Method for producing polyamine compounds and its applications

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

[Technical Field]

[0001] This disclosure relates to a method for producing polythiol compositions, a method for producing polyamine compounds, and applications thereof. [Background technology]

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

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

[0004] Patent document 1: Japanese Patent Application Laid-Open No. 63-46213 Patent document 2: Japanese Patent Application Laid-Open No. 2-270859 Patent document 3: Japanese Patent Application Laid-Open No. 7-252207 Patent Document 4: International Publication No. 2021 / 157701 Patent Document 5: International Publication No. 2021 / 157702 [Overview of the project] [Problems that the invention aims to solve]

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

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

[0007] The means for solving the above problems include the following embodiments. <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 formula (2) to produce a polythiol composition.

[0008] [ka]

[0009] In formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or an amino group (however, R 1 and R2 except when both are amino groups). In formula (2), R 3 represents an alkyl group having 1 to 3 carbon atoms.

[0010] <2> The production step includes reacting the thiourethane resin and the decomposing agent under a pressure higher than atmospheric pressure, and is a method for producing the polythiol composition according to <1>. <3> A method for producing a polythiol composition for producing an optical material, which is the method for producing a polythiol composition according to <1> or <2>. <4> The thiourethane resin is recovered in at least one of the process of manufacturing spectacle lenses, the process of manufacturing glasses, and the process of discarding glasses, and is a method for producing a polythiol composition according to any one of <1> to <3>. <5> 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 obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate compound by mixing the polythiol composition and the polyisocyanate compound. A method for producing a polymerizable composition including this.

[0011] <6> The step of obtaining the polymerizable composition is a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition by mixing the polythiol composition and a polyisocyanate composition containing a polyisocyanate compound, where the polyisocyanate composition contains xylylene diisocyanate, at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3), and includes when the polyisocyanate composition contains the compound (N1), gasThe peak area of the compound (N1) in the chromatographic measurement is 0.20 ppm or more with respect to the peak area 1 of xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), gas the peak area of the compound (N2) in the chromatographic measurement is 0.05 ppm or more with respect to the peak area 1 of xylylene diisocyanate, When the polyisocyanate composition contains the compound (N3), gas The method for producing a polymerizable composition according to <5>, wherein the peak area of the compound (N3) in the chromatographic measurement is 0.10 ppm or more with respect to the peak area 1 of xylylene diisocyanate.

[0012]

Chemical formula

[0013] <7> 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. A method for producing a resin comprising the above steps. <8> 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. A method for producing a polyamine compound comprising the above steps.

[0014]

Chemical formula

[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 (however, R 1 and R 2(Except when both are amino groups). In formula (3), R 11 and R 12 Each of these independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0016] <9> The decomposition agent represented by formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol. <8> A method for producing the polyamine compound described above. <10> The first step includes reacting the thiourethane resin with the decomposing agent represented by formula (1) under a pressure higher than atmospheric pressure. <8> or <9> A method for producing the polyamine compound described above. <11> The second step includes reacting the polyurea compound with the decomposition agent represented by formula (3) under a pressure higher than atmospheric pressure. <8> ~ <10> A method for producing a polyamine compound as described in any one of the following. <12> Step X1 involves decomposing a thiourethane resin with a decomposition agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polycarbamate compound, Step X2 involves decomposing the aforementioned polycarbamate compound with a decomposition agent represented by the following formula (3) to produce a polyamine compound, A method for producing polyamine compounds, including

[0017] [ka] [In formula (2), R 3 This represents an alkyl group with 1 to 3 carbon atoms. In formula (3), R 11 and R 12 Each of these independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0018] <13> The molecular weight of the tertiary amine compound is 1000 or less. The decomposition agent represented by formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol. <12> A method for producing the polyamine compound described above. <14> The aforementioned step X1 includes reacting the thiourethane resin with the decomposing agent represented by formula (2) under a pressure higher than atmospheric pressure. <12> or <13> A method for producing the polyamine compound described above. <15> Step X2 includes reacting the polycarbamate compound with the decomposition agent represented by formula (3) under a pressure higher than atmospheric pressure. <12> ~ <14> A method for producing a polyamine compound as described in any one of the following. <16> This is a method for producing polyamine compounds as raw materials for polyisocyanate compounds used in the manufacture of optical materials. <8> ~ <15> A method for producing a polyamine compound as described in any one of the following. <17> The thiourethane resin is recovered in at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. <8> ~< 16 A method for producing a polyamine compound as described in any one of the following: <18> <8> ~< 17 >A step of producing a polyamine compound by a method for producing a polyamine compound described in any one of the following, A step of reacting at least one of the polyamine compound and the hydrochloride salt of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound, A method for producing polyisocyanate compounds containing [the specified substance]. <19> <18> A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound described in [the relevant document], A step of obtaining a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound by mixing at least the polyisocyanate compound and the active hydrogen compound, A method for producing a polymerizable composition containing the above. <20> <19> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins. [Effects of the Invention]

[0019] According to one aspect of this disclosure, a method for producing a polythiol composition, a method for producing a polyamine compound, and applications thereof are provided, which offer excellent removal of the decomposing agent from the reaction system after a decomposition reaction in which a thiourethane resin is decomposed by the decomposing agent. [Modes for carrying out the invention]

[0020] In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved. In this disclosure, the amount of each component contained in the composition means the total amount of any multiple substances that constitute each component in the composition, unless otherwise specified. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. There may be overlaps between the multiple embodiments of this disclosure. That is, features of one embodiment may be present in another embodiment.

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

[0022] [ka]

[0023] In formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or an amino group (however, R 1 and R 2 (Except when both are amino groups). In formula (2), R 3 This represents an alkyl group with 1 to 3 carbon atoms.

[0024] In the method for producing the polythiol composition according to the first embodiment, a thiourethane resin is used with formula (1) Alternatively, the polythiol composition is produced by decomposition using a decomposing agent represented by formula (2). The method for producing the polythiol composition according to the first embodiment offers excellent removal of 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 above-mentioned decomposition agent is a low-boiling-point compound.

[0025] The following describes each step that may be included in the method for producing the polythiol composition according to the first embodiment.

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

[0027] (Thiourethane resin) Thiourethane resin is the starting material in the manufacturing process. There are no particular restrictions on the thiourethane resin, and examples include thiourethane resins described in publicly available documents such as Japanese Patent Publication No. 63-46213, Japanese Patent Publication No. 2-270859, Japanese Patent Publication No. 7-252207, International Publication No. 2008 / 047626, International Publication No. 2021 / 157701, and International Publication No. 2021 / 157702.

[0028] Thiourethane resins typically contain polymers of isocyanate compounds and polythiol compositions. That is, thiourethane resins are usually manufactured using isocyanate compounds and polythiol compositions as raw materials.

[0029] -Polythiol composition as a raw material for thiourethane resin- In this disclosure, "polythiol composition" (i.e., a polythiol composition as a raw material for thiourethane resin, and a polythiol composition that is the target product of the method for producing the polythiol composition of this disclosure described later) means a composition containing at least one polythiol compound. The polythiol compound can be any compound containing two or more thiol groups (also known as mercapto groups), and is not particularly limited in any other respect. Regarding polythiol compounds, you may refer to the aforementioned publicly available literature on thiourethane resins 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 its main component.

[0031] Here, "a polythiol composition contains at least one polythiol compound as its main component" means that the total content of at least one polythiol compound relative to the total amount of the polythiol composition is 50% or more. The total content of at least one polythiol compound relative to the total amount of the polythiol composition is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more.

[0032] Similarly, in this disclosure, "a composition contains a certain component (hereinafter referred to as "component X") as a main component" means that the content of component X (or, if component X consists of two or more compounds, the total content of the two or more compounds) is 50% or more of the total amount of the composition. The content of component X, which is the main component, is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, based on the total amount of the composition.

[0033] In the explanation of the phrase "contained as a main component" above, "%" refers to the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) to the total area of ​​all peaks of the composition (e.g., a polythiol composition), as determined by high-performance liquid chromatography.

[0034] In the following, the polythiol compounds contained in the polythiol composition will also be referred to as "polythiol components." Polythiol compositions as raw materials for thiourethane resins are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (3-mercaptopropionate), 2,5-Dimercaptomethyl-1,4-Dithiane, Bis(2-mercaptoethyl) sulfide, and Diethylene glycol bis(3-mercaptopropionate) It is preferable to include at least one selected from the group consisting of (hereinafter also referred to as "polythiol component A"). The polythiol composition more preferably contains polythiol component A as its main component. In this case, the polythiol composition may contain at least one other component besides polythiol component A (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[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, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and the like.

[0036] More specific embodiments of the polythiol composition as a raw material for thiourethane resin include, for example; An embodiment comprising 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A1") as the main component; Embodiments comprising 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter, these three compounds are collectively referred to as "polythiol component A2") as the main components; An embodiment comprising pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as "polythiol component A3") as the main component; Embodiments comprising polythiol component A1 and polythiol component A3 as main components; Embodiments comprising polythiol component A2 and polythiol component A3 as main components; These are some examples. Each embodiment of the polythiol composition may contain at least one other component besides the main component (for example, other polythiol compounds, components other than polythiol compounds, etc.).

[0037] -Isocyanate compounds as raw materials for thiourethane resins- The isocyanate compound used as a raw material for the thiourethane resin may be one type or two or more types. Examples of isocyanate compounds used as raw materials for thiourethane resins include the well-known isocyanate compounds described in the aforementioned publicly available literature. The isocyanate compound used as a raw material for thiourethane resin preferably includes a polyisocyanate compound containing two or more isocyanate groups. Isocyanate compounds as raw materials for thiourethane resins are It is more preferable to include a diisocyanate compound containing two isocyanate groups. It is even more preferable to include 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"). It is even more preferable that the product contains isocyanate component N as its main component.

[0038] The isocyanate compound used as a raw material for thiourethane resin is more preferably selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and bis(isocyanatocyclohexyl)methane (hereinafter also referred to as "isocyanate component N1"), and more preferably contains isocyanate component N1 as the main component.

[0039] -Other ingredients- The thiourethane resin may contain other components besides a polymer of at least one isocyanate compound and a polythiol composition. For other components that may be contained in the thiourethane resin, refer to the components that may be contained in the polymerizable composition described later as appropriate.

[0040] -Recovered thiourethane resin- Preferably, the thiourethane resin is recovered during at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. According to this embodiment, recycling of the thiourethane resin, which is a material for eyeglass lenses, is achieved. Here, The manufacturing process of eyeglass lenses refers to the process of producing resin by mixing monomers, which are the raw materials for resin, and casting polymerization, and / or the process of obtaining eyeglass lenses by cutting and shaping the resin molded product. The eyeglass manufacturing process refers to the process of manufacturing eyeglasses by combining eyeglass lenses with other components such as eyeglass frames. The eyeglasses disposal process refers to the process of disposing of eyeglasses that have been manufactured but are no longer needed, as well as used eyeglasses. In either process, thiourethane resin, the material used for eyeglass lenses, may be generated as waste. In this embodiment, a thiourethane resin produced in at least one of these processes is used as a starting material, and this thiourethane resin is reacted with a decomposition agent to obtain a polythiol composition, which is a decomposition product of the thiourethane resin.

[0041] -Processing waste containing thiourethane resin- In the production process, the thiourethane resin in the processing waste may be brought into contact with the decomposition agent to react with the thiourethane resin in the processing waste. This can further improve the reaction efficiency between the thiourethane resin and the decomposition agent.

[0042] There are no particular restrictions on the form of the processing waste containing thiourethane resin; it may be in powder or lump form.

[0043] There are no particular restrictions on the method of contacting the processing waste containing thiourethane resin with the amine compound. For example, one method is to place the processing waste and a decomposition agent (and a reaction solvent if necessary) in a reaction vessel and stir.

[0044] Preferably, the processing waste containing thiourethane resin is cutting waste (including the concept of polishing waste; the same applies hereinafter) from a molded body containing thiourethane resin and / or the cutting waste that has been sieved (i.e., cutting waste that has passed through the sieve). Cutting waste from molded bodies containing thiourethane resin is generated, for example, when manufacturing optical materials (e.g., lenses) by cutting molded bodies containing thiourethane resin.

[0045] -Resin mixture containing thiourethane resin- The production process may also involve contacting a resin mixture containing a thiourethane resin with a decomposing agent to react the thiourethane resin in the resin mixture with the decomposing agent and produce a polythiol composition.

[0046] The resin mixture containing thiourethane resin further contains components other than thiourethane resin. Other components besides thiourethane resin include resins other than thiourethane resin, inorganic materials for lens fabrication (e.g., glass), and so on.

[0047] There are no particular restrictions on resins other than thiourethane resin. for example; A hybrid material of thiourethane resin and urethane resin, produced by adding a polyol compound to the raw materials during the manufacturing of thiourethane resin; A hybrid material of thiourethane resin and urea resin, produced by adding a polyamine compound to the raw materials during the manufacturing of thiourethane resin; These also fall within the range of resin mixtures containing thiourethane resin and resins other than thiourethane resin.

[0048] In addition, resins other than thiourethane resin include: A polyolefin film that protects the surface of a resin molded body used for making eyeglass lenses. A hard coat or primer coat to protect the surface of a resin molded body used for making eyeglass lenses, and an abrasive used when polishing a resin molded body used for making eyeglass lenses. A resin material used to fix a resin molded body when machining a resin molded body for making eyeglass lenses. Tape or tape adhesive used to fix glass molds when creating resin molded parts for eyeglass lenses. Other examples include:

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

[0050] It is preferable that the resin mixture containing thiourethane resin is recovered during at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. The manufacturing process for eyeglass lenses, the manufacturing process for eyeglasses, and the disposal process for eyeglasses are as described above. The resin mixture containing thiourethane resin preferably contains cutting chips containing thiourethane resin.

[0051] (A decomposing agent represented by formula (1) or formula (2)) The decomposition agent used in this process is the decomposition agent represented by formula (1) or formula (2) above. Examples of decomposition agents represented by the above formula (1) include ammonia, monomethylamine, monoethylamine, monopropylamine, dimethylamine, diethylamine, dipropylamine, hydrazine, and the like. Among these, ammonia, monomethylamine, and diethylamine are preferred. Examples of decomposition agents represented by formula (2) above include methanol, ethanol, and propanol. Among these, methanol or ethanol is preferred, and methanol is more preferred.

[0052] (Amount of decomposition agent to be prepared) In the manufacturing process, the mass ratio of the decomposing agent to the thiourethane resin (i.e., the 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 mass ratio of the preparation [decomposing agent / thiourethane resin] is 0.10 or higher, the formation of the polythiol composition is further promoted. When the mass ratio of the charge [decomposing agent / thiourethane resin] is less than 2.0, the residual amount of decomposing agent in the reaction mixture can be further suppressed. The mass ratio of the preparation [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 decomposition agent added 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 equivalent amount of the decomposing agent to be added to the thiourethane resin (equivalent amount [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 equivalent amount of the charge [decomposing agent / thiourethane resin] is 1.0 or more, the formation of the polythiol composition is further promoted. When the equivalent amount of decomposing agent / thiourethane resin used is 15.0 or less, the residual amount of decomposing agent in the reaction mixture can be further suppressed.

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

[0056] The molecular weight of the tertiary amine compound used as a decomposition aid is preferably 1000 or less, more preferably 500 or less, even more preferably 300 or less, and even more preferably 200 or less. The lower limit of the molecular weight of the tertiary amine compound used as a decomposition aid is, for example, 59 or more, and preferably 70 or more.

[0057] There are no particular restrictions on the tertiary amine compound used as a decomposition aid, other than that it is a tertiary amine compound. As a tertiary amine compound used as a decomposition aid, Preferably, the compounds are 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 preferably, N,N-dimethylethanolamine, N,N-diethylamineaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 1,4-diazabicyclo[2,2,2]octane, diazabicyclononene, or diazabicycloundecene. More preferably, the solution is N,N-dimethylethanolamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, N-ethylmorpholine, or 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 formula (2) above (i.e., charge mass ratio [decomposition aid / decomposition agent]) can be adjusted as appropriate, but is preferably 0.001 to 2.00. The mass ratio of the preparation [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 a decomposition aid to the decomposition agent represented by formula (2) above (i.e., the molar ratio [decomposition aid / decomposition agent]) can be adjusted as appropriate, but is preferably 0.001 to 3.00. The molar ratio of the charge [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 process, it is preferable to react the thiourethane resin with a decomposition agent represented by formula (1) or formula (2) in the presence of a reaction solvent. As the reaction solvent, organic solvents are preferred, and hydrocarbon compounds having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9) are more preferred. The hydrocarbon 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 decomposition agent represented by formula (1) or formula (2) during the production process can be adjusted as appropriate. In the production process, it is preferable to bring the thiourethane resin into contact with a decomposing agent represented by formula (1) or formula (2) under temperature conditions of 50°C to 200°C (more preferably 60°C to 180°C, and even more preferably 70°C to 150°C) (i.e., the reaction temperature). When the reaction temperature is between 50°C and 200°C, the purity of the polythiol component as the main component in the target polythiol composition (i.e., the content of the main component relative to the total amount of the polythiol composition) can be further improved.

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

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

[0064] (The target product is the polythiol composition) In the method for producing the polythiol composition according to the first embodiment, the target polythiol composition is the same as the polythiol composition used as a raw material for thiourethane resin as described above, and the preferred embodiments are also the same.

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

[0066] The target polythiol composition may have the same polythiol component as the starting material, the polythiol composition used as a raw material for the thiourethane resin, and may also have a reduced amount of impurities. When the content of impurities is reduced in the target polythiol composition, the thickening of the polythiol composition is suppressed, which may have the advantage of a longer pot life.

[0067] There are no particular restrictions on the use of the target polythiol composition. The target polythiol composition can be used, for example, in the production of thiourethane resins. Specific applications of the target polythiol composition include polythiol compositions for the manufacture of optical materials (e.g., eyeglass lenses).

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

[0069] (Reaction mixture containing a polythiol composition) The production process may also involve decomposing a thiourethane resin with a decomposing agent to produce a polythiol composition, and obtaining a reaction mixture containing the target polythiol composition. Other components in the reaction mixture besides the polythiol composition include the aforementioned reaction solvent, residues of the raw materials (thiourethane resin and / or decomposition agent), impurities contained in the raw materials, the aforementioned polyurea compound, the aforementioned polycarbamate compound, and so on.

[0070] <Separation process> The method for producing the 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 restrictions on the separation method used in the separation process; known methods can be applied. Separation methods in the separation process include filtration, decantation, extraction, distillation, drying (including vacuum drying), and purification (e.g., column chromatography). Multiple separation methods may be used in combination.

[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, it is easier to remove solid components (e.g., solid components including by-products) contained in the reaction mixture.

[0072] In an embodiment in which the separation step includes obtaining a filtrate containing a polythiol composition, one more preferred embodiment is: The separation process is A filtrate containing the polythiol composition is obtained by filtering the reaction mixture containing the polythiol composition. The filtrate containing the polythiol composition is acid-washed, Separating the polythiol composition from the filtrate after acid washing, One example is an embodiment that includes (hereinafter referred to as separation embodiment A). According to separation method A, alkaline components (e.g., residues of amine compounds) can be easily removed from the filtrate by acid washing, thus obtaining a polythiol composition with higher purity of the polythiol component as the main component. In separation method A, water washing may be added after acid washing, and the polythiol composition may be separated from the filtrate after water washing.

[0073] In separation mode A, examples of acids used for acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, and the like.

[0074] In an embodiment in which the separation step includes obtaining a filtrate containing a polythiol composition, one more preferred embodiment is: The separation process is A filtrate containing the polythiol composition is obtained by filtering the reaction mixture containing the polythiol composition. By adding a base containing an alkali metal to a filtrate containing a polythiol composition, and then adding water to perform extraction, an aqueous extract containing the alkali metal salt of the polythiol composition is obtained. Adding an acid to an aqueous extract containing an alkali metal salt of a polythiol composition to obtain an aqueous liquid containing the polythiol composition, An extract containing the polythiol composition is obtained by adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to an aqueous liquid containing the polythiol composition and performing the extraction. Separating the polythiol composition from an extract containing the polythiol composition, An embodiment that includes this (hereinafter referred to as separation embodiment B) is also an example.

[0075] In separation method B, first, the polythiol composition in the filtrate containing the polythiol composition is converted to an alkali metal salt, and then extracted with water to obtain an aqueous extract containing the alkali metal salt of the polythiol composition. Next, by adding acid, the alkali metal salt of the polythiol composition is converted back to the polythiol composition. The polythiol composition is extracted from the obtained aqueous liquid containing the polythiol composition with the above 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 method B, even when the filtrate containing the polythiol composition contains a large amount of other components besides the polythiol composition, a polythiol composition with higher purity of the polythiol component as the main component can be obtained.

[0076] In separation mode B, the alkali metal in the alkali metal-containing base is preferably sodium, potassium, or lithium, and more preferably sodium or potassium. Examples of bases containing alkali metals include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Bases containing alkali metals can be added to the filtrate in the form of an alcoholic solution (methanol solution, ethanol solution, etc.) as needed.

[0077] In separation mode B, examples of acids added to the aqueous extract containing the alkali metal salt of the polythiol composition include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, and the like.

[0078] In separation mode B, the hydrocarbon compound used as the extraction solvent may be one type or two or more types. In separation mode B, the preferred embodiment of the hydrocarbon compound as the extraction solvent is the same as the preferred embodiment of the hydrocarbon compound as the reaction solvent described above. However, the reaction solvent and the extraction solvent may be the same or different.

[0079] In an embodiment in which the separation step includes obtaining a filtrate containing a polythiol composition, one more preferred embodiment is: The separation process is The reaction mixture containing the polythiol composition is separated by decantation to obtain a residue containing the polythiol composition, An aqueous extract containing the alkali metal salt of the polythiol composition is obtained by adding a base containing an alkali metal to the residue containing the polythiol composition, and then adding water to perform extraction. Adding an acid to an aqueous extract containing an alkali metal salt of a polythiol composition to obtain an aqueous liquid containing the polythiol composition, An extract containing the polythiol composition is obtained by adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to an aqueous liquid containing the polythiol composition and performing the extraction. Separating the polythiol composition from an extract containing the polythiol composition, An embodiment including this (hereinafter referred to as separation embodiment C) is also an example. Separation method C is the same as separation method B except that the residue containing the polythiol composition is obtained by decantation.

[0080] <Classification process> The method for producing the polythiol composition according to the first embodiment may further include a classification step of classifying cutting waste containing a thiourethane resin before the reaction step. In this case, the reaction step involves reacting the classified cutting waste with a decomposing agent represented by formula (1) or formula (2). If the method for producing the polythiol composition according to the first embodiment includes a classification step, the reaction step involves contacting cutting chips consisting of particles with 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 this disclosure, the average particle diameter can be, for example, the number-average particle diameter. Examples of particle size include the equivalent diameter of a circle. Classification methods include sieving and centrifugation. For details on the sieving process used for classification, please refer to the sieving process described below.

[0082] <Sieving process> The method for producing the polythiol composition according to the first embodiment may further include a sieving step in which cutting chips containing thiourethane resin are sieved before the production step. In this case, in the production step, the cutting chips that have passed through the sieve are brought into contact 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). If the method for producing the polythiol composition according to the first embodiment includes a sieving step, the production step involves contacting cutting shavings consisting of small particles 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).

[0083] There are no particular restrictions on the above sieve. The nominal mesh opening 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 Process> The method for producing the polythiol composition according to the first embodiment may further include a washing step in which the thiourethane resin is washed with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent before the production step. In this case, in the reaction step, the thiourethane resin washed in the washing step is reacted with a decomposition agent represented by formula (1) or formula (2). This yields a polythiol composition with a higher purity of the polythiol component as the main component. In particular, in the method for producing the polythiol composition according to the first embodiment, when cutting scraps containing thiourethane resin are used as the starting material, the above-mentioned cleaning step can effectively remove oil originating from the cutting machine adhering to the cutting scraps, thereby obtaining a polythiol composition with a higher purity of the polythiol component as the main component.

[0085] The hydrocarbon compound used as the washing solvent may be one type or two or more types. The preferred embodiment of the hydrocarbon compound as a washing solvent is the same as the preferred embodiment of the hydrocarbon compound as a reaction solvent described above. However, the reaction solvent and the washing solvent may be the same or different.

[0086] There are no particular restrictions on the cleaning method in the cleaning process, and known methods can be applied, such as adding the above-mentioned cleaning solvent to cutting waste containing thiourethane resin (e.g., thiourethane resin waste) and mixing it.

[0087] If the method for producing the polythiol composition according to the first embodiment includes the sieving step and the washing step described above, it is preferable to perform the sieving step and the washing step in this order. In this case, there is no need to wash the cutting debris that did not pass through the sieve, so the amount of washing solvent used can be further reduced.

[0088] [Method for producing polymerizable composition (first embodiment)] A method for producing a polymerizable composition according to the first embodiment of this disclosure is: A step of producing a polythiol composition by the method for producing a polythiol composition according to the first embodiment described above, The process involves a step of obtaining a polymerizable composition containing the polythiol composition and a polyisocyanate compound by mixing at least the above-mentioned polythiol composition and a polyisocyanate compound, Includes. The method for producing the polymerizable composition according to the first embodiment may include other steps as needed.

[0089] In the method for producing a polymerizable composition according to the first embodiment, In the process of producing a polythiol composition, a thiourethane resin (for example, thiourethane resin in the cutting waste of a molded thiourethane resin product) is used as a starting material to produce the polythiol composition. In the process of obtaining a polymerizable composition, a polymerizable composition is produced that contains the polythiol composition produced above and a polyisocyanate compound. The resulting polymerizable composition can be used again in the production of thiourethane resin. In this way, the method for producing a polymerizable composition according to the first embodiment enables the effective utilization (i.e., recycling) of materials (i.e., thiourethane resin and its raw material, the polythiol composition).

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

[0091] <Process for manufacturing polythiol composition> For the step of producing the polythiol composition in the method for producing the polymerizable composition according to the first embodiment, the method for producing the polythiol composition according to the first embodiment described above can be appropriately referenced.

[0092] <Steps to obtain a polymerizable composition> In the step of obtaining a polymerizable composition, a polymerizable composition containing the polythiol composition and the polyisocyanate compound is obtained by mixing at least the polythiol composition and the polyisocyanate compound.

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

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

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

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

[0097] Here, a 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 its main component. The meaning of "contains as a main component" is as explained 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 its main component.

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

[0102] [ka]

[0103] The following describes preferred embodiments of the XDI composition from the viewpoint of superior stability of the polyisocyanate composition and transparency of the resin formed using the polyisocyanate composition.

[0104] If the XDI composition contains compound (N1), it is preferable that the peak area of ​​compound (N1) in gas chromatography measurement under GC condition 1 below is 0.20 ppm or more relative to the peak area of ​​xylylene diisocyanate. -GC condition 1- Filler; DB-1 (film thickness) 1.5 μm Column; inner diameter 0.53 mm x length 60 m (manufactured by Agilent) Oven temperature: Increase temperature from 130°C to 220°C at a rate of 3°C / min, then increase to 300°C at a rate of 10°C / min. Split ratio; pulsed splitless method Inlet temperature: 280℃ Detector temperature: 300°C Carrier gas: N2 158kPa, H255kPa, Air 45kPa (constant pressure control) Solvent: Chloroform Sample concentration: 2.0% by mass chloroform solution Injection volume: 2μL Detection method; FID

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

[0106] If the XDI composition contains compound (N2), it is preferable that the peak area of ​​compound (N2) in gas chromatography measurement under GC condition 2 below is 0.05 ppm or more relative to the peak area of ​​xylylene diisocyanate. -GC condition 2- Column; HP-50+, inner diameter 0.25 mm x length 30 m x film thickness 0.25 μm (manufactured by Hewlett-Packard) Oven temperature: Increase from 50°C to 280°C at a rate of 10°C / min, hold for 6 minutes after reaching 280°C. Split ratio; pulsed splitless method Inlet temperature: 200℃ Detector temperature: 280°C Carrier gas; He Carrier gas flow rate: 1.0 ml / min (constant flow control) Sample concentration: 1.0% by mass dichloromethane solution Injection volume; 1.0μL Detection method; SIM (Monitoring ions: m / z 180, 215) (Content ratio of xylylene diisocyanate (XDI))

[0107] The peak area of ​​the above compound (N2) is more preferably 0.1 ppm or more, even more preferably 0.3 ppm or more, and even more preferably 0.6 ppm or more, relative to the peak area of ​​xylylene diisocyanate (1 ppm). The peak area of ​​the above compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 80 ppm or less, even more preferably 70 ppm or less, and even more preferably 60 ppm or less, relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​the above compound (N2) can be measured in accordance with the method described in paragraphs 0375 and 0376 of Japanese Patent Publication No. 6373536.

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

[0109] The acidity of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and even more preferably less than 15 ppm. The lower limit of the acidity of the XDI composition is not particularly limited, but the lower limit is, for example, 1 ppm. The acidity of the XDI composition can be measured in accordance with the method described in paragraph 0091 of International Publication No. 2021 / 256417. Furthermore, the XDI composition may contain a stabilizer.

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

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

[0112] As an internal release agent, an acidic phosphate ester can be used. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more types.

[0113] Examples of resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, olefin compounds including (meth)acrylate compounds, etc. Here, (meth)acrylate compounds mean at least one of acrylate compounds and methacrylate compounds.

[0114] In the process of obtaining a polymerizable composition, the mixing of the above-mentioned components can be carried out according to conventional methods, and the method of mixing is not particularly limited.

[0115] [Method for manufacturing resin (first embodiment)] The method for manufacturing the resin according to the first embodiment of this disclosure is: The method for producing a polymerizable composition according to the first embodiment described above includes a step for producing a polymerizable composition, A step of obtaining a resin by curing the above polymerizable composition, Includes. The resin manufacturing method according to the first embodiment may include other steps as needed.

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

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

[0118] The process of obtaining the resin may involve subjecting the polymer obtained by monomer polymerization to a treatment such as annealing. Typical annealing temperatures include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0119] [Method for manufacturing a molded article (first embodiment)] A method for manufacturing a molded article according to the first embodiment of this disclosure is a method for manufacturing a molded article containing a resin, The method for producing a polymerizable composition according to the first embodiment described above includes a step for producing a polymerizable composition, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing a molded article according to the first embodiment may include other steps as necessary.

[0120] In the process of obtaining a molded article containing resin, the polymerizable composition is cured to obtain a molded article containing resin. Preferred conditions for curing the above polymerizable composition, that is, for polymerization of monomers in the above polymerizable composition, can be appropriately referred to in the section on "Method for Producing Resins".

[0121] One example of polymerization in this process is casting polymerization. In casting polymerization, the polymerizable composition is first injected between molds held together by gaskets or tape. Degassing and filtration may be performed as needed during this process. Next, the monomers in the polymerizable composition injected between the molding molds are polymerized, thereby curing the composition between the molding molds to obtain a cured product. Then, the cured product is removed from the molding molds to obtain a molded body containing resin. Polymerization of the above monomers may be carried out by heating the polymerizable composition. This heating can be performed, for example, using a heating device equipped with a mechanism for heating the object to be heated in an oven, water, or the like.

[0122] [Manufacturing method for optical materials (first embodiment), manufacturing method for lenses (first embodiment)] A method for manufacturing an optical material (e.g., a lens) according to the first embodiment of this disclosure is a method for manufacturing an optical material (e.g., a lens) including a molded body containing a resin, The method for producing a polymerizable composition according to the first embodiment described above includes a step for producing a polymerizable composition, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing 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 manufacturing the optical material according to the first embodiment is an application of the method for manufacturing the molded article according to the first embodiment. For example, in the method for manufacturing a molded article according to the first embodiment, by appropriately selecting the shape of the molding mold used in the aforementioned casting polymerization, a molded article applicable to optical materials (e.g., lenses) can be obtained.

[0124] Examples of optical materials include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses), light-emitting diodes (LEDs), and the like.

[0125] The method for manufacturing an optical material (e.g., 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] Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers may be formed individually or in multiple layers. When coating layers are formed on both sides, similar coating layers may be formed on each side, or different coating layers may be formed on each side.

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

[0128] For eyeglass lenses and coating layers, you can refer to publicly available documents such as International Publication No. 2017 / 047745 as appropriate.

[0129] [Polymerizable composition (first embodiment)] The polymerizable composition according to the first embodiment of this disclosure contains a polythiol composition obtained by the method for producing the 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 the polymerizable composition according to the first embodiment described above. Preferred embodiments of the polymerizable composition according to the first embodiment can be appropriately referenced from the method for producing the polymerizable composition according to the first embodiment described above. However, the input mass [polythiol composition / polyisocyanate compound] shall be read as the content mass ratio [polythiol composition / polyisocyanate compound], and the total input mass of the polythiol composition and polyisocyanate compound shall be read as the total content mass of the polythiol composition and polyisocyanate compound.

[0130] [Resin (first embodiment), molded body (first embodiment), optical material (e.g., lens) (first embodiment)] The resin according to the first embodiment of this disclosure is a cured product of the polymerizable composition according to the first embodiment of this disclosure described above. The molded article according to the first embodiment of this 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) that includes the resin according to the first embodiment described above.

[0131] The resin according to the first embodiment, the molded article according to the first embodiment, and the optical material (e.g., lens) according to the first embodiment can be manufactured by the method for manufacturing the resin according to the first embodiment, the method for manufacturing the molded article according to the first embodiment, and the method for manufacturing the optical material (e.g., lens) according to the first embodiment, respectively. Preferred embodiments of the resin according to the first embodiment, the molded article according to the first embodiment, and the optical material (e.g., lens) according to the first embodiment can refer to the preferred embodiments of the method for manufacturing the resin according to the first embodiment, the method for manufacturing the molded article according to the first embodiment, and the method for manufacturing the optical material (e.g., lens) according to the first embodiment, respectively.

[0132] <Preferred performance of resin or molded article> 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, from the viewpoint of heat resistance. The above glass transition temperature Tg may be 130°C or lower, 120°C or lower, or 110°C or lower.

[0133] The refractive index (ne) of the resin (or molded article) according to the first embodiment is preferably 1.500 or higher, more preferably 1.540 or higher, and even more preferably 1.590 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the refractive index (ne) mentioned above, but a possible upper limit is 1.750.

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

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

[0136] ≪Second Embodiment≫ [Method for producing polyamine compounds (Second Embodiment)] The method for producing a polyamine compound according to the second embodiment is as follows: The first step involves decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) to produce a polyurea compound, A second step involves decomposing a polyurea compound with a decomposition agent represented by the following formula (3) to produce a polyamine compound, Includes.

[0137] [ka]

[0138] In formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or an amino group (however, R 1 and R 2 (Except when both are amino groups). In formula (3), R 11 and R 12 Each of these independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0139] The method for producing polyamine compounds according to the second embodiment offers excellent removal of 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. The reason for this effect is thought to be that the decomposing agent represented by formula (1) is a low-boiling-point compound. Here, the concept of "reaction system after the decomposition reaction in the first step" includes not only the reaction system after the first step but before the second step, but also the reaction system after the first step but during and after the second step. For example, the decomposition of the polyurea compound in the second step may generate a decomposing agent represented by formula (1) along with the target polyamine compound. Even in this case, the removal of the decomposing agent represented by formula (1) from the reaction system during and after the second step is excellent.

[0140] The method for producing polyamine compounds according to the second embodiment also offers excellent removal of the decomposing agent represented by formula (3) from the reaction system after the decomposition reaction in the second step. For example, the decomposing agent represented by formula (3) can be easily removed from the reaction system after the decomposition reaction in the second step 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 low-boiling-point compound.

[0141] The following describes each step that may be included in the method for producing a polyamine compound according to the second embodiment.

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

[0143] For the first step, refer to the production step in the method for producing the polythiol composition according to the first embodiment. In the first step, the thiourethane resin is decomposed with a decomposing agent represented by the above formula (1), thereby generating a polyurea compound and the aforementioned polythiol composition. The preferred embodiments of the thiourethane resin and the decomposing agent represented by formula (1) in the first step are the same as the preferred embodiments of the thiourethane resin and the decomposing agent represented by formula (1) in the method for producing the polythiol composition according to the first embodiment.

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

[0145] (Polyurea compounds) The polyurea compound produced in the first step is an amine decomposition product of the thiourethane resin, which is produced by the reaction of the thiourethane resin with the decomposition agent represented by formula (1) (i.e., amine decomposition). Polyurea compounds are compounds that contain two or more urea bonds. The polyurea compound is, for example, a polyurea compound having a structure in which all isocyanate groups in a polyisocyanate compound, which is one of the raw materials for thiourethane resin, react with the amino group or monoalkylamino group of amine compound A to form a urea bond. In this disclosure, a polyurea compound having such a structure may be referred to as the urea compound of a polyamine compound (e.g., m-xylylenediisocyanate (XDI)) corresponding to a polyisocyanate compound (e.g., m-xylylenediisocyanate (XDI)), which is one of the raw materials, and amine compound A (e.g., monoethanolamine (MEA)). Here, the polyamine compound corresponding to the polyisocyanate compound means a compound in which all isocyanate groups in the polyisocyanate compound are replaced with amino groups. The polyamine compound corresponding to the polyisocyanate compound is the target product in the method for producing the polyamine compound according to the second embodiment.

[0146] (First reaction step and first separation step) The first step is, A reaction step of reacting a thiourethane resin with a decomposition agent represented by formula (1) to obtain a reaction mixture containing a polyurea compound, A separation step to separate the polyurea-containing mixture from the above reaction mixture, It may include. In this case, in the second step described later, the polyurea-containing mixture separated in the first separation step described above is mixed with the decomposition agent represented by formula (3), thereby reacting the polyurea compound in the polyurea-containing mixture with the decomposition agent represented by formula (3). Here, a polyurea-containing mixture refers to a mixture of two or more urea compounds that include a polyurea compound. Hereinafter, the above reaction mixture, the above reaction step, and the above 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 mode of the reaction in the first reaction step is as described above.

[0148] There are no particular restrictions on the separation method in the first separation step, and known methods can be applied. Methods of separation in the first separation step include filtration, decantation, extraction, distillation, drying (including vacuum drying), and purification (e.g., column chromatography). Multiple separation methods may be used in combination.

[0149] If a polyurea-containing mixture is produced as a solid in the first reaction step, the first separation step preferably includes filtering the first reaction reaction to obtain a polyurea-containing mixture as a filtrate. The obtained filtrate may be subjected to operations such as washing. In this case, the filtrate obtained by filtering the first reaction mixture may contain a polythiol composition, which is a by-product (more specifically, a by-product when the polyurea-containing mixture is the main product) produced by the additive amine decomposition reaction. For preferred embodiments of the polythiol composition as a by-product, refer to the preferred embodiments of the polythiol composition as a raw material for thiourethane resin described above as appropriate. The polythiol composition, a by-product of the amine decomposition reaction, can be used as a raw material for the production of new thiourethane resins. This enables the effective utilization (i.e., recycling) of materials.

[0150] If the polyurea-containing mixture is produced in a liquid state and insoluble in the reaction solvent during the first reaction step, the first separation step preferably includes separating the supernatant and obtaining the polyurea-containing mixture as an extraction residue by decantation, which involves repeated extraction and washing. The obtained extraction residue may be subjected to operations such as washing. In this case, the supernatant liquid may contain a polythiol composition, which is a by-product (more specifically, a by-product when a polyurea-containing mixture is the main product) produced by the additive amine decomposition reaction. For preferred embodiments of the polythiol composition as a by-product, refer to the preferred embodiments of the polythiol composition as a raw material for thiourethane resin described above as appropriate. The polythiol composition, a by-product of the amine decomposition reaction, can be used as a raw material for the production of new thiourethane resins. This enables the effective utilization (i.e., recycling) of materials.

[0151] If the polyurea-containing mixture is dissolved in the first reaction solvent in the first reaction step, the first separation step is preferably: The first reaction mixture is filtered to obtain a filtrate, By adding a base containing an alkali metal to the filtrate, and then adding water to perform extraction, the alkali metal salt of the polythiol composition as a by-product is removed from the filtrate. The polyurea-containing mixture is separated from the filtrate from which the alkali metal salts have been removed. Includes. The polyurea-containing mixture can be separated from the filtrate from which the alkali metal salts have been removed by methods such as concentration and drying.

[0152] <Second process> The second step involves decomposing the polyurea compound produced in the first step using a decomposition agent represented by formula (3) to produce a polyamine compound. In the second step, the polyurea-containing mixture separated in the first separation step described above may be mixed with the decomposition agent represented by formula (3) to react the polyurea compound in the polyurea-containing mixture with the decomposition agent represented by formula (3).

[0153] The reaction in the second step (secondary amine decomposition) exhibits superior efficiency in polyamine compound production compared to known reactions that yield polyamine compounds by the reaction of a polyurea compound with sodium hydroxide. As a result, the amount of polyamine compound produced can be increased compared to when the above-mentioned known reaction is applied. This effect can be confirmed by analyzing the reaction mixture obtained in the second step using gas chromatography (GC).

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

[0155] (The decomposing agent represented by formula (3)) The decomposition 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 equivalent amount of the decomposition agent represented by formula (3) relative to the polyurea compound (equivalent amount [decomposition 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 equivalent charge [decomposition agent / polyurea compound represented by formula (3)] is 0.1 or greater, the formation of polyamine compounds is further promoted. When the equivalent charge [decomposing agent / polyurea compound represented by formula (3)] 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 reacting the polyurea compound in the polyurea-containing mixture with the decomposition agent represented by formula (3) by mixing the polyurea-containing mixture separated in the first separation step described above with the decomposition agent represented by formula (3), the amount of charge [decomposition agent represented by formula (3) / polyurea compound] may be determined by considering the entire amount of the polyurea-containing mixture as polyurea compounds.

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

[0158] (Second reaction temperature) The reaction temperature of the polyurea compound and the decomposing agent represented by the formula (3) in the second step (hereinafter also referred to as the second reaction temperature) is appropriately adjusted. In the second step, the polyurea compound and the decomposing agent represented by the formula (3) are preferably reacted under temperature conditions of 80°C to 200°C (more preferably 90°C to 200°C, still more preferably 100°C to 200°C, still more preferably 110°C to 190°C, still more preferably 120°C to 180°C) (that is, the second reaction temperature). Also, in the second step, the reaction may be carried out under pressure conditions. When the reaction is carried out under pressure conditions, the reaction time may be shortened in some cases.

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

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

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

[0162] There are no particular restrictions on the separation method in the second separation step, and known methods can be applied. Methods for separation in the second separation step include filtration, decantation, washing, extraction, distillation, reduced pressure (e.g., vacuum), and purification (e.g., column chromatography). Multiple separation methods may be used in combination.

[0163] A preferred embodiment of the second separation step is: The polyamine compound is extracted from the second reaction mixture using a second extraction solvent to obtain an extract. Separating polyamine compounds from the extract, Examples include embodiments that include (also referred to as "Second Separation Embodiment C"). In the second separation method C, the polyamine compound is not separated directly from the second reaction mixture, but rather from an extract obtained by extracting the polyamine compound from the second reaction mixture. This improves the isolation yield of the final polyamine compound. The reason for this is not clear, but it is thought to be because disproportionation in the second separation step (specifically, the reaction in which the polyamine compound reverts back to a polyurea compound) is more suppressed.

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

[0165] When separating the polyamine compound 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 removing insoluble components 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 extraction solvent in the second separation mode C include hydrocarbon compounds. For example, when a hydrocarbon compound is used as the second extraction solvent, a preferred embodiment of the hydrocarbon compound used as the second extraction solvent is the preferred embodiment of the hydrocarbon compound used as the first reaction solvent described above. However, in this case, the hydrocarbon compound used as the second extraction solvent and the hydrocarbon compound used as the first reaction solvent may be the same or different. In the second separation mode C, the separation of the polyamine compound from the extract preferably includes distillation.

[0167] (Polyamine compounds as the target product) In the method for producing polyamine compounds according to the second embodiment, the target polyamine compound is a decomposition product of a tipolyurea compound, which is produced by the reaction of a polyurea compound with a decomposition agent represented by formula (3). The target polyamine compound is preferably a polyamine compound corresponding to the polyisocyanate compound used as a raw material for the thiourethane resin, which is the starting material in the first step (more specifically, a compound in which the isocyanate group in the polyisocyanate compound is replaced with an amino group).

[0168] The target polyamine compound can be any compound containing two or more amino groups. The polyamine compound as the target product is Preferably, it contains a diamine compound containing two amino groups. Preferably, it 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"). It is more preferable that the polyamine component A is the 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"). It is even more preferable that the product contains polyamine component A1 as its main component.

[0170] There are no particular restrictions on the use of polyamine compounds as target products, and they can be applied to a variety of uses. The target polyamine compound can be used, for example, as a raw material for a polyisocyanate compound. The manufactured polyisocyanate compound can be used, for example, in the production of thiourethane resin or urethane resin.

[0171] Specific applications of the manufactured polyisocyanate compounds include those used in the manufacture of optical materials (e.g., lenses). That is, as a specific example of the method for producing a polyamine compound according to the second embodiment, a method for producing a polyamine compound as a raw material for a polyisocyanate compound for optical material production can be mentioned. In this specific example, when using, as a starting material, cutting waste containing a thiourethane resin generated during the production of an optical material, recycling of the materials (thiourethane resin, polyisocyanate compound) can be effectively achieved.

[0172] <Other steps> The method for producing a polyamine compound according to the second embodiment may include other steps other than those described above. Examples of other steps include a classification step (for example, 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)〕 The method for producing a polyisocyanate compound according to the second embodiment of the present disclosure is 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 above polyamine compound and the hydrochloride of the above polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound, and includes.

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

[0175] There are no particular restrictions on the uses of the polyisocyanate compound produced by the method for producing a polyisocyanate compound according to the second embodiment, and it can be applied to various uses. The polyisocyanate compound can be used, for example, in the production of a thiourethane resin or a urethane resin.

[0176] Specific examples of the target polyisocyanate compound include compounds similar to those specified as "Isocyanate Compounds as Raw Materials for Thiourethane Resins" in the section on "Method for Producing Polythiol Compositions."

[0177] Specific applications of the target polyisocyanate compounds include those used in the manufacture of 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 optical material manufacturing. In this specific example, if cutting waste containing thiourethane resin generated during the manufacture of optical materials is used as the starting material, the effective utilization (i.e., recycling) of the materials (thiourethane resin, polyisocyanate compound) is effectively realized.

[0178] In the process of obtaining a polyisocyanate compound, at least one of the above-mentioned polyamine compound and the hydrochloride salt of the above-mentioned polyamine compound is reacted with carbonyl dichloride (hereinafter also referred to as "phosgene") to change the amino group in the above-mentioned polyamine compound to an isocyanate group, thereby obtaining a polyisocyanate compound. This reaction itself is well known, and known methods for producing polyisocyanate compounds can be referenced as appropriate.

[0179] [Method for producing polymerizable composition (second embodiment)] A method for producing a polymerizable composition according to the second embodiment of this disclosure is: A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to the second embodiment described above, A step of obtaining a polymerizable composition containing a polyisocyanate compound and an active hydrogen compound by mixing at least a polyisocyanate compound and an active hydrogen compound, Includes. The method for producing the 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 process of producing polyisocyanate compounds, thiourethane resin (for example, thiourethane resin in the cutting waste of a molded thiourethane resin product) is used as a starting material to produce polyisocyanate compounds. In the process of obtaining a polymerizable composition, a polymerizable composition is produced that contains the polyisocyanate compound produced above and an active hydrogen compound. The resulting polymerizable composition can be used again in the production of thiourethane resin. In this way, the method for producing a polymerizable composition according to the second embodiment enables the effective utilization (i.e., recycling) of materials (i.e., thiourethane resin and its raw material, polyisocyanate compound).

[0181] <Process for manufacturing polyisocyanate compounds> For the process of producing the polyisocyanate compound, the method for producing the polyisocyanate compound according to the second embodiment described above can be appropriately referenced.

[0182] <Steps to obtain a polymerizable composition> In the step of obtaining a polymerizable composition, a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound is obtained by mixing at least the polyisocyanate compound and the active hydrogen compound.

[0183] Examples of active hydrogen compounds include polythiol compounds, polyol compounds, and polyamine compounds. The active hydrogen compound may be one type or two or more types. As the active hydrogen compound, a polythiol composition is preferred. Preferred embodiments of the polythiol composition as an active hydrogen compound are the same as preferred embodiments of the "polythiol composition as a raw material for thiourethane resin" described in the section on "Method for producing polyamine compounds".

[0184] In the process of obtaining a polymerizable composition, the mixing ratio of the active hydrogen compound and the polyisocyanate compound is not particularly limited. In the process of obtaining a polymerizable composition, the ratio of the mass of the active hydrogen compound to the mass of the polyisocyanate compound (i.e., 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. Furthermore, the molar ratio (mercapto group / isocyanato group) of the mercapto group of the polythiol compound and the isocyanate group of the polyisocyanate compound contained in the polythiol composition is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3.

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

[0186] In the process of obtaining a 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 process of obtaining the polymerizable composition, at least the polyisocyanate compound and the active hydrogen compound may be mixed, and then other components may be added to the mixture. For other components, refer to other components used in the method for producing the polymerizable composition according to the first embodiment.

[0187] In the process of obtaining a polymerizable composition, the mixing of the above-mentioned components can be carried out according to conventional methods, and the method of mixing is not particularly limited.

[0188] [Method for manufacturing resin (second embodiment)] A method for manufacturing a resin according to a second embodiment of this disclosure is: A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to the second embodiment described above, A step of obtaining a resin by curing the above polymerizable composition, Includes.

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

[0190] [Method for manufacturing a molded article (second embodiment)] A method for manufacturing a molded article according to a second embodiment of this disclosure is a method for manufacturing a molded article containing a resin, A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to the second embodiment described above, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes.

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

[0192] [Manufacturing method for optical materials (second embodiment), manufacturing method for lenses (second embodiment)] A method for manufacturing an optical material (e.g., a lens) according to a second embodiment of this disclosure is a method for manufacturing an optical material (e.g., a lens) including a molded body containing a resin, A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to the second embodiment described above, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing 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 manufacturing an optical material (e.g., a lens) according to the second embodiment is the same as the method for manufacturing an optical material (e.g., a lens) according to the first embodiment, except that the polymerizable composition is manufactured by the method for manufacturing a polymerizable composition according to the second embodiment instead of manufacturing the polymerizable composition by the method for manufacturing a polymerizable composition according to the first embodiment, and the preferred embodiments are also the same.

[0194] [Resin (second embodiment), molded body (second embodiment), optical material (e.g., lens) (second embodiment)] The resin according to the second embodiment of this disclosure is a cured product of the polymerizable composition according to the second embodiment of this disclosure described above. The molded article according to the second embodiment of this disclosure is a molded article comprising 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) that includes the resin according to the second embodiment described above.

[0195] The resin, molded article, and optical material (e.g., lens) according to the second embodiment are the same as those according to the first embodiment, except that the polymerizable composition is produced by the method for producing the polymerizable composition according to the second embodiment instead of the method for producing the polymerizable composition according to the first embodiment, and the preferred embodiments are also the same.

[0196] ≪Third Embodiment≫ [Method for producing polyamine compounds (third embodiment)] The method for producing a polyamine compound according to the third embodiment is as follows: Step X1 involves decomposing a thiourethane resin with a decomposition agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polycarbamate compound, Step X2 involves decomposing the aforementioned polycarbamate compound with a decomposition agent represented by the following formula (3) to produce a polyamine compound, Includes.

[0197] [ka]

[0198] In formula (2), R 3 This represents an alkyl group with 1 to 3 carbon atoms. In formula (3), R 11 and R 12 Each of these independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0199] The method for producing polyamine compounds according to the third embodiment offers excellent removal of 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. The reason for this effect is thought to be that the above-mentioned decomposition agent is a low-boiling-point compound. Here, the concept of "reaction system after the decomposition reaction in process X1" includes not only the reaction system after process X1 but before process X2, but also the reaction system after process X1 but during and after process X2. For example, the decomposition of the polycarbamate compound in step X2 may generate a decomposing agent represented by formula (2) along with the target polyamine compound. Even in this case, the removal of the decomposing agent represented by formula (2) from the reaction system during and after step X2 is excellent.

[0200] The method for producing polyamine compounds according to the third embodiment also offers excellent removal of 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 low-boiling-point compound.

[0201] The following describes each step that may be included in the method for producing a polyamine compound according to the third embodiment.

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

[0203] For step X1, refer to the production step in the method for producing the polythiol composition according to the first embodiment. In step X1, the thiourethane resin is decomposed with a decomposition agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid, thereby generating a polycarbamate compound and the aforementioned polythiol composition. In step X1, preferred embodiments of the thiourethane resin, the decomposition agent represented by formula (2), and the tertiary amine compound as a decomposition aid are the same as preferred embodiments of the thiourethane resin, the decomposition agent represented by formula (2), and the tertiary amine compound as a decomposition aid in the method for producing the polythiol composition according to the first embodiment.

[0204] (Reaction pressure) Step X1 preferably includes reacting a thiourethane resin with a decomposition 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 further suppresses the volatilization of the decomposition agent represented by formula (2). In this case, the method involves reacting a thiourethane resin with a decomposing agent represented by formula (2) under a pressure preferably 0.01 MPa or higher (more preferably 0.01 MPa to 2.0 MPa, and even more preferably 0.02 MPa to 1.0 MPa) higher than atmospheric pressure.

[0205] (Polycarbamate compounds) The polycarbamate compound produced in step X1 is an alcoholic decomposition product of the thiourethane resin, produced by the reaction of the thiourethane resin with the decomposition agent represented by formula (2) (i.e., alcoholic decomposition). Polycarbamate compounds are compounds (i.e., polyurethane compounds) that contain two or more carbamate bonds (i.e., urethane bonds). A polycarbamate compound is, for example, a polycarbamate compound (i.e., a polyurethane compound) having a structure in which all isocyanate groups in a polyisocyanate compound, which is one of the raw materials for thiourethane resins, react with the hydroxyl groups of an alcohol compound to form a carbamate bond (i.e., a urethane bond). In this 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, a polyamine compound corresponding to a polyisocyanate compound means a compound in which all isocyanate groups in the polyisocyanate compound are replaced with amino groups. The polyamine compound corresponding to a 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) Process X1 is, A reaction step in which a thiourethane resin is reacted with a decomposition agent represented by formula (2) to obtain a reaction mixture containing a polycarbamate compound, A separation step to separate the polycarbamate-containing mixture from the above reaction mixture, It may include. In this case, in step X2 described later, the polycarbamate-containing mixture separated in the separation step described above is mixed with the decomposition agent represented by formula (3), thereby reacting the polycarbamate compound in the polycarbamate-containing mixture with the decomposition agent represented by formula (3). Here, a polycarbamate-containing mixture means a mixture of two or more carbamate compounds that include a polycarbamate compound. Hereinafter, the above reaction mixture, the above reaction step, and the above 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 include a polycarbamate-containing mixture as the main product produced by alcohol decomposition, and other components other than the polycarbamate-containing mixture. Other components include by-products generated by alcohol decomposition (e.g., polythiol compositions), the aforementioned reaction solvent, residues from the 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, refer to the preferred embodiments of the polythiol composition as a raw material for thiourethane resin described above as appropriate. The polythiol composition, a by-product of the alcohol decomposition reaction, can be used as a raw material for the production of new thiourethane resins. This enables material recycling.

[0209] There are no particular restrictions on the separation method in separation step X2; known methods can be applied. Methods of separation in separation step X2 include filtration, decantation, extraction, distillation, drying (including vacuum drying), and purification (e.g., column chromatography). Multiple separation methods may be used in combination.

[0210] For example, one preferred embodiment of the separation step X2 is: The reaction mixture X1 is filtered to obtain a filtrate, The above filtrate is washed with acid, and then washed with water. To the filtrate washed with the above water, a base containing an alkali metal is added, and then washed with water to remove salts (for example, alkali metal salts of the reaction by-product, the polythiol composition), The process involves separating the polycarbamate-containing mixture from the filtrate from which salts have been removed, and One example is an embodiment that includes (hereinafter referred to as separation embodiment X1).

[0211] In separation method X1, the filtrate is first washed with acid (hereinafter also referred to as acid washing) to remove amines (e.g., tertiary amine compounds) from the filtrate. Acids that can be used for acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, etc. Next, the acid is removed from the filtrate by washing it with water after acid washing. At this stage, the filtrate contains the target product, a polycarbamate-containing mixture, but it is also thought to contain other by-products, such as polythiol compositions. In separation mode X1, a base containing an alkali metal is added to the filtrate that has been washed with water. This converts the polythiol composition in the filtrate into alkali metal salts. The alkali metal salts of the polythiol composition are then removed from the filtrate by washing it with water. In separation mode X1, a polycarbamate-containing mixture is separated from the filtrate from which the alkali metal salt of the polythiol composition has been removed by a known method.

[0212] In separation mode X1, the alkali metal in the alkali metal-containing base is preferably sodium, potassium, or lithium, and more preferably sodium or potassium. Examples of bases containing alkali metals include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Bases containing alkali metals can be added to the filtrate in the form of an alcoholic solution (methanol solution, ethanol solution, etc.) as needed.

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

[0214] <Process X2> Step X2 is a step in which the polycarbamate compound produced in step X1 is decomposed with a decomposition agent represented by formula (3) to produce a polyamine compound. In step X2, the polycarbamate-containing mixture separated in the separation step X2 described above may be mixed with the decomposition agent represented by formula (3) to react the polycarbamate compound in the polycarbamate-containing mixture with the decomposition agent represented by formula (3).

[0215] The reaction in step X2 exhibits superior efficiency in the production of polyamine compounds compared to known reactions that yield polyamine compounds by the reaction of a polycarbamate compound with sodium hydroxide. As a result, the amount of polyamine compound produced can be increased compared to when the above-mentioned known reactions are applied. This effect can be confirmed by analyzing the reaction mixture obtained in step X2 using gas chromatography (GC).

[0216] Step X2 in the method for producing a polyamine compound according to the third embodiment is the same as the second step in the method for producing a polyamine compound according to the third embodiment, except that the object to be decomposed by the decomposition agent represented by formula (3) is a polycarbamate compound produced in step X1 in the third embodiment, rather than a polyurea compound produced in the first step in the second embodiment, and the preferred embodiments are also the same.

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

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

[0219] The preferred embodiments and preferred uses of the polyamine compound as the target product in the third embodiment are the same as the preferred embodiments and preferred uses of the polyamine compound as the target product in the third embodiment.

[0220] <Other processes> The method for producing a polyamine compound according to the third embodiment may include other steps not described above. 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 the polythiol composition according to the first embodiment.

[0221] [Method for producing polyisocyanate compounds (third embodiment)] A method for producing a polyisocyanate compound according to the third embodiment of this disclosure is: A step of producing a polyamine compound by the method for producing a polyamine compound according to the third embodiment described above, A step of reacting at least one of the above polyamine compound and the hydrochloride salt of the above polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound, Includes.

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

[0223] [Method for producing polymerizable composition (second embodiment)] A method for producing a polymerizable composition according to the third embodiment of this disclosure is: A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to the third embodiment described above, A step of obtaining a polymerizable composition containing a polyisocyanate compound and an active hydrogen compound by mixing at least a polyisocyanate compound and an active hydrogen compound, Includes.

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

[0225] [Method for manufacturing resin (third embodiment)] A method for producing a resin according to a third embodiment of this disclosure is: The process of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to the third embodiment described above, A step of obtaining a resin by curing the above polymerizable composition, Includes.

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

[0227] [Method for manufacturing a molded article (second embodiment)] A method for manufacturing a molded article according to a second embodiment of this disclosure is a method for manufacturing a molded article containing a resin, A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to the second embodiment described above, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes.

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

[0229] [Manufacturing method for optical materials (third embodiment), manufacturing method for lenses (third embodiment)] A method for manufacturing an optical material (e.g., a lens) according to a third embodiment of this disclosure is a method for manufacturing an optical material (e.g., a lens) comprising a molded body containing a resin, The process of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to the third embodiment described above, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes.

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

[0231] [Resin (third embodiment), molded body (third embodiment), optical material (e.g., lens) (third embodiment)] The resin according to the third embodiment of this disclosure is a cured product of the polymerizable composition according to the third embodiment of this disclosure described above. The molded article according to the third embodiment of this disclosure is a molded article containing the resin according to the third embodiment described above. The optical material (e.g., lens) according to the third embodiment is an optical material (e.g., lens) that includes the resin according to the third embodiment described above.

[0232] The resin, molded article, and optical material (e.g., lens) according to the third embodiment are the same as those according to the second embodiment, except that the polymerizable composition is produced by the method for producing the polymerizable composition according to the third embodiment instead of the method for producing the polymerizable composition according to the second embodiment, and the preferred embodiments are also the same. [Examples]

[0233] The following are examples of the embodiments of this disclosure, but this disclosure is not limited to the following embodiments. In the following, unless otherwise specified, "parts" refers to mass, and "room temperature" refers to 25°C.

[0234] <Performance testing of resins> As part of the resin performance testing, a performance test was conducted on a flat molded plate with a thickness of 2.5 mm. The performance test items are as follows: • Yellowness (YI) The degree of yellowness was measured using a Konica Minolta CM-5 spectrophotometer. ·L*, a*, and b* Using a Konica Minolta CM-5 spectrophotometer, we measured L*, a*, and b* in the CIE1976 (L*, a*, b*) color system. • Refractive index (ne) and Abbe number (νe) Using a Shimadzu KPR-30 Pulfrich refractometer, the refractive indices (ne, nF', nC') were measured at 20°C at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line). Based on these measurement results, the refractive index (ne) and Abbe number (νe) were determined. ·Heat resistance Using a Shimadzu TMA-60 thermomechanical analyzer, the glass transition temperature (Tg) was measured by the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10℃ / min) and used as an indicator of heat resistance. ·Specific gravity d Measurements were taken at 20°C using the Archimedes method.

[0235] [Reference production example 1] <Manufacturing of molded articles containing thiourethane resin R1> In a flask equipped with a stirring device, The polymerization catalyst is dibutyltin dichloride (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) (1000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition), which is a release agent, m-xylylene diisocyanate (XDI) (52 parts by mass), which is a polyisocyanate compound, A polythiol composition (A) (48 parts by mass) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1), The mixture was added and stirred at room temperature (25°C) for 1 hour to obtain a polymerizable composition, which is a clear, homogeneous solution. Here, the polythiol composition (A) used was the one produced in Reference Production Example 3 described later. Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then degassed thoroughly under reduced pressure of 600 Pa until no more foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds fixed with tape, and then the pair of glass molds was placed in an oven with the oven temperature set to 10°C. Next, the oven temperature was raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded article containing thiourethane resin R1 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds (9.0 mm thick). Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven, and then the molded bodies were removed from the pair of glass molds to obtain the molded bodies.

[0236] [Reference production example 2] <Manufacturing of Thiourethane Resin Scraps R1> A lens was manufactured by machining the molded body obtained in Reference Manufacturing Example 1. The resulting machining waste was collected to obtain thiourethane resin waste R1 (i.e., resin waste 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 the reactor. 99.8 parts by mass of a 32% by mass aqueous sodium hydroxide solution was added dropwise over 40 minutes at 12°C to 35°C, followed by the dropwise addition of 73.8 parts by mass of epichlorohydrin at 29°C to 36°C over 4 hours, with stirring continued for 30 minutes. NMR data confirmed the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol. In a reactor where the formation of 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed, 332.0 parts by mass of 36% by mass hydrochloric acid was charged, followed by 183.8 parts by mass of 99.9% purity thiourea. The reaction was carried out by stirring at 110°C under reflux for 3 hours to carry out the thironium chloride reaction. After the thironium chloride reaction, the reactor was cooled to 45°C, then 355.0 parts by mass of toluene was added, and the reaction was then cooled to 30°C. Subsequently, 244.6 parts by mass of 25% by mass aqueous ammonia solution was charged over 44 minutes at 30°C to 40°C, and the reaction was carried out by stirring at 54°C to 62°C for 3 hours to carry out the hydrolysis reaction. This hydrolysis reaction yielded a toluene solution of polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1). To the obtained toluene solution, 147.8 parts by mass of 36% hydrochloric acid was added, and the mixture was acid-washed at 35°C to 40°C for 1 hour. After the aqueous phase was removed following the acid washing, 147.8 parts by mass of degassed water was added to the remaining organic phase, and the mixture was washed once at 35°C to 40°C for 10 minutes. To the organic phase after washing with degassed water, 147.8 parts by mass of 0.1% aqueous ammonia was added, and the mixture was washed for 10 minutes. To the organic phase after washing with aqueous ammonia, 147.8 parts by mass of degassed water was added, and the mixture was washed twice at 35°C to 40°C for 10 minutes each. From the organic phase after the two washes, toluene and trace amounts of water were removed under reduced pressure while heated, and then the mixture was filtered under reduced pressure using a 3.0 μm PTFE type membrane filter to obtain 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 polythiol component A1 in the polythiol composition (A) obtained in Reference Production Example 3 was 91.6%.

[0239] [Example 1] <Decomposition of thiourethane resin (addamine decomposition by ammonia as a decomposition agent represented by formula (1))> In a 100 mL pressure-resistant reaction vessel manufactured by San-ai Chemical Co., Ltd., Thiourethane resin waste R1 (18.0g) obtained in Reference Manufacturing Example 2, Toluene (31.9g) and 25% aqueous ammonia (10.1g) (equivalent to 0.15 mol of ammonia as a decomposition agent represented by formula (1)), The reaction solution was obtained by adding the substance, and then nitrogen gas was sealed into the reaction vessel. Next, under sealed conditions, the reaction solution in the reaction vessel was heated to 90°C and stirred for 6 hours under pressure conditions at least 0.01 MPa higher than atmospheric pressure to carry out the decomposition reaction of the thiourethane resin. After the decomposition reaction was complete, the reaction solution was cooled to room temperature and then filtered under reduced pressure. By vacuum filtration as described above, 10.1 g of polyurea compound B1 (yield: 91.4%) was obtained as the filtrate, and a toluene solution containing the polythiol composition was obtained as the filtrate. Here, both the polyurea compound B1 and the polythiol composition are decomposition products produced by the amine decomposition of thiourethane resin waste R1. During the vacuum filtration process described above, ammonia, which acts as a decomposition agent represented by formula (1), volatilized and was easily removed from the reaction system.

[0240] To the above filtrate (i.e., a toluene solution containing the polythiol composition), 30.0 g of 35% hydrochloric acid aqueous solution was added and acid washing was performed. After acid washing, the toluene solution was washed twice with 30.0 g of degassed water, and then 12.4 g of 32% sodium hydroxide aqueous solution and 20 g of degassed water were sequentially added to obtain an aqueous solution containing the alkali metal salt of the polythiol as the aqueous phase. An aqueous solution containing the alkali metal salt of the above-mentioned polythiol was washed twice with 20.0 g of toluene. Next, 40.0 g of toluene was added to the washed aqueous solution, followed by neutralization with 30.0 g of 35% hydrochloric acid aqueous solution. The aqueous phase was removed from the neutralized liquid, and 30.0 g of degassed water was added to the remaining organic phase, and two separate liquid-liquid washes were performed 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 6.9 g (yield: 79.9%) of a polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) was obtained by vacuum filtration through a 3.0 μm PTFE type membrane filter.

[0241] [Example 2] <Decomposition of thiourethane resin (addamine decomposition by methylamine as a decomposition agent represented by formula (1))> The procedure was the same as in Example 1, except that the "25% aqueous ammonia (10.1 g) (equivalent to 0.15 mol of ammonia as a decomposition agent represented by formula (1))" in Example 1 was changed to "40% aqueous methylamine (1.6 g) (equivalent to 0.15 mol of methylamine as a decomposition agent represented by formula (1))".

[0242] In this second example, 10.9 g of polyurea compound B2 (yield: 87.6%) was obtained as a filtrate by vacuum filtration after the decomposition reaction, and a toluene solution containing the polythiol composition was obtained as a filtrate. Here, both the polyurea compound B2 and the polythiol composition are decomposition products produced by the amine decomposition of thiourethane resin waste R1. During the vacuum filtration process described above, methylamine, represented by formula (1) as a decomposition agent, volatilized and was easily removed from the reaction system.

[0243] By subjecting a toluene solution containing the polythiol composition to the same treatment as in Example 1, 7.01 g (yield: 81.1%) of a polythiol composition (A) mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) was obtained.

[0244] [Example 3] <Decomposition of thiourethane resin (addamine decomposition by dimethylamine as a decomposition agent represented by formula (1))> The procedure was the same as in Example 1, except that "25% aqueous ammonia (10.1 g) (equivalent to 0.15 mol of ammonia as a decomposition agent represented by formula (1))" was replaced with "13.4 g of 50% aqueous dimethylamine solution (equivalent to 0.15 mol of dimethylamine as a decomposition agent represented by formula (1))".

[0245] In this third example, after the decomposition reaction was completed, an aqueous solution of polyurea compound B3 was obtained by liquid-liquid extraction. Water was then removed from the obtained aqueous solution to obtain 12.8 g of polyurea compound B3 (yield: 95.0%). The above liquid-liquid extraction yielded a toluene solution containing the polythiol composition as the organic phase. Here, both the polyurea compound B2 and the polythiol composition are decomposition products produced by the amine decomposition of thiourethane resin waste R1. During the above liquid-liquid extraction process, dimethylamine, represented by formula (1) as a decomposition agent, was removed from the reaction system.

[0246] [Example 4] <Decomposition of thiourethane resin (alcohol decomposition by methanol as a decomposition agent represented by formula (2))> In a 100 mL pressure-resistant reaction vessel manufactured by San-ai Chemical Co., Ltd., The thiourethane resin R1 (18.0g) obtained in Reference Manufacturing Example 2, 31.8 g (1.0 mol) of methanol as a decomposition agent represented by formula (2), 1,4-diazabicyclo-[2,2,2]-octane (1.1g; 0.010mol) as a tertiary amine (decomposition aid), The reaction solution was obtained by adding the substance, and then nitrogen gas was sealed into the reaction vessel. Next, under sealed conditions, the reaction solution in the reaction vessel was heated to 150°C and stirred for 9 hours under pressure conditions at least 0.01 MPa higher than atmospheric pressure to carry out the decomposition reaction of the thiourethane resin. After the decomposition reaction was complete, insoluble matter was removed from the reaction solution by vacuum filtration. Then, 30.0 g of 2-octanol was added, followed by 30.0 g of 35% hydrochloric acid aqueous solution for acid washing. After acid washing, the reaction solution was washed twice with 30.0 g of degassed water. Finally, 12.4 g of 32% sodium hydroxide aqueous solution and 20 g of degassed water were added sequentially to obtain the organic phase and the aqueous phase. As the organic phase, the alcohol solution in which the polycarbamate compound was dissolved was recovered, and the solvent was removed from the recovered organic phase under heating and reduced pressure to obtain 7.10 g of polycarbamate compound C1 (yield: 56.6%).

[0247] Meanwhile, an aqueous solution containing an alkali metal salt of a polythiol was obtained as the aqueous phase. An aqueous solution containing the alkali metal salt of the above-mentioned polythiol was washed twice with 20.0 g of toluene. Next, 40.0 g of toluene was added to the washed aqueous solution, followed by neutralization with 30.0 g of 35% hydrochloric acid aqueous solution. The aqueous phase was removed from the neutralized liquid, and 30.0 g of degassed water was added to the remaining organic phase, and two separate liquid-liquid washes were performed 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 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) was obtained by vacuum filtration through a 3.0 μm PTFE type membrane filter.

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

[0249] <Measurement of each polythiol composition (A)> The following measurements were performed 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 using the aforementioned method employing 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 polythiol composition (A) was determined by redox titration using a 0.05 M iodine aqueous solution.

[0253] [Table 1]

[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 the main component was obtained by decomposing the thiourethane resin with various decomposing agents.

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

[0256] Furthermore, a molded article containing thiourethane resin was obtained in the same manner as described 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 products> The following evaluations were performed on each of the above molded products. The results are shown in Table 2.

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

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

[0260] (Heat resistance) Using a Shimadzu TMA-60 thermomechanical analyzer, the glass transition temperature (Tg) of the molded body was measured by the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10℃ / min) and used as an indicator of heat resistance.

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

[0262] [Table 2]

[0263] As shown in Table 2, it was confirmed that when the polythiol composition (A) obtained in Examples 1 to 4 was used as a raw material, a molded article (i.e., a resin molded article) with performance suitable for use as an optical material (e.g., eyeglass lenses) could be manufactured, similar to when the polythiol composition (A) obtained in Reference Manufacturing Example 3 was used as a raw material.

[0264] [Example 6X] In Example 6X, the same procedure as in Example 6 was followed, except that the manufacturing of the molded body was modified 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 the production of the molded article. However, in Example 6X, the XDI (52 parts by mass) was replaced with XDI composition X1 (an amount containing 52 parts by mass), which is the aforementioned XDI composition. XDI composition X1 was prepared by adding trace amounts of compound (N1), compound (N2), and compound (N3) to the main component XDI, and then mixing them together.

[0266] In XDI composition X1, gas chromatography measurements were performed using GC condition 1 and GC condition 2 as described above, and the results were as follows: The peak area of ​​compound (N1) is 0.20 ppm or more (specifically 600 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N2) is 0.05 ppm or more (specifically 18 ppm) relative to the peak area of ​​xylylene diisocyanate. The peak area of ​​compound (N3) was 0.10 ppm or more (specifically 100 ppm) relative to the peak area of ​​xylylene diisocyanate.

[0267] [Example 7] <Production of polyamine compounds by reaction of polyurea compound B1 obtained in Example 1 with ethylenediamine> In a 25 mL pressure-resistant reaction vessel manufactured by San-ai Kagaku Co., Ltd., The polyurea compound B1 (2.0 g; 9.0 mmol) obtained in Example 1, Ethylenediamine (3.2 g; 54 mmol) as a decomposition agent represented by formula (3), The reaction solution was obtained by adding the substance, and then nitrogen gas was sealed into the reaction vessel. Next, the reaction solution in the reaction vessel was heated to 145°C under a sealed condition and stirred for 3 hours under a pressure at least 0.01 MPa higher than atmospheric pressure to carry out the reaction. Gas chromatography (GC) confirmed that the above reaction between polyurea compound B1 and ethylenediamine produced xylylenediamine (XDA), a polyamine compound. 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 yield was 74.6% (the two-step yield from thiourethane resin R1 was 68.2%). Furthermore, the decomposing agent (ammonia) represented by formula (1), which was produced by the decomposition of polyurea compound B1, volatilized and was easily removed from the reaction solution after the reaction. The decomposing agent (ethylenediamine) represented by formula (3) could also be easily removed from the reaction solution after the reaction by distillation.

[0268] [Example 8] <Production of polyamine compounds by reaction of polyurea compound B2 obtained in Example 2 with ethylenediamine> The procedure was the same as in Example 7, 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 xylylenediamine (XDA), a polyamine compound. The mass of the reaction solution after the reaction was 4.6 g, the concentration of XDA determined from the GC results was 18.2%, and the yield was 75.6% (the two-step yield from thiourethane resin R1 was 66.1%). Furthermore, the decomposition agent (methylamine) represented by formula (1), which was produced by the decomposition of polyurea compound B2, volatilized and was easily removed from the reaction solution after the reaction. The decomposition 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 polyamine compounds by reaction of polyurea compound B3 obtained in Example 3 with ethylenediamine> The procedure was the same as in Example 7, 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 reaction between polyurea compound B3 and ethylenediamine produced xylylenediamine (XDA), a polyamine compound. 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 yield was 81.9% (the two-step yield from thiourethane resin R1 was 77.8%). Furthermore, the decomposing agent represented by formula (3) (ethylenediamine) and the decomposing agent represented by formula (1) (dimethylamine), which is produced by the decomposition of polyurea compound B3, can be easily removed from the reaction solution after the reaction by distillation.

[0270] [Example 10] <Preparation of polyamine compounds using polycarbamate compound C1 obtained in Example 4> The procedure was the same as in Example 7, except that polyurea compound B1 was replaced with 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 xylylenediamine (XDA), a polyamine compound, was produced by the reaction of polycarbamate C1 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 15.6%, and the yield was 70.4% (the two-step yield from thiourethane resin R1 was 39.8%). Furthermore, the decomposing agent represented by formula (3) (ethylenediamine) and the decomposing agent represented by formula (2) (methanol), which is produced by the decomposition of polycarbamate C1, can be easily removed from the reaction solution after the reaction by distillation.

[0271] [Example 11] <Production of polyamine compounds by reaction of polyurea compound B1 obtained in Example 1 with N,N'-dimethylethylenediamine> The same procedure as in Example 7 was followed, except that 3.2 g (54 mmol) of ethylenediamine, represented by formula (3), was replaced with 4.8 g (54 mmol) of N,N'-dimethylethylenediamine, also represented by formula (3), as the decomposition agent. 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, the concentration of XDA determined from the GC results was 15.8%, and the yield was 85.5% (the two-step yield from thiourethane resin R1 was 78.1%). Furthermore, the decomposing agent (ammonia) represented by formula (1), which was produced by the decomposition of polyurea compound B1, volatilized and was easily removed from the reaction solution after the reaction. The decomposing agent (N,N'-dimethylethylenediamine) represented by formula (3) could also be easily removed from the reaction solution after the reaction by distillation.

[0272] [Example 12] <Production of polyamine compounds by reaction of polyurea compound B1 obtained in Example 1 with 2-aminoethanol> The procedure was the same as in Example 7, except that 3.2 g (54 mmol) of ethylenediamine, represented by formula (3), was replaced with 5.0 g (90 mmol) of 2-aminoethanol, also represented by formula (3), 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 xylylenediamine (XDA), a polyamine compound, 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, the concentration of XDA determined from the GC results was 10.2%, and the yield was 55.7% (the two-step yield from thiourethane resin R1 was 50.9%). Furthermore, the decomposing agent (ammonia) represented by formula (1), which was produced by the decomposition of polyurea compound B1, volatilized and was easily removed from the reaction solution after the reaction. The decomposing agent (2-aminoethanol) represented by formula (3) could also be easily removed from the reaction solution after the reaction by distillation.

[0273] [Example 13] <Production of polyamine compounds by reaction of polyurea compound B1 obtained in Example 1 with ethylene glycol> The same procedure as in Example 12 was followed, except that 3.2 g (54 mmol) of ethylenediamine, used as the decomposition agent represented by formula (3), was replaced with 5.6 g (90 mmol) of ethylene glycol. Gas chromatography (GC) confirmed that the reaction between polyurea compound B1 and ethylene glycol produced xylylenediamine (XDA), a polyamine compound. 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 yield was 40.6% (the two-step yield from thiourethane resin R1 was 37.1%). Furthermore, the decomposing agent (ammonia) represented by formula (1), which was produced by the decomposition of polyurea compound B1, volatilized and was easily removed from the reaction solution after the reaction. 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 explained above, in Examples 7 to 13, polyamine compounds could be produced using polyurea compounds or polycarbamate compounds generated by the decomposition of thiourethane resin as raw materials. Polyisocyanate compounds can be produced by reacting at least one of the manufactured polyamine compounds and the nitrates of these polyamine compounds with carbonyl dichloride. A polymerizable composition can be produced by mixing the obtained polyisocyanate compound with an active hydrogen compound. The resulting polymerizable composition can be used in the production of thiourethane resin or urethane resin.

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

Claims

1. A first step involves decomposing a thiourethane resin with a decomposing agent represented by the following formula (1) to produce a polyurea compound, A second step involves decomposing the aforementioned polyurea compound with a decomposition agent represented by the following formula (3) to produce a polyamine compound, A method for producing polyamine compounds, including 【Transformation 3】 [In formula (1), R １ and R ２ Each of these independently represents either a hydrogen atom or a C1 alkyl group. In formula (3), R １１ and R １２ Each of these independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

2. The decomposition agent represented by formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol. A method for producing a polyamine compound according to claim 1.

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

4. The method for producing a polyamine compound according to claim 1, wherein the second step includes reacting the polyurea compound with a decomposition agent represented by formula (3) under a pressure higher than atmospheric pressure.

5. Step X1 involves 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 aid to produce a polycarbamate compound, Step X2 involves decomposing the polycarbamate compound with a decomposition agent represented by the following formula (3) to produce a polyamine compound, A method for producing polyamine compounds, including 【Chemistry 4】 [In formula (2), R ３ This represents an alkyl group having 1 to 3 carbon atoms. In formula (3), R １１ and R １２ Each of these independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

6. The molecular weight of the tertiary amine compound is 1000 or less. The decomposition agent represented by formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol. A method for producing a polyamine compound according to claim 5.

7. The method for producing a polyamine compound according to claim 5, wherein step X1 includes reacting the thiourethane resin with a decomposing agent represented by formula (2) under a pressure higher than atmospheric pressure.

8. The method for producing a polyamine compound according to claim 5, wherein step X2 includes reacting the polycarbamate compound with a decomposition agent represented by formula (3) under a pressure higher than atmospheric pressure.

9. A method for producing a polyamine compound as a raw material for polyisocyanate compounds for the manufacture of optical materials, according to any one of claims 1 to 8.

10. The method for producing a polyamine compound according to any one of claims 1 to 8, wherein the thiourethane resin is recovered in at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses.

11. A step of producing a polyamine compound by a method for producing a polyamine compound according to any one of claims 1 to 8, A step of reacting at least one of the polyamine compound and the hydrochloride salt of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound, A method for producing polyisocyanate compounds containing [the specified substance].

12. A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound described in claim 11, A step of obtaining a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound by mixing at least the polyisocyanate compound and the active hydrogen compound, A method for producing a polymerizable composition containing the above.

13. A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 12, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins.

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