythiol compounds represented by formula (7), and polythiol compounds represented by formula (8), and,

[0423] A compound (XC) comprising replacing at least one of the thiol groups in polythiol component A2 with a group represented by the following formula (N1),

[0424] In high performance liquid chromatography determination, the peak area of ​​compound (NA2) is 0.50 to 1.50 relative to the total peak area 100 of the compounds contained in the polythiol composition.

[0425] [Chemical Formula 11]

[0426]

[0427] In equation (N1), * represents the bonding position.

[0428] One example of the polythiol composition involved in this disclosure can be referred to the second embodiment described above.

[0429] In HPLC determination, 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 100 of the compounds contained in the polythiol composition obtained through the purification process.

[0430] When the peak area of ​​compound (NA2) is 0.04 or more (more preferably 0.50 or more) relative to the total peak area 100 of the compounds contained in the polythiol composition, the heat resistance (e.g., glass transition temperature (Tg)) of the resin manufactured using the polythiol composition is further improved.

[0431] One example of this disclosure relates to a polymerizable composition comprising the polythiol composition and polyisocyanate compound described in one of the above examples.

[0432] One example of this disclosure relates to a polymerizable composition that may contain a polythiol composition as described in the above example, and a polyisocyanate composition containing a polyisocyanate compound.

[0433] The polyisocyanate composition preferably comprises phenylene diisocyanate (i.e., the aforementioned XDI composition).

[0434] The preferred mode of the XDI composition (e.g., including at least one selected from the group consisting of compound (N1), compound (N2) and compound (N3)) is shown in the "<Step of obtaining the polymeric composition>" section of the method for manufacturing the polymeric composition described in the foregoing text of this disclosure.

[0435] One example of this disclosure relates to a polymeric composition that can be manufactured using the aforementioned method for manufacturing polymeric compositions of this disclosure.

[0436] An example of this disclosure relates to a preferred mode of polymeric composition, which may suitably refer to the foregoing method of manufacturing the polymeric composition of this disclosure.

[0437] Wherein, the input mass [polythiol composition / polyisocyanate compound] is replaced by the content mass ratio [polythiol composition / polyisocyanate compound], and the total input mass of polythiol composition and polyisocyanate compound is replaced by the total content mass of polythiol composition and polyisocyanate compound.

[0438] One example of this disclosure relates to a resin that is a cured product of the polymeric composition described in one example of this disclosure.

[0439] One example of this disclosure relates to a molded body comprising the resin described in one example of this disclosure.

[0440] One example of this disclosure relates to an optical material (e.g., a lens) that is an optical material (e.g., a lens) containing the resin described in this disclosure.

[0441] The preferred embodiments of the resin, the molded body, and the optical material in one example of this disclosure are the same as those of the resin, the molded body, and the optical material in the foregoing disclosure.

[0442] Example

[0443] The following are examples of embodiments of this disclosure, but this disclosure is not limited to the following embodiments.

[0444] Unless otherwise specified, "portion" refers to a quantity based on mass, and "room temperature" refers to 25°C.

[0445] [Comparative Example 1]

[0446] <Preparation of crude polythiol composition (A1)>

[0447] According to the manufacturing method in Example A-1 of International Publication No. 2014 / 027427, a toluene solution of a crude polythiol composition (A1) with polythiol component A1 (i.e., the polythiol compound (4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane) represented by formula (5)) as the main component was obtained.

[0448] Details are shown below.

[0449] 125.4 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water were added to the reactor. 99.8 parts by mass of a 32% sodium hydroxide aqueous solution were added dropwise over 40 minutes at 12°C–35°C. Then, 73.8 parts by mass of epichlorohydrin, representing a epihalohydrin compound as shown in formula (1), were added dropwise over 4 hours at 29°C–36°C, and stirring was continued for 30 minutes. As a result, the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol, representing a polyol compound as shown in formula (2), was confirmed by NMR data.

[0450] Relative to the liquid from which 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed to be generated, 332.0 parts by mass of 36% hydrochloric acid were added, followed by 183.8 parts by mass of thiourea with a purity of 99.9%. The mixture was stirred under reflux at 110°C for 3 hours to carry out the thiourea onium salt reaction, yielding a reaction solution containing isothiourea onium salt.

[0451] After cooling the obtained reaction solution to 45°C, 355.0 parts by mass of toluene were added to it, and the solution was cooled to 30°C. After 44 minutes at 30°C to 40°C, 244.6 parts by mass of 25% by mass ammonia solution were added, and the solution was stirred at 54°C to 62°C for 3 hours to carry out the hydrolysis reaction, thereby obtaining a toluene solution of crude polythiol composition (A1) with polythiol component A1 as the main component.

[0452] <Purification of crude polythiol composition (A1)>

[0453] For the toluene solution of the crude polythiol composition (A1) obtained above, acid cleaning was performed at 35°C to 40°C for 1 hour using 147.8 parts by weight of 36% hydrochloric acid.

[0454] For the toluene solution after acid cleaning, use 147.8 parts by weight of degassed water and perform a cleaning once for 10 minutes at 35℃~40℃.

[0455] For the toluene solution after a single wash based on degassed water, a 10-minute wash was performed using 147.8 parts by weight of 0.1% ammonia.

[0456] For the toluene solution after cleaning with ammonia water, the operation of cleaning with 147.8 parts by weight of degassed water at 35℃~40℃ for 10 minutes was performed twice.

[0457] The crude polythiol composition (A1) is purified by the above operations, and the purified crude polythiol composition (A1) is obtained as a toluene solution of the polythiol composition (A1).

[0458] The toluene solution of the polythiol composition (A1) obtained by the above purification was subjected to heating and depressurization to remove toluene and trace amounts of water, and then subjected to depressurization filtration using a 3.0 μm PTFE membrane filter to obtain 200.0 parts by mass of the polythiol composition (A1).

[0459] Evaluation of the polythiol composition (A1)

[0460] The polythiol composition (A1) obtained above was evaluated as follows.

[0461] The results are shown in Table 1.

[0462] (Appearance confirmed)

[0463] The appearance of the polythiol composition (A1) was observed visually.

[0464] (Yellow Index (YI))

[0465] The polythiol composition (A1) was filled into a 10 mm thick glass sample cell, and the yellowness was determined by the transmittance.

[0466] Transmittance was measured using a Konica Minolta, Inc. spectrophotometer CM-5.

[0467] (Thiol value)

[0468] The thiol value (mmol / g) of the polythiol composition (A1) was determined by redox titration with 0.05M iodine aqueous solution.

[0469] (Refractive Index)

[0470] The refractive index of the polythiol composition (A1) was measured using a liquid refractive index meter RA600 manufactured by Kyoto Electronics Co., Ltd.

[0471] (HPLC determination)

[0472] The polythiol composition (A1) obtained above was determined by high performance liquid chromatography (HPLC) under the following HPLC determination conditions.

[0473] The contents of polythiol component A1, which is the main component, and compound (NA1) formed by replacing at least one of the thiol groups in polythiol component A1 with the group represented by the aforementioned formula (N1) were determined by HPLC (specifically, the area percentage (area%) relative to the total peak area of ​​the compounds contained in the polythiol composition (A1).

[0474] Compound (NA1) is the compound with a retention time of 4.3 min to 4.8 min in this assay.

[0475] -HPLC determination conditions-

[0476] The conditions are as follows:

[0477] As the column, Mightysil RP-18GP (registered trademark) manufactured by Kanto Chemical Co., Ltd. (particle size S: 5μm, column shape: Φ6mm×150mm, product number: 25477-9) was used.

[0478] As the mobile phase, a mixed solution of acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) was used.

[0479] As the assay solution, a mixture of 160 mg of the polythiol composition and 10 mL of acetonitrile was used.

[0480] An ultraviolet detector with a measurement wavelength of 230 nm was used as the detector.

[0481] Set the column temperature to 40℃.

[0482] Set the flow rate to 1.0 mL / min.

[0483] The injection volume is 2 μL.

[0484] <Preparation of Polymer Compositions>

[0485] Add the following to a flask equipped with a stir bar:

[0486] Dibutyltin dichloride (150 ppm by mass relative to the total amount of the polyisocyanate compound and polythiol composition (A)) was used as a polymerization catalyst.

[0487] Zelec-UN (manufactured by Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass relative to the total amount of the polyisocyanate compound and polythiol composition (A)).

[0488] Tinuvin 329 (manufactured by BASF Japan Ltd., 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol) (0.05% by mass relative to the total amount of the polyisocyanate compound and polythiol composition (A)) is used as a UV absorber.

[0489] as a polyisocyanate compound, isophthalene diisocyanate (XDI) (52 parts by weight), and

[0490] The above polythiol composition (A1) (48 parts by weight);

[0491] The mixture was stirred at 20°C for 5 minutes to obtain a polymerizable composition.

[0492] <Viscosity Changes in Polymer Compositions>

[0493] The viscosity (mPa·s) of the obtained polymeric composition at 20°C was measured using a Brookfield Company Type B viscometer.

[0494] Viscosity measurements were performed at the following times, thereby allowing for the observation of changes in viscosity over time:

[0495] Just 5 minutes after mixing (hereinafter referred to as "0h"),

[0496] After mixing for 5 minutes, let stand at 20°C for 1 hour (hereinafter referred to as "1h").

[0497] After mixing for 5 minutes, let stand at 20°C for 3 hours (hereinafter referred to as "1h").

[0498] Starting from 5 minutes of stirring and mixing, let stand at 20°C for 5 hours (hereinafter referred to as "1h"), and

[0499] After stirring and mixing for 5 minutes, let stand at 20°C for 7 hours (hereinafter referred to as "1h").

[0500] The less the viscosity changes, the better the pot life of the polymerizable composition.

[0501] <Preparation and Viscosity of Catalyst-Free Polymerizable Compositions>

[0502] Add the following to a flask equipped with a stir bar:

[0503] as a polyisocyanate compound, isophthalene diisocyanate (XDI) (52 parts by weight), and

[0504] The above polythiol composition (A1) (48 parts by weight);

[0505] The mixture was stirred at 30°C for 8 hours to obtain a catalyst-free polymerizable composition.

[0506] The viscosity (mPa·s) of the obtained catalyst-free polymerizable composition at 30°C was measured using a Brookfield Company Type B viscometer.

[0507] The results are shown in Table 1.

[0508] <Manufacturing of Resin Molded Components>

[0509] 52 parts by weight of isophthalene diisocyanate, 0.015 parts by weight of dibutyltin dichloride as a curing catalyst, 0.10 parts by weight of Zelc UN (trade name: Stepan Corporation; acid phosphate), and 0.05 parts by weight of Viosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.; ultraviolet absorber) were mixed and dissolved at 20°C. 48 parts by weight of polythiol composition (A) were then added and mixed to obtain a polymerizable composition for manufacturing resin molded articles, forming a homogeneous liquid. The obtained polymerizable composition was degassed at 600 Pa for 1 hour and then filtered using a 1 μm Teflon (registered trademark) filter. The filtered polymerizable composition was injected between a pair of glass molds secured with tape. The pair of glass molds were then placed in an oven at 10°C. The oven temperature was then increased from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compounds and polythiols) in the polymerizable composition are polymerized to form a resin mold containing thiouric acid ester resin (i.e., the cured polymerizable composition) between a pair of glass molds.

[0510] Next, the oven is cooled. After cooling, a pair of glass molds are removed from the oven, and then the resin molded body is removed from the pair of glass molds to obtain a flat resin molded body with a thickness of 9mm.

[0511] The obtained resin molded article was annealed at 120°C for 1 hour.

[0512] <Evaluation of Resin Molded Articles>

[0513] The following evaluation was performed on the annealed resin molded articles described above.

[0514] The results are shown in Table 1.

[0515] (Appearance confirmed)

[0516] The appearance of the resin molded body is observed visually.

[0517] (Yellow Index (YI), L*, a*, and b*)

[0518] The yellowness (YI), L*, a*, and b* of the resin molded body were measured using a Konica Minolta, Inc. CM-5 spectrophotometer.

[0519] (Refractive index (ne) and Abbe number (νe))

[0520] Using a Pulverge refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive indices (ne, nF', nC') of the molded body 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 measurements, the refractive index (ne) and Abbe number (νe) of the molded body were calculated.

[0521] (Heat resistance)

[0522] Using the Shimadzu TMA-60 thermomechanical analysis system, the glass transition temperature (Tg) of the resin molded body was determined by the TMA penetration method (50g load, 0.5mm φ needle tip, heating rate of 10℃ / min) as an indicator of heat resistance.

[0523] (Specific gravity d)

[0524] The specific gravity d of the molded body was determined at 20℃ using the Archimedes method.

[0525] [Example 1]

[0526] In the purification of the crude polythiol composition (A1), the following purification operation based on solvent X was performed before the acid washing based on hydrochloric acid. Otherwise, the same operation as in Comparative Example 1 was performed.

[0527] The results are shown in Table 1.

[0528] -Purification based on solvent X-

[0529] The toluene solution of the crude polythiol composition (A1) obtained in the "Preparation of Crude Polythiol Composition (A1)" will be washed three times at 35-40°C with 147.8 parts by mass of ethylene glycol as solvent X for 15 minutes each time.

[0530] [Example 2]

[0531] The polythiol composition (A1) (50 parts by mass) obtained in Example 1 was mixed with the polythiol composition (A1) (50 parts by mass) obtained in Comparative Example 1 to obtain the polythiol composition (A1) (100 parts by mass) in Example 2.

[0532] The polythiol composition (A1) in Comparative Example 1 was changed to the polythiol composition (A1) in Example 2. Otherwise, the same operation as in Comparative Example 1 was performed (specifically, the operation after "Evaluation of polythiol composition (A1)").

[0533] The results are shown in Table 1.

[0534] [Table 1]

[0535]

[0536] As shown in Table 1, in the polythiol compositions (A1) of Examples 1 and 2 obtained by purifying the crude polythiol composition (A1) based on solvent X, compared with the polythiol composition (A1) of Comparative Example 1 obtained by not purifying the crude polythiol composition (A1) based on solvent X, the effect of suppressing the viscosity change of the polymerizable composition containing the polythiol composition (A1) was confirmed (i.e., the effect of improving the pot life).

[0537] In the polythiol compositions (A1) of Examples 1 and 2, compared with the polythiol composition (A1) of Comparative Example 1, it was confirmed that the content of the impurity compound (NA1) was reduced.

[0538] Based on these results, it is believed that in the polymerizable composition of Comparative Example 1, the compound (NA1), as an impurity, functions as a polymerization catalyst, thereby promoting the polymerization of the polythiol composition (A1) and the polyisocyanate compound, which leads to an increase in viscosity. In contrast to Comparative Example 1, it is believed that in Examples 1 and 2, the content of compound (NA1) in the polythiol composition (A1) is reduced, thereby inhibiting the polymerization of the polythiol composition (A1) and the polyisocyanate compound, resulting in a reduction in the increase in viscosity.

[0539] Furthermore, the evaluation results of the polythiol composition (A1) and the resin molded articles confirmed that, in Examples 1 and 2, the performance of the polythiol composition (A1) and the performance of the resin molded articles were maintained at the same level as in Comparative Example 1.

[0540] As shown above, it was confirmed that in Examples 1 and 2, compared with Comparative Example 1, the pot life of the polymerizable composition was improved while maintaining the same level of performance of the polythiol composition (A1) and the resin molded article.

[0541] [Example 1X]

[0542] In Example 1X, the manufacturing of the molded body was modified as follows, except that the same operation as in Example 1 was performed, and the same results as in Example 1 were obtained (Table 1).

[0543] -Changes from Example 1-

[0544] In Example 1, 52 parts by mass of isophthalic diisocyanate (XDI) was used in the manufacture of the molded article, but in Example 1X, the XDI (52 parts by mass) was changed to XDI composition X1 as the aforementioned XDI composition (the amount of XDI contained therein was 52 parts by mass).

[0545] XDI composition X1 is manufactured by adding trace amounts of compound (N1), compound (N2), and compound (N3) to XDI, which is the main component, and mixing them together.

[0546] In the XDI composition X1, gas chromatography determination was performed using the aforementioned GC conditions 1 and GC conditions 2, respectively. The results...

[0547] The peak area of ​​compound (N1) is greater than 0.20 ppm (specifically 600 ppm) relative to the peak area of ​​phenylene diisocyanate.

[0548] The peak area of ​​compound (N2) is greater than 0.05 ppm (specifically 18 ppm) relative to the peak area of ​​phenylene diisocyanate.

[0549] The peak area of ​​compound (N3) is greater than 0.10 ppm (specifically 100 ppm) relative to the peak area of ​​phenylene diisocyanate.

[0550] [Comparative Example 101]

[0551] <Preparation of crude polythiol composition (A2)>

[0552] A toluene solution of a crude polythiol composition (A2) with polythiol component A2 as the main component was obtained according to the manufacturing method in Example C-1 of International Publication No. 2014 / 027428.

[0553] Details are shown below.

[0554] Here, polythiol component A2 is selected from at least one of the following groups: polythiol compound represented by formula (6) (i.e., 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), polythiol compound represented by formula (7) (i.e., 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane), and polythiol compound represented by formula (8) (i.e., 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane).

[0555] 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 aqueous solution of sodium hydroxide were added to the reactor and cooled to 10°C. Then, 107.68 parts by mass of epichlorohydrin, representing the epihalohydrin compound of formula (1), were added dropwise at 9°C to 11°C for 3.9 hours, and the mixture was stirred for 60 minutes to allow for aging. As a result, the formation of the compound represented by formula (3) was confirmed by NMR data.

[0556] Next, 262.09 parts by mass of a 17.3% sodium sulfide aqueous solution were added dropwise at 28℃~30℃ for 1.0 hour, and stirring was continued for 3.0 hours for aging. As a result, the formation of the polyol compound represented by formula (4) was confirmed by NMR data.

[0557] Next, 484.6 parts by mass of 36% hydrochloric acid were added, followed by 214.0 parts by mass of thiourea with a purity of 99.9%. The mixture was stirred under reflux at 110°C for 3 hours to carry out the thiourea onium salting reaction, resulting in a reaction solution containing isothiourea onium salt.

[0558] After cooling the obtained reaction solution to 45°C, 373.0 parts by mass of toluene were added to it, and the solution was cooled to 32°C. Then, 354.2 parts by mass of a 24.6% by mass ammonia solution were added at 30°C to 38°C for 25 minutes. The solution was then heated to 60°C and stirred at 60°C for 1 hour to carry out the hydrolysis reaction, thereby obtaining a toluene solution of crude polythiol composition (A2) with polythiol component A2 as the main component.

[0559] <Purification of crude polythiol composition (A2)>

[0560] For the toluene solution of the crude polythiol composition (A2) obtained above, acid cleaning was performed for 15 minutes at 35°C to 40°C using 101.1 parts by weight of 4% hydrochloric acid, followed by acid cleaning for 30 minutes at 35°C to 40°C using 101.1 parts by weight of 35% hydrochloric acid.

[0561] For the toluene solution after acid cleaning with 35% hydrochloric acid, a cleaning process of 30 minutes each using 101.1 parts by weight of degassed water at 35°C to 40°C will be performed 5 times.

[0562] The crude polythiol composition (A2) is purified by the above operations, and the purified crude polythiol composition (A2) is obtained as a toluene solution of the polythiol composition (A2).

[0563] The toluene solution of the polythiol composition (A2) obtained by the above purification was subjected to heating and pressure reduction to remove toluene and trace amounts of water, and then subjected to pressure filtration using a 3.0 μm PTFE membrane filter to obtain 200.0 parts by mass of the polythiol composition (A2).

[0564] Evaluation of the polythiol composition (A2)

[0565] The polythiol composition (A2) obtained above was evaluated in the same way as the polythiol composition (A1) in Comparative Example 1.

[0566] The results are shown in Table 2.

[0567] The contents of polythiol component A2, which is the main component, and compound (NA2) formed by replacing at least one of the thiol groups in polythiol component A2 with the group represented by the aforementioned formula (N1) were determined by HPLC determination in Comparative Example 101 (more specifically, the area percentage (area%) relative to the total peak area of ​​the compounds contained in the polythiol composition (A2).

[0568] Compound (NA2) is the compound with a retention time of 6.5 min to 8.0 min in this HPLC determination.

[0569] <Preparation and Viscosity Changes of Polymerizable Compositions>

[0570] The polythiol composition (A1) was changed to the polythiol composition (A2), and otherwise the same operation as in Comparative Example 1 was performed.

[0571] The results are shown in Table 2.

[0572] <Preparation and Viscosity of Catalyst-Free Polymerizable Compositions>

[0573] The polythiol composition (A1) was changed to the polythiol composition (A2), and otherwise the same operation as in Comparative Example 1 was performed.

[0574] The results are shown in Table 2.

[0575] <Manufacturing and Evaluation of Resin Molded Articles>

[0576] The polythiol composition (A1) was changed to the polythiol composition (A2), and otherwise the same operation as in Comparative Example 1 was performed.

[0577] The results are shown in Table 2.

[0578] [Example 101]

[0579] In the purification of the crude polythiol composition (A2), the following alcohol purification operation was performed before acid washing based on 4% hydrochloric acid by mass. Otherwise, the same operation as in Comparative Example 101 was performed.

[0580] The results are shown in Table 2.

[0581] -Purification based on solvent X-

[0582] The toluene solution of the crude polythiol composition (A2) obtained in the "Preparation of Crude Polythiol Composition (A2)" will be cleaned three times at 35°C to 40°C for 15 minutes each time using a mixed solvent of 75.8 parts by mass of ethylene glycol and 24.3 parts by mass of methanol.

[0583] [Example 102]

[0584] The polythiol composition (A2) (50 parts by mass) obtained in Example 101 was mixed with the polythiol composition (A2) (50 parts by mass) obtained in Comparative Example 101 to obtain the polythiol composition (A2) (100 parts by mass) in Example 102.

[0585] The polythiol composition (A2) in Comparative Example 101 was replaced with the polythiol composition (A1) (admixture) in Example 102. Otherwise, the same operations as in Comparative Example 101 were performed (specifically, the operations following "Evaluation of Polythiol Composition (A2)").

[0586] The results are shown in Table 2.

[0587] [Example 103]

[0588] The polythiol composition (A2) (70 parts by mass) obtained in Example 101 was mixed with the polythiol composition (A2) (30 parts by mass) obtained in Comparative Example 101 to obtain the polythiol composition (A2) (100 parts by mass) in Example 103.

[0589] The polythiol composition (A2) in Comparative Example 101 was replaced with the polythiol composition (A1) (admixture) in Example 103. Otherwise, the same operations as in Comparative Example 101 were performed (specifically, the operations after "Evaluation of Polythiol Composition (A2)").

[0590] The results are shown in Table 2.

[0591] [Table 2]

[0592]

[0593] As shown in Table 2, in the polythiol compositions (A2) of Examples 101 to 103 obtained by purifying the crude polythiol composition (A2) based on solvent X, compared with the polythiol composition (A2) of Comparative Example 1 obtained without purifying the crude polythiol composition (A2) based on solvent X, the effect of suppressing the viscosity change of the polymerizable composition containing the polythiol composition (A2) was confirmed (i.e., the effect of improving the pot life).

[0594] In the polythiol compositions (A2) of Examples 101-103, compared with the polythiol composition (A2) of Comparative Example 101, it was confirmed that the content of compound (NA2) as an impurity was reduced.

[0595] Based on these results, it is believed that in the polymerizable composition of Comparative Example 101, the compound (NA2), as an impurity, functions as a polymerization catalyst, thereby promoting the polymerization of the polythiol composition (A2) and the polyisocyanate compound, which leads to an increase in viscosity. In contrast to Comparative Example 101, it is believed that in Examples 101-103, the content of compound (NA2) in the polythiol composition (A2) was reduced, thereby inhibiting the polymerization of the polythiol composition (A2) and the polyisocyanate compound, resulting in a reduction in the increase in viscosity.

[0596] Furthermore, the evaluation results of the polythiol composition (A2) and the resin molded articles confirmed that, in Examples 101 to 103, compared with Comparative Example 101, the degradation of the properties of the polythiol composition (A2) and the resin molded articles was suppressed (i.e., the pot life of the polymerizable composition was improved without causing degradation of the properties of the polythiol composition (A2) and the resin molded articles).

[0597] In Examples 101-103, the resin molded articles of Examples 102 and 103, in which the peak area of ​​compound (NA2) in HPLC determination was 0.50 to 1.50 relative to the total peak area 100 of compounds contained in the polythiol composition (A2), maintained a higher Tg compared to the resin molded article of Example 101, in which the peak area of ​​compound (NA2) was less than 0.50 relative to the total peak area 100 of compounds contained in the polythiol composition (A2), thus confirming excellent heat resistance.

[0598] [Example 101X]

[0599] In Example 101X, the manufacturing of the molded body was modified as follows, except that the same operation as in Example 101 was performed, and as a result, the same result as in Example 101 (Table 2) was obtained.

[0600] -Changes from Example 101-

[0601] In Example 101, 52 parts by mass of isophthalic diisocyanate (XDI) was used in the manufacture of the molded article, but in Example 101X, the XDI (52 parts by mass) was changed to XDI composition X1 as the aforementioned XDI composition (the amount of XDI contained therein was 52 parts by mass).

[0602] XDI composition X1 is manufactured by adding trace amounts of compound (N1), compound (N2), and compound (N3) to XDI, which is the main component, and mixing them together.

[0603] In the XDI composition X1, gas chromatography determination was performed using the aforementioned GC conditions 1 and GC conditions 2, respectively. The results...

[0604] The peak area of ​​compound (N1) is greater than 0.20 ppm (specifically 600 ppm) relative to the peak area of ​​phenylene diisocyanate.

[0605] The peak area of ​​compound (N2) is greater than 0.05 ppm (specifically 18 ppm) relative to the peak area of ​​phenylene diisocyanate.

[0606] The peak area of ​​compound (N3) is greater than 0.10 ppm (specifically 100 ppm) relative to the peak area of ​​phenylene diisocyanate.

[0607] The full disclosure of Japanese Patent Application 2022-153094, filed on September 26, 2022, is incorporated herein by reference.

[0608] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the extent that each document, patent application and technical standard is incorporated by reference to the extent that it is specifically and separately described.

Claims

1. A method for producing a polythiol composition, comprising the following steps: a preparation step of preparing a polythiol composition before purification, i.e., a crude polythiol composition; and A purification step of obtaining a polythiol composition by purifying the crude polythiol composition using a solvent X containing an alkylene glycol.

2. The method for producing a polythiol composition according to claim 1, which satisfies at least one of the following conditions: The crude polythiol composition comprises a polythiol component A1 which is a polythiol compound represented by the following formula (5), and a compound (NA1) in which at least one of the thiol groups in the polythiol component A1 is replaced by a group represented by the following formula (N1); as well as, 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 by a group represented by the following formula (N1), [Chemical formula 1] In formula (N1), * represents a bonding position.

3. The method for producing a polythiol composition according to claim 2, wherein: The crude polythiol composition comprises the polythiol component A1 and the compound (NA1), The preparation process comprises the following steps: A step of reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following formula (1) to obtain a polyol compound represented by the following formula (2); A step of reacting the polyol compound represented by the formula (2) with thiourea under acidic conditions to obtain a reaction solution containing an isothiuronium salt; and a step of adding a base compound to a reaction solution containing the isothiuronium salt to hydrolyze the isothiuronium salt to obtain the crude polythiol composition, [Chemical formula 2] In the formula (1), X represents a halogen atom.

4. The method for producing a polythiol composition according to claim 2, wherein: The crude polythiol composition comprises the polythiol component A2 and the compound (NA2), The preparation process comprises the following steps: A step of reacting 2-mercaptoethanol with an epihalohydrin compound represented by the following formula (1) to obtain a compound represented by the following formula (3); A step of reacting the compound represented by the formula (3) with sodium sulfide to obtain a polyol compound represented by the following formula (4); A step of reacting the polyol compound represented by the formula (4) with thiourea under acidic conditions to obtain a reaction solution containing an isothiuronium salt; and a step of adding a base compound to a reaction solution containing the isothiuronium salt to hydrolyze the isothiuronium salt to obtain the crude polythiol composition, [Chemical formula 3] In the formula (1), X represents a halogen atom.

5. The method for producing a polythiol composition according to claim 1, wherein The solvent X includes at least one selected from the group consisting of ethylene glycol and propylene glycol.

6. The method for producing a polythiol composition according to claim 1, wherein The preparation step prepares a toluene solution of the crude polythiol composition, In the purification step, the toluene solution is mixed with the solvent X, thereby purifying the crude polythiol composition in the toluene solution using the solvent X.

7. The method for producing a polythiol composition according to claim 1, wherein The purification process comprises the following steps: A step of purifying the crude polythiol composition by using the solvent X to obtain a polythiol composition; and The obtained polythiol composition is subjected to an acid washing step.

8. A method for producing a polymerizable composition, comprising the following steps: A step of producing a polythiol composition using the method for producing a polythiol composition according to any one of claims 1 to 7; and A step of mixing the polythiol composition and the polyisocyanate compound to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate compound.

9. The method for producing a polymerizable composition according to claim 8, wherein: The step of obtaining the polymerizable composition is a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition by mixing the polythiol composition with a polyisocyanate composition containing the polyisocyanate compound. The polyisocyanate composition comprises: xylylene diisocyanate, and At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in high performance liquid chromatography is 0.20 ppm or more relative to 100 of the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in high performance liquid chromatography is 0.05 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, When the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in high performance liquid chromatography is 0.10 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, [Chemical formula 4] 10. A method for producing a resin, comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 8; and A step of obtaining a resin by curing the polymerizable composition.

11. A polythiol composition comprising a polythiol component A2 as a main component, wherein the polythiol component A2 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 wherein: The polythiol composition contains 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), In high performance liquid chromatography, the peak area of ​​the compound (NA2) is 0.50 to 1.50 relative to the total peak area 100 of the compounds contained in the polythiol composition. [Chemical formula 5] In formula (N1), * represents a bonding position.

12. A polymerizable composition comprising: The polythiol composition according to claim 11, and Polyisocyanate compounds.

13. The polymerizable composition according to claim 12, comprising a polyisocyanate composition comprising the polyisocyanate compound, The polyisocyanate composition comprises: xylylene diisocyanate, and At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in high performance liquid chromatography is 0.20 ppm or more relative to 100 of the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in high performance liquid chromatography is 0.05 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, When the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in high performance liquid chromatography is 0.10 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, [Chemical formula 6]

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