Method for producing thiourethane resin raw materials and its applications

Abstract

The present invention provides a method for producing a thiourethane resin starting material, the method comprising a reaction step for bringing a composition X containing a thiourethane resin and impurities into contact with an active hydrogen compound, to react the thiourethane resin in the composition X and the active hydrogen compound and produce a thiourethane resin starting material.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing thiourethane resin raw materials and its applications. [Background technology]

[0002] Plastic lenses, which contain resin, are lighter, less prone to breakage, and can be dyed compared to inorganic lenses, and have therefore become rapidly popular in recent years for applications such as eyeglass lenses and camera lenses. For example, various studies have been conducted on lenses containing thiourethane resin (see, for example, Patent Documents 1 to 3 below).

[0003] Patent document 1: Japanese Patent Application Laid-Open No. 63-46213 Patent document 2: Japanese Patent Application Laid-Open No. 2-270859 Patent Document 3: Japanese Patent Application Laid-Open No. 7-252207 [Overview of the project] [Problems that the invention aims to solve]

[0004] Typically, polythiol compositions and polyisocyanate compounds are used as raw materials for manufacturing thiourethane resins (hereinafter also referred to as "thiourethane resin raw materials"). Polyisocyanate compounds are produced, for example, from polyamine compounds. Polyamine compounds, which are raw materials for polyisocyanate compounds, also fall under the category of thiourethane resin raw materials (i.e., raw materials for manufacturing thiourethane resins). Furthermore, compounds that are raw materials for these polyamine compounds (for example, polyurea compounds, polycarbamate compounds, etc.) also fall under the category of thiourethane resin raw materials.

[0005] Lenses containing thiourethane resin may contain foreign matter (i.e., components other than thiourethane resin). Lenses containing thiourethane resin and foreign matter are manufactured by machining a molded body formed from a composition containing thiourethane resin and foreign matter (hereinafter referred to as "composition X"). During this process, a large amount of machining dust containing thiourethane resin and foreign matter is generated. Conventionally, this large amount of machining dust has simply been discarded and not effectively utilized. However, from the perspective of efficient material utilization (i.e., recycling), a technology is desired to produce thiourethane resin raw materials using thiourethane resin contained in cutting powder as a starting material. The produced thiourethane resin raw materials can then be used as raw materials for new thiourethane resin. Furthermore, there is a need for technology to manufacture thiourethane resin raw materials using thiourethane resin as a starting material, not limited to using thiourethane resin contained in cutting powder as a starting material.

[0006] An object of one aspect of this disclosure is to provide a method for producing a thiourethane resin raw material and its applications, which can be used to produce a thiourethane resin raw material from a composition X containing a thiourethane resin and foreign matter as starting materials. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments. <1> A method for producing a thiourethane resin raw material, comprising a reaction step of contacting a composition X containing a thiourethane resin and foreign matter with an active hydrogen compound to react the thiourethane resin in the composition X with the active hydrogen compound to produce a thiourethane resin raw material. <2> The aforementioned foreign substance includes at least one selected from the group consisting of resins other than thiourethane resin, polymerization catalysts, metals, ultraviolet absorbers, internal mold release agents, plasticizers, dyes, machine oils, and water. <1> A method for producing the thiourethane resin raw material described above. <3> The thiourethane resin raw material includes at least one selected from the group consisting of polythiol compositions, polyurea compounds, polycarbamate compounds, polyamine compounds, polyisocyanate compounds, and polyurethane compounds. <1> or <2> A method for producing the thiourethane resin raw material described above. <4> The active hydrogen compound is at least one selected from the group consisting of amine compounds and alcohol compounds. <1> ~ <3> A method for producing a thiourethane resin raw material as described in any one of the following. <5> The reaction step involves contacting the composition X with the active hydrogen compound in the presence of a reaction solvent to react the thiourethane resin in the composition X with the active hydrogen compound to obtain a reaction mixture containing the thiourethane resin raw material. Furthermore, the process includes a separation step of separating the thiourethane resin raw material from the reaction mixture containing the thiourethane resin raw material. <1> ~ <4> A method for producing a thiourethane resin raw material as described in any one of the following. <6> The thiourethane resin raw material comprises a polythiol composition, The separation step is, By filtering the reaction mixture containing the thiourethane resin raw material, a filtrate containing the polythiol composition is obtained. A filtrate containing the polythiol composition is to be mixed with a base containing an alkali metal, and then water is added to perform extraction, thereby obtaining an aqueous extract containing the alkali metal salt of the polythiol composition. An aqueous liquid containing the polythiol composition is obtained by adding an acid to an aqueous extract containing an alkali metal salt of the polythiol composition. An extract containing the polythiol composition is obtained by adding an extraction solvent to an aqueous liquid containing the polythiol composition and performing extraction. This includes separating the polythiol composition from an extract containing the polythiol composition. <5> A method for producing the thiourethane resin raw material described above. <7> The composition X is recovered in at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. <1> ~ <6> A method for producing a thiourethane resin raw material as described in any one of the following. <8> The composition X includes the thiourethane resin and the cutting powder containing the foreign matter. <1> ~ <7> A method for producing a thiourethane resin raw material as described in any one of the following. <9> <1> ~ <8> A step of manufacturing a thiourethane resin raw material by a method for manufacturing a thiourethane resin raw material described in any one of the following, A step of producing a polymerizable composition using at least a portion of the thiourethane resin raw materials as at least a portion of the raw materials, A method for producing a polymerizable composition containing the above. <10> <9> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins. <11> A method for manufacturing a molded article containing resin, <9> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing a molded article containing [the specified ingredient]. <12> A method for producing an optical material including a molded body containing a resin, <9> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing optical materials containing [specific material]. <13> A method for manufacturing a lens including a molded body containing resin, <9> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing lenses that include [specific components / materials]. <14> A polymerizable composition comprising at least a part of a thiourethane resin raw material obtained by the method for producing a thiourethane resin raw material according to any one of <1> to <8>. <15> A resin which is a cured product of the polymerizable composition according to <14>. <16> A molded article comprising the resin according to <15>. <17> An optical material comprising the molded article according to <16>. <18> A lens comprising the molded article according to <16>.

Effects of the Invention

[0008] According to one aspect of the present disclosure, there are provided a method for producing a thiourethane resin raw material, which enables production of a thiourethane resin raw material using a composition X containing a thiourethane resin and foreign matter as a starting material, and an application thereof.

Mode for Carrying Out the Invention

[0009] In the present disclosure, a numerical range represented by using "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present disclosure, the term "step" includes not only an independent step, but also a case that cannot be clearly distinguished from other steps, as long as the intended object of the step is achieved. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component contained in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described stepwise in the present disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical ranges described in other stepwise descriptions. Further, in the numerical ranges described in the present disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.

[0010] [Method for Producing Thiourethane Resin Raw Material] The method for producing a thiourethane resin raw material according to the present disclosure includes a reaction step of contacting a composition X containing a thiourethane resin and foreign matter with an active hydrogen compound to react the thiourethane resin in composition X with the active hydrogen compound and produce a thiourethane resin raw material. According to the method for producing thiourethane resin raw materials of this disclosure, a thiourethane resin raw material can be produced as the target product using a composition X containing thiourethane resin and foreign matter as the starting material. In the above reaction process, the thiourethane resin is chemically decomposed by the reaction with the active hydrogen compound, and the target product, the thiourethane resin raw material, is produced.

[0011] <Reaction Process> The reaction step involves contacting composition X, which contains thiourethane resin and foreign matter, with an active hydrogen compound to react the thiourethane resin and the active hydrogen compound in composition X, thereby producing a thiourethane resin raw material.

[0012] There are no particular limitations on the method of contacting composition X with the active hydrogen compound. For example, one method is to place composition X and the active hydrogen compound (and a reaction solvent if necessary) in a reaction vessel and stir. In this example, composition X and the active hydrogen compound (and a reaction solvent if necessary) are placed in the reaction vessel and stirred. There are no particular restrictions on the order in which the solvents are added.

[0013] (Composition X) Composition X is one of the starting materials in the reaction process. Composition X contains a thiourethane resin and foreign matter. Composition X may contain other components as needed.

[0014] It is preferable that composition X is recovered in at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. According to this embodiment, the recycling of thiourethane resin as a material for eyeglass lenses is realized. Here, The manufacturing process of eyeglass lenses refers to the process of producing resin by mixing monomers, which are the raw materials for resin, and casting polymerization, and / or the process of obtaining eyeglass lenses by cutting and shaping the resin molded product. The eyeglass manufacturing process refers to the process of manufacturing eyeglasses by combining eyeglass lenses with other components such as eyeglass frames. The eyeglasses disposal process refers to the process of disposing of eyeglasses that have been manufactured but are no longer needed, as well as used eyeglasses. In either process, composition X, which includes thiourethane resin (a material for eyeglass lenses) and foreign matter, may be generated as waste. In this embodiment, composition X produced in at least one of these processes is used as a starting material, and a thiourethane resin raw material, which is a decomposition product of thiourethane resin, is obtained by reacting the thiourethane resin in composition X with an active hydrogen compound.

[0015] - Thiourethane resin - Composition X contains at least one thiourethane resin. As the thiourethane resin, known thiourethane resins can be used, for example, thiourethane resins described in publicly available documents such as Japanese Patent Publication No. 63-46213, Japanese Patent Publication No. 2-270859, Japanese Patent Publication No. 7-252207, Japanese Patent Publication No. 60-199016, Japanese Patent Publication No. 60-217229, International Publication No. 2007 / 052329, and International Publication No. 2008 / 047626 can be used.

[0016] The thiourethane resin content in composition X is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of composition X.

[0017] Thiourethane resins typically contain polymers of isocyanate compounds and polythiol compositions. That is, thiourethane resins are usually manufactured using isocyanate compounds and polythiol compositions as raw materials.

[0018] -Isocyanate compounds as raw materials for thiourethane resins- The isocyanate compound used as a raw material for the thiourethane resin may be one type or two or more types. Examples of isocyanate compounds used as raw materials for thiourethane resins include the well-known isocyanate compounds described in the aforementioned publicly available literature. The isocyanate compound used as a raw material for thiourethane resin preferably includes a polyisocyanate compound containing two or more isocyanate groups. Isocyanate compounds as raw materials for thiourethane resins are It is more preferable to include a diisocyanate compound containing two isocyanate groups. Pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohex Sun, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane It is even more preferable to include at least one selected from the group consisting of diisocyanates and phenylenediisocyanates (hereinafter also referred to as "isocyanate component A"), It is even more preferable that the product contains isocyanate component A as its main component.

[0019] Isocyanate compounds as raw materials for thiourethane resins are considered to have the following properties in mind when used as raw materials for thiourethane resins: [for example, optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.] It is even more preferable to include at least one selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane (hereinafter also referred to as "isocyanate component N1"), It is even more preferable that the product contains isocyanate component N1 as its main component.

[0020] -Polythiol composition as a raw material for thiourethane resin- The polythiol composition used as a raw material for the thiourethane resin may consist of only one type or two or more types.

[0021] In this disclosure, "polythiol composition" means a composition containing at least one polythiol compound. Here, there are no particular restrictions on the polythiol compound as long as it contains two or more thiol groups (also known as mercapto groups).

[0022] The polythiol composition may contain components other than the polythiol compound as impurities. The polythiol composition preferably contains at least one polythiol compound as its main component. Here, "a polythiol composition contains at least one polythiol compound as its main component" means that the total content of at least one polythiol compound relative to the total amount of the polythiol composition is 50% or more. The total content of at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

[0023] Similarly, in this disclosure, "a composition contains a certain component (hereinafter referred to as "component X") as a main component" means that the content of component X (or, if component X consists of two or more compounds, the total content of the two or more compounds) is 50% or more of the total amount of the composition. The content of component X, which is the main component, is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, based on the total amount of the composition.

[0024] In the explanation of the phrase "contained as a main component" above, "%" refers to the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) to the total area of ​​all peaks of the composition (e.g., a polythiol composition), as determined by high-performance liquid chromatography.

[0025] Examples of polythiol compounds included in the polythiol composition as a raw material for thiourethane resin include known polythiol compounds described in the aforementioned prior art documents.

[0026] Polythiol compositions as raw materials for thiourethane resins are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (3-mercaptopropionate), 2,5-Dimercaptomethyl-1,4-Dithiane, Bis(mercaptoethyl) sulfide, and Diethylene glycol bis(mercaptopropionate) It is preferable to include at least one selected from the group consisting of (hereinafter also referred to as "polythiol component T"). The polythiol composition more preferably contains polythiol component T as its main component. In this case, the polythiol composition may contain at least one other component besides the polythiol component T (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0027] Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and the like.

[0028] More specific embodiments of the polythiol composition as a raw material for thiourethane resin include: An embodiment comprising 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component T1") as the main component; Embodiments comprising 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter, these three compounds are collectively referred to as "polythiol component T2") as the main components; An embodiment comprising pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as "polythiol component T3") as the main component; Embodiments comprising polythiol component T1 and polythiol component T3 as main components; Embodiments comprising polythiol component T2 and polythiol component T3 as main components; These are some examples. Each embodiment of the polythiol composition may contain at least one other component besides the main component (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0029] -Foreign object- Composition X contains at least one foreign substance. Here, "foreign matter" refers to components other than thiourethane resin.

[0030] The foreign matter preferably includes at least one selected from the group consisting of resins other than thiourethane resin, polymerization catalysts, metals, ultraviolet absorbers, internal mold release agents, plasticizers, dyes, machine oils, and water.

[0031] There are no particular restrictions on resins other than thiourethane resin. for example; A hybrid material of thiourethane resin and urethane resin, produced by adding a polyol compound to the raw materials during the manufacturing of thiourethane resin; A hybrid material of thiourethane resin and urea resin, produced by adding a polyamine compound to the raw materials during the manufacturing of thiourethane resin; These also fall within the range of resin mixtures containing thiourethane resin and resins other than thiourethane resin.

[0032] Furthermore, it is preferable that the resin other than the thiourethane resin includes at least one selected from the group consisting of polycarbonate resin, polyallyl carbonate resin, acrylic resin, urethane resin, and episulfide resin. These resins, like thiourethane resins, can also be used as materials for eyeglass lenses.

[0033] In addition, resins other than thiourethane resin include: A polyolefin film that protects the surface of a resin molded body used for making eyeglass lenses. A hard coat or primer coat to protect the surface of a resin molded body used for making eyeglass lenses, and an abrasive used when polishing a resin molded body used for making eyeglass lenses. A resin material used to fix a resin molded body when machining a resin molded body for making eyeglass lenses. Tape or tape adhesive used to fix glass molds when creating resin molded parts for eyeglass lenses. Other examples include:

[0034] Examples of polymerization catalysts include those used in the formation of thiourethane resins (i.e., polymerization of monomers). Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0035] Examples of metals include pure metals and alloys. Specifically, as a metal, Various pure metals such as Al, Ti, Zr, Au, Pt, Ag, Cu, Fe, Bi, Pb, Sn, In, Ga, etc. Alloys containing at least one pure metallic element (e.g., stainless steel); Examples include Metals can be mixed into the thiourethane resin in at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses.

[0036] Each of the UV absorbers, internal release agents, and dyes can be added, for example, to thiourethane resins for lens (e.g., eyeglass lenses) manufacturing. Specific examples of these components can be found in reference to other components that may be included in polymerizable compositions. The UV absorbers may refer to those used in the manufacturing method according to Embodiment A, described below. Plasticizers may be included, for example, in gaskets used to hold a mold when producing a molded article of thiourethane resin by casting polymerization. Each of the machine oil and water is used, for example, to manufacture lenses (e.g., eyeglass lenses). It is used when grinding and / or polishing molded articles of urethane resin, and can be mixed with thiourethane resin powder during that process.

[0037] The foreign matter may contain other components not listed above. Other components that may be included can be found in the polymerizable composition described later.

[0038] The amount of foreign matter in composition X is preferably 0.001 to 150 parts by mass, more preferably 0.001 to 100 parts by mass, even more preferably 0.001 to 10 parts by mass, even more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 3 parts by mass, based on the total amount of thiourethane resin in composition X being 100 parts by mass.

[0039] The total content of thiourethane resin and foreign matter in composition X is preferably 80% to 100% by mass, and more preferably 90% to 100% by mass, based on the total amount of composition X.

[0040] -A powdered composition X containing thiourethane resin and foreign matter- As composition X, a powdery composition containing thiourethane resin and foreign matter is preferred. In other words, in the reaction step, it is preferable to react the thiourethane resin and the active hydrogen compound in the powdered composition X by bringing the powdered composition X, which is a powdered composition containing thiourethane resin and foreign matter (hereinafter also referred to as "powdered composition X"), into contact with the active hydrogen compound. This makes it possible to further improve the reaction efficiency between the thiourethane resin and the active hydrogen compound. There are no particular restrictions on the method of contacting the powdered composition X with the active hydrogen compound. For example, one method is to place the powdered composition X and the active hydrogen compound (and a reaction solvent if necessary) in a reaction vessel and stir. In this example, there are no particular restrictions on the order in which the powdered composition X and the active hydrogen compound (and a reaction solvent if necessary) are placed in the reaction vessel.

[0041] The powdered composition X is preferably a cutting powder (including the concept of abrasive powder; the same applies hereinafter) containing a thiourethane resin and foreign matter. Cutting powder from molded bodies containing thiourethane resin and foreign matter is generated, for example, when manufacturing optical materials (e.g., lenses) by cutting molded bodies containing thiourethane resin and foreign matter.

[0042] (Active hydrogen compounds) In the reaction process, the active hydrogen compound functions as a decomposing agent for the thiourethane resin in composition X, which is the starting material. From the viewpoint of the above functions, it is preferable that the active hydrogen compound is at least one selected from the group consisting of amine compounds and alcohol compounds.

[0043] -Amine compounds- As one of the preferred active hydrogen compounds, an amine compound can be any known amine compound without particular limitation. The amine compounds used in the reaction step may be one type or two or more types.

[0044] From the viewpoint of further improving the reactivity between the thiourethane resin and the amine compound, the molecular weight of the amine compound is preferably 1000 or less, more preferably 500 or less, even more preferably 300 or less, and even more preferably 200 or less. The lower limit of the molecular weight of the amine compound is, for example, 45 or more, preferably 59 or more. More preferably, it is 60 or higher.

[0045] As for the amine compound, an amine compound is preferred in which at least one of an amino group and a monoalkylamino group is included, and the total number of amino groups and monoalkylamino groups is 1 to 6 (preferably 1 to 3, more preferably 1 or 2).

[0046] As an example of a preferred amine compound, Examples include amine compounds with a molecular weight of 300 or less, which contain at least one of an amino group and a monoalkylamino group, and have a total number of amino groups and monoalkylamino groups of 1 or 2.

[0047] Examples of amine compounds include alkylamines with 2 to 10 carbon atoms, aralkylamines with 7 to 10 carbon atoms (e.g., benzylamine), dialkylamines with 2 to 10 carbon atoms (e.g., di-n-butylamine), alkyldiamines with 2 to 10 carbon atoms (e.g., ethylenediamine, bis(2-aminoethyl) ether), alkyltriamines with 2 to 10 carbon atoms (e.g., bis(2-aminoethyl)amine), hydroxyalkylamines with 2 to 10 carbon atoms (e.g., monoethanolamine), bis(hydroxyalkyl)amines with 2 to 10 carbon atoms (e.g., bis(hydroxyethyl)amine), cyclic amines with 2 to 10 carbon atoms (e.g., morpholine), and secondary amines such as alkyl(hydroxyalkyl)amines with 2 to 10 carbon atoms (e.g., methylethanolamine, isopropylethanolamine). Preferred amine compounds include benzylamine, di-n-butylamine, ethylenediamine, or monoethanolamine.

[0048] -Amount of amine compound added- When an amine compound is used as the active hydrogen compound, the mass ratio of the amine compound to the thiourethane resin (i.e., the mass ratio [amine compound / thiourethane resin]) can be adjusted as appropriate, but is preferably 0.10 or more and less than 1.0. When the mass ratio of the preparation [amine compound / thiourethane resin] is 0.10 or higher, the formation of the polythiol composition is further promoted. When the mass ratio of the charge [amine compound / thiourethane resin] is less than 1.0, the residual amount of amine compound in the reaction mixture can be further suppressed. The mass ratio of the preparation [amine compound / thiourethane resin] is preferably 0.15 to 0.95, and more preferably 0.20 to 0.90.

[0049] When an amine compound is used as the active hydrogen compound, the number of millimoles of the amine compound added per 1 g of thiourethane resin is preferably 1.0 mmol / g to 30 mmol / g, more preferably 2.0 mmol / g to 20 mmol / g, and even more preferably 3.0 mmol / g to 10.0 mmol / g.

[0050] When an amine compound is used as the active hydrogen compound, the equivalent amount of the amine compound relative to the thiourethane resin (equivalent amount [amine compound / thiourethane resin]) is preferably 1.0 to 2.0, more preferably greater than 1.0 and 1.8 or less, and even more preferably greater than 1.0 and 1.6 or less. When the equivalent amount of the charge [amine compound / thiourethane resin] is 1.0 or more, the formation of the polythiol composition is further promoted. When the equivalent charge [amine compound / thiourethane resin] is 2.0 or less, the residual amount of amine compound in the reaction mixture can be further suppressed. Here, the equivalent amount of amine compound added to the thiourethane resin (equivalent amount [amine compound / thiourethane resin]) refers to the ratio of the total number of amino groups and monoalkylamino groups in the amine compound added to the total number of thiourethane bonds in the thiourethane resin added. do.

[0051] -Alcohol compounds- The alcohol compound, which is one of the preferred active hydrogen compounds, may be a monoalcohol compound containing only one hydroxyl group, or a polyol compound containing two or more hydroxyl groups.

[0052] From the viewpoint of further improving reactivity with thiourethane resin, the molecular weight of the alcohol compound is preferably 1000 or less, more preferably 500 or less, even more preferably 300 or less, and even more preferably 200 or less. The lower limit of the molecular weight of the alcohol compound is, for example, 40 or more, preferably 50 or more, and more preferably 60 or more.

[0053] The alcohol compound preferably includes an alcohol compound having a boiling point of 135°C to 250°C (hereinafter also referred to as "alcohol compound A").

[0054] In this disclosure, boiling point means the boiling point at 1 atmosphere (101325 Pa).

[0055] The proportion of alcohol compound A in the total amount of alcohol compound is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass.

[0056] As an alcohol compound, Preferably, the substance is benzyl alcohol, phenethyl alcohol, 2-octanol, 2-ethyl-1-hexanol, 1-decanol, 1-nonanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, propylene glycol, or ethylene glycol. More preferably, benzyl alcohol, phenethyl alcohol, 1-decanol, 1-nonanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, propylene glycol, or ethylene glycol. More preferably, the substance is benzyl alcohol, phenethyl alcohol, 2-octanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, or propylene glycol.

[0057] When using an alcohol compound as the active hydrogen compound, the preferred range for the amount of alcohol compound to be charged is the same as the preferred range for the amount of amine compound to be charged when using an amine compound as the active hydrogen compound, as described above.

[0058] When using amine compounds and alcohol compounds as active hydrogen compounds, the preferred range for the total amount of amine compounds and alcohol compounds charged is the same as the preferred range for the amount of amine compounds charged when using amine compounds as active hydrogen compounds, as described above.

[0059] (reaction solvent) In the reaction step, it is preferable to bring composition X into contact with the active hydrogen compound in the presence of a reaction solvent. As the reaction solvent, organic solvents are preferred, and hydrocarbon compounds having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9) are more preferred. The hydrocarbon compounds mentioned above are preferably hexane, heptane, octane, nonane, decane, xylene, mesitylene, or toluene, more preferably heptane, octane, nonane, xylene, mesitylene, or toluene, and particularly preferably xylene or It is toluene. The reaction solvent may be one type or two or more types.

[0060] (Reaction temperature) The reaction temperature between the thiourethane resin and the activated hydrogen compound in the reaction process can be adjusted as appropriate. Here, the reaction temperature between the thiourethane resin and the active hydrogen compound refers to the temperature at which composition X is brought into contact with the active hydrogen compound. In the reaction step, it is preferable to bring composition X and the active hydrogen compound into contact under temperature conditions of 50°C to 150°C (more preferably 60°C to 145°C, and even more preferably 70°C to 140°C) (i.e., the reaction temperature). For example, in an embodiment for obtaining a target polythiol composition, if the reaction temperature is 50°C to 150°C, the purity of the main component polythiol in the target polythiol composition (i.e., the content of the main component relative to the total amount of the polythiol composition) can be further improved.

[0061] (Reaction time) The reaction time between the thiourethane resin and the active hydrogen compound in the reaction step (i.e., the time during which composition X is in contact with the active hydrogen compound) can be adjusted as appropriate, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and even more preferably 1 to 10 hours.

[0062] (Thiourethane resin raw material as the target product) In the reaction process, a thiourethane resin is reacted with an activated hydrogen compound to produce a thiourethane resin raw material, which is both a decomposition product of the thiourethane resin and the target product. The target material for thiourethane resin is a material obtained as a decomposition product of thiourethane resin (i.e., a compound or composition; the same applies hereinafter), and is also a material that can be used as a raw material for manufacturing new thiourethane resin. The thiourethane resin raw material used as the target product and the thiourethane resin raw material used as the raw material for the thiourethane resin in composition X, which is the starting material, do not need to be completely identical. The following describes preferred embodiments of the thiourethane resin raw material as the target product of the manufacturing method of this disclosure.

[0063] The thiourethane resin raw material, as the target product, preferably contains at least one selected from the group consisting of polythiol compositions, polyurea compounds, polycarbamate compounds, polyamine compounds, polyisocyanate compounds, and polyurethane compounds.

[0064] -Polythiol compositions as target products, polyisocyanate compounds as target products- Among the raw materials for thiourethane resin, the polythiol composition and the polyisocyanate compound are direct raw materials for producing thiourethane resin. That is, thiourethane resin can be produced by the reaction of the polythiol composition and the polyisocyanate compound. For polythiol compositions and polyisocyanate compounds, publicly available literature on thiourethane resins can be consulted as appropriate. The preferred embodiment of the polyisocyanate compound as the target product is the same as the preferred embodiment of the isocyanate compound as a raw material for thiourethane resin described above. The preferred embodiment of the polythiol composition as the target product is the same as the preferred embodiment of the polythiol composition as a raw material for thiourethane resin described above.

[0065] The target product is a polythiol composition, and the starting material is a thiourethane resin in composition X. The polythiol composition used as a raw material does not need to be exactly the same as the other material. However, from the viewpoint of the performance of the thiourethane resin produced by the polythiol composition as the target product, it is preferable that the type of polythiol component as the main component in the polythiol composition as the target product and the type of polythiol component as the main component in the polythiol composition as the raw material are the same. In this case, for example, it is possible to produce optical material B (an optical material containing composition X) having performance comparable to optical material A, using cutting powder (composition X) generated during the production of optical material A as a raw material.

[0066] -Polyamine compounds as the target product- The target polyamine compound is a compound that can be used as a raw material for polyisocyanate compounds. Specifically, a polyamine compound can be produced by reacting a polyamine compound with phosgene (i.e., carbonyl dichloride). The target polyamine compound can be produced, for example, by reacting a polyurea compound with an amine compound as described later (see Examples 201-211 below). The target polyamine compound can be produced, for example, by reacting a polycarbamate compound with an amine compound, as described later.

[0067] -Polyurea compounds as target products- The target product, the polyurea compound, is a compound that can be used as a raw material for polyamine compounds. Specifically, polyamine compounds can be produced by reacting a polyurea compound with an amine compound. The target polyurea compound can be produced, for example, by decomposing the thiourethane resin through a reaction with an amine compound. Specifically, by reacting the thiourethane resin with an amine compound, the thiourethane resin can be decomposed into a polythiol composition and a polyurea compound (additive amine decomposition).

[0068] Examples of amine decomposition can be found in Examples 1-13 (examples for obtaining polythiol compositions) and Examples 201-211 (examples for obtaining polyurea compounds), which are described later. Examples 201-211, described later, also show the process for obtaining polyamine compounds from polyurea compounds (second step).

[0069] -Polycarbamate compounds as target products- The target product, the polycarbamate compound, is a compound that can be used as a raw material for polyamine compounds. Specifically, polyamine compounds can be produced by reacting a polycarbamate compound with an amine compound. The target polycarbamate compound can be produced, for example, by decomposing the thiourethane resin through a reaction with an alcohol compound. Specifically, by reacting the thiourethane resin with an alcohol compound, the thiourethane resin can be decomposed into a polythiol composition and a polycarbamate compound (alcohol decomposition).

[0070] There are no particular restrictions on the use of the thiourethane resin raw material as the target product. Specific applications of thiourethane resin raw materials as target products include raw materials for the manufacture of optical materials (for example, lenses, preferably spectacle lenses). In other words, a specific example of the method for producing thiourethane resin raw materials of this disclosure is a method for producing thiourethane resin raw materials for the manufacture of optical materials. In this specific example, if the starting material composition X is a cutting powder containing thiourethane resin and foreign matter generated during the manufacture of optical materials, the effective utilization (i.e., recycling) of the material (thiourethane resin and its raw material, thiourethane resin raw material) is effectively realized.

[0071] Furthermore, when a polythiol composition is obtained by the reaction of a thiourethane resin with an active hydrogen compound in the reaction process, a polythiol composition with a higher purity of the polythiol component as the main component can be obtained compared to known methods (for example, a method of obtaining a polythiol composition by the reaction of a thiourethane resin with sodium hydroxide). Therefore, even when the polythiol composition is used as the target material in the manufacture of optical materials (e.g., lenses), optical materials with good performance can be obtained. The properties of optical materials include optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.

[0072] (Reaction mixture containing thiourethane resin raw materials) The reaction step may also be a step in which composition X and an active hydrogen compound are brought into contact in the presence of a reaction solvent (preferably an organic solvent, more preferably a hydrocarbon compound having 5 to 12 carbon atoms) to react the thiourethane resin in composition X with the active hydrogen compound, thereby obtaining a reaction mixture containing the target thiourethane resin raw material. The reaction mixture may contain a thiourethane resin raw material as the main product produced by decomposition, and other components other than the thiourethane resin raw material. Other components include by-products generated by decomposition, reaction solvents, residues from the raw materials, and impurities contained in the raw materials.

[0073] <Separation process> The method for producing a thiourethane resin raw material according to this disclosure may include a separation step of separating the thiourethane resin raw material as the target product from a reaction mixture containing the thiourethane resin raw material. There are no particular restrictions on the separation method used in the separation process; known methods can be applied. Separation methods in the separation process include filtration, decantation, extraction, distillation, drying (including vacuum drying), and purification (e.g., column chromatography). Multiple separation methods may be used in combination.

[0074] When the thiourethane resin raw material contains a polythiol composition, the separation step preferably includes filtering the reaction mixture containing the thiourethane resin raw material obtained in the reaction step to obtain a filtrate containing the polythiol composition. According to this embodiment, it is easier to remove solid components (e.g., solid components including by-products) contained in the reaction mixture. The solid content includes, for example, polyurea compounds and / or polycarbamate compounds. As mentioned above, polyurea compounds and polycarbamate compounds can also be used as raw materials for thiourethane resins.

[0075] One preferred embodiment in which the separation step includes obtaining a filtrate containing a polythiol composition is: The separation process is By filtering the reaction mixture containing the thiourethane resin raw material, a filtrate containing the polythiol composition is obtained. The filtrate containing the polythiol composition is acid-washed, Separating the polythiol composition from the filtrate after acid washing, One example is an embodiment that includes (hereinafter referred to as separation embodiment A). According to separation method A, alkaline components (e.g., residues of active hydrogen compounds) can be easily removed from the filtrate by acid washing, thus obtaining a polythiol composition with higher purity of the polythiol component as the main component. In separation method A, water washing may be added after acid washing, and the polythiol composition may be separated from the filtrate after water washing.

[0076] In separation mode A, examples of acids used for acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, and the like.

[0077] Another preferred embodiment in which the separation step includes obtaining a filtrate containing a polythiol composition is, The separation process is By filtering the reaction mixture containing the thiourethane resin raw material, a filtrate containing the polythiol composition is obtained. By adding a base containing an alkali metal to a filtrate containing a polythiol composition, and then adding water to perform extraction, an aqueous extract containing an alkali metal salt of the polythiol composition is obtained. Adding an acid to an aqueous extract containing an alkali metal salt of a polythiol composition to obtain an aqueous liquid containing the polythiol composition, An extract containing the polythiol composition is obtained by adding an extraction solvent (preferably an organic solvent, more preferably a hydrocarbon compound having 5 to 12 carbon atoms) to an aqueous liquid containing the polythiol composition and performing extraction. Separating the polythiol composition from an extract containing the polythiol composition, An embodiment that includes this (hereinafter referred to as separation embodiment B) is also an example.

[0078] In separation method B, first, the polythiol composition in the filtrate containing the polythiol composition is converted to an alkali metal salt, and then extracted with water to obtain an aqueous extract containing the alkali metal salt of the polythiol composition. Next, by adding acid, the alkali metal salt of the polythiol composition is converted back to the polythiol composition. The polythiol composition is extracted from the obtained aqueous liquid containing the polythiol composition with a reaction solvent to obtain an extract containing the polythiol composition. The polythiol composition is separated from the obtained extract containing the polythiol composition. According to separation method B, even when the filtrate containing the polythiol composition contains a large amount of other components besides the polythiol composition, a polythiol composition with higher purity of the polythiol component as the main component can be obtained. In particular, even if foreign matter is present in the filtrate containing the polythiol composition, it is possible to suppress the contamination of the final obtained polythiol composition with foreign matter.

[0079] In separation mode B, the alkali metal in the alkali metal-containing base is preferably sodium, potassium, or lithium, and more preferably sodium or potassium. Examples of bases containing alkali metals include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Bases containing alkali metals can be added to the filtrate in the form of an alcoholic solution (methanol solution, ethanol solution, etc.) as needed.

[0080] In separation mode B, examples of acids added to the aqueous extract containing the alkali metal salt of the polythiol composition include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, and the like.

[0081] In separation mode B, the hydrocarbon compound used as the extraction solvent may be one type or two or more types. In separation mode B, the preferred embodiment of the hydrocarbon compound as the extraction solvent is the same as the preferred embodiment of the hydrocarbon compound as the reaction solvent described above. However, the reaction solvent and the extraction solvent may be the same or different.

[0082] In separation method B, when separating the polythiol composition from the extract containing the polythiol composition, it is particularly preferable to first filter the extract and then separate the polythiol composition from the filtered extract. This removes components insoluble in the extraction solvent (e.g., oligomeric components such as decomposition defects and oxidized forms) from the extract, thereby obtaining a polythiol composition with higher purity of the polythiol component as the main component.

[0083] <Sieving process> The method for producing a thiourethane resin raw material of this disclosure may further include a sieving step, prior to the reaction step, in which cutting powder as a powdered composition X containing thiourethane resin and foreign matter is sieved to obtain a powdered composition X containing thiourethane resin and foreign matter that has passed through the sieve. In this case, in the reaction step, the thiourethane resin in the powdered composition X that has passed through the sieve is reacted with an amine compound by contacting the powdered composition X with an active hydrogen compound. If the method for producing the polythiol composition of this disclosure includes a sieving step, the powdered composition X that has passed through a sieve made of small particles is brought into contact with the active hydrogen compound in the reaction step, thereby further improving the reaction efficiency between the thiourethane resin and the active hydrogen compound.

[0084] There are no particular restrictions on the above sieve. The nominal mesh size of the sieve, as defined in JIS Z-8801-1:2019, is, for example, 0.1 mm to 2 mm, preferably 0.3 mm to 2 mm, and more preferably 0.5 mm to 1.5 mm.

[0085] <Washing process> The method for producing the thiourethane resin raw material of this disclosure may further include a washing step before the reaction step in which the powdered composition X (i.e., powder containing thiourethane resin and foreign matter) is washed with a washing solvent (preferably an organic solvent, more preferably a hydrocarbon compound having 5 to 12 carbon atoms). In this case, in the reaction step, the thiourethane resin in the powdered composition X washed in the washing step is reacted with an active hydrogen compound. This yields a polythiol composition with a higher purity of the polythiol component as the main component. In particular, in the method for producing the polythiol composition of this disclosure, when cutting powder as a powdered composition X containing thiourethane resin and foreign matter is used as a starting material, the above washing step can effectively remove oil from the cutting machine adhering to the cutting powder, thereby obtaining a polythiol composition with a higher purity of the polythiol component as the main component.

[0086] The organic solvent used as the washing solvent may be one type or two or more types. The preferred embodiment of the organic solvent as a washing solvent is the same as the preferred embodiment of the organic solvent as a reaction solvent described above. However, the reaction solvent and the washing solvent may be the same or different.

[0087] There are no particular restrictions on the cleaning method in the cleaning process; known methods can be applied, such as adding the above-mentioned cleaning solvent to the powdered composition X and mixing it.

[0088] If the method for producing the thiourethane resin raw material of this disclosure includes the sieving step and the washing step described above, it is preferable to carry out the sieving step and the washing step in that order. In this case, there is no need to wash the cutting powder that did not pass through the sieve, so the amount of washing solvent used can be further reduced.

[0089] Furthermore, if the powdered composition X (i.e., the powder containing thiourethane resin and foreign matter) contains moisture, a drying step may be included before the reaction step for the purpose of removing the moisture.

[0090] <Embodiment A> Hereinafter, Embodiment A, which is one of the preferred embodiments of the method for producing the thiourethane resin raw material of this disclosure, is shown. Embodiment A is an embodiment of the method for producing a thiourethane resin raw material of the present disclosure, which is limited to a combination in which the foreign substance is an ultraviolet absorber, the active hydrogen compound is an amine compound, and the thiourethane resin raw material is a polythiol composition. Embodiment A is similar to the method for producing the thiourethane resin raw material of the present disclosure, except that it is limited to a combination in which the foreign substance is an ultraviolet absorber, the active hydrogen compound is an amine compound, and the thiourethane resin raw material is a polythiol composition, and the preferred embodiments are also the same.

[0091] The method for producing the thiourethane resin raw material according to Embodiment A may be rephrased as the method for producing the polythiol composition according to Embodiment A.

[0092] According to the method for producing a thiourethane resin raw material (i.e., a method for producing a polythiol composition) of Embodiment A, a polythiol composition can be produced using composition XA, which contains a thiourethane resin and an ultraviolet absorber, as a starting material. In detail, the reaction step in Embodiment A is a step in which a thiourethane resin and an ultraviolet absorber are brought into contact with an amine compound, thereby reacting the thiourethane resin and the amine compound in composition XA to produce a polythiol composition. In the reaction step of Embodiment A, additive amine decomposition occurs, in which the thiourethane resin is decomposed by an amine compound, and this additive amine decomposition generates the target product, the polythiol composition.

[0093] The preferred embodiments of the amine compound and the polythiol composition in Embodiment A are as described above.

[0094] In Embodiment A, composition XA contains at least one ultraviolet absorber. Examples of UV absorbers include: 2,2'-dihydroxy-4-methoxybenzophenone, 2-Hydroxy-4-acryloyloxybenzophenone, 2-Hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, 2-Hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone, Benzophenone-based UV absorbers such as; 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-Bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, Triazine-based UV absorbers such as; 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, 2,2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], Benzotriazole-based UV absorbers such as; These are some examples.

[0095] The ultraviolet absorber preferably contains a benzotriazole-based ultraviolet absorber. In this case, the content of the benzotriazole-based ultraviolet absorber in the total amount of the ultraviolet absorber is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass.

[0096] The amount of ultraviolet absorber in composition XA is preferably 0.001% to 10% by mass, more preferably 0.01% to 5% by mass, and even more preferably 0.01% to 3% by mass, relative to the total amount of thiourethane resin in composition XA.

[0097] The total content of thiourethane resin and ultraviolet absorber in composition XA is preferably 80% to 100% by mass, and more preferably 90% to 100% by mass, relative to the total amount of composition XA.

[0098] The polythiol composition used as the target product in Embodiment A may contain components other than the polythiol compound as impurities. For example, the manufactured polythiol composition may contain (i.e., be mixed with) ultraviolet absorbers derived from the raw materials. However, when manufacturing a polythiol composition as a raw material for thiourethane resin for optical components (e.g., lenses), from the viewpoint of the optical properties of the optical component (e.g., the hue of the lens), the amount of ultraviolet absorber in the manufactured polythiol composition is preferably 4% by mass or less, more preferably 1% by mass or less, even more preferably less than 0.1% by mass, and even more preferably 0.05% by mass or less, based on the total amount of the polythiol composition.

[0099] Furthermore, as a raw material for thiourethane resin for optical components (e.g., lenses), a blend of the polythiol composition used as the target product in Embodiment A (for example, a polythiol composition with a high content of ultraviolet absorbers) and a polythiol composition produced by the method described in the publicly available literature (for example, Japanese Patent Publication No. 63-46213, Japanese Patent Publication No. 2-270859, Japanese Patent Publication No. 7-252207, Japanese Patent Publication No. 60-199016, Japanese Patent Publication No. 60-217229, International Publication No. 2007 / 052329, International Publication No. 2008 / 047626, etc.) (for example, a polythiol composition that substantially does not contain ultraviolet absorbers) can also be used.

[0100] [Method for producing polymerizable compositions] The method for producing the polymerizable composition disclosed herein is: A step of manufacturing a thiourethane resin raw material by the method for manufacturing a thiourethane resin raw material described above in this disclosure, A step of obtaining a polymerizable composition by using at least a portion of the thiourethane resin raw materials as at least a portion of the raw materials, Includes. The method for producing the polymerizable composition of this disclosure may include other steps as necessary.

[0101] In the method for producing the polymerizable composition disclosed herein, In the process of manufacturing thiourethane resin raw materials, a composition X containing thiourethane resin and foreign matter (for example, thiourethane resin and foreign matter in grinding powder of a molded body containing thiourethane resin and foreign matter) is used as a starting material to manufacture thiourethane resin raw materials, In the process of obtaining a polymerizable composition, at least a portion of the thiourethane resin raw materials produced above is used as at least a portion of the raw materials to produce the polymerizable composition. The resulting polymerizable composition can be used again in the production of thiourethane resin. In this way, the method for producing the polymerizable composition of the present disclosure enables the effective utilization (i.e., recycling) of materials (i.e., thiourethane resin and its raw materials).

[0102] Furthermore, as described above, the method for producing the thiourethane resin raw material of this disclosure yields a polythiol composition with a higher purity of the polythiol component as the main component compared to known methods (for example, a method for obtaining a polythiol composition by reacting a thiourethane resin with sodium hydroxide). Since the method for producing a polymerizable composition according to the present disclosure uses such a polythiol composition, a polymerizable composition obtained by the method for producing a polymerizable composition according to the present disclosure can be used to produce a resin with excellent properties [for example, optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.]. Therefore, the polymerizable composition obtained by the method for producing the polymerizable composition of this disclosure is particularly suitable as a composition for producing thiourethane resins for optical materials.

[0103] Furthermore, as described above, the method for producing the thiourethane resin raw material of this disclosure yields a polythiol composition with a higher purity of the polythiol component as the main component compared to known methods (for example, a method for obtaining a polythiol composition by reacting a thiourethane resin with sodium hydroxide). Since the method for producing a polymerizable composition according to the present disclosure uses such a polythiol composition, a polymerizable composition obtained by the method for producing a polymerizable composition according to the present disclosure can be used to produce a resin with excellent properties [for example, optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.]. Therefore, the polymerizable composition obtained by the method for producing the polymerizable composition of this disclosure is particularly suitable as a composition for producing thiourethane resins for optical materials.

[0104] <Process for manufacturing thiourethane resin raw materials> For the process of manufacturing the thiourethane resin raw material, the method for manufacturing the thiourethane resin raw material described above can be appropriately referenced.

[0105] <Steps to obtain a polymerizable composition> In the process of obtaining a polymerizable composition, at least a portion of the thiourethane resin raw materials obtained in the process of manufacturing thiourethane resin raw materials is used as at least a portion of the raw materials to obtain a polymerizable composition.

[0106] In the process of obtaining a polymerizable composition, at least a portion of the thiourethane resin raw material obtained in the process of manufacturing the thiourethane resin raw material is used, but if necessary, at least a portion of the above may be mixed with other components.

[0107] Other components include thiourethane resin raw materials other than those obtained in the process of manufacturing thiourethane resin raw materials (i.e., recycled thiourethane resin raw materials) (for example, new thiourethane resin raw materials).

[0108] The polymerizable composition preferably contains a polythiol composition and a polyisocyanate compound as monomers. In this case, it is preferable that the polythiol composition includes a recycled polythiol composition.

[0109] Other components may include polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion enhancers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and the like.

[0110] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids. As an internal release agent, an acidic phosphate ester can be used. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more types. Examples of resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, olefin compounds including (meth)acrylate compounds, etc. Here, (meth)acrylate compounds mean at least one of acrylate compounds and methacrylate compounds. Examples of UV absorbers include triazine-based UV absorbers and benzotriazole-based UV absorbers.

[0111] <When Embodiment A applies> In the method for producing the polymerizable composition of this disclosure, Embodiment A described above may be applied to the step of producing the thiourethane resin raw material. In other words, the step of producing the thiourethane resin raw material may be the step of producing the polythiol composition by the method for producing the polythiol composition according to Embodiment A described above. When Embodiment A is applied, the step of obtaining the polymerizable composition may involve producing a polymerizable composition containing a polythiol composition produced by the method for producing a polythiol composition according to Embodiment A described above, and a polyisocyanate compound. The preferred embodiment of the polyisocyanate compound is the same as the preferred embodiment of the "isocyanate compound as a raw material for thiourethane resin" described in the section on "Method for producing a raw material for thiourethane resin". When Embodiment A is applied, the mixing ratio of the polythiol composition and the polyisocyanate compound is not particularly limited. The molar ratio (mercapto group / isocyanate group) of the mercapto group of the polythiol compound and the isocyanate group of the polyisocyanate compound in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3. When the mixing ratio is within the above range, it tends to be possible to satisfy various properties such as refractive index and heat resistance required for plastic lenses, etc., in a well-balanced manner. When Embodiment A is applied, 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, based on the total amount of polymerizable composition produced. In the step of obtaining a polymerizable composition when Embodiment A is applied, at least the polythiol composition and the polyisocyanate compound are mixed, but if necessary, the polythiol composition and the polyisocyanate compound may be mixed with other components. Furthermore, in the process of obtaining a polymerizable composition, at least the polythiol composition and the polyisocyanate compound may be mixed, and then other components may be added to the mixture. Other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion enhancers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and the like.

[0112] [Method of manufacturing resin] The method for manufacturing the resin disclosed herein is: A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a resin by curing the above polymerizable composition, Includes. The resin manufacturing method of this disclosure may include other steps as necessary. The resin manufacturing method of this disclosure provides the same effects as the method for manufacturing the polymerizable composition of this disclosure described above.

[0113] The resin produced by the resin manufacturing method of this disclosure and the resin of this disclosure described later are both thiourethane resins, but in order to distinguish them from thiourethane resin, which is one of the starting materials for thiourethane resin raw materials, they are simply referred to as "resin" in this disclosure.

[0114] In the process of obtaining the resin, the polymerizable composition is cured to obtain the resin. The polymerizable composition described above can be cured by polymerizing the monomers in the polymerizable composition (for example, the polythiol composition and the polyisocyanate compound; the same applies hereinafter). As a pretreatment for polymerization, the polymerizable composition may be subjected to treatments such as filtration and degassing. The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the above polymerizable composition are set appropriately, taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, and, if a mold described later is used, the properties of the mold. Examples of polymerization temperatures include -50°C to 150°C and 10°C to 150°C. Polymerization times can range from 1 hour to 200 hours, 1 hour to 80 hours, and so on.

[0115] The process of obtaining the resin may involve subjecting the polymer obtained by monomer polymerization to a treatment such as annealing. The annealing temperature is preferably 50°C to 150°C, more preferably 90°C to 140°C, and even more preferably 100°C to 130°C.

[0116] [Method for manufacturing molded products] The method for manufacturing a molded article according to this disclosure is a method for manufacturing a molded article containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing a molded article according to this disclosure may include other steps as necessary. The method for producing a molded article according to this disclosure provides the same effects as the method for producing a polymerizable composition according to this disclosure described above.

[0117] In the process of obtaining a molded article containing resin, the polymerizable composition is cured to obtain a molded article containing resin. Preferred conditions for curing the above polymerizable composition, that is, for polymerization of monomers in the above polymerizable composition, can be appropriately referred to in the section on "Method for Producing Resins".

[0118] One example of polymerization in this process is casting polymerization. In casting polymerization, the polymerizable composition is first injected between molds held together by gaskets or tape. Degassing and filtration may be performed as needed during this process. Next, the monomers in the polymerizable composition injected between the molding molds are polymerized, thereby curing the composition between the molding molds to obtain a cured product. Then, the cured product is removed from the molding molds to obtain a molded body containing resin. The polymerization of the above monomers may be carried out by heating the polymerizable composition. This heating can be performed, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, or the like.

[0119] [Manufacturing methods for optical materials, manufacturing methods for lenses] The method for manufacturing an optical material (e.g., a lens) according to this disclosure is a method for manufacturing an optical material (e.g., a lens) comprising a molded body containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing the optical material (e.g., a lens; the same applies hereinafter) described herein may include other steps as necessary. The method for producing optical materials according to this disclosure provides the same effects as the method for producing polymerizable compositions according to this disclosure described above.

[0120] The method for manufacturing optical materials of this disclosure is an application of the method for manufacturing molded articles of this disclosure. For example, in the method for manufacturing a molded article according to the present disclosure, by appropriately selecting the shape of the molding mold used in the aforementioned casting polymerization, a molded article applicable to optical materials (e.g., lenses) can be obtained.

[0121] Examples of optical materials include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses), light-emitting diodes (LEDs), and the like.

[0122] The method for manufacturing an optical material (e.g., a lens) according to this disclosure may include a step of forming a coating layer on one or both sides of a molded body containing a resin.

[0123] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers may be formed individually or as a multilayer structure of multiple coating layers. When coating layers are formed on both sides, the same process is applied to each surface. One coating layer may be formed, or different coating layers may be formed.

[0124] The components of the coating layer can be selected as appropriate depending on the purpose. The components of the coating layer include, for example, resins (e.g., urethane resin, epoxy resin, polyester resin, melamine resin, polyvinyl acetal resin, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, and the like.

[0125] For eyeglass lenses and coating layers, you can refer to the descriptions in publicly available documents such as Japanese Patent Publication No. 2002-194083 and International Publication No. 2017 / 047745 as appropriate.

[0126] [Polymerizable composition] The polymerizable composition of this disclosure contains at least a portion of the thiourethane resin raw material obtained by the method for producing the thiourethane resin raw material of this disclosure described above. The polymerizable composition of this disclosure can be produced by the method for producing the polymerizable composition of this disclosure described above. The polymerizable composition of this disclosure provides the same effects as the method for producing the polymerizable composition of this disclosure described above. Preferred embodiments of the polymerizable composition of this disclosure can be appropriately referenced to the method for producing the polymerizable composition of this disclosure described above.

[0127] [Resins, molded products, optical materials (e.g., lenses)] The resin of this disclosure is a cured product of the polymerizable composition of this disclosure described above. The molded article of this disclosure is a molded article comprising the resin of this disclosure as described above. The optical material (e.g., lens) of this disclosure is an optical material (e.g., lens) comprising the resin of this disclosure as described above. The resins, molded articles, and optical materials (e.g., lenses) of the present disclosure provide effects similar to those described above for the methods of producing polymerizable compositions of the present disclosure.

[0128] The resins of the present disclosure, the molded articles of the present disclosure, and the optical materials (e.g., lenses) of the present disclosure can be manufactured by the methods described above for manufacturing the resins of the present disclosure, the molded articles of the present disclosure, and the optical materials (e.g., lenses), respectively. Preferred embodiments of the resins of the Disclosure, the molded articles of the Disclosure, and the optical materials (e.g., lenses) of the Disclosure can be referenced to preferred embodiments of the methods for manufacturing the resins of the Disclosure, the molded articles of the Disclosure, and the optical materials (e.g., lenses) of the Disclosure, respectively.

[0129] <Preferred performance of resin or molded article> The glass transition temperature Tg of the resin (or molded article) of this disclosure is preferably 80°C or higher, and more preferably 85°C or higher, from the viewpoint of heat resistance. The above glass transition temperature Tg may be 105°C or lower, or 100°C or lower.

[0130] The refractive index (nd) of the resin (or molded article) of this disclosure is preferably 1.550 or higher, more preferably 1.600 or higher, and even more preferably 1.650 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the refractive index (nd) mentioned above, but a possible upper limit is 1.700.

[0131] The Abbe number of the resin (or molded article) of this disclosure is preferably 28 or higher, and more preferably 30 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the Abbe number mentioned above, but the upper limit is, for example, 40, preferably 35. be.

[0132] The specific gravity d of the resin (or molded article) of this disclosure is preferably 1.00 or higher from the viewpoint of application to optical materials. There is no particular upper limit to the specific gravity d mentioned above, but the upper limit is, for example, 1.50, and preferably 1.40. [Examples]

[0133] The following are examples of the embodiments of this disclosure, but this disclosure is not limited to the following embodiments. Unless otherwise specified, "%" below refers to mass percentage, and "room temperature" refers to 25°C.

[0134] Hereinafter, the purity (mass%) of polythiol component T2 in the polythiol composition refers to the content (mass%) of polythiol component T2 relative to the total amount of the polythiol composition. More specifically, it refers to the content (mass%) of polythiol component T2 relative to the total amount of the polythiol composition, measured by high-performance liquid chromatography under the following conditions and determined using an internal standard.

[0135] (Conditions for high-performance liquid chromatography) Column: YMC-Pack ODS-A (particle size S: 5 μm, pore size: 12 nm, color (Shape: Φ6mm x 150mm) Mobile phase: Acetonitrile / 0.01 mol potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Column temperature: 40℃ Flow rate: 1.0ml / min Detector: UV detector, wavelength 230nm Preparation of the measurement solution: Dissolve and mix 160 mg of the sample in 10 ml of acetonitrile. Injection volume: 2μL

[0136] [Reference production example 1] (Manufacturing of molded article 1 containing thiourethane resin) In a flask equipped with a stirring device, Dimethyltin dichloride (trade name: Nestin P, manufactured by Honjo Chemical Co., Ltd.), which is a polymerization catalyst (100 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition below), Zelec-UN (manufactured by Stepan; acidic phosphate ester) (1000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition below), m-xylylene diisocyanate (XDI) (50.8 parts by mass), which is a polyisocyanate compound, A polythiol composition (hereinafter referred to as "polythiol composition TA") (49.2 parts by mass) mainly comprising 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., polythiol component T2) (hereinafter referred to as "polythiol composition TA"), Adding this, the mixture was stirred and mixed at room temperature for 1 hour to obtain a polymerizable composition, which is a clear, homogeneous solution. Here, the purity of the polythiol component T2 in the polythiol composition TA (i.e., the content of the polythiol component T2 relative to the total amount of the polythiol composition TA) is 85.5%.

[0137] Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then thoroughly degassed under reduced pressure of 600 Pa until no more foaming was observed. This degassed polymerizable composition was then poured between a pair of glass molds fixed with tape, and then... The pair of glass molds were then placed in an oven, and the oven temperature was set to 25°C. Next, the oven temperature was increased from 25°C to 120°C over 24 hours. Through this process, the monomers (polyisocyanate compound and polythiol composition TA) in the degassed polymerizable composition were polymerized, and a molded article containing thiourethane resin R1 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven, and then the molded bodies were removed from the pair of glass molds to obtain the molded bodies.

[0138] (Manufacturing of thiourethane resin powder R1) Lenses were manufactured by machining the molded body obtained above. The resulting machining dust was collected and passed through a sieve with a nominal mesh size of 2 mm as specified in JIS Z-8801-1:2019 to obtain thiourethane resin powder R1 (i.e., powder containing thiourethane resin R1) that passed through the sieve.

[0139] [Example 1] -Reaction Process- Composition X1 was obtained by placing 40g of thiourethane resin powder R1 obtained in Reference Manufacturing Example 1 and 4g of commercially available CR-39 resin (ADC (allyl diglycol carbonate) resin) cutting powder as a foreign substance into a 300mL flask equipped with a condenser. To this composition X1, monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (15.8 g; 0.26 mol) and toluene (144 g) were added, and the mixture was heated and stirred at 100°C for 5 hours to obtain a reaction mixture containing a polythiol composition (hereinafter referred to as "polythiol composition TB"), which is a raw material for thiourethane resin (end of reaction step).

[0140] -Separation process (Separation method B)- The reaction mixture obtained in the reaction step was subjected to a separation step according to separation method B described above, including extraction, to separate the polythiol composition from the reaction mixture. Details are described below. The reaction mixture obtained in the reaction step was cooled to room temperature, and then solid matter was removed by filtration to obtain a filtrate containing the polythiol composition. 20 g of 35% hydrochloric acid was added to the obtained filtrate, and after stirring, the mixture was separated. The obtained organic layer was washed twice with 100 mL of water. 22.0 g of 28% sodium methoxide methanol solution was added to the washed organic layer and stirred. 100 g of water was then added to extract the soluble components, and an aqueous extract was obtained. The obtained aqueous extract was washed twice with 50 g of toluene, then 30 g of 35% hydrochloric acid was added and stirred to obtain an aqueous liquid. The soluble components were extracted from the resulting aqueous liquid using 100 ml of toluene to obtain a toluene extract. This toluene extract was washed twice with 100g of water to obtain a toluene solution of the polythiol composition. Toluene was removed from the obtained toluene solution by distillation using a rotary evaporator. The resulting mixture was subjected to removal of low-boiling point components by vacuum pump and filtration using a 3-micron PTFE membrane filter in that order, thereby obtaining 11.4 g of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., polythiol component T2) (separation step).

[0141] The SH value of the obtained polythiol composition, and high-performance liquid chromatography The results of the purity analysis of the polythiol component T2 are shown in Table 1 below.

[0142] [Examples 2-11] The same procedure as in Example 1 was followed, except that the type and amount of foreign matter added to composition X1 prepared in the reaction step were changed as shown in Table 1 or Table 2. The SH value and the results of the purity analysis of the polythiol component T2 by high-performance liquid chromatography of the obtained polythiol composition are shown in Table 1 or Table 2 below.

[0143] The details of the types of foreign objects in Tables 1 and 2 are as follows: • CR-39… Cutting powder of ADC (allyl diglycol carbonate) resin • Polyurethane resin… Cutting powder from polyurethane resin molded products • Acrylic resin… Cutting powder from acrylic resin molded products • Polycarbonate resin… Cutting powder from molded polycarbonate resin products • Protective film… Cut pieces of commercially available polyethylene film used to protect the surface of molded resin products. • Machine oil… Kure 5-56 manufactured by Kure Industries Co., Ltd. • Bismuth (Bi) ... Granular Bi manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Hard coat material: A hard coat material obtained by machining commercially available hard-coated lenses. • Dimethyltin dichloride… Dimethyltin dichloride (product name: Nestin P, manufactured by Honjo Chemical Co., Ltd.) is a polymerization catalyst. ·Plast Blue… Dye. Plast Blue 8514 manufactured by Arimoto Chemical Industry Co., Ltd. • Zelec-UN… Zelec-UN (manufactured by Stepan; acidic phosphate ester), a release agent.

[0144] [Example 12] -Reaction Process- 40g of thiourethane resin powder R1 obtained in Reference Production Example 1 and 40g of distilled water (i.e., "water" as a foreign substance) were placed in a 300mL flask equipped with a condenser to obtain composition X1. To this composition X1, monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (15.8 g; 0.26 mol) and toluene (144 g) were added, and the mixture was heated and stirred in an oil bath at 100°C for 9 hours to obtain a reaction mixture containing a polythiol composition, which is a raw material for thiourethane resin (the above is the reaction step).

[0145] -Separation process (Separation method A)- The reaction mixture obtained in the reaction step was subjected to a separation step according to separation method A described above, including acid washing, to separate the polythiol composition from the reaction mixture. Details are described below. The reaction mixture obtained in the reaction step was cooled to room temperature, and then solid matter was removed by filtration to obtain a filtrate containing the polythiol composition. The obtained filtrate was mixed with 20 g of 35% hydrochloric acid, stirred, and then separated. After washing twice with 100 mL of water, a toluene solution of the polythiol composition was obtained. Toluene was removed from the obtained toluene solution by distillation using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling point components using a vacuum pump, followed by filtration using a 3-micron PTFE membrane filter, thereby obtaining 9.3 g of a polythiol composition mainly composed of polythiol component T2 (separation process).

[0146] The SH value and the purity analysis results of the polythiol component T2 in the obtained polythiol composition by high-performance liquid chromatography are shown in Table 2 below.

[0147] [Example 13] -Reaction Process- Composition X1 was obtained by placing 40g of thiourethane resin powder R1 obtained in Reference Production Example 1 and 40g of distilled water (i.e., "water" as a foreign substance) into a 300mL flask equipped with a condenser and a Dean Stark tube. To this composition X1, monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (15.8 g; 0.26 mol) and toluene (144 g) were added, and the mixture was heated and stirred for 5 hours while removing the water using an oil bath at 120°C to obtain a reaction mixture containing the polythiol composition (end of reaction steps).

[0148] -Separation process (Separation method A)- The reaction mixture obtained in the reaction step was subjected to a separation step according to separation method A, including acid washing, similar to that in Example 12, to separate the polythiol composition from the reaction mixture. The SH value and the purity analysis results of the polythiol component T2 in the obtained polythiol composition by high-performance liquid chromatography are shown in Table 2 below.

[0149] [Table 1]

[0150] [Table 2]

[0151] As shown in Tables 1 and 2, in all of Examples 1 to 13, a reaction step was performed in which a composition X1 containing a thiourethane resin and foreign matter was brought into contact with an amine compound, which is an active hydrogen compound. This reaction caused the thiourethane resin in composition X1 to react with the amine compound, thereby producing a polythiol composition TB, which is a raw material for thiourethane resin. Furthermore, in Examples 1 to 13, by performing a separation step on the reaction mixture obtained in the reaction step, it was possible to separate the polythiol composition TB, which had excellent purity of the polythiol component T2, from the reaction mixture.

[0152] [Example 101] (Manufacturing of molded articles containing thiourethane resin) A molded article containing thiourethane resin was obtained by performing the same procedure as in Reference Production Example 1, except that the polythiol composition TA (49.2 parts by mass) was replaced with the polythiol composition TB (49.2 parts by mass) obtained in Example 1. The resulting molded product had good transparency, was free of distortion, and had a good appearance. Performance tests were conducted on the molded bodies obtained as described above. The results are shown in Table 3.

[0153] The performance tests included optical properties (refractive index and Abbe number), heat resistance, and hue. Each test was conducted using the following testing method. • Refractive index (ne), Abbe number (νe): Using a Shimadzu KPR-30 Pulfrich refractometer, the refractive indices (ne, nF', nC') were measured at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line), respectively, and the refractive index (ne) and Abbe number (νe) were determined. ·Heat resistance: The glass transition temperature (Tg) was measured by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10°C / min) using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, and used as an index of heat resistance. ·Yellowness Index (YI): Using a spectrophotometer (CM-5 manufactured by Konica Minolta), the yellowness index (YI) was measured on a flat plate with a thickness of 2 mm, and used as an index of hue in the optical material.

[0154] [Examples 102 to 113] The same procedure as in Example 101 was carried out, except that the polythiol composition TB (49.2 parts by mass) obtained in Example 1 was changed to the polythiol composition TB obtained in the Examples shown in Table 3. The results are shown in Table 3. In Table 3, composition TA means the polythiol composition TA used in Reference Production Example 1, and Examples 1 to 13 each mean the polythiol composition TB obtained in Examples 1 to 13, respectively.

[0155] [Table 3]

[0156] As shown in Table 3, the molded articles of each Example produced using the polythiol composition TB of each Example (that is, the polythiol composition obtained by bringing the powdery composition X obtained by cutting the molded article of Reference Production Example 1 into contact with an amine compound) had performance comparable to that of the molded article of Reference Production Example 1.

[0157] [Example 201] In the above-mentioned Example 1, a polythiol composition as a raw material for polyurethane resin was produced using the filtrate generated by filtration in the separation step. In contrast, in Example 201 shown below, a polyamine compound as a raw material for polyurethane resin was produced using the filter residue (that is, the solid matter) generated by filtration in the separation step of Example 1. That is, in the reaction step of Example 1, the thiourethane resin in composition X1 is reacted with monoethanolamine (MEA) to decompose into a polythiol composition serving as a thiourethane resin raw material and a polyurea compound serving as a thiourethane resin raw material (amine addition decomposition), whereby a reaction mixture containing these thiourethane resin raw materials was obtained. By filtering the reaction mixture, a filtrate containing the polythiol composition serving as a thiourethane resin raw material was obtained (Example 1), and a filtrate (i.e., a solid material) containing the polyurea compound serving as a thiourethane resin raw material was obtained (Example 201). Furthermore, by reacting this polyurea compound with an amine compound, a polyamine compound serving as a thiourethane resin raw material was obtained.

[0158] Hereinafter, the details of Example 201 will be described.

[0159] (First Step) In the separation step of Example 1, the solid material (i.e., the filtrate) generated by filtration was left to stand at room temperature and dried, whereby 40.3 g of a mixture (hereinafter also referred to as polyurea-containing mixture P1) containing, as a main component, a urea product (polyurea compound) of m-xylylenediamine (XDA) and monoethanolamine (MEA) was obtained.

[0160] Here, XDA forming the urea product is derived from m-xylylene diisocyanate (XDI) in the polythiol composition TA which is a raw material of the thiourethane resin powder R1 used as a raw material. Monoethanolamine (MEA) forming the urea product is an active hydrogen compound used for decomposing the thiourethane resin powder R1 (for details, refer to the reaction step of Example 1).

[0161] (Second Step) In a 100 mL flask fitted with a condenser, 31.0 g of the polyurea-containing mixture P1 obtained in the first step was weighed, and 31.0 g (0.30 mol) of the amine compound diethylenetriamine (DET) (manufactured by Fujifilm Wako Pure Chemical Industries) was added, and the mixture was heated at 145°C for 3 hours. Subsequently, 16.0 g (0.40 mol) of sodium hydroxide (NaOH) was added. The mixture was added and heated at 145°C for 3 hours to obtain the second reaction mixture.

[0162] The second reaction mixture was diluted with methanol, and the diluted solution was filtered under reduced pressure to remove the by-product sodium carbonate. The obtained filtrate was concentrated under reduced pressure to obtain a mixed amine mass. The resulting mixed amine mass was sampled, and the concentration of XDA in the second reaction mixture (hereinafter also referred to as GC concentration) was determined by gas chromatographic analysis. The results are shown in Table 4. Furthermore, assuming that the entire amount of the polyurea-containing mixture obtained in the first step was the urea form (polyurea compound) of XDA and MEA, the production rate of XDA (hereinafter also referred to as GC yield) was determined based on the GC concentration, and the results are shown in Table 4. Here, XDA is the target product, a polyamine compound used as a raw material for thiourethane resin.

[0163] [Examples 202-211] The procedure was the same as in Example 201, except that the solid material (i.e., filtered material) produced in the separation step of Example 1 was replaced with the solid material (i.e., filtered material) produced in the separation steps of Examples 2 to 11. The GC concentration and GC yield of XDA in the second reaction mixture are shown in Tables 4 and 5.

[0164] [Table 4]

[0165] [Table 5]

[0166] As shown in Tables 4 and 5, in Examples 201 to 211, a reaction step was performed in which a composition X1 containing a thiourethane resin and foreign matter was brought into contact with an amine compound (monoethanolamine (MEA)), which is an active hydrogen compound. This reaction caused the thiourethane resin in composition X1 to react with the amine compound (MEA) to obtain a polyurea compound, which is a raw material for thiourethane resin (end of first step). This polyurea compound was then reacted with an amine compound (DET) to obtain a polyamine compound (XDA), which is a raw material for thiourethane resin (end of second step).

[0167] Furthermore, by reacting the above polyamine compound (XDA) with phosgene, a polyisocyanate compound (XDI; xylylene diisocyanate), which is a more direct raw material for thiourethane resin, can be obtained.

[0168] Examples and Comparative Examples of Embodiment A The following are examples and comparative examples of Embodiment A (i.e., an embodiment limited to the combination in which the foreign substance is an ultraviolet absorber, the active hydrogen compound is an amine compound, and the thiourethane resin raw material is a polythiol composition in the method for producing the thiourethane resin raw material of the present disclosure).

[0169] Hereafter, "UV absorber" refers to an ultraviolet light absorber. Hereinafter, the purity (mass%) of polythiol component T1 in the polythiol composition refers to the content (mass%) of polythiol component T1 relative to the total amount of the polythiol composition. More specifically, it refers to the content (mass%) of polythiol component T1 relative to the total amount of the polythiol composition, measured by high-performance liquid chromatography under the following conditions and determined using an internal standard. Similarly, the content (mass%) of the UV absorber in the polythiol composition means the content (mass%) of the UV absorber relative to the total amount of the polythiol composition. More specifically, it means the content (mass%) of the UV absorber relative to the total amount of the polythiol composition, which is measured by high-performance liquid chromatography under the following conditions and determined using an internal standard substance.

[0170] (Conditions for high-performance liquid chromatography) Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm) Mobile phase: measurement is performed with changing the concentration from acetonitrile / 0.01M-potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) to acetonitrile / 0.01M-potassium dihydrogen phosphate aqueous solution = 80 / 20 (vol / vol). Column temperature: 40°C Flow rate: 1.0mL / min Detector: UV detector, wavelength 230nm Preparation of measurement solution: 150 mg of an internal standard substance (1,2,4-trimethylbenzene) and 160 mg of a sample are dissolved and mixed in 5 mL of acetonitrile. Injection volume: 1μL

[0171] [Reference Production Example 301] (Production of molded article 301 containing thiourethane resin and a UV absorber) Into a flask equipped with a stirrer,[[""END]] dibutyltin dichloride serving as a polymerization catalyst (100 mass ppm relative to the total amount of the polyisocyanate compound described below and the polythiol composition described below), Tinuvin 329 serving as a UV absorber (manufactured by BASF Japan Ltd., 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol) (1.5 parts by mass), Zelec-UN serving as a release agent (manufactured by Stepan; acidic phosphate ester) (1000 mass ppm relative to the total amount of the polyisocyanate compound described below and the polythiol composition described below), m-xylylene diisocyanate (XDI) serving as a polyisocyanate compound (52 parts by mass), A polythiol composition TC (48 parts by mass) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1), The mixture was added and stirred at room temperature (25°C) for 1 hour to obtain a polymerizable composition, which is a clear, homogeneous solution. Here, the purity of the polythiol component T1 in the polythiol composition TC (i.e., the content of polythiol component T1 relative to the total amount of the polythiol composition TC) is 92.2%. Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then degassed thoroughly under reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds fixed with tape, and then the pair of glass molds was placed in an oven with the oven temperature set to 10°C. Next, the oven temperature was raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded article containing thiourethane resin and UV absorber (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. Then, the molded body was removed from the pair of glass molds to obtain a molded body 301 containing thiourethane resin and a UV absorber.

[0172] (Manufacturing of powdered composition X301) A lens was manufactured by machining the molded body 301 obtained above. The machining dust generated at this time was collected and passed through a sieve with a nominal mesh size of 1 mm as specified in JIS Z-8801-1:2019. The powder that passed through the sieve was recovered to obtain a powdered composition X301 as composition XA, which contains thiourethane resin and a UV absorber.

[0173] [Reference production example 302] (Manufacturing of molded article 302 containing thiourethane resin and UV absorber) Molded article 302 containing thiourethane resin and UV absorber was obtained by the same procedure as in Reference Manufacturing Example 301, except that the amount of Tinuvin 329, a UV absorber, was changed from 1.5 parts by mass to 0.05 parts by mass.

[0174] (Manufacturing of powdered composition X302) A lens was manufactured by machining the molded body 302 obtained above. The machining dust generated at this time was collected and passed through a sieve with a nominal mesh size of 1 mm as specified in JIS Z-8801-1:2019. The powder that passed through the sieve was recovered to obtain a powdered composition X302 as composition XA, which contains thiourethane resin and a UV absorber.

[0175] [Example 301] -Reaction Process- The powdered composition X301 (100g) [Composition X] obtained in Reference Production Example 301 was entirely placed into a 500mL flask equipped with a condenser. Monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (40.5g; 0.663mol) and toluene (193g) were added thereto, and the mixture was heated and stirred at 90°C for 7 hours to obtain a reaction mixture containing the polythiol composition (end of reaction process).

[0176] -Separation process (Separation method B)- The reaction mixture obtained in the reaction step was subjected to a separation step according to separation method B, which includes extraction, to separate the polythiol composition from the reaction mixture. Details are described below. The reaction mixture obtained in the reaction step was cooled to 60°C, and then solid matter was removed by filtration. 70.5 g of 31% sodium hydroxide aqueous solution was added to the obtained filtrate and stirred. 75 g of water was added to extract the soluble components, and the resulting aqueous extract was washed with 50 g of toluene. Then, 75 g of 35% hydrochloric acid was added and stirred. From the resulting aqueous liquid, the soluble components were extracted with 120 g of toluene to obtain a toluene extract. This toluene extract was washed with 80 g of water, then with 80 g of 0.1% aqueous ammonia, and then washed twice with 80 g of water to obtain a toluene solution of the polythiol composition. Toluene was removed from the obtained toluene solution by distillation using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling point components using a vacuum pump, followed by filtration using a 1-micron PTFE membrane filter, thereby obtaining 33.38 g of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) (separation step).

[0177] (measurement) The following measurements were performed on the obtained polythiol composition. The results are shown in Table 6.

[0178] -Purity (mass%) of polythiol component T1 and UV absorber content (mass%)- High-performance liquid chromatography under the aforementioned conditions, The purity (mass%) of the polythiol component T1 in the polythiol composition, The content (mass%) of UV absorbers in the polythiol composition, Each of these was measured.

[0179] -SH value (mmol / g)- Using a potentiometric automatic titrator manufactured by Kyoto Electronics Manufacturing Co., Ltd., the SH value (mmol / g) (i.e., the number of millimoles of thiol groups per gram of polythiol composition; the same applies hereinafter) of the polythiol composition was measured using a 0.05 mol / L iodine solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0180] - UV absorber content (mass%) in the polythiol composition - Based on the amount of raw materials used to obtain molded body 301, the mass of the UV absorber in the starting material (powdered composition X301 (100g)) (hereinafter referred to as mass M1) was determined. Based on the amount of polythiol composition obtained in the separation process (33.38 g) and the UV absorber content (mass%), the mass of the UV absorber in the polythiol composition (hereinafter referred to as mass M2) was determined. Based on mass M1 and mass M2, the content (mass%) of the UV absorber in the polythiol composition was determined by the following formula. Content (mass%) of UV absorber in polythiol composition =(mass M2 / mass M1)×100

[0181] -Refractive Index- For the polythiol composition, the refractive index was measured using a refractometer RA-600 manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0182] -YI (Yellowness Index), L * , a * , and b * - For the polythiol composition, YI (Yellowness Index) and L in the CIE1976 (L * , a * , b * ) color system were measured using a spectrophotometer (CM-5 manufactured by Konica Minolta, Inc.) under the condition of a cell length of 1 cm. * , a * , and b * , respectively.

[0183] -Appearance- The appearance of the obtained polythiol composition was visually observed.

[0184] [Example 302] -Reaction Step- The entire amount of the powdery composition X302 (200 g) [composition XA] obtained in Reference Production Example 302 was charged into a 1000 mL flask equipped with a cooling tube. Monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Corporation) (81.0 g; 1.326 mol) and 386 g of toluene were added thereto, and the mixture was heated and stirred at 90°C for 5 hours to obtain a reaction mixture containing a polythiol composition (the above is the reaction step).

[0185] -Separation Step (Separation Mode B)- The polythiol composition was separated from the reaction mixture by performing a separation step according to Separation Mode B including extraction and the like on the reaction mixture obtained in the reaction step. Details will be described below. The reaction mixture obtained in the reaction step was cooled to 60°C, and then solid matter was removed by filtration. 143 g of 31% sodium hydroxide aqueous solution was added to the obtained filtrate and stirred. 150 g of water was added to extract the soluble components, and the resulting aqueous extract was washed with 50 g of toluene. Then, 150 g of 35% hydrochloric acid was added and stirred. From the resulting aqueous liquid, the soluble components were extracted with 200 g of toluene to obtain a toluene extract. This toluene extract was washed with 160 g of water, then with 160 g of 0.1% aqueous ammonia, and then washed twice with 160 g of water to obtain a toluene solution of the polythiol composition. The obtained toluene solution was subjected to distillation to remove toluene using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling point components using a vacuum pump, followed by filtration using a 1-micron PTFE membrane filter, thereby obtaining 74.15 g of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) (separation steps).

[0186] The obtained polythiol composition was subjected to the same measurements as in Example 301. The results are shown in Table 6.

[0187] [Example 303] The procedure was the same as in Example 302, except that an additional step was added between the step of obtaining the toluene extract and the step of washing the toluene extract with 160 g of water in the separation process, to remove toluene-insoluble matter from the toluene extract by filtration. The results are shown in Table 6. In this Example 303, 80.02 g of a polythiol composition mainly composed of polythiol component T1 was obtained.

[0188] [Example 304] The procedure was the same as in Example 302, except that the step of adding monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (81.0 g; 1.326 mol) and toluene (386 g) in the reaction step was changed to adding monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (94.5 g; 1.547 mol) and toluene (roughly speaking, the amount of monoethanolamine and toluene added was changed). The results are shown in Table 6. In this Example 304, 82.18 g of a polythiol composition mainly composed of polythiol component T1 was obtained.

[0189] [Example 305] The same procedure as in Example 301 was followed, except that the separation step according to separation mode B, which includes extraction, was changed to the following separation step according to separation mode A, which includes acid washing. The results are shown in Table 6.

[0190] -Separation process (Example 305) (Separation method A)- The reaction mixture obtained in the reaction step was subjected to a separation step according to separation method A, which included acid washing, to separate the polythiol composition from the reaction mixture. Details are described below. The reaction mixture obtained in the reaction step was cooled to 60°C, and then solid matter was removed by filtration. The resulting filtrate was washed with 23 g of 35% hydrochloric acid to remove excess amine compounds (i.e., monoethanolamine) (acid washing). The filtrate after acid washing was washed with 80 g of water, then with 80 g of 0.1% aqueous ammonia, and then washed twice with 80 g of water to obtain a toluene solution of the polythiol composition. Toluene was removed from the obtained toluene solution by distillation using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling point components using a vacuum pump, followed by filtration using a 1-micron PTFE membrane filter, thereby obtaining 43.20 g of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) (separation step).

[0191] [Example 306] The same procedure as in Example 302 was followed, except that the separation step according to separation mode B, which includes extraction, was changed to the following separation step according to separation mode A, which includes acid washing. The results are shown in Table 6.

[0192] -Separation process (Example 306) (Separation method A)- The reaction mixture obtained in the reaction step was subjected to a separation step according to separation method A, which included acid washing, to separate the polythiol composition from the reaction mixture. Details are described below. The reaction mixture obtained in the reaction step was cooled to 60°C, and then solid matter was removed by filtration. The resulting filtrate was washed with 46 g of 35% hydrochloric acid to remove excess amine compounds (i.e., monoethanolamine) (acid washing). The filtrate after acid washing was washed with 160 g of water, then with 160 g of 0.1% aqueous ammonia, and then washed twice with 160 g of water to obtain a toluene solution of the polythiol composition. Toluene was removed from the obtained toluene solution by distillation using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling point components using a vacuum pump, followed by filtration using a 1-micron PTFE membrane filter, thereby obtaining 88.58 g of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) (separation step).

[0193] [Table 6]

[0194] As shown in Table 6, in all of Examples 301 to 306, a reaction step was performed in which composition XA, which contains a thiourethane resin and an ultraviolet absorber, was brought into contact with an amine compound, thereby reacting the thiourethane resin in composition XA with the amine compound and producing a polythiol composition. Furthermore, in these Examples 301 to 306, by performing a separation step on the reaction mixture obtained in the reaction step, it was possible to separate a polythiol composition with excellent purity of polythiol component T1 from the reaction mixture. In particular, in Examples 301 to 304, where a separation process by separation method B, including extraction, was carried out, it was possible to reduce the amount of UV absorber in the polythiol composition and the amount of UV absorber mixed into the polythiol composition (i.e., the ratio of the mass of UV absorber in the polythiol composition to the mass of UV absorber in the starting material).

[0195] [Example 401] (Manufacturing of molded articles containing thiourethane resin) A molded article containing thiourethane resin was obtained by performing the same procedure as in Reference Production Example 301, except that the polythiol composition TC (48 parts by mass) was replaced with the polythiol composition obtained in Example 302 (48 parts by mass). The resulting molded product had good transparency, was free of distortion, and had a good appearance.

[0196] Performance tests were conducted on the molded bodies obtained as described above. The results are shown in Table 7. The performance tests included optical properties (refractive index and Abbe number), heat resistance, and hue. Each test was conducted using the following test methods. • Refractive index (ne), Abbe number (νe): Using a Shimadzu KPR-30 Pulfrich refractometer, the refractive indices (ne, nF', nC') were measured at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line), respectively, and the refractive index (ne) and Abbe number (νe) were determined. ·Heat resistance: Using a Shimadzu TMA-60 thermomechanical analyzer, the glass transition temperature (Tg) was measured by the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10℃ / min) and used as an indicator of heat resistance. ·Yellowness (YI): Using a spectrophotometer (Konica Minolta CM-5), the yellowness (YI) was measured on a 9mm thick flat plate and used as an index of hue in optical materials.

[0197] Similar performance tests were also conducted on the molded articles in the aforementioned reference manufacturing example 301. The results are shown in Table 7.

[0198] [Examples 402-403] The procedure was the same as in Example 401, except that the polythiol composition (48 parts by mass) obtained in Example 302 was replaced with the polythiol composition shown in Table 7. The results are shown in Table 7.

[0199] In Table 7, Composition TC refers to the polythiol composition TC used in Reference Production Example 301, and Examples 302, 304, and 306 refer to the polythiol compositions obtained in Examples 302, 304, and 306, respectively, in Table 6.

[0200] [Table 7]

[0201] As shown in Table 7, the molded articles of each example produced using the polythiol composition of each example (i.e., the polythiol composition obtained by contacting the powdered composition X302 obtained by machining the molded article of Reference Production Example 302 with an amine compound) exhibited performance comparable to that of the molded article of Reference Production Example 301, with a particular improvement in heat resistance being confirmed. In particular, the molded articles of Examples 401 and 402, produced using the polythiol compositions obtained in Examples 302 and 304 (both using separation mode B), showed reduced YI and superior hue compared to the molded article of Example 403, produced using the polythiol composition obtained in Example 306 (using separation mode A).

[0202] The disclosures of Japanese Patent Application No. 2020-192462, filed on 19 November 2020, and Japanese Patent Application No. 2021-125570, filed on 30 July 2021, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. The process includes a reaction step of contacting a composition X containing a thiourethane resin and foreign matter with an activated hydrogen compound to react the thiourethane resin in the composition X with the activated hydrogen compound to produce a thiourethane resin raw material. The reaction step involves contacting the composition X with the active hydrogen compound in the presence of a reaction solvent to react the thiourethane resin in the composition X with the active hydrogen compound to obtain a reaction mixture containing the thiourethane resin raw material. Furthermore, the process includes a separation step of separating the thiourethane resin raw material from the reaction mixture containing the thiourethane resin raw material. The thiourethane resin raw material comprises a polythiol composition, The separation step is, By filtering the reaction mixture containing the thiourethane resin raw material, a filtrate containing the polythiol composition is obtained. A filtrate containing the polythiol composition is to be mixed with a base containing an alkali metal, and then water is added to perform extraction, thereby obtaining an aqueous extract containing the alkali metal salt of the polythiol composition. An aqueous liquid containing the polythiol composition is obtained by adding an acid to an aqueous extract containing an alkali metal salt of the polythiol composition. An extract containing the polythiol composition is obtained by adding an extraction solvent to an aqueous liquid containing the polythiol composition and performing extraction. This includes separating the polythiol composition from an extract containing the polythiol composition. A method for producing thiourethane resin raw materials.

2. The method for producing a thiourethane resin raw material according to claim 1, wherein the foreign substance comprises at least one selected from the group consisting of resins other than thiourethane resin, polymerization catalysts, metals, ultraviolet absorbers, internal mold release agents, plasticizers, dyes, machine oils, and water.

3. A method for producing a thiourethane resin raw material according to claim 1 or claim 2, wherein the thiourethane resin raw material comprises at least one selected from the group consisting of a polythiol composition, a polyurea compound, a polycarbamate compound, a polyamine compound, a polyisocyanate compound, and a polyurethane compound.

4. A method for producing a thiourethane resin raw material according to any one of claims 1 to 3, wherein the active hydrogen compound is at least one selected from the group consisting of amine compounds and alcohol compounds.

5. The method for producing a thiourethane resin raw material according to any one of claims 1 to 4, wherein the composition X is recovered in at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses.

6. The method for producing a thiourethane resin raw material according to any one of claims 1 to 5, wherein the composition X includes the thiourethane resin and the cutting powder containing the foreign matter.

7. By a method for producing a thiourethane resin raw material according to any one of claims 1 to 6 The process for manufacturing thiourethane resin raw materials, A step of producing a polymerizable composition using at least a portion of the thiourethane resin raw materials as at least a portion of the raw materials, A method for producing a polymerizable composition containing the above.

8. A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 7, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins.

9. A method for manufacturing a molded article containing resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 7, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing a molded article containing [the specified ingredient].

10. A method for producing an optical material including a molded body containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 7, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing optical materials containing [specific material].

11. A method for manufacturing a lens including a molded body containing resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 7, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing lenses that include [specific components / materials].

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