Method for producing polythiol composition, method for producing polyamine compound and applications of these

Abstract

This method for producing a polythiol composition comprises a production step in which a polythiol composition is produced by decomposing a thiourethane resin by means of a decomposer that is represented by formula (1) or formula (2). In formula (1), each of R1 and R2 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an amino group (excluding the cases where both R1 and R2 are amino groups). In formula (2), R3 represents an alkyl group having 1 to 3 carbon atoms.

Description

Method for producing polythiol composition, method for producing polyamine compound, and applications thereof

[0001] The present disclosure relates to a method for producing a polythiol composition, a method for producing a polyamine compound, and applications thereof.

[0002] Plastic lenses, which are lenses containing resin, are lighter and less likely to break than inorganic lenses, and can be dyed, and therefore have rapidly become popular in recent years for use as eyeglass lenses, camera lenses, etc. For example, lenses containing thiourethane resins have been widely studied (see, for example, Patent Documents 1 to 3).

[0003] Also known is a method for producing a thiourethane resin raw material (i.e., a raw material for producing a thiourethane resin, such as a polythiol composition or a polyamine compound) using a thiourethane resin as a starting material. For example, Patent Document 4 discloses a method for producing a polythiol composition, including a reaction step of reacting a thiourethane resin with an amine compound to produce a polythiol composition. Patent Document 5 also discloses a method for producing a polyamine compound, including a first step of reacting a thiourethane resin with an amine compound A to produce a polyurea compound, and a second step of reacting the polyurea compound with an amine compound B to produce a polyamine compound. Patent Document 5 also discloses a method for producing a polyamine compound, including a step X1 of reacting a thiourethane resin with an alcohol compound in the presence of an amine compound XA, which is a tertiary amine compound, to produce a polycarbamate compound, and a step X2 of reacting the polycarbamate compound with an amine compound XB to produce a polyamine compound.

[0004] Patent Document 1: JP 63-46213 A Patent Document 2: JP 2-270859 A Patent Document 3: JP 7-252207 A Patent Document 4: WO 2021 / 157701 Patent Document 5: WO 2021 / 157702

[0005] In the production methods described in Patent Documents 4 and 5, an amine compound or an alcohol compound is used as a decomposing agent for decomposing a thiourethane resin, and the thiourethane resin is decomposed by the decomposing agent to obtain a polythiol composition or a polyamine compound as the target product. In the production methods described in Patent Documents 4 and 5, there is a need in some cases for further improving the removability of the decomposing agent when removing it from the reaction system after the decomposition reaction in which the thiourethane resin is decomposed by the decomposing agent (i.e., the amine compound or the alcohol compound).

[0006] An object of one aspect of the present disclosure is to provide a method for producing a polythiol composition, a method for producing a polyamine compound, and applications thereof, which are excellent in terms of removing the decomposing agent from the reaction system after the decomposition reaction in which a thiourethane resin is decomposed by the decomposing agent.

[0007] Means for solving the above problems include the following aspects: <1> A method for producing a polythiol composition, including a production step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) or the following formula (2) to produce a polythiol composition.

[0008]

[0009] In formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (provided that R １ and R ２ and R are both amino groups. ３ represents an alkyl group having 1 to 3 carbon atoms.

[0010] <2> The method for producing a polythiol composition according to <1>, wherein the producing step comprises reacting the thiourethane resin with the decomposer under a pressure higher than atmospheric pressure. <3> The method for producing a polythiol composition according to <1> or <2>, wherein the method is a method for producing a polythiol composition for use in producing optical materials. <4> The method for producing a polythiol composition according to any one of <1> to <3>, wherein the thiourethane resin is recovered during at least one of a process for producing eyeglass lenses, a process for producing eyeglasses, and a process for disposing of eyeglasses. <5> A method for producing a polymerizable composition, comprising: a step of producing a polythiol composition by the method for producing a polythiol composition according to any one of <1> to <4>; and a step of mixing the polythiol composition with a polyisocyanate compound to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate compound.

[0011] <6> The step of obtaining a polymerizable composition is a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition by mixing the polythiol composition with a polyisocyanate composition containing a polyisocyanate compound, wherein the polyisocyanate composition contains xylylene diisocyanate and at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3), wherein when the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by high performance liquid chromatography is 0.20 ppm or more relative to 100 ppm of the peak area of ​​xylylene diisocyanate, and when the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by high performance liquid chromatography is 0.05 ppm or more relative to 100 ppm of the peak area of ​​xylylene diisocyanate, <5> The method for producing a polymerizable composition according to <5>, wherein, when the polyisocyanate composition contains the compound (N3), a peak area of ​​the compound (N3) measured by high performance liquid chromatography is 0.10 ppm or more relative to 100 of a peak area of ​​xylylene diisocyanate.

[0012]

[0013] <7> A method for producing a resin, comprising: a step of producing a polymerizable composition by the method for producing a polymerizable composition according to <5>; and a step of obtaining a resin by curing the polymerizable composition. <8> A method for producing a polyamine compound, comprising: a first step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) to produce a polyurea compound, and a second step of decomposing the polyurea compound with a decomposing agent represented by the following formula (3):

[0014]

[0015] In formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (provided that R １ and R ２ and R are both amino groups. １１ and R １２ each independently represents a hydroxy group, a mercapto group, an amino group, or a monomethylamino group.

[0016] <9> The method for producing a polyamine compound according to <8>, wherein the decomposing agent represented by formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol. <10> The method for producing a polyamine compound according to <8> or <9>, wherein the first step comprises reacting the thiourethane resin with the decomposing agent represented by formula (1) under a pressure higher than atmospheric pressure. <11> The method for producing a polyamine compound according to any one of <8> to <10>, wherein the second step comprises reacting the polyurea compound with the decomposing agent represented by formula (3) under a pressure higher than atmospheric pressure. <12> A method for producing a polyamine compound, comprising: a step X1 of decomposing a thiourethane resin with a decomposing agent represented by formula (2) in the presence of a tertiary amine compound as a decomposition assistant to produce a polycarbamate compound; and a step X2 of decomposing the polycarbamate compound with a decomposing agent represented by formula (3) to produce a polyamine compound.

[0017] [In formula (2), R ３ represents an alkyl group having 1 to 3 carbon atoms. １１ and R １２ each independently represents a hydroxy group, a mercapto group, an amino group, or a monomethylamino group.

[0018] <13> The method for producing a polyamine compound according to <12>, wherein the molecular weight of the tertiary amine compound is 1,000 or less, and the decomposing agent represented by formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol. <14> The method for producing a polyamine compound according to <12> or <13>, wherein the step X1 comprises reacting the thiourethane resin with the decomposing agent represented by formula (2) under a pressure higher than atmospheric pressure. <15> The method for producing a polyamine compound according to any one of <12> to <14>, wherein the step X2 comprises reacting the polycarbamate compound with the decomposing agent represented by formula (3) under a pressure higher than atmospheric pressure. <16> The method for producing a polyamine compound according to any one of <8> to <15>, wherein the method is a method for producing a polyamine compound as a raw material for a polyisocyanate compound used in producing optical materials. <17> The method for producing a polyamine compound according to any one of <8> to <15>, wherein the thiourethane resin is recovered during at least one of the processes of producing eyeglass lenses, producing eyeglasses, and disposing of eyeglasses. <18> A method for producing a polyisocyanate compound, comprising: a step of producing a polyamine compound by the method for producing a polyamine compound according to any one of <8> to <16>; and a step of reacting at least one of the polyamine compound and a hydrochloride salt of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound. <19> A method for producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to <18>; and a step of mixing at least the polyisocyanate compound with an active hydrogen compound to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound. <20> A method for producing a resin, comprising: a step of producing a polymerizable composition by the method for producing a polymerizable composition according to <19>; and a step of curing the polymerizable composition to obtain a resin.

[0019] According to one aspect of the present disclosure, there are provided a method for producing a polythiol composition, a method for producing a polyamine compound, and applications thereof, which are excellent in terms of removing a decomposing agent from a reaction system after a decomposition reaction in which a thiourethane resin is decomposed by the decomposing agent.

[0020] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. In the present disclosure, the amount of each component contained in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. In the numerical ranges described in stages in the present disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. There may be overlap between multiple embodiments in the present disclosure. That is, the features of one embodiment may be included in another embodiment.

[0021] First Embodiment Method for Producing Polythiol Composition (First Embodiment) A method for producing a polythiol composition according to a first embodiment of the present disclosure includes a production step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) or the following formula (2) to produce a polythiol composition.

[0022]

[0023] In formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (provided that R １ and R ２ and R are both amino groups. ３ represents an alkyl group having 1 to 3 carbon atoms.

[0024] In the method for producing a polythiol composition according to the first embodiment, a thiourethane resin is decomposed using a decomposing agent represented by formula (1) or formula (2) to produce a polythiol composition. The method for producing a polythiol composition according to the first embodiment is excellent in terms of the ability to remove the decomposing agent from the reaction system after the decomposition reaction of the thiourethane resin. For example, the decomposing agent can be easily removed from the reaction system after the decomposition reaction by volatilization, distillation, or the like. The reason for this effect is thought to be that the decomposing agent is a compound with a low boiling point.

[0025] Hereinafter, each step that can be included in the method for producing the polythiol composition according to the first embodiment will be described.

[0026] <Production Step> The production step is a step of decomposing a thiourethane resin with a decomposing agent represented by the above formula (1) or (2) (i.e., reacting the thiourethane resin with the decomposing agent) to produce a polythiol composition. The decomposing agent represented by the above formula (1) is an amine compound. The decomposition reaction in which a thiourethane resin is decomposed with the decomposing agent represented by formula (1) is an amine decomposition reaction. The decomposing agent represented by formula (1) is an alcohol compound. The decomposition reaction in which a thiourethane resin is decomposed with the decomposing agent represented by formula (1) is an alcoholysis reaction.

[0027] (Thiourethane resin) The thiourethane resin is a starting material in the production process. There are no particular limitations on the thiourethane resin, and examples thereof include thiourethane resins described in known documents such as JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, WO 2008 / 047626, WO 2021 / 157701, and WO 2021 / 157702.

[0028] The thiourethane resin typically contains a polymer of an isocyanate compound and a polythiol composition, that is, the thiourethane resin is typically produced using an isocyanate compound and a polythiol composition as raw materials.

[0029] -Polythiol Composition as a Raw Material for Thiourethane Resin-In the present disclosure, a polythiol composition (i.e., a polythiol composition as a raw material for a thiourethane resin, and a polythiol composition that is the target of the method for producing a polythiol composition of the present disclosure described below) refers to a composition containing at least one polythiol compound. The polythiol compound may be any compound that contains two or more thiol groups (also known as mercapto groups), and is not otherwise particularly limited. For information on polythiol compounds, the above-mentioned publicly known literature on thiourethane resins may be referenced as appropriate.

[0030] The polythiol composition may contain components other than the polythiol compound as impurities. The polythiol composition preferably contains at least one polythiol compound as a main component.

[0031] 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 relative to the total amount of the polythiol composition is 50% or more. The total content of the at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

[0032] Similarly, in the present disclosure, the expression "containing a certain component (hereinafter referred to as "component X") as a "major component" means that the content of component X (when component X consists of two or more compounds, the total content of the two or more compounds) is 50% or more of the total amount of the composition. The content of component X as the major component is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more of the total amount of the composition.

[0033] The term "%" in the explanation of the above phrase "contains as a major component" means the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) to the total area of ​​all peaks of the composition (e.g., a polythiol composition) determined by high performance liquid chromatography.

[0034] Hereinafter, the polythiol compound contained in the polythiol composition will also be referred to as the "polythiol component." Polythiol compositions as raw materials for thiourethane resins include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl)sulfide, and diethylene glycol bis(3-mercaptopropionate). It is preferable that the polythiol composition contains at least one selected from the group consisting of (hereinafter also referred to as "polythiol component A"). It is more preferable that the polythiol composition contains polythiol component A as a main component. In this case, the polythiol composition may contain at least one component other than polythiol component A (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0035] Other polythiol compounds include, for example, methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiane.

[0036] More specific embodiments of the polythiol composition as a raw material for the thiourethane resin include, for example: an embodiment containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A1") as the main component; 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 A2") as the main component; an embodiment containing pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as "polythiol component A3") as the main component; An embodiment including polythiol component A1 and polythiol component A3 as the main components; An embodiment including polythiol component A2 and polythiol component A3 as the main components; etc. The polythiol composition of each embodiment may contain at least one component other than the main components (e.g., other polythiol compound, component other than polythiol compound, etc.).

[0037] -Isocyanate Compound as a Raw Material for Thiourethane Resin- The isocyanate compound as a raw material for the thiourethane resin may be one type only, or two or more types. Examples of the isocyanate compound as a raw material for the thiourethane resin include known isocyanate compounds described in the above-mentioned known literature. The isocyanate compound as a raw material for the thiourethane resin preferably includes a polyisocyanate compound containing two or more isocyanato groups. The isocyanate compound as a raw material for the thiourethane resin more preferably contains a diisocyanate compound containing two isocyanato groups, more preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate (hereinafter also referred to as "isocyanate component N"), and even more preferably contains isocyanate component N as a main component.

[0038] From the viewpoint of the performance of the thiourethane resin [for example, optical properties (for example, refractive index and / or Abbe number), heat resistance, specific gravity d, etc.], the isocyanate compound used as a raw material for the thiourethane resin more preferably contains at least one selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and bis(isocyanatocyclohexyl)methane (hereinafter also referred to as "isocyanate component N1"), and even more preferably contains isocyanate component N1 as the main component.

[0039] -Other Components- The thiourethane resin may contain other components in addition to the polymer of at least one isocyanate compound and a polythiol composition. For other components that can be contained in the thiourethane resin, reference can be made to the components that can be contained in the polymerizable composition described below.

[0040] -Recovered Thiourethane Resin- The thiourethane resin is preferably recovered during at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses. This embodiment realizes recycling of thiourethane resin, a material for eyeglass lenses. Here, the "process of manufacturing eyeglass lenses" refers to the process of producing a resin by blending monomers, which are resin raw materials, and performing cast polymerization, and / or the process of cutting a resin molded body to obtain eyeglass lenses. The "process of manufacturing eyeglasses" refers to the process of manufacturing eyeglasses by combining eyeglass lenses with other components such as eyeglass frames. The "process of disposing of eyeglasses" refers to the process of disposing of eyeglasses that have been manufactured but are no longer needed, used eyeglasses, etc. In any of these processes, thiourethane resin, a material for eyeglass lenses, can be generated as waste. In this embodiment, thiourethane resin produced during at least one of these processes is used as a starting material, and this thiourethane resin is reacted with a decomposing agent to obtain a polythiol composition, which is a decomposition product of the thiourethane resin.

[0041] In the generating step, the thiourethane resin-containing processing waste may be brought into contact with a decomposing agent to react with the thiourethane resin in the processing waste, thereby further improving the reaction efficiency between the thiourethane resin and the decomposing agent.

[0042] There are no particular limitations on the form of the processing waste containing the thiourethane resin, and it may be in the form of powder or lumps.

[0043] There are no particular limitations on the method for contacting the processing waste containing the thiourethane resin with the amine compound, and examples include a method in which the processing waste and the decomposing agent (and, if necessary, a reaction solvent) are placed in a reaction vessel and stirred.

[0044] The thiourethane resin-containing processing waste is preferably cutting waste (including the concept of polishing waste, the same applies hereinafter) of a molded body containing a thiourethane resin and / or the above cutting waste that has been sieved (i.e., cutting waste that has passed through a sieve). Cutting waste of a molded body containing a thiourethane resin is generated, for example, when a molded body containing a thiourethane resin is cut to produce an optical material (e.g., a lens).

[0045] -Resin mixture containing thiourethane resin- The production step may be a step of contacting a resin mixture containing a thiourethane resin with a decomposition agent to react the thiourethane resin in the resin mixture with the decomposition agent to produce a polythiol composition.

[0046] The resin mixture containing the thiourethane resin further contains components other than the thiourethane resin, such as resins other than the thiourethane resin and inorganic materials (e.g., glass) for lens production.

[0047] The resin other than the thiourethane resin is not particularly limited. For example, a hybrid material of a thiourethane resin and a urethane resin produced by adding a polyol compound to the raw materials when producing the thiourethane resin; a hybrid material of a thiourethane resin and a urea resin produced by adding a polyamine compound to the raw materials when producing the thiourethane resin; etc. are also included in the scope of the resin mixture containing a thiourethane resin and a resin other than the thiourethane resin.

[0048] Further, examples of resins other than thiourethane resins include polyolefin films that protect the surfaces of resin molded articles for use in producing eyeglass lenses, hard coats or primer coats that protect the surfaces of resin molded articles for use in producing eyeglass lenses, abrasives used when polishing resin molded articles for use in producing eyeglass lenses, resin materials for fixing resin molded articles for use in cutting the resin molded articles for use in producing eyeglass lenses, and tapes or tape glues used to fix glass molds used in producing resin molded articles for use in producing eyeglass lenses.

[0049] The resin mixture preferably contains, as a resin other than the thiourethane resin, at least one resin selected from the group consisting of polycarbonate resin, polyallyl carbonate resin, acrylic resin, urethane resin, and episulfide resin. Similar to the thiourethane resin, these resins can also be used as materials for eyeglass lenses.

[0050] The resin mixture containing the thiourethane resin is preferably recovered during at least one of the processes for manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses. The processes for manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses are as described above. The resin mixture containing the thiourethane resin preferably contains cutting waste containing the thiourethane resin.

[0051] (Decomposer represented by formula (1) or formula (2)) The decomposer used in this step is a decomposer represented by formula (1) or formula (2). Examples of decomposers represented by formula (1) include ammonia, monomethylamine, monoethylamine, monopropylamine, dimethylamine, diethylamine, dipropylamine, and hydrazine. Of these, ammonia, monomethylamine, and diethylamine are preferred. Examples of decomposers represented by formula (2) include methanol, ethanol, and propanol. Of these, methanol or ethanol is preferred, and methanol is more preferred.

[0052] (Amount of decomposing agent charged) In the production step, the charged mass ratio of the decomposing agent to the thiourethane resin (i.e., the charged mass ratio [decomposing agent / thiourethane resin]) can be adjusted as appropriate, but is preferably 0.10 or more and less than 2.0. When the charged mass ratio [decomposing agent / thiourethane resin] is 0.10 or more, the production of the polythiol composition is further promoted. When the charged mass ratio [decomposing agent / thiourethane resin] is less than 2.0, the decomposing agent remaining in the reaction mixture can be further suppressed. The charged mass ratio [decomposing agent / thiourethane resin] is more preferably 0.10 or more and less than 1.0, even more preferably 0.15 to 0.95, and even more preferably 0.20 to 0.90.

[0053] The number of millimoles of the decomposing agent charged per 1 g of thiourethane resin is preferably 1.0 mmol / g to 50.0 mmol / g, more preferably 2.0 mmol / g to 30.0 mmol / g, and even more preferably 3.0 mmol / g to 20.0 mmol / g.

[0054] The charge equivalent of the decomposing agent relative to the thiourethane resin (charge equivalent [decomposing agent / thiourethane resin]) is preferably 1.0 to 15.0, more preferably 1.0 to 10.0, and even more preferably greater than 1.0 and 10.0 or less. When the charge equivalent [decomposing agent / thiourethane resin] is 1.0 or more, the production of the polythiol composition is further promoted. When the charge equivalent [decomposing agent / thiourethane resin] is 15.0 or less, the decomposing agent can be further suppressed from remaining in the reaction mixture.

[0055] (Tertiary amine compound as decomposition aid) When using a decomposition aid represented by the above formula (2) as a decomposition aid, in the production step, it is preferable to decompose the thiourethane resin with the decomposition aid represented by the above formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polythiol composition. There are no particular limitations on the tertiary amine compound as a decomposition aid other than that it is a tertiary amine compound. The tertiary amine compound as a decomposition aid may be a chain amine compound or a cyclic amine compound.

[0056] The molecular weight of the tertiary amine compound used as the decomposition assistant is preferably 1,000 or less, more preferably 500 or less, even more preferably 300 or less, and still more preferably 200 or less. The lower limit of the molecular weight of the tertiary amine compound used as the decomposition assistant is, for example, 59 or more, preferably 70 or more.

[0057] The tertiary amine compound used as the decomposition aid is not particularly limited as long as it is a tertiary amine compound. The tertiary amine compound used as the decomposition aid is preferably N,N-dimethylethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 4-(2-hydroxyethyl)morpholine, 1,4-diazabicyclo[2,2,2]octane, diazabicyclononene, or diazabicycloundecene. More preferred are N,N-dimethylethanolamine, N,N-diethylaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 1,4-diazabicyclo[2,2,2]octane, diazabicyclononene, and diazabicycloundecene, and even more preferred are N,N-dimethylethanolamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, N-ethylmorpholine, and 1,4-diazabicyclo[2,2,2]octane.

[0058] The charge mass ratio of the tertiary amine compound as a decomposition aid to the decomposition agent represented by the above formula (2) as a decomposition agent (i.e., charge mass ratio [decomposition aid / decomposition agent]) can be appropriately adjusted, but is preferably 0.001 to 2.00. The charge mass ratio [decomposition aid / decomposition agent] is more preferably 0.002 to 1.50, and even more preferably 0.004 to 1.20.

[0059] The molar ratio of the tertiary amine compound as the decomposition aid to the decomposition agent represented by the formula (2) as the decomposition agent (i.e., the molar ratio [decomposition aid / decomposition agent]) can be appropriately adjusted, but is preferably 0.001 to 3.00. The molar ratio [decomposition aid / decomposition agent] is more preferably 0.002 to 2.50, even more preferably 0.003 to 2.00, even more preferably 0.004 to 1.50, and even more preferably 0.004 to 1.00.

[0060] (Reaction Solvent) In the production step, it is preferable to react the thiourethane resin with the decomposing agent represented by formula (1) or formula (2) in the presence of a reaction solvent. The reaction solvent is preferably an organic solvent, and more preferably a hydrocarbon compound having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9). The hydrocarbon compound is preferably hexane, heptane, octane, nonane, decane, xylene, mesitylene, or toluene, more preferably heptane, octane, nonane, xylene, mesitylene, or toluene, and particularly preferably xylene or toluene. The reaction solvent may be one type or two or more types.

[0061] (Reaction Temperature) The reaction temperature between the thiourethane resin and the decomposing agent represented by formula (1) or formula (2) in the production step can be adjusted as appropriate. In the production step, the thiourethane resin and the decomposing agent represented by formula (1) or formula (2) are preferably contacted under temperature conditions (i.e., reaction temperature) of 50°C to 200°C (more preferably 60°C to 180°C, and even more preferably 70°C to 150°C). When the reaction temperature is 50°C to 200°C, the purity of the polythiol component as the main component in the polythiol composition as the target product (i.e., the content of the main component relative to the total amount of the polythiol composition) can be further improved.

[0062] (Reaction Time) The reaction time between the thiourethane resin and the decomposing agent represented by formula (1) or formula (2) in the production step can be adjusted as appropriate, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and even more preferably 1 to 10 hours.

[0063] (Reaction Pressure) The production step preferably includes reacting the thiourethane resin with the decomposing agent represented by formula (1) or formula (2) under a pressure higher than atmospheric pressure. This further suppresses volatilization of the decomposing agent represented by formula (1) or formula (2). In this case, the production step includes reacting the thiourethane resin with the decomposing agent represented by formula (1) or formula (2) under a pressure higher than atmospheric pressure, preferably by 0.01 MPa or more (more preferably 0.01 MPa or more and 2.0 MPa or less, and even more preferably 0.02 MPa or more and 1.0 MPa or less).

[0064] (Polythiol Composition as Target Product) Examples of the polythiol composition as the target product in the method for producing a polythiol composition according to the first embodiment include those similar to the polythiol composition that is a raw material for the thiourethane resin described above, and preferred embodiments are also similar.

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

[0066] The polythiol composition as the target product may have the same polythiol component as the main component and a reduced content of impurities as the polythiol composition as the raw material of the thiourethane resin as the starting material. When the impurity content in the polythiol composition as the target product is reduced, thickening of the polythiol composition is suppressed, which can have the advantage of extending the pot life of the polythiol composition.

[0067] The use of the target polythiol composition is not particularly limited. The target polythiol composition can be used, for example, to produce a thiourethane resin. Specific uses of the target polythiol composition include a polythiol composition for producing optical materials (e.g., eyeglass lenses).

[0068] (Polyurea Compound or Polycarbamate Compound) In the production step in the first embodiment, the thiourethane resin is decomposed by a decomposing agent to produce a polythiol composition, and a polyurea compound or polycarbamate compound may also be produced. Specifically, when a decomposing agent represented by formula (1) is used as the decomposing agent, a polythiol composition and a polyurea compound may be produced by decomposition of the thiourethane resin. In this case, the production step in the production method of a polythiol composition may also correspond to step 1 in the production method of a polyamine compound according to the second embodiment described below. When a decomposing agent represented by formula (2) is used as the decomposing agent, a polythiol composition and a polycarbamate compound may be produced by decomposition of the thiourethane resin. In this case, the production step in the production method of a polythiol composition may also correspond to step X1 in the production method of a polyamine compound according to the third embodiment described below.

[0069] (Reaction mixture containing polythiol composition) The production step may be a step of decomposing a thiourethane resin with a decomposing agent to produce a polythiol composition and obtaining a reaction mixture containing the polythiol composition as the target product. Other components in the reaction mixture other than the polythiol composition include the above-mentioned reaction solvent, residues of the raw materials (thiourethane resin and / or decomposing agent), impurities contained in the raw materials, the above-mentioned polyurea compound, the above-mentioned polycarbamate compound, etc.

[0070] <Separation Step> The method for producing a polythiol composition according to the first embodiment may include a separation step of separating the polythiol composition from the reaction mixture containing the polythiol composition produced in the production step. There are no particular limitations on the separation method in the separation step, and known methods can be applied. Examples of the separation method in the separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), and purification (e.g., column chromatography). A plurality of separation methods may be used in combination.

[0071] The separation step preferably includes filtering the reaction mixture containing the polythiol composition obtained in the reaction step to obtain a filtrate containing the polythiol composition. According to this embodiment, solids contained in the reaction mixture (e.g., solids containing by-products) can be more easily removed.

[0072] A more preferred embodiment of the separation step comprising obtaining a filtrate containing a polythiol composition is one in which the separation step comprises: filtering a reaction mixture containing the polythiol composition to obtain a filtrate containing the polythiol composition; acid-washing the filtrate containing the polythiol composition; and separating the polythiol composition from the filtrate after the acid wash (hereinafter referred to as Separation Mode A). According to Separation Mode A, since the acid wash makes it easy to remove alkaline components (e.g., residues of amine compounds) from the filtrate, a polythiol composition having a higher purity of the polythiol component as the main component can be obtained. In Separation Mode A, water washing may be added after the acid wash, and the polythiol composition may be separated from the filtrate after the water wash.

[0073] In Separation Mode 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.

[0074] A more preferred embodiment of the separation step comprising obtaining a filtrate containing a polythiol composition includes an embodiment (hereinafter referred to as separation embodiment B) in which the separation step comprises: filtering a reaction mixture containing the polythiol composition to obtain a filtrate containing the polythiol composition; adding an alkali metal-containing base to the filtrate containing the polythiol composition, and then adding water to perform extraction, thereby obtaining an aqueous extract containing an alkali metal salt of the polythiol composition; 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; adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to the aqueous liquid containing the polythiol composition, thereby performing extraction, thereby obtaining an extract containing the polythiol composition; and separating the polythiol composition from the extract containing the polythiol composition.

[0075] In separation mode B, first, the polythiol composition in the filtrate containing the polythiol composition is converted to an alkali metal salt, and then extracted with water to obtain an aqueous extract containing the alkali metal salt of the polythiol composition. Next, an acid is added to the extract to return 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 with the extraction solvent to obtain an extract containing the polythiol composition. The polythiol composition is separated from the obtained extract containing the polythiol composition. According to separation 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.

[0076] In the separation mode B, the alkali metal in the alkali metal-containing base is preferably sodium, potassium, or lithium, more preferably sodium or potassium. Examples of the alkali metal-containing base include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. The alkali metal-containing base can be added to the filtrate in the form of an alcohol solution (e.g., methanol solution, ethanol solution), if necessary.

[0077] In separation mode 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.

[0078] In Separation Mode B, the hydrocarbon compound used as the extraction solvent may be one type only, or two or more types may be used. In Separation Mode B, preferred embodiments of the hydrocarbon compound used as the extraction solvent are the same as the preferred embodiments of the hydrocarbon compound used as the reaction solvent described above. However, the reaction solvent and the extraction solvent may be the same or different.

[0079] A more preferred embodiment of the separation step comprising obtaining a filtrate containing a polythiol composition includes the following steps (hereinafter referred to as Separation Mode C): separating a reaction mixture containing the polythiol composition by decantation to obtain a residue containing the polythiol composition; adding an alkali metal-containing base to the residue containing the polythiol composition, and then adding water to perform extraction to obtain an aqueous extract containing an alkali metal salt of the polythiol composition; 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; adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to the aqueous liquid containing the polythiol composition to perform extraction to obtain an extract containing the polythiol composition; and separating the polythiol composition from the extract containing the polythiol composition. Separation Mode C is the same as Separation Step B, except that the residue containing the polythiol composition is obtained by decantation.

[0080] <Classification step> The method for producing a polythiol composition according to the first embodiment may further include a classification step of classifying cutting chips containing a thiourethane resin before the reaction step. In this case, the reaction step involves reacting the classified cutting chips with a decomposing agent represented by formula (1) or formula (2). When the method for producing a polythiol composition according to the first embodiment includes a classification step, the reaction step involves contacting cutting chips consisting of particles with a small particle size (i.e., average particle diameter) with a decomposing agent represented by formula (1) or formula (2), thereby further improving the reaction efficiency between the thiourethane resin and the decomposing agent represented by formula (1) or formula (2).

[0081] In the present disclosure, the average particle size may be, for example, a number average particle size. The particle size may be, for example, a circle-equivalent diameter. Classification methods include sieving, centrifugation, and the like. Regarding the embodiment in which sieving is performed as classification, the sieving step described below can be referred to.

[0082] <Sieving step> The method for producing a polythiol composition according to the first embodiment may further include a sieving step of sieving the cutting chips containing the thiourethane resin before the production step. In this case, in the production step, the cutting chips that have passed through the sieve are contacted with a decomposing agent represented by formula (1) or formula (2), thereby reacting the thiourethane resin in the cutting chips that have passed through the sieve with the decomposing agent represented by formula (1) or formula (2). When the method for producing a polythiol composition according to the first embodiment includes a sieving step, the cutting chips consisting of particles with small particle sizes are contacted with the decomposing agent represented by formula (1) or formula (2) in the production step, thereby further improving the reaction efficiency between the thiourethane resin and the decomposing agent represented by formula (1) or formula (2).

[0083] The sieve is not particularly limited. The nominal mesh size of the sieve as defined in JIS Z-8801-1:2019 is, for example, 0.1 mm to 20 mm, preferably 0.1 mm to 10 mm, more preferably 0.1 mm to 5 mm, even more preferably 0.1 mm to 2 mm, even more preferably 0.3 mm to 2 mm, and even more preferably 0.5 mm to 1.5 mm.

[0084] <Washing Step> The method for producing a polythiol composition according to the first embodiment may further include a washing step, prior to the production step, of washing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent. In this case, in the reaction step, the thiourethane resin washed in the washing step is reacted with a decomposing agent represented by formula (1) or formula (2). This results in a polythiol composition having a higher purity of the polythiol component as the main component. In particular, when cutting chips containing a thiourethane resin are used as the starting material in the method for producing a polythiol composition according to the first embodiment, the washing step can effectively remove oil originating from the cutting machine that is attached to the cutting chips, thereby resulting in a polythiol composition having a higher purity of the polythiol component as the main component.

[0085] The hydrocarbon compound used as the washing solvent may be one kind or two or more kinds. Preferred embodiments of the hydrocarbon compound used as the washing solvent are the same as the preferred embodiments of the hydrocarbon compound used as the reaction solvent described above. However, the reaction solvent and the washing solvent may be the same or different.

[0086] There are no particular limitations on the washing method used in the washing step, and known methods can be used, such as adding the washing solvent to cutting waste containing thiourethane resin (for example, thiourethane resin waste) and mixing the same.

[0087] When the method for producing a polythiol composition according to the first embodiment includes the sieving step and the washing step, the sieving step and the washing step are preferably performed in this order. In this case, since it is not necessary to wash away the cutting chips that did not pass through the sieve, the amount of washing solvent used can be further reduced.

[0088] [Method for Producing Polymerizable Composition (First Embodiment)] The method for producing a polymerizable composition according to the first embodiment of the present disclosure includes the steps of producing a polythiol composition by the method for producing a polythiol composition according to the first embodiment described above, and mixing at least the polythiol composition with a polyisocyanate compound to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate compound. The method for producing a polymerizable composition according to the first embodiment may include other steps as necessary.

[0089] In the method for producing a polymerizable composition according to the first embodiment, in the step of producing a polythiol composition, a polythiol composition is produced using a thiourethane resin (e.g., thiourethane resin in cutting waste from a molded product of a thiourethane resin) as a starting material; and in the step of obtaining a polymerizable composition, a polymerizable composition is produced containing the polythiol composition produced above and a polyisocyanate compound. The obtained polymerizable composition can be reused to produce a thiourethane resin. In this way, the method for producing a polymerizable composition according to the first embodiment achieves effective utilization (i.e., recycling) of materials (i.e., thiourethane resin and the polythiol composition that is its raw material).

[0090] Furthermore, the method for producing a polythiol composition according to the first embodiment provides a polythiol composition with a high purity of the polythiol component as the main component, compared to known methods (e.g., a method for producing a polythiol composition by reacting a thiourethane resin with sodium hydroxide). The method for producing a polymerizable composition according to the first embodiment uses such a polythiol composition, and therefore the polymerizable composition obtained by the method for producing a polymerizable composition according to the first embodiment can produce a resin with excellent performance properties (e.g., optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.). Therefore, the polymerizable composition obtained by the method for producing a polymerizable composition according to the first embodiment is particularly suitable as a composition for producing a thiourethane resin for optical materials.

[0091] <Step of Producing Polythiol Composition> For the step of producing a polythiol composition in the method for producing a polymerizable composition according to the first embodiment, the method for producing a polythiol composition according to the first embodiment described above can be referred to as appropriate.

[0092] <Step of Obtaining Polymerizable Composition> In the step of obtaining a polymerizable composition, at least the polythiol composition and a polyisocyanate compound are mixed to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate compound.

[0093] A preferred embodiment of the polyisocyanate compound used in the step of obtaining the polymerizable composition is the same as the preferred embodiment of the "isocyanate compound as a raw material for a thiourethane resin" described in the section "Method for producing a polythiol composition."

[0094] In the step of obtaining a polymerizable composition, the mixing ratio of the polythiol composition and the polyisocyanate compound is not particularly limited. In the step of obtaining a polymerizable composition, the ratio of the charged mass of the polythiol composition to the charged mass of the polyisocyanate compound (i.e., charged mass [polythiol composition / polyisocyanate compound]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, even more preferably 0.50 to 1.50, and even more preferably 0.70 to 1.30. Furthermore, the molar ratio of mercapto groups of the polythiol compound contained in the polythiol composition to isocyanato groups of the polyisocyanate compound (mercapto groups / isocyanato groups) is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3.

[0095] In the step of obtaining the polymerizable composition, the total charged mass of the polythiol composition and the polyisocyanate compound is not particularly limited, but is preferably 60 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, based on the total amount of the polymerizable composition to be produced.

[0096] The step of obtaining the polymerizable composition may be a step of mixing the polythiol composition with a polyisocyanate composition containing a polyisocyanate compound to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate composition.

[0097] Here, the polyisocyanate composition means a composition containing at least one polyisocyanate compound.

[0098] The polyisocyanate composition may contain components other than the polyisocyanate compound as impurities. The polyisocyanate composition preferably contains at least one polyisocyanate compound as a main component. The meaning of "containing as a main component" is as described above.

[0099] The polyisocyanate composition preferably contains xylylene diisocyanate.

[0100] Hereinafter, a polyisocyanate composition containing xylylene diisocyanate will also be referred to as an XDI composition. The XDI composition preferably contains xylylene diisocyanate as a main component.

[0101] The XDI composition preferably contains at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).

[0102]

[0103] Below, preferred embodiments of the XDI composition will be described from the viewpoint of achieving excellent stability of the polyisocyanate composition and transparency of the resin formed using the polyisocyanate composition.

[0104] When the XDI composition contains compound (N1), it is preferable that the peak area of ​​compound (N1) measured by gas chromatography under the following GC condition 1 is 0.20 ppm or more relative to the peak area 1 of xylylene diisocyanate. -GC condition 1- Packing material: DB-1 (film thickness) 1.5 μm Column: inner diameter 0.53 mm × length 60 m (manufactured by Agilent) Oven temperature: heating from 130°C to 220°C at 3°C / min, and after reaching 220°C, heating to 300°C at 10°C / min Split ratio: pulsed splitless method Injection port temperature: 280°C Detector temperature: 300°C Carrier gas: N ２ 158 kPa, H ２ 55 kPa, Air 45 kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0 mass% chloroform solution Injection amount: 2 μL Detection method: FID

[0105] The peak area of ​​the compound (N1) is more preferably 5.0 ppm or more, even more preferably 50 ppm or more, and even more preferably 100 ppm or more, relative to the peak area of ​​xylylene diisocyanate 1. The peak area of ​​the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 1000 ppm or less, relative to the peak area of ​​xylylene diisocyanate 1. The peak area of ​​the compound (N1) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0106] When the XDI composition contains compound (N2), the peak area of ​​compound (N2) measured by gas chromatography under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, 1. -GC condition 2- Column: HP-50+, inner diameter 0.25 mm × length 30 m × film thickness 0.25 μm (manufactured by Hewlett-Packard Company) Oven temperature: temperature increased from 50°C to 280°C at a rate of 10°C / min, and held for 6 minutes after reaching 280°C. Split ratio: pulsed splitless method Injection port temperature: 200°C Detector temperature: 280°C Carrier gas: He Carrier gas flow rate: 1.0 ml / min (constant flow rate control) Sample concentration: 1.0 mass% dichloromethane solution Injection amount: 1.0 μL Detection method: SIM (monitoring ions: m / z 180, 215) (content ratio of xylylene diisocyanate (XDI))

[0107] The peak area of ​​the compound (N2) is more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and even more preferably 0.6 ppm or more, relative to the peak area of ​​xylylene diisocyanate 1. The peak area of ​​the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and even more preferably 60 ppm or less, relative to the peak area of ​​xylylene diisocyanate 1. The peak area of ​​the compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6,373,536.

[0108] When the XDI composition contains compound (N3), the peak area of ​​compound (N3) measured by gas chromatography under the above-mentioned GC condition 1 is preferably 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) is more preferably 0.1 ppm or more, even more preferably 3.0 ppm or more, and even more preferably 5.0 ppm or more relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 300 ppm or less, even more preferably 100 ppm or less, and even more preferably 75 ppm or less relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) can be measured in accordance with the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0109] The acid content of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm. The lower limit of the acid content of the XDI composition is not particularly limited, but the lower limit is, for example, 1 ppm. The acid content of the XDI composition can be measured in accordance with the method described in paragraph 0091 of WO 2021 / 256417. The XDI composition may also contain a stabilizer.

[0110] In the step of obtaining a polymerizable composition, at least the polythiol composition and the polyisocyanate compound are mixed, but if necessary, the polythiol composition, the polyisocyanate compound, and other components may be mixed. Furthermore, in the step of obtaining a polymerizable composition, after mixing at least the polythiol composition and the polyisocyanate compound, other components may be added to the mixture. Examples of these other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, and inorganic pigments.

[0111] Examples of the polymerization catalyst include tertiary amine compounds, their inorganic or organic acid salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0112] The internal mold release agent may be an acidic phosphate ester. Examples of the acidic phosphate ester include a phosphate monoester and a phosphate diester, and these may be used alone or in combination of two or more.

[0113] Examples of the resin modifier include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, organic acid anhydrides, olefin compounds including (meth)acrylate compounds, etc. Here, the (meth)acrylate compound means at least one of an acrylate compound and a methacrylate compound.

[0114] In the step of obtaining the polymerizable composition, the above-mentioned components can be mixed in accordance with a conventional method, and the mixing method is not particularly limited.

[0115] [Method for Producing Resin (First Embodiment)] A method for producing a resin according to a first embodiment of the present disclosure includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment described above, and curing the polymerizable composition to obtain a resin. The method for producing a resin according to the first embodiment may include other steps as necessary.

[0116] The resin produced by the resin production method according to the first embodiment and the resin according to the first embodiment described below are both thiourethane resins, but in the present disclosure they are simply referred to as "resins" to distinguish them from the thiourethane resin that is one of the starting materials for the polythiol composition.

[0117] In the step of obtaining a resin, the polymerizable composition is cured to obtain a resin. The curing of the polymerizable composition can be carried out by polymerizing the monomers in the polymerizable composition (specifically, the polythiol composition and the polyisocyanate compound; the same applies hereinafter). As a pretreatment for polymerization, the polymerizable composition may be subjected to filtration, degassing, or other treatments. The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition are appropriately set taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, and, if a mold described below is used, the properties of the mold. Examples of polymerization temperatures include -50°C to 150°C, 10°C to 150°C, etc. Examples of polymerization times include 1 hour to 200 hours, 1 hour to 80 hours, etc.

[0118] In the step of obtaining the resin, the polymer obtained by polymerization of the monomer may be subjected to a treatment such as annealing, etc. The annealing temperature may be 50°C to 150°C, 90°C to 140°C, or 100°C to 130°C, etc.

[0119] [Method for Producing Molded Article (First Embodiment)] A method for producing a molded article according to a first embodiment of the present disclosure is a method for producing a molded article containing a resin, and includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment described above, and curing the polymerizable composition to obtain a molded article containing a resin. The method for producing a molded article according to the first embodiment may include other steps as necessary.

[0120] In the step of obtaining a molded article containing a resin, the polymerizable composition is cured to obtain a molded article containing a resin. For preferred conditions for curing the polymerizable composition, i.e., for polymerizing the monomers in the polymerizable composition, see the section "Method for producing a resin" as appropriate.

[0121] An example of polymerization in this step is cast polymerization. In cast polymerization, the polymerizable composition is first injected between molds held together by a gasket, tape, or the like. At this time, degassing, filtration, or the like may be performed as necessary. Next, the monomer in the polymerizable composition injected between the molds is polymerized to harden the composition between the molds and obtain a cured product. The cured product is then removed from the molds to obtain a molded product containing the resin. Polymerization of the monomer may be performed by heating the polymerizable composition. This heating can be performed, for example, using a heating device equipped with a mechanism for heating an object to be heated in an oven, water, or the like.

[0122] [Method for Producing Optical Material (First Embodiment), Method for Producing Lens (First Embodiment)] A method for producing an optical material (e.g., a lens) according to a first embodiment of the present disclosure is a method for producing an optical material (e.g., a lens) comprising a molded article containing a resin, and includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment described above, and curing the polymerizable composition to obtain a molded article containing a resin. The method for producing an optical material (e.g., a lens; the same applies hereinafter) according to the first embodiment may include other steps as necessary.

[0123] The method for producing an optical material according to the first embodiment is an application of the method for producing a molded article according to the first embodiment. For example, in the method for producing a molded article according to the first embodiment, by appropriately selecting the shape of the mold used in the above-described cast polymerization, it is possible to obtain a molded article that can be used as an optical material (for example, a lens).

[0124] Examples of optical materials include lenses (for example, eyeglass lenses, camera lenses, and polarized lenses), light-emitting diodes (LEDs), and the like.

[0125] The method for producing an optical material (for example, a lens) according to the first embodiment may include a step of forming a coating layer on one or both sides of a molded body containing a resin.

[0126] Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water-repellent layer. Each of these coating layers may be formed alone, or a plurality of coating layers may be formed in a multilayer structure. When coating layers are formed on both sides, the same coating layer may be formed on each side, or different coating layers may be formed on each side.

[0127] The components of the coating layer can be appropriately selected depending on the purpose, and examples of the components of the coating layer include resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, and antistatic agents.

[0128] For details about eyeglass lenses and coating layers, reference can be made as appropriate to the descriptions in publicly known documents such as International Publication No. WO 2017 / 047745.

[0129] [Polymerizable Composition (First Embodiment)] The polymerizable composition according to the first embodiment of the present disclosure contains a polythiol composition obtained by the method for producing a polythiol composition according to the first embodiment described above, and a polyisocyanate compound. The polymerizable composition according to the first embodiment can be produced by the method for producing a polymerizable composition according to the first embodiment described above. For preferred aspects of the polymerizable composition according to the first embodiment, the method for producing a polymerizable composition according to the first embodiment described above can be referenced as appropriate. However, the term "charged mass [polythiol composition / polyisocyanate compound]" should be read as the content mass ratio [polythiol composition / polyisocyanate compound], and the term "total charged mass of the polythiol composition and the polyisocyanate compound" should be read as the total content mass of the polythiol composition and the polyisocyanate compound.

[0130] [Resin (First Embodiment), Molded Article (First Embodiment), Optical Material (E.g., Lens) (First Embodiment)] The resin according to the first embodiment of the present disclosure is a cured product of the polymerizable composition according to the first embodiment of the present disclosure described above. The molded article according to the first embodiment of the present disclosure is a molded article containing the resin according to the first embodiment described above. The optical material (e.g., lens) according to the first embodiment is an optical material (e.g., lens) containing the resin according to the first embodiment described above.

[0131] The resin according to the first embodiment, the molded product according to the first embodiment, and the optical material (e.g., a lens) according to the first embodiment can be manufactured by the above-described method for manufacturing a resin according to the first embodiment, the method for manufacturing a molded product according to the first embodiment, and the method for manufacturing an optical material (e.g., a lens) according to the first embodiment, respectively. For preferred aspects of the resin according to the first embodiment, the molded product according to the first embodiment, and the optical material (e.g., a lens) according to the first embodiment, reference can be made to the preferred aspects of the above-described method for manufacturing a resin according to the first embodiment, the method for manufacturing a molded product according to the first embodiment, and the method for manufacturing an optical material (e.g., a lens) according to the first embodiment, respectively.

[0132] <Preferred Performance of Resin or Molded Article> From the viewpoint of heat resistance, the glass transition temperature Tg of the resin (or molded article) according to the first embodiment is preferably 70° C. or higher, more preferably 80° C. or higher, and even more preferably 85° C. or higher. The glass transition temperature Tg may be 130° C. or lower, 120° C. or lower, or 110° C. or lower.

[0133] From the viewpoint of application to optical materials, the refractive index (ne) of the resin (or molded product) according to the first embodiment is preferably 1.500 or more, more preferably 1.540 or more, and even more preferably 1.590 or more. There is no particular upper limit to the refractive index (ne), but the upper limit is, for example, 1.750.

[0134] From the viewpoint of application to optical materials, the Abbe number of the resin (or molded product) according to the first embodiment is preferably 28 or more, and more preferably 30 or more. There is no particular upper limit to the Abbe number, but the upper limit is, for example, 50, and preferably 45.

[0135] From the viewpoint of application to optical materials, the specific gravity d of the resin (or molded article) according to the first embodiment is preferably 1.10 or more, more preferably 1.20 or more. There is no particular upper limit to the specific gravity d, but the upper limit is, for example, 1.50, and preferably 1.40.

[0136] Second Embodiment [Method for Producing Polyamine Compound (Second Embodiment)] A method for producing a polyamine compound according to a second embodiment includes: a first step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) to produce a polyurea compound; and a second step of decomposing the polyurea compound with a decomposing agent represented by the following formula (3) to produce a polyamine compound.

[0137]

[0138] In formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (provided that R １ and R ２ and R are both amino groups. １１ and R １２ each independently represents a hydroxy group, a mercapto group, an amino group, or a monomethylamino group.

[0139] The method for producing a polyamine compound according to the second embodiment is excellent in the ability to remove the decomposing agent represented by formula (1) from the reaction system after the decomposition reaction in the first step. For example, the decomposing agent represented by formula (1) can be easily removed from the reaction system after the decomposition reaction in the first step by volatilization, distillation, or the like. This effect is believed to be due to the fact that the decomposing agent represented by formula (1) is a low-boiling compound. Here, the concept of "the reaction system after the decomposition reaction in the first step" encompasses not only the reaction system after the first step and before the second step, but also the reaction system after the first step and during and after the second step. For example, the decomposition of the polyurea compound in the second step may produce the decomposing agent represented by formula (1) together with the target polyamine compound. Even in this case, the method is excellent in the ability to remove the decomposing agent represented by formula (1) from the reaction system during and after the second step.

[0140] The method for producing a polyamine compound according to the second embodiment is also excellent in the ability to remove the decomposing agent represented by formula (3) from the reaction system after the decomposition reaction in step 2. For example, the decomposing agent represented by formula (3) can be easily removed from the reaction system after the decomposition reaction in step 2 by volatilization, distillation, or the like. The reason for this effect is thought to be that the decomposing agent represented by formula (3) is a compound with a low boiling point.

[0141] Hereinafter, each step that can be included in the method for producing a polyamine compound according to the second embodiment will be described.

[0142] <First Step> The first step is a step of decomposing a thiourethane resin with a decomposing agent represented by the above formula (1) to produce a polyurea compound.

[0143] For the first step, reference can be made to the production step in the method for producing a polythiol composition according to the first embodiment. In the first step, a polyurea compound and the aforementioned polythiol composition can be produced by decomposing a thiourethane resin with a decomposing agent represented by the above formula (1). Preferred aspects of the thiourethane resin and the decomposing agent represented by formula (1) in the first step are the same as the preferred aspects of the thiourethane resin and the decomposing agent represented by formula (1) in the method for producing a polythiol composition according to the first embodiment.

[0144] (Reaction Pressure) The first step preferably includes reacting the thiourethane resin with the decomposing agent represented by formula (1) under a pressure higher than atmospheric pressure. This can further suppress volatilization of the decomposing agent represented by formula (1). In this case, the first step includes reacting the thiourethane resin with the decomposing agent represented by formula (1) under a pressure higher than atmospheric pressure, preferably by 0.01 MPa or more (more preferably 0.01 MPa or more and 2.0 MPa or less, and even more preferably 0.02 MPa or more and 1.0 MPa or less).

[0145] (Polyurea Compound) The polyurea compound produced in the first step is an amination product of a thiourethane resin, produced by the reaction (i.e., amination) of a thiourethane resin with a decomposer represented by formula (1). The polyurea compound is a compound containing two or more urea bonds. For example, the polyurea compound is a polyurea compound having a structure in which all isocyanato groups in a polyisocyanate compound, which is one of the raw materials for the thiourethane resin, react with amino groups or monoalkylamino groups in an amine compound A to form urea bonds. In the present disclosure, a polyurea compound having such a structure may be referred to as a urea compound of a polyamine compound (e.g., m-xylylene diisocyanate (XDI)) corresponding to one of the raw materials, the polyisocyanate compound, (e.g., m-xylylene diisocyanate (XDI)), and an amine compound A (e.g., monoethanolamine (MEA)). Here, a polyamine compound corresponding to a polyisocyanate compound refers to a compound in which all isocyanato groups in a polyisocyanate compound are replaced with amino groups. The polyamine compound corresponding to the polyisocyanate compound is the target product in the method for producing a polyamine compound according to the second embodiment.

[0146] (First Reaction Step and First Separation Step) The first step may include a reaction step of reacting a thiourethane resin with a decomposer represented by formula (1) to obtain a reaction mixture containing a polyurea-containing mixture containing a polyurea compound, and a separation step of separating the polyurea-containing mixture from the reaction mixture. In this case, in the second step described below, the polyurea-containing mixture separated in the first separation step is mixed with the decomposer represented by formula (3), thereby reacting the polyurea compound in the polyurea-containing mixture with the decomposer represented by formula (3). Hereinafter, the polyurea-containing mixture refers to a mixture of two or more urea compounds containing a polyurea compound. Hereinafter, the reaction mixture, the reaction step, and the separation step will also be referred to as the first reaction mixture, the first reaction step, and the first separation step, respectively.

[0147] The preferred embodiment of the reaction in the first reaction step is as described above.

[0148] The separation method in the first separation step is not particularly limited, and known methods can be applied. Examples of the separation method in the first separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), and purification (e.g., column chromatography). A plurality of separation methods may be used in combination.

[0149] When the polyurea-containing mixture is produced as a solid in the first reaction step, the first separation step preferably includes filtering the first reaction mixture to obtain the polyurea-containing mixture as a residue. The resulting residue may be subjected to washing or other operations. In this case, the filtrate obtained by filtering the first reaction mixture may contain a polythiol composition, which is a by-product generated by the aminolysis reaction (more specifically, a by-product when the polyurea-containing mixture is the main product). For preferred aspects of the polythiol composition as a by-product, the above-mentioned preferred aspects of the polythiol composition as a raw material for thiourethane resins can be referenced as appropriate. The polythiol composition as a by-product generated by the aminolysis reaction can be used as a raw material for producing new thiourethane resins. This allows for effective use of materials (i.e., recycling).

[0150] When the polyurea-containing mixture is produced in the first reaction step as a liquid insoluble in the reaction solvent, the first separation step preferably involves separating the supernatant and obtaining the polyurea-containing mixture as an extraction residue by a decantation method involving repeated extraction and washing. The resulting extraction residue may be subjected to washing or other operations. In this case, the supernatant may contain a polythiol composition, which is a by-product generated by the aminolysis reaction (more specifically, a by-product when the polyurea-containing mixture is the main product). For preferred aspects of the polythiol composition as a by-product, the preferred aspects of the polythiol composition as a raw material for thiourethane resins, described above, can be referenced as appropriate. The polythiol composition as a by-product generated by the aminolysis reaction can be used as a raw material for producing new thiourethane resins. This allows for effective use of materials (i.e., recycling).

[0151] When the polyurea-containing mixture is dissolved in the first reaction solvent in the first reaction step, the first separation step preferably includes: filtering the first reaction mixture to obtain a filtrate; adding an alkali metal-containing base to the filtrate, and then adding water to perform extraction to remove the alkali metal salt of the polythiol composition as a by-product from the filtrate; and separating the polyurea-containing mixture from the filtrate from which the alkali metal salt has been removed. The separation of the polyurea-containing mixture from the filtrate from which the alkali metal salt has been removed can be performed by, for example, methods such as concentration or drying.

[0152] <Second Step> The second step is a step of generating a polyamine compound by decomposing the polyurea compound generated in the first step with a decomposing agent represented by formula (3). In the second step, the polyurea-containing mixture separated in the first separation step may be mixed with the decomposing agent represented by formula (3), thereby causing the polyurea compound in the polyurea-containing mixture to react with the decomposing agent represented by formula (3).

[0153] The reaction in the second step (second aminolysis) is superior in the efficiency of producing polyamine compounds compared to known reactions that produce polyamine compounds by reacting a polyurea compound with sodium hydroxide. As a result, the amount of polyamine compounds produced can be increased compared to when the above known reactions are applied. This effect can be confirmed by analyzing the reaction mixture obtained in the second step by gas chromatography (GC).

[0154] (Reaction Pressure) The second step preferably includes reacting the polyurea compound with the decomposing agent represented by formula (3) under a pressure higher than atmospheric pressure. This can further suppress volatilization of the decomposing agent represented by formula (3). In this case, the second step includes reacting the polyurea compound with the decomposing agent represented by formula (3) under a pressure higher than atmospheric pressure, preferably by 0.01 MPa or more (more preferably 0.01 MPa or more and 2.0 MPa or less, and even more preferably 0.02 MPa or more and 1.0 MPa or less).

[0155] (Decomposing Agent Represented by Formula (3)) The decomposing agent represented by formula (3) used in the second step is preferably ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol.

[0156] In the second step, the charge equivalent of the decomposing agent represented by formula (3) relative to the polyurea compound (charge equivalent [decomposing agent represented by formula (3) / polyurea compound]) is preferably 0.1 to 50, more preferably 0.15 to 45, and even more preferably 0.2 to 40. When the charge equivalent [decomposing agent represented by formula (3) / polyurea compound] is 0.1 or more, the production of the polyamine compound is further promoted. When the charge equivalent [decomposing agent represented by formula (3) / polyurea compound] is 50 or less, it is advantageous in terms of reducing the amount of decomposing agent represented by formula (3) used. In the second step, when the polyurea-containing mixture separated in the first separation step is mixed with the decomposing agent represented by formula (3) to react the polyurea compound in the polyurea-containing mixture with the decomposing agent represented by formula (3), the charge equivalent [decomposing agent represented by formula (3) / polyurea compound] may be determined by regarding the entire polyurea-containing mixture as the polyurea compound.

[0157] In the second step, the polyurea compound can be reacted with the decomposing agent represented by formula (3) in the absence of a reaction solvent. For example, by directly mixing a polyurea-containing mixture containing the polyurea compound with the decomposing agent represented by formula (3) in the absence of a reaction solvent, the polyurea compound can be reacted with the decomposing agent represented by formula (3) in the absence of a reaction solvent. However, in the second step, the polyurea compound can also be reacted with the decomposing agent represented by formula (3) in the presence of a reaction solvent.

[0158] (Second Reaction Temperature) The reaction temperature (hereinafter also referred to as the second reaction temperature) between the polyurea compound and the decomposing agent represented by formula (3) in the second step is adjusted as appropriate. In the second step, it is preferable to react the polyurea compound and the decomposing agent represented by formula (3) under temperature conditions (i.e., the second reaction temperature) of 80°C to 200°C (more preferably 90°C to 200°C, even more preferably 100°C to 200°C, even more preferably 110°C to 190°C, and even more preferably 120°C to 180°C). In addition, in the second step, the reaction may be carried out under pressurized conditions. When the reaction is carried out under pressurized conditions, the reaction time may be shortened in some cases.

[0159] (Second Reaction Time) The reaction time between the polyurea compound and the decomposing agent represented by formula (3) in the second step can be appropriately adjusted, but is preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours, and even more preferably 1 to 10 hours.

[0160] (Second reaction step and second separation step) The second step may include a reaction step of reacting a polyurea compound with a decomposing agent represented by formula (3) to obtain a reaction mixture containing a polyamine compound, and a separation step of separating the polyamine compound from the reaction mixture. Hereinafter, the reaction mixture, the reaction step, and the separation step will also be referred to as a second reaction mixture, a second reaction step, and a second separation step, respectively.

[0161] The preferred embodiment of the reaction in the second reaction step is as described above.

[0162] The separation method in the second separation step is not particularly limited, and known methods can be applied. Examples of the separation method in the second separation step include filtration, decantation, washing, extraction, distillation, reduced pressure (e.g., vacuuming), purification (e.g., column chromatography), etc. A plurality of separation methods may be used in combination.

[0163] A preferred embodiment of the second separation step includes an embodiment (also referred to as "second separation embodiment C") that includes: extracting the polyamine compound from the second reaction mixture with a second extraction solvent to obtain an extract; and separating the polyamine compound from the extract. In second separation embodiment C, the polyamine compound is not separated directly from the second reaction mixture, but is separated from the extract obtained by extracting the polyamine compound from the second reaction mixture. This further improves the isolation yield of the polyamine compound obtained. The reason for this is unclear, but it is thought to be because disproportionation (more specifically, the reaction in which the polyamine compound returns to the polyurea compound) in the second separation step is further suppressed.

[0164] A preferred embodiment of the second separation step includes separating the polyamine compound from the second reaction mixture by distillation.

[0165] When the polyamine compound is separated from the second reaction mixture by distillation, insoluble components may be removed from the second reaction mixture by filtration, and the polyamine compound may be separated from the second reaction mixture from which the insoluble components have been removed by distillation. When the insoluble components are removed from the second reaction mixture by filtration, the second reaction mixture may be diluted before filtration, and the diluted second reaction mixture may be filtered.

[0166] Examples of the second extractant in the second separation mode C include hydrocarbon compounds. For example, when a hydrocarbon compound is used as the second extractant, preferred examples of the hydrocarbon compound as the second extractant include the preferred examples of the hydrocarbon compound as the first reaction solvent described above. In this case, however, the hydrocarbon compound as the second extractant and the hydrocarbon compound as the first reaction solvent may be the same or different. In the second separation mode C, the operation of separating the polyamine compound from the extract preferably includes distillation.

[0167] (Polyamine Compound as Target Product) The polyamine compound as the target product in the method for producing a polyamine compound according to the second embodiment is a decomposition product of a thiopolyurea compound produced by the reaction of a polyurea compound with a decomposition agent represented by formula (3). The polyamine compound as the target product is preferably a polyamine compound corresponding to the polyisocyanate compound used as the raw material for the thiourethane resin, which is the starting material in the first step (more specifically, a compound in which the isocyanato groups in the polyisocyanate compound have been replaced with amino groups).

[0168] The polyamine compound as the target product may be any compound containing two or more amino groups. The polyamine compound as the target product preferably contains a diamine compound containing two amino groups, and preferably contains at least one selected from the group consisting of pentamethylenediamine, hexamethylenediamine, m-xylylenediamine, p-xylylenediamine, isophoronediamine, bis(aminomethyl)cyclohexane, bis(aminocyclohexyl)methane, 2,5-bis(aminomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(aminomethyl)bicyclo-[2.2.1]-heptane, tolylenediamine, 4,4'-diphenylmethanediamine, and phenylenediamine (hereinafter also referred to as "polyamine component A"), and more preferably contains polyamine component A as a main component.

[0169] The target polyamine compound more preferably contains at least one selected from the group consisting of m-xylylenediamine, 2,5-bis(aminomethyl)bicyclo-[2.2.1]-heptane, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, and 2,6-bis(aminomethyl)bicyclo-[2.2.1]-heptane (hereinafter also referred to as "polyamine component A1"), and even more preferably contains polyamine component A1 as a main component.

[0170] The use of the polyamine compound as the target product is not particularly limited and can be applied to various uses. The polyamine compound as the target product can be used, for example, as a raw material for a polyisocyanate compound. The produced polyisocyanate compound can be used, for example, to produce a thiourethane resin or a urethane resin.

[0171] Specific applications of the produced polyisocyanate compound include polyisocyanate compounds for producing optical materials (e.g., lenses). In other words, a specific example of the method for producing a polyamine compound according to the second embodiment is a method for producing a polyamine compound as a raw material for polyisocyanate compounds for producing optical materials. In this specific example, when cutting waste containing thiourethane resin generated during the production of optical materials is used as a starting material, recycling of the materials (thiourethane resin, polyisocyanate compound) is effectively achieved.

[0172] <Other Steps> The method for producing a polyamine compound according to the second embodiment may include other steps in addition to those described above. Examples of other steps include a classification step (e.g., a sieving step) and a washing step, which may also be included in the method for producing a polythiol composition according to the first embodiment.

[0173] [Method for Producing Polyisocyanate Compound (Second Embodiment)] A method for producing a polyisocyanate compound according to a second embodiment of the present disclosure includes: a step of producing a polyamine compound by the method for producing a polyamine compound according to the second embodiment described above; and a step of reacting at least one of the polyamine compound and a hydrochloride salt of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound.

[0174] According to the method for producing a polyisocyanate compound, a thiourethane resin is used as a starting material and a polyisocyanate compound can be obtained as a target product, thereby realizing recycling of materials (thiourethane resin and the polyisocyanate compound that is the raw material for the thiourethane resin).

[0175] The polyisocyanate compound produced by the method for producing a polyisocyanate compound according to the second embodiment may be used in a variety of applications without any particular limitations. The polyisocyanate compound may be used, for example, in the production of a thiourethane resin or a urethane resin.

[0176] Specific examples of the target polyisocyanate compound include the same compounds as the specific examples of "isocyanate compound as a raw material for thiourethane resin" in the section "Method for producing polythiol composition."

[0177] A specific application of the target polyisocyanate compound is a polyisocyanate compound for producing optical materials (e.g., lenses). In other words, a specific example of the method for producing a polyisocyanate compound according to the second embodiment is a method for producing a polyisocyanate compound for producing optical materials. In this specific example, when cutting chips containing thiourethane resin generated during the production of optical materials are used as the starting material, effective utilization (i.e., recycling) of the materials (thiourethane resin, polyisocyanate compound) is effectively realized.

[0178] In the step of obtaining a polyisocyanate compound, at least one of the polyamine compound and the hydrochloride salt of the polyamine compound is reacted with carbonyl dichloride (hereinafter also referred to as "phosgene") to convert the amino groups in the polyamine compound to isocyanato groups, thereby obtaining a polyisocyanate compound. This reaction itself is known, and known methods for producing polyisocyanate compounds can be referred to as appropriate.

[0179] [Method for Producing Polymerizable Composition (Second Embodiment)] A method for producing a polymerizable composition according to a second embodiment of the present disclosure includes the steps of: producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to the second embodiment described above; and mixing at least the polyisocyanate compound and an active hydrogen compound to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound. The method for producing a polymerizable composition according to the second embodiment may include other steps as necessary.

[0180] In the method for producing a polymerizable composition according to the second embodiment, in the step of producing a polyisocyanate compound, a polyisocyanate compound is produced using a thiourethane resin (e.g., thiourethane resin in cutting waste from a molded product of a thiourethane resin) as a starting material; and in the step of obtaining a polymerizable composition, a polymerizable composition containing the polyisocyanate compound produced above and an active hydrogen compound is produced. The obtained polymerizable composition can be reused to produce a thiourethane resin. In this way, the method for producing a polymerizable composition according to the second embodiment achieves effective utilization (i.e., recycling) of materials (i.e., thiourethane resin and its raw material, the polyisocyanate compound).

[0181] <Step of Producing Polyisocyanate Compound> For the step of producing a polyisocyanate compound, the above-described method for producing a polyisocyanate compound according to the second embodiment can be referred to as appropriate.

[0182] <Step of Obtaining Polymerizable Composition> In the step of obtaining a polymerizable composition, at least the polyisocyanate compound and the active hydrogen compound are mixed to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound.

[0183] Examples of the active hydrogen compound include polythiol compounds, polyol compounds, polyamine compounds, etc. The active hydrogen compound may be one type or two or more types. The active hydrogen compound is preferably a polythiol composition. A preferred embodiment of the polythiol composition as the active hydrogen compound is the same as the preferred embodiment of the "polythiol composition as a raw material for a thiourethane resin" described in the section "Method for producing a polyamine compound."

[0184] In the step of obtaining a polymerizable composition, the mixing ratio of the active hydrogen compound and the polyisocyanate compound is not particularly limited. In the step of obtaining a polymerizable composition, the ratio of the charged mass of the active hydrogen compound to the charged mass of the polyisocyanate compound (i.e., charged mass [active hydrogen compound / polyisocyanate compound]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, even more preferably 0.50 to 1.50, and even more preferably 0.70 to 1.30. In addition, the molar ratio of mercapto groups of the polythiol compound to isocyanato groups of the polyisocyanate compound (mercapto groups / isocyanato groups) contained in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3.

[0185] In the step of obtaining a polymerizable composition, the total charged mass of the active hydrogen compound and the polyisocyanate compound is not particularly limited, but is preferably 60 mass % or more, more preferably 80 mass % or more, and even more preferably 90 mass % or more, based on the total amount of the polymerizable composition to be produced.

[0186] In the step of obtaining the polymerizable composition, at least the polyisocyanate compound and the active hydrogen compound are mixed, but if necessary, the polyisocyanate compound and the active hydrogen compound may be mixed with other components. Furthermore, in the step of obtaining the polymerizable composition, after mixing at least the polyisocyanate compound and the active hydrogen compound, other components may be added to the mixture. For other components, reference can be made to the other components used in the method for producing a polymerizable composition according to the first embodiment.

[0187] In the step of obtaining the polymerizable composition, the above-mentioned components can be mixed in accordance with a conventional method, and the mixing method is not particularly limited.

[0188] [Method for Producing Resin (Second Embodiment)] A method for producing a resin according to a second embodiment of the present disclosure includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the second embodiment described above, and curing the polymerizable composition to obtain a resin.

[0189] The method for producing a resin according to the second embodiment is the same as the method for producing a resin according to the first embodiment, except that, instead of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment, a polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment, and preferred aspects are also the same.

[0190] [Method for Producing Molded Article (Second Embodiment)] A method for producing a molded article according to a second embodiment of the present disclosure is a method for producing a molded article containing a resin, and includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the second embodiment described above, and curing the polymerizable composition to obtain a molded article containing a resin.

[0191] The method for producing a molded article according to the second embodiment is the same as the method for producing a molded article according to the first embodiment, except that instead of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment, a polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment, and preferred aspects are also the same.

[0192] [Method for producing optical material (second embodiment), method for producing lens (second embodiment)] A method for producing an optical material (e.g., a lens) according to a second embodiment of the present disclosure is a method for producing an optical material (e.g., a lens) comprising a molded body containing a resin, and includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the second embodiment described above, and curing the polymerizable composition to obtain a molded body containing a resin. The method for producing an optical material (e.g., a lens; the same applies hereinafter) according to the second embodiment may include other steps as necessary.

[0193] The method for producing an optical material (e.g., a lens) according to the second embodiment is the same as the method for producing an optical material (e.g., a lens) according to the first embodiment, except that, instead of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment, a polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment, and preferred aspects are also the same.

[0194] [Resin (Second Embodiment), Molded Article (Second Embodiment), Optical Material (E.g., Lens) (Second Embodiment)] The resin according to the second embodiment of the present disclosure is a cured product of the polymerizable composition according to the second embodiment of the present disclosure described above. The molded article according to the second embodiment of the present disclosure is a molded article containing the resin according to the second embodiment described above. The optical material (e.g., lens) according to the second embodiment is an optical material (e.g., lens) containing the resin according to the second embodiment described above.

[0195] The resin, molded article, and optical material (for example, a lens) according to the second embodiment are similar to the resin, molded article, and optical material (for example, a lens) according to the first embodiment, except that a polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment instead of by the method for producing a polymerizable composition according to the first embodiment, and preferred aspects are also similar.

[0196] Third Embodiment Method for Producing Polyamine Compound (Third Embodiment) A method for producing a polyamine compound according to a third embodiment includes: a step X1 of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition assistant to produce a polycarbamate compound; and a step X2 of decomposing the polycarbamate compound with a decomposing agent represented by the following formula (3) to produce a polyamine compound.

[0197]

[0198] In formula (2), R ３ represents an alkyl group having 1 to 3 carbon atoms. １１ and R １２each independently represents a hydroxy group, a mercapto group, an amino group, or a monomethylamino group.

[0199] The method for producing a polyamine compound according to the third embodiment is excellent in the ability to remove the decomposing agent represented by formula (2) from the reaction system after the decomposition reaction in step X1. For example, the decomposing agent represented by formula (2) can be easily removed from the reaction system after the decomposition reaction in step X1 by volatilization, distillation, or the like. This effect is believed to be due to the fact that the decomposing agent is a low-boiling point compound. Here, the concept of "the reaction system after the decomposition reaction in step X1" encompasses not only the reaction system after step X1 and before step X2, but also the reaction system after step X1 and during and after step X2. For example, the decomposition of a polycarbamate compound in step X2 can produce the decomposing agent represented by formula (2) together with the target polyamine compound. Even in this case, the method is excellent in the ability to remove the decomposing agent represented by formula (2) from the reaction system during and after step X2.

[0200] The method for producing a polyamine compound according to the third embodiment is also excellent in the ability to remove the decomposing agent represented by formula (3) from the reaction system after the decomposition reaction in step X2. For example, the decomposing agent represented by formula (3) can be easily removed from the reaction system after the decomposition reaction in step X2 by volatilization, distillation, or the like. The reason for this effect is thought to be that the decomposing agent represented by formula (3) is a compound with a low boiling point.

[0201] Hereinafter, each step that can be included in the method for producing a polyamine compound according to the third embodiment will be described.

[0202] <Step X1> Step X1 is a step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition assistant to produce a polycarbamate compound.

[0203] For step X1, reference can be made to the production step in the method for producing a polythiol composition according to the first embodiment. In step X1, a thiourethane resin is decomposed with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition assistant, thereby producing a polycarbamate compound and the aforementioned polythiol composition. Preferred aspects of the thiourethane resin, the decomposing agent represented by formula (2), and the tertiary amine compound as a decomposition assistant in step X1 are the same as the preferred aspects of the thiourethane resin, the decomposing agent represented by formula (2), and the tertiary amine compound as a decomposition assistant in the method for producing a polythiol composition according to the first embodiment, respectively.

[0204] (Reaction Pressure) Step X1 preferably includes reacting the thiourethane resin with the decomposing agent represented by formula (2) under a pressure higher than atmospheric pressure in the presence of a tertiary amine compound as a decomposition aid. This can further suppress volatilization of the decomposing agent represented by formula (2). In this case, the reaction includes reacting the thiourethane resin with the decomposing agent represented by formula (2) under a pressure higher than atmospheric pressure, preferably by 0.01 MPa or more (more preferably 0.01 MPa or more and 2.0 MPa or less, and even more preferably 0.02 MPa or more and 1.0 MPa or less).

[0205] (Polycarbamate Compound) The polycarbamate compound produced in step X1 is an alcoholysis product of a thiourethane resin, produced by reacting a thiourethane resin with a decomposing agent represented by formula (2) (i.e., alcoholysis). The polycarbamate compound is a compound (i.e., a polyurethane compound) containing two or more carbamate bonds (i.e., urethane bonds). The polycarbamate compound is, for example, a polycarbamate compound (i.e., a polyurethane compound) having a structure in which all isocyanato groups in a polyisocyanate compound, which is one of the raw materials for the thiourethane resin, react with hydroxy groups in an alcohol compound to form carbamate bonds (i.e., urethane bonds). In the present disclosure, a polycarbamate compound having such a structure may be referred to as a carbamate of a polyamine compound (e.g., XDA) corresponding to a polyisocyanate compound (e.g., XDI), which is one of the raw materials, and an alcohol compound (e.g., 1-octanol). Here, the polyamine compound corresponding to the polyisocyanate compound means a compound in which all of the isocyanato groups in the polyisocyanate compound have been replaced with amino groups. The polyamine compound corresponding to the polyisocyanate compound is the target product in the method for producing a polyamine compound according to the third embodiment.

[0206] (Reaction Step X1 and Separation Step X2) Step X1 may include: a reaction step of reacting a thiourethane resin with a decomposing agent represented by formula (2) to obtain a reaction mixture containing a polycarbamate compound; and a separation step of separating the polycarbamate compound from the reaction mixture. In this case, in step X2 described below, the polycarbamate compound in the polycarbamate compound-containing mixture is reacted with the decomposing agent represented by formula (3) by mixing the polycarbamate compound-containing mixture separated in the separation step with the decomposing agent represented by formula (3). Hereinafter, the polycarbamate-containing mixture refers to a mixture of two or more carbamate compounds containing a polycarbamate compound. Hereinafter, the reaction mixture, the reaction step, and the separation step will also be referred to as reaction mixture X1, reaction step X1, and separation step X2, respectively.

[0207] The preferred conditions for reaction step X1 are as described above.

[0208] The reaction mixture produced in reaction step X1 may contain a polycarbamate-containing mixture as the main product produced by alcoholysis, and other components other than the polycarbamate-containing mixture. Examples of other components include by-products produced by alcoholysis (e.g., a polythiol composition), the reaction solvent described above, residues of raw materials (thiourethane resin and / or alcohol compounds), and impurities contained in the raw materials. For preferred embodiments of the polythiol composition as a by-product, the preferred embodiments of the polythiol composition as a raw material for thiourethane resin described above can be referenced as appropriate. The polythiol composition as a by-product produced by the alcoholysis reaction can be used as a raw material for producing new thiourethane resin. This allows for material recycling.

[0209] The separation method in the separation step X2 is not particularly limited, and known methods can be applied. Examples of the separation method in the separation step X2 include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (e.g., column chromatography), etc. A plurality of separation methods may be used in combination.

[0210] For example, one preferred embodiment of the separation step X2 includes the following (hereinafter referred to as separation embodiment X1): filtering the reaction mixture X1 to obtain a filtrate; washing the filtrate with an acid and then with water; adding an alkali metal-containing base to the filtrate washed with water, and then washing with water to remove salts (e.g., alkali metal salts of the polythiol composition, which is a reaction by-product); and separating the polycarbamate-containing mixture from the filtrate from which the salts have been removed.

[0211] In separation mode X1, the filtrate is first washed with acid (hereinafter also referred to as acid washing), thereby removing amines (e.g., tertiary amine compounds) from the filtrate. Examples of acids used in acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, and oxalic acid. The acid is then removed from the filtrate by washing it with water. At the stage where the acid has been removed, the filtrate contains the target polycarbamate-containing mixture, but it is believed that it may also contain the by-product polythiol composition. In separation mode X1, a base containing an alkali metal is added to the filtrate washed with water. This converts the polythiol composition in the filtrate into an alkali metal salt. The filtrate is then washed with water, thereby removing the alkali metal salt of the polythiol composition from the filtrate. In separation mode X1, the polycarbamate-containing mixture is separated by a known method from the filtrate from which the alkali metal salt of the polythiol composition has been removed.

[0212] In Separation Mode X1, the alkali metal in the alkali metal-containing base is preferably sodium, potassium, or lithium, more preferably sodium or potassium. Examples of the alkali metal-containing base include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. The alkali metal-containing base can be added to the filtrate in the form of an alcohol solution (e.g., methanol solution, ethanol solution), as needed.

[0213] In addition, in separation mode X1, a solvent (hereinafter also referred to as separation solvent X1) may be added to the filtrate obtained by filtering reaction mixture X1 before washing the filtrate with acid, and the filtrate to which separation solvent X1 has been added may be sequentially subjected to acid washing and water washing. As separation solvent X1, the same solvent as the reaction solvent may be used, or an alcohol solvent may be used. Furthermore, when a reaction solvent is used in reaction step X1, the addition of separation solvent X1 to the filtrate may be omitted.

[0214] <Step X2> Step X2 is a step of producing a polyamine compound by decomposing the polycarbamate compound produced in step X1 with a decomposing agent represented by formula (3). In step X2, the polycarbamate-containing mixture separated in the aforementioned separation step X2 may be mixed with the decomposing agent represented by formula (3), thereby reacting the polycarbamate compound in the polycarbamate-containing mixture with the decomposing agent represented by formula (3).

[0215] The reaction in step X2 is superior in the efficiency of producing a polyamine compound compared to the known reaction of obtaining a polyamine compound by reacting a polycarbamate compound with sodium hydroxide. As a result, the amount of polyamine compound produced can be increased compared to the case where the known reaction is applied. This effect can be confirmed by analyzing the reaction mixture obtained in step X2 by gas chromatography (GC).

[0216] Step X2 in the method for producing a polyamine compound according to the third embodiment is similar to step 2 in the method for producing a polyamine compound according to the third embodiment, and preferred aspects are also similar to step 2 in the method for producing a polyamine compound according to the third embodiment, except that the substance to be decomposed by the decomposing agent represented by formula (3) is not the polyurea compound produced in step 1 in the second embodiment, but the polycarbamate compound produced in step X1 in the third embodiment.

[0217] (Reaction Pressure) Step X2 preferably includes reacting the polycarbamate compound with the decomposing agent represented by formula (3) under a pressure higher than atmospheric pressure. This can further suppress volatilization of the decomposing agent represented by formula (3). In this case, the reaction includes reacting the polycarbamate compound with the decomposing agent represented by formula (3) under a pressure higher than atmospheric pressure, preferably by 0.01 MPa or more (more preferably 0.01 MPa or more and 2.0 MPa or less, and even more preferably 0.02 MPa or more and 1.0 MPa or less).

[0218] (Polyamine Compound as Target Product) The polyamine compound as the target product in the method for producing a polyamine compound according to the third embodiment is a decomposition product of a thiourethane resin produced by the reaction of a polycarbamate compound with a decomposing agent represented by formula (3). The polyamine compound as the target product is preferably a polyamine compound corresponding to the polyisocyanate compound used as the raw material for the thiourethane resin, which is the starting material in step X1 (more specifically, a compound in which the isocyanato groups in the polyisocyanate compound have been replaced with amino groups).

[0219] The preferred aspects and preferred uses of the polyamine compound as the target substance in the third embodiment are the same as the preferred aspects and preferred uses of the polyamine compound as the target substance in the third embodiment, respectively.

[0220] <Other Steps> The method for producing a polyamine compound according to the third embodiment may include other steps in addition to those described above. Examples of other steps include a classification step (e.g., a sieving step) and a washing step, which may also be included in the method for producing a polythiol composition according to the first embodiment.

[0221] [Method for Producing Polyisocyanate Compound (Third Embodiment)] A method for producing a polyisocyanate compound according to a third embodiment of the present disclosure includes: a step of producing a polyamine compound by the method for producing a polyamine compound according to the third embodiment described above; and a step of reacting at least one of the polyamine compound and a hydrochloride salt of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound.

[0222] The method for producing a polyisocyanate compound according to the third embodiment is the same as the method for producing a polyisocyanate compound according to the second embodiment, except that a polyamine compound is produced by the method for producing a polyamine compound according to the third embodiment instead of by the method for producing a polyamine compound according to the second embodiment, and preferred aspects are also the same.

[0223] [Method for Producing Polymerizable Composition (Second Embodiment)] A method for producing a polymerizable composition according to a third embodiment of the present disclosure includes: a step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to the third embodiment described above; and a step of mixing at least the polyisocyanate compound and an active hydrogen compound to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound.

[0224] The method for producing a polymerizable composition according to the third embodiment is the same as the method for producing a polymerizable composition according to the second embodiment, except that, instead of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to the second embodiment, a polyisocyanate compound is produced by the method for producing a polyisocyanate compound according to the third embodiment, and preferred aspects are also the same.

[0225] [Method for Producing Resin (Third Embodiment)] A method for producing a resin according to a third embodiment of the present disclosure includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the third embodiment described above, and curing the polymerizable composition to obtain a resin.

[0226] The method for producing a resin according to the third embodiment is the same as the method for producing a resin according to the second embodiment, except that, instead of producing a polymerizable composition by the method for producing a polymerizable composition according to the second embodiment, a polymerizable composition is produced by the method for producing a polymerizable composition according to the third embodiment, and preferred aspects are also the same.

[0227] [Method for Producing Molded Article (Second Embodiment)] A method for producing a molded article according to a second embodiment of the present disclosure is a method for producing a molded article containing a resin, and includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the second embodiment described above, and curing the polymerizable composition to obtain a molded article containing a resin.

[0228] The method for producing a molded article according to the second embodiment is the same as the method for producing a molded article according to the first embodiment, except that instead of producing a polymerizable composition by the method for producing a polymerizable composition according to the first embodiment, a polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment, and preferred aspects are also the same.

[0229] [Method for Producing Optical Material (Third Embodiment), Method for Producing Lens (Third Embodiment)] A method for producing an optical material (e.g., a lens) according to a third embodiment of the present disclosure is a method for producing an optical material (e.g., a lens) including a molded article containing a resin, and includes the steps of producing a polymerizable composition by the method for producing a polymerizable composition according to the third embodiment described above, and obtaining a molded article containing a resin by curing the polymerizable composition.

[0230] The method for producing an optical material (e.g., a lens) according to the third embodiment is the same as the method for producing an optical material (e.g., a lens) according to the second embodiment, except that, instead of producing a polymerizable composition by the method for producing a polymerizable composition according to the second embodiment, a polymerizable composition is produced by the method for producing a polymerizable composition according to the third embodiment, and preferred aspects are also the same.

[0231] [Resin (Third Embodiment), Molded Article (Third Embodiment), Optical Material (E.g., Lens) (Third Embodiment)] A resin according to the third embodiment of the present disclosure is a cured product of the polymerizable composition according to the third embodiment of the present disclosure described above. A molded article according to the third embodiment of the present disclosure is a molded article containing the resin according to the third embodiment described above. An optical material (e.g., a lens) according to the third embodiment is an optical material (e.g., a lens) containing the resin according to the third embodiment described above.

[0232] The resin, molded article, and optical material (for example, a lens) according to the third embodiment are similar to the resin, molded article, and optical material (for example, a lens) according to the second embodiment, except that a polymerizable composition is produced by the method for producing a polymerizable composition according to the third embodiment instead of by the method for producing a polymerizable composition according to the second embodiment, and preferred aspects are also similar.

[0233] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. Unless otherwise specified, "parts" are by mass and "room temperature" is 25°C.

[0234] <Performance Test of Resin> As a performance test of the resin, a performance test was carried out on a 2.5 mm thick plate-shaped molded body. The performance test items are as follows. Yellowness Index (YI) Yellowness was measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. L*, a*, and b* L*, a*, and b* in the CIE 1976 (L*, a*, b*) color system were measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. Refractive index (ne) and Abbe number (νe) Using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive indexes (ne, nF', nC') at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line) were measured at 20 ° C. Based on these measurement results, the refractive index (ne) and Abbe number (νe) were determined. Heat resistance Using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, the glass transition temperature (Tg) was measured by the TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10 ° C. / min) and used as an index of heat resistance. Specific gravity d was measured by the Archimedes method at 20 ° C.

[0235] Reference Production Example 1 Production of a Molded Article Comprising Thiourethane Resin R1 In a flask equipped with a stirrer, the following were added: dibutyltin dichloride as a polymerization catalyst (100 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition); Zelec-UN (manufactured by Stepan; acidic phosphate ester) as a mold release agent (1,000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition); m-xylylene diisocyanate (XDI) as a polyisocyanate compound (52 parts by mass); and polythiol composition (A) (48 parts by mass) composed primarily of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1). The mixture was stirred and mixed at room temperature (25°C) for 1 hour to obtain a transparent, homogeneous solution of a polymerizable composition. The polythiol composition (A) used here was the one produced in Reference Production Example 3 described below. Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then thoroughly degassed under a reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven, and the oven temperature was set to 10 ° C. Next, the oven temperature was raised from 10 ° C to 120 ° C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded product containing thiourethane resin R1 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds (9.0 mm thick). Subsequently, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven, and then the molded product was removed from the pair of glass molds to obtain a molded product.

[0236] Reference Production Example 2 Production of Thiourethane Resin Scrap R1 Lenses were produced by cutting the molded article obtained in Reference Production Example 1. Cutting scraps generated during this process were collected to obtain thiourethane resin scrap R1 (i.e., resin scraps containing thiourethane resin R1).

[0237] Reference Production Example 3 Production of Polythiol Composition (A) 125.4 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of degassed water were charged into a reactor. 99.8 parts by mass of a 32% by mass aqueous sodium hydroxide solution was added dropwise over 40 minutes at 12°C to 35°C, followed by dropwise addition of 73.8 parts by mass of epichlorohydrin at 29°C to 36°C over 4 hours, followed by stirring for 30 minutes. NMR data confirmed the production of 1,3-bis(2-hydroxyethylthio)-2-propanol. 332.0 parts by mass of 36% by mass hydrochloric acid was added into the reactor in which the production of 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed, followed by addition of 183.8 parts by mass of 99.9% pure thiourea. The mixture was stirred at 110°C under reflux for 3 hours to carry out a thiuronium chloride reaction. After the thiuronium chloride reaction, the reactor interior was cooled to 45°C, and then 355.0 parts by mass of toluene was added thereto. The mixture was then cooled to 30°C. Next, 244.6 parts by mass of a 25% by mass aqueous ammonia solution was added at 30°C to 40°C over 44 minutes, and then a hydrolysis reaction was carried out with stirring at 54°C to 62°C for 3 hours. This hydrolysis reaction yielded a toluene solution of a polythiol composition (A) primarily composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1). To the resulting toluene solution, 147.8 parts by mass of 36% by mass hydrochloric acid was added, and the mixture was acid-washed for 1 hour at 35°C to 40°C. After the acid wash, the aqueous phase was removed, and 147.8 parts by mass of degassed water was added to the remaining organic phase, and washing was carried out once for 10 minutes at 35°C to 40°C. To the organic phase after washing with degassed water, 147.8 parts by mass of 0.1% by mass ammonia water was added, and washing was carried out for 10 minutes. To the organic phase after washing with ammonia water, 147.8 parts by mass of degassed water was added, and washing was carried out twice for 10 minutes at 35°C to 40°C. From the organic phase after the two washes, toluene and trace amounts of water were removed under reduced pressure by heating, and then the organic phase was filtered under reduced pressure using a 3.0 μm PTFE-type membrane filter, yielding 200.0 parts by mass of a polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1).

[0238] The purity of the polythiol component A1 in the polythiol composition (A) obtained in Reference Production Example 3 was 91.6%.

[0239] Example 1 Decomposition of Thiourethane Resin (Aminolysis with Ammonia as the Decomposing Agent Represented by Formula (1)) To a 100 mL pressure-resistant reactor manufactured by San-Ai Chemical Co., Ltd., were added the following: 18.0 g of thiourethane resin scrap R1 obtained in Reference Production Example 2, 31.9 g of toluene, and 10.1 g of 25% aqueous ammonia (equivalent to 0.15 mol of ammonia as the decomposing agent represented by Formula (1)). A reaction solution was obtained, and nitrogen gas was then sealed inside the reactor. The reaction solution in the sealed reactor was then heated to 90°C and stirred for 6 hours under a pressure at least 0.01 MPa higher than atmospheric pressure, thereby carrying out the decomposition reaction of the thiourethane resin. After completion of the decomposition reaction, the reaction solution was cooled to room temperature and subjected to vacuum filtration. The vacuum filtration yielded 10.1 g (yield: 91.4%) of polyurea compound B1 as a filtrate, and a toluene solution containing a polythiol composition as a filtrate. Here, the polyurea compound B1 and the polythiol composition are both decomposition products produced by aminolysis of the thiourethane resin waste R1. During the above-mentioned vacuum filtration process, ammonia, which serves as the decomposition agent represented by formula (1), volatilized and was easily removed from the reaction system.

[0240] The filtrate (i.e., the toluene solution containing the polythiol composition) was added with 30.0 g of 35% aqueous hydrochloric acid to perform acid washing. After the acid washing, the toluene solution was washed twice with 30.0 g of degassed water, and then 12.4 g of 32% aqueous sodium hydroxide and 20 g of degassed water were added sequentially to obtain an aqueous solution containing an alkali metal salt of polythiol as the aqueous phase. The aqueous solution containing the alkali metal salt of polythiol was washed twice with 20.0 g of toluene. Next, 40.0 g of toluene was added to the washed aqueous solution, and then 30.0 g of 35% aqueous hydrochloric acid was added to perform neutralization. The aqueous phase was extracted from the neutralized liquid, and 30.0 g of degassed water was added to the remaining organic phase, and separation washing was performed twice to obtain a toluene solution in which the polythiol composition was dissolved. Toluene and trace amounts of water were removed from the resulting toluene solution under heating and reduced pressure, and then the solution was filtered under reduced pressure using a 3.0 μm PTFE-type membrane filter to obtain 6.9 g (yield: 79.9%) of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as a main component.

[0241] Example 2 Decomposition of Thiourethane Resin (Aminolysis with Methylamine as Decomposing Agent Represented by Formula (1)) The same procedure as in Example 1 was carried out, except that "25% aqueous ammonia (10.1 g) (corresponding to 0.15 mol of ammonia as the decomposing agent represented by Formula (1))" in Example 1 was changed to "40% aqueous methylamine solution (1.6 g) (corresponding to 0.15 mol of methylamine as the decomposing agent represented by Formula (1))."

[0242] In Example 2, after the decomposition reaction was completed, 10.9 g (yield: 87.6%) of polyurea compound B2 was obtained as a filter cake by filtration, and a toluene solution containing a polythiol composition was obtained as a filtrate. Here, polyurea compound B2 and the polythiol composition were both decomposition products produced by the aminolysis of thiourethane resin waste R1. During the above-mentioned vacuum filtration process, methylamine, the decomposition agent represented by formula (1), volatilized and was easily removed from the reaction system.

[0243] The toluene solution containing the polythiol composition was treated in the same manner as in Example 1 to obtain 7.01 g (yield: 81.1%) of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as a main component.

[0244] Example 3 Decomposition of Thiourethane Resin (Aminolysis with Dimethylamine as Decomposing Agent Represented by Formula (1)) The same procedure as in Example 1 was carried out, except that "25% aqueous ammonia (10.1 g) (equivalent to 0.15 mol of ammonia as the decomposing agent represented by Formula (1))" in Example 1 was changed to "13.4 g of a 50% aqueous dimethylamine solution (equivalent to 0.15 mol of dimethylamine as the decomposing agent represented by Formula (1))."

[0245] In Example 3, after the decomposition reaction was completed, separation and extraction was performed to obtain an aqueous solution of polyurea compound B3, and water was distilled off from the obtained aqueous solution to obtain 12.8 g of polyurea compound B3 (yield: 95.0%). The separation and extraction yielded a toluene solution containing a polythiol composition as the organic phase. Here, both polyurea compound B2 and the polythiol composition were decomposition products produced by the aminolysis of thiourethane resin waste R1. During the separation and extraction process, dimethylamine, the decomposition agent represented by formula (1), was removed from the reaction system.

[0246] Example 4 Decomposition of Thiourethane Resin (Alcoholysis with Methanol as Decomposing Agent Represented by Formula (2)) To a 100 mL pressure-resistant reactor manufactured by San-Ai Chemical Co., Ltd., were added 18.0 g of the thiourethane resin R1 obtained in Reference Production Example 2, 31.8 g (1.0 mol) of methanol as the decomposing agent represented by Formula (2), and 1.1 g (0.010 mol) of 1,4-diazabicyclo-[2.2.2]-octane as a tertiary amine (decomposing aid), to obtain a reaction solution. Nitrogen gas was then sealed in the reactor. Next, the reaction solution in the sealed reactor was heated to 150°C and stirred for 9 hours under a pressure at least 0.01 MPa higher than atmospheric pressure, thereby carrying out the decomposition reaction of the thiourethane resin. After completion of the decomposition reaction, insoluble matter was removed from the reaction solution by filtration under reduced pressure, and then 30.0 g of 2-octanol was added thereto, followed by 30.0 g of 35% aqueous hydrochloric acid for acid washing. After the acid washing, the reaction solution was washed twice with water, with 30.0 g of degassed water added. Then, 12.4 g of 32% aqueous sodium hydroxide and 20 g of degassed water were added sequentially to obtain an organic phase and an aqueous phase. An alcohol solution in which the polycarbamate compound had been dissolved was recovered as the organic phase, and the solvent was distilled off from the recovered organic phase under heating and reduced pressure to obtain 7.10 g of polycarbamate compound C1 (yield: 56.6%).

[0247] On the other hand, an aqueous solution containing an alkali metal salt of polythiol was obtained as the aqueous phase. The aqueous solution containing the alkali metal salt of polythiol was washed twice with 20.0 g of toluene. Next, 40.0 g of toluene was added to the washed aqueous solution, and then 30.0 g of 35% aqueous hydrochloric acid was added to neutralize it. The aqueous phase was extracted from the neutralized liquid, and 30.0 g of degassed water was added to the remaining organic phase and subjected to separation washing twice to obtain a toluene solution in which the polythiol composition was dissolved. From the obtained toluene solution, toluene and trace amounts of water were removed under heating and reduced pressure, and then the solution was filtered under reduced pressure using a 3.0 μm PTFE-type membrane filter to obtain 5.1 g (yield: 59.0%) of a polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1).

[0248] In Example 4, methanol, which was the decomposing agent represented by formula (2), was volatilized during the process of vacuum filtration after the completion of the decomposition reaction and was easily removed from the reaction system.

[0249] <Measurements of Each Polythiol Composition (A)> The following measurements were carried out on the polythiol compositions (A) obtained in Examples 1 to 4. The results are shown in Table 1.

[0250] (Purity (%) of Polythiol Component A1 in Polythiol Composition (A)) The purity (%) of polythiol component A1 in polythiol composition (A) was measured by the above-described method using high performance liquid chromatography.

[0251] (Refractive Index) The refractive index of the polythiol composition (A) was measured using a liquid refractometer RA600 manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0252] (Thiol Value) The thiol value of the polythiol composition (A) was determined by oxidation-reduction titration using a 0.05 M aqueous iodine solution.

[0253]

[0254] As shown in Table 1, in all of Examples 1 to 4, it was confirmed that a polythiol composition (A) containing polythiol component A1 as a main component could be obtained by decomposing the thiourethane resin with various decomposing agents.

[0255] Example 6 Production of Molded Article A molded article containing a thiourethane resin was obtained in the same manner as in Reference Production Example 1 (i.e., using the polythiol composition (A) produced in Reference Production Example 3 as the polythiol composition (A)), except that the thickness between the pair of glass molds was changed from 9.0 mm to 2.5 mm.

[0256] Furthermore, a molded article containing a thiourethane resin was obtained in the same manner as above, except that the polythiol composition (A) produced in Reference Production Example 3 was replaced with the polythiol composition (A) produced in Examples 1 to 4.

[0257] <Evaluation of Molded Articles> The following evaluations were carried out on each of the above molded articles. The results are shown in Table 2.

[0258] (Yellow Index (YI), L*, a*, and b*) The yellow index (YI), L*, a*, and b* of the molded product were measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc.

[0259] (Refractive index (ne) and Abbe number (νe)) Using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive indexes (ne, nF', nC') of the molded body were measured at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line) at 20° C. Based on these measurement results, the refractive index (ne) and Abbe number (νe) of the molded body were each determined.

[0260] (Heat Resistance) Using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, the glass transition temperature (Tg) of the molded article was measured by the TMA penetration method (50 g load, pin tip 0.5 mmφ, temperature rise rate 10°C / min) and used as an index of heat resistance.

[0261] (Specific Gravity d) The specific gravity d of the molded body was measured at 20°C by the Archimedes method.

[0262]

[0263] As shown in Table 2, when the polythiol compositions (A) obtained in Examples 1 to 4 were used as raw materials, it was confirmed that molded articles (i.e., resin molded articles) having properties usable as optical materials (e.g., eyeglass lenses) could be produced, similarly to the case where the polythiol composition (A) obtained in Reference Production Example 3 was used as raw material.

[0264] [Example 6X] In Example 6X, the same procedure as in Example 6 was carried out except that the production of the molded body was changed as follows, and the same results as in Example 6 (Table 2) were obtained.

[0265] - Changes from Example 6 - In Example 6, m-xylylene diisocyanate (XDI) (52 parts by mass) was used in producing the molded body, but in Example 6X, XDI (52 parts by mass) was changed to XDI composition X1 (an amount such that the amount of XDI contained was 52 parts by mass) as the XDI composition described above. XDI composition X1 was produced by adding trace amounts of compound (N1), compound (N2), and compound (N3) to XDI, which is the main component, and mixing them.

[0266] The XDI composition X1 was subjected to gas chromatography measurement under the above-mentioned GC conditions 1 and 2. As a result, the peak area of ​​the compound (N1) was 0.20 ppm or more (specifically, 600 ppm) relative to the peak area 1 of xylylene diisocyanate, the peak area of ​​the compound (N2) was 0.05 ppm or more (specifically, 18 ppm) relative to the peak area 1 of xylylene diisocyanate, and the peak area of ​​the compound (N3) was 0.10 ppm or more (specifically, 100 ppm) relative to the peak area 1 of xylylene diisocyanate.

[0267] Example 7 Production of a Polyamine Compound by Reaction of Polyurea Compound B1 Obtained in Example 1 with Ethylenediamine A 25 mL pressure-resistant reactor manufactured by San-Ai Scientific Co., Ltd. was charged with the polyurea compound B1 obtained in Example 1 (2.0 g; 9.0 mmol), and ethylenediamine (3.2 g; 54 mmol) as a decomposing agent represented by formula (3). Nitrogen gas was then sealed in the reactor. The reaction solution in the sealed reactor was then heated to 145°C and stirred for 3 hours under a pressure at least 0.01 MPa higher than atmospheric pressure. Gas chromatography (GC) confirmed that the polyamine compound xylylenediamine (XDA) was produced by the reaction of polyurea compound B1 with ethylenediamine. The mass of the reaction solution after the reaction was 4.9 g, the concentration of XDA determined from the GC results was 18.6%, and the production yield was 74.6% (the two-stage yield from thiourethane resin R1 was 68.2%). The decomposing agent (ammonia) represented by formula (1) produced by decomposition of polyurea compound B1 volatilized from the reaction solution after the reaction and was easily removed. The decomposing agent (ethylenediamine) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0268] Example 8 Production of a Polyamine Compound by Reacting Polyurea Compound B2 Obtained in Example 2 with Ethylenediamine The same procedure as in Example 7 was carried out, except that polyurea compound B1 was replaced with polyurea compound B2 (2.0 g; 8.0 mmol) obtained in Example 2 and the amount of ethylenediamine was changed to 2.9 g (48 mmol). Gas chromatography (GC) confirmed that the reaction between polyurea compound B2 and ethylenediamine produced the polyamine compound xylylenediamine (XDA). The mass of the reaction solution after the reaction was 4.6 g, and the concentration of XDA determined from the GC results was 18.2%, resulting in a production yield of 75.6% (the two-stage yield from thiourethane resin R1 was 66.1%). Note that the decomposing agent (methylamine) represented by formula (1) produced by decomposition of polyurea compound B2 volatilized from the reaction solution after the reaction and was easily removed. The decomposing agent (ethylenediamine) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0269] Example 9 Production of a Polyamine Compound by Reacting Polyurea Compound B3 Obtained in Example 3 with Ethylenediamine The same procedure as in Example 7 was carried out, except that polyurea compound B1 was replaced with polyurea compound B3 (2.0 g; 7.2 mmol) obtained in Example 3 and the amount of ethylenediamine was changed to 2.6 g (43 mmol). Gas chromatography (GC) confirmed that the polyamine compound xylylenediamine (XDA) was produced by the reaction of polyurea compound B3 with ethylenediamine. The mass of the reaction solution after the reaction was 4.2 g, the concentration of XDA determined from the GC results was 19.3%, and the production yield was 81.9% (the two-stage yield from thiourethane resin R1 was 77.8%). The decomposing agent represented by formula (3) (ethylenediamine) and the decomposing agent represented by formula (1) (dimethylamine) produced by decomposition of polyurea compound B3 could be easily removed from the reaction solution after the reaction by distillation.

[0270] Example 10 Production of a Polyamine Compound Using the Polycarbamate Compound C1 Obtained in Example 4 The same procedure as in Example 7 was carried out, except that the polyurea compound B1 was replaced with the polycarbamate C1 (2.0 g; 79 mmol) obtained in Example 4, and the amount of ethylenediamine was changed to 2.9 g (48 mmol). Gas chromatography (GC) confirmed that the polyamine compound xylylenediamine (XDA) was produced by the reaction of polycarbamate C1 with ethylenediamine. The mass of the reaction solution after the reaction was 4.9 g, and the concentration of XDA determined from the GC results was 15.6%, resulting in a production yield of 70.4% (the two-stage yield from thiourethane resin R1 was 39.8%). The decomposing agent represented by formula (3) (ethylenediamine) and the decomposing agent represented by formula (2) (methanol) produced by decomposition of polycarbamate C1 could be easily removed from the reaction solution after the reaction by distillation.

[0271] Example 11 Production of a Polyamine Compound by Reacting Polyurea Compound B1 Obtained in Example 1 with N,N'-Dimethylethylenediamine The same procedure as in Example 7 was carried out, except that 3.2 g (54 mmol) of ethylenediamine as the decomposing agent represented by formula (3) was replaced with 4.8 g (54 mmol) of N,N'-dimethylethylenediamine as the decomposing agent represented by formula (3). Gas chromatography (GC) confirmed that the polyamine compound xylylenediamine (XDA) was produced by the reaction of polyurea compound B1 with N,N'-dimethylethylenediamine. The mass of the reaction solution after the reaction was 6.7 g, and the concentration of XDA determined from the GC results was 15.8%, resulting in a production yield of 85.5% (two-stage yield from thiourethane resin R1: 78.1%). The decomposing agent (ammonia) represented by formula (1) produced by decomposition of polyurea compound B1 volatilized from the reaction solution after the reaction and was easily removed. The decomposing agent (N,N'-dimethylethylenediamine) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0272] Example 12 Production of a Polyamine Compound by Reacting Polyurea Compound B1 Obtained in Example 1 with 2-Aminoethanol The same procedure as in Example 7 was carried out, except that the decomposing agent represented by formula (3) was changed from 3.2 g (54 mmol) of ethylenediamine to 5.0 g (90 mmol) of 2-aminoethanol, the reaction temperature was changed from 145°C to 180°C, and the reaction time was changed from 3 hours to 6 hours. Gas chromatography (GC) confirmed that the polyamine compound xylylenediamine (XDA) was produced by the reaction of polyurea compound B1 with 2-aminoethanol. The mass of the reaction solution after the reaction was 6.7 g, and the concentration of XDA determined from the GC results was 10.2%, resulting in a production yield of 55.7% (the two-stage yield from thiourethane resin R1 was 50.9%). The decomposing agent (ammonia) represented by formula (1) produced by decomposition of polyurea compound B1 volatilized from the reaction solution after the reaction and was easily removed. The decomposing agent (2-aminoethanol) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0273] Example 13 Production of a Polyamine Compound by Reacting Polyurea Compound B1 Obtained in Example 1 with Ethylene Glycol The same procedure as in Example 12 was carried out, except that 3.2 g (54 mmol) of ethylenediamine as the decomposing agent represented by formula (3) was replaced with 5.6 g (90 mmol) of ethylene glycol. Gas chromatography (GC) confirmed that the polyamine compound xylylenediamine (XDA) was produced by the reaction of polyurea compound B1 with ethylene glycol. The mass of the reaction solution after the reaction was 6.9 g, the concentration of XDA determined from the GC results was 7.1%, and the production yield was 40.6% (the two-stage yield from thiourethane resin R1 was 37.1%). Note that the decomposing agent (ammonia) represented by formula (1) produced by decomposition of polyurea compound B1 volatilized from the reaction solution after the reaction and was easily removed. The decomposing agent (ethylene glycol) represented by formula (3) could also be easily removed from the reaction solution after the reaction by distillation.

[0274] As described above, in Examples 7 to 13, polyamine compounds were successfully produced using polyurea compounds or polycarbamate compounds produced by decomposition of thiourethane resins as raw materials. Polyisocyanate compounds can be produced by reacting at least one of the produced polyamine compounds and nitrates of these polyamine compounds with carbonyl dichloride. A polymerizable composition can be produced by mixing the resulting polyisocyanate compound with an active hydrogen compound. The resulting polymerizable composition can be used to produce thiourethane resins or urethane resins.

[0275] The disclosure of Japanese Patent Application No. 2022-135892, filed on August 29, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a polythiol composition, comprising a production step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) or the following formula (2) to produce a polythiol composition. 【Chemistry 1】 [In formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (provided that R １ and R ２ and both are amino groups). In formula (2), R ３ represents an alkyl group having 1 to 3 carbon atoms.

2. The method for producing a polythiol composition according to claim 1 , wherein the generating step includes reacting the thiourethane resin with the decomposing agent under a pressure higher than atmospheric pressure.

3. The method for producing the polythiol composition according to claim 1, which is a method for producing a polythiol composition for use in producing an optical material.

4. The method for producing a polythiol composition according to claim 1 , wherein the thiourethane resin is recovered during at least one of a process for producing eyeglass lenses, a process for producing eyeglasses, and a process for disposing of eyeglasses.

5. A step of producing a polythiol composition by the method for producing a polythiol composition according to any one of claims 1 to 4; A step of mixing the polythiol composition with a polyisocyanate compound to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate compound; A method for producing a polymerizable composition comprising the steps of:

6. the step of obtaining a polymerizable composition is a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition by mixing the polythiol composition with a polyisocyanate composition containing a polyisocyanate compound, The polyisocyanate composition comprises: Xylylene diisocyanate, At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); Including, When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) measured by high performance liquid chromatography is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) measured by high performance liquid chromatography is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) measured by high performance liquid chromatography is 0.10 ppm or more relative to the peak area of ​​xylylene diisocyanate. A method for producing the polymerizable composition according to claim 5 . 【Chemistry 2】

7. A step of producing a polymerizable composition by the method for producing a polymerizable composition according to claim 5; curing the polymerizable composition to obtain a resin; A method for producing a resin comprising the steps of:

8. A first step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) to generate a polyurea compound; A second step of decomposing the polyurea compound with a decomposing agent represented by the following formula (3) to generate a polyamine compound; The method for producing a polyamine compound includes the steps of: 【Chemistry 3】 [In formula (1), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (provided that R １ and R ２ and both are amino groups). In formula (3), R １１ and R １２ each independently represents a hydroxy group, a mercapto group, an amino group, or a monomethylamino group.

9. The decomposition agent represented by the formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol; The method for producing the polyamine compound according to claim 8 .

10. The method for producing a polyamine compound according to claim 8 , wherein the first step comprises reacting the thiourethane resin with the decomposing agent represented by the formula (1) under a pressure higher than atmospheric pressure.

11. The method for producing a polyamine compound according to claim 8, wherein the second step comprises reacting the polyurea compound with the decomposing agent represented by the formula (3) under a pressure higher than atmospheric pressure.

12. A step X1 of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition assistant to generate a polycarbamate compound; a step X2 of decomposing the polycarbamate compound with a decomposing agent represented by the following formula (3) to produce a polyamine compound; The method for producing a polyamine compound includes the steps of: 【Chemistry 4】 [In formula (2), R ３ represents an alkyl group having 1 to 3 carbon atoms. In formula (3), R １１ and R １２ each independently represents a hydroxy group, a mercapto group, an amino group, or a monomethylamino group.

13. The molecular weight of the tertiary amine compound is 1000 or less, The decomposition agent represented by the formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol; The method for producing the polyamine compound according to claim 12.

14. The method for producing a polyamine compound according to claim 12, wherein the step X1 comprises reacting the thiourethane resin with the decomposing agent represented by the formula (2) under a pressure higher than atmospheric pressure.

15. The method for producing a polyamine compound according to claim 12, wherein the step X2 comprises reacting the polycarbamate compound with the decomposing agent represented by the formula (3) under a pressure higher than atmospheric pressure.

16. The method for producing a polyamine compound according to any one of claims 8 to 15, which is a method for producing a polyamine compound as a raw material for a polyisocyanate compound for producing an optical material.

17. The method for producing a polyamine compound according to any one of claims 8 to 15, wherein the thiourethane resin is recovered during at least one of a process for producing eyeglass lenses, a process for producing eyeglasses, and a process for disposing of eyeglasses.

18. A step of producing a polyamine compound by the method for producing a polyamine compound according to any one of claims 8 to 15; a step of reacting at least one of the polyamine compound and the hydrochloride of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound; A method for producing a polyisocyanate compound comprising the steps of:

19. A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to claim 18; A step of mixing at least the polyisocyanate compound and an active hydrogen compound to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound; A method for producing a polymerizable composition comprising the steps of:

20. A step of producing a polymerizable composition by the method for producing a polymerizable composition according to claim 19; curing the polymerizable composition to obtain a resin; A method for producing a resin comprising the steps of:

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