Method for producing polythiol composition, method for producing polymerizable composition, and method for producing resin

Abstract

A method for producing a polythiol composition, the method including a reaction step of reacting a thiocarbamate resin with a quaternary ammonium salt comprising a quaternary ammonium cation and a counter anion to produce a polythiol composition.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a polythiol composition, a method for manufacturing a polymerizable composition, and a method for manufacturing a resin. Background Art

[0002] Compared with inorganic lenses, plastic lenses made of resin are lightweight, less likely to break, and can be dyed. Therefore, they have been rapidly popularized in recent years for uses such as spectacle lenses and camera lenses.

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

[0004] As a raw material for manufacturing a thiocarbamate resin (hereinafter, also referred to as "thiocarbamate resin raw material"), for example, a polythiol composition such as 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and a polyisocyanate compound such as m-xylylene diisocyanate (XDI) can be used. The polyisocyanate compound is, for example, manufactured from a polyamine compound. The polyamine compound as a raw material for the polyisocyanate compound also belongs to the thiocarbamate resin raw material (that is, the raw material for manufacturing a thiocarbamate resin).

[0005] A lens containing a thiocarbamate resin (such as a spectacle lens) can be manufactured by cutting a molded body containing the thiocarbamate resin. As a result, during the manufacturing process of the lens, a large amount of cutting powder containing the thiocarbamate resin is sometimes generated as waste. In addition, in the process of manufacturing a molded body containing the thiocarbamate resin, defective molded products or defective processed products sometimes occur. Such waste is usually not effectively utilized (that is, recycled) and is only subjected to incineration treatment or landfill treatment.

[0006] Therefore, from the viewpoint of effective utilization of materials, a technique has been developed for manufacturing a polythiol composition using, as a starting material, cutting powder of a thiocarbamate resin, molded, and processed defective products that are waste (for example, refer to Patent Document 4).

[0007] Here, Patent Document 4 discloses obtaining a polythiol composition by reacting an amine compound as a base with an organic solvent that is not easily miscible with water (high-boiling alcohol, toluene).

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 63-46213

[0011] Patent Document 2: Japanese Patent Laid-Open No. 2-270859

[0012] Patent Document 3: Japanese Patent Laid-Open No. 7-252207

[0013] Patent Document 4: International Publication No. 2021 / 157701

[0014] Content of the Invention

[0015] Problems to be Solved by the Invention

[0016] However, the reaction in the production of a polythiol composition is usually carried out in a high-temperature range and cannot be carried out in a low-temperature range. Therefore, from the viewpoints of reducing energy consumption and suppressing by-product formation, there is an urgent need to develop a reaction system that can produce a polythiol composition using a thiocarbamate resin as a starting material even in a low-temperature range.

[0017] In such a situation, an object of one aspect of the present disclosure is to provide a method for producing a polythiol composition capable of producing a polythiol composition using a thiocarbamate resin as a starting material in a wide temperature range (15 to 110°C) including a low-temperature range, a method for producing a polymerizable composition using the method for producing the polythiol composition, and a method for producing a resin using the method for producing the polymerizable composition.

[0018] Means for Solving the Problems

[0019] Embodiments of the present disclosure relate to the following [1] to

[10] .

[0020] [1] A method for producing a polythiol composition, the method comprising:

[0021] a reaction step of reacting a thiocarbamate resin with a quaternary ammonium salt formed by a quaternary ammonium cation and a counter anion to produce a polythiol composition.

[0022] [2] The method for producing a polythiol composition according to the above [1], wherein

[0023] the counter anion is a hydroxide ion.

[0024] [3] The method for producing a polythiol composition according to the above [1] or [2], wherein

[0025] the reaction system in the reaction step further contains an alcohol.

[0026] [4] The method for producing a polythiol composition according to the above [3], wherein

[0027] the alcohol contains one or more water-miscible alcohols.

[0028] [5] The production method of the polythiol composition according to [1] or [2] above, wherein,

[0029] The quaternary ammonium cation is represented by NR4 + and all four Rs are the same group.

[0030] [6] The production method of the polythiol composition according to [1] or [2] above, wherein,

[0031] The quaternary ammonium cation is represented by NR4 + and three of the four Rs are the same group, and the other one of the four Rs is a group different from the same group.

[0032] [7] The production method of the polythiol composition according to [1] or [2] above, wherein,

[0033] The quaternary ammonium cation is represented by NR4 + and the four Rs are each independently a group selected from an alkyl group, an aromatic group, a heteroaryl group, and a group containing an ether group.

[0034] [8] The production method of the polythiol composition according to [7] above, wherein,

[0035] The alkyl group has 1 to 20 carbon atoms and is linear, branched, or cyclic.

[0036] [9] A production method of a polymerizable composition, the method comprising:

[0037] a step of producing a polythiol composition by the production method of the polythiol composition according to any one of [1] to [8] above; and

[0038] a step of obtaining a polymerizable composition containing the produced polythiol composition and a polyisocyanate compound by mixing the produced polythiol composition with a polyisocyanate compound.

[0039]

[10] A production method of a resin, the method comprising:

[0040] a step of producing a polymerizable composition by the production method of the polymerizable composition according to [9] above, and

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

[0042] Effects of the invention

[0043] According to one aspect of the present disclosure, there can be provided a method for manufacturing a polythiol composition capable of manufacturing a polythiol composition using a thiocarbamate resin as a starting material within a wide temperature range (15 to 110°C) including a low temperature range, a method for manufacturing a polymerizable composition using the polythiol composition manufacturing method, and a method for manufacturing a resin using the polymerizable composition manufacturing method. Detailed Embodiments

[0044] Hereinafter, an example of an embodiment of the present disclosure will be described. However, the embodiments shown below are examples for embodying the technical idea of the present disclosure, and the present disclosure is not limited to the following description.

[0045] A mode obtained by arbitrarily selecting the matters described in this specification or a mode obtained by arbitrarily combining them is also included in the present disclosure.

[0046] In this specification, as a preferable regulation, it can be considered that a combination of preferable regulations is more preferable.

[0047] In this specification, the description "XX to YY" means "XX or more and YY or less".

[0048] In this specification, for a preferable numerical range (for example, a range of content, etc.), the lower limit value and the upper limit value described stepwise can be combined independently of each other. For example, according to the description "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" can be combined with the "more preferable upper limit value (60)" to set it as "10 to 60".

[0049] In this specification, when there are multiple substances belonging to each component in the composition, unless otherwise specified, the amount of each component contained in the composition refers to the total amount of these multiple substances present in the composition.

[0050] In this specification, the term "process" does not only refer to an independent process, but also includes this term as long as it can achieve the intended purpose of the process when it cannot be clearly distinguished from other processes.

[0051] In this specification, the term "reaction system" refers to "the reaction system in the reaction process of the method for manufacturing a polythiol composition".

[0052] It should be noted that in the reaction system in the reaction process, in addition to the essential components formed by the thiocarbamate resin and the quaternary ammonium salt, optional components such as alcohol, water, and reaction solvent may also be included. Therefore, the content (% by mass) in the reaction system refers to the content (% by mass) when the total content of the essential components and the optional components is set to 100% by mass.

[0053] In this specification, in the case of a reaction system containing a compound belonging to both alcohols and amine compounds such as monoethanolamine, the alcohols and amine compounds are not counted repeatedly, and only one of the alcohols and amine compounds is counted to calculate the "total content of essential components and optional components in the reaction system". Here, the "content of alcohol in the reaction system (mass%)" is a value obtained by dividing the "mass of the compound belonging to both alcohols and amine compounds" by the "total content of essential components and optional components in the reaction system" calculated by counting only one of the alcohols and amine compounds.

[0054] In this specification, that the reaction system (composition) "contains a certain component (hereinafter referred to as 'component X') as the main component" means that the content of component X (when component X contains two or more compounds, it is the total content of two or more compounds) is 50% by mass or more relative to the total amount of the reaction system (composition).

[0055] The content of component X as the main component is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total amount of the reaction system (composition).

[0056] In this specification, "high boiling point" in "high boiling point alcohol" means 140 °C or higher.

[0057] In this specification, R 3 、R 4 、R 5 、R 6 、R 11 、R 12 are defined and exemplified in the same way as R in quaternary ammonium.

[0058] [Method for manufacturing a polythiol composition]

[0059] The method for manufacturing a polythiol composition according to an embodiment of the present disclosure includes a reaction step of reacting a thiocarbamate resin with a quaternary ammonium salt formed by a quaternary ammonium cation and a counter anion to produce a polythiol composition.

[0060] For the method for manufacturing a polythiol composition according to an embodiment of the present disclosure, since a thiocarbamate resin is reacted with a quaternary ammonium salt formed by a quaternary ammonium cation and a counter anion, a polythiol composition can be manufactured using a thiocarbamate resin as a starting material in a wide temperature range (15 to 110 °C) including a low temperature range.

[0061] When the reaction system further contains alcohol, in the above reaction step, alcoholysis in which the thiocarbamate resin is further decomposed by alcohol occurs, and through this alcoholysis, the target polythiol composition can be produced.

[0062] In the case where the reaction system further contains an alcohol, it can be considered that, in the above reaction step, the alcohol functions as a decomposing agent in alcoholysis, and the quaternary ammonium salt functions as a decomposition assistant in alcoholysis. Specifically, it can be speculated that the "R" on the right side generated by the following reaction formula (1) 3 O - " promotes the decomposition of the thiocarbamate resin. Here, the left side of the following reaction formula (1) represents "quaternary ammonium salt (quaternary ammonium cation NR4 + + counter anion X - )" and "alcohol R 3 OH".

[0063] In the case where the reaction system does not contain an alcohol, it can be considered that the counter anion in the quaternary ammonium salt as a nitrogen-containing compound undergoes a nucleophilic reaction with the carbon of the carbonyl group of the thiocarbamate resin (refer to the reaction formula (X) described later).

[0064] [Chemical formula 1]

[0065]

[0066] [Chemical formula 2]

[0067]

[0068] The method for manufacturing a polythiol composition according to an embodiment of the present disclosure includes at least a reaction step, and may include, as needed: a separation step; other steps such as a fractionation step, a screening step, a washing step, and a crushing (pulverizing) step.

[0069] Hereinafter, each step that may be included in the method for manufacturing a polythiol composition will be described.

[0070] [Reaction step]

[0071] The reaction step is a step of reacting any components such as a thiocarbamate resin, a quaternary ammonium salt, and an alcohol added as needed to produce a polythiol composition.

[0072] [Thiocarbamate resin]

[0073] The thiocarbamate resin is a starting material in this step and the method for manufacturing a polythiol composition.

[0074] The thiocarbamate resin is not particularly limited, and examples thereof include thiocarbamate resins described in publicly known documents such as Japanese Patent Laid-Open No. 63-46213, Japanese Patent Laid-Open No. 2-270859, Japanese Patent Laid-Open No. 7-252207, and International Publication No. 2008 / 047626.

[0075] Thiocarbamate resins are usually produced in the form of reaction products from polyisocyanate compounds and polythiol compositions as raw materials.

[0076] Examples of thiocarbamate resins include, for example: thiocarbamate resins obtained from MR-6, MR-7, MR-8, MR-8Plus, MR-60, MR-10, MR-20 (the above are manufactured by Mitsui Chemicals, Inc.) which are high refractive index lens materials; EYAS1.60 (manufactured by Hoya Corporation); and the like.

[0077] The thiocarbamate resin is preferably a resin recovered in at least one of the processes of manufacturing spectacle lenses, manufacturing spectacles, and discarding spectacles. According to this method, the reuse of the thiocarbamate resin as a material for spectacle lenses can be achieved.

[0078] Here, the process of manufacturing spectacle lenses refers to the process of manufacturing a resin by casting polymerization by blending monomers as resin raw materials and / or the process of obtaining spectacle lenses by cutting a resin molded body. The process of manufacturing spectacles refers to the process of manufacturing spectacles by combining spectacle lenses and other components such as spectacle frames. The process of discarding spectacles refers to the process of discarding unnecessary spectacles after manufacturing, used spectacles, etc.

[0079] In any of these processes, the thiocarbamate resin as a material for spectacle lenses is generated as waste.

[0080] Preferably, the thiocarbamate resin generated in at least one of these processes is used as a starting material, and the thiocarbamate resin, a quaternary ammonium salt, and any components such as an alcohol added as needed are reacted to obtain a polythiol composition which is a decomposition product of the thiocarbamate resin.

[0081] As described above, in the method for manufacturing the polythiol composition of the present disclosure, in order to manufacture the polythiol composition, by using the used thiocarbamate resin, the amount of the thiocarbamate resin incinerated and discarded can be reduced. As a result, the generation of greenhouse gases such as carbon dioxide, sulfur oxides, nitrogen oxides and other air pollutants can be reduced. In addition, since thiourea is not used in the manufacture of the polythiol composition, wastewater containing thiourea is not generated, and it is an environmentally friendly manufacturing method.

[0082] Specific examples are given for illustration. When 1 kg of the thiocarbamate resin is incinerated and discarded, the content rates of carbon atoms, nitrogen atoms, and sulfur atoms in the thiocarbamate resin are 48.5% by mass, 7.6% by mass, and 30.2% by mass, respectively. When the thiocarbamate resin is burned, various oxides of carbon atoms, nitrogen atoms, and sulfur atoms are generated as gases depending on the combustion method. If the products are set as carbon dioxide, nitric oxide, and sulfur dioxide, 1.78 kg of carbon dioxide, 0.16 kg of nitric oxide, and 0.6 kg of sulfur dioxide are generated when 1 kg of the thiocarbamate resin is discarded.

[0083] In the method for manufacturing the polythiol composition of the present disclosure, the generation of these carbon dioxide, nitric oxide, and sulfur dioxide can be reduced.

[0084] The above starting material preferably contains cutting powders containing a thiocarbamate resin.

[0085] In the process of generating the polythiol composition in this mode, by bringing into contact the cutting powders containing a thiocarbamate resin, a quaternary ammonium salt, and optional components such as an alcohol added as needed, the above thiocarbamate resin, the above quaternary ammonium salt, and the above optional components such as an alcohol are reacted.

[0086] In this mode, since the reactivity of the thiocarbamate resin, the quaternary ammonium salt, and the above optional components such as an alcohol in the starting material is more excellent, the polythiol composition can be generated more effectively.

[0087] (Powder containing thiocarbamate resin)

[0088] In the reaction process, it is preferable to bring into contact the powder containing a thiocarbamate resin (hereinafter, also referred to as "thiocarbamate resin powder"), a quaternary ammonium salt, and optional components such as an alcohol, so that the thiocarbamate resin, the quaternary ammonium salt, and the optional components such as an alcohol in the above powder are reacted. Thereby, the reaction efficiency of the thiocarbamate resin, the quaternary ammonium salt, and the optional components such as an alcohol can be further improved.

[0089] As a method for bringing the thiocarbamate resin, the quaternary ammonium salt, and optional components such as an alcohol into contact, there is no particular limitation. For example, a method of adding the thiocarbamate resin powder and the quaternary ammonium salt (and an alcohol, a reaction solvent, etc. added as needed) to a reaction vessel and stirring can be cited. In this example, the order of adding the thiocarbamate resin powder and the quaternary ammonium salt (and an alcohol, a reaction solvent, etc. added as needed) to the reaction vessel is not particularly limited.

[0090] The thiourethane resin powder is not particularly limited, but is preferably cut powder (including the concept of ground powder, the same applies hereinafter) containing a molded body of the thiourethane resin and / or a powder obtained by sieving the cut powder (i.e., sieved cut powder).

[0091] Cutting powder of a molded body containing a thiourethane resin is generated, for example, when an optical material (for example, a lens) is produced by cutting a molded body containing a thiourethane resin.

[0092] The thiourethane resin powder may be a bulk powder obtained by crushing and / or pulverizing a molded body containing a thiourethane resin.

[0093] The content of the thiourethane resin in the reaction system of the reaction step is not particularly limited, but is preferably 2 to 50% by mass, more preferably 4 to 30% by mass, and particularly preferably 6 to 20% by mass from the viewpoint of further improving the reactivity of the thiourethane resin.

[0094] (Polyisocyanate compound as raw material of thiourethane resin)

[0095] The polyisocyanate compound as a raw material of the thiourethane resin may be one kind or two or more kinds.

[0096] The polyisocyanate compound as a raw material of the thiourethane resin preferably contains a polyisocyanate compound having two or more isocyanate groups.

[0097] Examples of the polyisocyanate compound as a raw material of the thiourethane resin include known polyisocyanate compounds described in the above-mentioned known documents (ie, JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, WO 2008 / 047626, etc.).

[0098] (Polythiol composition as raw material of thiourethane resin)

[0099] The polythiol composition as a raw material of the thiourethane resin may be composed of only one type of polythiol compound or two or more types of polythiol compounds.

[0100] The polythiol composition as a raw material of the thiourethane resin is not particularly limited as long as it contains a polythiol compound having two or more thiol groups (ie, mercapto groups).

[0101] Examples of the polythiol composition used as a raw material for the thiocarbamate resin include known polythiol compositions described in the above-mentioned known documents (i.e., JP-A-63-46213, JP-A-2-270859, JP-A-7-252207, WO 2008 / 047626, etc.).

[0102] The thiocarbamate resin may contain other components in addition to the polymer of at least one polyisocyanate compound and the polythiol composition.

[0103] Regarding other components that can be included in the thiocarbamate resin, reference can be appropriately made to the components that can be included in the polymerizable composition described later.

[0104] <<Quaternary ammonium salt>>

[0105] The quaternary ammonium salt may be formed from a quaternary ammonium cation and a counter anion, and is not particularly limited. Examples thereof include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAOH), benzyltrimethylammonium hydroxide, tetrahexylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, N,N,N-tris(polyoxyethylene)-N-methylammonium hydroxide, trimethylphenylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetrabutylammonium fluoride (TBAF), tetrabutylammonium chloride (TBACl), tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide (TBAI), benzyltriethylammonium hydroxide, cetyltrimethylammonium hydroxide, benzethonium hydroxide, benzalkonium hydroxide, cetylpyridinium hydroxide, etc.

[0106] When the reaction system contains an alcohol as an optional component, as shown in the following reaction formula (1), the "quaternary ammonium salt (quaternary ammonium cation NR4 + and counter anion X - )" on the left reacts with "alcohol R 3 OH" to generate "NR4 + " and "R 3 O - " on the right. As shown in the following reaction formula (2), it is speculated that the generated "R 3 O - " promotes the decomposition of the thiocarbamate resin.

[0107] It should be noted that when the reaction system does not contain an alcohol as an optional component, as shown in the following reaction formula (X), it is speculated that the generated "X- "Promotes the decomposition of the thiocarbamate resin.

[0108] [Chemical formula 3]

[0109]

[0110] [Chemical formula 4]

[0111]

[0112] [Chemical formula 5]

[0113]

[0114] The content of the quaternary ammonium salt in the reaction system as the reaction step is not particularly limited. From the viewpoint of further improving the reactivity with the thiocarbamate resin, it is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

[0115] (Addition amount of quaternary ammonium salt)

[0116] In the reaction step, the addition mass ratio of the quaternary ammonium salt to the thiocarbamate resin (i.e., addition mass ratio [quaternary ammonium salt / thiocarbamate resin]) can be appropriately adjusted, and is preferably 0.1 to 10, more preferably 0.2 to 9, and particularly preferably 0.4 to 6.

[0117] When the addition mass ratio [quaternary ammonium salt / thiocarbamate resin] is 0.1 or more, the formation of the polythiol composition can be further promoted.

[0118] When the addition mass ratio [quaternary ammonium salt / thiocarbamate resin] is 10 or less, the residue of the quaternary ammonium salt in the reaction mixture can be further inhibited.

[0119] In the reaction step, the addition millimoles of the quaternary ammonium salt per 1 g of the thiocarbamate resin is preferably 1.0 to 100.0 mmol / g, more preferably 2.0 to 50.0 mmol / g, and particularly preferably 3.0 to 25.0 mmol / g.

[0120] In the reaction step, the addition equivalent of the quaternary ammonium salt to the thiocarbamate resin (addition equivalent [quaternary ammonium salt / thiocarbamate resin]) is preferably 1.0 to 10.0, more preferably 1.0 to 8.0, and particularly preferably 1.0 to 6.0.

[0121] When the addition equivalent [quaternary ammonium salt / thiocarbamate resin] is 1.0 or more, the formation of the polythiol composition can be further promoted.

[0122] When the addition equivalent amount of [quaternary ammonium salt / thiocarbamate resin] is 6.0 or less, the residue of the quaternary ammonium salt in the reaction mixture can be further suppressed.

[0123] Here, the addition equivalent amount of the quaternary ammonium salt relative to the thiocarbamate resin (addition equivalent amount [quaternary ammonium salt / thiocarbamate resin]) refers to the ratio of the number of quaternary ammonium cations in the added quaternary ammonium salt to the total number of thiocarbamate bonds in the added thiocarbamate resin.

[0124] (Quaternary ammonium cation)

[0125] The quaternary ammonium cation is represented by NR4 + Four Rs can all be the same group, or three of the four Rs can be the same group, and the other of the four Rs can be a group different from the above-mentioned same group.

[0126] As a specific example of the quaternary ammonium cation (NR4 + ), for example, tetramethylammonium ion (all 4 Rs are methyl groups), tetraethylammonium ion (all 4 Rs are ethyl groups), tetrabutylammonium ion (all 4 Rs are butyl groups), benzyltrimethylammonium ion (3 of the 4 Rs are methyl groups, and the other is benzyl), etc. can be cited.

[0127] As the four Rs in the quaternary ammonium cation NR4 + There is no particular limitation, and for example, each is independently a group selected from an alkyl group, an aromatic group, a heteroaryl group, and an ether-containing group.

[0128] As the alkyl group, there is no particular limitation, and preferably it has 1 to 20 carbon atoms and is linear, branched, or cyclic. Here, the alkyl group can be a substituted alkyl group having a substituent or an unsubstituted alkyl group without a substituent. As such a substituent, for example, nitro group, hydroxyl group, etc. can be cited. It should be noted that the number of carbon atoms of the alkyl group represents the number of carbon atoms of the alkyl group when it is unsubstituted, and does not include the carbon atoms of the substituent when it is substituted.

[0129] As a specific example of the unsubstituted alkyl group without a substituent, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, etc. can be cited.

[0130] As the aromatic group, there is no particular limitation, and preferably it has 4 to 20 carbon atoms. Here, the aromatic group can be a substituted aromatic group having a substituent or an unsubstituted aromatic group without a substituent. As such a substituent, for example, methyl group, nitro group, hydroxyl group, etc. can be cited. It should be noted that the number of carbon atoms of the aromatic group represents the number of carbon atoms of the aromatic group when it is unsubstituted, and does not include the carbon atoms of the substituent when it is substituted.

[0131] Specific examples of unsubstituted aromatic groups without substituents include, for example: benzyl, phenyl, naphthyl, phenethyl, anthryl, pyrenyl, phenylthio group, etc.

[0132] The heteroaryl group is not particularly limited, and preferably has 4 to 20 carbon atoms. Here, the heteroaryl group can be a substituted heteroaryl group having a substituent or an unsubstituted heteroaryl group without a substituent. Examples of the substituent include, for example: methyl, nitro, hydroxyl group, etc. It should be noted that the number of carbon atoms of the heteroaryl group represents the number of carbon atoms when the heteroaryl group is unsubstituted and does not include the number of carbon atoms of the substituent when it is substituted.

[0133] Specific examples of unsubstituted heteroaryl groups without substituents include, for example: by removing one hydrogen atom on a carbon atom or a nitrogen atom of a monocyclic or ring assembly selected from pyrrole, imidazole, pyrazole, triazole, furan, thiophene, thiazole, isothiazole, azole, iso azole, diazole, thiadiazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, bipyrrole, terpyrrole, bithiophene, terthiophene, bipyridine and terpyridine to obtain a monovalent residue, that is, a non-condensed heteroaryl group; by removing one hydrogen atom on a carbon atom or a nitrogen atom of a compound selected from indole, carbazole, imidazole, benzimidazole, bis(benzimidazolo)benzene[1,3,5]triaza , (benzimidazolo)benzimidazole, (benzimidazolo)phenanthridine, (benzoindolo)benzazaa , dibenzofuran, and dibenzothiophene to obtain a monovalent residue, that is, a condensed heteroaryl group; etc.

[0134] The ether-containing group is not particularly limited, and preferably has 2 to 20 carbon atoms. Here, the ether-containing group can be a substituted ether-containing group having a substituent or an unsubstituted ether-containing group without a substituent. Examples of the substituent include, for example: methyl, nitro, hydroxyl group, etc. It should be noted that the number of carbon atoms of the ether-containing group represents the number of carbon atoms when the ether-containing group is unsubstituted and does not include the number of carbon atoms of the substituent when it is substituted.

[0135] Specific examples of unsubstituted ether-containing groups without substituents include, for example: polyoxyalkylene group, polyglyceryl group, tetrahydrofuranyl group, benzofuranyl group, etc.

[0136] (Counter anion (balancing ion))

[0137] As the counter anion X - , there is no particular limitation, and examples include: halide ions such as fluoride ion, chloride ion, bromide ion, iodide ion; hydroxide ion, etc. in the form of OR 2-An anion represented; etc. These can be used alone or in combination of two or more. It should be noted that R 2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0138] Among them, from the viewpoint of the detachment ability, a hydroxide ion is preferably used.

[0139] <Any component>

[0140] As the optional component, there is no particular limitation, and examples thereof include: alcohols, water, reaction solvents, amine compounds, bases other than quaternary ammonium salts such as sodium hydroxide, etc.

[0141] (Alcohol)

[0142] In the reaction step, it is preferable to react at least one alcohol as an optional component with the thiocarbamate resin.

[0143] It can be considered that the alcohol as an optional component functions as a decomposing agent for the thiocarbamate resin.

[0144] As the alcohol as an optional component in the reaction system of the reaction step, a known alcohol can be used without particular limitation.

[0145] The alcohol as an optional component in the reaction system of the reaction step (i.e., the alcohol optionally reacting with the thiocarbamate resin) can be only one kind or two or more kinds.

[0146] The alcohol as an optional component in the reaction system of the reaction step can be a monohydric alcohol containing only one hydroxyl group or a polyhydric alcohol containing two or more hydroxyl groups.

[0147] The alcohol as an optional component in the reaction system of the reaction step can be a primary alcohol such as ethanol, n-propanol, monoethanolamine, etc.; a secondary alcohol such as isopropanol (2-propanol); a tertiary alcohol such as tert-butanol. From the viewpoint of the reaction in a low temperature range, lower alcohols such as methanol and ethanol are preferred.

[0148] Specific examples of the alcohol as an optional component in the reaction system of the reaction step are not particularly limited, and examples thereof include: methanol, ethanol, tert-butanol, isopropanol (2-propanol), n-propanol, propylene glycol, ethylene glycol, diethylene glycol, benzyl alcohol, phenethyl alcohol, 2-octanol, 2-ethyl-1-hexanol, 1-decanol, 1-nonanol, 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, propylene glycol, ethylene glycol, monoethanolamine, etc. These can be used alone or in combination of two or more.

[0149] Among them, from the viewpoint of the miscibility with the quaternary ammonium salt aqueous solution, it is preferable to contain one or more alcohols that can be mixed with water.

[0150] Examples of the alcohol capable of being mixed with water include methanol, ethanol, tert-butanol, isopropanol (2-propanol), n-propanol, propylene glycol, ethylene glycol, diethylene glycol, monoethanolamine, and the like.

[0151] It should be noted that in this specification, the term "capable of being mixed" means that "at normal temperature (25°C) and normal pressure (one atmosphere), 10 g or more of an alcohol compound dissolves in 1 kg of water".

[0152] From the viewpoint of further improving the reactivity with the thiocarbamate resin, the molecular weight of the alcohol as an optional component in the reaction step is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and particularly preferably 200 or less.

[0153] The lower limit of the molecular weight of the alcohol as an optional component in the reaction system of the reaction step is, for example, 30 or more.

[0154] The molecular weight of the alcohol as an optional component in the reaction system of the reaction step is not particularly limited, and is preferably 30 to 1000, more preferably 30 to 500, still more preferably 30 to 300, and particularly preferably 30 to 200.

[0155] The alcohol as an optional component in the reaction system of the reaction step preferably contains an alcohol having a boiling point of 60°C to 250°C (hereinafter, also referred to as "alcohol A"). In this specification, the boiling point means the boiling point under one atmosphere (101325 Pa).

[0156] The proportion of alcohol A in the total amount of the alcohol as an optional component in the reaction system of the reaction step is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and particularly preferably 80% by mass to 100% by mass.

[0157] The content of the alcohol as an optional component in the reaction system of the reaction step is not particularly limited, and from the viewpoint of further improving the reactivity with the thiocarbamate resin, it is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and particularly preferably 35 to 70% by mass.

[0158] The following shows the preferred addition amount of the alcohol as an optional component in the reaction system of the reaction step.

[0159] The preferred addition amounts shown below also conform to the preferred addition amounts of alcohol A (i.e., an alcohol having a boiling point of 60°C to 250°C).

[0160] ((Addition amount of the alcohol as an optional component in the reaction system of the reaction step))

[0161] In the reaction step, the addition mass ratio of the alcohol as an optional component to the thiocarbamate resin (i.e., the addition mass ratio [alcohol / thiocarbamate resin]) can be adjusted as appropriate, preferably 0.10 to 20, more preferably 0.30 to 15, and particularly preferably 0.40 to 10.

[0162] When the addition mass ratio [alcohol / thiocarbamate resin] is 0.10 or more, the formation of the polythiol composition can be further promoted.

[0163] When the addition mass ratio [alcohol / thiocarbamate resin] is 20 or less, the residue of the alcohol in the reaction mixture can be further suppressed.

[0164] In the reaction step, the addition millimoles of the alcohol as an optional component per 1 g of the thiocarbamate resin is preferably 1.0 to 100.0 mmol / g, more preferably 10.0 to 90.0 mmol / g, and particularly preferably 50.0 to 85.0 mmol / g.

[0165] In the reaction step, the addition equivalent of the alcohol to the thiocarbamate resin (addition equivalent [alcohol / thiocarbamate resin]) is preferably 1.0 to 25, more preferably 1.2 to 20, and particularly preferably 1.5 to 15.

[0166] When the addition equivalent [alcohol / thiocarbamate resin] is 1.0 or more, the formation of the polythiol composition can be further promoted.

[0167] When the addition equivalent [alcohol / thiocarbamate resin] is 25 or less, the residue of the alcohol in the reaction mixture can be further suppressed.

[0168] Here, the addition equivalent of the alcohol to the thiocarbamate resin (addition equivalent [alcohol / thiocarbamate resin]) means the ratio of the number of hydroxyl groups in the added alcohol to the total number of thiocarbamate bonds in the added thiocarbamate resin.

[0169] (Water)

[0170] The content of water in the reaction system of the reaction step is not particularly limited. From the viewpoint of further improving the reactivity between the thiocarbamate resin and the alcohol, it is preferably 0 to 50% by mass, more preferably 5 to 50% by mass, further preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass.

[0171] (Reaction solvent)

[0172] In the reaction step, the thiocarbamate resin, the quaternary ammonium salt, and the alcohol as an optional component can be reacted in the presence of a reaction solvent.

[0173] The reaction solvent refers to a reaction solvent other than alcohol and water as an optional component, and examples thereof include hydrocarbons having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), ethers having 4 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 4 to 12 carbon atoms, and nitriles having 2 to 12 carbon atoms. These may be used alone or in combination of two or more.

[0174] The hydrocarbon 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.

[0175] As the ether, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane or 1,4-dimethoxyethane is preferred. Alkane, more preferably dimethoxyethane.

[0176] The ketone is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone or 2-octanone, and more preferably methyl isobutyl ketone.

[0177] The ester is preferably ethyl acetate, butyl acetate or pentyl acetate, and more preferably pentyl acetate.

[0178] As the nitrile, acetonitrile or propionitrile is preferred, and acetonitrile is more preferred.

[0179] The content of the reaction solvent in the reaction system of the reaction step is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 20% by mass or less from the viewpoint of further improving the reactivity with the thiourethane resin.

[0180] <Reaction Temperature>

[0181] The reaction temperature of the thiourethane resin, the quaternary ammonium salt, and the alcohol as an optional component in the reaction step can be adjusted appropriately.

[0182] In the reaction step, the thiourethane resin, the quaternary ammonium salt, and the alcohol as an optional component are reacted preferably under a temperature condition (ie, reaction temperature) of 15 to 110° C. (more preferably 15° C. or higher and lower than 50° C., particularly preferably 15 to 40° C.).

[0183] When the reaction temperature is 15 to 110° C., the purity of the polythiol component as the main component in the polythiol composition as the target product (ie, the content of the main component relative to the total amount of the polythiol composition) can be further increased.

[0184] In addition, in the reaction step, the reaction can be carried out under pressurized conditions. When the reaction is carried out under pressurized conditions, the reaction time can sometimes be shortened.

[0185] It should be noted that in the existing reaction system using alcohol (R 3 OH) and tertiary amine (NR 4 R 5 R 6 ), as the reason why the reaction does not proceed in the low temperature range, it can be speculated that the existing reaction system using alcohol and tertiary amine is a reaction system that needs to be set to high temperature conditions to shift the reaction equilibrium to the right in order to generate "R 3 O - " on the right side of the following reaction formula (3). On the other hand, it can be speculated that in the reaction system of the above reaction formula (1), the reaction equilibrium shifts to the right even in the low temperature range to generate "R 3 O - " on the right side.

[0186] [Chemical formula 6]

[0187]

[0188] <Reaction time>

[0189] The reaction time of the thiocarbamate resin, quaternary ammonium salt, and alcohol as an optional component in the reaction step can be adjusted appropriately, preferably 0.1 to 50.0 hours, more preferably 0.5 to 30.0 hours, and particularly preferably 1.0 to 20.0 hours.

[0190] <Polythiol composition>

[0191] In the present disclosure, the polythiol composition refers to a composition containing at least one polythiol compound, and may also contain other components such as polyisocyanate compounds and polyamine compounds.

[0192] In the present disclosure, the polythiol compound contained in the polythiol composition is also referred to as the "polythiol component".

[0193] The polythiol composition preferably contains at least one polythiol compound as the main component. Here, "the polythiol composition contains at least one polythiol compound as the main component" means that the total content of at least one polythiol compound is 50% by mass or more relative to the total amount of the polythiol composition. The total content of at least one polythiol compound is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more relative to the total amount of the polythiol composition.

[0194] As the target product, a polythiol composition containing a known polythiol compound can be cited.

[0195] The polythiol composition as the target product and the polythiol composition as the raw material of the thiocarbamate resin as the starting material do not need to be exactly the same.

[0196] Among them, from the viewpoint of the performance of the thiocarbamate resin produced from the polythiol composition as the target product, it is preferable that the types of the polythiol components as the main components in the polythiol composition as the target product are the same as those of the polythiol components as the main components in the polythiol composition as the raw material. In this case, for example, the cutting powder (thiocarbamate resin) generated during the production of optical material A can be used as a raw material to produce an optical material B (an optical material containing a thiocarbamate resin) having performance comparable to that of optical material A.

[0197] In the polythiol composition as the target product, compared with the polythiol composition as the raw material of the thiocarbamate resin as the starting material, the polythiol components as the main components can be the same, and the content of impurities can be reduced.

[0198] In the polythiol composition as the target product, when the content of impurities decreases, there are advantages such as suppression of thickening of the polythiol composition and a long pot life of the polythiol composition.

[0199] The use of the polythiol composition as the target product is not particularly limited.

[0200] The polythiol composition as the target product can be used, for example, in the production of thiocarbamate resins.

[0201] Specific uses of the polythiol composition as the target product include a polythiol composition for the production of optical materials (such as spectacle lenses).

[0202] In other words, as a specific example of the method for producing the polythiol composition of the present disclosure, a method for producing a polythiol composition for the production of optical materials can be cited. In this specific example, when the cutting powder containing a thiocarbamate resin generated during the production of optical materials is used as the starting material, effective utilization (i.e., reuse) of the materials (thiocarbamate resin and the polythiol composition as its raw material) can be effectively achieved.

[0203] In addition, in the reaction process of the present disclosure, compared with a known method (for example, a method of obtaining a polythiol composition by reacting a thiocarbamate resin with sodium hydroxide), by reacting a thiocarbamate resin with a quaternary ammonium salt to obtain a polythiol composition, a polythiol composition with a high purity of the polythiol component as the main component can be obtained.

[0204] Therefore, even when the polythiol composition as the target product is used in the production of optical materials (such as lenses), an optical material with good performance can be obtained.

[0205] Examples of the performance of the optical material include: optical physical properties (such as refractive index and / or Abbe number), heat resistance, specific gravity, etc.

[0206] (Polythiol compound)

[0207] The polythiol compound is not particularly limited as long as it is a compound containing two or more mercapto groups (alias: thiol group).

[0208] Regarding the polythiol compound, the above-mentioned publicly known documents (i.e., Japanese Patent Laid-Open No. 63-46213, Japanese Patent Laid-Open No. 2-270859, Japanese Patent Laid-Open No. 7-252207, International Publication No. 2008 / 047626, etc.) can be appropriately referred to.

[0209] The polythiol compound is not particularly limited, and examples thereof include: 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, pentaerythritol tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, diethylene glycol bis(3-mercaptopropionate), etc. (hereinafter also referred to as "polythiol component A"). These can be used alone or in combination of two or more.

[0210] The polythiol composition more preferably contains polythiol component A as the main component. In this case, the polythiol composition may contain at least one other component (such as other polythiol compounds, components other than polythiol compounds, etc.) in addition to polythiol component A.

[0211] As other polythiol compounds, there is no particular limitation, and examples thereof include: methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetra(mercaptomethylthio)methane, tetra(2-mercaptoethylthio)methane, tetra(3-mercaptopropylthio)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimethyl-2,5-dimercaptomethyl-1,4-dithiane, 1,1,3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, etc. These can be used alone or in combination of two or more.

[0212] (Polyisocyanate compound)

[0213] The polyisocyanate compound only needs to be a compound containing two or more isocyanate groups.

[0214] As the polyisocyanate compound, there is no particular limitation, and examples thereof include: pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, etc. These can be used alone or in combination of two or more.

[0215] Among them, m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane are preferred.

[0216] (Polyamine compound)

[0217] The polyamine compound can be a compound containing two or more amino groups.

[0218] The polyamine compound, there is no particular limitation, and examples thereof include: pentamethylene diamine, hexamethylene diamine, m-xylylenediamine, p-xylylenediamine, isophorone diamine, bis(aminomethyl)cyclohexane, bis(aminocyclohexyl)methane, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, toluene diamine, 4,4'-diphenylmethane diamine, phenylenediamine, etc. These can be used alone or in combination of two or more.

[0219] Among them, preferably m-xylylenediamine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane.

[0220] (Preferred mode of the process for producing the polythiol composition)

[0221] The process for producing the polythiol composition is preferably a process in which a thiocarbamate resin, a quaternary ammonium salt, and an alcohol as an optional component are reacted to produce a polythiol compound and an optional polyamine compound as the polythiol composition.

[0222] In such a preferred mode, an alcoholysis reaction occurs in which the barium thiocarbamate resin as a decomposing agent decomposes into a polythiol compound and an optional polyamine compound. The above decomposition reaction is an alcoholysis reaction.

[0223] (Resin mixture containing a thiocarbamate resin)

[0224] The process for producing the polythiol composition may be a process in which a resin mixture containing a thiocarbamate resin, a quaternary ammonium salt, and an alcohol as an optional component are brought into contact with each other to react the thiocarbamate resin, the quaternary ammonium salt, and the alcohol as an optional component in the resin mixture to produce the polythiol composition.

[0225] The resin mixture containing a thiocarbamate resin further contains components other than the thiocarbamate resin.

[0226] Examples of the components other than the thiocarbamate resin include: resins other than the thiocarbamate resin, inorganic materials (such as glass) for making lenses, etc.

[0227] Examples of the resin other than the thiocarbamate resin are not particularly limited, and may include, for example: a mixed material of a thiocarbamate resin and a urethane resin produced by adding a polyol to the raw materials when producing the thiocarbamate resin, a mixed material of a thiocarbamate resin and a urea resin produced by adding a polyamine compound to the raw materials when producing the thiocarbamate resin, a polyolefin film for protecting the surface of a resin molded body for making spectacle lenses, a hard coat or a primer coat for protecting the surface of a resin molded body for making spectacle lenses, an abrasive used when grinding a resin molded body for making spectacle lenses, a resin material for fixing a resin molded body when performing machining on a resin molded body for making spectacle lenses, a tape or glue used for fixing a glass mold used when producing a resin molded body for making spectacle lenses, etc.

[0228] As specific examples of resins other than the thiocarbamate resin, there is no particular limitation, and examples thereof may include, for example: polycarbonate resin, polyallyl carbonate resin, acrylic resin, urethane resin, episulfide resin, etc.

[0229] The resin mixture containing the thiocarbamate resin is preferably a resin mixture recovered in at least one of the processes of manufacturing spectacle lenses, manufacturing spectacles, and discarding spectacles.

[0230] Regarding the processes of manufacturing spectacle lenses, manufacturing spectacles, and discarding spectacles, as described above.

[0231] The resin mixture containing the thiocarbamate resin preferably contains a cutting powder containing the thiocarbamate resin.

[0232] (Reaction mixture containing a polythiol composition)

[0233] The step of generating the polythiol composition may also be a step of reacting a thiocarbamate resin, a quaternary ammonium salt, and an alcohol as an optional component to generate a reaction mixture containing the polythiol composition as a target product.

[0234] The reaction mixture may contain a polythiol composition as a main product produced by alcoholysis and other components other than the polythiol composition.

[0235] As other components other than the polythiol composition in the reaction mixture, examples include: by-products produced by alcoholysis (such as polyurethane), the above reaction solvent, residues of raw materials (thiocarbamate resin, quaternary ammonium salt, and / or alcohol as an optional component), impurities contained in the raw materials, etc.

[0236] [[Separation step]]

[0237] The method for producing the polythiol composition may include a separation step of separating the polythiol composition as a target product from the reaction mixture containing the above polythiol composition.

[0238] As the separation method in the separation step, there is no particular limitation, and examples include: filtration, decantation, extraction, distillation, drying (including vacuum drying), purification (such as column chromatography), and other known methods. These can be used alone or in combination of two or more.

[0239] The separation step preferably includes: filtering the reaction mixture containing the polythiol composition obtained in the reaction step to obtain a filtrate containing the polythiol composition.

[0240] According to this method, it is easier to remove the solid components contained in the reaction mixture.

[0241] As a method for separating a polythiol compound in a polythiol composition, a method of extraction with an organic solvent or an inorganic solvent capable of dissolving the polythiol compound can be cited.

[0242] As a method for purifying a polythiol compound, general purification methods such as column purification, distillation purification, recrystallization purification, and salting-out extraction can be used.

[0243] As a method for separating a polyamine compound in a polythiol composition, a method of extraction with an organic solvent or an inorganic solvent capable of dissolving the polyamine compound can be cited.

[0244] As a method for purifying a polyamine compound, general purification methods such as column purification, distillation purification, recrystallization purification, and salting-out extraction can be used.

[0245] When the step of producing the polythiol composition is the above step of producing a polythiol compound and a polyamine compound, the separation step preferably includes at least one of the following steps: a step of obtaining a filtrate containing the polythiol compound as a filtrate by filtering a reaction mixture containing the polythiol compound and a polyamine compound derivative, and a step of obtaining a mixture containing the polyamine compound derivative as a filter cake.

[0246] When the separation step includes the step of obtaining a filtrate containing the polythiol compound as a filtrate, the polythiol compound as a polythiol composition can be obtained by separating the polythiol compound from the filtrate.

[0247] As an example of the separation step in this case, a method including the following steps can be cited: a step of filtering a reaction mixture containing the polythiol compound and the polyamine compound as a polythiol composition to obtain a filtrate containing the polythiol compound; a step of adding an alkali containing an alkali metal to the filtrate containing the polythiol compound, and then performing extraction by adding water to obtain an aqueous extract containing a metal salt of the polythiol compound; a step of adding an acid to the aqueous extract containing the metal salt of the polythiol compound to obtain an aqueous liquid containing the polythiol compound; a step of performing extraction by adding a hydrocarbon having 5 to 12 carbon atoms as an extraction solvent to the aqueous liquid containing the polythiol compound to obtain an extract containing the polythiol compound; and a step of separating the polythiol compound from the extract containing the polythiol compound.

[0248] In this example, first, the polythiol compound in the filtrate containing the polythiol compound is converted into an alkali metal salt, and then extracted with water to obtain an aqueous extract containing the alkali metal salt of the polythiol compound. Then, by adding an acid thereto, the alkali metal salt of the polythiol compound is converted back into the polythiol compound. The polythiol compound is extracted from the aqueous liquid containing the obtained polythiol compound using the above extraction solvent to obtain an extract containing the polythiol compound. The polythiol compound is separated from the extract containing the obtained polythiol compound.

[0249] According to this example, even when the filtrate containing the polythiol compound contains a large amount of other components in addition to the polythiol compound, a polythiol compound with a higher purity of the polythiol component as the main component can be obtained.

[0250] The alkali metal in the alkali containing the alkali metal is not particularly limited, and sodium, potassium, and lithium are preferred, and sodium and potassium are more preferred.

[0251] The alkali containing the alkali metal is not particularly limited, and examples thereof include sodium methoxide, sodium ethoxide, sodium propoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.

[0252] The alkali containing the alkali metal can be added to the filtrate in the form of an alcohol solution (such as a methanol solution, an ethanol solution, etc.) as needed.

[0253] The acid added to the aqueous extract containing the alkali metal salt of the polythiol compound is not particularly limited, and examples thereof include hydrochloric acid, carbonic acid, nitric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, etc.

[0254] The extraction solvent can be one kind or two or more kinds.

[0255] The preferred mode of the extraction solvent is the same as the preferred mode of the above reaction solvent.

[0256] However, the reaction solvent and the extraction solvent can be the same or different.

[0257] [[Other processes]]

[0258] The manufacturing method of the polythiol composition may include other processes in addition to the above processes as needed.

[0259] Examples of other processes include, for example, a fractionation process, a screening process, a cleaning process, a crushing (pulverizing) process, etc.

[0260] <Fractionation process>

[0261] The method for producing a polythiol composition may further include, before the reaction step for generating the polythiol composition: a classification step, in which a powder containing a thiocarbamate resin obtained by classifying a cutting powder containing a thiocarbamate resin is obtained, having an average particle size (e.g., the arithmetic mean of the equivalent circle diameters) smaller than that of the above-mentioned cutting powder (i.e., the cutting powder with reduced average particle size).

[0262] In the reaction step for generating the polythiol composition when including this classification step, by bringing the above-mentioned powder, the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component into contact, the thiocarbamate resin, the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component in the above-mentioned powder react.

[0263] When the method for producing a polythiol composition includes a classification step, since in the reaction step, a powder formed of particles with a small particle size (i.e., average particle size), the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component are brought into contact, the reaction efficiency of the thiocarbamate resin, the above-mentioned quaternary ammonium salt, and the alcohol as an optional component in the above-mentioned powder can be further improved.

[0264] As the average particle size, for example, the arithmetic average particle size can be cited.

[0265] As the particle size, for example, the equivalent circle diameter can be cited.

[0266] As the classification method, for example, screening, centrifugal separation, etc. can be cited.

[0267] Regarding performing screening as the classification method, the following screening step can be referred to.

[0268] <Screening step>

[0269] The method for producing a polythiol composition may include, before the reaction step for generating the above-mentioned polythiol composition: a screening step, in which a powder containing a thiocarbamate resin obtained by screening a cutting powder containing a thiocarbamate resin is obtained (i.e., the cutting powder that has passed through the sieve).

[0270] In the reaction step for generating the polythiol composition when including this screening step, by bringing the above-mentioned powder, the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component into contact, the thiocarbamate resin, the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component in the above-mentioned powder react.

[0271] When the method for producing a polythiol composition includes a screening step, since in the reaction step, a powder formed of particles with a small particle size, the quaternary ammonium salt, and the alcohol as an optional component are brought into contact, the reaction efficiency of the thiocarbamate resin, the quaternary ammonium salt, and the alcohol as an optional component can be further improved.

[0272] The above-mentioned sieve is not particularly limited.

[0273] The nominal aperture of the sieve based on JIS Z-8801-1:2019 is, for example, 0.1 to 20 mm, preferably 0.1 to 10 mm, more preferably 0.1 to 5 mm, further preferably 0.1 to 2 mm, further preferably 0.3 to 2 mm, and particularly preferably 0.5 to 1.5 mm.

[0274] <Cleaning process>

[0275] The method for producing the polythiol composition may include, before the reaction step of producing the above-mentioned polythiol composition: a cleaning step of cleaning the thiocarbamate resin powder (i.e., the powder containing the thiocarbamate resin) with a hydrocarbon having 5 to 12 carbon atoms as a cleaning solvent.

[0276] In the reaction step of producing the polythiol composition when including this cleaning step, by bringing the above-mentioned powder cleaned in the cleaning step, the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component into contact, the thiocarbamate resin, the above-mentioned quaternary ammonium salt, and the above-mentioned alcohol as an optional component in the above-mentioned powder are reacted. Thereby, a polythiol composition with a higher purity of the polythiol component as the main component can be obtained.

[0277] Especially when using a cutting powder containing a thiocarbamate resin as a starting material in the method for producing the polythiol composition, the oil derived from the cutting machine attached to the cutting powder can be effectively removed through the above-mentioned cleaning step, so a polythiol composition with a higher purity of the polythiol component as the main component can be obtained.

[0278] The hydrocarbon as the cleaning solvent can be used alone or in combination of two or more.

[0279] The preferred form of the hydrocarbon as the cleaning solvent is the same as the preferred form of the hydrocarbon as the above-mentioned reaction solvent.

[0280] However, the reaction solvent and the cleaning solvent can be the same or different.

[0281] As the cleaning method in the cleaning step, there is no particular limitation, and known methods such as a method of adding the above-mentioned cleaning solvent to the thiocarbamate resin powder and mixing can be applied.

[0282] When the method for producing the polythiol composition includes the above-mentioned sieving step and cleaning step, it is preferable to sequentially perform the sieving step and the cleaning step. In this case, since it is not necessary to clean the cutting powder that has not passed through the sieve, the amount of the cleaning solvent used can be further reduced.

[0283] <Crushing (pulverizing) process>

[0284] The method for producing a polythiol composition may include, before the reaction step for producing the polythiol composition, a crushing (pulverizing) process of crushing and / or pulverizing a thiocarbamate resin.

[0285] As the method for crushing (pulverizing) in the crushing (pulverizing) process, there is no particular limitation, and known methods can be applied.

[0286] 〔Method for producing a polymerizable composition〕

[0287] The method for producing a polymerizable composition according to the present disclosure includes: a step of producing a polythiol composition by the method for producing a polythiol composition according to the present disclosure; a step of obtaining a polymerizable composition containing the polythiol composition, a polyisocyanate, and any other components by mixing at least the polythiol composition containing the polythiol composition produced above with a polyisocyanate; and other steps may be further included as needed.

[0288] For the method for producing a polymerizable composition according to the present disclosure, in the step of producing a polythiol composition, a thiocarbamate resin (for example, the thiocarbamate resin in the ground powder of a molded body of a thiocarbamate resin) is used as a starting material to produce a polythiol composition, and in the step of obtaining a polymerizable composition, a polymerizable composition containing the polythiol composition and a polyisocyanate compound produced above is produced.

[0289] The obtained polymerizable composition can be used again for the production of a thiocarbamate resin.

[0290] In this way, effective utilization (i.e., reuse) of materials (i.e., thiocarbamate resin and the polythiol composition as its raw material) can be achieved in the method for producing a polymerizable composition.

[0291] In addition, as described above, according to the method for producing a polythiol composition, a polythiol composition with a high purity of the polythiol component as the main component can be obtained compared with known methods (for example, a method of obtaining a polythiol composition by reacting a thiocarbamate resin with sodium hydroxide). According to the polymerizable composition obtained by the method for producing a polymerizable composition, a resin with excellent various properties [for example, optical properties (for example, refractive index and / or Abbe number), heat resistance, specific gravity, etc.] can be produced.

[0292] Therefore, the polymerizable composition obtained by the method for producing a polymerizable composition according to the present disclosure is particularly suitable as a composition for producing a thiocarbamate resin for optical materials.

[0293] Process for producing a polythiol composition

[0294] Regarding the process for producing a polythiol composition, reference may be appropriately made to the above-described method for producing a polythiol composition of the present disclosure.

[0295] Process for obtaining a polymerizable composition

[0296] In the process for obtaining a polymerizable composition, a polymerizable composition containing the above polythiol composition and polyisocyanate compound is obtained by mixing at least the above polythiol composition and polyisocyanate compound.

[0297] The preferred mode of the polyisocyanate compound used in the process for obtaining a polymerizable composition is described in the section "Polythiol composition" and is the same as the preferred mode of the "polyisocyanate compound".

[0298] In the process for obtaining a polymerizable composition, the mixing ratio of the polythiol composition and the polyisocyanate compound is not particularly limited.

[0299] In the process for obtaining a polymerizable composition, the ratio of the added mass of the polythiol composition to the added mass of the polyisocyanate compound (i.e., added mass [polythiol composition / polyisocyanate compound]) is preferably from 0.10 to 10.00, more preferably from 0.20 to 5.00, still more preferably from 0.50 to 1.50, and particularly preferably from 0.70 to 1.30.

[0300] In addition, as the molar ratio of the mercapto group of the polythiol compound contained in the polythiol composition to the isocyanate group of the polyisocyanate compound (mercapto group / isocyanate group), it is preferably from 0.5 to 3.0, more preferably from 0.6 to 2.0, and particularly preferably from 0.8 to 1.3.

[0301] In the process for obtaining a polymerizable composition, the total added mass of the polythiol composition and the polyisocyanate compound is not particularly limited, and is preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total amount of the polymerizable composition produced.

[0302] In the process for obtaining a polymerizable composition, at least the above polythiol composition and polyisocyanate compound are mixed, and if necessary, the above polythiol composition and polyisocyanate may be mixed with other components.

[0303] In addition, in the process for obtaining a polymerizable composition, other components may be added to the mixture after at least mixing the above polythiol composition and polyisocyanate compound.

[0304] As other components, there are no particular limitations, and examples thereof may include: polymerization catalysts, internal mold release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent brighteners, fluorescent pigments, inorganic pigments, etc.

[0305] <Polymerization catalyst>

[0306] As the polymerization catalyst, there are no particular limitations, and examples thereof may include: tertiary amines, inorganic or organic acid salts of tertiary amines, metal compounds such as dimethyldichlorotin, quaternary ammonium salts, organic sulfonic acids, etc. These can be used alone or in combination of two or more.

[0307] <Internal mold release agent>

[0308] As the internal mold release agent, there are no particular limitations, and examples thereof may include: acidic phosphoric acid esters such as monoesters of phosphoric acid and diesters of phosphoric acid. These can be used alone or in combination of two or more.

[0309] <Resin modifier>

[0310] As the resin modifier, there are no particular limitations, and examples thereof may include: episulfides, epoxides, organic acids, organic acid anhydrides, (meth)acrylates, olefins, etc. These can be used alone or in combination of two or more.

[0311] It should be noted that (meth)acrylate refers to at least one of acrylate and methacrylate.

[0312] In the process of obtaining the polymerizable composition, the mixing of the above components can be carried out by conventional methods, and the mixing method is not particularly limited.

[0313] [Manufacturing method of resin]

[0314] The manufacturing method of the resin of the present disclosure includes: a process of manufacturing a polymerizable composition by the above-described manufacturing method of the polymerizable composition, and a process of obtaining a resin by curing the above polymerizable composition.

[0315] The manufacturing method of the resin of the present disclosure may include other processes as needed.

[0316] According to the manufacturing method of the resin of the present disclosure, the same effects as those of the above-described manufacturing method of the polymerizable composition of the present disclosure can be achieved.

[0317] The resin manufactured by the manufacturing method of the resin of the present disclosure is a thiocarbamate resin, but in order to distinguish it from the thiocarbamate resin which is one of the starting materials of the polythiol composition, it is simply referred to as "resin" in the present disclosure.

[0318] In the step of obtaining the resin, the resin is obtained by curing the above-mentioned polymerizable composition.

[0319] The curing of the above-mentioned polymerizable composition can be carried out by polymerizing the monomers (specifically, the polythiol composition and the polyisocyanate compound. The same applies hereinafter) in the above-mentioned polymerizable composition. As a pretreatment for polymerization, treatments such as filtration and degassing can be performed on the polymerizable composition.

[0320] The polymerization conditions (such as 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 types and amounts of the monomers in the composition, the types and amounts of the polymerization catalysts in the composition, the characteristics of the mold when using the mold described below, etc.

[0321] The polymerization temperature is not particularly limited, and is preferably -50 to 150 °C, more preferably 10 to 150 °C.

[0322] The polymerization time is not particularly limited, and is preferably 1 to 200 hours, more preferably 1 to 80 hours.

[0323] In the step of obtaining the resin, the polymer obtained by the polymerization of the monomers can be subjected to treatments such as annealing to obtain the resin.

[0324] The annealing temperature is not particularly limited, and is preferably 50 to 150 °C, more preferably 90 to 140 °C, and particularly preferably 100 to 130 °C.

[0325] 〔〔Manufacturing method of molded article〕〕

[0326] The manufacturing method of the molded article is a method for manufacturing a molded article containing a resin, and the method includes: a step of manufacturing a polymerizable composition by the above-mentioned manufacturing method of the polymerizable composition, and a step of obtaining a molded article containing a resin by curing the above-mentioned polymerizable composition, and may also include other steps as needed.

[0327] According to the manufacturing method of the molded article, the same effects as those of the above-mentioned manufacturing method of the polymerizable composition can be obtained.

[0328] In the step of obtaining a molded article containing a resin, a molded article containing a resin is obtained by curing the above-mentioned polymerizable composition.

[0329] The curing of the above-mentioned polymerizable composition, that is, the preferred conditions for the polymerization of the monomers in the above-mentioned polymerizable composition can be appropriately referred to the item of "Manufacturing method of resin".

[0330] As an example of the polymerization in this step, casting polymerization can be cited.

[0331] In casting polymerization, first, the above-mentioned polymerizable composition is injected between molding dies held by gaskets, tapes, or the like. At this time, defoaming treatment, filtration treatment, etc. can be carried out as needed.

[0332] Next, by polymerizing the monomers in the polymerizable composition injected between the molding dies, the composition is cured between the molding dies to obtain a cured product. Then, the cured product is taken out from the molding die to obtain a molded article containing resin.

[0333] The polymerization of the above-mentioned monomers can be carried out by heating the polymerizable composition. This heating can be carried out using a heating device equipped with a mechanism for heating an object to be heated, such as in an oven or in water.

[0334] [[Manufacturing method of optical material, manufacturing method of lens]]

[0335] The manufacturing method of an optical material (such as a lens) is a method for manufacturing an optical material (such as a lens) containing a molded article containing resin. This method includes: a step of manufacturing a polymerizable composition by the above-mentioned manufacturing method of the polymerizable composition, and a step of obtaining a molded article containing resin by curing the above-mentioned polymerizable composition. Other steps may also be included as needed.

[0336] According to the manufacturing method of the optical material, the same effects as those of the manufacturing method of the above-mentioned polymerizable composition can be obtained.

[0337] The manufacturing method of the optical material is an application of the manufacturing method of the molded article.

[0338] For example, in the manufacturing method of the molded article, by appropriately selecting the shape of the molding die used in the above-mentioned casting polymerization, a molded article applicable to an optical material (such as a lens) can be obtained.

[0339] Examples of optical materials include: lenses (such as spectacle lenses, camera lenses, polarizing lenses), light-emitting diodes (LEDs), etc.

[0340] The manufacturing method of an optical material (such as a lens) may include: a step of forming a coating on one or both surfaces of a molded article containing resin.

[0341] Specific examples of coatings include: primer coats, hard coats, antireflection layers, antifogging coatings, antifouling layers, water-repellent layers, etc.

[0342] These coatings can be formed separately or multiple coatings can be multilayered. When forming coatings on both surfaces, the same coating can be formed on each surface, or different coatings can be formed.

[0343] The composition of the coating can be appropriately selected according to the purpose.

[0344] Examples of the components of the coating include resins such as urethane resin, epoxy resin, polyester resin, melamine resin, and polyvinyl acetal resin; infrared absorbers; light stabilizers; antioxidants; photochromic compounds; dyes; pigments; antistatic agents; and the like.

[0345] Regarding the spectacle lens and the coating, reference can be appropriately made to the descriptions in publicly known documents such as International Publication No. 2017 / 047745.

[0346] [[Polymerizable composition]]

[0347] The polymerizable composition contains a polythiol composition obtained by the method for producing a polythiol composition and a polyisocyanate compound.

[0348] The polymerizable composition can be produced by the method for producing the polymerizable composition described above.

[0349] With the polymerizable composition, the same effects as those of the method for producing the polymerizable composition described above can be obtained.

[0350] Preferred embodiments of the polymerizable composition can be appropriately referred to the method for producing the polymerizable composition described above.

[0351] Among them, the added mass [[polythiol composition / polyisocyanate compound]] is replaced with the contained mass ratio [[polythiol composition / polyisocyanate compound]], and the total added mass of the polythiol composition and the polyisocyanate compound is replaced with the total contained mass of the polythiol composition and the polyisocyanate compound.

[0352] [[Resin, molded article, optical material (e.g., lens)]]

[0353] The resin is a cured product of the polymerizable composition described above.

[0354] The molded article is a molded article containing the above resin.

[0355] The optical material (e.g., lens) is an optical material (e.g., lens) containing the above resin.

[0356] With the resin, molded article, and optical material (e.g., lens), the same effects as those of the method for producing the polymerizable composition described above can be obtained.

[0357] The resin, molded article, and optical material (e.g., lens) can be produced by the method for producing the resin, the method for producing the molded article, and the method for producing the optical material (e.g., lens) described above, respectively.

[0358] Preferred embodiments of the resin, molded article, and optical material (e.g., lens) can be referred to the preferred embodiments of the manufacturing method of the resin, the manufacturing method of the molded article, and the manufacturing method of the optical material (e.g., lens), respectively.

[0359] <Preferred properties of the resin or molded article>

[0360] The glass transition temperature Tg of the resin (or molded article) is not particularly limited. From the viewpoint of heat resistance, it is preferably 70 °C or higher, more preferably 80 °C or higher, and particularly preferably 85 °C or higher.

[0361] The upper limit of the glass transition temperature Tg is not particularly limited and may be 130 °C or lower, may be 120 °C or lower, or may be 110 °C or lower.

[0362] The glass transition temperature Tg is not particularly limited and is preferably 70 °C to 130 °C, more preferably 80 °C to 120 °C, and particularly preferably 85 °C to 110 °C.

[0363] The refractive index (ne) of the resin (or molded article) is not particularly limited. From the viewpoint of applicability to optical materials, it is preferably 1.500 or higher, more preferably 1.540 or higher, and particularly preferably 1.590 or higher.

[0364] The upper limit of the refractive index (ne) is not particularly limited and is preferably 1.750.

[0365] The refractive index (ne) is not particularly limited and is preferably 1.500 to 1.750, more preferably 1.540 to 1.750, and particularly preferably 1.590 to 1.750.

[0366] The Abbe number of the resin (or molded article) is not particularly limited. From the viewpoint of applicability to optical materials, it is preferably 28 or higher, more preferably 30 or higher.

[0367] The upper limit of the Abbe number is not particularly limited and is preferably 50, more preferably 45.

[0368] The Abbe number is not particularly limited and is preferably 28 to 50, more preferably 30 to 45.

[0369] The specific gravity of the resin (or molded article) is not particularly limited. From the viewpoint of applicability to optical materials, it is preferably 1.10 or higher, more preferably 1.20 or higher.

[0370] The upper limit of the specific gravity is not particularly limited and is preferably 1.50, more preferably 1.40.

[0371] The above ratio is not particularly limited, preferably 1.10 to 1.50, more preferably 1.20 to 1.40.

[0372] In the present disclosure, for the examples, contents, and various physical properties of the above components, the matters described as examples or within the preferred ranges in the detailed description of the invention can be arbitrarily combined.

[0373] In addition, for the compositions described in the examples, if adjusted according to the compositions described in the detailed description of the invention, the invention can be implemented throughout the entire range of the compositions of the claims in the same manner as in the examples.

[0374] Examples

[0375] Hereinafter, the examples of the present disclosure will be further described. However, the present disclosure is not limited to the embodiments shown.

[0376] [Production Example 1]

[0377] [Production of a molded article containing a thiocarbamate resin]

[0378] Dimethyldichlorotin as a polymerization catalyst (0.0075 parts by mass based on 100 parts by mass of the total amount of the following polyisocyanate compound and the following polythiol composition), JP-506H (manufactured by Kitashiro Kagaku Kogyo Co., Ltd.; acidic phosphate) as a mold release agent (0.15 parts by mass based on 100 parts by mass of the total amount of the following polyisocyanate compound and the following polythiol composition), and isophthalic acid dimethyl diisocyanate (XDI) as a polyisocyanate compound (49.6 parts by mass) were added to a flask equipped with a stirring device. After stirring until the various additives were fully dissolved, a polythiol composition (50.4 parts by mass) mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a polythiol component was added and mixed to obtain a polymerizable composition as a transparent and homogeneous solution. The polymerizable composition was degassed at 300 Pa for 30 minutes or more and then filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 5 μm. Then, it was poured into a molding mold formed by a glass mold and a gasket having a desired lens shape. The molding mold filled with the polymerizable composition was polymerized in an oven at a temperature range of 10°C to 120°C for 24 hours according to the shape of its lens. The molding mold was taken out of the oven and demolded to obtain a spectacle lens molding formed of an optical member resin. The obtained molding was annealed at 120°C for 2 hours.

[0379] <Manufacture of Thiocarbamate Resin Powder>

[0380] A lens was manufactured by machining the above-obtained molded body. The machining powder generated at this time was collected and passed through a sieve with a nominal aperture of 1 mm specified in JIS Z-8801-1:2019 to obtain a sieved thiocarbamate resin powder (i.e., a powder containing thiocarbamate resin).

[0381] [Example 1-1]

[0382] <Decomposition of Thiocarbamate Resin Based on Tetramethylammonium Hydroxide and Ethanol>

[0383] (Reaction Step)

[0384] Weighed 15.0 g of the thiocarbamate resin powder obtained in Production Example 1, placed all of it in a 300 mL flask equipped with a condenser tube, added 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution (43.8 g; 0.12 mol) as a quaternary ammonium salt aqueous solution and ethanol (55.3 g; 1.2 mol) as an alcohol thereto, and heated and stirred at 40 °C (reaction temperature) for 3 hours (reaction time) to obtain a reaction mixture containing a polythiol composition (the above is the reaction step). It should be noted that the water content in the reaction system (15.0 + 55.3 + 43.8) is 28.8 mass% (43.8×0.75 / (15.0 + 55.3 + 43.8)×100).

[0385] (Separation Step)

[0386] The reaction mixture obtained in the above reaction step was cooled to room temperature, and then the solid matter was removed by filtration. Toluene (45.0 g) as a separation solvent was added to the obtained filtrate. The obtained liquid was washed twice with 100 mL of 1M hydrochloric acid to remove the excess tetramethylammonium hydroxide (TMAH), and then washed twice with 100 mL of water to remove the excess hydrochloric acid. 28 mass% sodium methoxide methanol solution (16.4 g; 0.085 mol) was added to the obtained liquid and stirred. 200.0 g of water was added to extract the soluble components, and the resulting aqueous extract was washed twice with 45.0 g of toluene, and then 21 g of 1M hydrochloric acid was added and stirred. The soluble components were extracted from the obtained aqueous liquid with 200.0 g of toluene, and the resulting extract was subjected to two washing / liquid separation operations with 100 mL of water to obtain a toluene solution of the polythiol composition.

[0387] The highly polar by-products were removed from the obtained toluene solution through a silica gel column, and then, toluene was removed by distillation using a rotary evaporator. For the obtained mixture, removal of low-boiling components using a vacuum pump and filtration using a 1-μm PTFE membrane filter were successively carried out, whereby 3.1 g of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., polythiol components) was obtained (yield: 41% by mass) (the above is the separation step).

[0388] [Example 1-2]

[0389] In Example 1-1, the reaction temperature was set at room temperature (15 °C) instead of 40 °C for the reaction temperature in the reaction step, and the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 0.6 g of a polythiol composition was obtained (yield: 8% by mass). It should be noted that the water content in the reaction system was 28.8% by mass.

[0390] [Example 1-3]

[0391] In Example 1-1, the reaction temperature was set at 60 °C instead of 40 °C for the reaction temperature in the reaction step, and the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 3.2 g of a polythiol composition was obtained (yield: 42% by mass). It should be noted that the water content in the reaction system was 28.8% by mass.

[0392] [Example 1-4]

[0393] In Example 1-1, the heating set temperature was set at 110 °C and heated to reflux to replace the reaction temperature in the reaction step with 40 °C, and the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 3.7 g of a polythiol composition was obtained (yield: 49% by mass). It should be noted that the water content in the reaction system was 28.8% by mass.

[0394] [Example 2-1]

[0395] In Example 1-1, methanol (38.4 g; 1.2 mol) was used in the reaction step instead of ethanol (55.3 g; 1.2 mol), and the reaction step and separation step were carried out in the same manner as in Example 1-1. As a result, 1.8 g of a polythiol composition was obtained (yield: 24% by mass). It should be noted that the water content in the reaction system (15.0 + 38.4 + 43.8) was 33.8% by mass (43.8×0.75 / (15.0 + 38.4 + 43.8)×100).

[0396] [Example 2-2]

[0397] In Example 2-1, the reaction temperature was set to room temperature (15 °C) instead of setting the reaction temperature of the reaction step to 40 °C, and the reaction step and separation step were carried out in the same manner as in Example 2-1. As a result, 0.5 g of a polythiol composition was obtained (yield: 6% by mass). It should be noted that the water content in the reaction system was 33.8% by mass.

[0398] [Example 2-3]

[0399] In Example 2-1, the reaction temperature was set to 60 °C instead of setting the reaction temperature of the reaction step to 40 °C, and the reaction step and separation step were carried out in the same manner as in Example 2-1. As a result, 3.9 g of a polythiol composition was obtained (yield: 51% by mass). It should be noted that the water content in the reaction system was 33.8% by mass.

[0400] [Example 2-4]

[0401] In Example 2-1, the heating set temperature was set to 110 °C and heated to reflux to replace setting the reaction temperature of the reaction step to 40 °C, and the reaction step and separation step were carried out in the same manner as in Example 2-1. As a result, 4.1 g of a polythiol composition was obtained (yield: 54% by mass). It should be noted that the water content in the reaction system was 33.8% by mass.

[0402] [Example 3-1]

[0403] In Example 1-1, isopropanol (2-propanol) (72.1 g; 1.2 mol) was used in the reaction step instead of ethanol (55.3 g; 1.2 mol). Except for this, the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 1.8 g of a polythiol composition was obtained (yield: 24% by mass). It should be noted that the water content in the reaction system (15.0 + 72.1 + 43.8) was 25.1% by mass (43.8×0.75 / (15.0 + 72.1 + 43.8)×100).

[0404] [Example 3-2]

[0405] In Example 3-1, the reaction temperature was set to room temperature (15°C) instead of setting the reaction temperature of the reaction step to 40°C. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 3-1. As a result, 0.3 g of a polythiol composition was obtained (yield: 4% by mass). It should be noted that the water content in the reaction system was 25.1% by mass.

[0406] [Example 3-3]

[0407] In Example 3-1, the reaction temperature was set to 60°C instead of setting the reaction temperature of the reaction step to 40°C. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 3-1. As a result, 2.1 g of a polythiol composition was obtained (yield: 27% by mass). It should be noted that the water content in the reaction system was 25.1% by mass.

[0408] [Example 3-4]

[0409] In Example 3-1, the heating set temperature was set to 110°C and heated to reflux to replace setting the reaction temperature of the reaction step to 40°C. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 3-1. As a result, 2.5 g of a polythiol composition was obtained (yield: 33% by mass). It should be noted that the water content in the reaction system was 25.1% by mass.

[0410] [Example 4-1]

[0411] In Example 1-1, benzyl alcohol (129.8 g; 1.2 mol) was used in the reaction step instead of ethanol (55.3 g; 1.2 mol), and the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 2.8 g of a polythiol composition was obtained (yield: 37% by mass). It should be noted that the water content in the reaction system (15.0 + 129.8 + 43.8) was 17.4% by mass (43.8×0.75 / (15.0 + 129.8 + 43.8)×100).

[0412] [Example 4-2]

[0413] In Example 4-1, the reaction temperature was set to room temperature (15 °C) instead of setting the reaction temperature of the reaction step to 40 °C, and the reaction step and the separation step were carried out in the same manner as in Example 4-1. As a result, 0.3 g of a polythiol composition was obtained (yield: 4% by mass). It should be noted that the water content in the reaction system was 17.4% by mass.

[0414] [Example 4-3]

[0415] In Example 4-1, the reaction temperature was set to 60 °C instead of setting the reaction temperature of the reaction step to 40 °C, and the reaction step and the separation step were carried out in the same manner as in Example 4-1. As a result, 3.1 g of a polythiol composition was obtained (yield: 42% by mass). It should be noted that the water content in the reaction system was 17.4% by mass.

[0416] [Example 4-4]

[0417] In Example 4-1, the reaction temperature was set to 110 °C instead of setting the reaction temperature of the reaction step to 40 °C, and the reaction step and the separation step were carried out in the same manner as in Example 4-1. As a result, 3.5 g of a polythiol composition was obtained (yield: 47% by mass). It should be noted that the water content in the reaction system was 17.4% by mass.

[0418] [Example 5-1]

[0419] In Example 2-1, water was not used in the reaction step (a 10% by mass tetramethylammonium hydroxide (TMAH) methanol solution was used instead of a 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution), and the reaction step and the separation step were carried out in the same manner as in Example 2-1. As a result, 2.4 g of a polythiol composition was obtained (yield: 32% by mass). It should be noted that the water content in the reaction system was 0.0% by mass.

[0420] [Example 5-2]

[0421] In Example 5-1, the reaction temperature was set to room temperature (15 °C) instead of setting the reaction temperature of the reaction step to 40 °C. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 5-1. As a result, 0.7 g of a polythiol composition was obtained (yield: 10% by mass). It should be noted that the water content in the reaction system was 0.0% by mass.

[0422] [Example 5-3]

[0423] In Example 5-1, the reaction temperature was set to 60 °C instead of setting the reaction temperature of the reaction step to 40 °C. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 5-1. As a result, 2.9 g of a polythiol composition was obtained (yield: 38% by mass). It should be noted that the water content in the reaction system was 0.0% by mass.

[0424] [Example 5-4]

[0425] In Example 5-1, “methanol (98.4 g; 3.1 mol) + ethanol (55.2 g; 1.2 mol) (molar ratio (methanol∶ethanol) = 5∶2)” was used in the reaction step instead of using methanol (38.4 g; 1.2 mol). Except for this, the reaction step and the separation step were carried out in the same manner as in Example 5-1. As a result, 1.2 g of a polythiol composition was obtained (yield: 16% by mass). It should be noted that the water content in the reaction system was 0.0% by mass.

[0426] [Example 6-1]

[0427] In Example 2-1, a 10% by mass aqueous solution of tetraethylammonium hydroxide (TEAH) (176.7 g; 0.12 mol) was used in the reaction step instead of using a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 2-1. As a result, 2.6 g of a polythiol composition was obtained (yield: 35% by mass). It should be noted that the water content in the reaction system (15.0 + 38.4 + 176.7) of water (176.7×0.9) was 69.1% by mass (176.7×0.9 / (15.0 + 38.4 + 176.7)×100).

[0428] [Example 6-2]

[0429] In Example 1-1, in the reaction step, a 10% by mass aqueous solution of tetraethylammonium hydroxide (TEAH) (176.7 g; 0.12 mol) was used instead of a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 2.7 g of a polythiol composition was obtained (yield: 35% by mass). It should be noted that the content of water (176.7×0.9) in the reaction system (15.0 + 55.3 + 176.7) was 64.4% by mass (176.7×0.9 / (15.0 + 55.3 + 176.7)×100).

[0430] [Example 6-3]

[0431] In Example 3-1, in the reaction step, a 10% by mass aqueous solution of tetraethylammonium hydroxide (TEAH) (176.7 g; 0.12 mol) was used instead of a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 3-1. As a result, 2.2 g of a polythiol composition was obtained (yield: 29% by mass). It should be noted that the content of water (176.7×0.9) in the reaction system (15.0 + 72.1 + 70.7) was 60.3% by mass (176.7×0.9 / (15.0 + 72.1 + 176.7)×100).

[0432] [Example 6-4]

[0433] In Example 4-1, in the reaction step, a 10% by mass aqueous solution of tetraethylammonium hydroxide (TEAH) (70.7 g; 0.12 mol) was used instead of a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 4-1. As a result, 0.7 g of a polythiol composition was obtained (yield: 10% by mass). It should be noted that the content of water (176.7×0.9) in the reaction system (15.0 + 129.8 + 70.7) was 49.5% by mass (176.7×0.9 / (15.0 + 129.8 + 176.7)×100).

[0434] [Example 7-1]

[0435] In Example 2-1, in the reaction step, 40% by mass aqueous solution of tetrabutylammonium hydroxide (TBAOH) (77.84 g; 0.12 mol) was used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 2-1. As a result, 2.3 g of the polythiol composition was obtained (yield: 30% by mass). It should be noted that the content of water (124.6×0.75) in the reaction system (15.0 + 38.4 + 77.84) was 35.6% by mass (77.84×0.6 / (15.0 + 38.4 + 77.84)×100).

[0436] [Example 7-2]

[0437] In Example 1-1, in the reaction step, 40% by mass aqueous solution of tetrabutylammonium hydroxide (TBAOH) (77.84 g; 0.12 mol) was used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 2.0 g of the polythiol composition was obtained (yield: 27% by mass). It should be noted that the content of water (77.84×0.6) in the reaction system (15.0 + 55.3 + 77.84) was 31.5% by mass (77.84×0.6 / (15.0 + 55.3 + 77.84)×100).

[0438] [Example 7-3]

[0439] In Example 3-1, in the reaction step, 40% by mass aqueous solution of tetrabutylammonium hydroxide (TBAOH) (77.84 g; 0.12 mol) was used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 3-1. As a result, 1.5 g of the polythiol composition was obtained (yield: 19% by mass). It should be noted that the content of water (124.6×0.75) in the reaction system (15.0 + 72.1 + 124.6) was 28.3% by mass (77.84×0.6 / (15.0 + 72.1 + 77.84)×100).

[0440] [Example 7-4]

[0441] In Example 4-1, in the reaction step, 40% by mass aqueous solution of tetrabutylammonium hydroxide (TBAOH) (77.84 g; 0.12 mol) was used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 4-1. As a result, 1.0 g of the polythiol composition was obtained (yield: 13% by mass). It should be noted that the content of water (124.6×0.75) in the reaction system (15.0 + 129.8 + 124.6) was 21.0% by mass (77.84×0.6 / (15.0 + 129.8 + 77.84)×100).

[0442] [Example 7-5]

[0443] In Example 1-1, in the reaction step, 40% by mass aqueous solution of tetrabutylammonium hydroxide (TBAOH) (77.84 g; 0.12 mol) and toluene (180.0 g) were used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) and ethanol (53.1 g) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 2.4 g of the polythiol composition was obtained (yield: 32% by mass). It should be noted that the content of water (77.84×0.6) in the reaction system (15.0 + 55.3 + 77.84) was 17.1% by mass (77.84×0.6 / (15.0 + 180.0 + 77.84)×100).

[0444] [Example 8-1]

[0445] In Example 2-1, in the reaction step, 40% by mass aqueous solution of benzyltrimethylammonium hydroxide (50.2 g; 0.12 mol) was used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 2-1. As a result, 1.7 g of the polythiol composition was obtained (yield: 23% by mass). It should be noted that the content of water (50.2×0.6) in the reaction system (15.0 + 38.4 + 50.2) was 29.1% by mass (50.2×0.6 / (15.0 + 38.4 + 50.2)×100).

[0446] [Example 8-2]

[0447] In Example 1-1, in the reaction step, 40% by mass aqueous solution of benzyltrimethylammonium hydroxide (50.2 g; 0.12 mol) was used instead of 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 1-1. As a result, 1.8 g of the polythiol composition was obtained (yield: 24% by mass). It should be noted that the content of water (50.2×0.6) in the reaction system (15.0 + 55.3 + 50.2) was 25.0% by mass (50.2×0.6 / (15.0 + 55.3 + 50.2)×100).

[0448] [Example 8-3]

[0449] In Example 3-1, in the reaction step, 40% by mass aqueous solution of benzyltrimethylammonium hydroxide (50.2 g; 0.12 mol) was used instead of using 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 3-1. As a result, 1.0 g of the polythiol composition was obtained (yield: 13% by mass). It should be noted that the content of water (50.2×0.6) in the reaction system (15.0 + 72.1 + 50.2) was 21.9% by mass (50.2×0.6 / (15.0 + 72.1 + 50.2)×100).

[0450] [Example 8-4]

[0451] In Example 4-1, in the reaction step, 40% by mass aqueous solution of benzyltrimethylammonium hydroxide (50.2 g; 0.12 mol) was used instead of using 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (43.8 g; 0.12 mol) as the quaternary ammonium salt aqueous solution. Except for this, the reaction step and the separation step were carried out in the same manner as in Example 4-1. As a result, 0.7 g of the polythiol composition was obtained (yield: 10% by mass). It should be noted that the content of water (50.2×0.6) in the reaction system (15.0 + 129.8 + 50.2) was 15.4% by mass (50.2×0.6 / (15.0 + 129.8 + 50.2)×100).

[0452] [Comparative Example 1-1]

[0453] <Decomposition of Thiolcarbamate Resin Based on Monoethanolamine>

[0454] (Reaction Step)

[0455] Weighed 15.0 g of the thiocarbamate resin powder obtained in Production Example 1, and charged it all into a 300 mL flask equipped with a condenser tube. Added monoethanolamine (7.4 g; 0.12 mol) as an amine compound and an alcohol, and toluene (180.0 g) as a reaction solvent thereto, and heated and stirred at 40 °C (reaction temperature) for 6 hours (reaction time), thereby obtaining a reaction mixture containing a polythiol composition (the above is the reaction step). It should be noted that the water content in the reaction system was 0.0 mass%.

[0456] (Separation step)

[0457] Cooled the reaction mixture obtained in the above reaction step to room temperature, and then removed the solid matter by filtration. Washed the obtained filtrate twice with 50 mL of 1M hydrochloric acid to remove the excess monoethanolamine, and then washed it twice with 50 mL of water to remove the excess hydrochloric acid. Removed the high-polarity by-products from the obtained toluene solution through a silica gel column, and then distilled off the toluene through a rotary evaporator. Successively carried out the removal of low-boiling components using a vacuum pump and filtration using a 1-μm PTFE membrane filter on the obtained mixture, thereby obtaining 0.2 g of a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (i.e., polythiol components) (yield: 3 mass%) (the above is the separation step).

[0458] [Comparative Example 1-2]

[0459] In Comparative Example 1-1, the reaction temperature was set to room temperature (15 °C) instead of 40 °C in the reaction step of the reaction step, and the reaction step and the separation step were carried out in the same manner as in Comparative Example 1-1. As a result, 0.0 g of a polythiol composition was obtained (yield: 0 mass%). It should be noted that the water content in the reaction system was 0.0 mass%.

[0460] [Comparative Example 1-3]

[0461] In Comparative Example 1-1, the reaction temperature was set to 60 °C instead of 40 °C in the reaction step of the reaction step, and the reaction step and the separation step were carried out in the same manner as in Comparative Example 1-1. As a result, 2.4 g of a polythiol composition was obtained (yield: 32 mass%). It should be noted that the water content in the reaction system was 0.0 mass%.

[0462] [Comparative Example 1-4]

[0463] In Comparative Example 1-1, the reaction temperature was set to 110 °C instead of 40 °C for the reaction temperature of the reaction step. Except for this, the reaction step and the separation step were carried out in the same manner as in Comparative Example 1-1. As a result, 5.8 g of the polythiol composition was obtained (yield: 76% by mass). It should be noted that the water content in the reaction system was 0.0% by mass.

[0464] [Evaluation of Yield]

[0465] The yields of Examples 1-1 to 8-4 and Comparative Examples 1-1 to 1-4 are shown in Table 1.

[0466]

[0467] As described above, from Table 1, according to the method for producing a polythiol composition in Examples 1-1 to 8-4, which includes a reaction step of reacting a thiocarbamate resin with a quaternary ammonium salt formed by a quaternary ammonium cation and a counter anion, a polythiol composition can be produced using a thiocarbamate resin as a starting material within a wide temperature range (15 to 110 °C) including a low temperature range.

[0468] It should be understood that the embodiments disclosed herein are illustrative in all respects and not restrictive. The scope of the present disclosure is represented by the claims rather than the above description, and is intended to include all modifications within the meaning and scope equivalent to the claims.

[0469] In the present disclosure, for the examples, contents, and various physical properties of the above components, the examples in the detailed description of the invention or the matters described as the preferred ranges can be arbitrarily combined.

[0470] In addition, for the compositions described in the examples, if they can be adjusted to the compositions described in the detailed description of the invention, the disclosed embodiments can be implemented in the same manner as in the examples throughout the entire composition range of the claims.

Claims

1. A method for manufacturing a polythiol composition, the method comprising: A reaction step of reacting a thiocarbamate resin with a quaternary ammonium salt formed from a quaternary ammonium cation and a counter anion to produce a polythiol composition.

2. The method for manufacturing a polythiol composition according to claim 1, wherein The counter anion is a hydroxide ion.

3. The method for manufacturing a polythiol composition according to claim 1 or 2, wherein The reaction system in the reaction step further contains an alcohol.

4. The method for manufacturing a polythiol composition according to claim 3, wherein The alcohol contains one or more water-miscible alcohols.

5. The method for manufacturing a polythiol composition according to claim 1 or 2, wherein The quaternary ammonium cation is represented by NR4 + and all four Rs are the same group.

6. The method for manufacturing a polythiol composition according to claim 1 or 2, wherein The quaternary ammonium cation is represented by NR4 + wherein three of the four Rs are the same group, and the other of the four Rs is a group different from the same group.

7. The method for manufacturing a polythiol composition according to claim 1 or 2, wherein The quaternary ammonium cation is represented by NR4 + wherein the four Rs are each independently a group selected from an alkyl group, an aromatic group, a heteroaryl group, and a group containing an ether group.

8. The method for manufacturing a polythiol composition according to claim 7, wherein The alkyl group has 1 to 20 carbon atoms and is linear, branched or cyclic.

9. A method for manufacturing a polymerizable composition, the method comprising: A step of manufacturing a polythiol composition by the method for manufacturing a polythiol composition according to any one of claims 1 to 8; And A step of obtaining a polymerizable composition containing the polythiol composition and a polyisocyanate compound by mixing the manufactured polythiol composition with a polyisocyanate compound.

10. A method for manufacturing a resin, the method comprising: A step of manufacturing a polymerizable composition by the method for manufacturing a polymerizable composition according to claim 9, and A step of obtaining a resin by curing the polymerizable composition.

Images