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

Abstract

A method for producing a polythiol composition, said method comprising a production step for producing a polythiol composition by decomposing a thionocarbamate resin with a decomposing agent represented by formula (1) or formula (2). In formula (1), R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1-3 carbon atoms, or an amino group (excluding the case where both R1 and R2 are an amino group). In formula (2), R3 represents an alkyl group having 1-3 carbon atoms. # imgabs0 #

Description

Technical Field

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

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

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

[0004] In addition, there is known a method for producing a thiourethane resin raw material, which uses a thiourethane resin as a starting material to produce a thiourethane resin raw material (that is, a raw material for producing a thiourethane resin. For example, a polythiol composition and a polyamine compound).

[0005] For example, Patent Document 4 discloses a method for producing a polythiol composition, which includes a reaction step of reacting a thiourethane resin with an amine compound to produce the polythiol composition.

[0006] Patent Document 5 discloses a method for producing a polyamine compound, which includes a first step of reacting a thiourethane resin with an amine compound A to produce a polyurea compound, and a second step of reacting the polyurea compound with an amine compound B to produce a polyamine compound.

[0007] In addition, Patent Document 5 discloses a method for producing a polyamine compound, which includes the following steps: a step X1 of reacting a thiourethane resin with an alcohol compound in the presence of an amine compound XA as a tertiary amine compound to produce a polyurethane compound; and a step X2 of reacting a polyurethane compound with an amine compound XB to produce a polyamine compound.

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 63-46213

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2-270859

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 7-252207

[0011] Patent Document 4: International Publication No. 2021 / 157701

[0012] Patent Document 5: International Publication No. 2021 / 157702 Summary of the invention

[0013] Problems to be solved by the invention

[0014] In the production methods described in Patent Documents 4 and 5, an amine compound or an alcohol compound is used as a decomposing agent for decomposing a thiourethane resin, and the thiourethane resin is decomposed by the decomposing agent to obtain a polythiol composition or a polyamine compound as a target product.

[0015] In the production methods described in Patent Documents 4 and 5, there is a need to further improve the removability of the decomposing agent (ie, amine compound or alcohol compound) from the reaction system after the decomposition reaction of the thiourethane resin.

[0016] An object of one embodiment of the present disclosure is to provide a method for producing a polythiol composition and a method for producing a polyamine compound, which are excellent in removability of a decomposition agent from a reaction system after a decomposition reaction in which a thiourethane resin is decomposed by the decomposition agent, and uses thereof.

[0017] Means for solving problems

[0018] Means for solving the above-mentioned problems include the following.

[0019] <1> A method for producing a polythiol composition comprises the step of decomposing a thiourethane resin using a decomposing agent represented by the following formula (1) or (2) to produce the polythiol composition.

[0020] [Chemical formula 1]

[0021] R 3 —OH (2)

[0022] In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (excluding R 1 and R 2 are all amino groups).

[0023] In formula (2), R 3 It represents an alkyl group having 1 to 3 carbon atoms.

[0024] <2> like <1> In the method for producing the polythiol composition, the generating step includes a step of reacting the thiourethane resin with the decomposing agent under a pressure higher than atmospheric pressure.

[0025] <3> like <1> or <2> The method for producing the polythiol composition is a method for producing the polythiol composition for producing optical materials.

[0026] <4> like <1> ~ <3> The method for producing a polythiol composition according to any one of the preceding claims, wherein the thiourethane resin is recovered in at least one of a process for producing eyeglass lenses, a process for producing eyeglasses, and a process for discarding eyeglasses.

[0027] <5> A method for producing a polymerizable composition, comprising the following steps:

[0028] use <1> ~ <4> The method for producing a polythiol composition according to any one of the preceding claims, comprising a step of producing a polythiol composition; and

[0029] A step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate compound by mixing the polythiol composition and the polyisocyanate compound.

[0030] <6> like <5> The method for producing a polymerizable composition, wherein the step of obtaining the polymerizable composition is a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition by mixing the polythiol composition with a polyisocyanate composition containing a polyisocyanate compound,

[0031] The aforementioned polyisocyanate composition comprises:

[0032] xylylene diisocyanate, and

[0033] At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3);

[0034] When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in high performance liquid chromatography is 0.20 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate,

[0035] When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in high performance liquid chromatography is 0.05 ppm or more relative to 100 of the peak area of ​​xylylene diisocyanate,

[0036] When the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in high performance liquid chromatography measurement is 0.10 ppm or more relative to 100 of the peak area of ​​xylylene diisocyanate.

[0037] [Chemical formula 2]

[0038]

[0039] <7> A method for producing a resin, comprising the following steps:

[0040] use <5> The method for producing a polymerizable composition comprises a step of producing a polymerizable composition; and

[0041] A step of obtaining a resin by curing the polymerizable composition.

[0042] <8> A method for producing a polyamine compound, comprising the following steps:

[0043] A first step of decomposing a thiourethane resin using a decomposing agent represented by the following formula (1) to produce a polyurea compound; and

[0044] A second step is to decompose the polyurea compound using a decomposing agent represented by the following formula (3) to produce a polyamine compound.

[0045] [Chemical formula 3]

[0046]

[0047] In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (excluding R 1 and R 2 are all amino groups).

[0048] In formula (3), R 11 and R 12 Each independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0049] <9> like <8> The method for producing a polyamine compound, wherein the decomposing agent represented by the above formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol.

[0050] <10> like <8> or <9> The method for producing a polyamine compound is characterized in that the first step includes a step of reacting the thiourethane resin with the decomposing agent represented by the formula (1) under a pressure higher than atmospheric pressure.

[0051] <11> like <8> ~ <10> The method for producing a polyamine compound according to any one of the preceding claims, wherein the second step includes a step of reacting the polyurea compound with the decomposition agent represented by the formula (3) under a pressure higher than atmospheric pressure.

[0052] <12> A method for producing a polyamine compound, comprising the following steps:

[0053] Step X1 of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polyurethane compound; and

[0054] Step X2 of decomposing the polyurethane compound using a decomposing agent represented by the following formula (3) to produce a polyamine compound.

[0055] [Chemical formula 4]

[0056] R 3 —OH (2)

[0057] [In formula (2), R 3 It represents an alkyl group having 1 to 3 carbon atoms.

[0058] In formula (3), R 11 and R 12 Each independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.]

[0059] <13> like <12> The method for producing a polyamine compound, wherein the molecular weight of the tertiary amine compound is 1000 or less,

[0060] The decomposing agent represented by the above formula (3) is ethylenediamine, N,N'-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol.

[0061] <14> like <12> or <13> In the method for producing a polyamine compound, the step X1 includes reacting the thiourethane resin with the decomposition agent represented by the formula (2) under a pressure higher than atmospheric pressure.

[0062] <15> like <12> ~ <14> The method for producing a polyamine compound according to any one of the preceding claims, wherein the step X2 includes reacting the polyurethane compound with the decomposition agent represented by the formula (3) under a pressure higher than atmospheric pressure.

[0063] <16> like <8> ~ <15> The method for producing a polyamine compound described in any one of the above is a method for producing a polyamine compound as a raw material of a polyisocyanate compound for producing an optical material.

[0064] <17> like <8> ~ <15> The method for producing a polyamine compound according to any one of the preceding claims, wherein the thiourethane resin is recovered in at least one of a process for producing eyeglass lenses, a process for producing eyeglasses, and a process for discarding eyeglasses.

[0065] <18> A method for producing a polyisocyanate compound, comprising the following steps:

[0066] use <8> ~ <16> The method for producing a polyamine compound according to any one of the preceding claims, comprising a step of producing a polyamine compound; and

[0067] A step of reacting at least one of the polyamine compound and the hydrochloride of the polyamine compound with phosgene to obtain a polyisocyanate compound.

[0068] <19> A method for producing a polymerizable composition, comprising the following steps:

[0069] use <18> The method for producing a polyisocyanate compound comprises a step of producing a polyisocyanate compound; and

[0070] 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.

[0071] <20> A method for producing a resin, comprising the following steps:

[0072] use <19> The method for producing a polymerizable composition comprises a step of producing a polymerizable composition; and

[0073] A step of obtaining a resin by curing the polymerizable composition.

[0074] Effects of the Invention

[0075] According to one embodiment of the present disclosure, there can be provided a method for producing a polythiol composition, a method for producing a polyamine compound, and uses thereof, which are excellent in removability of a decomposing agent from a reaction system after a decomposition reaction in which a thiourethane resin is decomposed by the decomposing agent. DETAILED DESCRIPTION

[0076] In the present disclosure, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0077] In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0078] In the present disclosure, when the amount of each component contained in the composition contains a plurality of substances belonging to each component, unless otherwise specified, it means the total amount of the plurality of substances present in the composition.

[0079] In the numerical range recorded in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment.

[0080] There may be overlapping parts between the multiple embodiments in the present disclosure, that is, the features in one embodiment may be possessed by other embodiments.

[0081] 《First Implementation Method》

[0082] [Method for producing polythiol composition (first embodiment)]

[0083] The method for producing a polythiol composition according to the first embodiment of the present disclosure includes a step of generating a polythiol composition by decomposing a thiourethane resin using a decomposing agent represented by the following formula (1) or (2).

[0084] [Chemical formula 5]

[0085] R 3 —OH (2)

[0086] In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (excluding R 1 and R 2 are all amino groups).

[0087] In formula (2), R 3 It represents an alkyl group having 1 to 3 carbon atoms.

[0088] In the method for producing the polythiol composition according to the first embodiment, the polythiol composition is produced by decomposing the thiourethane resin using the decomposing agent represented by the formula (1) or (2).

[0089] In the method for producing the polythiol composition according to the first embodiment, the decomposition agent is excellent in removability from the reaction system after the decomposition reaction of the thiourethane resin. For example, the decomposition agent can be easily removed from the reaction system after the decomposition reaction by volatilization, distillation, or the like.

[0090] It is considered that the reason why such an effect can be obtained is that the above-mentioned decomposition agent is a compound with a low boiling point.

[0091] Hereinafter, each step that may be included in the method for producing the polythiol composition according to the first embodiment will be described.

[0092] <Generation process>

[0093] The generating step is a step of generating a polythiol composition by decomposing the thiourethane resin with a decomposing agent represented by the above formula (1) or (2) (ie, reacting the thiourethane resin with the decomposing agent).

[0094] The decomposing agent represented by the above formula (1) is an amine compound.

[0095] The decomposition reaction of the thiourethane resin by the decomposing agent represented by the formula (1) is an aminolysis reaction.

[0096] The decomposing agent represented by the above formula (1) is an alcohol compound.

[0097] The decomposition reaction of the thiourethane resin by the decomposing agent represented by the formula (1) is an alcoholysis reaction.

[0098] (Thiourea Resin)

[0099] Thiourethane resin is the starting material in the production process.

[0100] The thiourethane resin is not particularly limited, and examples thereof include thiourethane resins described in known documents such as JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, International Publication No. 2008 / 047626, International Publication No. 2021 / 157701, and International Publication No. 2021 / 157702.

[0101] The thiourethane resin generally includes a polymer of an isocyanate compound and a polythiol composition. That is, the thiourethane resin is generally produced using an isocyanate compound and a polythiol composition as raw materials.

[0102] -Polythiol composition as raw material of thiourethane resin-

[0103] In the present disclosure, the polythiol composition (i.e., the polythiol composition as a raw material of the thiourethane resin and the polythiol composition as a target product of the method for producing the polythiol composition of the present disclosure described below) refers to a composition containing at least one polythiol compound.

[0104] The polythiol compound is not particularly limited as long as it is a compound containing two or more thiol groups (also known as mercapto groups).

[0105] Regarding the polythiol compound, reference may be appropriately made to the aforementioned known literature regarding the thiourethane resin.

[0106] The polythiol composition may contain components other than the polythiol compound as impurities.

[0107] The polythiol composition preferably contains at least one polythiol compound as a main component.

[0108] Here, “the polythiol composition contains at least one polythiol compound as a main component” means that the total content of the at least one polythiol compound is 50% or more based on the total amount of the polythiol composition.

[0109] The total content of at least one polythiol compound is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more, based on the total amount of the polythiol composition.

[0110] Similarly, in the present disclosure, when a composition "contains" a certain component (hereinafter referred to as "component X") "as a main component", it means that the content of component X (when component X is formed by two or more compounds, it is the total content of the two or more compounds) is 50% or more relative to the total amount of the composition.

[0111] The content of the main component, Component X, 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.

[0112] The “%” in the above description of the term “comprising… as a main component” means: the ratio (area %) of the total area of ​​all peaks of component X (e.g., at least one polythiol compound) to the total area of ​​all peaks of the composition (e.g., polythiol composition) obtained by high performance liquid chromatography.

[0113] Hereinafter, the polythiol compound contained in the polythiol composition is also referred to as a "polythiol component".

[0114] The polythiol composition as a raw material of the thiourethane resin preferably contains at least one member selected from the group consisting of

[0115] 4-Mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,

[0116] 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0117] 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0118] 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,

[0119] Pentaerythritol tetrakis(2-thioglycolate),

[0120] Pentaerythritol tetrakis(3-mercaptopropionate),

[0121] 2,5-dimercaptomethyl-1,4-dithiocyclohexane,

[0122] Bis(2-mercaptoethyl)sulfide, and

[0123] Diethylene glycol bis(3-mercaptopropionate).

[0124] The polythiol composition more preferably contains the polythiol component A as a main component.

[0125] In this case, the polythiol composition may contain at least one of other components other than the polythiol component A (for example, other polythiol compounds, components other than the polythiol compound, etc.).

[0126] Examples of other polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiol, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiol, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiol.

[0127] More specific embodiments of the polythiol composition as a raw material of the thiourethane resin include, for example:

[0128] An embodiment comprising 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A1") as a main component;

[0129] An embodiment comprising 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter, these three compounds are also collectively referred to as "polythiol component A2") as main components;

[0130] An embodiment comprising pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as “polythiol component A3”) as a main component;

[0131] A method comprising the polythiol component A1 and the polythiol component A3 as main components;

[0132] A method comprising the polythiol component A2 and the polythiol component A3 as main components;

[0133] etc.

[0134] The polythiol composition of each embodiment may contain at least one of other components (for example, other polythiol compounds, components other than the polythiol compound, etc.) other than the main component.

[0135] - Isocyanate compound as raw material of thiourethane resin -

[0136] The isocyanate compound as a raw material of the thiourethane resin may be only one kind or two or more kinds.

[0137] As for the isocyanate compound which is a raw material of a thiourethane resin, the known isocyanate compounds described in the above-mentioned known documents are mentioned, for example.

[0138] The isocyanate compound as a raw material of the thiourethane resin preferably contains a polyisocyanate compound having two or more isocyanate groups.

[0139] Regarding the isocyanate compound as the raw material of the thiourethane resin,

[0140] More preferably, it contains a diisocyanate compound containing two isocyanate groups,

[0141] It is further preferred that the isocyanate component contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4′-diphenylmethane diisocyanate and phenylene diisocyanate (hereinafter also referred to as “isocyanate component N”),

[0142] It is further preferred that the isocyanate component N is contained as a main component.

[0143] The isocyanate compound as a raw material of the thiourethane resin preferably contains at least one selected from the group consisting of m-xylylene diisocyanate, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane and bis(isocyanatecyclohexyl)methane (hereinafter also referred to as “isocyanate component N1”), and more preferably contains the isocyanate component N1 as a main component, from the viewpoint of the performance of the thiourethane resin [e.g., optical properties (e.g., refractive index and / or Abbe number), heat resistance, specific gravity d, etc.].

[0144] -Other ingredients-

[0145] The thiourethane resin may contain other components in addition to the polymer of at least one isocyanate compound and the polythiol composition.

[0146] Regarding other components that may be contained in the thiourethane resin, the components that may be contained in the polymerizable composition described later may be appropriately referred to.

[0147] -Recovered Thiourethane Resin-

[0148] The thiourethane resin is preferably recovered in at least one of a process for manufacturing eyeglass lenses, a process for manufacturing eyeglasses, and a process for discarding eyeglasses. According to this embodiment, the thiourethane resin, which is a material for eyeglass lenses, can be recycled.

[0149] Here,

[0150] The manufacturing process of eyeglass lenses refers to: a process of manufacturing resin by blending monomers as resin raw materials and casting polymerization and / or a process of obtaining eyeglass lenses by cutting a resin molded body;

[0151] The manufacturing process of glasses refers to the process of manufacturing glasses by combining glasses lenses with other components such as glasses frames;

[0152] The process of discarding glasses refers to the process of discarding glasses that have become useless after manufacture or glasses that have been used.

[0153] In any process, thiourethane resin, which is a material for eyeglass lenses, can be generated as waste.

[0154] In the present embodiment, a thiourethane resin produced in at least one of these processes is used as a starting material, and the thiourethane resin is reacted with a decomposition agent to obtain a polythiol composition as a decomposition product of the thiourethane resin.

[0155] -Processing scraps containing thiourea resin-

[0156] In the production step, the thiourethane resin-containing chips may be brought into contact with the decomposing agent to react with the thiourethane resin in the chips. This can further improve the reaction efficiency of the thiourethane resin and the decomposing agent.

[0157] The form of the processing scraps containing the thiourethane resin is not particularly limited, and may be in a powdery form or a block form.

[0158] The method of bringing the processing scraps containing the thiourethane resin into contact with the amine compound is not particularly limited, and examples thereof include a method of placing processing scraps and a decomposing agent (and a reaction solvent used as required) in a reaction container and stirring the mixture.

[0159] The processing chips containing thiourethane resin are preferably cutting chips (including grinding chips, the same applies hereinafter) of a molded body containing thiourethane resin and / or processing chips obtained by sieving the cutting chips (i.e., cutting chips passed through a sieve).

[0160] Cutting chips of a molded body containing a thiourethane resin are generated, for example, when an optical material (for example, a lens) is produced by cutting a molded body containing a thiourethane resin.

[0161] -Resin mixture containing thiourethane resin-

[0162] The generating step may be a step of contacting a resin mixture containing a thiourethane resin with a decomposing agent to thereby react the thiourethane resin in the resin mixture with the decomposing agent to generate the polythiol composition.

[0163] The resin mixture containing the thiourethane resin further contains components other than the thiourethane resin.

[0164] As components other than the thiourethane resin, there may be mentioned resins other than the thiourethane resin, inorganic materials for producing lenses (for example, glass), and the like.

[0165] The resin other than the thiourethane resin is not particularly limited.

[0166] For example, the following materials are also included in the scope of the resin mixture containing the thiourethane resin and a resin other than the thiourethane resin:

[0167] A hybrid material of thiourethane resin and polyurethane resin produced by adding a polyol compound to the raw materials when producing thiourethane resin;

[0168] A hybrid material of thiourethane resin and urea resin produced by adding a polyamine compound to the raw materials when producing thiourethane resin; and the like.

[0169] In addition, examples of resins other than the thiourethane resin include:

[0170] Polyolefin films for protecting the surface of resin molded bodies used to make eyeglass lenses,

[0171] A hard coating or primer coating for protecting the surface of a resin molded body used to make eyeglass lenses,

[0172] Abrasives used when grinding resin molded bodies for making eyeglass lenses.

[0173] A resin material for fixing a resin molded body when cutting a resin molded body for manufacturing eyeglass lenses,

[0174] Tape or tape paste used to fix a glass mold used when a resin molded body for producing eyeglass lenses is formed.

[0175] The resin mixture preferably contains at least one selected from the group consisting of polycarbonate resins, polyallyl carbonate resins, acrylic resins, urethane resins, and episulfide resins as a resin other than the thiourethane resin.

[0176] These resins are also resins that can be used as materials for eyeglass lenses, similar to thiourethane resins.

[0177] The resin mixture containing the thiourethane resin is preferably recovered in at least one of a process for manufacturing eyeglass lenses, a process for manufacturing eyeglasses, and a process for discarding eyeglasses.

[0178] The manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses are as described above.

[0179] The resin mixture containing the thiourethane resin preferably contains cutting chips containing the thiourethane resin.

[0180] (Decomposing agent represented by formula (1) or formula (2))

[0181] The decomposition agent used in this step is a decomposition agent represented by the above formula (1) or the above formula (2).

[0182] Examples of the decomposing agent represented by the formula (1) include ammonia, monomethylamine, monoethylamine, monopropylamine, dimethylamine, diethylamine, dipropylamine, and hydrazine. Among them, ammonia, monomethylamine, and diethylamine are preferred.

[0183] Examples of the decomposing agent represented by the above formula (2) include methanol, ethanol, and propanol. Among them, methanol or ethanol is preferred, and methanol is more preferred.

[0184] (Amount of decomposition agent)

[0185] In the production step, the input mass ratio of the decomposing agent to the thiourethane resin (ie, input mass ratio [decomposing agent / thiourethane resin]) can be appropriately adjusted, but is preferably 0.10 or more and less than 2.0.

[0186] When the input mass ratio [decomposer / thiourethane resin] is 0.10 or more, the production of the polythiol composition can be further promoted.

[0187] When the input mass ratio [decomposing agent / thiourethane resin] is less than 2.0, the residual decomposing agent in the reaction mixture can be further suppressed.

[0188] The charging mass ratio [decomposer / thiourethane resin] is more preferably 0.10 or more and less than 1.0, further preferably 0.15 to 0.95, and further preferably 0.20 to 0.90.

[0189] The millimole number of the decomposing agent charged per 1 g of the thiourethane resin is preferably 1.0 mmol / g to 50.0 mmol / g, more preferably 2.0 mmol / g to 30.0 mmol / g, and even more preferably 3.0 mmol / g to 20.0 mmol / g.

[0190] The charge equivalent of the decomposer to the thiourethane resin (charge equivalent [decomposer / thiourethane resin]) is preferably 1.0 to 15.0, more preferably 1.0 to 10.0, and even more preferably greater than 1.0 and 10.0 or less.

[0191] When the input equivalent (decomposing agent / thiourethane resin) is 1.0 or more, the production of the polythiol composition can be further promoted.

[0192] When the input equivalent (decomposing agent / thiourethane resin) is 15.0 or less, the residual decomposing agent in the reaction mixture can be further suppressed.

[0193] (Tertiary amine compound as decomposition aid)

[0194] When the decomposition agent represented by the above formula (2) is used as the decomposition agent, in the production step, the thiourethane resin is preferably decomposed by the decomposition agent represented by the above formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce the polythiol composition.

[0195] The tertiary amine compound as the decomposition aid is not particularly limited except that it is a tertiary amine compound.

[0196] The tertiary amine compound as the decomposition aid may be a chain amine compound or a cyclic amine compound.

[0197] The molecular weight of the tertiary amine compound as the decomposition aid is preferably 1,000 or less, more preferably 500 or less, further preferably 300 or less, and further preferably 200 or less.

[0198] The lower limit of the molecular weight of the tertiary amine compound as the decomposition aid is, for example, 59 or more, and preferably 70 or more.

[0199] The tertiary amine compound as the decomposition aid is not particularly limited except that it is a tertiary amine compound.

[0200] Regarding tertiary amine compounds as decomposition aids,

[0201] Preferred are N,N-dimethylethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 4-(2-hydroxyethyl)morpholine, 1,4-diazabicyclo[2,2,2]octane, diazabicyclononene, or diazabicycloundecene,

[0202] More preferably, it is N,N-dimethylethanolamine, N,N-diethylaminoethanol, N-methyldiethanolamine, diisopropylethylamine, triisopropylamine, triisobutylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, dimethylpiperazine, 1-ethylpiperidine, 1,4-diazabicyclo[2,2,2]octane, diazabicyclononene, or diazabicycloundecene,

[0203] More preferred is N,N-dimethylethanolamine, diisopropylethylamine, N,N-dimethylcyclohexylamine, N-ethylmorpholine, or 1,4-diazabicyclo[2,2,2]octane.

[0204] The input mass ratio of the tertiary amine compound as a decomposition aid to the decomposition agent represented by the above formula (2) as a decomposition agent (ie, input mass ratio [decomposition aid / decomposition agent]) can be adjusted appropriately, but is preferably 0.001 to 2.00.

[0205] The input mass ratio [decomposition aid / decomposition agent] is more preferably 0.002 to 1.50, and even more preferably 0.004 to 1.20.

[0206] The charging molar ratio of the tertiary amine compound as a decomposition aid to the decomposition agent represented by the above formula (2) as a decomposition agent (ie, charging molar ratio [decomposition aid / decomposition agent]) can be adjusted appropriately, but is preferably 0.001 to 3.00.

[0207] The charging molar ratio [decomposition aid / decomposition agent] is more preferably 0.002 to 2.50, further preferably 0.003 to 2.00, further preferably 0.004 to 1.50, further preferably 0.004 to 1.00.

[0208] (Reaction solvent)

[0209] In the production step, the thiourethane resin is preferably reacted with the decomposition agent represented by the formula (1) or (2) in the presence of a reaction solvent.

[0210] The reaction solvent is preferably an organic solvent, more preferably a hydrocarbon compound having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9).

[0211] The hydrocarbon compound is preferably hexane, heptane, octane, nonane, decane, xylene, mesitylene or toluene, more preferably heptane, octane, nonane, xylene, mesitylene or toluene, particularly preferably xylene or toluene.

[0212] The reaction solvent may be one kind or two or more kinds.

[0213] (Reaction temperature)

[0214] The reaction temperature of the thiourethane resin and the decomposition agent represented by the formula (1) or (2) in the production step can be adjusted appropriately.

[0215] In the production step, the thiourethane resin is preferably brought into contact with the decomposition agent represented by formula (1) or (2) under temperature conditions (i.e., reaction temperature) of 50°C to 200°C (more preferably 60°C to 180°C, and even more preferably 70°C to 150°C).

[0216] When the reaction temperature is 50° C. to 200° C., the purity of the polythiol component as the main component in the target polythiol composition (that is, the content of the main component relative to the total amount of the polythiol composition) can be further increased.

[0217] (Reaction time)

[0218] The reaction time of the thiourethane resin and the decomposition agent represented by formula (1) or (2) in the production step can be adjusted appropriately, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and even more preferably 1 to 10 hours.

[0219] (Reaction pressure)

[0220] The production step preferably includes a step of reacting the thiourethane resin with the decomposition agent represented by formula (1) or (2) under a pressure higher than atmospheric pressure. This can further suppress the volatilization of the decomposition agent represented by formula (1) or (2).

[0221] In this case, the method includes reacting the thiourethane resin with the decomposition agent represented by formula (1) or (2) at a pressure preferably 0.01 MPa or higher (more preferably 0.01 MPa or higher and 2.0 MPa or lower, and further preferably 0.02 MPa or higher and 1.0 MPa or lower) higher than atmospheric pressure.

[0222] (Polythiol Composition as Target)

[0223] Examples of the polythiol composition that is the target product in the method for producing the polythiol composition according to the first embodiment include the same polythiol composition as the raw material of the thiourethane resin described above, and preferred embodiments are also the same.

[0224] The target polythiol composition and the polythiol composition of the raw material of the thiourethane resin as the starting material do not need to be completely the same.

[0225] However, from the viewpoint of the performance of the thiourethane resin produced using the target polythiol composition, the type of the polythiol component as the main component in the target polythiol composition and the type of the polythiol component as the main component in the polythiol composition as the raw material of the thiourethane resin as the starting material are preferably the same. In this case, for example, it is possible to produce an optical material B (optical material containing a thiourethane resin) having performance comparable to that of the optical material A using as a raw material the cutting chips (thiourethane resin) generated when producing the optical material A.

[0226] The target polythiol composition may have the same polythiol component as the raw material of the thiourethane resin as the starting material, and may have a reduced content of impurities.

[0227] When the content of impurities in the target polythiol composition is reduced, the thickening of the polythiol composition can be suppressed, and there is an advantage that the pot life of the polythiol composition is prolonged.

[0228] The use of the target polythiol composition is not particularly limited.

[0229] The target polythiol composition can be used, for example, in the production of thiourethane resin.

[0230] Specific uses of the target polythiol composition include polythiol compositions for producing optical materials (eg, eyeglass lenses).

[0231] (polyurea compound or polyurethane compound)

[0232] In the production step in the first embodiment, the thiourethane resin is decomposed by the decomposing agent to produce the polythiol composition, and also the polyurea compound or the polyurethane compound is produced.

[0233] Specifically, when a decomposition agent represented by formula (1) is used as the decomposition agent, a polythiol composition and a polyurea compound are generated by decomposing the thiourethane resin. The generation step in the method for producing the polythiol composition in this case may also correspond to the first step in the method for producing the polyamine compound according to the second embodiment described later.

[0234] When the decomposition agent represented by formula (2) is used as the decomposition agent, the polythiol composition and the polyurethane compound are generated by decomposing the thiourethane resin. The generation step in the method for producing the polythiol composition in this case may also correspond to step X1 in the method for producing the polyamine compound according to the third embodiment described below.

[0235] (Reaction mixture containing polythiol composition)

[0236] The generating step may be a step of generating a polythiol composition by decomposing the thiourethane resin with a decomposing agent, thereby obtaining a reaction mixture containing the target polythiol composition.

[0237] Examples of other components in the reaction mixture other than the polythiol composition include the aforementioned reaction solvent, residues of the raw materials (thiourethane resin and / or decomposition agent), impurities contained in the raw materials, the aforementioned polyurea compound, the aforementioned polyurethane compound, and the like.

[0238] <Separation process>

[0239] The method for producing the polythiol composition according to the first embodiment may include a separation step of separating the polythiol composition from the reaction mixture containing the polythiol composition produced in the generation step.

[0240] The separation method in the separation step is not particularly limited, and a known method can be applied.

[0241] Examples of the separation method in the separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (for example, column chromatography), etc. As the separation method, a plurality of methods may be used in combination.

[0242] The separation step preferably includes a step of filtering the reaction mixture containing the polythiol composition obtained in the reaction step to obtain a filtrate containing the polythiol composition.

[0243] According to this embodiment, it is easier to remove the solid components contained in the reaction mixture (for example, the solid components including by-products).

[0244] As one of the more preferred embodiments in which the separation step includes the step of obtaining a filtrate containing a polythiol composition, there can be mentioned an embodiment in which the separation step includes the following steps (hereinafter referred to as separation embodiment A):

[0245] A step of filtering the reaction mixture containing the polythiol composition to obtain a filtrate containing the polythiol composition;

[0246] a step of subjecting the filtrate comprising the polythiol composition to acid washing; and

[0247] A step of separating the polythiol composition from the filtrate after acid washing.

[0248] According to separation method A, the alkali component (for example, the residue of the amine compound) can be easily removed from the filtrate by acid washing, and therefore a polythiol composition having a higher purity of the polythiol component as a main component can be obtained.

[0249] In the separation method A, water washing may be added after the acid washing to separate the polythiol composition from the filtrate after the water washing.

[0250] In the separation method A, examples of the acid used in the acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, and oxalic acid.

[0251] As one of the more preferred embodiments in which the separation step includes the step of obtaining a filtrate containing a polythiol composition, there can be mentioned an embodiment in which the separation step includes the following steps (hereinafter referred to as separation embodiment B):

[0252] A step of filtering the reaction mixture containing the polythiol composition to obtain a filtrate containing the polythiol composition;

[0253] A step of adding a base containing an alkali metal to a filtrate containing a polythiol composition, followed by adding water and performing extraction, thereby obtaining a water extract containing an alkali metal salt of the polythiol composition;

[0254] A step of adding an acid to a water extract containing an alkali metal salt of a polythiol composition to obtain an aqueous liquid containing a polythiol composition;

[0255] a step of adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to an aqueous liquid containing a polythiol composition to perform extraction, thereby obtaining an extract containing the polythiol composition; and

[0256] The step of separating the polythiol composition from the extract containing the polythiol composition.

[0257] In separation method B, the polythiol composition in the filtrate containing the polythiol composition is first converted into an alkali metal salt, and then extracted with water to obtain an aqueous extract containing the alkali metal salt of the polythiol composition. Then, an acid is added thereto to restore the alkali metal salt of the polythiol composition to the polythiol composition. The polythiol composition is extracted from the obtained aqueous liquid containing the polythiol composition using the above-mentioned extraction solvent to obtain an extract containing the polythiol composition. The polythiol composition is separated from the obtained extract containing the polythiol composition.

[0258] According to the separation mode B, even when the filtrate containing the polythiol composition contains a large amount of components other than the polythiol composition, a polythiol composition having a higher purity of the polythiol component as a main component can be obtained.

[0259] In the separation method B, the alkali metal in the base containing an alkali metal is preferably sodium, potassium or lithium, and more preferably sodium or potassium.

[0260] Examples of the base composed of an alkali metal include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0261] The base including an alkali metal may be added to the filtrate in the form of an alcohol solution (methanol solution, ethanol solution, etc.) as necessary.

[0262] In the separation method B, examples of the acid added to the aqueous extract containing the alkali metal salt of the polythiol composition include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, and oxalic acid.

[0263] In the separation method B, the hydrocarbon compound used as the extraction solvent may be only one kind or two or more kinds.

[0264] In the separation method B, the preferred embodiment of the hydrocarbon compound as the extraction solvent is the same as the preferred embodiment of the hydrocarbon compound as the reaction solvent described above.

[0265] The reaction solvent and the extraction solvent may be the same or different.

[0266] As one of the more preferred embodiments in which the separation step includes the step of obtaining a filtrate containing a polythiol composition, there can be mentioned an embodiment in which the separation step includes the following steps (hereinafter referred to as separation embodiment C):

[0267] A step of separating the reaction mixture containing the polythiol composition by decantation to obtain a residue containing the polythiol composition;

[0268] A step of adding a base containing an alkali metal to a residue containing a polythiol composition, and then adding water to perform extraction, thereby obtaining a water extract containing an alkali metal salt of the polythiol composition;

[0269] A step of adding an acid to a water extract containing an alkali metal salt of a polythiol composition to obtain an aqueous liquid containing a polythiol composition;

[0270] a step of adding a hydrocarbon compound having 5 to 12 carbon atoms as an extraction solvent to an aqueous liquid containing a polythiol composition to perform extraction, thereby obtaining an extract containing the polythiol composition; and

[0271] The step of separating the polythiol composition from the extract containing the polythiol composition.

[0272] Separation method C is the same as separation step B except that a residue containing the polythiol composition is obtained by decantation.

[0273] <Classification process>

[0274] The method for producing the polythiol composition according to the first embodiment may further include a classification step of classifying the cutting chips containing the thiourethane resin before the reaction step. In this case, in the reaction step, the classified cutting chips are reacted with the decomposition agent represented by formula (1) or formula (2).

[0275] When the method for producing the polythiol composition involved in the first embodiment includes a classification step, in the reaction step, the cutting chips formed by particles with a small particle size (i.e., an average particle size) are brought into contact with the decomposition agent represented by formula (1) or formula (2), thereby further improving the reaction efficiency of the thiourethane resin and the decomposition agent represented by formula (1) or formula (2).

[0276] As the average particle diameter in the present disclosure, for example, a number average particle diameter can be mentioned.

[0277] As a particle diameter, an equivalent circle diameter is mentioned, for example.

[0278] Examples of the classification method include sieving and centrifugal separation.

[0279] Regarding the method of performing sieving as classification, the following sieving process can be referred to.

[0280] <Screening process>

[0281] The method for producing a polythiol composition according to the first embodiment may further include a sieving step of sieving the cutting chips containing the thiourethane resin before the generating step. In this case, in the generating step, the cutting chips passing through the sieve are brought into contact with the decomposing agent represented by the formula (1) or (2), thereby causing the thiourethane resin in the cutting chips passing through the sieve to react with the decomposing agent represented by the formula (1) or (2).

[0282] When the method for producing the polythiol composition involved in the first embodiment includes a screening step, in the generation step, the cutting chips formed by particles with a small particle size are brought into contact with the decomposition agent represented by formula (1) or formula (2), thereby further improving the reaction efficiency of the thiourethane resin and the decomposition agent represented by formula (1) or formula (2).

[0283] The above sieve is not particularly limited.

[0284] The nominal mesh size of the sieve as specified 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, further preferably 0.1 mm to 2 mm, further preferably 0.3 mm to 2 mm, further preferably 0.5 mm to 1.5 mm.

[0285] <Cleaning process>

[0286] The method for producing a polythiol composition according to the first embodiment may further include a washing step of washing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent before the generating step. In this case, in the reaction step, the thiourethane resin washed in the washing step is reacted with a decomposition agent represented by formula (1) or formula (2). Thus, a polythiol composition having a higher purity of the polythiol component as a main component can be obtained.

[0287] In particular, in the method for producing the polythiol composition involved in the first embodiment, when cutting chips containing a thiourethane resin are used as the starting material, the oil derived from the cutting machine adhering to the cutting chips can be effectively removed by the above-mentioned cleaning step, thereby obtaining a polythiol composition having a higher purity of the polythiol component as the main component.

[0288] The hydrocarbon compound used as the washing solvent may be only one kind or two or more kinds.

[0289] Preferred embodiments of the hydrocarbon compound as the washing solvent are the same as the preferred embodiments of the hydrocarbon compound as the reaction solvent described above.

[0290] The reaction solvent and the washing solvent may be the same or different.

[0291] The cleaning method in the cleaning step is not particularly limited, and a known method such as a method of adding the above-mentioned cleaning solvent to cutting chips containing thiourethane resin (for example, thiourethane resin chips) and mixing the mixture can be applied.

[0292] When the method for producing the polythiol composition according to the first embodiment includes the above-mentioned screening step and washing step, it is preferred to perform the screening step and washing step in sequence. In this case, it is not necessary to wash the cutting chips that have not passed through the screen, so the amount of washing solvent used can be further reduced.

[0293] [Method for producing polymerizable composition (first embodiment)]

[0294] The method for producing a polymerizable composition according to the first embodiment of the present disclosure includes the following steps:

[0295] a step of producing a polythiol composition by using the method for producing a polythiol composition according to the first embodiment; and

[0296] A step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate compound by mixing at least the polythiol composition and the polyisocyanate compound.

[0297] The method for producing the polymerizable composition according to the first embodiment may include other steps as necessary.

[0298] In the method for producing a polymerizable composition according to the first embodiment,

[0299] In the step of producing the polythiol composition, the polythiol composition is produced using a thiourethane resin (for example, a thiourethane resin in cutting scraps of a molded body of the thiourethane resin) as a starting material.

[0300] In the step of obtaining a polymerizable composition, a polymerizable composition containing the polythiol composition produced above and a polyisocyanate compound is produced.

[0301] The obtained polymerizable composition can be used again for the production of thiourethane resin.

[0302] As described above, in the method for producing the polymerizable composition according to the first embodiment, effective utilization (ie, recycling) of the materials (ie, the thiourethane resin and the polythiol composition as the raw material thereof) can be achieved.

[0303] Furthermore, according to the method for producing the polythiol composition of the first embodiment, a polythiol composition having a high purity of the polythiol component as a main component can be obtained compared with a known method (for example, a method of obtaining a polythiol composition by reacting a thiourethane resin with sodium hydroxide).

[0304] In the method for producing a polymerizable composition involved in the first embodiment, the above-mentioned polythiol composition is used. Therefore, according to the polymerizable composition obtained by the method for producing a polymerizable composition involved in the first embodiment, a resin excellent in various properties [for example, optical properties (for example, refractive index and / or Abbe number), heat resistance, specific gravity d, etc.] can be produced.

[0305] Therefore, the polymerizable composition obtained by the method for producing a polymerizable composition according to the first embodiment is particularly suitable as a composition for producing a thiourethane resin for an optical material.

[0306] <Step of producing a polythiol composition>

[0307] Regarding the step of producing the polythiol composition in the method for producing the polymerizable composition according to the first embodiment, the method for producing the polythiol composition according to the first embodiment described above can be appropriately referred to.

[0308] <Step of Obtaining a Polymerizable Composition>

[0309] In the step of obtaining the polymerizable composition, at least the polythiol composition and the polyisocyanate compound are mixed to obtain a polymerizable composition containing the polythiol composition and the polyisocyanate compound.

[0310] Preferred embodiments of the polyisocyanate compound used in the step of obtaining the polymerizable composition are the same as the preferred embodiments of the “isocyanate compound as a raw material of the thiourethane resin” described in the section “Method for producing a polythiol composition”.

[0311] In the step of obtaining the polymerizable composition, the mixing ratio of the polythiol composition and the polyisocyanate compound is not particularly limited.

[0312] In the step of obtaining the polymerizable composition, the ratio of the input mass of the polythiol composition to the input mass of the polyisocyanate compound (i.e., input mass [polythiol composition / polyisocyanate compound]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, further preferably 0.50 to 1.50, and further preferably 0.70 to 1.30.

[0313] The molar ratio of the mercapto group of the polythiol compound to the isocyanate group of the polyisocyanate compound (mercapto group / isocyanate group) 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.

[0314] In the step of obtaining the polymerizable composition, the total input mass of the polythiol composition and the polyisocyanate compound is not particularly limited, but is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, relative to the total amount of the polymerizable composition produced.

[0315] The step of obtaining the polymerizable composition may be a step of mixing a polythiol composition and a polyisocyanate composition containing a polyisocyanate compound to obtain a polymerizable composition containing a polythiol composition and a polyisocyanate composition.

[0316] Here, the polyisocyanate composition refers to a composition containing at least one polyisocyanate compound.

[0317] The polyisocyanate composition may contain components other than the polyisocyanate compound as impurities.

[0318] The polyisocyanate composition preferably contains at least one polyisocyanate compound as a main component.

[0319] The meaning of “comprising… as a main component” is as described above.

[0320] The polyisocyanate composition preferably comprises xylylene diisocyanate.

[0321] Hereinafter, a polyisocyanate composition containing xylylenediisocyanate is also referred to as an XDI composition.

[0322] The XDI composition preferably contains xylylene diisocyanate as a main component.

[0323] The XDI composition preferably contains at least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3).

[0324] [Chemical formula 6]

[0325]

[0326] Hereinafter, preferred embodiments of the XDI composition will be described from the viewpoint of achieving more excellent stability of the polyisocyanate composition and transparency of a resin formed using the polyisocyanate composition.

[0327] When the XDI composition contains the compound (N1), the peak area of ​​the compound (N1) in gas chromatography measurement under the following GC condition 1 is preferably 0.20 ppm or more relative to the peak area 1 of xylylenediisocyanate.

[0328] -GC Condition 1-

[0329] Filler: DB-1 (film thickness) 1.5 μm

[0330] Column: inner diameter 0.53 mm × length 60 m (manufactured by Agilent)

[0331] Column box temperature: increase from 130°C to 220°C at 3°C / min, and then increase to 300°C at 10°C / min after reaching 220°C.

[0332] Split ratio: Pulse splitless method

[0333] Inlet temperature: 280℃

[0334] Detector temperature: 300°C

[0335] Carrier gas: N2 158kPa, H2 55kPa, air 45kPa (constant pressure control)

[0336] Solvent: Chloroform

[0337] Sample concentration: 2.0 mass% chloroform solution

[0338] Injection volume: 2μL

[0339] Detection method: FID

[0340] The peak area of ​​the compound (N1) is more preferably 5.0 ppm or more, further preferably 50 ppm or more, and further preferably 100 ppm or more, relative to the peak area 1 of xylylenediisocyanate.

[0341] The peak area of ​​the compound (N1) is preferably 4000 ppm or less, more preferably 3000 ppm or less, further preferably 2000 ppm or less, further preferably 1500 ppm or less, further preferably 1000 ppm or less, relative to the peak area 1 of xylylenediisocyanate.

[0342] The peak area of ​​the compound (N1) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0343] When the XDI composition contains the compound (N2), the peak area of ​​the compound (N2) in gas chromatography measurement under the following GC condition 2 is preferably 0.05 ppm or more relative to the peak area 1 of xylylene diisocyanate.

[0344] -GC Condition 2-

[0345] Column: HP-50+, inner diameter 0.25 mm×length 30 m×film thickness 0.25 μm (manufactured by Hewlett-Packard)

[0346] Column box temperature: increase from 50°C to 280°C at 10°C / min, and maintain at 280°C for 6 min.

[0347] Split ratio: Pulse splitless method

[0348] Inlet temperature: 200℃

[0349] Detector temperature: 280°C

[0350] Carrier gas: He

[0351] Carrier gas flow rate: 1.0ml / min (constant flow control)

[0352] Sample concentration: 1.0 mass% dichloromethane solution

[0353] Injection volume: 1.0 μL

[0354] Detection method: SIM (monitoring ions: m / z 180, 215) (content ratio of xylylenediisocyanate (XDI))

[0355] The peak area of ​​the compound (N2) is more preferably 0.1 ppm or more, further preferably 0.3 ppm or more, and further preferably 0.6 ppm or more, relative to the peak area 1 of xylylenediisocyanate.

[0356] The peak area of ​​the compound (N2) is preferably 200 ppm or less, more preferably 150 ppm or less, further preferably 100 ppm or less, further preferably 80 ppm or less, further preferably 70 ppm or less, further preferably 60 ppm or less, relative to the peak area 1 of xylylenediisocyanate.

[0357] The peak area of ​​the compound (N2) can be measured according to the method described in paragraphs 0375 and 0376 of Japanese Patent No. 6373536.

[0358] When the XDI composition contains the compound (N3), the peak area of ​​the compound (N3) in the gas chromatography measurement under the above-mentioned GC condition 1 is preferably 0.10 ppm or more relative to the peak area 1 of xylylenediisocyanate.

[0359] The peak area of ​​the compound (N3) is more preferably 0.1 ppm or more, further preferably 3.0 ppm or more, and further preferably 5.0 ppm or more, relative to the peak area 1 of xylylenediisocyanate.

[0360] The peak area of ​​the compound (N3) is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 300 ppm or less, further preferably 100 ppm or less, further preferably 75 ppm or less, relative to the peak area 1 of xylylenediisocyanate.

[0361] The peak area of ​​the compound (N3) can be measured according to the method described in paragraph 0377 of Japanese Patent No. 6373536.

[0362] The acid content of the XDI composition is preferably 3000 ppm or less, more preferably 2000 ppm or less, further preferably 1000 ppm or less, further preferably 100 ppm or less, further preferably 50 ppm or less, further preferably 30 ppm or less, further preferably less than 15 ppm.

[0363] The lower limit of the acid content of the XDI composition is not particularly limited, and the lower limit is, for example, 1 ppm.

[0364] The acid content of the XDI composition can be measured according to the method described in paragraph 0091 of International Publication No. 2021 / 256417.

[0365] Additionally, the XDI composition may also contain a stabilizer.

[0366] In the step of obtaining the polymerizable composition, at least the polythiol composition and the polyisocyanate compound are mixed. If necessary, the polythiol composition and the polyisocyanate compound may be mixed with other components.

[0367] In addition, in the step of obtaining the polymerizable composition, after at least the polythiol composition and the polyisocyanate compound are mixed, other components may be added to the mixture.

[0368] Examples of these other components include polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, free radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, inorganic pigments, and the like.

[0369] Examples of the polymerization catalyst include tertiary amine compounds, inorganic acid salts or organic acid salts thereof, metal compounds, quaternary ammonium salts, and organic sulfonic acids.

[0370] As the internal mold release agent, an acidic phosphate ester can be used. Examples of the acidic phosphate ester include phosphoric acid monoesters and phosphoric acid diesters, and these can be used alone or in combination of two or more.

[0371] Examples of the resin modifier include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, olefin compounds including (meth)acrylate compounds, etc. Here, the (meth)acrylate compound refers to at least one of an acrylate compound and a methacrylate compound.

[0372] In the step of obtaining the polymerizable composition, the above-mentioned components can be mixed by a conventional method, and the mixing method is not particularly limited.

[0373] [Method for producing resin (first embodiment)]

[0374] The method for producing a resin according to the first embodiment of the present disclosure includes the following steps:

[0375] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the first embodiment; and

[0376] A step of obtaining a resin by curing the polymerizable composition.

[0377] The method for producing the resin according to the first embodiment may include other steps as necessary.

[0378] The resin produced by the method for producing a resin according to the first embodiment and the resin according to the first embodiment described below are both thiourethane resins, but are simply referred to as “resins” in the present disclosure to distinguish them from thiourethane resins which are one of the starting materials of the polythiol composition.

[0379] In the step of obtaining the resin, the resin is obtained by curing the polymerizable composition.

[0380] The curing of the polymerizable composition can be performed by polymerizing the monomers in the polymerizable composition (specifically, the polythiol composition and the polyisocyanate compound, hereinafter the same). As a pre-polymerization treatment, the polymerizable composition can be subjected to treatment such as filtration and degassing.

[0381] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the above-mentioned polymerizable composition can be appropriately set in consideration of the composition of the composition, the type and amount of the monomers in the composition, the type and amount of the polymerization catalyst in the composition, the properties of the mold when using the mold described later, etc.

[0382] Examples of the polymerization temperature include -50°C to 150°C and 10°C to 150°C.

[0383] Examples of the polymerization time include 1 hour to 200 hours and 1 hour to 80 hours.

[0384] In the step of obtaining the resin, the polymer obtained by polymerizing the monomers may be subjected to treatment such as annealing to obtain the resin.

[0385] Examples of the annealing temperature include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0386] [Method for producing molded article (first embodiment)]

[0387] A method for producing a molded article according to a first embodiment of the present disclosure is a method for producing a molded article containing a resin, and includes the following steps:

[0388] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the first embodiment; and

[0389] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0390] The method for producing the molded article according to the first embodiment may include other steps as necessary.

[0391] In the step of obtaining a molded article containing a resin, the molded article containing a resin is obtained by curing the polymerizable composition.

[0392] Preferred conditions for curing the polymerizable composition, that is, polymerization of the monomers in the polymerizable composition, may be appropriately referred to in the section "Method for producing the resin".

[0393] An example of the polymerization in this step is cast polymerization.

[0394] In cast polymerization, first, the polymerizable composition is injected into a mold held by a gasket, a tape, etc. At this time, a degassing treatment, a filtration treatment, etc. may be performed as necessary.

[0395] Next, the monomers in the polymerizable composition injected between the molding dies are polymerized, thereby curing the composition between the molding dies to obtain a cured product. Next, the cured product is removed from the molding dies to obtain a molded body containing a resin.

[0396] The polymerization of the monomers can be carried out by heating the polymerizable composition. The heating can be carried out, for example, using a heating device having a mechanism for heating a heating object in an oven, water, or the like.

[0397] [Method for producing optical material (first embodiment), method for producing lens (first embodiment)]

[0398] A method for producing an optical material (e.g., a lens) according to a first embodiment of the present disclosure is a method for producing an optical material (e.g., a lens) comprising a molded body, wherein the molded body comprises a resin, and the method comprises the following steps:

[0399] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the first embodiment; and

[0400] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0401] The method for producing the optical material (eg, lens, hereinafter the same) according to the first embodiment may include other steps as necessary.

[0402] The method for producing an optical material according to the first embodiment is an application of the method for producing a molded body according to the first embodiment.

[0403] For example, in the method for producing a molded product according to the first embodiment, by appropriately selecting the shape of the molding die used in the above-mentioned cast polymerization, a molded product suitable for use in an optical material (eg, lens) can be obtained.

[0404] Examples of the optical material include lenses (for example, eyeglass lenses, camera lenses, and polarizing lenses), light emitting diodes (LEDs), and the like.

[0405] The method for manufacturing an optical material (eg, a lens) according to the first embodiment may include the following steps: forming a coating layer on one or both surfaces of a molded body including a resin.

[0406] Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifog coat layer, an antifouling layer, and a water-repellent layer.

[0407] These coating layers may be formed individually or in multiple layers. When coating layers are formed on both sides, the same coating layers may be formed on each side, or different coating layers may be formed.

[0408] The components of the coating layer can be appropriately selected according to the purpose.

[0409] Examples of the components of the coating layer include resins (e.g., polyurethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, and the like.

[0410] Regarding the eyeglass lens and the coating layer, the description of known documents such as International Publication No. 2017 / 047745 can be appropriately referred to.

[0411] [Polymerizable composition (first embodiment)]

[0412] The polymerizable composition according to the first embodiment of the present disclosure contains a polythiol composition obtained by the method for producing a polythiol composition according to the first embodiment described above, and a polyisocyanate compound.

[0413] The polymerizable composition according to the first embodiment can be produced by the above-described method for producing a polymerizable composition according to the first embodiment.

[0414] Preferred aspects of the polymerizable composition according to the first embodiment can refer to the above-described method for producing the polymerizable composition according to the first embodiment as appropriate.

[0415] The input mass [polythiol composition / polyisocyanate compound] is replaced by the content mass ratio [polythiol composition / polyisocyanate compound], and the total input mass of the polythiol composition and the polyisocyanate compound is replaced by the total content mass of the polythiol composition and the polyisocyanate compound.

[0416] [Resin (first embodiment), molded article (first embodiment), optical material (for example, lens) (first embodiment)]

[0417] The resin according to the first embodiment of the present disclosure is a cured product of the polymerizable composition according to the first embodiment of the present disclosure described above.

[0418] The molded product according to the first embodiment of the present disclosure is a molded product including the resin according to the above-mentioned first embodiment.

[0419] The optical material (eg, lens) according to the first embodiment is an optical material (eg, lens) including the resin according to the first embodiment described above.

[0420] The resin involved in the first embodiment, the molded body involved in the first embodiment, and the optical material involved in the first embodiment (e.g., a lens) can be manufactured using the aforementioned method for manufacturing the resin involved in the first embodiment, the method for manufacturing the molded body involved in the first embodiment, and the method for manufacturing the optical material involved in the first embodiment (e.g., a lens), respectively.

[0421] The preferred methods of the resin involved in the first embodiment, the molded body involved in the first embodiment, and the optical material (such as a lens) involved in the first embodiment can refer to the aforementioned preferred methods of manufacturing the resin involved in the first embodiment, the molded body involved in the first embodiment, and the optical material (such as a lens) involved in the first embodiment, respectively.

[0422] <Preferred properties of resin or molded article>

[0423] From the viewpoint of heat resistance, the glass transition temperature Tg of the resin (or molded article) according to the first embodiment is preferably 70° C. or higher, more preferably 80° C. or higher, and even more preferably 85° C. or higher.

[0424] The glass transition temperature Tg may be 130° C. or lower, 120° C. or lower, or 110° C. or lower.

[0425] From the viewpoint of application to optical materials, the refractive index (ne) of the resin (or molded article) according to the first embodiment is preferably 1.500 or more, more preferably 1.540 or more, and even more preferably 1.590 or more.

[0426] The upper limit of the refractive index (ne) is not particularly limited, and is, for example, 1.750.

[0427] From the viewpoint of application to optical materials, the Abbe number of the resin (or molded article) according to the first embodiment is preferably 28 or more, and more preferably 30 or more.

[0428] The upper limit of the Abbe number is not particularly limited, and is, for example, 50, preferably 45.

[0429] From the viewpoint of application to optical materials, the specific gravity d of the resin (or molded article) according to the first embodiment is preferably 1.10 or more, and more preferably 1.20 or more.

[0430] The upper limit of the specific gravity d is not particularly limited, and is, for example, 1.50, and preferably 1.40.

[0431] <<Second Implementation Method>>

[0432] [Method for producing polyamine compound (second embodiment)]

[0433] The method for producing a polyamine compound according to the second embodiment includes the following steps:

[0434] A first step of decomposing a thiourethane resin using a decomposing agent represented by the following formula (1) to produce a polyurea compound; and

[0435] The second step is to decompose the polyurea compound using a decomposing agent represented by the following formula (3) to generate a polyamine compound.

[0436] [Chemical formula 7]

[0437]

[0438] In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (excluding R 1 and R 2 are all amino groups).

[0439] In formula (3), R 11 and R 12 Each independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0440] In the method for producing a polyamine compound according to the second embodiment, the decomposition agent represented by formula (1) is excellent in removability from the reaction system after the decomposition reaction in step 1. For example, the decomposition agent represented by formula (1) can be easily removed from the reaction system after the decomposition reaction in step 1 by volatilization, distillation, etc.

[0441] It is considered that the reason why such an effect can be obtained is that the decomposition agent represented by formula (1) is a compound having a low boiling point.

[0442] Here, the concept of "reaction system after the decomposition reaction in the first step" includes not only the reaction system after the first step and before the second step but also the reaction system after the first step and during and after the second step.

[0443] For example, the decomposition of the polyurea compound in the second step can generate the decomposition agent represented by formula (1) together with the target polyamine compound. In this case, the decomposition agent represented by formula (1) is also highly removable from the reaction system in and after the second step.

[0444] In the method for producing a polyamine compound according to the second embodiment, the decomposition agent represented by formula (3) is also excellent in removability from the reaction system after the decomposition reaction in the second step. For example, the decomposition agent represented by formula (3) can be easily removed from the reaction system after the decomposition reaction in the second step by volatilization, distillation, etc.

[0445] It is considered that the reason why such an effect can be obtained is that the decomposition agent represented by formula (3) is a compound having a low boiling point.

[0446] Hereinafter, each step that may be included in the method for producing a polyamine compound according to the second embodiment will be described.

[0447] <1st step>

[0448] The first step is a step of decomposing the thiourethane resin using the decomposing agent represented by the above formula (1) to generate a polyurea compound.

[0449] Regarding the first step, the generation step in the method for producing the polythiol composition according to the first embodiment can be referred to.

[0450] In the first step, the thiourethane resin is decomposed by the decomposing agent represented by the above formula (1), thereby generating a polyurea compound and the above-mentioned polythiol composition.

[0451] Preferred embodiments of the thiourethane resin and the decomposing agent represented by formula (1) in the first step are respectively the same as the preferred embodiments of the thiourethane resin and the decomposing agent represented by formula (1) in the method for producing a polythiol composition according to the first embodiment.

[0452] (Reaction pressure)

[0453] The first step preferably includes a step of reacting the thiourethane resin with the decomposition agent represented by the formula (1) under a pressure higher than the atmospheric pressure. This can further suppress the volatilization of the decomposition agent represented by the formula (1).

[0454] In this case, the process includes reacting the thiourethane resin with the decomposing agent represented by formula (1) at a pressure preferably 0.01 MPa or higher (more preferably 0.01 MPa or higher and 2.0 MPa or lower, and further preferably 0.02 MPa or higher and 1.0 MPa or lower) higher than atmospheric pressure.

[0455] (Polyurea Compounds)

[0456] The polyurea compound produced in the first step is an aminolysis product of the thiourethane resin produced by the reaction (ie, aminolysis) of the thiourethane resin and the decomposing agent represented by the formula (1).

[0457] The polyurea compound is a compound containing two or more urea bonds.

[0458] The polyurea compound is, for example, a polyurea compound having a structure in which all isocyanate groups in a polyisocyanate compound, which is one of the raw materials of the thiourea resin, react with the amino group or monoalkylamino group of the amine compound A to form a urea bond. In the present disclosure, the polyurea compound having the above structure is sometimes referred to as a urea body of a polyamine compound (e.g., meta-xylylenediisocyanate (XDI)) corresponding to a polyisocyanate compound as one of the raw materials, and an amine compound A (e.g., monoethanolamine (MEA)). Here, the so-called polyamine compound corresponding to the polyisocyanate compound refers to a compound in which all isocyanate groups in the polyisocyanate compound are replaced with amino groups. The polyamine compound corresponding to the polyisocyanate compound is the target in the method for producing the polyamine compound according to the second embodiment.

[0459] (First reaction step and first separation step)

[0460] The first step may include:

[0461] a reaction step of reacting a thiourethane resin with a decomposing agent represented by formula (1) to obtain a reaction mixture containing a polyurea mixture containing a polyurea compound; and

[0462] A separation step of separating a polyurea-containing mixture from the reaction mixture.

[0463] In this case, in the second step described later, the polyurea-containing mixture separated in the first separation step is mixed with the decomposing agent represented by formula (3), thereby reacting the polyurea compound in the polyurea-containing mixture with the decomposing agent represented by formula (3).

[0464] Here, the polyurea-containing mixture refers to a mixture of two or more urea compounds including a polyurea compound.

[0465] Hereinafter, the reaction mixture, the reaction step, and the separation step are also referred to as a first reaction mixture, a first reaction step, and a first separation step, respectively.

[0466] The preferred embodiment of the reaction in the first reaction step is as described above.

[0467] The separation method in the first separation step is not particularly limited, and a known method can be applied.

[0468] Examples of the separation method in the first separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (for example, column chromatography), etc. As the separation method, a plurality of methods may be used in combination.

[0469] When the polyurea-containing mixture is generated as a solid component in the first reaction step, the first separation step preferably includes filtering the first reaction mixture to obtain the polyurea-containing mixture as a filtrate. The obtained filtrate may be subjected to operations such as washing.

[0470] In this case, the filtrate obtained by filtering the first reaction mixture may contain a polythiol composition as a by-product generated by the aminolysis reaction (specifically, a by-product when the polyurea-containing mixture is a main product). For preferred embodiments of the polythiol composition as a by-product, the preferred embodiments of the polythiol composition as a raw material of the thiourethane resin described above can be appropriately referred to.

[0471] The polythiol composition produced as a by-product of the aminolysis reaction can be used as a raw material for producing a new thiourethane resin, thereby achieving effective utilization (ie, recycling) of the material.

[0472] In the case where the polyurea-containing mixture is generated in a liquid state and insoluble in the reaction solvent in the first reaction step, the first separation step preferably includes the steps of separating the supernatant and obtaining the polyurea-containing mixture as an extraction residue by a decantation method in which extraction and washing are repeated. The obtained extraction residue may be subjected to operations such as washing.

[0473] In this case, the supernatant may contain a polythiol composition as a by-product generated by the aminolysis reaction (specifically, a by-product when a polyurea-containing mixture is a main product). Regarding preferred embodiments of the polythiol composition as a by-product, the preferred embodiments of the polythiol composition as a raw material of the thiourethane resin described above can be appropriately referred to.

[0474] The polythiol composition produced as a by-product of the aminolysis reaction can be used as a raw material for producing a new thiourethane resin, thereby achieving effective utilization (ie, recycling) of the material.

[0475] In the first reaction step, when the polyurea-containing mixture is dissolved in the first reaction solvent, the first separation step preferably includes:

[0476] a step of filtering the first reaction mixture to obtain a filtrate,

[0477] a step of adding a base containing an alkali metal to the filtrate, followed by adding water and performing extraction, thereby removing the alkali metal salt of the polythiol composition as a by-product from the filtrate; and

[0478] A step of separating the polyurea-containing mixture from the filtrate from which the alkali metal salt has been removed.

[0479] The polyurea-containing mixture can be separated from the filtrate from which the alkali metal salt has been removed by, for example, concentration, drying or the like.

[0480] <Step 2>

[0481] The second step is a step of decomposing the polyurea compound produced in the first step by using a decomposing agent represented by formula (3) to produce a polyamine compound.

[0482] In the second step, the polyurea-containing mixture separated in the first separation step is mixed with the decomposing agent represented by the formula (3), thereby reacting the polyurea compound in the polyurea-containing mixture with the decomposing agent represented by the formula (3).

[0483] The reaction in the second step (second aminolysis) is superior to the known reaction of obtaining a polyamine compound by reacting a polyurea compound with sodium hydroxide in terms of the efficiency of producing the polyamine compound. As a result, the amount of polyamine compound produced can be increased compared to the case where the known reaction is applied. The above effect can be confirmed by analyzing the reaction mixture obtained in the second step using gas chromatography (GC).

[0484] (Reaction pressure)

[0485] The second step preferably includes a step of reacting the polyurea compound with the decomposition agent represented by formula (3) under a pressure higher than atmospheric pressure. This can further suppress the volatilization of the decomposition agent represented by formula (3).

[0486] In this case, the step of reacting the polyurea compound with the decomposition agent represented by formula (3) is included at a pressure higher than atmospheric pressure by preferably 0.01 MPa or more (more preferably 0.01 MPa or more and 2.0 MPa or less, and further preferably 0.02 MPa or more and 1.0 MPa or less).

[0487] (Decomposing agent represented by formula (3))

[0488] The decomposing agent represented by the formula (3) used in the second step is preferably ethylenediamine, N,N′-dimethylethylenediamine, 2-aminoethanol, or ethylene glycol.

[0489] In the second step, the charge equivalent of the decomposing agent represented by formula (3) to the polyurea compound (charge equivalent [decomposing agent represented by formula (3) / polyurea compound]) is preferably 0.1 to 50, more preferably 0.15 to 45, and even more preferably 0.2 to 40.

[0490] When the input equivalent (decomposing agent represented by formula (3) / polyurea compound) is 0.1 or more, the production of the polyamine compound can be further promoted.

[0491] When the input equivalent (decomposing agent represented by formula (3) / polyurea compound) is 50 or less, it is advantageous from the viewpoint of reducing the amount of the decomposing agent represented by formula (3) used.

[0492] In the second step, when the polyurea-containing mixture separated in the first separation step is mixed with the decomposing agent represented by formula (3) so that the polyurea compound in the polyurea-containing mixture reacts with the decomposing agent represented by formula (3), the total amount of the polyurea-containing mixture can be regarded as the polyurea compound to determine the input equivalent amount [decomposing agent represented by formula (3) / polyurea compound].

[0493] In the second step, the polyurea compound and the decomposition agent represented by formula (3) may be reacted in the absence of a reaction solvent. For example, a polyurea-containing mixture containing a polyurea compound and the decomposition agent represented by formula (3) may be directly mixed in the absence of a reaction solvent, thereby reacting the polyurea compound and the decomposition agent represented by formula (3) in the absence of a reaction solvent.

[0494] In the second step, the polyurea compound and the decomposition agent represented by the formula (3) may be reacted in the presence of a reaction solvent.

[0495] (Second reaction temperature)

[0496] The reaction temperature of the polyurea compound and the decomposition agent represented by the formula (3) in the second step (hereinafter also referred to as the second reaction temperature) can be adjusted as appropriate.

[0497] In the second step, the polyurea compound is reacted with the decomposition agent represented by formula (3) preferably under a temperature condition of 80°C to 200°C (more preferably 90°C to 200°C, further preferably 100°C to 200°C, further preferably 110°C to 190°C, further preferably 120°C to 180°C) (i.e., the second reaction temperature).

[0498] In the second step, the reaction may be carried out under pressure. When the reaction is carried out under pressure, the reaction time may be shortened.

[0499] (Second reaction time)

[0500] The reaction time of the polyurea compound and the decomposition agent represented by the formula (3) in the second step can be adjusted appropriately, and is preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours, and even more preferably 1 to 10 hours.

[0501] (Second Reaction Step and Second Separation Step)

[0502] The second step may include:

[0503] a reaction step of reacting the polyurea compound with a decomposing agent represented by the formula (3) to obtain a reaction mixture containing a polyamine compound; and

[0504] A separation step of separating the polyamine compound from the reaction mixture.

[0505] Hereinafter, the reaction mixture, the reaction step, and the separation step are also referred to as a second reaction mixture, a second reaction step, and a second separation step, respectively.

[0506] The preferred embodiment of the reaction in the second reaction step is as described above.

[0507] The separation method in the second separation step is not particularly limited, and a known method can be applied.

[0508] Examples of the separation method in the second separation step include filtration, decantation, washing, extraction, distillation, decompression (eg, vacuuming), purification (eg, column chromatography), etc. As the separation method, a plurality of methods may be used in combination.

[0509] As a preferred embodiment of the second separation step, there can be mentioned a method comprising the following steps (also referred to as "second separation method C"):

[0510] a step of extracting the polyamine compound from the second reaction mixture using a second extraction solvent to obtain an extract; and

[0511] The step of separating the polyamine compound from the extract.

[0512] In the second separation method C, the polyamine compound is not separated directly from the second reaction mixture, but is separated from the extract obtained by extracting the polyamine compound from the second reaction mixture. As a result, the separation yield of the polyamine compound finally obtained is further improved. Although the reason is not clear, it is believed that this is because the heterogeneity in the second separation step (specifically, the reaction of the polyamine compound returning to the polyurea compound) is further suppressed.

[0513] Another preferred embodiment of the second separation step includes an embodiment including a step of separating the polyamine compound from the second reaction mixture by distillation.

[0514] When the polyamine compound is separated from the second reaction mixture by distillation, the insoluble components may be removed from the second reaction mixture by filtration, and the polyamine compound may be separated from the second reaction mixture from which the insoluble components have been removed by distillation.

[0515] When the insoluble components are removed from the second reaction mixture by filtration, the second reaction mixture may be diluted before filtration, and the diluted second reaction mixture may be filtered.

[0516] Examples of the second extraction solvent in the second separation method C include hydrocarbon compounds.

[0517] For example, when a hydrocarbon compound is used as the second extraction solvent, the preferred embodiment of the hydrocarbon compound as the second extraction solvent may be the preferred embodiment of the hydrocarbon compound as the first reaction solvent described above. In this case, the hydrocarbon compound as the second extraction solvent may be the same as or different from the hydrocarbon compound as the first reaction solvent.

[0518] The operation of separating the polyamine compound from the extract in the second separation method C preferably includes distillation.

[0519] (Polyamine compound as target substance)

[0520] The polyamine compound that is the target product in the method for producing a polyamine compound according to the second embodiment is a decomposition product of a polyurea compound generated by a reaction between a polyurea compound and a decomposing agent represented by formula (3).

[0521] The target polyamine compound is preferably a polyamine compound corresponding to the polyisocyanate compound as a raw material of the thiourethane resin (which is the starting material in the first step) (specifically, a compound in which the isocyanate groups in the polyisocyanate compound are replaced with amino groups).

[0522] The target polyamine compound may be a compound containing two or more amino groups.

[0523] For the target polyamine compound,

[0524] Preferably, it contains a diamine compound containing two amino groups,

[0525] Preferably, the polyamine 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, toluenediamine, 4,4′-diphenylmethanediamine and phenylenediamine (hereinafter also referred to as “polyamine component A”),

[0526] More preferably, the polyamine component A is contained as a main component.

[0527] The target polyamine compound further 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(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane and 2,6-bis(aminomethyl)bicyclo-[2.2.1]-heptane (hereinafter also referred to as "polyamine component A1"),

[0528] More preferably, the polyamine component A1 is contained as a main component.

[0529] The target polyamine compound can be used for any purpose without any particular limitation, and can be used for various purposes.

[0530] The target polyamine compound can be used as a raw material of a polyisocyanate compound, for example.

[0531] The produced polyisocyanate compound can be used, for example, for the production of thiourethane resin or polyurethane resin.

[0532] Specific uses of the produced polyisocyanate compound include polyisocyanate compounds used for producing optical materials (eg, lenses).

[0533] In other words, as a specific example of the method for producing the polyamine compound according to the second embodiment, there can be cited a method for producing a polyamine compound as a raw material of a polyisocyanate compound for producing an optical material. In this specific example, when cutting chips containing a thiourethane resin generated when producing an optical material are used as a starting material, the recycling of the materials (thiourethane resin, polyisocyanate compound) can be effectively achieved.

[0534] <Other Processes>

[0535] The method for producing a polyamine compound according to the second embodiment may include other steps than those described above.

[0536] As other steps, there can be mentioned a classification step (for example, a screening step) and a washing step which may be included in the method for producing the polythiol composition according to the first embodiment.

[0537] [Method for producing polyisocyanate compound (second embodiment)]

[0538] The method for producing a polyisocyanate compound according to the second embodiment of the present disclosure includes the following steps:

[0539] a step of producing a polyamine compound by using the method for producing a polyamine compound according to the second embodiment; and

[0540] A step of reacting at least one of the polyamine compound and the hydrochloride of the polyamine compound with phosgene to obtain a polyisocyanate compound.

[0541] According to the method for producing a polyisocyanate compound, the target polyisocyanate compound can be obtained by using the thiourethane resin as a starting material, and therefore, recycling of materials (thiourethane resin and the polyisocyanate compound as the raw material thereof) can be achieved.

[0542] The use of the polyisocyanate compound produced by the method for producing a polyisocyanate compound according to the second embodiment is not particularly limited, and the polyisocyanate compound can be applied to various uses.

[0543] The polyisocyanate compound can be used, for example, in the production of thiourethane resin or polyurethane resin.

[0544] Specific examples of the target polyisocyanate compound include the same compounds as the specific examples of the “isocyanate compound as a raw material of the thiourethane resin” in the section “method for producing a polythiol composition”.

[0545] Specific uses of the target polyisocyanate compound include polyisocyanate compounds for producing optical materials (eg, lenses).

[0546] In other words, as a specific example of the method for producing the polyisocyanate compound involved in the second embodiment, a method for producing a polyisocyanate compound for producing an optical material can be cited. In this specific example, when cutting chips containing thiourethane resin generated when producing an optical material are used as a starting material, effective utilization (i.e., recycling) of the materials (thiourethane resin, polyisocyanate compound) can be effectively achieved.

[0547] In the step of obtaining the polyisocyanate compound, at least one of the polyamine compound and the hydrochloride of the polyamine compound is reacted with phosgene (hereinafter also referred to as "phosgene") to convert the amino group in the polyamine compound into an isocyanate group, thereby obtaining the polyisocyanate compound.

[0548] This reaction itself is known, and a known method for producing a polyisocyanate compound can be appropriately referred to.

[0549] [Method for producing polymerizable composition (second embodiment)]

[0550] The method for producing a polymerizable composition according to the second embodiment of the present disclosure includes the following steps:

[0551] a step of producing a polyisocyanate compound by using the method for producing a polyisocyanate compound according to the second embodiment; and

[0552] 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.

[0553] The method for producing the polymerizable composition according to the second embodiment may include other steps as necessary.

[0554] In the method for producing a polymerizable composition according to the second embodiment,

[0555] In the step of producing the polyisocyanate compound, the polyisocyanate compound is produced using a thiourethane resin (for example, a thiourethane resin in cutting chips of a molded body of the thiourethane resin) as a starting material.

[0556] In the step of obtaining a polymerizable composition, a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound produced above is produced.

[0557] The obtained polymerizable composition can be used again for the production of thiourethane resin.

[0558] As described above, in the method for producing the polymerizable composition according to the second embodiment, effective utilization (ie, recycling) of the materials (ie, the thiourethane resin and the polyisocyanate compound serving as the raw material thereof) can be achieved.

[0559] <Process for producing polyisocyanate compound>

[0560] Regarding the step of producing the polyisocyanate compound, the method for producing the polyisocyanate compound according to the second embodiment described above can be appropriately referred to.

[0561] <Step of Obtaining a Polymerizable Composition>

[0562] In the step of obtaining the polymerizable composition, at least the polyisocyanate compound and the active hydrogen compound are mixed to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound.

[0563] Examples of the active hydrogen compound include polythiol compounds, polyol compounds, and polyamine compounds.

[0564] The active hydrogen compound may be only one kind or two or more kinds.

[0565] As the active hydrogen compound, a polythiol composition is preferred.

[0566] Preferred embodiments of the polythiol composition as the active hydrogen compound are the same as the preferred embodiments of the “polythiol composition as a raw material of the thiourethane resin” described in the section “Method for producing a polyamine compound”.

[0567] In the step of obtaining the polymerizable composition, the mixing ratio of the active hydrogen compound and the polyisocyanate compound is not particularly limited.

[0568] In the step of obtaining the polymerizable composition, the ratio of the charged mass of the active hydrogen compound to the charged mass of the polyisocyanate compound (i.e., charged mass [active hydrogen compound / polyisocyanate compound]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, further preferably 0.50 to 1.50, and further preferably 0.70 to 1.30.

[0569] The molar ratio of the mercapto group of the polythiol compound to the isocyanate group of the polyisocyanate compound (mercapto group / isocyanate group) 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.

[0570] In the step 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 mass of the produced polymerizable composition.

[0571] In the step of obtaining the polymerizable composition, at least the polyisocyanate compound and the active hydrogen compound are mixed, and the polyisocyanate compound and the active hydrogen compound may be mixed with other components as necessary.

[0572] In the step of obtaining the polymerizable composition, after at least the polyisocyanate compound and the active hydrogen compound are mixed, other components may be added to the mixture.

[0573] Regarding other components, reference may be made to other components used in the method for producing the polymerizable composition according to the first embodiment.

[0574] In the step of obtaining the polymerizable composition, the above-mentioned components can be mixed by a conventional method, and the mixing method is not particularly limited.

[0575] [Method for producing resin (second embodiment)]

[0576] The method for producing a resin according to the second embodiment of the present disclosure includes the following steps:

[0577] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the second embodiment; and

[0578] A step of obtaining a resin by curing the polymerizable composition.

[0579] The method for producing a resin according to the second embodiment is the same as the method for producing a resin according to the first embodiment, except that the polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment instead of by the method for producing a polymerizable composition according to the first embodiment, and the preferred embodiments are also the same.

[0580] [Method for producing molded article (Second embodiment)]

[0581] A method for producing a molded article according to a second embodiment of the present disclosure is a method for producing a molded article containing a resin, and includes the following steps:

[0582] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the second embodiment; and

[0583] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0584] The method for producing a molded article according to the second embodiment is the same as the method for producing a molded article according to the first embodiment, except that the polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment instead of by the method for producing a polymerizable composition according to the first embodiment, and the preferred embodiments are also the same.

[0585] [Method for producing optical material (second embodiment), method for producing lens (second embodiment)]

[0586] A method for producing an optical material (e.g., a lens) according to a second embodiment of the present disclosure is a method for producing an optical material (e.g., a lens) comprising a molded body, wherein the molded body comprises a resin, and the method comprises the following steps:

[0587] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the second embodiment; and

[0588] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0589] The method for producing the optical material (eg, lens, hereinafter the same) according to the second embodiment may include other steps as necessary.

[0590] The method for producing an optical material (e.g., a lens) according to the second embodiment is the same as the method for producing an optical material (e.g., a lens) according to the first embodiment, except that the polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment instead of by the method for producing a polymerizable composition according to the first embodiment, and the preferred embodiment is also the same.

[0591] [Resin (Second Embodiment), Molded Article (Second Embodiment), Optical Material (For example, Lens) (Second Embodiment)]

[0592] The resin according to the second embodiment of the present disclosure is a cured product of the polymerizable composition according to the second embodiment of the present disclosure described above.

[0593] A molded product according to a second embodiment of the present disclosure is a molded product including the resin according to the above-described second embodiment.

[0594] The optical material (eg, lens) according to the second embodiment is an optical material (eg, lens) including the resin according to the second embodiment described above.

[0595] The resin, molded article, and optical material (e.g., lens) involved in the second embodiment are the same as the resin, molded article, and optical material (e.g., lens) involved in the first embodiment, except that the polymerizable composition is manufactured by the method for manufacturing a polymerizable composition involved in the second embodiment instead of by the method for manufacturing a polymerizable composition involved in the first embodiment, and the preferred embodiments are also the same.

[0596] 《Third Implementation Method》

[0597] [Method for producing polyamine compound (third embodiment)]

[0598] The method for producing a polyamine compound according to the third embodiment includes the following steps:

[0599] Step X1 of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polyurethane compound; and

[0600] Step X2 of decomposing the polyurethane compound using a decomposing agent represented by the following formula (3) to produce a polyamine compound.

[0601] [Chemical formula 8]

[0602] R 3 —OH (2)

[0603] In formula (2), R 3 It represents an alkyl group having 1 to 3 carbon atoms.

[0604] In formula (3), R 11 and R 12 Each independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

[0605] In the method for producing a polyamine compound according to the third embodiment, the decomposition agent represented by formula (2) is excellent in removability from the reaction system after the decomposition reaction in step X1. For example, the decomposition agent represented by formula (2) can be easily removed from the reaction system after the decomposition reaction in step X1 by volatilization, distillation, etc.

[0606] It is considered that the reason why such an effect can be obtained is that the above-mentioned decomposition agent is a compound with a low boiling point.

[0607] Here, the concept of “the reaction system after the decomposition reaction in step X1” includes not only the reaction system after step X1 and before step X2 but also the reaction system after step X1 and in step X2 and after step X2.

[0608] For example, the decomposition of the polyurethane compound in step X2 can generate a decomposition agent represented by formula (2) together with the target polyamine compound. In this case, the decomposition agent represented by formula (2) is also highly removable from the reaction system in and after step X2.

[0609] In the method for producing a polyamine compound according to the third embodiment, the decomposition agent represented by formula (3) is also excellent in removability from the reaction system after the decomposition reaction in step X2. For example, the decomposition agent represented by formula (3) can be easily removed from the reaction system after the decomposition reaction in step X2 by volatilization, distillation, etc.

[0610] It is considered that the reason why such an effect can be obtained is that the decomposition agent represented by formula (3) is a compound having a low boiling point.

[0611] Hereinafter, each step that may be included in the method for producing a polyamine compound according to the third embodiment will be described.

[0612] <Process X1>

[0613] Step X1 is a step of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polyurethane compound.

[0614] Regarding step X1, the generation step in the method for producing the polythiol composition according to the first embodiment can be referred to.

[0615] In step X1, the thiourethane resin is decomposed by a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid, thereby generating a polyurethane compound and the aforementioned polythiol composition.

[0616] Preferred embodiments of the thiourethane resin, the decomposition agent represented by formula (2), and the tertiary amine compound as a decomposition aid in step X1 are the same as the preferred embodiments of the thiourethane resin, the decomposition agent represented by formula (2), and the tertiary amine compound as a decomposition aid in the method for producing the polythiol composition involved in the first embodiment.

[0617] (Reaction pressure)

[0618] Step X1 preferably includes the step of reacting the thiourethane resin with the decomposition agent represented by formula (2) in the presence of a tertiary amine compound as a decomposition aid at a pressure higher than atmospheric pressure. This can further suppress the volatilization of the decomposition agent represented by formula (2).

[0619] In this case, the process includes reacting the thiourethane resin with the decomposing agent represented by formula (2) at a pressure preferably 0.01 MPa or higher (more preferably 0.01 MPa or higher and 2.0 MPa or lower, and further preferably 0.02 MPa or higher and 1.0 MPa or lower) higher than atmospheric pressure.

[0620] (Polyurethane compound)

[0621] The polyurethane compound produced in step X1 is an alcoholysis product of the thiourethane resin produced by the reaction (ie, alcoholysis) of the thiourethane resin and the decomposing agent represented by formula (2).

[0622] The polyurethane compound is a compound including two or more urethane bonds (ie, urethane bonds) (ie, a polyurethane compound).

[0623] For example, a polyurethane compound is a polyurethane compound (i.e., a polyurethane compound) having a structure in which all isocyanate groups in a polyisocyanate compound, which is one of the raw materials of a thiourethane resin, react with a hydroxyl group of an alcohol compound to form a carbamate bond (i.e., an urethane bond). In the present disclosure, a polyurethane compound having the above structure is sometimes referred to as a carbamate of a polyamine compound (e.g., XDA) corresponding to a polyisocyanate compound (e.g., XDI) as one of the raw materials and an alcohol compound (e.g., 1-octanol). Here, the so-called polyamine compound corresponding to a polyisocyanate compound refers to a compound in which all isocyanate groups in a polyisocyanate compound are replaced with amino groups. The polyamine compound corresponding to a polyisocyanate compound is the target in the method for producing a polyamine compound according to the third embodiment.

[0624] (Reaction step X1 and separation step X2)

[0625] Step X1 may include:

[0626] a reaction step of reacting the thiourethane resin with a decomposing agent represented by the formula (2) to obtain a reaction mixture containing a polyurethane-containing mixture containing a polyurethane compound; and

[0627] A separation step of isolating a mixture containing polyurethane from the reaction mixture.

[0628] In this case, in step X2 described later, the polyurethane-containing mixture separated in the above-mentioned separation step is mixed with the decomposition agent represented by formula (3), thereby reacting the polyurethane compound in the polyurethane-containing mixture with the decomposition agent represented by formula (3).

[0629] Here, the polyurethane-containing mixture refers to a mixture of two or more types of carbamate compounds containing a polyurethane compound.

[0630] Hereinafter, the reaction mixture, the reaction step, and the separation step are also referred to as a reaction mixture X1, a reaction step X1, and a separation step X2, respectively.

[0631] Preferred conditions for the reaction step X1 are as described above.

[0632] The reaction mixture produced in the reaction step X1 may contain the polyurethane-containing mixture as a main product produced by alcoholysis and other components other than the polyurethane-containing mixture.

[0633] Examples of other components include by-products generated by alcoholysis (for example, a polythiol composition), the aforementioned reaction solvent, residues of the raw materials (thiourethane resin and / or alcohol compound), and impurities contained in the raw materials.

[0634] Regarding the preferred embodiment of the polythiol composition as a by-product, the preferred embodiment of the polythiol composition as a raw material of the thiourethane resin described above can be appropriately referred to.

[0635] The polythiol composition produced as a by-product of the alcoholysis reaction can be used as a raw material for producing new thiourethane resins, thereby enabling the recycling of materials.

[0636] The separation method in the separation step X2 is not particularly limited, and a known method can be applied.

[0637] Examples of the separation method in the separation step X2 include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (eg, column chromatography), etc. As the separation method, a plurality of methods may be used in combination.

[0638] For example, as a preferred embodiment of the separation step X2, there can be mentioned a method comprising the following steps (hereinafter referred to as separation method X1):

[0639] A step of filtering the reaction mixture X1 to obtain a filtrate;

[0640] The step of washing the filtrate with an acid and then washing with water;

[0641] a step of adding a base containing an alkali metal to the filtrate washed with water, followed by washing with water to remove salts (for example, an alkali metal salt of the polythiol composition as a reaction by-product); and

[0642] A step of separating the polyurethane-containing mixture from the filtrate from which the salts have been removed.

[0643] In separation method X1, first, the filtrate is washed with an acid (hereinafter also referred to as acid washing) to remove amines (for example, tertiary amine compounds) from the filtrate. Examples of the acid used for acid washing include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, and oxalic acid.

[0644] Next, the filtrate after the acid washing is washed with water to remove the acid from the filtrate. At the stage where the acid has been removed, the filtrate contains the target polyurethane-containing mixture, but it is considered that it may also contain a polythiol composition as a by-product.

[0645] In separation method X1, a base containing an alkali metal is added to the filtrate washed with water, thereby converting the polythiol composition in the filtrate into an alkali metal salt. Then, the filtrate is washed with water to remove the alkali metal salt of the polythiol composition from the filtrate.

[0646] In separation mode X1, the polyurethane-containing mixture is separated from the filtrate from which the alkali metal salt of the polythiol composition has been removed by a known method.

[0647] In separation mode X1, the alkali metal in the base containing an alkali metal is preferably sodium, potassium or lithium, and more preferably sodium or potassium.

[0648] Examples of the base composed of an alkali metal include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0649] The base including an alkali metal may be added to the filtrate in the form of an alcohol solution (methanol solution, ethanol solution, etc.) as necessary.

[0650] In separation method X1, before the filtrate obtained by filtering the reaction mixture X1 is washed with an acid, a solvent (hereinafter also referred to as separation solvent X1) may be added to the filtrate, and the filtrate to which the separation solvent X1 has been added may be sequentially washed with acid and with water.

[0651] As the separation solvent X1, the same solvent as the reaction solvent may be used, or an alcohol solvent may be used.

[0652] Furthermore, when a reaction solvent is used in the reaction step X1, the addition of the separation solvent X1 to the filtrate may be omitted.

[0653] <Process X2>

[0654] Step X2 is a step of decomposing the polyurethane compound produced in step X1 with a decomposing agent represented by formula (3) to produce a polyamine compound.

[0655] In step X2, the polyurethane-containing mixture separated in the separation step X2 can be mixed with the decomposition agent represented by formula (3) to react the polyurethane compound in the polyurethane-containing mixture with the decomposition agent represented by formula (3).

[0656] The reaction in step X2 is superior to the known reaction of obtaining a polyamine compound by reacting a polyurethane compound with sodium hydroxide in terms of the efficiency of producing the polyamine compound. As a result, the amount of polyamine compound produced can be increased compared to the case where the known reaction is applied. The above effect can be confirmed by analyzing the reaction mixture obtained in step X2 using gas chromatography (GC).

[0657] Step X2 in the method for producing a polyamine compound according to the third embodiment is the same as step 2 in the method for producing a polyamine compound according to the third embodiment, excluding the point that the object of decomposition caused by the decomposition agent represented by formula (3) is not the polyurea compound produced in the first step of the second embodiment but the polyurethane compound produced in step X1 of the third embodiment, and the preferred embodiment is also the same.

[0658] (Reaction pressure)

[0659] Step X2 preferably includes a step of reacting the polyurethane compound with the decomposition agent represented by formula (3) under a pressure higher than atmospheric pressure. This can further suppress the volatilization of the decomposition agent represented by formula (3).

[0660] In this case, the step of reacting the polyurethane compound with the decomposition agent represented by formula (3) is included under a pressure preferably 0.01 MPa or higher (more preferably 0.01 MPa or higher and 2.0 MPa or lower, and further preferably 0.02 MPa or higher and 1.0 MPa or lower) higher than atmospheric pressure.

[0661] (Polyamine compound as target substance)

[0662] The polyamine compound that is the target product in the method for producing a polyamine compound according to the third embodiment is a decomposition product of a thiourethane resin generated by a reaction between a polyurethane compound and a decomposition agent represented by the formula (3).

[0663] The target polyamine compound is preferably a polyamine compound corresponding to the polyisocyanate compound as a raw material of the thiourethane resin (which is the starting material in step X1) (specifically, a compound in which the isocyanate groups in the polyisocyanate compound are replaced with amino groups).

[0664] Preferred embodiments and preferred uses of the target polyamine compound in the third embodiment are the same as the preferred embodiments and preferred uses of the target polyamine compound in the third embodiment, respectively.

[0665] <Other Processes>

[0666] The method for producing a polyamine compound according to the third embodiment may include other steps than those described above.

[0667] As other steps, there can be mentioned a classification step (for example, a screening step) and a washing step which may be included in the method for producing the polythiol composition according to the first embodiment.

[0668] [Method for producing polyisocyanate compound (third embodiment)]

[0669] The method for producing a polyisocyanate compound according to the third embodiment of the present disclosure includes the following steps:

[0670] a step of producing a polyamine compound by using the method for producing a polyamine compound according to the third embodiment; and

[0671] A step of reacting at least one of the polyamine compound and the hydrochloride of the polyamine compound with phosgene to obtain a polyisocyanate compound.

[0672] The method for producing a polyisocyanate compound according to the third embodiment is the same as the method for producing a polyisocyanate compound according to the second embodiment, except that the polyamine compound is produced by the method for producing a polyamine compound according to the third embodiment instead of by the method for producing a polyamine compound according to the second embodiment, and the preferred embodiment is also the same.

[0673] [Method for producing polymerizable composition (second embodiment)]

[0674] The method for producing a polymerizable composition according to the third embodiment of the present disclosure includes the following steps:

[0675] a step of producing a polyisocyanate compound by using the method for producing a polyisocyanate compound according to the third embodiment; and

[0676] 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.

[0677] The method for producing a polymerizable composition according to the third embodiment is the same as the method for producing a polymerizable composition according to the second embodiment, except that the polyisocyanate compound is produced by the method for producing a polyisocyanate compound according to the third embodiment instead of by the method for producing a polyisocyanate compound according to the second embodiment, and the preferred embodiment is also the same.

[0678] [Method for producing resin (third embodiment)]

[0679] The method for producing a resin according to the third embodiment of the present disclosure includes the following steps:

[0680] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the third embodiment; and

[0681] A step of obtaining a resin by curing the polymerizable composition.

[0682] The method for producing a resin according to the third embodiment is the same as the method for producing a resin according to the second embodiment, except that the polymerizable composition is produced by the method for producing a polymerizable composition according to the third embodiment instead of by the method for producing a polymerizable composition according to the second embodiment, and the preferred embodiments are also the same.

[0683] [Method for producing molded article (Second embodiment)]

[0684] A method for producing a molded article according to a second embodiment of the present disclosure is a method for producing a molded article containing a resin, and includes the following steps:

[0685] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the second embodiment; and

[0686] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0687] The method for producing a molded article according to the second embodiment is the same as the method for producing a molded article according to the first embodiment, except that the polymerizable composition is produced by the method for producing a polymerizable composition according to the second embodiment instead of by the method for producing a polymerizable composition according to the first embodiment, and the preferred embodiments are also the same.

[0688] [Method for producing optical material (third embodiment), method for producing lens (third embodiment)]

[0689] A method for producing an optical material (e.g., a lens) according to a third embodiment of the present disclosure is a method for producing an optical material (e.g., a lens) comprising a molded body, wherein the molded body comprises a resin, and the method comprises the following steps:

[0690] a step of producing a polymerizable composition by using the method for producing a polymerizable composition according to the third embodiment; and

[0691] A step of obtaining a molded product containing a resin by curing the polymerizable composition.

[0692] The method for producing an optical material (e.g., a lens) according to the third embodiment is the same as the method for producing an optical material (e.g., a lens) according to the second embodiment, except that the polymerizable composition is produced by the method for producing a polymerizable composition according to the third embodiment instead of by the method for producing a polymerizable composition according to the second embodiment, and the preferred embodiment is also the same.

[0693] [Resin (third embodiment), molded article (third embodiment), optical material (for example, lens) (third embodiment)]

[0694] The resin according to the third embodiment of the present disclosure is a cured product of the polymerizable composition according to the third embodiment of the present disclosure described above.

[0695] The molded product according to the third embodiment of the present disclosure is a molded product including the resin according to the third embodiment described above.

[0696] The optical material (eg, lens) according to the third embodiment is an optical material (eg, lens) including the resin according to the third embodiment described above.

[0697] The resin, molded article, and optical material (e.g., lens) involved in the third embodiment are the same as the resin, molded article, and optical material (e.g., lens) involved in the second embodiment, except that the polymerizable composition is manufactured by the method for manufacturing a polymerizable composition involved in the third embodiment instead of by the method for manufacturing a polymerizable composition involved in the second embodiment, and the preferred embodiments are also the same.

[0698] Example

[0699] Hereinafter, examples of the present disclosure will be described, but the present disclosure is not limited to the following examples.

[0700] Hereinafter, "part" is based on mass, and "room temperature" is 25°C unless otherwise specified.

[0701] <Resin Performance Test>

[0702] As a performance test of the resin, a performance test of a flat plate-shaped molded body having a thickness of 2.5 mm was carried out.

[0703] The items of the performance test are as follows.

[0704] Yellowness (Yellow Index; YI)

[0705] The yellowness was measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc.

[0706] L*, a*, and b*

[0707] Using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc., L*, a*, and b* in the CIE 1976 (L*, a*, b*) colorimetric system were measured.

[0708] Refractive index (ne) and Abbe number (νe)

[0709] The refractive index (ne, nF', nC') at each wavelength of 546.1 nm (mercury e-line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line) was measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation at 20° C. Based on these measurement results, the refractive index (ne) and the Abbe number (νe) were obtained.

[0710] Heat resistance

[0711] The glass transition temperature (Tg) was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min) as an indicator of heat resistance.

[0712] Specific gravity d

[0713] The measurement was performed at 20°C using the Archimedes method.

[0714] [Reference Production Example 1]

[0715] <Production of Molded Article Containing Thiourethane Resin R1>

[0716] In a stirred flask add:

[0717] Dibutyltin dichloride as a polymerization catalyst (100 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition),

[0718] Zelec-UN (produced by Stepan; acidic phosphate ester) as a release agent (1000 ppm by mass relative to the total amount of the polyisocyanate compound and the polythiol composition),

[0719] meta-xylylene diisocyanate (XDI) (52 parts by mass) as a polyisocyanate compound, and

[0720] A polythiol composition (A) (48 parts by mass) having 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (ie, polythiol component A1) as a main component;

[0721] The mixture was stirred and mixed at room temperature (25° C.) for 1 hour to obtain a polymerizable composition as a transparent uniform solution. Here, the polythiol composition (A) used was the polythiol composition produced in Reference Production Example 3 described later.

[0722] Next, the polymerizable composition was filtered under reduced pressure using a PTFE (polytetrafluoroethylene) filter, and then fully degassed under a reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was injected between a pair of glass molds fixed with tape, and then the pair of glass molds were placed in an oven, and the temperature in the oven was set to 10°C. Next, the temperature in the oven was raised from 10°C to 120°C over 38 hours. Through the above process, the monomers (polyisocyanate compounds and polythiol compositions) in the degassed polymerizable composition were polymerized to form a molded body containing the thiourethane resin R1 (i.e., a cured product of the polymerizable composition) between a pair of glass molds (9.0 mm thick).

[0723] Next, the oven is cooled, and after cooling, the pair of glass molds are taken out of the oven, and then the molded body is taken out from the pair of glass molds to obtain a molded body.

[0724] [Reference Production Example 2]

[0725] <Manufacturing of Thiourethane Resin Chips R1>

[0726] A lens was produced by cutting the molded article obtained in Reference Production Example 1. Cutting chips generated at this time were collected to obtain thiourethane resin chips R1 (ie, resin chips containing thiourethane resin R1).

[0727] [Reference Production Example 3]

[0728] <Production of Polythiol Composition (A)>

[0729] 125.4 parts by mass of 2-mercaptoethanol and 18.3 parts by mass of deaerated water were placed in the reactor. 99.8 parts by mass of a 32% sodium hydroxide aqueous solution was added dropwise at 12°C to 35°C over 40 minutes, and then 73.8 parts by mass of epichlorohydrin was added dropwise at 29°C to 36°C over 4 hours, and stirring was continued for 30 minutes. The formation of 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed based on NMR data.

[0730] Into the reactor where the production of 1,3-bis(2-hydroxyethylthio)-2-propanol was confirmed, 332.0 parts by mass of 36% hydrochloric acid was charged, and then 183.8 parts by mass of thiourea with a purity of 99.9% was charged, and the mixture was stirred at reflux at 110°C for 3 hours to perform a thiourea salting reaction. After the thiourea salting reaction, the reactor was cooled to 45°C, and then 355.0 parts by mass of toluene was added thereto, and then cooled to 30°C, and then 244.6 parts by mass of a 25% aqueous ammonia solution was charged at 30°C to 40°C over 44 minutes, and then stirred at 54°C to 62°C for 3 hours to perform a hydrolysis reaction. Through the hydrolysis reaction, a toluene solution of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as a main component was obtained.

[0731] To the obtained toluene solution, 147.8 parts by mass of 36% hydrochloric acid was added, and acid washing was performed at 35°C to 40°C for 1 hour. After the acid washing, the aqueous phase was taken out, and then 147.8 parts by mass of degassed water was added to the remaining organic phase, and washing was performed once at 35°C to 40°C for 10 minutes. 147.8 parts by mass of 0.1% ammonia water was added to the organic phase after washing with degassed water, and washing was performed for 10 minutes. 147.8 parts by mass of degassed water was added to the organic phase after washing with ammonia water, and washing was performed twice at 35°C to 40°C for 10 minutes. Toluene and a trace amount of water were removed from the organic phase after washing twice under heating and reduced pressure, and then reduced pressure filtration was performed using a 3.0 μm PTFE type membrane filter, thereby obtaining 200.0 parts by mass of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as the main component.

[0732] The purity of the polythiol component A1 in the polythiol composition (A) obtained in Reference Production Example 3 was 91.6%.

[0733] [Example 1]

[0734] <Decomposition of Thiourethane Resin (Amine Decomposition by Ammonia as Decomposing Agent Represented by Formula (1))>

[0735] In a 100 mL pressure-resistant reaction vessel manufactured by San Ai Chemical Co., Ltd., add:

[0736] Thiourethane resin chips R1 (18.0 g) obtained in Reference Preparation Example 2,

[0737] Toluene (31.9 g), and

[0738] 25% ammonia water (10.1 g) (corresponding to 0.15 mol of ammonia as the decomposing agent represented by formula (1));

[0739] After obtaining the reaction solution, the reaction container was sealed by filling it with nitrogen.

[0740] Next, the reaction solution in the reaction container was heated to 90° C. in a sealed state, and stirred for 6 hours under a pressure condition that was 0.01 MPa or more higher than the atmospheric pressure, thereby performing a decomposition reaction of the thiourethane resin.

[0741] After the decomposition reaction was completed, the reaction solution was cooled to room temperature and filtered under reduced pressure.

[0742] By the reduced pressure filtration, 10.1 g (yield: 91.4%) of a polyurea compound B1 was obtained as a filtrate, and a toluene solution containing a polythiol composition was obtained as a filtrate.

[0743] Here, both the polyurea compound B1 and the polythiol composition are decomposition products generated by aminolysis of the thiourethane resin chips R1.

[0744] During the above-mentioned vacuum filtration process, ammonia as the decomposing agent represented by formula (1) is volatilized and easily removed from the reaction system.

[0745] To the filtrate (i.e., the toluene solution containing the polythiol composition), 30.0 g of a 35% hydrochloric acid aqueous solution was added to perform acid washing. After the acid washing, 30.0 g of degassed water was added to the toluene solution to perform water washing, and after the water washing was performed twice, 12.4 g of a 32% sodium hydroxide aqueous solution and 20 g of degassed water were added in sequence to obtain an aqueous solution containing an alkali metal salt of polythiol as an aqueous phase.

[0746] The aqueous solution containing the alkali metal salt of polythiol was washed twice with 20.0 g of toluene. Then, 40.0 g of toluene was added to the washed aqueous solution, and then 30.0 g of a 35% hydrochloric acid aqueous solution was added to neutralize it. The aqueous phase was taken out from the neutralized liquid, and 30.0 g of degassed water was added to the remaining organic phase, and the separation and washing were performed twice, thereby obtaining a toluene solution in which the polythiol composition was dissolved.

[0747] After removing toluene and a trace amount of water from the obtained toluene solution under heating and reduced pressure, the solution was filtered under reduced pressure using a 3.0 μm PTFE membrane filter to obtain 6.9 g (yield: 79.9%) of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as the main component.

[0748] [Example 2]

[0749] <Decomposition of Thiourethane Resin (Amine Decomposition by Methylamine as Decomposing Agent Represented by Formula (1))>

[0750] The same operation as in Example 1 was performed except that the "25% ammonia water (10.1 g) (equivalent to 0.15 mol of ammonia as the decomposition agent represented by formula (1))" in Example 1 was changed to "40% methylamine aqueous solution (1.6 g) (equivalent to 0.15 mol of methylamine as the decomposition agent represented by formula (1))".

[0751] In Example 2, by filtration under reduced pressure after the decomposition reaction, 10.9 g (yield: 87.6%) of polyurea compound B2 was obtained as a filtrate, and a toluene solution containing a polythiol composition was obtained as a filtrate.

[0752] Here, both the polyurea compound B2 and the polythiol composition are decomposition products generated by aminolysis of the thiourethane resin chips R1.

[0753] During the above-mentioned vacuum filtration process, the methylamine as the decomposition agent represented by the formula (1) is volatilized and easily removed from the reaction system.

[0754] The toluene solution containing the polythiol composition was treated in the same manner as in Example 1 to obtain 7.01 g (yield: 81.1%) of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as a main component.

[0755] [Example 3]

[0756] <Decomposition of Thiourethane Resin (Amine Decomposition by Dimethylamine as Decomposing Agent Represented by Formula (1))>

[0757] The same operation as in Example 1 was performed except that the "25% ammonia water (10.1 g) (equivalent to 0.15 mol of ammonia as the decomposition agent represented by formula (1))" in Example 1 was changed to "13.4 g of 50% dimethylamine aqueous solution (equivalent to 0.15 mol of dimethylamine as the decomposition agent represented by formula (1))".

[0758] In Example 3, after the decomposition reaction was completed, separation and extraction were performed to obtain an aqueous solution of polyurea compound B3, and water was distilled off from the obtained aqueous solution to obtain 12.8 g (yield: 95.0%) of polyurea compound B3. By the separation and extraction, a toluene solution containing a polythiol composition was obtained as an organic phase.

[0759] Here, both the polyurea compound B2 and the polythiol composition are decomposition products generated by aminolysis of the thiourethane resin chips R1.

[0760] In the above-mentioned separation and extraction process, dimethylamine as the decomposition agent represented by formula (1) is removed from the reaction system.

[0761] [Example 4]

[0762] <Decomposition of Thiourethane Resin (Alcoholysis by Methanol as Decomposition Agent Represented by Formula (2))>

[0763] In a 100 mL pressure-resistant reaction vessel manufactured by San Ai Chemical Co., Ltd., add:

[0764] Referring to the thiourethane resin R1 (18.0 g) obtained in Preparation Example 2,

[0765] 31.8 g (1.0 mol) of methanol as a decomposition agent represented by formula (2), and

[0766] 1,4-diazabicyclo-[2,2,2]-octane (1.1 g; 0.010 mol) as tertiary amine (decomposition aid);

[0767] After obtaining the reaction solution, the reaction container was sealed by filling it with nitrogen.

[0768] Next, the reaction solution in the reaction container was heated to 150° C. in a sealed state, and stirred for 9 hours under a pressure condition that was 0.01 MPa or more higher than the atmospheric pressure, thereby performing a decomposition reaction of the thiourethane resin.

[0769] After the decomposition reaction was completed, insoluble matter was removed from the reaction solution by filtration under reduced pressure, and then 30.0 g of 2-octanol was added thereto, and further 30.0 g of a 35% hydrochloric acid aqueous solution was added thereto to perform acid washing. The reaction solution after the acid washing was washed with water by adding 30.0 g of degassed water, and this water washing was repeated twice, and then 12.4 g of a 32% sodium hydroxide aqueous solution and 20 g of degassed water were added in sequence to obtain an organic phase and an aqueous phase.

[0770] The alcohol solution in which the polyurethane compound was dissolved was recovered as an organic phase, and the solvent was distilled off from the recovered organic phase under heating and reduced pressure to obtain 7.10 g (yield: 56.6%) of a polyurethane compound C1.

[0771] On the other hand, an aqueous solution containing an alkali metal salt of polythiol is obtained as an aqueous phase.

[0772] The aqueous solution containing the alkali metal salt of polythiol was washed twice with 20.0 g of toluene. Then, 40.0 g of toluene was added to the washed aqueous solution, and then 30.0 g of a 35% hydrochloric acid aqueous solution was added to neutralize it. The aqueous phase was taken out from the neutralized liquid, and 30.0 g of degassed water was added to the remaining organic phase, and the separation and washing were performed twice, thereby obtaining a toluene solution in which the polythiol composition was dissolved.

[0773] After removing toluene and a trace amount of water from the obtained toluene solution under heating and reduced pressure, the solution was filtered under reduced pressure using a 3.0 μm PTFE membrane filter to obtain 5.1 g (yield: 59.0%) of a polythiol composition (A) containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (i.e., polythiol component A1) as the main component.

[0774] In Example 4, during the process of vacuum filtration after the completion of the above-mentioned decomposition reaction, methanol as the decomposition agent represented by formula (2) volatilizes and is easily removed from the reaction system.

[0775] <Measurement of Each Polythiol Composition (A)>

[0776] The polythiol compositions (A) obtained in Examples 1 to 4 were subjected to the following measurements.

[0777] The results are shown in Table 1.

[0778] (Purity (%) of Polythiol Component A1 in Polythiol Composition (A))

[0779] The purity (%) of the polythiol component A1 in the polythiol composition (A) was measured by the above-mentioned method using high performance liquid chromatography.

[0780] (Refractive Index)

[0781] The refractive index of the polythiol composition (A) was measured using a liquid refractometer RA600 manufactured by Kyoto Electronics Industry Co., Ltd.

[0782] (Mercaptan value)

[0783] The thiol value of the polythiol composition (A) was determined by redox titration using a 0.05 M iodine aqueous solution.

[0784] [Table 1]

[0785]

[0786] As shown in Table 1, it was confirmed that in any of Examples 1 to 4, by decomposing the thiourethane resin with various decomposing agents, a polythiol composition (A) containing the polythiol component A1 as a main component was obtained.

[0787] [Example 6]

[0788] <Manufacturing of Molded Article>

[0789] A molded body containing a thiourethane resin was obtained in the same manner as in Reference Production Example 1 (i.e., the polythiol composition (A) produced in Reference Production Example 3 was used as the polythiol composition (A)) except that the thickness between the pair of glass molds was changed from 9.0 mm to 2.5 mm.

[0790] Furthermore, a molded body containing a thiourethane resin was obtained in the same manner as above except that the polythiol composition (A) produced in Reference Production Example 3 was changed to the polythiol composition (A) produced in Examples 1 to 4.

[0791] <Evaluation of Molded Article>

[0792] The following evaluations were performed on each of the above-mentioned molded products.

[0793] The results are shown in Table 2.

[0794] (Yellow Index (YI), L*, a*, and b*)

[0795] The yellowness (YI), L*, a*, and b* of the molded article were measured using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc.

[0796] (Refractive index (ne) and Abbe number (νe))

[0797] The refractive index (ne, nF', nC') of the molded article at each wavelength of 546.1 nm (mercury e-line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line) was measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation at 20° C. Based on these measurement results, the refractive index (ne) and Abbe number (νe) of the molded article were obtained.

[0798] (Heat resistance)

[0799] The glass transition temperature (Tg) of the molded body was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min) as an indicator of heat resistance.

[0800] (Specific gravity d)

[0801] The specific gravity d of the molded body was measured at 20°C by the Archimedean method.

[0802] [Table 2]

[0803]

[0804] As shown in Table 2, it was confirmed that when the polythiol composition (A) obtained in Examples 1 to 4 was used as a raw material, a molded product (i.e., a resin molded product) having properties that can be used as an optical material (e.g., eyeglass lenses) can be produced, similarly to the case where the polythiol composition (A) obtained in Reference Production Example 3 was used as a raw material.

[0805] [Example 6X]

[0806] In Example 6X, the same operation as in Example 6 was performed except that the production of the molded body was changed as follows. As a result, the same results as those of Example 6 (Table 2) were obtained.

[0807] - Changes from Example 6 -

[0808] In Example 6, meta-xylylene diisocyanate (XDI) (52 parts by mass) was used in the manufacture of the molded body, but in Example 6X, XDI (52 parts by mass) was changed to XDI composition X1 (the amount of XDI contained was 52 parts by mass) which is the aforementioned XDI composition.

[0809] The XDI composition X1 is produced by adding a trace amount of the compound (N1), a trace amount of the compound (N2), and a trace amount of the compound (N3) to XDI as a main component and mixing them.

[0810] In XDI composition X1, gas chromatography was performed under the above-mentioned GC conditions 1 and GC conditions 2, respectively. As a result,

[0811] The peak area of ​​the compound (N1) is 0.20 ppm or more (specifically, 600 ppm) relative to the peak area 1 of xylylenediisocyanate,

[0812] The peak area of ​​the compound (N2) is 0.05 ppm or more (specifically, 18 ppm) relative to the peak area 1 of xylylenediisocyanate,

[0813] The peak area of ​​the compound (N3) is 0.10 ppm or more (specifically, 100 ppm) relative to the peak area 1 of xylylenediisocyanate.

[0814] [Example 7]

[0815] <Production of Polyamine Compound by Reaction of Polyurea Compound B1 Obtained in Example 1 with Ethylenediamine>

[0816] In a 25 mL pressure-resistant reaction vessel manufactured by San Ai Scientific Co., Ltd., add:

[0817] The polyurea compound B1 obtained in Example 1 (2.0 g; 9.0 mmol), and

[0818] Ethylenediamine (3.2 g; 54 mmol) as a decomposing agent represented by formula (3);

[0819] After obtaining the reaction solution, the reaction container was sealed by filling it with nitrogen.

[0820] Next, the reaction solution in the reaction vessel was heated to 145° C. in a sealed state, and stirred for 3 hours under a pressure condition that was 0.01 MPa or more higher than the atmospheric pressure, thereby carrying out a reaction.

[0821] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the above-mentioned reaction between the polyurea compound B1 and ethylenediamine.

[0822] The mass of the reaction solution after the reaction was 4.9 g. The concentration of XDA determined from the results of GC was 18.6%, and the yield was 74.6% (the two-stage yield from the thiourethane resin R1 was 68.2%).

[0823] The decomposition agent (ammonia) represented by formula (1) generated by the decomposition of the polyurea compound B1 is easily removed by volatilization from the reaction solution after the reaction. The decomposition agent (ethylenediamine) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0824] [Example 8]

[0825] <Production of a polyamine compound by reaction of the polyurea compound B2 obtained in Example 2 with ethylenediamine>

[0826] The same operation as in Example 7 was carried out except that the polyurea compound B1 was changed to the polyurea compound B2 (2.0 g; 8.0 mmol) obtained in Example 2 and the amount of ethylenediamine was changed to 2.9 g (48 mmol).

[0827] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the reaction between the polyurea compound B2 and ethylenediamine.

[0828] The mass of the reaction solution after the reaction was 4.6 g. The concentration of XDA determined from the results of GC was 18.2%, and the yield was 75.6% (the two-stage yield from the thiourethane resin R1 was 66.1%).

[0829] The decomposition agent (methylamine) represented by formula (1) generated by the decomposition of the polyurea compound B2 is easily removed by volatilization from the reaction solution after the reaction. The decomposition agent (ethylenediamine) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0830] [Example 9]

[0831] <Production of a polyamine compound by reaction of the polyurea compound B3 obtained in Example 3 with ethylenediamine>

[0832] The same operation as in Example 7 was carried out except that the polyurea compound B1 was changed to the polyurea compound B3 (2.0 g; 7.2 mmol) obtained in Example 3 and the amount of ethylenediamine was changed to 2.6 g (43 mmol).

[0833] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the reaction between the polyurea compound B3 and ethylenediamine.

[0834] The mass of the reaction solution after the reaction was 4.2 g. The concentration of XDA determined from the results of GC was 19.3%, and the yield was 81.9% (the two-stage yield from the thiourethane resin R1 was 77.8%).

[0835] The decomposition agent (ethylenediamine) represented by formula (3) and the decomposition agent (dimethylamine) represented by formula (1) produced by decomposition of the polyurea compound B3 can be easily removed by distillation from the reaction solution after the reaction.

[0836] [Example 10]

[0837] <Production of Polyamine Compound Using Polyurethane Compound C1 Obtained in Example 4>

[0838] The same operation as in Example 7 was carried out except that the polyurea compound B1 was changed to the polyurethane C1 (2.0 g; 79 mmol) obtained in Example 4 and the amount of ethylenediamine was changed to 2.9 g (48 mmol).

[0839] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the reaction between polyurethane C1 and ethylenediamine.

[0840] The mass of the reaction solution after the reaction was 4.9 g. The concentration of XDA determined from the results of GC was 15.6%, and the yield was 70.4% (the two-stage yield from the thiourethane resin R1 was 39.8%).

[0841] The decomposition agent (ethylenediamine) represented by the formula (3) and the decomposition agent (methanol) represented by the formula (2) generated by the decomposition of the polyurethane C1 can be easily removed by distillation from the reaction solution after the reaction.

[0842] [Example 11]

[0843] <Production of a polyamine compound by reaction of the polyurea compound B1 obtained in Example 1 with N,N′-dimethylethylenediamine>

[0844] The same operation as in Example 7 was carried out except that 3.2 g (54 mmol) of ethylenediamine as the decomposition agent represented by formula (3) was changed to 4.8 g (54 mmol) of N,N′-dimethylethylenediamine as the decomposition agent represented by formula (3).

[0845] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the reaction of the polyurea compound B1 and N,N′-dimethylethylenediamine.

[0846] The mass of the reaction solution after the reaction was 6.7 g. The concentration of XDA determined from the results of GC was 15.8%, and the yield was 85.5% (the two-stage yield from the thiourethane resin R1 was 78.1%).

[0847] It should be noted that the decomposition agent (ammonia) represented by formula (1) generated by the decomposition of polyurea compound B1 is easily removed by volatilization from the reaction solution after the reaction. The decomposition agent (N,N'-dimethylethylenediamine) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0848] [Example 12]

[0849] <Production of a polyamine compound by reaction of the polyurea compound B1 obtained in Example 1 with 2-aminoethanol>

[0850] The same operation as in Example 7 was carried out except that 3.2 g (54 mmol) of ethylenediamine as the decomposition agent represented by formula (3) was replaced by 5.0 g (90 mmol) of 2-aminoethanol as the decomposition agent represented by formula (3), the reaction temperature was changed from 145° C. to 180° C., and the reaction time was changed from 3 hours to 6 hours.

[0851] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the reaction between the polyurea compound B1 and 2-aminoethanol.

[0852] The mass of the reaction solution after the reaction was 6.7 g. The concentration of XDA determined from the results of GC was 10.2%, and the yield was 55.7% (the two-stage yield from the thiourethane resin R1 was 50.9%).

[0853] The decomposition agent (ammonia) represented by formula (1) generated by the decomposition of the polyurea compound B1 is easily removed by volatilization from the reaction solution after the reaction. The decomposition agent (2-aminoethanol) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0854] [Example 13]

[0855] <Production of Polyamine Compound by Reaction of Polyurea Compound B1 Obtained in Example 1 with Ethylene Glycol>

[0856] The same operation as in Example 12 was carried out except that 3.2 g (54 mmol) of ethylenediamine as the decomposition agent represented by the formula (3) was changed to 5.6 g (90 mmol) of ethylene glycol.

[0857] Gas chromatography (GC) confirmed that xylylenediamine (XDA) as a polyamine compound was generated by the reaction between the polyurea compound B1 and ethylene glycol.

[0858] The mass of the reaction solution after the reaction was 6.9 g. The concentration of XDA determined from the results of GC was 7.1%, and the yield was 40.6% (the two-stage yield from the thiourethane resin R1 was 37.1%).

[0859] The decomposition agent (ammonia) represented by formula (1) generated by the decomposition of the polyurea compound B1 is easily removed by volatilization from the reaction solution after the reaction. The decomposition agent (ethylene glycol) represented by formula (3) can also be easily removed from the reaction solution after the reaction by distillation.

[0860] As described above, in Examples 7 to 13, the polyamine compound can be produced using the polyurea compound or polyurethane compound generated by decomposition of the thiourethane resin as a raw material.

[0861] The polyisocyanate compound can be produced by reacting at least one of the produced polyamine compounds and nitrates of these polyamine compounds with phosgene.

[0862] By mixing the obtained polyisocyanate compound and the active hydrogen compound, a polymerizable composition can be produced.

[0863] The obtained polymerizable composition can be used for the production of thiourethane resin or polyurethane resin.

[0864] The entire disclosure of Japanese Patent Application No. 2022-135892 filed on August 29, 2022 is incorporated into this specification by reference.

[0865] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

Claims

1. A method for producing a polythiol composition, comprising the step of decomposing a thiourethane resin using a decomposing agent represented by the following formula (1) or the following formula (2) to produce a polythiol composition, [Chemical formula 1] In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (wherein, Not including R 1 and R 2 All of them are amino groups), In formula (2), R 3 It represents an alkyl group having 1 to 3 carbon atoms.

2. The method for producing a polythiol composition according to claim 1, wherein The generating step includes a step of reacting the thiourethane resin with the decomposing agent under a pressure higher than atmospheric pressure. 3 . The method for producing a polythiol composition according to claim 1 , which is a method for producing a polythiol composition for producing an optical material.

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

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

6. The method for producing a polymerizable composition according to claim 5, wherein: The step of obtaining the polymerizable composition is a step of obtaining a polymerizable composition containing the polythiol composition and the polyisocyanate composition by mixing the polythiol composition with a polyisocyanate composition containing a polyisocyanate compound. The polyisocyanate composition comprises: xylylene diisocyanate, and At least one selected from the group consisting of the following compound (N1), the following compound (N2), and the following compound (N3); When the polyisocyanate composition contains the compound (N1), the peak area of ​​the compound (N1) in high performance liquid chromatography is 0.20 ppm or more relative to 100 of the peak area of ​​xylylene diisocyanate, When the polyisocyanate composition contains the compound (N2), the peak area of ​​the compound (N2) in high performance liquid chromatography is 0.05 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, When the polyisocyanate composition contains the compound (N3), the peak area of ​​the compound (N3) in high performance liquid chromatography is 0.10 ppm or more relative to 100 of the peak area of ​​xylylenediisocyanate, [Chemical formula 2] 7. A method for producing a resin, comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 5; and A step of obtaining a resin by curing the polymerizable composition.

8. A method for producing a polyamine compound, comprising the following steps: a first step of decomposing the thiourethane resin using a decomposing agent represented by the following formula (1) to produce a polyurea compound; and a second step of decomposing the polyurea compound using a decomposing agent represented by the following formula (3) to generate a polyamine compound; [Chemical formula 3] In formula (1), R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an amino group (wherein, Not including R 1 and R 2 All of them are amino groups), In formula (3), R 11 and R 12 Each independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

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

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

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

12. A method for producing a polyamine compound, comprising the following steps: Step X1 of decomposing a thiourethane resin with a decomposing agent represented by the following formula (2) in the presence of a tertiary amine compound as a decomposition aid to produce a polyurethane compound; and Step X2 of decomposing the polyurethane compound using a decomposition agent represented by the following formula (3) to generate a polyamine compound, [Chemical formula 4] In formula (2), R 3 represents an alkyl group having 1 to 3 carbon atoms, In formula (3), R 11 and R 12 Each independently represents a hydroxyl group, a mercapto group, an amino group, or a monomethylamino group.

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

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

15. The method for producing a polyamine compound according to claim 12, wherein The step X2 includes reacting the polyurethane compound with the decomposition agent represented by the formula (3) under a pressure higher than atmospheric pressure. 16 . The method for producing a polyamine compound according to claim 8 , which is a method for producing a polyamine compound as a raw material of a polyisocyanate compound for producing an optical material.

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

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

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

20. A method for producing a resin, comprising the following steps: A step of producing a polymerizable composition using the method for producing a polymerizable composition according to claim 19; and A step of obtaining a resin by curing the polymerizable composition.

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