Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
  • C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
  • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses

Definitions

• the present disclosure relates to a method for producing pentaerythritol mercaptocarboxylic acid ester, a polymerizable composition, a resin, an optical material, and a spectacle lens.
• Plastic eyeglass lenses have been widely known for a long time.
• Polythiourethane resin is used as a material for eyeglass lenses (for example, Patent Document 1).
• Polythiourethane resin is a material that has a suitable refractive index, so it can be used as an eyeglass lens with a suitable thickness, and is easy to ensure processability and impact resistance, so it is widely used.
• Pentaerythritol mercaptocarboxylic acid ester is used as a monomer of polythiourethane resin (Patent Document 2).
• Pentaerythritol mercaptocarboxylic acid ester is obtained by dehydrating mercaptocarboxylic acid and pentaerythritol.
• the dehydration reaction is a reversible equilibrium reaction, and the conversion rate can be increased by performing the reaction while discharging water from the system. Therefore, water is discharged from the reaction system by refluxing toluene, which is azeotropic with water, using a Dean-Stark trap or the like.
• toluene solvent increases the purification load and has the problem of coloring the product.
• One embodiment of the present disclosure provides a method for producing a pentaerythritol mercaptocarboxylic acid ester with less purification load and less coloring, a polymerizable composition containing the pentaerythritol mercaptocarboxylic acid ester, and a cured product of the polymerizable composition.
• a resin, an optical material containing the resin, and a spectacle lens containing the resin are provided.
• the present inventors have discovered that the above-mentioned problems can be solved by subjecting mercaptocarboxylic acid and pentaerythritol to a dehydration reaction under solvent-free conditions.
• One embodiment according to the present disclosure includes: dehydrating mercaptocarboxylic acid and pentaerythritol under solvent-free conditions;
• the present invention relates to a method for producing pentaerythritol mercaptocarboxylic acid ester.
• a method for producing a pentaerythritol mercaptocarboxylic acid ester with low purification load and little coloring a polymerizable composition containing the pentaerythritol mercaptocarboxylic acid ester, and curing of the polymerizable composition. It is possible to provide a resin as a product, an optical material containing the resin, and a spectacle lens containing the resin.
• the present embodiment an embodiment of the present disclosure (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. be.
• the notation of a numerical range of "1 to 100” includes both the lower limit value "1” and the upper limit value "100”. The same applies to other numerical ranges.
• One embodiment of the present disclosure relates to a method for producing pentaerythritol mercaptocarboxylic acid ester, which includes dehydrating mercaptocarboxylic acid and pentaerythritol under solvent-free conditions.
• a method for producing a pentaerythritol mercaptocarboxylic acid ester with low purification load and little coloring a polymerizable composition containing the pentaerythritol mercaptocarboxylic acid ester, and curing of the polymerizable composition. It is possible to provide a resin as a product, an optical material containing the resin, and a spectacle lens containing the resin.
• the method for producing pentaerythritol mercaptocarboxylic acid ester according to the present embodiment includes, for example, dehydrating mercaptocarboxylic acid and pentaerythritol under solvent-free conditions (hereinafter also referred to as “reaction step”); Washing the pentaerythritol mercaptocarboxylic acid ester obtained by the dehydration reaction (hereinafter also referred to as "cleaning step”) including.
• reaction step dehydrating mercaptocarboxylic acid and pentaerythritol under solvent-free conditions
• cleaning step washing the pentaerythritol mercaptocarboxylic acid ester obtained by the dehydration reaction
• reaction process In the reaction step, mercaptocarboxylic acid and pentaerythritol are subjected to a dehydration reaction under solvent-free conditions.
• solvent-free conditions means conditions in which no organic solvent such as toluene is used, and specifically, the amount of organic solvent is 20% of the total mass of mercaptocarboxylic acid and pentaerythritol. It means less than % by mass.
• the amount of organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, based on the total mass of mercaptocarboxylic acid and pentaerythritol.
• the mercaptocarboxylic acid preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
• the mercaptocarboxylic acid is preferably 2-mercaptoacetic acid or 3-mercaptopropionic acid.
• an ester bond is formed by a dehydration reaction by the reaction of mercaptocarboxylic acid and pentaerythritol, and pentaerythritol mercaptocarboxylic acid ester is obtained.
• Pentaerythritol preferably has a purity of 90% by mass or more, more preferably a purity of 95% by mass or more, and even more preferably a purity of 98% by mass or more.
• Pentaerythritol may contain more than 1.0% by mass of sodium. Even when containing such a high concentration of sodium, a pentaerythritol mercaptocarboxylic acid ester having a low Hazen color number (APHA) can be obtained.
• APHA Hazen color number
• the molar ratio of mercaptocarboxylic acid and pentaerythritol is preferably 3.5 to 6.0, more preferably 4.0 to 5.0, even more preferably 4. 1 to 5.5.
• a sulfonic acid compound acts as acid catalysts and promote dehydration reactions.
• the sulfonic acid compound include aromatic sulfonic acids such as toluenesulfonic acid, and alkylsulfonic acids.
• alkylsulfonic acids are preferred from the viewpoint of reducing coloring.
• the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, and trifluoromethanesulfonic acid. Among these, methanesulfonic acid is preferred from the viewpoint of reducing coloring.
• the amount of the sulfonic acid compound is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and even more preferably 0. .3 to 3% by mass.
• the reaction step is preferably carried out under reduced pressure while excluding water from the system.
• water from the system By excluding water from the system, the equilibrium of the ester reaction can be tilted toward the product side, and the yield can be improved.
• the reaction step is preferably carried out at a temperature of 90 to 100°C from the viewpoint of reducing coloration.
• the temperature of the reaction step is preferably 90-98°C, more preferably 92-97°C, even more preferably 93-96°C.
• washing step the pentaerythritol mercaptocarboxylic acid ester obtained in the reaction step is washed. Washing is performed, for example, by washing the mixture obtained in the reaction step with water. Thereby, catalysts such as sulfonic acid compounds can be removed.
• Pentaerythritol mercaptocarboxylic acid ester is obtained by the production method according to the present embodiment.
• the Hazen color number (APHA) of the obtained pentaerythritol mercaptocarboxylic acid ester is preferably 15 or less, more preferably 10 or less, still more preferably 7 or less, and still more preferably 6 or less.
• the measured value (g/eq) of the SH number of the obtained pentaerythritol mercaptocarboxylic acid ester/the theoretical value (g/eq) of the SH number of the pentaerythritol mercaptocarboxylic acid ester is preferably 1. It is 10 or less, more preferably 1.08 or less, still more preferably 1.06 or less.
• the actual measured value of the SH number is based on the measurement method described in Examples.
• the polymerizable composition according to this embodiment includes pentaerythritol mercaptocarboxylic acid ester obtained by the production method according to this embodiment and polyiso(thio)cyanate. Pentaerythritol mercaptocarboxylic acid ester is polymerized by reacting with polyiso(thio)cyanate to obtain a cured product.
• polyiso(thio)cyanate examples include polyisocyanate compounds having an aromatic ring, alicyclic polyisocyanate compounds, and linear or branched aliphatic polyisocyanate compounds.
• polyisocyanate compound having an aromatic ring examples include diisocyanatobenzene, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, and dimethylphenylene diisocyanate.
• Examples of the alicyclic polyisocyanate compound include 1,3-diisocyanatocyclohexane, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, Dicyclohexylmethane-4,4'-diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.
• Heptane 2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis Examples include (isocyanatomethyl)-1,3-dithiolane and 4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane.
• linear or branched aliphatic polyisocyanate compounds include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1 , 3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1 , 8-diisocyanato-4-isocyanatomethyloctane, bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl)ether, lysine diisocyanatomethyl ester, lysine triisocyanate, bis(isocyanatomethyl) sulfide, bis( isocyanatoethyl) sulfide, bis(isocyanatopropyl)
• the polyiso(thio)cyanate is preferably bis(isocyanatomethyl)bicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)benzene, tolylene diisocyanate, diphenylmethane diisocyanate.
• the compound contains at least one compound selected from the group consisting of isocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate (hereinafter also referred to as "preferred isocyanate compound”), and more preferably bis( isocyanatomethyl)benzene, tolylene diisocyanate, and diphenylmethane diisocyanate.
• Bis(isocyanatomethyl)bicyclo[2.2.1]heptane is, for example, 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo [2.2.1] One or more selected from the group consisting of heptane, preferably 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl) (natomethyl)bicyclo[2.2.1]heptane.
• Examples of bis(isocyanatomethyl)cyclohexane include 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane. Among these, 1,3-bis(isocyanatomethyl)cyclohexane is preferred.
• Examples of bis(isocyanatomethyl)benzene include 1,3-bis(isocyanatomethyl)benzene and 1,4-bis(isocyanatomethyl)benzene. Among these, 1,3-bis(isocyanatomethyl)benzene is preferred.
• Examples of tolylene diisocyanate include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
• 2,4-tolylene diisocyanate is preferred.
• diphenylmethane diisocyanate include 4,4'-diphenylmethane diisocyanate.
• dicyclohexylmethane diisocyanate include dicyclohexylmethane-4,4'-diisocyanate.
• the polyiso(thio)cyanato compound is bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)cyclohexane, It is preferable to contain at least one selected from (isocyanatomethyl)benzene, isophorone diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate, and among these, bis(isocyanatomethyl)bicyclo[2.2.1]heptane, Alternatively, 1,3-bis(isocyanatomethyl)cyclohexane and bis(isocyanatomethyl)benzene are preferred.
• suitable isocyanate compound in the polyiso(thio)cyanate is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more and 100% by mass or less. It is.
• the equivalent ratio of the mercapto group of the pentaerythritol mercaptocarboxylic acid ester to the isocyanato group of the polyiso(thio)cyanate is preferably 40/60 or more, more preferably 43/57 or more, and even more preferably 45 /55 or more, and preferably 60/40 or less, more preferably 55/45 or less, even more preferably 53/47 or less.
• a polymerization catalyst may be used for curing the isocyanate component and thiol component.
• the polymerization catalyst include tin compounds and nitrogen-containing compounds.
• the tin compound include alkyltin compounds and alkyltin halide compounds.
• the alkyltin compound include dibutyltin diacetate and dibutyltin dilaurate.
• the alkyltin halide compound include dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin fluoride, and dimethyltin dibromide.
• dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dimethyltin dichloride are preferred, and dimethyltin dichloride is more preferred.
• nitrogen-containing compounds examples include tertiary amines, quaternary ammonium salts, imidazole compounds, and pyrazole compounds.
• the tertiary amine is preferably a hindered amine.
• tertiary amine examples include triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N,N-dimethylcyclohexyl Amine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, N-methylmorpholine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine, 1,4-diazabicyclo[2 .2.2] octane (DABCO).
• DABCO octane
• hindered amines include 1,2,2,6,6-pentamethyl-4-piperidinol, 1,2,2,6,6-pentamethyl-4-hydroxyethyl-4-piperidinol, methyl-1,2,2 , 6,6-pentamethyl-4-piperidyl sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl ) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, tetrakis(1 , 2,2,6,6-pentamethyl-4-piperid
• Examples of quaternary ammonium salts include tetraethylammonium hydroxide.
• imidazole compounds include imidazole, 1-methyl-2-mercapto-1H-imidazole, 1,2-dimethylimidazole, benzylmethylimidazole, and 2-ethyl-4-imidazole.
• pyrazole compounds include pyrazole and 3,5-dimethylpyrazole. Among these, tertiary amines such as hindered amines, imidazole compounds, and pyrazole compounds are preferred, imidazole compounds are more preferred, and 1-methyl-2-mercapto-1H-imidazole is even more preferred.
• the amount of the polymerization catalyst used is preferably 0.001 to 2 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.007 parts by mass, based on 100 parts by mass of the total amount of the isocyanate component and thiol component. ⁇ 0.5 part by mass.
• the resin according to this embodiment is a cured product of the polymerizable composition according to the above embodiment.
• the cured product is obtained by polymerizing the components in the polymerizable composition.
• the polymerization conditions can be appropriately set depending on the polymerizable composition.
• the polymerization initiation temperature is preferably 0°C or higher, more preferably 10°C or higher, and preferably 50°C or lower, more preferably 40°C or lower. It is preferable to raise the temperature from the polymerization initiation temperature and then heat to cure and form.
• the maximum heating temperature is usually 110°C or more and 130°C or less.
• Resins are used in various optical materials such as eyeglass lenses, camera lenses, prisms, optical fibers, and base materials used in these, recording medium substrates used in optical disks or magnetic disks, and optical filters attached to computer displays. used. Among these optical materials, it is preferable to use them as eyeglass lenses.
• the eyeglass lens according to this embodiment includes the resin according to this embodiment. Further, the spectacle lens according to the present embodiment preferably includes a lens base material containing the resin according to the present embodiment.
• the lens base material preferably contains the resin according to the present embodiment in an amount of 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more.
• the lens base material may contain other additives such as a mold release agent, a coloring agent, an antioxidant, an anti-coloring agent, and a fluorescent whitening agent. These may be used alone or in combination of two or more.
• the lens base material may be either a finished lens or a semi-finished lens.
• the surface shape of the lens base material is not particularly limited, and may be a flat surface, a convex surface, a concave surface, or the like.
• the lens base material may be used for any purpose such as a single focus lens, a multifocal lens, or a progressive power lens.
• a progressive power lens a near vision region (near vision region) and a progressive vision region (intermediate region) are usually included in the lower region, and a distance vision region (distance vision region) is included in the lower region. is included in the upper region.
• a colorless one is usually used, but a colored one can also be used as long as the transparency is not impaired.
• the refractive index ne of the lens base material is preferably 1.60 or more.
• the upper limit of the refractive index ne of the lens base material is not particularly limited, but may be, for example, 1.80 or less.
• the spectacle lens according to this embodiment may include at least one layer selected from the group consisting of a hard coat layer, a base layer, and an antireflection layer.
• the method for producing a spectacle lens according to the present embodiment includes curing a polymerizable composition containing a thiol component containing the compound (1) obtained by the production method of the present embodiment and an isocyanate component in a mold. include. Odor is suppressed by using the compound obtained by the method for producing compound (1) according to the above-described embodiment. Further, according to the method for manufacturing a spectacle lens according to the present embodiment, a polythiourethane resin having a high refractive index and a colorless and transparent appearance can be obtained. The method for manufacturing a spectacle lens according to the present embodiment may include annealing the cured resin.
• the polymerization is preferably a cast polymerization method.
• the lens base material can be obtained, for example, by injecting a polymerizable composition into a mold made of a combination of a glass or metal mold and a tape or gasket, and polymerizing the composition.
• the polymerization conditions can be appropriately set depending on the polymerizable composition.
• the polymerization initiation temperature is preferably 0°C or higher, more preferably 10°C or higher, and preferably 50°C or lower, more preferably 40°C or lower. It is preferable to raise the temperature from the polymerization initiation temperature and then heat to cure and form.
• the maximum heating temperature is usually 110°C or more and 130°C or less.
• the lens base material may be released from the mold and annealing treatment may be performed.
• the temperature of the annealing treatment is preferably 100 to 150°C.
• a method for producing pentaerythritol mercaptocarboxylic acid ester comprising: ⁇ 2> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to ⁇ 1>, wherein the mercaptocarboxylic acid has 2 to 4 carbon atoms.
• ⁇ 3> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to ⁇ 1> or ⁇ 2>, wherein the mercaptocarboxylic acid is 2-mercaptoacetic acid or 3-mercaptopropionic acid.
• ⁇ 4> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to any one of ⁇ 1> to ⁇ 3>, wherein the dehydration reaction is performed in the presence of a sulfonic acid compound.
• ⁇ 5> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to ⁇ 4>, wherein the amount of the sulfonic acid compound is 0.1 to 10% by mass based on the total amount of the mercaptocarboxylic acid and the pentaerythritol.
• ⁇ 6> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to ⁇ 4> or ⁇ 5>, wherein the sulfonic acid compound is an alkylsulfonic acid.
• ⁇ 7> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to any one of ⁇ 1> to ⁇ 6>, wherein the dehydration reaction is carried out under reduced pressure while excluding water from the system.
• ⁇ 8> The method for producing pentaerythritol mercaptocarboxylic acid ester according to any one of ⁇ 1> to ⁇ 7>, wherein the dehydration reaction is performed at a temperature of 90 to 98°C.
• ⁇ 9> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to any one of ⁇ 1> to ⁇ 8>, wherein the Hazen color number (APHA) of the pentaerythritol mercaptocarboxylic acid ester is 15 or less.
• APHA Hazen color number
• ⁇ 10> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to any one of ⁇ 1> to ⁇ 9>, wherein the pentaerythritol contains more than 1.0% by mass of sodium.
• ⁇ 11> The method for producing a pentaerythritol mercaptocarboxylic acid ester according to any one of ⁇ 1> to ⁇ 10>, which comprises washing the pentaerythritol mercaptocarboxylic acid ester obtained by the dehydration reaction.
• ⁇ 12> A polymerizable composition comprising a pentaerythritol mercaptocarboxylic acid ester obtained by the production method according to any one of ⁇ 1> to ⁇ 11> and polyiso(thio)cyanate.
• ⁇ 13> A resin that is a cured product of the polymerizable composition according to ⁇ 12>.
• ⁇ 14> An optical material containing the resin according to ⁇ 13>.
• ⁇ 15> A spectacle lens containing the resin according to ⁇ 13>.
• Hazen color number (APHA) The Hazen color number (APHA) of the obtained pentaerythritol mercaptocarboxylic acid ester was measured according to the method of JIS K0071-1:2017. Using chromaticity standard solution "1000" (product name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dilute it with pure water to prepare solutions of APHA, 0, 5, 10, 15, 20, 25, and draw the calibration curve. It was created.
• the obtained pentaerythritol mercaptocarboxylic acid ester was filled into a quartz cell with an optical path length of 50 mm, and APHA was measured using a spectrochromatic hazemeter "COH7700" (product name, manufactured by Nippon Denshoku Industries Co., Ltd.).
• ⁇ Refractive index> The refractive index of pentaerythritol mercaptocarboxylic acid ester was measured at 25° C. using a refractometer “RA-600” (product name, manufactured by Kyoto Electronics Industry Co., Ltd.).
• SHV SH value
• Blank measurements were performed by placing only the solvent in a conical beaker and placing it in a cold water bath at 10 ⁇ 5° C., and performing iodine titration using a burette containing 0.05 mol/L iodine aqueous solution while stirring at 300 rpm with a stirrer. The point at which the color changed to yellow was defined as the end point, the amount dropped was recorded, and this was used as a blank. Next, the sample dissolved in a solvent was subjected to iodine titration using the same procedure as described above. Check the end point and record the amount dropped. The dropped amount was input into the SH-value calculation formula to determine the SH value.
• SHV (g/eq) (S x 1000) / ⁇ (AB) x f x 0.1 ⁇
• f Factor of 0.05 mol/L iodine solution
• Example 1 Add 37.3 parts by mass (0.274 mol) of pentaerythritol, 120.0 parts by mass (1.131 mol) of 3-mercaptopropionic acid, and 0.835 parts by mass of methanesulfonic acid into a 1000 mL flask and heat to around 100°C. The mixture was immersed in a temperature-controlled oil bath and reacted with stirring for 3 hours while degassing using a vacuum pump (inner temperature 95°C). After the reaction was completed, it was washed three times with 200 mL of water, and water was removed using a vacuum pump.
• the refractive index of the synthesized pentaerythritol mercaptocarboxylic acid ester was nd (25°C) 1.528, and the APHA was 5. 53.15 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter also referred to as "HXDI"), 0.22 parts by mass of acidic phosphate ester "JP506H” (trade name, manufactured by Johoku Kagaku Kogyo Co., Ltd.), and 0.072 parts by mass of dimethyltin dichloride (DMTDCl) and 0.12 parts by mass of the ultraviolet absorber "SEESORB707" (trade name, manufactured by Shipro Kasei Co., Ltd.) were mixed and dissolved, and 66.85 parts by mass of the pentaerythritol mercaptocarboxylic acid ester described above was dissolved.
• HXDI 1,3-bis(isocyanatomethyl)cyclohexane
• Example 4 Pentaerythritol mercaptocarboxylic acid ester and resin cylinders were obtained in the same manner as in Example 1 except that a mixture containing 37.3 parts by mass of pentaerythritol and 1.10 parts by mass of NaCl was used as pentaerythritol. The obtained resin cylinders were evaluated as described above, and the results are shown in Table 1.
• the dehydration reaction under solvent-free conditions provides a method for producing pentaerythritol mercaptocarboxylic acid ester with less purification load and less coloring.

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