Method for producing polythiol compounds, and method for producing polyamine compounds and their applications.

Abstract

This invention provides a method for producing polythiol compounds, which can be manufactured using thiourethane resin as a starting material. [Solution] A method for producing a polythiol compound, comprising the step of reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polyurea compound and a polythiol compound.

Description

[Technical Field]

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

[0002] Plastic lenses, which contain resin, are lighter, less prone to breakage, and can be dyed compared to inorganic lenses, and have therefore become rapidly popular in recent years for applications such as eyeglass lenses and camera lenses. For example, various studies have been conducted on lenses containing thiourethane resin (see, for example, Patent Documents 1 to 3). Furthermore, Patent Document 4 discloses a method for producing a polythiol composition using thiourethane resin as a starting material. Patent Document 4 also discloses that the produced polythiol composition can be used as a raw material for thiourethane resin. Furthermore, Patent Document 5 discloses a method for producing polyamine compounds using thiourethane resin as a starting material. Patent Document 4 also discloses that the produced polyamine compounds can be used in the production of polyisocyanate compounds, which are raw materials for thiourethane resin. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 63-46213 [Patent Document 2] Japanese Patent Application Publication No. 2-270859 [Patent Document 3] Japanese Patent Application Publication 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]

[0004] Thiourethane resins are typically manufactured using polythiol compounds and polyisocyanate compounds as raw materials. Lenses containing thiourethane resin are manufactured by machining a molded body containing thiourethane resin. This process generates a large amount of machining waste containing thiourethane resin. Traditionally, this large amount of machining waste has simply been discarded and not effectively utilized. Furthermore, defective molded or processed products are generated during the manufacturing process of molded articles containing thiourethane resin. Conventionally, these defective molded and processed products were simply discarded and were not effectively utilized. However, from the perspective of effective use of materials (i.e., recycling), a technology for producing polythiol compounds using thiourethane resin contained in cutting waste as a starting material is also desirable. Similarly, a technology is also desired to produce polyamine compounds that serve as raw materials for polyisocyanate compounds, using thiourethane resin contained in cutting waste as a starting material. The produced polyamine compounds can be used as raw materials for new polyisocyanate compounds, and these new polyisocyanate compounds can be used as raw materials for new thiourethane resins. Furthermore, it is desirable to have a technology that produces polythiol compounds and polyamine compounds using thiourethane resin as a starting material, not limited to using thiourethane resin contained in cutting waste as the starting material.

[0005] The method for producing polyamine compounds described in the aforementioned Patent Document 5 (International Publication No. 2021 / 157702) was made in consideration of the above-mentioned requirements. In some cases, there is a need for a method of producing polyamine compounds that uses an inorganic base and a thiourethane resin as a starting material.

[0006] An object of one embodiment of this disclosure is to provide a method for producing a polythiol compound using a thiourethane resin as a starting material, and a method for producing a polyamine compound using an inorganic base and a thiourethane resin as a starting material, as well as its applications. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments. <1> A method for producing polyamine compounds, comprising the step of reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polythiol compound and a polyurea compound. <2> The polythiol compound comprises at least one selected from the group consisting of 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). <1> A method for producing the polythiol compound described above. <3> The amine compound A is at least one selected from the group consisting of benzylamine, ethylenediamine, monoethanolamine, N-methylethanolamine, n-butylamine, m-xylylenediamine, di-n-butylamine, dipropylamine, morpholine, piperidine, N-(2-aminoethyl)piperazine, 1-methylpiperazine, diethylenetriamine, and N,N'-dimethylethylenediamine. <1> or <2> A method for producing the polythiol compound described above. <4> This is a method for producing polythiol compounds for optical material manufacturing. <1> ~ <3> A method for producing a polythiol compound as described in any one of the following. <5> A method for producing a polyamine compound, comprising the step of reacting a polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compound B to produce a polyamine compound. <6> A step of reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polyurea compound and a polythiol compound, A method for producing a polyamine compound, comprising the step of reacting the polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compound B to produce a polyamine compound. <7> In the step of producing the polyamine compound, the polyurea compound is reacted with at least one of the inorganic base and the amine compound B under a temperature of 100°C to 180°C. <5> or <6> A method for producing the polyamine compound described above. <8> The inorganic base comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and calcium hydroxide. <5> ~ <7> A method for producing a polyamine compound as described in any one of the following. <9> The polyurea compound is a compound represented by the following formula (1): <5> ~ <8> A method for producing a polyamine compound as described in any one of the following.

[0008] [ka]

[0009] In formula (1), R 1 , R 2 , R 11 , and R 12 Each of these independently represents a monovalent organic group containing a hydrocarbon group, L 1 This represents a divalent hydrocarbon group.

[0010] <10> The method for producing a polyamine compound according to any one of <5> to <9>, wherein the polyamine compound 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.

[0011] <11> The method for producing a polyamine compound according to any one of <5> to <10>, which is a method for producing a polyamine compound as a raw material for a polyisocyanate compound for producing an optical material. <12> The method for producing a polyamine compound according to any one of <6> to <11>, wherein 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. <13> A step of producing a polyamine compound by the method for producing a polyamine compound according to any one of <5> to <12>, 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 a polyisocyanate compound comprising the above. <14> A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to <13>, 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 comprising the above. <15> A step of producing a polymerizable composition by the method for producing a polymerizable composition according to <14>, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins. <16> A method for manufacturing a molded article containing resin, <14> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing a molded article containing [the specified ingredient]. <17> A method for producing an optical material including a molded body containing a resin, <14> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing optical materials containing [specific material]. <18> A method for manufacturing a lens including a molded body containing resin, <14> A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition described above, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing lenses that include [specific components / materials]. [Effects of the Invention]

[0012] According to one embodiment of the present disclosure, a method for producing a polythiol compound using a thiourethane resin as a starting material is provided, as well as a method for producing a polyamine compound using an inorganic base and a thiourethane resin as a starting material, and its applications. [Modes for carrying out the invention]

[0013] 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.

[0014] [Method for producing polyamine compounds] The method for producing the polythiol compound according to this disclosure includes a step (hereinafter also referred to as the first step) of reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polythiol compound and a polyurea compound.

[0015] According to the method for producing polythiol compounds of this disclosure, a polythiol compound as the target product and a polyurea compound as a by-product can be produced using a thiourethane resin as a starting material. In detail, in the first step, a reaction called additive amine decomposition (hereinafter also referred to as additive amine decomposition) occurs in which the thiourethane resin is decomposed by amine compound A. Through this additive amine decomposition, the thiourethane resin is broken down into a polythiol compound and a polyurea compound, thereby obtaining the polythiol compound and the polyurea compound.

[0016] The first step of the method for producing the polythiol compound of this disclosure will be described below.

[0017] <1st process> The first step involves reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polythiol compound and a polyurea compound.

[0018] (Thiourethane resin) As the thiourethane resin used in the first step, known thiourethane resins can be used, for example, thiourethane resins described in publicly available documents such as Japanese Patent Publication No. 63-46213, Japanese Patent Publication No. 2-270859, Japanese Patent Publication No. 7-252207, Japanese Patent Publication No. 60-199016, and International Publication No. 2008 / 047626 can be used.

[0019] The thiourethane resin used in the first step is preferably recovered from at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. This embodiment enables the recycling of the thiourethane resin, which is a material for eyeglass lenses. 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 amine compound A to obtain a polythiol compound and a polyurea compound, which are decomposition products of the thiourethane resin.

[0020] The above starting materials preferably include cutting shavings containing thiourethane resin. In the first step of this embodiment, the thiourethane resin and the amine compound A are reacted by bringing cutting waste containing the thiourethane resin into contact with the amine compound A. In this embodiment, the reactivity between amine compound A and the thiourethane resin in the starting material is superior, making it possible to produce polythiol compounds and polyurea compounds more effectively.

[0021] Cutting chips can take the form of powder, chips (i.e., tipped), lumps, etc. In this disclosure, cutting chips may be referred to as resin chips, and powdery cutting chips may be referred to as resin powder.

[0022] 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.

[0023] -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 A"). It is even more preferable that the product contains isocyanate component A as its main component.

[0024] Here, "containing isocyanate component A as the main component" means that the total content of isocyanate component A is 50% or more of the total amount of isocyanate compounds used as raw materials for the thiourethane resin. The total content of isocyanate component A relative to the total amount of the above isocyanate compound is preferably 60% or more, more preferably 70% by mass or more, and even more preferably 80% or more.

[0025] 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.

[0026] 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 to the total area of ​​all peaks of the composition, determined by chromatography (specifically, gas chromatography for component X, which is an isocyanate compound, and high-performance liquid chromatography for component X, which is a polythiol compound).

[0027] Isocyanate compounds as raw materials for thiourethane resins are considered to have the following properties in mind when used as raw materials for thiourethane resins: [for example, optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.] It is even more preferable to include at least one selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and bis(isocyanatocyclohexyl)methane (hereinafter also referred to as "isocyanate component A1"). It is even more preferable that the product contains isocyanate component A1 as its main component.

[0028] -Polythiol composition as a raw material for thiourethane resin- The polythiol composition used as a raw material for thiourethane resin contains at least one polythiol compound. The polythiol compound used as a raw material for thiourethane resin can be any compound containing two or more thiol groups (i.e., mercapto groups), and is not particularly limited in any other respect. Examples of polythiol compounds included in the polythiol composition as a raw material for thiourethane resin include known polythiol compounds described in the aforementioned prior art documents.

[0029] 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.).

[0030] 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.

[0031] 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; An embodiment comprising at least one selected from the group consisting of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter also referred to as "polythiol component A2") as the main component; 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.).

[0032] -Other ingredients- The thiourethane resin may contain other components besides a polymer of at least one isocyanate compound and a polythiol compound. 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.

[0033] - Resin waste containing thiourethane resin - In the first step, it is preferable to react the thiourethane resin in the resin waste with the amine compound A by bringing the resin waste containing thiourethane resin (hereinafter also referred to as "thiourethane resin waste") into contact with the amine compound A. This makes it possible to further improve the reaction efficiency between the thiourethane resin and the amine compound A. There are no particular restrictions on the method of contacting the thiourethane resin scrap with amine compound A. For example, one method is to place the thiourethane resin scrap and amine compound A (and reaction solvent as needed) in a reaction vessel and stir. In this example, there are no particular restrictions on the order in which the thiourethane resin scrap and amine compound A (and reaction solvent as needed) are placed in the reaction vessel.

[0034] There are no particular limitations on the thiourethane resin waste, but preferably it is cutting waste (including the concept of abrasive powder; the same applies hereinafter) from a molded article 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. Furthermore, the thiourethane resin scrap may be in the form of lumps obtained by crushing and / or pulverizing a molded body containing thiourethane resin.

[0035] (Resin mixture containing thiourethane resin) The first step may be a step of producing a polyurea compound by contacting a resin mixture containing a thiourethane resin with amine compound A, thereby reacting the thiourethane resin in the resin mixture with amine compound A.

[0036] 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.

[0037] 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.

[0038] 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:

[0039] 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.

[0040] 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.

[0041] (Amine compound A) The amine compound A used in the first step contains at least one of a primary amino group (i.e., a -NH2 group) and a secondary amino group (i.e., a -NH- group). The amine compound A may further contain a tertiary amino group (i.e., a -NR2 group (where R is an organic group)). The amine compound A used in the first step may be one type or two or more types. The amine compound A used in the first step may be a chain-like amine compound or a cyclic amine compound (for example, morpholine, piperidine, piperazine, etc.).

[0042] The molecular weight of amine compound A 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 amine compound A is, for example, 45 or more, preferably 59 or more, and more preferably 60 or more.

[0043] Amine compound A may be an amine compound containing monoalkylamino groups, wherein the total number of monoalkylamino groups is 1 to 6 (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1).

[0044] As an example of amine compound A, Examples include amine compounds containing monoalkylamino groups, with a total number of monoalkylamino groups of 1 and a molecular weight of 300 or less.

[0045] Specifically, as amine compound A, for example, Dialkylamines with 2 to 10 carbon atoms (e.g., dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, etc.), Alkyltriamines with 2 to 10 carbon atoms (e.g., bis(2-aminoethyl)amine, etc.), Bis(hydroxyalkyl)amines with 2 to 10 carbon atoms (e.g., bis(hydroxyethyl)amine, etc.) Cyclic amines with 2 to 10 carbon atoms (e.g., morpholine, piperidine, piperazine), Alkyl (hydroxyalkyl)amines with 2 to 10 carbon atoms (e.g., N-methylethanolamine (NMEA), N-ethylethanolamine, Nn-propylethanolamine, N-isopropylethanolamine, etc.), These are some examples.

[0046] Furthermore, amine compound A may be at least one selected from the group consisting of, for example, benzylamine, ethylenediamine, monoethanolamine, N-methylethanolamine, n-butylamine, m-xylylenediamine, di-n-butylamine, dipropylamine, morpholine, piperidine, N-(2-aminoethyl)piperazine, 1-methylpiperazine, diethylenetriamine, and N,N'-dimethylethylenediamine.

[0047] Amine compound A may contain a hydroxyl group. Examples of amine compound A containing a hydroxyl group include alkyl (hydroxyalkyl)amines having 2 to 10 carbon atoms (for example, N-methylethanolamine).

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

[0049] In the first step, the number of millimoles of amine compound A added per 1 g of thiourethane resin is preferably 1.0 mmol / g to 30 mmol / g, more preferably 2.0 mmol / g to 20 mmol / g, and even more preferably 3.0 mmol / g to 10.0 mmol / g.

[0050] In the first step, the equivalent amount of amine compound A added to the thiourethane resin (equivalent amount [amine compound A / thiourethane resin]) is preferably 1.0 to 2.0, more preferably greater than 1.0 and 1.8 or less, and even more preferably greater than 1.0 and 1.6 or less. When the equivalent amount of the charge [amine compound A / thiourethane resin] is 1.0 or more, the formation of the polythiol compound and polyurea compound in the first step is further promoted. When the equivalent charge [amine compound A / thiourethane resin] is 2.0 or less, the residual amount of amine compound A in the reaction mixture can be further suppressed. Here, the equivalent amount of amine compound A relative to the thiourethane resin (equivalent amount [amine compound A / thiourethane resin]) refers to the molar ratio of amine compound A to the thiourethane bonds in the charged thiourethane resin.

[0051] (First reaction solvent) In the first step, it is preferable to react the thiourethane resin with amine compound A in the presence of a reaction solvent (hereinafter also referred to as the first reaction solvent). The first reaction solvent is preferably a hydrocarbon compound having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), an ether compound having 4 to 12 carbon atoms, a ketone compound having 3 to 12 carbon atoms, an ester compound having 4 to 12 carbon atoms, an alcohol compound having 2 to 12 carbon atoms, or a nitrile compound having 2 to 12 carbon atoms. 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 ether compound is preferably diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, or 1,4-dioxane, and is particularly preferably dimethoxyethane. The ketone compound is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, or 2-octanone, and particularly preferably methyl isobutyl ketone. The ester compound is preferably ethyl acetate, butyl acetate, or pentyl acetate, and particularly preferably pentyl acetate. The above alcohol compound is preferably ethanol, 1-propanol, isopropanol, 1-butanol, 1-octanol, 2-octanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, or methyl cellosolve, and is particularly preferably benzyl alcohol or ethylene glycol. The nitrile compound is preferably acetonitrile or propionitrile, and particularly preferably acetonitrile. The compound used as the first reaction solvent may be one type or two or more types.

[0052] (First reaction temperature) The reaction temperature between the thiourethane resin and amine compound A in the first step (hereinafter also referred to as the first reaction temperature) is adjusted as appropriate. In the first step, it is preferable to react the thiourethane resin and amine compound A under temperature conditions of 50°C to 150°C (more preferably 60°C to 145°C, and even more preferably 70°C to 140°C) (i.e., the first reaction temperature).

[0053] (First reaction time) The reaction time between the thiourethane resin and amine compound A in the first step can be adjusted as appropriate, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and even more preferably 1 to 10 hours.

[0054] (Polythiol compounds) The polythiol compound produced in the first step (i.e., the polythiol compound obtained by the method for producing the polythiol compound of this disclosure) is one of the amine decomposition products of the thiourethane resin produced by the reaction (i.e., amine decomposition) of the thiourethane resin with amine compound A, similar to the polyurea compound produced in the first step described later (the target product of the method for producing the polythiol compound of this disclosure). In the first step, the aforementioned polythiol composition (i.e., a composition containing at least one polythiol compound) may be produced. Specific examples of polythiol compounds produced in the first step include compounds similar to those mentioned above as specific examples of polythiol compounds used as raw materials for thiourethane resins.

[0055] The polythiol compound produced in the first step includes, for example, at least one selected from the group consisting of 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).

[0056] The specific applications of the polythiol compound produced in the first step are preferably for use in the manufacture of optical materials (e.g., lenses). In other words, a specific example of the method for producing a polythiol compound according to this disclosure is a method for producing a polythiol compound for the manufacture of optical materials. 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, polythiol compound) can be effectively realized.

[0057] (Polyurea compounds) The polyurea compound produced in the first step is, like the polythiol compound (the target product) produced in the first step as described above, one of the amine-decomposition products of the thiourethane resin produced by the reaction (i.e., amine decomposition) of the thiourethane resin with amine compound A (a by-product of the target polythiol compound). Polyurea compounds are compounds that contain two or more urea bonds. A polyurea compound is, for example, a polyurea compound having a structure in which a urea bond is formed by the reaction of all isocyanate groups in a polyisocyanate compound, which is one of the raw materials for thiourethane resins, with a primary amino group or a secondary amino group in amine compound A. 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 (XDA)) corresponding to a polyisocyanate compound (e.g., m-xylylenediamine (XDI)), which is one of the raw materials, and amine compound A (e.g., monoethanolamine (MEA)). 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 in this disclosure.

[0058] The polyurea compound is preferably a compound represented by the following formula (1).

[0059] [ka]

[0060] In formula (1), R 1 , R 2 , R 11 , and R 12 each independently represents a monovalent organic group containing a hydrocarbon group, and L 1 represents a divalent hydrocarbon group.

[0061] L 1 is preferably the residue obtained by removing two isocyanato groups from a diisocyanate compound as a polyisocyanate compound. R 1 and R 2 are preferably two residues obtained by removing a secondary amino group (i.e., -NH- group) from a secondary amine compound. R 11 and R 12 are preferably two residues obtained by removing a secondary amino group (i.e., -NH- group) from a secondary amine compound.

[0062] (First reaction step and first separation step) The first step is a first reaction step of reacting a thiourethane resin with an amine compound A to obtain a first reaction mixture containing a polythiol compound and a polyurea-containing mixture containing a polyurea compound, a first separation step of separating a polythiol compound or a polyurea-containing mixture from the above reaction mixture, and may include. Here, the polyurea-containing mixture means a mixture of two or more urea compounds containing a polyurea compound. In the first separation step, when the polythiol compound is separated from the reaction mixture, the separated polythiol compound can be used as a raw material for the production of a new thiourethane resin. Thereby, effective utilization (i.e., recycling) of materials is realized. In the first separation step, when the polyurea-containing mixture is separated from the reaction mixture, the separated polyurea-containing mixture can be used as a starting material in the method for producing a polyamine compound described below. In the first separation step, the polythiol compound and the polyurea-containing mixture may be separated from the reaction mixture, respectively.

[0063] The preferred mode of the reaction in the first reaction step is as described above.

[0064] 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.

[0065] 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 contains a polythiol compound produced by the additive amine decomposition reaction. Preferred embodiments of the polythiol compound are as described above. The polythiol compounds produced by the amine decomposition reaction can be used as raw materials for the manufacture of new thiourethane resins. This enables the effective use (i.e., recycling) of materials.

[0066] 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 may contain polythiol compounds produced by the additive amine decomposition reaction. Preferred embodiments of the polythiol compounds as by-products are as described above. The polythiol compounds produced by the amine decomposition reaction can be used as raw materials for the manufacture of new thiourethane resins. This enables the effective use (i.e., recycling) of materials.

[0067] 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 salts of the polythiol compounds are 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.

[0068] <Classification process> The method for producing a polythiol compound according to the present disclosure may further include a classification step prior to the first step, in which cutting waste containing a thiourethane resin is classified to obtain cutting waste with a smaller average particle diameter (e.g., the average number of circle equivalent diameters) than the aforementioned cutting waste (i.e., cutting waste with a reduced average particle diameter, e.g., cutting waste). In this case, the first step involves contacting the classified cutting waste with amine compound A to react the thiourethane resin in the classified cutting waste with amine compound A. If the method for producing the polyamine compound according to this disclosure includes a classification step, in the first step, cutting chips with a small particle size (i.e., average particle diameter) (e.g., cutting chips) are brought into contact with the amine compound A, thereby further improving the reaction efficiency between the thiourethane resin and the amine compound A.

[0069] 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.

[0070] <Sieving process> The method for producing the polyamine compound of this disclosure may further include a sieving step before the first step, in which cutting chips containing thiourethane resin are sieved to obtain a powder containing thiourethane resin that has passed through the sieve (i.e., cutting chips that have passed through the sieve). In this case, in the first step, the thiourethane resin in the powder is brought into contact with amine compound A to react with amine compound A. If the method for producing a polyamine compound according to this disclosure includes a sieving step, the first step involves contacting a powder consisting of small particles with amine compound A, thereby further promoting the reaction between the thiourethane resin and amine compound A (i.e., the reaction for the formation of a polyurea compound). As a result, the amount of the final target product, the polyamine compound, can be increased.

[0071] 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.

[0072] <Washing Process> The method for producing a polyamine compound according to this disclosure may further include a cleaning step before the first step, in which thiourethane resin scrap (i.e., cutting scrap containing thiourethane resin) is cleaned with a hydrocarbon compound having 5 to 12 carbon atoms as a cleaning solvent. In this case, the first step involves reacting the thiourethane resin in the thiourethane resin scrap cleaned in the cleaning step with amine compound A. This further promotes the reaction between the thiourethane resin and amine compound A (i.e., the reaction to produce a polyurea compound). As a result, the amount of the final target polyamine compound produced can be increased. In particular, in the method for producing polyamine compounds according to this disclosure, when cutting scraps containing thiourethane resin are used as the starting material, this cleaning step can effectively remove oil originating from the cutting machine that is attached to the cutting scraps, thus achieving the above effect more effectively.

[0073] 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 the washing solvent is the same as the preferred embodiment of the hydrocarbon compound as the first reaction solvent described above. However, the first reaction solvent and the washing solvent may be the same or different.

[0074] There are no particular restrictions on the cleaning method in the cleaning process; known methods can be applied, such as adding the above-mentioned cleaning solvent to cutting debris containing thiourethane resin and mixing it.

[0075] If the method for producing the polyamine compound of this disclosure includes the sieving step and the washing step described above, it is preferable to perform the sieving step and the washing step in that order. In this case, there is no need to wash the cutting chips that did not pass through the sieve, so the amount of washing solvent used can be further reduced.

[0076] [Method for producing polyamine compounds] The method for producing a polyamine compound according to this disclosure includes a step (hereinafter also referred to as the second step) of reacting a polyurea compound with an inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compounds B, to produce a polyamine compound.

[0077] According to the method for producing polyamine compounds of this disclosure, polyamine compounds can be produced using at least one of an inorganic base and amine compound B. In detail, in the second step, a reaction occurs in which the polyurea compound is decomposed by at least one of the inorganic base and amine compound B, and this decomposition by the inorganic base produces the target polyamine compound.

[0078] The following describes each step in the method for producing the polyamine compound of this disclosure.

[0079] (Polyurea compounds) A preferred embodiment of the polyurea compound that is the starting material for the second step of the method for producing the polyamine compound of this disclosure is the same as the preferred embodiment of the polyurea compound produced in the first step of the method for producing the polythiol compound of this disclosure described above. As the polyurea compound, a pre-prepared polyurea compound may be used, or one produced by the first step of the method for producing the polythiol compound described herein may be used. In other words, the term "second" in the second step of the method for producing the polyamine compound of this disclosure is a term used for convenience and does not mean the second step.

[0080] When using a polyurea compound produced by the first step of the method for producing the polythiol compound of this disclosure described above, the method for producing the polyamine compound of this disclosure is as follows: A first step involves reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polyurea compound and a polythiol compound. The process includes a second step of reacting the polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compound B, to produce a polyamine compound. The method may also be a method for producing polyamine compounds.

[0081] The second step of the method for producing the polyamine compound of this disclosure will be described below.

[0082] <Second process> The second step involves reacting a polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides (hereinafter also referred to as "specific inorganic base") and at least one of amine compounds B (i.e., either the specific inorganic base and amine compound B, or both; hereinafter also referred to as "specific inorganic base and / or amine compound B") to produce the target polyamine compound. In the second step, the polyurea-containing mixture separated in the first separation step of the method for producing the polythiol compound of the present disclosure may be mixed with a specific inorganic base to react the polyurea compound in the polyurea-containing mixture with at least one of the specific inorganic base and amine compound B.

[0083] (Specific inorganic bases) The specific inorganic base that can be used in the second step is at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. The alkali metal element in the alkali metal hydroxide is preferably lithium, sodium, or potassium, more preferably sodium or potassium, and even more preferably sodium. In alkaline earth metal hydroxides, the alkaline earth metal element is preferably calcium or magnesium, and more preferably calcium.

[0084] The specific inorganic base preferably includes at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0085] (Amine compound B) Any known amine compound can be used as amine compound B in the second step without any particular limitations. Amine compound B may be one type or two or more types.

[0086] One preferred embodiment of amine compound B is an amine compound having a molecular weight of 2000 or less, comprising at least one of an amino group and a monoalkylamino group, with a total number of amino groups and monoalkylamino groups ranging from 1 to 50.

[0087] Examples of amine compound B include benzylamine, monoethanolamine, N-methylethanolamine, hexylamine, heptylamine, octylamine, aminopropanol, propylenediamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylethanolamine, polyethyleneimine, and others.

[0088] Amine compound B preferably contains an amino group. From the viewpoint of being able to raise the second reaction temperature, amine compound B is preferably an amine compound with a boiling point of 100°C or higher. Amine compound B may be an amine compound with a boiling point of 230°C or lower, from the viewpoint of ease of removal by distillation after the reaction. From the viewpoint of volumetric efficiency, amine compound B is preferably an amine compound in which the molecular weight per amino group in the compound is 200 or less (more preferably 150 or less). Examples of such amine compounds B include benzylamine, monoethanolamine, hexylamine, heptylamine, octylamine, aminopropanol, propylenediamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylethanolamine, polyethyleneimine, and others. As amine compound B, 1,3-propanediamine, diethylenetriamine, aminoethylethanolamine, benzylamine, or monoethanolamine are preferred, and aminoethylethanolamine, diethylenetriamine, or monoethanolamine are particularly preferred.

[0089] In the second step, the charge equivalent of the specific inorganic base and / or amine compound B relative to the polyurea compound (charge equivalent [specific inorganic base and amine compound B / 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 amount of charge [specific inorganic base and amine compound B / polyurea compound] is 0.1 or higher, the formation of polyamine compounds is further promoted. When the equivalent amount of charge [specific inorganic base and amine compound B / polyurea compound] is 50 or less, it is advantageous in terms of reducing the amount of specific inorganic base and / or amine compound B used. Here, the equivalent amount of a specific inorganic base added to a polyurea compound (equivalent amount [specific inorganic base and amine compound B / polyurea compound]) refers to the ratio of the total number of specific inorganic bases added to the total number of urea bonds in the polyurea compound added. In the second step, when reacting the polyurea compound in the polyurea-containing mixture with the specific inorganic base and / or amine compound B by mixing the polyurea-containing mixture separated in the first separation step in the method for producing the polythiol compound of the present disclosure described above with a specific inorganic base and / or amine compound B, the amount of charge [specific inorganic base and amine compound B / polyurea compound] may be determined by considering the entire amount of the polyurea-containing mixture as the polyurea compound.

[0090] In the second step, the polyurea compound can be reacted with a specific inorganic base and / or amine compound B in the absence of a reaction solvent. For example, the polyurea compound can be reacted with a specific inorganic base and / or amine compound B in the absence of a reaction solvent by directly mixing a polyurea-containing mixture containing the polyurea compound with the specific inorganic base and / or amine compound B in the absence of a reaction solvent. However, in the second step, the polyurea compound may be reacted with a specific inorganic base and / or amine compound B in the presence of a reaction solvent.

[0091] (Second reaction temperature) The reaction temperature between the polyurea compound and the specific inorganic base and / or amine compound B in the second step (hereinafter also referred to as the second reaction temperature) is adjusted as appropriate. In the second step, it is preferable to react the polyurea compound with a specific inorganic base and / or amine compound B under temperature conditions of 80°C to 180°C (more preferably 90°C to 180°C, even more preferably 100°C to 180°C, even more preferably 110°C to 170°C, and even more preferably 120°C to 160°C) (i.e., the second reaction temperature). Furthermore, the reaction in the second step may be carried out under pressurized conditions. Carrying the reaction under pressurized conditions may shorten the reaction time.

[0092] (Second reaction time) The reaction time between the polyurea compound and the specific inorganic base and / or amine compound B in the second step can be adjusted as appropriate, but is preferably 0.1 hours to 40 hours, more preferably 0.5 hours to 20 hours, and even more preferably 1 hour to 10 hours.

[0093] In the method for producing polyamine compounds according to this disclosure, the reaction in the second step may be carried out in the presence of an alcohol compound having a boiling point of 100°C to 250°C. This allows the reaction to proceed efficiently.

[0094] Examples of alcohol compounds with a boiling point of 100°C to 250°C include aliphatic alcohols with 4 to 10 carbon atoms having one hydroxyl group, alicyclic alcohols with 5 to 10 carbon atoms having one hydroxyl group, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and butanediol, with ethylene glycol being preferred.

[0095] (Second reaction step and second separation step) The second step is, A reaction step of reacting a polyurea compound with a specific inorganic base and / or amine compound B to obtain a reaction mixture containing a polyamine compound, A separation step for separating the polyamine compound from the above reaction mixture, It 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.

[0096] The preferred mode of the reaction in the second reaction step is as described above.

[0097] 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.

[0098] (Polyamine compounds as the target product) In the method for producing polyamine compounds according to this disclosure, the target polyamine compound is produced by the reaction of a polyurea compound with a specific inorganic base.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] Specific applications of the manufactured 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 polyamine compounds according to this disclosure is a method for producing polyamine compounds as raw materials for polyisocyanate compounds used in the manufacture of optical materials. 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) can be effectively realized.

[0103] [Method for producing polyisocyanate compounds] The method for producing the polyisocyanate compound described herein is: A step of producing a polyamine compound by the method for producing a polyamine compound described above in this disclosure, 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.

[0104] According to the method for producing polyisocyanate compounds, a thiourethane resin is used as a starting material, and a polyisocyanate compound is obtained as the target product, thus enabling the effective utilization of materials (thiourethane resin and its raw material, the polyisocyanate compound).

[0105] There are no particular limitations on the uses of the polyisocyanate compounds produced by the method for producing polyisocyanate compounds of this disclosure, and they can be applied to a variety of uses. Polyisocyanate compounds can be used, for example, in the production of thiourethane resins or urethane resins.

[0106] 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 polyisocyanate compounds according to this disclosure is a method for producing polyisocyanate compounds for the manufacture of optical materials. 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.

[0107] 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 convert the amino group in the above-mentioned polyamine compound into 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.

[0108] [Method for producing polymerizable compositions] The method for producing the polymerizable composition disclosed herein is: A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound described above in this disclosure, 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 of this disclosure may include other steps as necessary.

[0109] In the method for producing the polymerizable composition disclosed herein, In the process of producing polyisocyanate compounds, thiourethane resin (for example, thiourethane resin in grinding waste from molded thiourethane resin products) 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 the polymerizable composition of the present disclosure enables the effective utilization (i.e., recycling) of materials (i.e., thiourethane resin and its raw material, polyisocyanate compound).

[0110] <Process for manufacturing polyisocyanate compounds> For the process of producing the polyisocyanate compound, the method for producing the polyisocyanate compound described above can be appropriately referenced.

[0111] <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.

[0112] 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".

[0113] 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.

[0114] 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.

[0115] 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. 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.

[0116] Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] [Method of manufacturing resin] The method for manufacturing the resin disclosed herein is: A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a resin by curing the above polymerizable composition, Includes. The resin manufacturing method of this disclosure may include other steps as necessary. The resin manufacturing method of this disclosure provides the same effects as the method for manufacturing the polymerizable composition of this disclosure described above.

[0121] The resin produced by the resin production method of this disclosure is a urethane resin or a thiourethane resin, but in order to distinguish it from thiourethane resin, which is one of the starting materials for polyamine compounds, it is simply referred to as "resin" in this disclosure.

[0122] 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.

[0123] 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.

[0124] [Method for manufacturing molded products] The method for manufacturing a molded article according to this disclosure is a method for manufacturing a molded article containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing a molded article according to this disclosure may include other steps as necessary. The method for producing a molded article according to this disclosure provides the same effects as the method for producing a polymerizable composition according to this disclosure described above.

[0125] 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".

[0126] 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.

[0127] The glass transition temperature Tg of the resin (or molded article) in this disclosure 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.

[0128] The refractive index (ne) of the resin (or molded article) in this disclosure 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.

[0129] The Abbe number of the resin (or molded article) in this disclosure is preferably 28 or higher, and more preferably 30 or higher, from the viewpoint of application to optical materials. There is no particular upper limit to the Abbe number mentioned above, but the upper limit is, for example, 50, and preferably 45.

[0130] In this disclosure, the specific gravity d of the resin (or molded article) 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.

[0131] [Manufacturing methods for optical materials, manufacturing methods for lenses] The method for manufacturing an optical material (e.g., a lens) according to this disclosure is a method for manufacturing an optical material (e.g., a lens) comprising a molded body containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described above in this disclosure, A step of obtaining a molded article containing resin by curing the above polymerizable composition, Includes. The method for manufacturing the optical material (e.g., a lens; the same applies hereinafter) described herein may include other steps as necessary. The method for producing optical materials according to this disclosure provides the same effects as the method for producing polymerizable compositions according to this disclosure described above.

[0132] The method for manufacturing optical materials of this disclosure is an application of the method for manufacturing molded articles of this disclosure. For example, in the method for manufacturing a molded article according to the present disclosure, by appropriately selecting the shape of the molding mold used in the aforementioned casting polymerization, a molded article applicable to optical materials (e.g., lenses) can be obtained.

[0133] Examples of optical materials include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses), light-emitting diodes (LEDs), and the like.

[0134] The method for manufacturing an optical material (e.g., a lens) according to this disclosure may include a step of forming a coating layer on one or both sides of a molded body containing a resin.

[0135] 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.

[0136] 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.

[0137] For eyeglass lenses and coating layers, you can refer to publicly available documents such as International Publication No. 2017 / 047745 as appropriate. [Examples]

[0138] The present disclosure will be described in detail below with reference to examples. However, the present disclosure is not limited in any way to the descriptions of these examples. Unless otherwise specified, "parts" refers to mass. In the following, "room temperature" refers to 25°C unless otherwise specified.

[0139] Hereinafter, the purity (%) of the polythiol compound (polythiol component A1 or A2) in the polythiol composition refers to the ratio (area%) of the peak area of ​​polythiol component A1 or A2 to the total peak area of ​​all compounds in the polythiol composition (100). This peak area ratio (area%) was determined by performing high-performance liquid chromatography (HPLC) measurements under the following conditions. (HPLC conditions) Column: YMC-Pack ODS-A (S5Φ6mm×150mm) Mobile phase: Acetonitrile / 0.01 mol / L potassium dihydrogen phosphate aqueous solution = 60 / 40 (vol / vol) Column temperature: 40℃ Flow rate: 1.0ml / min Detector: UV detector, wavelength 230nm Preparation of the measurement solution: Dissolve and mix 160 mg of the polythiol composition in 10 ml of acetonitrile. Injection volume: 2μL

[0140] [Reference production example 1] (Manufacturing of molded articles containing thiourethane resin R1) In a flask equipped with a stirring device, Dibutyltin dichloride (100 ppm by mass relative to the total amount of the polymerizable composition obtained) is used as a polymerization catalyst, Zelec-UN (manufactured by Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass relative to the total amount of the polymerizable composition obtained), m-xylylene diisocyanate (XDI) (52 parts by mass), which is a polyisocyanate compound, A polythiol composition X1 (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 purity of polythiol component A1 in polythiol composition X1 (i.e., the content of polythiol component A1 relative to the total amount of polythiol composition X1) is 92.2%. Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then degassed thoroughly under reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds fixed with tape, and then the pair of glass molds was placed in an oven with the oven temperature set to 10°C. Next, the oven temperature was raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded article containing thiourethane resin R1 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. Then, the molded bodies were removed from the pair of glass molds to obtain the molded bodies.

[0141] (Manufacturing and cleaning of thiourethane resin powder R1) The lens was manufactured by machining the molded body obtained as described above. The cutting waste (specifically, cutting powder) generated during this process was collected to obtain thiourethane resin powder R1.

[0142] [Reference production example 2] (Manufacturing of molded articles containing thiourethane resin R2) In a flask equipped with a stirring device, Dimethyltin dichloride (trade name: Nestin P, manufactured by Honjo Chemical Co., Ltd.) as a polymerization catalyst (100 ppm by mass relative to the total amount of the polymerizable composition obtained), Zelec-UN (manufactured by Stefan; acidic phosphate ester) as a release agent (1000 ppm by mass relative to the total amount of the polymerizable composition obtained), m-xylylene diisocyanate (XDI) (50.8 parts by mass), which is a polyisocyanate compound, A polythiol composition X (49.2 parts by mass) mainly comprising 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., polythiol component A2), Adding this, the mixture was stirred and mixed at room temperature for 1 hour to obtain a polymerizable composition, which is a clear, homogeneous solution. Here, the purity of polythiol component A2 in polythiol composition X (i.e., the content of polythiol component A2 relative to the total amount of polythiol composition X) is 85.5%. Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then degassed thoroughly under reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was poured between a pair of glass molds fixed with tape, and then the pair of glass molds was placed in an oven with the oven temperature set to 10°C. Next, the oven temperature was raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compound and polythiol composition) in the degassed polymerizable composition were polymerized, and a molded article containing thiourethane resin R2 (i.e., a cured product of the polymerizable composition) was formed between the pair of glass molds. Next, the oven was cooled, and after cooling, the pair of glass molds were removed from the oven. Then, the molded bodies were removed from the pair of glass molds to obtain the molded bodies.

[0143] (Manufacturing and cleaning of thiourethane resin powder R2) The lens was manufactured by machining the molded body obtained as described above. The cutting debris (specifically, cutting powder) generated during this process was collected to obtain thiourethane resin powder R2.

[0144] <Resin powder decomposition process> [Example 1-1] (Decomposition of thiourethane resin by benzylamine) -Cleaning process- 30 g of the powdered composition R2 obtained in Reference Manufacturing Example 2 was weighed out. To this 30 g of thiourethane resin powder, 150 g of toluene was added and the mixture was stirred and washed, and then the toluene was removed by filtration. This process was repeated three times (the above is the washing process).

[0145] -Reaction Process- The thiourethane resin powder washed in the above washing step was entirely placed into a 500 mL flask equipped with a condenser. Benzylamine (manufactured by Fujifilm Wako Pure Chemical Industries) (25.98 g; 0.242 mol) and toluene (349 g) were added, and the mixture was heated and stirred at 100°C for 3 hours to obtain a reaction mixture containing the polythiol composition (end of reaction step).

[0146] -Separation process- The reaction mixture obtained in the above reaction step was cooled to 30°C, and then the solid matter was removed by filtration. The filtered solid residue was dried with nitrogen gas to obtain a mixture mainly composed of a polyurea compound, which is a urea derivative of XDA and benzylamine. The excess amine was removed from the filtrate by washing it twice with 150 mL of 1 N hydrochloric acid. The resulting liquid was then washed twice with 100 mL of water to obtain a toluene solution of the polythiol composition. From the obtained toluene solution, highly polar by-products were removed by silica gel column chromatography, and then toluene was removed by distillation using a rotary evaporator. The resulting mixture was subjected to removal of low-boiling-point components by vacuum pump chromatography, followed by filtration using a 3-micron PTFE membrane filter, in that order to obtain 9.10 g of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., polythiol component A2) (separation step). The results above are summarized in Table 1.

[0147] [Examples 1-2] (Decomposition of thiourethane resin by ethylenediamine) The benzylamine used in Example 1-1 was replaced with ethylenediamine, and the same procedure as in Example 1-1 was performed under the conditions summarized in Table 1. The results are summarized in Table 1.

[0148] [Examples 1-3] (Decomposition of thiourethane resin by monoethanolamine) -Reaction Process- The powdered composition R1 (200 g) obtained in Reference Production Example 1 was entirely placed into a 1000 mL flask equipped with a condenser. Monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) (81.0 g; 1.326 mol) and 386 g of toluene were added, and the mixture was heated and stirred at 90°C for 5 hours to obtain a reaction mixture containing the polythiol composition (end of reaction process).

[0149] -Separation process- The reaction mixture obtained in the reaction step was cooled to 60°C, and then the solid matter was removed by filtration. The filtered solid residue was dried with nitrogen gas to obtain a mixture mainly composed of a polyurea compound, which is a urea derivative of XDA and monoethanolamine. To the obtained filtrate, 143 g of 31% sodium hydroxide aqueous solution was added and stirred. 150 g of water was then added to extract the soluble components. The resulting aqueous extract was washed with 50 g of toluene, and then 150 g of 35% hydrochloric acid was added and stirred. From the resulting aqueous liquid, the soluble components were extracted with 200 g of toluene to obtain a toluene extract. This toluene extract was washed with 160 g of water, then with 160 g of 0.1% aqueous ammonia, and then twice with 160 g of water to obtain a toluene solution of the polythiol composition. The obtained toluene solution was subjected to distillation to remove toluene using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling point components using a vacuum pump, followed by filtration using a 1-micron PTFE membrane filter, thereby obtaining 74.15 g of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) (separation steps). The results above are summarized in Table 1.

[0150] [Examples 1-4] (Decomposition of thiourethane resin by n-butylamine) In Examples 1-3, the monoethanolamine used was replaced with n-butylamine, and the same procedure as in Examples 1-3 was carried out under the conditions summarized in Table 1. The reaction mixture obtained in the reaction step became gel-like, and separation of solid matter by filtration was not possible, so the purification was discontinued.

[0151] [Examples 1-5] (Decomposition of thiourethane resin by m-xylylenediamine) In Examples 1-3, the monoethanolamine was replaced with m-xylylenediamine, and the same procedure as in Examples 1-3 was carried out under the conditions summarized in Table 2. The reaction mixture obtained in the reaction step became gel-like, and separation of solid matter by filtration was not possible, so the purification was discontinued.

[0152] [Examples 1-6] (Decomposition of thiourethane resin by di-n-butylamine) The benzylamine used in Example 1-1 was replaced with di-n-butylamine, and the same procedure as in Example 1-1 was performed under the conditions summarized in Table 2. The results are summarized in Table 2.

[0153] [Examples 1-7] (Decomposition of thiourethane resin by dipropylamine) The monoethanolamine used in Examples 1-3 was replaced with dipropylamine, and the same procedure as in Examples 1-3 was performed under the conditions summarized in Table 2. The results are summarized in Table 2.

[0154] [Examples 1-8] (Decomposition of thiourethane resin by morpholine) The monoethanolamine used in Examples 1-3 was replaced with morpholine, and the same procedure as in Examples 1-3 was performed under the conditions summarized in Table 2. The results are summarized in Table 2.

[0155] [Examples 1-9] (Decomposition of thiourethane resin by piperidine) The monoethanolamine used in Examples 1-3 was replaced with piperidine, and the same procedure as in Examples 1-3 was performed under the conditions summarized in Table 2. The results are summarized in Table 2.

[0156] [Examples 1-10] (Decomposition of thiourethane resin by N-(2-aminoethyl)piperazine) -Reaction Process- The powdered composition R1 (130.0 g) obtained in Reference Production Example 1 was entirely placed into a 1000 mL flask equipped with a condenser. N-(2-aminoethyl)piperazine (manufactured by Tokyo Chemical Industry Co., Ltd.) (130.0 g; 1.006 mol), 177.7 g of toluene, and 65.7 g of pure water were added thereto, and the mixture was heated and stirred at 85°C for 4 hours to obtain a reaction mixture containing the polythiol composition (end of reaction process).

[0157] -Separation process- The reaction mixture obtained in the reaction step was cooled to 60°C, and the layer of the mixture mainly consisting of a polyurea compound, which is a urea derivative of XDA and N-(2-aminoethyl)piperazine, and the toluene layer mainly consisting of a polythiol composition were separated by liquid-liquid extraction to obtain 232.1 g of the polyurea-containing mixture. To the toluene layer obtained by liquid-liquid separation, 59.9 g of 35% hydrochloric acid was added and the mixture was stirred and washed at 37-40°C. After stirring and washing, the aqueous layer was separated by liquid-liquid separation to obtain a toluene solution. This toluene solution was washed with 44.3 g of degassed water at 37-40°C to obtain a toluene solution of the polythiol composition. To the obtained toluene solution, 74.6 g of 30.7% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred at 37°C to 40°C for 15 minutes. Then, 44.3 g of degassed water was added, and the mixture was stirred at 37°C to 40°C for 15 minutes to extract the components soluble in the aqueous layer. Subsequently, the mixture was filtered through 7 μm filter paper. The toluene layer was separated from the obtained filtrate by liquid-liquid separation to obtain the aqueous layer. To the obtained aqueous layer, 97.1 g of toluene and 77.2 g of 35% hydrochloric acid were added, and the mixture was washed by stirring at 37°C to 40°C. After washing by stirring, the aqueous layer was separated by liquid-liquid separation to obtain the toluene solution. This toluene solution was washed twice with 44.3 g of degassed water at 37°C to 40°C to obtain the toluene solution of the polythiol composition. This toluene solution was washed with 44.3 g of 0.1% aqueous ammonia at 37°C to 40°C to obtain the toluene solution of the polythiol composition. This toluene solution was then washed twice with 44.3 g of degassed water at 37°C to 40°C to obtain a toluene solution of the polythiol composition. Toluene was removed from the obtained toluene solution by distillation using a rotary evaporator. The resulting mixture was then subjected to removal of low-boiling-point components using a vacuum pump, followed by filtration using a 3-micron PTFE membrane filter, in that order. 47.27 g of a polythiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) was obtained (separation step). The results are summarized in Table 3.

[0158] [Examples 1-11] (Decomposition of thiourethane resin by 1-methylpiperazine) In Examples 1-10, N-(2-aminoethyl)piperazine was replaced with 1-methylpiperazine, and the same procedure as in Examples 1-10 was performed under the conditions summarized in Table 3. The results are summarized in Table 3.

[0159] [Examples 1-12] (Decomposition of thiourethane resin by diethylenetriamine) In Examples 1-10, N-(2-aminoethyl)piperazine was replaced with diethylenetriamine, and the same procedure as in Examples 1-10 was performed under the conditions summarized in Table 3. The results are summarized in Table 3.

[0160] [Examples 1-13] (Decomposition of thiourethane resin by N,N'-dimethylethylenediamine) In Examples 1-10, N-(2-aminoethyl)piperazine was replaced with N,N'-dimethylethylenediamine, and the same procedure as in Examples 1-10 was performed under the conditions summarized in Table 3. The results are summarized in Table 3.

[0161] [Examples 1-14] (Decomposition of thiourethane resin by N-methylethanolamine) In Examples 1-10, N-(2-aminoethyl)piperazine was replaced with N-methylethanolamine, and the same procedure as in Examples 1-10 was performed under the conditions summarized in Table 3. The results are summarized in Table 3.

[0162]

Table 1

[0163]

Table 2

[0164]

Table 3

[0165] As shown in Tables 1 to 3, a thiourethane resin and an amine compound A containing at least one of a primary amino group and a secondary amino group were reacted to produce a polyurea compound and a polythiol compound.

[0166] [Example 2-1] (Decomposition of monoethanolamine urea form by monoethanolamine) Weighed 10.0 g of the polyurea-containing compound obtained in the step of Example 1-3 into a 100 mL flask equipped with a condenser tube, added 39.1 g (0.64 mol) of monoethanolamine (MEA) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as amine compound B, and heated at 140 °C for 3 hours to obtain a reaction mixture containing XDA as a polyamine compound. The reaction mixture was sampled, and the concentration of XDA in the reaction mixture was determined by gas chromatogram analysis. Assuming that the total amount of the polyurea-containing mixture was the urea form (polyurea compound) of XDA and MEA, the production rate (GC yield) of XDA was determined based on the GC concentration. The results were as shown in Table 4.

[0167] [Example 2-2] (Decomposition of ethylenediamine urea form by monoethanolamine) The polyurea-containing compound obtained in the step of Example 1-3 used in Example 2-1 was changed to the polyurea-containing compound obtained in the step of Example 1-2, and the same operations as in Example 2-1 were carried out under the conditions summarized in Table 4. The results were summarized in Table 4.

[0168] [Examples 2-3] (Decomposition of dipropylamine urea compound by NaOH) In a 100 mL flask fitted with a condenser, add the polyurea-containing solution obtained in the steps of Examples 1-7. 30.0 g of the compound was weighed, and 13.3 g (0.32 mol) of 97% sodium hydroxide (NaOH) (manufactured by Fujifilm Wako Pure Chemical Industries) was added as an inorganic base. Furthermore, 47.7 g of ethylene glycol was added as an additive. The resulting mixture was heated and stirred at 130°C for 4 hours, removing dipropylamine by distillation, to allow the reaction to proceed. This reacted XDA-dipropylamine urea in the polyurea-containing mixture with NaOH, yielding a reaction mixture containing XDA as a polyamine compound. The reaction mixture was sampled, and the concentration of XDA in the reaction mixture was determined by gas chromatographic analysis. Assuming that the entire polyurea-containing mixture consisted of the urea compound of XDA and MEA, the production rate of XDA (GC yield) was determined based on the GC concentration. The results are shown in Table 4.

[0169] [Examples 2-4] (Decomposition of morpholine urea compound by NaOH) In Example 2-3, the polyurea-containing compound obtained in the process of Example 1-7 was replaced with the polyurea-containing compound obtained in the process of Example 1-8, and the same procedure as in Example 2-3 was performed under the conditions summarized in Table 4. The results are summarized in Table 4.

[0170] [Examples 2-5] (Decomposition of monoethanolamine urea compound with NaOH) In Example 2-3, the polyurea-containing compound obtained in the process of Example 1-7 was replaced with the polyurea-containing compound obtained in the process of Example 1-3, and the same procedure as in Example 2-3 was performed under the conditions summarized in Table 5. The results are summarized in Table 5.

[0171] [Examples 2-6] (Decomposition of N-(2-aminoethyl)piperazine urea compound by NaOH) In a 500 mL flask equipped with a condenser, 173.9 g of the polyurea-containing compound obtained in the steps of Examples 1-10 was weighed. 40.95 g (0.99 mol) of 97% sodium hydroxide (NaOH) (manufactured by Fujifilm Wako Pure Chemical Industries) was added as an inorganic base, and then 57.87 g of N-(2-aminoethyl)piperazine was added. The resulting mixture was heated and stirred at 145°C for 3 hours, removing low-boiling components by distillation, to allow the reaction to proceed. This reacted XDA-N-(2-aminoethyl)piperazine urea in the polyurea-containing mixture with NaOH, yielding a reaction mixture containing XDA as a polyamine compound. The reaction mixture was sampled, and the concentration of XDA in the reaction mixture was determined by gas chromatography analysis. The purity of the urea compound (polyurea compound) of XDA and N-(2-aminoethyl)piperazine in the polyurea-containing mixture used as raw material was calculated using HPLC, and the production rate (GC yield) of XDA was determined based on the purity of the raw material. The results are shown in Table 5.

[0172] [Examples 2-7] (Decomposition of N-methylethanolamineurea compound by NaOH) In Example 2-6, the polyurea-containing compound obtained in the process of Example 1-10 was replaced with the polyurea-containing compound obtained in the process of Example 1-14, and the same procedure as in Example 2-6 was performed under the conditions summarized in Table 5. The results are summarized in Table 5.

[0173] [Examples 2-8] (Decomposition of monoethanolamine urea compound with NaOH / in combination with DET) 31.0 g of the polyurea-containing compound obtained in the steps of Examples 1-3 was weighed into a 100 mL flask equipped with a condenser, and 30.9 g (0.30 mol) of diethylenetriamine (manufactured by Fujifilm Wako Pure Chemical Industries) was added. The mixture was reacted at 145°C for 3 hours, removing low-boiling components by distillation, to obtain a reaction mixture containing XDA as a polyamine compound. Subsequently, 16.9 g (0.41 mol) of 97% sodium hydroxide (NaOH) (manufactured by Fujifilm Wako Pure Chemical Industries) was added as an inorganic base to the obtained reaction mixture, and the mixture was heated and stirred at 145°C for 3 hours to allow the reaction to proceed. This decomposed the imidazolidinone intermediate formed by the reaction of diethylenetriamine and the polyurea compound with NaOH. The reaction mixture was sampled, and the concentration of XDA in the reaction mixture was determined by gas chromatographic analysis. Assuming that the entire polyurea-containing mixture consisted of the urea form (polyurea compound) of XDA and MEA, the production rate of XDA (GC yield) was determined based on the GC concentration. The results are shown in Table 5.

[0174] [Examples 2-9] (Decomposition of 1-methylpiperazine urea compound with NaOH / in combination with DET) In Example 2-8, the polyurea-containing compound obtained in the process of Example 1-3 was replaced with the polyurea-containing compound obtained in the process of Example 1-11, and the same procedure as in Example 2-8 was carried out under the conditions summarized in Table 6. The purity of the urea compound (polyurea compound) of XDA and 1-methylpiperazine in the polyurea-containing mixture used as raw material was calculated using HPLC, and the production rate of XDA (GC yield) was determined based on the purity of the raw material. The results are shown in Table 6.

[0175] [Examples 2-10] (Decomposition of diethylenetriamineurea compound with NaOH / in combination with DET) In Example 2-8, the polyurea-containing compound obtained in the steps of Examples 1-3 was changed to the polyurea-containing compound obtained in the steps of Examples 1-12, and the same operations as in Example 2-8 were carried out under the conditions summarized in Table 6. The purity of the urea form (polyurea compound) of XDA and diethylenetriamine in the polyurea-containing mixture used as the raw material was calculated using HPLC, and based on the raw material purity, the production rate (GC yield) of XDA was determined. The results were as shown in Table 6.

[0176] [Example 2-11] (Decomposition of monoethanolamine urea form by NaOH / combined use of aminoethylethanolamine) The diethylenetriamine described in Example 2-10 was changed to aminoethylethanolamine, and the same operations as in Example 2-10 were carried out under the conditions summarized in Table 6. Assuming that the total amount of the polyurea-containing mixture was the urea form (polyurea compound) of XDA and MEA, the production rate (GC yield) of XDA was determined based on the GC concentration. The results were as shown in Table 6.

[0177] [Example 2-12] (Decomposition of monoethanolamine urea form by NaOH / combined use of tetraethylenepentamine) The diethylenetriamine described in Example 2-10 was changed to tetraethylenepentamine, and the same operations as in Example 2-10 were carried out under the conditions summarized in Table 6. Assuming that the total amount of the polyurea-containing mixture was the urea form (polyurea compound) of XDA and MEA, the production rate (GC yield) of XDA was determined based on the GC concentration. The results were as shown in Table 6.

[0178] [Table 4]

[0179] [Table 5]

[0180] [Table 6]

[0181] As shown in Tables 4 to 6, polyamine compounds could be produced by reacting a polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compound B.

Claims

1. A method for producing a polythiol compound, comprising the step of reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polyurea compound and a polythiol compound.

2. A method for producing a polythiol compound according to claim 1, wherein the polythiol compound comprises at least one selected from the group consisting of 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).

3. A method for producing a polythiol compound according to claim 1, wherein the amine compound A is at least one selected from the group consisting of benzylamine, ethylenediamine, monoethanolamine, N-methylethanolamine, n-butylamine, m-xylylenediamine, di-n-butylamine, dipropylamine, morpholine, piperidine, N-(2-aminoethyl)piperazine, 1-methylpiperazine, diethylenetriamine, and N,N'-dimethylethylenediamine.

4. A method for producing a polythiol compound for the manufacture of optical materials, as described in claim 1.

5. A method for producing a polyamine compound, comprising the step of reacting a polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compound B to produce a polyamine compound.

6. A step of reacting a thiourethane resin with an amine compound A containing at least one of a primary amino group and a secondary amino group to produce a polyurea compound and a polythiol compound, A method for producing a polyamine compound, comprising the step of reacting the polyurea compound with at least one inorganic base selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and at least one of amine compound B to produce a polyamine compound.

7. A method for producing a polyamine compound according to claim 5 or 6, wherein in the step of producing the polyamine compound, the polyurea compound is reacted with at least one of the inorganic base and the amine compound B under a temperature condition of 100°C to 180°C.

8. The method for producing a polyamine compound according to claim 5 or claim 6, wherein the inorganic base comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and calcium hydroxide.

9. A method for producing a polyamine compound according to claim 5 or claim 6, wherein the polyurea compound is a compound represented by the following formula (1). 【Chemistry 1】 [In formula (1), R １ , R ２ , R １１ , and R １２ Each of these independently represents a monovalent organic group containing a hydrocarbon group, L １ This represents a divalent hydrocarbon group.

10. A method for producing a polyamine compound according to claim 5 or claim 6, wherein the polyamine compound comprises 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.

11. A method for producing a polyamine compound as a raw material for polyisocyanate compounds for the manufacture of optical materials, as described in claim 5 or claim 6.

12. The method for producing a polyamine compound according to claim 6, wherein the thiourethane resin is recovered in at least one of the processes of manufacturing eyeglass lenses, manufacturing eyeglasses, and disposing of eyeglasses.

13. A step of producing a polyamine compound by the method for producing a polyamine compound described in claim 5 or claim 6, 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].

14. A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound described in claim 13, 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.

15. A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 14, A step of obtaining a resin by curing the polymerizable composition, A method for producing resins containing resins.

16. A method for manufacturing a molded article containing resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 14, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing a molded article containing [the specified ingredient].

17. A method for producing an optical material including a molded body containing a resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 14, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing optical materials containing [specific material].

18. A method for manufacturing a lens including a molded body containing resin, A step of producing a polymerizable composition by the method for producing a polymerizable composition described in claim 14, A step of obtaining a molded article containing resin by curing the polymerizable composition, A method for manufacturing lenses that include [the specified element].

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