Preparation method and application of thiourea resin raw material

Abstract

A method for producing a thiourethane resin raw material includes the following reaction step: contacting a composition X containing a thiourethane resin and a foreign substance with an active hydrogen compound to react the thiourethane resin in the composition X with the active hydrogen compound to produce the thiourethane resin raw material.

Description

Technical Field

[0001] The present disclosure relates to a method for preparing a thiourethane resin raw material and its application. Background Art

[0002] Plastic lenses, which are lenses made of resin, are lighter and less likely to break than inorganic lenses and can be dyed. Therefore, they have rapidly become popular in applications such as eyeglass lenses and camera lenses in recent years.

[0003] For example, various studies have been conducted on lenses containing thiourethane resin (for example, see Patent Documents 1 to 3 listed below).

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 63-46213

[0005] Patent Document 2: Japanese Patent Application Laid-Open No. 2-270859

[0006] Patent Document 3: Japanese Patent Application Laid-Open No. 7-252207 Summary of the invention

[0007] Problems to be solved by the invention

[0008] As raw materials for producing thiourethane resins (hereinafter also referred to as "thiourethane resin raw materials"), polythiol compositions and polyisocyanate compounds are generally used. Polyisocyanate compounds are produced, for example, from polyamine compounds. Polyamine compounds, which are raw materials of polyisocyanate compounds, also belong to thiourethane resin raw materials (i.e., raw materials for producing thiourethane resins). Furthermore, compounds that are raw materials of the polyamine compounds (e.g., polyurea compounds, polyurethane compounds, etc.) also belong to thiourethane resin raw materials.

[0009] A lens containing a thiourethane resin may contain foreign matter (ie, components other than the thiourethane resin).

[0010] The lens containing thiourethane resin and foreign matter is manufactured by cutting a molded body obtained by molding a composition containing thiourethane resin and foreign matter (hereinafter referred to as "composition X"). At this time, a large amount of cutting powder containing thiourethane resin and foreign matter is generated. In the past, the large amount of cutting powder generated was simply discarded and not effectively utilized.

[0011] However, from the viewpoint of effective utilization (ie, recycling) of materials, a technology for producing a thiourethane resin raw material using the thiourethane resin contained in cutting powder as a starting material is desired. The produced thiourethane resin raw material can be used as a raw material for new thiourethane resin.

[0012] Furthermore, it is desired to have a technology for producing a thiourethane resin raw material using not only the thiourethane resin contained in the cutting powder as a starting material but also the thiourethane resin as a starting material.

[0013] An object of one embodiment of the present disclosure is to provide a method for producing a thiourethane resin raw material, which can produce a thiourethane resin raw material using a composition X containing a thiourethane resin and a foreign substance as a starting material, and use thereof.

[0014] Means for solving problems

[0015] Means for solving the above-mentioned problems include the following aspects.

[0016] <1> A method for producing a thiourethane resin raw material comprises the following reaction step: contacting a composition X containing a thiourethane resin and a foreign substance with an active hydrogen compound, thereby reacting the thiourethane resin in the composition X with the active hydrogen compound to produce the thiourethane resin raw material.

[0017] <2> like <1> The method for producing a thiourethane resin raw material, wherein the foreign matter includes at least one selected from the group consisting of resins other than thiourethane resins, polymerization catalysts, metals, ultraviolet absorbers, internal mold release agents, plasticizers, dyes, engine oils, and water.

[0018] <3> like <1> or <2> The method for producing a thiourethane resin raw material, wherein the thiourethane resin raw material comprises at least one selected from the group consisting of a polythiol composition, a polyurea compound, a polyurethane compound, a polyamine compound, a polyisocyanate compound, and a polyurethane compound.

[0019] <4> like <1> ~ <3> The method for producing a thiourethane resin raw material according to any one of the preceding claims, wherein the active hydrogen compound is at least one selected from the group consisting of amine compounds and alcohol compounds.

[0020] <5> like <1> ~ <4> The method for producing a thiourethane resin raw material according to any one of the preceding claims, wherein the reaction step is a step of contacting the composition X with the active hydrogen compound in the presence of a reaction solvent, thereby reacting the thiourethane resin in the composition X with the active hydrogen compound to obtain a reaction mixture containing the thiourethane resin raw material;

[0021] The production method further includes a separation step of separating the thiourethane resin raw material from the reaction mixture containing the thiourethane resin raw material.

[0022] <6> like <5> The method for producing a thiourethane resin raw material, wherein the thiourethane resin raw material comprises a polythiol composition,

[0023] The aforementioned separation process comprises the following steps:

[0024] A step of filtering the reaction mixture containing the thiourethane resin raw material to obtain a filtrate containing the polythiol composition;

[0025] A step of adding a base containing an alkali metal to the filtrate containing the polythiol composition, and then adding water to perform extraction, thereby obtaining a water extract containing an alkali metal salt of the polythiol composition;

[0026] A step of adding an acid to the water extract containing the alkali metal salt of the polythiol composition to obtain an aqueous liquid containing the polythiol composition;

[0027] A step of adding an extraction solvent to an aqueous liquid containing the polythiol composition to perform extraction, thereby obtaining an extract containing the polythiol composition; and

[0028] The step of separating the aforementioned polythiol composition from the extract containing the aforementioned polythiol composition.

[0029] <7> like <1> ~ <6> The method for producing a thiourethane resin raw material according to any one of the preceding claims, wherein the composition X is recovered in at least one of a process for producing eyeglass lenses, a process for producing eyeglasses, and a process for discarding eyeglasses.

[0030] <8> like <1> ~ <7> The method for producing a thiourethane resin raw material according to any one of the preceding claims, wherein the composition X contains cutting powder containing the thiourethane resin and the foreign matter.

[0031] <9> A method for producing a polymerizable composition, comprising the following steps:

[0032] use <1> ~ <8> The method for producing a thiourethane resin raw material according to any one of the preceding claims, comprising a step of producing a thiourethane resin raw material; and

[0033] A step of producing a polymerizable composition using at least a part of the thiourethane resin raw material as at least a part of the raw material.

[0034] <10> A method for producing a resin, comprising the following steps:

[0035] use <9> The method for producing a polymerizable composition comprises a step of producing a polymerizable composition; and

[0036] A step of obtaining a resin by curing the polymerizable composition.

[0037] <11> A method for producing a molded body, which is a method for producing a molded body containing a resin, comprising the following steps:

[0038] use <9> The method for producing a polymerizable composition comprises a step of producing a polymerizable composition; and

[0039] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0040] <12> A method for producing an optical material, which is a method for producing an optical material containing a molded body containing a resin, the method comprising the following steps:

[0041] use <9> The method for producing a polymerizable composition comprises a step of producing a polymerizable composition; and

[0042] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0043] <13> A method for manufacturing a lens, which is a method for manufacturing a lens including a molded body containing a resin, the manufacturing method comprising the following steps:

[0044] use <9> The method for producing a polymerizable composition comprises a step of producing a polymerizable composition; and

[0045] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0046] <14> A polymerizable composition comprising <1> ~ <8> At least a part of the thiourethane resin raw material obtained by the method for producing a thiourethane resin raw material as described in any one of the above.

[0047] <15> Resin, which is <14> A cured product of the polymerizable composition.

[0048] <16> A molded body comprising <15> The resin.

[0049] <17> Optical material comprising <16> The molded body.

[0050] <18> A lens comprising <16> The molded body.

[0051] Effects of the Invention

[0052] According to one embodiment of the present disclosure, a method for producing a thiourethane resin raw material and its use can be provided, which can produce a thiourethane resin raw material using a composition X containing a thiourethane resin and a foreign substance as a starting material. DETAILED DESCRIPTION

[0053] In the present disclosure, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0054] In the present disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0055] In the present disclosure, when there are plural kinds of substances belonging to each component in the composition, the amount of each component contained in the composition refers to the total amount of the plural kinds of substances present in the composition unless otherwise specified.

[0056] In the numerical range recorded in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment.

[0057] [Method for producing thiourethane resin raw material]

[0058] The method for producing a thiourethane resin raw material of the present disclosure includes a reaction step of contacting a composition X containing a thiourethane resin and a foreign substance with an active hydrogen compound to react the thiourethane resin in the composition X with the active hydrogen compound to produce the thiourethane resin raw material.

[0059] According to the method for producing a thiourethane resin raw material of the present disclosure, the target thiourethane resin raw material can be produced using the composition X containing a thiourethane resin and foreign matter as a starting material.

[0060] In the above reaction step, the thiourethane resin is chemically decomposed by the reaction between the thiourethane resin and the active hydrogen compound, thereby generating the target thiourethane resin raw material.

[0061] <Reaction process>

[0062] The reaction step is a step of contacting the composition X containing the thiourethane resin and the 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.

[0063] The method for contacting the composition X with the active hydrogen compound is not particularly limited, and for example, a method of charging the composition X and the active hydrogen compound (and a reaction solvent as required) into a reaction container and stirring the mixture can be mentioned. In this example, the order of charging the composition X and the active hydrogen compound (and a reaction solvent as required) into the reaction container is not particularly limited.

[0064] (Composition X)

[0065] Composition X is one of the starting materials in the reaction step.

[0066] The composition X comprises a thiourethane resin and a foreign substance.

[0067] The composition X may contain other ingredients as desired.

[0068] The composition X is preferably recovered in at least one of the manufacturing process of eyeglass lenses, the manufacturing process of glasses, and the disposal process of glasses. According to this embodiment, the thiourethane resin, which is a material of eyeglass lenses, can be recycled.

[0069] Here, the manufacturing process of the eyeglass lens refers to a process of preparing a resin by mixing monomers as a resin raw material and performing cast polymerization and / or a process of obtaining an eyeglass lens by cutting a resin molded body.

[0070] The manufacturing process of glasses refers to the process of combining glasses lenses with other components such as glasses frames to manufacture glasses.

[0071] The so-called eyeglass disposal process refers to the process of discarding eyeglasses that have been manufactured but become useless, eyeglasses that have been used, etc.

[0072] In any process, a composition X containing thiourethane resin, which is a material of eyeglass lenses, and foreign matter is generated as waste.

[0073] In the present embodiment, the composition X produced in at least one of these processes is used as a starting material, and the thiourethane resin in the composition X is reacted with an active hydrogen compound to obtain a thiourethane resin raw material which is a decomposition product of the thiourethane resin.

[0074] -Thiourea Resin-

[0075] Composition X comprises at least one thiourethane resin.

[0076] As the thiourethane resin, a known thiourethane resin can be used, for example, thiourethane resins described in known documents such as JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, JP-A-60-199016, JP-A-60-217229, International Publication No. 2007 / 052329, and International Publication No. 2008 / 047626 can be used.

[0077] The content of the thiourethane resin in the composition X is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of the composition X.

[0078] The thiourethane resin generally contains a polymer of an isocyanate compound and a polythiol composition. That is, the thiourethane resin is generally produced using an isocyanate compound and a polythiol composition as raw materials.

[0079] - Isocyanate compound as raw material of thiourethane resin -

[0080] The isocyanate compound as a raw material of the thiourethane resin may be only one kind or two or more kinds.

[0081] As the isocyanate compound as a raw material of the thiourethane resin, for example, known isocyanate compounds described in the above-mentioned known documents can be mentioned.

[0082] The isocyanate compound as a raw material of the thiourethane resin preferably contains a polyisocyanate compound containing two or more isocyanate groups.

[0083] The isocyanate compound as a raw material of the thiourethane resin more preferably includes a diisocyanate compound containing two isocyanate groups.

[0084] It is further preferred that the isocyanate component contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, meta-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4′-diphenylmethane diisocyanate and phenylene diisocyanate (hereinafter also referred to as “isocyanate component A”),

[0085] More preferably, the isocyanate component A is contained as a main component.

[0086] From the viewpoint of the performance of the thiourethane resin [e.g., optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.], the isocyanate compound as a raw material of the thiourethane resin further preferably contains at least one selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane (hereinafter also referred to as "isocyanate component N1"),

[0087] More preferably, the isocyanate component N1 is contained as a main component.

[0088] -Polythiol composition as raw material of thiourethane resin-

[0089] The polythiol composition as a raw material of the thiourethane resin may be only one kind or two or more kinds.

[0090] In the present disclosure, the polythiol composition refers to a composition containing at least one polythiol compound.

[0091] Here, the polythiol compound is not particularly limited as long as it is a compound containing two or more thiol groups (also known as mercapto groups).

[0092] The polythiol composition may contain components other than the polythiol compound as impurities.

[0093] It is preferred that the polythiol composition contains at least one polythiol compound as a main component.

[0094] Here, “the polythiol composition contains at least one polythiol compound as a main component” means that the total content of the at least one polythiol compound is 50% or more based on the total amount of the polythiol composition.

[0095] The total content of at least one polythiol compound is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, based on the total amount of the polythiol composition.

[0096] Similarly, in the present disclosure, when a composition contains a certain component (hereinafter referred to as "component X") "as a main component", it means that the content of component X (when component X is composed of two or more compounds, the total content of the two or more compounds) is 50% or more relative to the total amount of the composition.

[0097] The content of the component X as 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.

[0098] The “%” in the above description of the term “comprising… as a main component” 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., polythiol composition), as determined by high performance liquid chromatography.

[0099] Examples of the polythiol compound contained in the polythiol composition as a raw material of the thiourethane resin include known polythiol compounds described in the above-mentioned known documents.

[0100] The polythiol composition as a raw material of the thiourethane resin preferably contains at least one selected from the group consisting of the following components (hereinafter also referred to as “polythiol component T”):

[0101] 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,

[0102] 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0103] 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0104] 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0105] Pentaerythritol tetrakis(2-thioglycolate),

[0106] Pentaerythritol tetrakis(3-mercaptopropionate),

[0107] 2,5-dimercaptomethyl-1,4-dithiol,

[0108] Bis(mercaptoethyl) sulfide, and

[0109] Diethylene glycol bis(mercaptopropionate).

[0110] The polythiol composition more preferably contains the polythiol component T as a main component.

[0111] In this case, the polythiol composition may contain at least one component other than the polythiol component T (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0112] Examples of other polythiol compounds include 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-dithiol, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiol, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiol.

[0113] More specific embodiments of the polythiol composition as a raw material of the thiourethane resin include:

[0114] An embodiment containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component T1") as a main component;

[0115] An embodiment containing 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 main components;

[0116] An embodiment comprising pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as “polythiol component T3”) as a main component;

[0117] A method comprising the polythiol component T1 and the polythiol component T3 as main components;

[0118] A method comprising the polythiol component T2 and the polythiol component T3 as main components;

[0119] etc.

[0120] The polythiol composition of each embodiment may contain at least one other component (for example, other polythiol compounds, components other than polythiol compounds, etc.) other than the main component.

[0121] -foreign body-

[0122] The composition X contains at least one foreign substance.

[0123] Here, the foreign matter refers to components other than the thiourethane resin.

[0124] The foreign matter preferably includes at least one selected from the group consisting of a resin other than thiourethane resin, a polymerization catalyst, a metal, an ultraviolet absorber, an internal mold release agent, a plasticizer, a dye, engine oil, and water.

[0125] The resin other than the thiourethane resin is not particularly limited.

[0126] For example, the following materials and the like are also included in the scope of the resin mixture containing the thiourethane resin and a resin other than the thiourethane resin:

[0127] A hybrid material of thiourethane resin and polyurethane resin produced by adding a polyol compound to the raw materials when producing thiourethane resin;

[0128] A hybrid material of thiourethane resin and urea resin produced by adding a polyamine compound to the raw materials when producing thiourethane resin.

[0129] The resin other than the thiourethane resin preferably includes at least one selected from the group consisting of polycarbonate resins, polyallyl carbonate resins, acrylic resins, polyurethane resins, and episulfide resins.

[0130] These resins are also resins that can be used as materials for eyeglass lenses, similar to thiourethane resins.

[0131] In addition, examples of resins other than the thiourethane resin include:

[0132] Polyolefin film for protecting the surface of a resin molded body for manufacturing eyeglass lenses,

[0133] A hard coating or primer coating for protecting the surface of a resin molded body for manufacturing eyeglass lenses.

[0134] Abrasives used when grinding resin molded bodies for making eyeglass lenses.

[0135] A resin material used to fix a resin molded body when cutting a resin molded body for manufacturing eyeglass lenses,

[0136] Tape or tape paste used to fix the glass mold used when making a resin molded body for making eyeglass lenses,

[0137] etc.

[0138] Examples of the polymerization catalyst include polymerization catalysts used in the formation of thiourethane resins (that is, polymerization of monomers).

[0139] Examples of the polymerization catalyst include tertiary amine compounds, inorganic acid salts or organic acid salts thereof, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0140] Examples of the metal include pure metals and alloys.

[0141] Specific examples of the metal include:

[0142] Various pure metals such as Al, Ti, Zr, Au, Pt, Ag, Cu, Fe, Bi, Pb, Sn, In, Ga, etc.

[0143] Alloys containing at least one pure metallic element (e.g. stainless steel);

[0144] etc.

[0145] Metal may be mixed into the thiourethane resin during at least one of the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses, for example.

[0146] The ultraviolet absorber, the internal mold release agent, and the dye can each be added to the thiourethane resin for manufacturing a lens (e.g., a spectacle lens). Specific examples of these components can refer to other components that can be contained in the polymerizable composition. As the ultraviolet absorber, the ultraviolet absorber that can be used in the manufacturing method involved in the embodiment A described later can be referred to.

[0147] The plasticizer may be contained in, for example, a gasket for holding a molding die when a molded body of a thiourethane resin is produced by cast polymerization.

[0148] The engine oil and water are each used, for example, when grinding and / or polishing a molded body of the thiourethane resin in order to manufacture a lens (for example, a spectacle lens), and are mixed into the thiourethane resin powder at this time.

[0149] The foreign matter may contain other components besides the above.

[0150] As other components that may be contained, reference may be made to other components that may be contained in the polymerizable composition described later.

[0151] When the total amount of the thiourethane resin in the composition X is 100 parts by mass, the content of the foreign matter in the composition X is preferably 0.001 to 150 parts by mass, more preferably 0.001 to 100 parts by mass, further preferably 0.001 to 10 parts by mass, further preferably 0.01 to 5 parts by mass, further preferably 0.01 to 3 parts by mass.

[0152] The total content of the thiourethane resin and foreign matter in the composition X is preferably 80% by mass to 100% by mass, and more preferably 90% by mass to 100% by mass, based on the total amount of the composition X.

[0153] -Powdered composition X containing thiourethane resin and foreign matter-

[0154] The composition X is preferably a powdery composition containing a thiourethane resin and foreign matter.

[0155] That is, in the reaction step, it is preferred that a powdery composition containing a thiourethane resin and foreign matter (hereinafter also referred to as "powdered composition X") as composition X is brought into contact with an active hydrogen compound, thereby reacting the thiourethane resin in the powdered composition X with the active hydrogen compound. This can further improve the reaction efficiency of the thiourethane resin and the active hydrogen compound.

[0156] The method for contacting the powdered composition X with the active hydrogen compound is not particularly limited, and for example, a method of charging the powdered composition X and the active hydrogen compound (and a reaction solvent as required) into a reaction container and stirring the mixture can be mentioned. In this example, the order of charging the powdered composition X and the active hydrogen compound (and a reaction solvent as required) into the reaction container is not particularly limited.

[0157] The powdery composition X is preferably cutting powder (including the concept of grinding powder, the same applies hereinafter) containing a thiourethane resin and foreign matter.

[0158] Cutting powder of a molded body containing thiourethane resin and foreign matter is generated, for example, when an optical material (eg, a lens) is manufactured by cutting a molded body containing thiourethane resin and foreign matter.

[0159] (Active Hydrogen Compound)

[0160] In the reaction step, the active hydrogen compound functions as a decomposing agent for the thiourethane resin in the composition X which is the starting material.

[0161] From the viewpoint of the above-mentioned function, the active hydrogen compound is preferably at least one selected from the group consisting of amine compounds and alcohol compounds.

[0162] -Amine compounds-

[0163] As for the amine compound which is one of the preferred active hydrogen compounds, known amine compounds can be used without particular limitation.

[0164] The amine compound used in the reaction step may be one kind or two or more kinds.

[0165] 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 1,000 or less, more preferably 500 or less, further preferably 300 or less, and further preferably 200 or less.

[0166] The lower limit of the molecular weight of the amine compound is, for example, 45 or more, preferably 59 or more, and more preferably 60 or more.

[0167] The amine compound is preferably an amine compound containing at least one of an amino group and a monoalkylamino group, wherein the total number of the amino group and the monoalkylamino group is 1 to 6 (preferably 1 to 3, more preferably 1 or 2).

[0168] As an example of a preferred amine compound, there can be mentioned:

[0169] An amine compound having a molecular weight of 300 or less, containing at least one of an amino group and a monoalkylamino group, wherein the total number of the amino group and the monoalkylamino group is 1 or 2.

[0170] Specific examples of the amine compound include alkylamines having 2 to 10 carbon atoms, aralkylamines having 7 to 10 carbon atoms (e.g., benzylamine), dialkylamines having 2 to 10 carbon atoms (e.g., di-n-butylamine), alkyldiamines having 2 to 10 carbon atoms (e.g., ethylenediamine, bis(2-aminoethyl)ether), alkyltriamines having 2 to 10 carbon atoms (e.g., bis(2-aminoethyl)amine), hydroxyalkylamines having 2 to 10 carbon atoms (e.g., monoethanolamine), bis(hydroxyalkyl)amines having 2 to 10 carbon atoms (e.g., bis(hydroxyethyl)amine), cyclic amines having 2 to 10 carbon atoms (e.g., morpholine), and secondary amines such as alkyl(hydroxyalkyl)amines having 2 to 10 carbon atoms (e.g., methylethanolamine, isopropylethanolamine).

[0171] The amine compound is preferably benzylamine, di-n-butylamine, ethylenediamine, or monoethanolamine.

[0172] -Amount of amine compound added-

[0173] When an amine compound is used as the active hydrogen compound, the charging mass ratio of the amine compound to the thiourethane resin (ie, charging mass ratio [amine compound / thiourethane resin]) can be appropriately adjusted and is preferably 0.10 or more and less than 1.0.

[0174] When the input mass ratio [amine compound / thiourethane resin] is 0.10 or more, the production of the polythiol composition can be further promoted.

[0175] When the input mass ratio [amine compound / thiourethane resin] is less than 1.0, the residual amine compound in the reaction mixture can be further suppressed.

[0176] The charging mass ratio [amine compound / thiourethane resin] is preferably 0.15 to 0.95, more preferably 0.20 to 0.90.

[0177] When an amine compound is used as the active hydrogen compound, the amount of the amine compound charged per 1 g of the thiourethane resin is preferably 1.0 to 30 mmol / g, more preferably 2.0 to 20 mmol / g, and even more preferably 3.0 to 10.0 mmol / g.

[0178] When an amine compound is used as the active hydrogen compound, the charge equivalent of the amine compound to the thiourethane resin (charge equivalent [amine compound / thiourethane resin]) is preferably 1.0 to 2.0, more preferably greater than 1.0 and 1.8 or less, and further preferably greater than 1.0 and 1.6 or less.

[0179] When the input equivalent (amine compound / thiourethane resin) is 1.0 or more, the production of the polythiol composition can be further promoted.

[0180] When the input equivalent (amine compound / thiourethane resin) is 2.0 or less, the residual amine compound in the reaction mixture can be further suppressed.

[0181] Here, the charge equivalent of the amine compound to the thiourethane resin (charge equivalent [amine compound / thiourethane resin]) refers to the ratio of the total number of amino groups and monoalkylamino groups in the charged amine compound to the total number of thiourethane bonds in the charged thiourethane resin.

[0182] - Alcohol compounds -

[0183] The alcohol compound, which is one of the preferred active hydrogen compounds, may be a monohydric alcohol compound containing only one hydroxyl group, or may be a polyhydric alcohol compound containing two or more hydroxyl groups.

[0184] From the viewpoint of further improving the reactivity with the thiourethane resin, the molecular weight of the alcohol compound is preferably 1,000 or less, more preferably 500 or less, further preferably 300 or less, and further preferably 200 or less.

[0185] 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.

[0186] The alcohol compound preferably contains an alcohol compound having a boiling point of 135°C to 250°C (hereinafter, also referred to as "alcohol compound A").

[0187] In the present disclosure, the boiling point refers to the boiling point at 1 atmosphere (101325 Pa).

[0188] The ratio of the alcohol compound A to the total amount of the alcohol compounds is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.

[0189] As alcohol compounds,

[0190] Preferably, 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,

[0191] More preferably, it is benzyl alcohol, phenethyl alcohol, 1-decanol, 1-nonanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, propylene glycol, or ethylene glycol,

[0192] More preferably, it is benzyl alcohol, phenethyl alcohol, 2-octanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, or propylene glycol.

[0193] The preferred range of the amount of the alcohol compound to be charged when an alcohol compound is used as the active hydrogen compound is the same as the preferred range of the amount of the amine compound to be charged when an amine compound is used as the active hydrogen compound as described above.

[0194] The preferred range of the total amount of the amine compound and the alcohol compound charged when the amine compound and the alcohol compound are used as the active hydrogen compound is the same as the preferred range of the amount of the amine compound charged when the amine compound is used as the active hydrogen compound described above.

[0195] (Reaction solvent)

[0196] In the reaction step, the composition X is preferably brought into contact with the active hydrogen compound in the presence of a reaction solvent.

[0197] The reaction solvent is preferably an organic solvent, more preferably a hydrocarbon compound having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9).

[0198] The hydrocarbon compound is preferably hexane, heptane, octane, nonane, decane, xylene, mesitylene or toluene, more preferably heptane, octane, nonane, xylene, mesitylene or toluene, particularly preferably xylene or toluene.

[0199] The reaction solvent may be one kind or two or more kinds.

[0200] (Reaction temperature)

[0201] The reaction temperature of the thiourethane resin and the active hydrogen compound in the reaction step can be adjusted appropriately.

[0202] Here, the reaction temperature of the thiourethane resin and the active hydrogen compound refers to the temperature at which the composition X and the active hydrogen compound are brought into contact with each other.

[0203] In the reaction step, the composition X and the active hydrogen compound are preferably brought into contact under a temperature condition (ie, reaction temperature) of 50°C to 150°C (more preferably 60°C to 145°C, and even more preferably 70°C to 140°C).

[0204] For example, in a method of obtaining a target polythiol composition, when the reaction temperature is 50°C to 150°C, the purity of the polythiol component as the main component 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.

[0205] (Reaction time)

[0206] The reaction time of the thiourethane resin and the active hydrogen compound in the reaction step (i.e., the time for contacting the composition X with the active hydrogen compound) can be adjusted appropriately and is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and even more preferably 1 to 10 hours.

[0207] (Thiourethane resin raw material as target product)

[0208] In the reaction step, the thiourethane resin and the active hydrogen compound are reacted to produce a thiourethane resin raw material as a decomposition product of the thiourethane resin and a target product.

[0209] The target thiourethane resin raw material is a material (ie, a compound or a composition, hereinafter the same) obtained as a decomposition product of a thiourethane resin and is also a material that can be used as a raw material for producing a new thiourethane resin.

[0210] The target thiourethane resin raw material and the thiourethane resin raw material in the composition X, which is the starting material, need not be completely the same.

[0211] Hereinafter, preferred embodiments of the thiourethane resin raw material which is the target product of the production method of the present disclosure will be described.

[0212] The target thiourethane resin raw material preferably contains at least one selected from the group consisting of a polythiol composition, a polyurea compound, a polyurethane compound, a polyamine compound, a polyisocyanate compound, and a polyurethane compound.

[0213] - Target polythiol composition, target polyisocyanate compound - Among the target thiourethane resin raw materials, the polythiol composition and the polyisocyanate compound are direct raw materials for producing the thiourethane resin. That is, the thiourethane resin can be produced by the reaction of the polythiol composition and the polyisocyanate compound.

[0214] Regarding the polythiol composition and the polyisocyanate compound, known documents related to thiourethane resins can be appropriately referred to.

[0215] Preferred embodiments of the target polyisocyanate compound are the same as the preferred embodiments of the isocyanate compound as a raw material of the thiourethane resin described above.

[0216] Preferred embodiments of the target polythiol composition are the same as the preferred embodiments of the polythiol composition as a raw material of the thiourethane resin described above.

[0217] The target polythiol composition and the polythiol composition of the thiourethane resin in the composition X, which is the starting material, do not need to be completely identical.

[0218] However, from the viewpoint of the performance of the thiourethane resin produced using the target polythiol composition, it is preferred that the type of the polythiol component as the main component in the target polythiol composition is the same as the type of the polythiol component as the main component in the polythiol composition as the raw material. In this case, for example, the cutting powder (composition X) generated when producing the optical material A can be used as a raw material to produce an optical material B (optical material containing composition X) having performance comparable to that of the optical material A.

[0219] -Polyamine compounds as target substances-

[0220] The target polyamine compound is a compound that can be used as a raw material for a polyisocyanate compound. Specifically, the polyamine compound can be produced by reacting the polyamine compound with phosgene (ie, carbonyl chloride).

[0221] The target polyamine compound can be produced by, for example, reacting a polyurea compound described later with an amine compound (see Examples 201 to 211 described later).

[0222] The target polyamine compound can be produced by, for example, reacting a polyurethane compound described below with an amine compound.

[0223] -Polyurea compound as target product-

[0224] The target polyurea compound is a compound that can be used as a raw material for a polyamine compound. Specifically, a polyamine compound can be generated by reacting a polyurea compound with an amine compound.

[0225] The target polyurea compound can be produced, for example, by decomposing a thiourethane resin by reacting the thiourethane resin with an amine compound. Specifically, the thiourethane resin can be decomposed into a polythiol composition and a polyurea compound by reacting the thiourethane resin with an amine compound (aminolysis).

[0226] As examples of aminolysis, reference can be made to Examples 1 to 13 (Examples for obtaining polythiol compositions) and Examples 201 to 211 (Examples for obtaining polyurea compounds) described below. Examples 201 to 211 described below also show the steps (second step) until a polyamine compound is obtained from a polyurea compound.

[0227] -Polyurethane compound as target product-

[0228] The target polyurethane compound is a compound that can be used as a raw material for a polyamine compound. Specifically, a polyamine compound can be generated by reacting a polyurethane compound with an amine compound.

[0229] The target polyurethane compound can be produced, for example, by decomposing a thiourethane resin by reacting the thiourethane resin with an alcohol compound. Specifically, the thiourethane resin can be decomposed into a polythiol composition and a polyurethane compound by reacting the thiourethane resin with an alcohol compound (alcoholysis).

[0230] The use of the target thiourethane resin raw material is not particularly limited.

[0231] Specific uses of the target thiourethane resin raw material include thiourethane resin raw materials for producing optical materials (eg, lenses, preferably eyeglass lenses).

[0232] In other words, as a specific example of the method for producing a thiourethane resin raw material of the present disclosure, there can be cited a method for producing a thiourethane resin raw material for producing an optical material. In this specific example, when the cutting powder containing the composition X containing the thiourethane resin and foreign matter generated when producing the optical material is used as the starting raw material, i.e., the composition X, the material (thiourethane resin and the thiourethane resin raw material as the raw material thereof) can be effectively utilized (i.e., recycled).

[0233] Furthermore, when the polythiol composition is obtained by reacting a thiourethane resin with an active hydrogen compound in the reaction step, a polythiol composition having a high purity of the polythiol component as the main component can be obtained compared with a known method (for example, a method of obtaining a polythiol composition by reacting a thiourethane resin with sodium hydroxide).

[0234] Therefore, even when the target polythiol composition is used to produce an optical material (eg, a lens), an optical material having good performance can be obtained.

[0235] Examples of the performance of the optical material include optical properties (for example, refractive index and / or Abbe number), heat resistance, and specific gravity d.

[0236] (Reaction mixture containing thiourethane resin raw material)

[0237] The reaction step may be a step of contacting the composition X with an active hydrogen compound 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 the composition X with the active hydrogen compound to obtain a reaction mixture containing the target thiourethane resin raw material.

[0238] The reaction mixture may contain the thiourethane resin raw material as a main product generated by decomposition, and other components other than the thiourethane resin raw material.

[0239] Examples of other components include by-products generated by decomposition, reaction solvents, residues of raw materials, and impurities contained in the raw materials.

[0240] <Separation process>

[0241] The method for producing a thiourethane resin raw material of the present disclosure may include a separation step of separating the thiourethane resin raw material as a target product from a reaction mixture containing the thiourethane resin raw material.

[0242] The separation method in the separation step is not particularly limited, and a known method can be applied.

[0243] Examples of the separation method in the separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (for example, column chromatography), etc. As the separation method, a plurality of methods may be used in combination.

[0244] 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.

[0245] According to this embodiment, it is easier to remove the solid components contained in the reaction mixture (for example, the solid components including by-products).

[0246] In addition, the solid content includes, for example, a polyurea compound and / or a polyurethane compound. As described above, the polyurea compound and the polyurethane compound can also be used as a raw material for a thiourethane resin.

[0247] As a preferred embodiment in which the separation step includes a step of obtaining a filtrate containing a polythiol composition, there can be mentioned an embodiment in which the separation step includes the following steps (hereinafter referred to as separation embodiment A):

[0248] A step of filtering a reaction mixture containing a thiourethane resin raw material to obtain a filtrate containing a polythiol composition;

[0249] a step of subjecting the filtrate comprising the polythiol composition to acid washing; and

[0250] A step of separating the polythiol composition from the filtrate after acid washing.

[0251] According to separation method A, the alkali component (for example, the residue of the active hydrogen compound) can be easily removed from the filtrate by acid washing, so that a polythiol composition having a higher purity of the polythiol component as the main component can be obtained.

[0252] In the separation method A, water washing may be added after the acid washing to separate the polythiol composition from the filtrate after the water washing.

[0253] In separation method A, examples of the acid used for acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, and oxalic acid.

[0254] As another preferred embodiment in which the separation step includes the step of obtaining a filtrate containing a polythiol composition, there can be mentioned an embodiment in which the separation step includes the following steps (hereinafter referred to as separation embodiment B):

[0255] A step of filtering a reaction mixture containing a thiourethane resin raw material to obtain a filtrate containing a polythiol composition;

[0256] A step of adding a base containing an alkali metal to a filtrate containing a polythiol composition, followed by adding water and performing extraction to obtain a water extract containing an alkali metal salt of the polythiol composition;

[0257] A step of adding an acid to the aqueous extract containing the alkali metal salt of the polythiol composition to obtain an aqueous liquid containing the polythiol composition;

[0258] A step of adding an extraction solvent (preferably an organic solvent, more preferably a hydrocarbon compound having 5 to 12 carbon atoms) to an aqueous liquid containing a polythiol composition to perform extraction, thereby obtaining an extract containing the polythiol composition; and

[0259] The step of separating the polythiol composition from the extract containing the polythiol composition.

[0260] In separation method B, first, the polythiol composition in the filtrate containing the polythiol composition is converted into an alkali metal salt, and then extracted with water to obtain an aqueous extract containing the alkali metal salt of the polythiol composition. Then, an acid is added thereto to restore the alkali metal salt of the polythiol composition to the polythiol composition. The polythiol composition is extracted from the obtained aqueous liquid containing the polythiol composition using a reaction solvent to obtain an extract containing the polythiol composition. The polythiol composition is separated from the obtained extract containing the polythiol composition.

[0261] According to the separation mode B, even when the filtrate containing the polythiol composition contains a large amount of components other than the polythiol composition, a polythiol composition having a higher purity of the polythiol component as the main component can be obtained.

[0262] In particular, even when foreign matter is contained in the filtrate containing the polythiol composition, it is possible to suppress the foreign matter from being mixed into the finally obtained polythiol composition.

[0263] In the separation method B, the alkali metal in the base containing an alkali metal is preferably sodium, potassium or lithium, and more preferably sodium or potassium.

[0264] Examples of the base composed of an alkali metal include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0265] The base including an alkali metal may be added to the filtrate in the form of an alcohol solution (methanol solution, ethanol solution, etc.) as necessary.

[0266] In the separation method B, examples of the acid 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, and oxalic acid.

[0267] In the separation method B, the hydrocarbon compound used as the extraction solvent may be only one kind or two or more kinds.

[0268] In the separation method 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.

[0269] However, the reaction solvent and the extraction solvent may be the same or different.

[0270] In separation method B, when separating the polythiol composition from the extract containing the polythiol composition, it is particularly preferred that the extract is first filtered and the polythiol composition is separated from the filtered extract. In this way, components insoluble in the extraction solvent (for example, oligomer components such as undecomposed products and oxidized products) can be removed from the extract, so that a polythiol composition having a higher purity of the polythiol component as the main component can be obtained.

[0271] <Screening process>

[0272] The method for producing a thiourethane resin raw material of the present disclosure may further include a sieving step before the reaction step, wherein the powdered composition X containing the thiourethane resin and foreign matter is sieved to obtain the sieved powdered composition X containing the thiourethane resin and foreign matter. In this case, in the reaction step, the powdered composition X is contacted with an active hydrogen compound to react the thiourethane resin in the sieved powdered composition X with the amine compound.

[0273] When the method for producing a polythiol composition of the present disclosure includes a sieving step, the powdery composition X having small particles and having passed through the sieve 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.

[0274] The above sieve is not particularly limited.

[0275] The nominal mesh size of the sieve as specified 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.

[0276] <Cleaning process>

[0277] The method for producing a thiourethane resin raw material of the present disclosure may further include a washing step before the reaction step: washing the powdery composition X (i.e., the powder containing the thiourethane resin and foreign matter) 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 powdery composition X washed in the washing step is reacted with an active hydrogen compound. Thus, a polythiol composition having a higher purity of the polythiol component as the main component can be obtained.

[0278] In particular, in the method for producing a polythiol composition of the present disclosure, when cutting powder, which is a powdery composition X containing a thiourethane resin and foreign matter, is used as a starting material, the oil from the cutting machine adhering to the cutting powder can be effectively removed by the above-mentioned cleaning step, thereby obtaining a polythiol composition having a higher purity of the polythiol component as the main component.

[0279] The organic solvent used as the washing solvent may be only one kind or two or more kinds.

[0280] Preferred embodiments of the organic solvent as the washing solvent are the same as the preferred embodiments of the organic solvent as the reaction solvent described above.

[0281] However, the reaction solvent and the washing solvent may be the same or different.

[0282] The washing method in the washing step is not particularly limited, and a known method such as a method of adding the above-mentioned washing solvent to the powdery composition X and mixing the mixture can be applied.

[0283] When the method for producing the thiourethane resin raw material of the present disclosure includes the above-mentioned sieving step and washing step, it is preferred to perform the sieving step and washing step in sequence. In this case, it is not necessary to wash the cutting powder that does not pass through the sieve, so the amount of washing solvent used can be further reduced.

[0284] When the powdery composition X (ie, the powder containing the thiourethane resin and the foreign matter) contains water, a drying step may be included before the reaction step for the purpose of removing the water.

[0285] <Implementation A>

[0286] Embodiment A which is one of the preferred embodiments of the method for producing a thiourethane resin raw material of the present disclosure is shown below.

[0287] Embodiment A is an embodiment in which, in the method for producing a thiourethane resin raw material of the present disclosure, the foreign matter is a UV absorber, the active hydrogen compound is an amine compound, and the thiourethane resin raw material is a polythiol composition.

[0288] Embodiment A is the same as the method for producing a thiourethane resin raw material of the present disclosure, and preferred embodiments are also the same, except that the foreign matter is a UV absorber, the active hydrogen compound is an amine compound, and the thiourethane resin raw material is a polythiol composition.

[0289] The method for producing the thiourethane resin raw material according to the embodiment A can be referred to as the method for producing the polythiol composition according to the embodiment A.

[0290] According to the method for producing a thiourethane resin raw material (that is, the method for producing a polythiol composition) according to Embodiment A, the polythiol composition can be produced using the composition XA containing a thiourethane resin and a UV absorber as a starting material.

[0291] Specifically, the reaction step in Embodiment A is a step of contacting a composition XA containing a thiourethane resin and a UV absorber with an amine compound to react the thiourethane resin and the amine compound in the composition XA to produce a polythiol composition.

[0292] In the reaction step in Embodiment A, a reaction in which the thiourethane resin is decomposed by the amine compound, that is, aminolysis occurs, and the target polythiol composition is produced by the aminolysis.

[0293] Preferred aspects of the amine compound and the polythiol composition in Embodiment A are as described above, respectively.

[0294] The composition XA in embodiment A contains at least one ultraviolet light absorber.

[0295] Examples of the ultraviolet absorber include:

[0296] 2,2'-Dihydroxy-4-methoxybenzophenone,

[0297] 2-Hydroxy-4-acryloyloxybenzophenone,

[0298] 2-Hydroxy-4-acryloyloxy-5-tert-butylbenzophenone,

[0299] 2-Hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone,

[0300] Benzophenone-based UV absorbers;

[0301] 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,

[0302] 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,

[0303] 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,

[0304] 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine,

[0305] 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine,

[0306] etc. triazine-based UV absorbers;

[0307] 2-(2H-Benzotriazol-2-yl)-4-methylphenol,

[0308] 2-(2H-Benzotriazol-2-yl)-4-tert-octylphenol,

[0309] 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol,

[0310] 2-(2H-Benzotriazol-2-yl)-4,6-di-tert-amylphenol,

[0311] 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol,

[0312] 2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol,

[0313] 2,2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol],

[0314] Benzotriazole UV absorbers;

[0315] etc.

[0316] The ultraviolet absorber preferably includes a benzotriazole ultraviolet absorber. In this case, the content of the benzotriazole 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 further preferably 80% to 100% by mass.

[0317] The content of the ultraviolet absorber in the 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, based on the total amount of the thiourethane resin in the composition XA.

[0318] The total content of the thiourethane resin and the ultraviolet absorber in the composition XA is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, based on the total amount of the composition XA.

[0319] The target polythiol composition in Embodiment A may contain components other than the polythiol compound as impurities.

[0320] For example, the produced polythiol composition may be mixed with (that is, contain) an ultraviolet absorber derived from the raw materials.

[0321] However, in the case of producing a polythiol composition as a raw material of a thiourethane resin for an optical component (e.g., a lens), from the viewpoint of the optical properties of the optical component (e.g., the hue of the lens), the content of the ultraviolet absorber in the produced polythiol composition is preferably 4% by mass or less, more preferably 1% by mass or less, further preferably less than 0.1% by mass, and further preferably 0.05% by mass or less, relative to the total amount of the polythiol composition.

[0322] In addition, as a raw material of the thiourethane resin for an optical member (e.g., a lens), a blend of the target polythiol composition in Embodiment A (e.g., a polythiol composition having a high content of ultraviolet absorber) and a polythiol composition produced by a method described in a known document (e.g., JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, JP-A-60-199016, JP-A-60-217229, International Publication No. 2007 / 052329, International Publication No. 2008 / 047626, etc.) (e.g., a polythiol composition substantially containing no ultraviolet absorber) may be used.

[0323] [Method for producing polymerizable composition]

[0324] The method for producing the polymerizable composition of the present disclosure includes the following steps:

[0325] A process for producing a thiourethane resin raw material by using the method for producing a thiourethane resin raw material of the present disclosure; and

[0326] A step of obtaining a polymerizable composition using at least a part of the thiourethane resin raw material as at least a part of the raw material.

[0327] The method for producing the polymerizable composition of the present disclosure may include other steps as necessary.

[0328] In the method for producing a polymerizable composition of the present disclosure,

[0329] In the step of producing a thiourethane resin raw material, a composition X containing a thiourethane resin and foreign matter (for example, thiourethane resin and foreign matter in ground powder of a molded body containing thiourethane resin and foreign matter) is used as a starting material to produce a thiourethane resin raw material.

[0330] In the step of obtaining the polymerizable composition, the polymerizable composition is produced using at least a part of the thiourethane resin raw material produced above as at least a part of the raw material.

[0331] The obtained polymerizable composition can be used again for the production of thiourethane resin.

[0332] By operating as described above, in the method for producing the polymerizable composition of the present disclosure, effective utilization (ie, recycling) of materials (ie, thiourethane resin and its raw material) can be achieved.

[0333] Furthermore, as described above, according to the method for producing a thiourethane resin raw material of the present disclosure, a polythiol composition having a high purity of the polythiol component as a main component can be obtained compared to known methods (e.g., a method for obtaining a polythiol composition by reacting a thiourethane resin with sodium hydroxide).

[0334] In the method for producing a polymerizable composition of the present disclosure, the above-mentioned polythiol composition is used. Therefore, according to the polymerizable composition obtained by the method for producing a polymerizable composition of the present disclosure, a resin having excellent various properties (for example, optical properties (for example, refractive index and / or Abbe number), heat resistance, specific gravity d, etc.) can be produced.

[0335] Therefore, the polymerizable composition obtained by the method for producing a polymerizable composition of the present disclosure is particularly suitable as a composition for producing a thiourethane resin for an optical material.

[0336] Furthermore, as described above, according to the method for producing a thiourethane resin raw material of the present disclosure, a polythiol composition having a high purity of the polythiol component as a main component can be obtained compared to known methods (e.g., a method for obtaining a polythiol composition by reacting a thiourethane resin with sodium hydroxide).

[0337] In the method for producing a polymerizable composition of the present disclosure, the above-mentioned polythiol composition is used. Therefore, according to the polymerizable composition obtained by the method for producing a polymerizable composition of the present disclosure, a resin having excellent various properties (for example, optical properties (for example, refractive index and / or Abbe number), heat resistance, specific gravity d, etc.) can be produced.

[0338] Therefore, the polymerizable composition obtained by the method for producing a polymerizable composition of the present disclosure is particularly suitable as a composition for producing a thiourethane resin for an optical material.

[0339] <Process for producing thiourethane resin raw material>

[0340] Regarding the process of producing the thiourethane resin raw material, the method for producing the thiourethane resin raw material of the present disclosure described above can be appropriately referred to.

[0341] <Step of Obtaining a Polymerizable Composition>

[0342] In the step of obtaining the polymerizable composition, the polymerizable composition is obtained using at least a part of the thiourethane resin raw material obtained in the step of producing the thiourethane resin raw material as at least a part of the raw material.

[0343] In the step of obtaining the polymerizable composition, at least a portion of the thiourethane resin raw material obtained in the step of producing the thiourethane resin raw material is used, but the at least a portion may be mixed with other components as necessary.

[0344] Examples of other components include thiourethane resin raw materials (for example, new thiourethane resin raw materials) other than the thiourethane resin raw materials obtained in the step of producing the thiourethane resin raw materials (that is, thiourethane resin raw materials that are recycled products).

[0345] The polymerizable composition preferably contains a polythiol composition and a polyisocyanate compound as monomers.

[0346] The polythiol composition in this case preferably includes a polythiol composition which is a regenerated product.

[0347] Other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, free radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, inorganic pigments, etc.

[0348] Examples of the polymerization catalyst include tertiary amine compounds, inorganic acid salts or organic acid salts thereof, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0349] As the internal mold release agent, an acidic phosphate ester can be used. Examples of the acidic phosphate ester include phosphoric acid monoesters and phosphoric acid diesters, and each of them can be used alone or in combination of two or more.

[0350] Examples of the resin modifier include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, olefin compounds including (meth)acrylate compounds, etc. Here, the (meth)acrylate compound refers to at least one of an acrylate compound and a methacrylate compound.

[0351] Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers.

[0352] <When Implementation A is Applied>

[0353] In the step of producing the thiourethane resin raw material in the method for producing a polymerizable composition of the present disclosure, the aforementioned embodiment A can be applied.

[0354] That is, the step of producing the thiourethane resin raw material may be a step of producing the polythiol composition by the method for producing the polythiol composition according to the above-described embodiment A.

[0355] When Embodiment A is applied, in the step of obtaining a polymerizable composition, a polymerizable composition containing a polythiol composition produced by the method for producing a polythiol composition according to Embodiment A and a polyisocyanate compound can be produced. Preferred embodiments of the polyisocyanate compound are the same as the preferred embodiments of the “isocyanate compound as a raw material of a thiourethane resin” described in the section “Method for producing a raw material of a thiourethane resin”.

[0356] When embodiment A is applied, the mixing ratio of the polythiol composition and the polyisocyanate compound is not particularly limited. The molar ratio of the mercapto group of the polythiol compound and the isocyanate group of the polyisocyanate compound contained in the polythiol composition (mercapto group / isocyanate group) is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and further preferably 0.8 to 1.3. If the mixing ratio is within the above range, there is a tendency to be able to satisfy various properties such as the refractive index and heat resistance required as a plastic lens with good balance.

[0357] When embodiment A is applied, the total input 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 further preferably 90% by mass or more, relative to the total amount of the polymerizable composition produced.

[0358] In the step of obtaining the polymerizable composition when the embodiment A is applied, at least the polythiol composition and the polyisocyanate compound are mixed. However, the polythiol composition and the polyisocyanate compound may be mixed with other components as necessary.

[0359] In the step of obtaining the polymerizable composition, after at least the polythiol composition and the polyisocyanate compound are mixed, other components may be added to the mixture.

[0360] Examples of these other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, free radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, inorganic pigments, and the like.

[0361] [Manufacturing method of resin]

[0362] The method for producing the resin of the present disclosure comprises the following steps:

[0363] A step of producing a polymerizable composition using the method for producing a polymerizable composition of the present disclosure; and

[0364] A step of obtaining a resin by curing the polymerizable composition.

[0365] The method for producing the resin of the present disclosure may include other steps as necessary.

[0366] According to the method for producing a resin of the present disclosure, the same effects as those of the method for producing a polymerizable composition of the present disclosure described above can be achieved.

[0367] The resin produced by the resin production method of the present disclosure and the resin of the present disclosure described below are both thiourethane resins, but are simply referred to as "resins" in the present disclosure to distinguish them from thiourethane resins which are one of the starting materials of thiourethane resins.

[0368] In the step of obtaining the resin, the resin is obtained by curing the polymerizable composition.

[0369] The curing of the polymerizable composition can be performed by polymerizing the monomers in the polymerizable composition (for example, the polythiol composition and the polyisocyanate compound, hereinafter the same). As a pre-polymerization treatment, the polymerizable composition can be subjected to a treatment such as filtration and degassing.

[0370] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the above-mentioned polymerizable composition can be appropriately set in consideration of the composition of the composition, the type and amount of the monomers in the composition, the type and amount of the polymerization catalyst in the composition, the properties of the mold when using the mold described later, etc.

[0371] Examples of the polymerization temperature include -50°C to 150°C and 10°C to 150°C.

[0372] Examples of the polymerization time include 1 hour to 200 hours and 1 hour to 80 hours.

[0373] The step of obtaining the resin can be performed by subjecting a polymer obtained by polymerization of the monomers to treatment such as annealing to obtain the resin.

[0374] The annealing temperature is preferably 50°C to 150°C, more preferably 90°C to 140°C, and further preferably 100°C to 130°C.

[0375] [Method for producing molded article]

[0376] The method for producing a molded article of the present disclosure is a method for producing a molded article containing a resin, and the method comprises the following steps:

[0377] A step of producing a polymerizable composition using the method for producing a polymerizable composition of the present disclosure; and

[0378] A step of obtaining a molded body containing a resin by curing the polymerizable composition.

[0379] The method for producing a molded article of the present disclosure may include other steps as necessary.

[0380] According to the method for producing a molded article of the present disclosure, the same effects as those of the method for producing a polymerizable composition of the present disclosure described above can be achieved.

[0381] In the step of obtaining a molded article containing a resin, the molded article containing a resin is obtained by curing the polymerizable composition.

[0382] Preferred conditions for curing the polymerizable composition, that is, polymerization of the monomers in the polymerizable composition, can be appropriately referred to in the section "Method for producing a resin".

[0383] An example of the polymerization in this step is cast polymerization.

[0384] In cast polymerization, first, the polymerizable composition is injected into a mold held by a gasket, tape, etc. At this time, a degassing treatment, a filtration treatment, etc. may be performed as necessary.

[0385] Next, the monomers in the polymerizable composition injected between the molding dies are polymerized, thereby curing the composition between the molding dies to obtain a cured product. Next, the cured product is removed from the molding dies to obtain a molded body containing a resin.

[0386] The polymerization of the monomers can be carried out by heating the polymerizable composition. The heating can be carried out using a heating device having a mechanism for heating a heating object, for example, in an oven or in water.

[0387] [Method for producing optical materials, method for producing lenses]

[0388] The method for producing an optical material (e.g., a lens) of the present disclosure is a method for producing an optical material (e.g., a lens) containing a molded body containing a resin, and the method comprises the following steps:

[0389] A step of producing a polymerizable composition using the method for producing a polymerizable composition of the present disclosure; and

[0390] A step of obtaining a molded body containing a resin by curing the polymerizable composition.

[0391] The method for producing the optical material (eg, lens, hereinafter the same) of the present disclosure may also include other steps as required.

[0392] According to the method for producing an optical material of the present disclosure, the same effects as those of the method for producing a polymerizable composition of the present disclosure described above can be achieved.

[0393] The method for producing an optical material of the present disclosure is an application of the method for producing a molded body of the present disclosure.

[0394] For example, by appropriately selecting the shape of a molding die used for the aforementioned cast polymerization in the method for producing a molded body of the present disclosure, a molded body applicable to an optical material (eg, a lens) can be obtained.

[0395] Examples of the optical material include lenses (for example, eyeglass lenses, camera lenses, polarizing lenses), light emitting diodes (LEDs), and the like.

[0396] The method for producing an optical material (eg, a lens) of the present disclosure may include a step of forming a coating layer on one or both surfaces of a molded body including a resin.

[0397] Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifog coat layer, an antifouling layer, and a hydrophobic layer.

[0398] These coating layers may be formed individually or in multiple layers. When coating layers are formed on both sides, the same coating layers may be formed on each side, or different coating layers may be formed.

[0399] The components of the coating layer can be appropriately selected according to the purpose.

[0400] As components of the coating layer, for example, there can be mentioned resins (for example, polyurethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, etc.

[0401] Regarding the eyeglass lens and the coating layer, for example, the descriptions of known documents such as Japanese Patent Application Publication No. 2002-194083 and International Publication No. 2017 / 047745 can be appropriately referred to.

[0402] [Polymerizable composition]

[0403] The polymerizable composition of the present disclosure contains at least a part of the thiourethane resin raw material obtained by the aforementioned method for producing a thiourethane resin raw material of the present disclosure.

[0404] The polymerizable composition of the present disclosure can be produced by the aforementioned method for producing the polymerizable composition of the present disclosure.

[0405] According to the polymerizable composition of the present disclosure, the same effects as those of the above-mentioned method for producing the polymerizable composition of the present disclosure can be exhibited.

[0406] Preferred embodiments of the polymerizable composition of the present disclosure can refer to the aforementioned method for producing the polymerizable composition of the present disclosure as appropriate.

[0407] 〔Resins, molded products, optical materials (e.g. lenses)〕

[0408] The resin of the present disclosure is a cured product of the above-mentioned polymerizable composition of the present disclosure.

[0409] The molded product of the present disclosure is a molded product containing the resin of the present disclosure described above.

[0410] The optical material (eg, lens) of the present disclosure is an optical material (eg, lens) comprising the above-mentioned resin of the present disclosure.

[0411] The resin of the present disclosure, the molded article of the present disclosure, and the optical material (eg, lens) of the present disclosure can exert the same effects as the above-mentioned method for producing the polymerizable composition of the present disclosure.

[0412] The resin of the present disclosure, the molded body of the present disclosure, and the optical material (e.g., lens) of the present disclosure can each be manufactured using the aforementioned method for manufacturing the resin of the present disclosure, the method for manufacturing the molded body of the present disclosure, and the method for manufacturing the optical material (e.g., lens) of the present disclosure.

[0413] The preferred embodiments of the resin of the present disclosure, the molded body of the present disclosure, and the optical material (e.g., lens) of the present disclosure can each refer to the preferred embodiments of the method for producing the resin of the present disclosure, the method for producing the molded body of the present disclosure, and the method for producing the optical material (e.g., lens) of the present disclosure.

[0414] <Preferred properties of resin or molded article>

[0415] From the viewpoint of heat resistance, the glass transition temperature Tg of the resin (or molded article) of the present disclosure is preferably 80° C. or higher, more preferably 85° C. or higher.

[0416] The glass transition temperature Tg may be 105° C. or lower, or 100° C. or lower.

[0417] From the viewpoint of application to optical materials, the refractive index (nd) of the resin (or molded article) of the present disclosure is preferably 1.550 or more, more preferably 1.600 or more, and even more preferably 1.650 or more.

[0418] The upper limit of the refractive index (nd) is not particularly limited, and is, for example, 1.700.

[0419] From the viewpoint of application to optical materials, the Abbe number of the resin (or molded article) of the present disclosure is preferably 28 or more, more preferably 30 or more.

[0420] The upper limit of the Abbe number is not particularly limited, and is, for example, 40, preferably 35.

[0421] From the viewpoint of application to optical materials, the specific gravity d of the resin (or molded article) of the present disclosure is preferably 1.00 or more.

[0422] The upper limit of the specific gravity d is not particularly limited, and is, for example, 1.50, and preferably 1.40.

[0423] Example

[0424] Hereinafter, examples of the present disclosure will be described, but the present disclosure is not limited to the following examples.

[0425] Hereinafter, "%" means mass % and "room temperature" means 25°C unless otherwise specified.

[0426] Hereinafter, the purity (mass %) of the polythiol component T2 in the polythiol composition refers to the content (mass %) of the polythiol component T2 relative to the total amount of the polythiol composition, and more specifically, refers to the content (mass %) of the polythiol component T2 relative to the total amount of the polythiol composition measured by high performance liquid chromatography under the following conditions and obtained using an internal standard.

[0427] (High Performance Liquid Chromatography Conditions)

[0428] Column: YMC-Pack ODS-A (particle size S: 5 μm, pore size: 12 nm, column shape: Φ6 mm × 150 mm)

[0429] Mobile phase: acetonitrile / 0.01 mol potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol)

[0430] Column temperature: 40°C

[0431] Flow rate: 1.0ml / min

[0432] Detector: UV detector, wavelength 230nm

[0433] Preparation of the measurement solution: 160 mg of the sample was dissolved and mixed with 10 ml of acetonitrile.

[0434] Injection volume: 2μL

[0435] [Reference Production Example 1]

[0436] (Manufacture of Molded Article 1 Containing Thiourethane Resin)

[0437] In a stirred flask add:

[0438] Dimethyltin dichloride (trade name: NESTIN P, manufactured by Honjo Chemical Corporation) as a polymerization catalyst (100 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition described below),

[0439] Zelec-UN (produced by Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition described below),

[0440] meta-xylylene diisocyanate (XDI) (50.8 parts by mass) as a polyisocyanate compound, and

[0441] A polythiol composition (hereinafter referred to as “polythiol composition TA”) containing 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) as main components (49.2 parts by mass),

[0442] The mixture was stirred and mixed at room temperature for 1 hour to obtain a polymerizable composition as a transparent uniform solution.

[0443] Here, the purity of the polythiol component T2 in the polythiol composition TA (that is, the content of the polythiol component T2 relative to the total amount of the polythiol composition TA) was 85.5%.

[0444] Next, the polymerizable composition is filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then fully degassed under a reduced pressure of 600 Pa until no foaming is observed. The degassed polymerizable composition is injected between a pair of glass molds fixed with tape, and then the pair of glass molds are placed in an oven, and the temperature in the oven is set to 25°C. Next, the temperature in the oven is raised from 25°C to 120°C over 24 hours. Through the above process, the monomers (polyisocyanate compounds and polythiol composition TA) in the degassed polymerizable composition are polymerized to form a molded body containing the thiourethane resin R1 (i.e., a cured product of the polymerizable composition) between a pair of glass molds.

[0445] Next, the oven is cooled, and after cooling, the pair of glass molds are taken out of the oven, and then the molded body is taken out from the pair of glass molds to obtain a molded body.

[0446] (Manufacturing of Thiourethane Resin Powder R1)

[0447] The molded body obtained above was cut to produce a lens. The cut powder produced was collected and sieved (nominal mesh size specified in JIS Z-8801-1:2019: 2 mm) to obtain thiourethane resin powder R1 that passed the sieve (i.e., powder containing thiourethane resin R1).

[0448] [Example 1]

[0449] -Reaction process-

[0450] Thiourethane resin powder R1 (40 g) obtained in Reference Production Example 1 and cutting powder (4 g) of commercially available CR-39 resin (ADC (allyl diglycol carbonate) resin) as foreign matter were placed in a 300 mL flask equipped with a condenser to obtain composition X1.

[0451] Monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (15.8 g; 0.26 mol) and toluene (144 g) were added to the composition X1, 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”) as a raw material for a thiourethane resin (the above is a reaction step).

[0452] -Separation process (separation method B)-

[0453] The reaction mixture obtained in the reaction step is subjected to the separation step using the above-described separation method B including extraction or the like, thereby separating the polythiol composition from the reaction mixture.

[0454] The reaction mixture obtained in the reaction step is cooled to room temperature, and then the solid matter is removed by filtration to obtain a filtrate containing a polythiol composition.

[0455] 20 g of 35% hydrochloric acid was added to the obtained filtrate, and the mixture was separated after stirring. 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 added thereto to extract the soluble components to obtain a water extract.

[0456] The obtained water extract was washed twice with 50 g of toluene, and then 30 g of 35% hydrochloric acid was added and stirred to obtain an aqueous liquid.

[0457] The soluble component was extracted from the obtained aqueous liquid with 100 ml of toluene to obtain a toluene extract.

[0458] The toluene extract was washed twice with 100 g of water to obtain a toluene solution of a polythiol composition.

[0459] Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to sequential removal of low boiling point components using a vacuum pump and filtration using a 3-micron PTFE membrane filter, thereby obtaining 11.4 g of a polythiol composition containing 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) as main components (the above is the separation step).

[0460] The SH value of the obtained polythiol composition and the results of purity analysis of the polythiol component T2 by high performance liquid chromatography are shown in Table 1 described below.

[0461] [Examples 2 to 11]

[0462] The same operation as in Example 1 was carried out except that the type and addition amount of the foreign matter in the composition X1 prepared in the reaction step were changed as shown in Table 1 or Table 2.

[0463] The SH value of the obtained polythiol composition and the results of purity analysis of the polythiol component T2 by high performance liquid chromatography are shown in Table 1 or Table 2 described later.

[0464] In Tables 1 and 2, the details of the types of foreign matter are as follows.

[0465] CR-39…ADC (allyl diglycol carbonate) resin cutting powder

[0466] · Polyurethane resin…Cutting powder of polyurethane resin molded body

[0467] ·Acrylic resin…Cutting powder for acrylic resin molded bodies

[0468] · Polycarbonate resin…Cutting powder of polycarbonate resin molded body

[0469] · Protective film: a cut piece of a commercially available polyethylene film used to protect the surface of a resin molded body

[0470] · Engine oil: “CRE 5-56” manufactured by Kure Industry Co., Ltd.

[0471] Bismuth (Bi) ... Granular Bi manufactured by FUJIFILM Wako Pure Chemical Corporation.

[0472] Hard coat material: A hard coat material obtained by cutting a commercially available hard-coated lens.

[0473] Dimethyltin dichloride ...Dimethyltin dichloride (trade name: NESTIN P, manufactured by Honjo Chemical Corporation) as a polymerization catalyst.

[0474] ·Plast Blue…Dye. Plast Blue 8514 manufactured by Arimoto Chemical Industry Co., Ltd.

[0475] Zelec-UN ...Zelec-UN (manufactured by Stepan; acidic phosphate ester) as a mold release agent.

[0476] [Example 12]

[0477] -Reaction process-

[0478] Thiourethane resin powder R1 (40 g) obtained in Reference Production Example 1 and 40 g of distilled water (ie, "water" as a foreign matter) were placed in a 300 mL flask equipped with a condenser to obtain a composition X1.

[0479] Monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (15.8 g; 0.26 mol) and toluene (144 g) were added to the composition X1, and heated and stirred for 9 hours in an oil bath at 100° C. to obtain a reaction mixture containing a polythiol composition as a raw material of a thiourethane resin (the above is a reaction step).

[0480] -Separation process (separation method A)-

[0481] The reaction mixture obtained in the reaction step is subjected to the separation step according to the above-described separation method A including acid washing, etc., to separate the polythiol composition from the reaction mixture.

[0482] The reaction mixture obtained in the reaction step is cooled to room temperature, and then the solid matter is removed by filtration to obtain a filtrate containing a polythiol composition.

[0483] To the obtained filtrate was added 20 g of 35% hydrochloric acid, and the mixture was stirred and then separated, and washed twice with 100 mL of water to obtain a toluene solution of a polythiol composition.

[0484] Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to sequential removal of low-boiling point components using a vacuum pump and filtration using a 3-micron PTFE membrane filter, thereby obtaining 9.3 g of a polythiol composition containing the polythiol component T2 as a main component (the above is the separation step).

[0485] The SH value of the obtained polythiol composition and the results of purity analysis of the polythiol component T2 by high performance liquid chromatography are shown in Table 2 described below.

[0486] [Example 13]

[0487] -Reaction process-

[0488] Thiourethane resin powder R1 (40 g) obtained in Reference Production Example 1 and 40 g of distilled water (ie, "water" as a foreign matter) were placed in a 300 mL flask equipped with a condenser and a Dean-Stark tube to obtain a composition X1.

[0489] Monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (15.8 g; 0.26 mol) and toluene (144 g) were added to the composition X1, and the mixture was heated and stirred for 5 hours using a 120°C oil bath while distilling off water, thereby obtaining a reaction mixture containing a polythiol composition (the above is a reaction step).

[0490] -Separation process (separation method A)-

[0491] The reaction mixture obtained in the reaction step was subjected to a separation step using separation method A including acid washing and the like in the same manner as in Example 12, thereby separating the polythiol composition from the reaction mixture.

[0492] The SH value in the obtained polythiol composition and the results of purity analysis of the polythiol component T2 by high performance liquid chromatography are shown in Table 2 described below.

[0493] [Table 1]

[0494]

[0495] [Table 2]

[0496]

[0497] As shown in Tables 1 and 2, in Examples 1 to 13, the polythiol composition TB as a raw material of the thiourethane resin can be produced by reacting the thiourethane resin in the composition X1 with the amine compound through a reaction step of bringing the composition X1 containing the thiourethane resin and the foreign matter into contact with the amine compound as an active hydrogen compound.

[0498] Furthermore, in Examples 1 to 13, by subjecting the reaction mixture obtained in the reaction step to the separation step, the polythiol composition TB having excellent purity of the polythiol component T2 can be separated from the reaction mixture.

[0499] [Example 101]

[0500] (Production of Molded Article Containing Thiourethane Resin)

[0501] A molded body containing a thiourethane resin was obtained by performing the same operation as in Reference Production Example 1 except that the polythiol composition TA (49.2 parts by mass) was changed to the polythiol composition TB (49.2 parts by mass) obtained in Example 1.

[0502] The obtained molded product had good transparency, no strain, and good appearance.

[0503] The properties of the molded products obtained above were tested.

[0504] The results are shown in Table 3.

[0505] The performance test items are set to optical properties (refractive index and Abbe number), heat resistance, and color.

[0506] Each test was carried out using the following test method.

[0507] Refractive index (ne), Abbe number (νe):

[0508] The refractive index (ne, nF', nC') at a wavelength of 546.1 nm (mercury e-line), a wavelength of 480.0 nm (Cd F' line), and a wavelength of 643.9 nm (Cd C' line) was measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, and the refractive index (ne) and the Abbe number (νe) were respectively determined.

[0509] Heat resistance:

[0510] The glass transition temperature (Tg) was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min) as an indicator of heat resistance.

[0511] Yellowness (YI):

[0512] The yellowness (YI) was measured on a 2 mm thick plate using a spectrocolorimeter (CM-5 manufactured by Konica Minolta) as an index of the hue in the optical material.

[0513] [Examples 102 to 113]

[0514] The same operation 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.

[0515] The results are shown in Table 3.

[0516] In Table 3, Composition TA refers to the polythiol composition TA used in Reference Production Example 1, and Examples 1 to 13 refer to the polythiol compositions TB obtained in Examples 1 to 13, respectively.

[0517] [Table 3]

[0518]

[0519] As shown in Table 3, the molded body of each example manufactured using the polythiol composition TB of each example (i.e., a polythiol composition obtained by contacting the powdered composition X obtained by cutting the molded body of Reference Production Example 1 with an amine compound) has performance that is not inferior to that of the molded body of Reference Production Example 1.

[0520] [Example 201]

[0521] In the above-mentioned Example 1, a polythiol composition as a raw material of a polyurethane resin was produced using the filtrate obtained by filtration in the separation step.

[0522] On the other hand, in Example 201 shown below, a polyamine compound as a raw material of a polyurethane resin was produced using the filtration residue (ie, solid matter) produced by filtration in the separation step of Example 1.

[0523] That is, in the reaction step of Example 1, the thiourethane resin in the composition X1 is decomposed (aminolyzed) into a polythiol composition as a raw material for the thiourethane resin and a polyurea compound as a raw material for the thiourethane resin by reacting with monoethanolamine (MEA), thereby obtaining a reaction mixture containing these thiourethane resin raw materials.

[0524] The reaction mixture was filtered to obtain a filtrate containing a polythiol composition as a raw material for a thiourethane resin (Example 1), and a filtration residue (i.e., a solid matter) containing a polyurea compound as a raw material for a thiourethane resin (Example 201). Furthermore, the polyurea compound was reacted with an amine compound to obtain a polyamine compound as a raw material for a thiourethane resin.

[0525] The details of Example 201 are described below.

[0526] (1st step)

[0527] In the separation step of Example 1, the solid matter (i.e., filter residue) produced by filtration was allowed to stand at room temperature and dried, thereby obtaining 40.3 g of a mixture containing urea (polyurea compound) of meta-xylylenediamine (XDA) and monoethanolamine (MEA) as main components (hereinafter also referred to as polyurea-containing mixture P1).

[0528] Here, XDA that forms a urea body is derived from meta-xylylene diisocyanate (XDI) in the polythiol composition TA which is a raw material of the thiourethane resin powder R1 used as a raw material.

[0529] Monoethanolamine (MEA) that forms a urea body is an active hydrogen compound used for decomposing the thiourethane resin powder R1 (for details, refer to the reaction process of Example 1).

[0530] (Second step)

[0531] The polyurea-containing mixture P1 (31.0 g) obtained in the first step was weighed in a 100 mL flask equipped with a condenser, and 31.0 g (0.30 mol) of diethylenetriamine (DET) (manufactured by FUJIFILM Wako Pure Chemical) as an amine compound was added thereto, and heated at 145° C. for 3 hours. 16.0 g (0.40 mol) of sodium hydroxide (NaOH) was then added thereto, and heated at 145° C. for 3 hours to obtain a second reaction mixture.

[0532] Methanol was added to the second reaction mixture to dilute it, and then the dilution was filtered under reduced pressure to remove sodium carbonate produced as a by-product of the reaction.

[0533] The obtained filtrate is concentrated under reduced pressure to obtain a mixed amine material.

[0534] The obtained mixed amine material was sampled and analyzed by gas chromatography to determine the concentration of XDA in the second reaction mixture (hereinafter also referred to as GC concentration).

[0535] The results are shown in Table 4.

[0536] In addition, assuming that the entire amount of the polyurea-containing mixture obtained in the first step is urea (polyurea compound) of XDA and MEA, the generation rate of XDA (hereinafter also referred to as GC yield) was calculated based on the GC concentration. The results are shown in Table 4.

[0537] Here, XDA is a target polyamine compound which is a raw material of a thiourethane resin.

[0538] [Examples 202 to 211]

[0539] The same operation as in Example 201 was performed except that the solid matter (i.e., filter residue) produced in the separation step of Example 1 was changed to the solid matter (i.e., filter residue) produced in the separation steps of Examples 2 to 11, respectively.

[0540] Tables 4 and 5 show the GC concentration and GC yield of XDA in the second reaction mixture.

[0541] [Table 4]

[0542]

[0543] [Table 5]

[0544]

[0545] As shown in Tables 4 and 5, in Examples 201 to 211, a reaction step of bringing a composition X1 containing a thiourethane resin and a foreign substance into contact with an amine compound (monoethanolamine (MEA)) as an active hydrogen compound can be used to react the thiourethane resin in the composition X1 with the amine compound (MEA) to obtain a polyurea compound as a raw material for the thiourethane resin (the above is the first step), and the polyurea compound can be reacted with an amine compound (DET) to obtain a polyamine compound (XDA) as a raw material for the thiourethane resin (the above is the second step).

[0546] Furthermore, by reacting the above-mentioned polyamine compound (XDA) with phosgene, a polyisocyanate compound (XDI; xylylene diisocyanate) which is a more direct raw material for a thiourethane resin can be obtained.

[0547] 《Examples and Comparative Examples of Implementation A》

[0548] Examples and comparative examples of embodiment A (i.e., an embodiment in which the foreign matter in the method for producing a thiourethane resin raw material of the present disclosure is limited to a combination of an ultraviolet absorber, an amine compound as an active hydrogen compound, and a polythiol composition as a thiourethane resin raw material) are shown below.

[0549] Hereinafter, "UV absorber" means an ultraviolet absorber.

[0550] Hereinafter, the purity (mass %) of the polythiol component T1 in the polythiol composition refers to the content (mass %) of the polythiol component T1 relative to the total amount of the polythiol composition, and more specifically, refers to the content (mass %) of the polythiol component T1 relative to the total amount of the polythiol composition measured by high performance liquid chromatography under the following conditions and obtained using an internal standard.

[0551] Similarly, the content (mass %) of the UV absorber in the polythiol composition refers to the content (mass %) of the UV absorber relative to the total amount of the polythiol composition, and more specifically, refers to the content (mass %) of the UV absorber relative to the total amount of the polythiol composition measured by high performance liquid chromatography under the following conditions and obtained using an internal standard.

[0552] (High Performance Liquid Chromatography Conditions)

[0553] Column: YMC-Pack ODS-A A-312 (S5Φ6mm×150mm)

[0554] Mobile phase: The concentration was changed 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) for measurement.

[0555] Column temperature: 40°C

[0556] Flow rate: 1.0mL / min

[0557] Detector: UV detector, wavelength 230nm

[0558] Preparation of the measurement solution: 150 mg of the internal standard (1,2,4-trimethylbenzene) and 160 mg of the sample were dissolved and mixed in 5 mL of acetonitrile.

[0559] Injection volume: 1μL

[0560] [Reference Production Example 301]

[0561] (Manufacture of Molded Article 301 Containing Thiourethane Resin and UV Absorber)

[0562] In a stirred flask add:

[0563] Dibutyltin dichloride as a polymerization catalyst (100 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition described below),

[0564] Tinuvin 329 (manufactured by BASF Japan Ltd., 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol) as a UV absorber (1.5 parts by mass),

[0565] Zelec-UN (produced by Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition described below),

[0566] meta-xylylene diisocyanate (XDI) (52 parts by mass) as a polyisocyanate compound, and

[0567] A polythiol composition TC (48 parts by mass) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) as a main component,

[0568] The mixture was stirred and mixed at room temperature (25° C.) for 1 hour to obtain a polymerizable composition as a transparent uniform solution.

[0569] Here, the purity of the polythiol component T1 in the polythiol composition TC (that is, the content of the polythiol component T1 relative to the total amount of the polythiol composition TC) was 92.2%.

[0570] Next, the polymerizable composition is filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then fully degassed under a reduced pressure of 600 Pa until no foaming is observed. The degassed polymerizable composition is injected between a pair of glass molds fixed with tape, and then the pair of glass molds are placed in an oven, and the temperature in the oven is set to 10°C. Next, the temperature in the oven is raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compounds and polythiol compositions) in the degassed polymerizable composition are polymerized to form a molded body (i.e., a cured product of the polymerizable composition) containing a thiourethane resin and a UV absorber between a pair of glass molds.

[0571] Next, the oven is cooled, and after cooling, the pair of glass molds are taken out of the oven, and then the molded body is taken out from the pair of glass molds, thereby obtaining a molded body 301 containing a thiourethane resin and a UV absorber.

[0572] (Manufacturing of Powdered Composition X301)

[0573] The molded body 301 obtained above was subjected to cutting to produce a lens. The cutting powder generated at this time was collected and sieved (the nominal mesh size specified in JIS Z-8801-1:2019 is 1 mm), and the powder that passed through the sieve was recovered to obtain a powdery composition X301 as a composition XA containing a thiourethane resin and a UV absorber.

[0574] [Reference Production Example 302]

[0575] (Manufacture of Molded Article 302 Containing Thiourethane Resin and UV Absorber)

[0576] A molded body 302 containing a thiourethane resin and a UV absorber was obtained by the same operation as in Reference Production Example 301 except that the amount of Tinuvin 329 as a UV absorber was changed from 1.5 parts by mass to 0.05 parts by mass.

[0577] (Manufacturing of Powdered Composition X302)

[0578] The molded body 302 obtained above was subjected to cutting to produce a lens. The cutting powder generated at this time was collected and sieved (the nominal mesh size specified in JIS Z-8801-1:2019 is 1 mm), and the powder that passed through the sieve was recovered to obtain a powdery composition X302 as a composition XA containing a thiourethane resin and a UV absorber.

[0579] [Example 301]

[0580] -Reaction process-

[0581] The entire amount of the powdered composition X301 (100 g) [Composition X] obtained in Reference Production Example 301 was placed in a 500-mL flask with a condenser, and monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (40.5 g; 0.663 mol) and toluene (193 g) were added thereto, and the mixture was heated and stirred at 90°C for 7 hours to obtain a reaction mixture containing a polythiol composition (the above is the reaction process).

[0582] -Separation process (separation method B)-

[0583] The reaction mixture obtained in the reaction step is subjected to a separation step using separation method B including extraction or the like, thereby separating the polythiol composition from the reaction mixture.

[0584] The reaction mixture obtained in the reaction step is cooled to 60°C, and then the solid matter is removed by filtration. 70.5 g of a 31% sodium hydroxide aqueous solution is added to the obtained filtrate and stirred. 75 g of water is added thereto to extract the soluble components, and the resulting water extract is washed with 50 g of toluene, and then 75 g of 35% hydrochloric acid is added and stirred. The soluble components are extracted from the obtained aqueous liquid using 120 g of toluene to obtain a toluene extract. The toluene extract is washed with 80 g of water, then washed with 80 g of 0.1% ammonia water, and then washed twice with 80 g of water to obtain a toluene solution of a polythiol composition.

[0585] Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling components using a vacuum pump and filtration using a 1-micron PTFE membrane filter, thereby obtaining 33.38 g of a polythiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) as a main component (the above is the separation step).

[0586] (Measurement)

[0587] The following measurements were performed on the obtained polythiol composition.

[0588] The results are shown in Table 6.

[0589] -Purity (mass %) of polythiol component T1 and content (mass %) of UV absorber-

[0590] The following were determined using high performance liquid chromatography under the aforementioned conditions:

[0591] The purity (mass %) of the polythiol component T1 in the polythiol composition, and

[0592] Content (mass %) of UV absorber in the polythiol composition.

[0593] -SH value (mmol / g)-

[0594] The SH value (mmol / g) (i.e., the number of millimoles of thiol groups per 1 g of the polythiol composition, the same below) in the polythiol composition was measured using a 0.05 mol / L iodine solution (manufactured by FUJIFILM Wako Pure Chemical) using a potentiometric automatic titrator manufactured by Kyoto Electronics Co., Ltd.

[0595] -Mixing ratio of UV absorber in polythiol composition (mass %)-

[0596] Based on the input amounts of the raw materials for obtaining the molded body 301, the mass (hereinafter referred to as mass M1) of the UV absorber in the starting material (powdered composition X301 (100 g)) was determined.

[0597] Based on the amount of the polythiol composition obtained in the separation step (33.38 g) and the content (mass %) of the UV absorber, the mass of the UV absorber in the polythiol composition (hereinafter referred to as mass M2) was determined.

[0598] Based on the mass M1 and the mass M2, the mixing ratio (mass %) of the UV absorber in the polythiol composition was determined from the following formula.

[0599] Mixing ratio of UV absorber in polythiol composition (mass %)

[0600] =(mass M2 / mass M1)×100

[0601] -Refractive Index-

[0602] The refractive index of the polythiol composition was measured using a refractometer RA-600 manufactured by Kyoto Electronics Industries, Ltd.

[0603] -YI (yellowness), L * 、a * , and b * -

[0604] The polythiol composition was measured using a spectrophotometer (CM-5 manufactured by Konica Minolta) with a cuvette length of 1 cm to measure the YI (yellowness) and CIE1976 (L * ,a * ,b* )L in the color system * 、a * , and b * .

[0605] -Appearance-

[0606] The appearance of the obtained polythiol composition was visually observed.

[0607] [Example 302]

[0608] -Reaction process-

[0609] The entire amount of the powdered composition X302 (200 g) [Composition XA] obtained in Reference Production Example 302 was placed in a 1000-mL flask with a condenser, and monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (81.0 g; 1.326 mol) and 386 g of toluene were added thereto. 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 process).

[0610] -Separation process (separation method B)-

[0611] The reaction mixture obtained in the reaction step is subjected to a separation step using separation method B including extraction or the like, thereby separating the polythiol composition from the reaction mixture.

[0612] The reaction mixture obtained in the reaction step is cooled to 60°C, and then the solid matter is removed by filtration. 143 g of a 31% sodium hydroxide aqueous solution is added to the obtained filtrate and stirred. 150 g of water is added thereto to extract the soluble components, and the resulting water extract is washed with 50 g of toluene, and then 150 g of 35% hydrochloric acid is added and stirred. The soluble components are extracted from the obtained aqueous liquid using 200 g of toluene to obtain a toluene extract. The toluene extract is washed with 160 g of water, then washed with 160 g of 0.1% ammonia water, and then washed twice with 160 g of water to obtain a toluene solution of a polythiol composition.

[0613] The obtained toluene solution was distilled off by a rotary evaporator. The obtained mixture was sequentially subjected to removal of low boiling point components by a vacuum pump and filtration by a 1-micron PTFE membrane filter, thereby obtaining 74.15 g of a polythiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) as a main component (the above is the separation step).

[0614] The same measurement as in Example 301 was performed on the obtained polythiol composition.

[0615] The results are shown in Table 6.

[0616] [Example 303]

[0617] The same operations as in Example 302 were performed except that an operation of removing toluene insoluble matter from the toluene extract by filtration was added between the operation of obtaining the toluene extract and the operation of washing the toluene extract with 160 g of water in the separation step.

[0618] The results are shown in Table 6.

[0619] In this Example 303, 80.02 g of a polythiol composition containing the polythiol component T1 as a main component was obtained.

[0620] [Example 304]

[0621] The same operations as in Example 302 were performed except that the operation of adding monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (81.0 g; 1.326 mol) and 386 g of toluene in the reaction step was changed to the operation of adding monoethanolamine (manufactured by FUJIFILM Wako Pure Chemical) (94.5 g; 1.547 mol) and 372 g of toluene (roughly, the input amounts of monoethanolamine and toluene were changed).

[0622] The results are shown in Table 6.

[0623] In this Example 304, 82.18 g of a polythiol composition containing the polythiol component T1 as a main component was obtained.

[0624] [Example 305]

[0625] The same operation as in Example 301 was performed except that the separation step based on the separation method B including extraction etc. was changed to the following separation step based on the separation method A including acid washing etc.

[0626] The results are shown in Table 6.

[0627] -Separation process (Example 305) (Separation method A)-

[0628] The reaction mixture obtained in the reaction step is subjected to a separation step using separation method A including acid washing or the like, thereby separating the polythiol composition from the reaction mixture.

[0629] The reaction mixture obtained in the reaction step was cooled to 60°C, and then the 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) from the filtrate (acid washing). The filtrate after the acid washing was washed with 80 g of water, then with 80 g of 0.1% ammonia water, and then washed twice with 80 g of water to obtain a toluene solution of a polythiol composition.

[0630] Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling components using a vacuum pump and filtration using a 1-micron PTFE membrane filter, thereby obtaining 43.20 g of a polythiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) as a main component (the above is the separation step).

[0631] [Example 306]

[0632] The same operation as in Example 302 was performed except that the separation step based on separation method B including extraction etc. was changed to the following separation step based on separation method A including acid washing etc.

[0633] The results are shown in Table 6.

[0634] -Separation process (Example 306) (Separation method A)-

[0635] The reaction mixture obtained in the reaction step is subjected to a separation step using separation method A including acid washing or the like, thereby separating the polythiol composition from the reaction mixture.

[0636] The reaction mixture obtained in the reaction step was cooled to 60°C and then filtered to remove the solid matter. The resulting filtrate was washed with 46 g of 35% hydrochloric acid to remove excess amine compounds (i.e., monoethanolamine) from the filtrate (acid washing). The filtrate after the acid washing was washed with 160 g of water, then with 160 g of 0.1% ammonia water, and then washed twice with 160 g of water to obtain a toluene solution of a polythiol composition.

[0637] Toluene was distilled off from the obtained toluene solution using a rotary evaporator. The obtained mixture was subjected to removal of low-boiling components using a vacuum pump and filtration using a 1-micron PTFE membrane filter, thereby obtaining 88.58 g of a polythiol composition containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component T1) as a main component (the above is the separation step).

[0638] [Table 6]

[0639]

[0640] As shown in Table 6, in Examples 301 to 306, the polythiol composition can be produced by reacting the thiourethane resin in the composition XA with the amine compound through a reaction step of contacting the composition XA containing the thiourethane resin and the ultraviolet absorber with the amine compound.

[0641] Furthermore, in Examples 301 to 306, by subjecting the reaction mixture obtained in the reaction step to a separation step, a polythiol composition having an excellent purity of the polythiol component T1 can be separated from the reaction mixture.

[0642] Among Examples 301 to 306, especially in Examples 301 to 304 in which a separation process based on separation method B including extraction or the like is implemented, the content of the UV absorber in the polythiol composition and the mixing rate of the UV absorber in the polythiol composition (i.e., the ratio of the mass of the UV absorber in the polythiol composition to the mass of the UV absorber in the starting material) can be reduced.

[0643] [Example 401]

[0644] (Production of Molded Article Containing Thiourethane Resin)

[0645] A molded body containing a thiourethane resin was obtained by performing the same operation as in Reference Production Example 301, except that the polythiol composition TC (48 parts by mass) was changed to the polythiol composition (48 parts by mass) obtained in Example 302.

[0646] The obtained molded product had good transparency, no strain, and good appearance.

[0647] The properties of the molded products obtained above were tested.

[0648] The results are shown in Table 7.

[0649] The performance test items were set to optical properties (refractive index and Abbe number), heat resistance, and hue. Each test was carried out by the following test method.

[0650] Refractive index (ne), Abbe number (νe):

[0651] The refractive index (ne, nF', nC') at a wavelength of 546.1 nm (mercury e-line), a wavelength of 480.0 nm (Cd F' line), and a wavelength of 643.9 nm (Cd C' line) was measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, and the refractive index (ne) and the Abbe number (νe) were respectively determined.

[0652] Heat resistance:

[0653] The glass transition temperature (Tg) was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min) as an indicator of heat resistance.

[0654] Yellowness (YI):

[0655] The yellowness (YI) was measured on a 9 mm thick flat plate using a spectrophotometer (CM-5 manufactured by Konica Minolta) as an index of the hue in the optical material.

[0656] The same performance test was also carried out on the molded body in the aforementioned reference production example 301.

[0657] The results are shown in Table 7.

[0658] [Examples 402-403]

[0659] The same operation as in Example 401 was carried out except that the polythiol composition (48 parts by mass) obtained in Example 302 was changed to the polythiol composition shown in Table 7.

[0660] The results are shown in Table 7.

[0661] 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 in Table 6, respectively.

[0662] [Table 7]

[0663]

[0664] As shown in Table 7, the molded bodies of each example manufactured using the polythiol composition of each example (i.e., the polythiol composition obtained by contacting the powdered composition X302 obtained by cutting the molded body of reference manufacturing example 302 with an amine compound) have performance that is not inferior to the molded body of reference manufacturing example 301, and in particular, an improvement in heat resistance is confirmed.

[0665] In particular, it was confirmed that the YI of the molded bodies of Examples 401 and 402 manufactured using the polythiol compositions obtained in Examples 302 and 304 (both using separation method B) was reduced compared to the molded body of Example 403 manufactured using the polythiol composition obtained in Example 306 (applying separation method A), and was superior in hue.

[0666] The entire disclosure of Japanese Patent Application No. 2020-192462 filed on November 19, 2020 and Japanese Patent Application No. 2021-125570 filed on July 30, 2021 are incorporated into this specification by reference.

[0667] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

Claims

1. A method for producing a thiourethane resin raw material, comprising: contacting a composition X containing a thiourethane resin and a foreign substance with an active hydrogen compound, thereby reacting the thiourethane resin in the composition X with the active hydrogen compound to produce a thiourethane resin raw material; in, The reaction step is a step of: contacting the composition X with the active hydrogen compound in the presence of a reaction solvent, thereby reacting the thiourethane resin in the composition X with the active hydrogen compound to obtain a reaction mixture containing the thiourethane resin raw material; The production method further includes a separation step of separating the thiourethane resin raw material from a reaction mixture containing the thiourethane resin raw material. The thiourethane resin raw material comprises a polythiol composition, The separation process comprises the following steps: A step of filtering a reaction mixture containing the thiourethane resin raw material to obtain a filtrate containing the polythiol composition; A step of adding a base containing an alkali metal to a filtrate containing the polythiol composition, followed by adding water and performing extraction, thereby obtaining a water extract containing an alkali metal salt of the polythiol composition; A step of adding an acid to a water extract containing an alkali metal salt of the polythiol composition to obtain an aqueous liquid containing the polythiol composition; A step of adding an extraction solvent to an aqueous liquid containing the polythiol composition and performing extraction to obtain an extract containing the polythiol composition; and a step of separating the polythiol composition from an extract containing the polythiol composition, wherein the foreign matter includes at least one selected from the group consisting of a resin other than thiourethane resin, a polymerization catalyst, a metal, an ultraviolet absorber, an internal mold release agent, a plasticizer, a dye, engine oil, and water; The active hydrogen compound is at least one selected from the group consisting of amine compounds and alcohol compounds.

2. The method for producing a thiourethane resin raw material according to claim 1, wherein The composition X is recovered in at least one of a process of manufacturing eyeglass lenses, a process of manufacturing eyeglasses, and a process of discarding eyeglasses.

3. The method for producing a thiourethane resin raw material according to claim 1 or claim 2, wherein: The composition X contains cutting powder including the thiourethane resin and the foreign matter.

4. A method for producing a polymerizable composition, comprising the following steps: A step of producing a thiourethane resin raw material by using the method for producing a thiourethane resin raw material according to any one of claims 1 to 3; and A step of producing a polymerizable composition using at least a part of the thiourethane resin raw material as a raw material.

5. A method for producing a resin, comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 4; and A step of obtaining a resin by curing the polymerizable composition.

6. A method for producing a molded article, which is a method for producing a molded article containing a resin, the method comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 4; and A step of obtaining a molded body containing a resin by curing the polymerizable composition.

7. A method for producing an optical material, which is a method for producing an optical material containing a molded body containing a resin, the method comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 4; and A step of obtaining a molded body containing a resin by curing the polymerizable composition.

8. A method for manufacturing a lens, which is a method for manufacturing a lens including a molded body containing a resin, the manufacturing method comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 4; and A step of obtaining a molded body containing a resin by curing the polymerizable composition.

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