JP2005336104A - Method for producing pentaerythritol mercaptocarboxylic acid ester and polymerizable composition composed thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pentaerythritol mercaptocarboxylic acid ester obtained by reacting pentaerythritol with a mercaptocarboxylic acid and giving a polyurethane lens free from clouding phenomenon by polymerizing with a poly(iso)thiocyanate. <P>SOLUTION: A pentaerythritol mercaptocarboxylic acid ester is produced by reacting pentaerythritol having a sodium and calcium content of ≤1.0 wt.% in total and a bispentaerythritol content of ≤5.0 wt.% with a mercaptocarboxylic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a pentaerythritol mercaptocarboxylic acid ester and a method for producing the same, and a polymerizable composition comprising a pentaerythritol mercaptocarboxylic acid ester and a polyiso (thio) cyanate compound used for a polyurethane-based lens giving good optical properties.

  In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.

  Plastic lens resins are required to have higher performance, and higher refractive index, higher Abbe number, lower specific gravity, higher heat resistance, and the like have been demanded. Various resin materials for lenses have been developed and used so far.

  Among them, proposals relating to polyurethane resins have been actively made, and the present inventors have also made various proposals relating to plastic lenses using the polyurethane resins. (See Patent Document 1, Patent Document 2, and Patent Document 3.)

  Among them, the resin obtained by reacting pentaerythritol mercaptocarboxylic acid ester and polyiso (thio) cyanate compound as the most representative resin is colorless and transparent, has a high refractive index and low dispersion, and has impact, dyeability and processing. It is one of the most suitable resins for plastic lenses with excellent properties.

Pentaerythritol mercaptocarboxylic acid ester is produced by a so-called direct esterification method in which ordinary polyhydric alcohol and mercaptocarboxylic acid are distilled out in the presence of an esterification catalyst while distilling water out of the system. . (See Patent Document 4)

  Pentaerythritol, which is a raw material for this ester compound, is usually produced by condensing acetaldehyde and formaldehyde. Its purity is usually about 90% by weight and contains several impurities. Among these, bispentaerythritol, which is a formaldehyde bimolecular condensate of pentaerythritol, can be mentioned. If this bispentaerythritol is contained in an amount exceeding 5% by weight, it is difficult to release from the mold after the polymerization with the polyisocyanate compound, or bubbles are generated in the obtained lens. It is known to occur. (See Patent Documents 5 and 6).

  Pentaerythritol containing such bispentaerythritol can be made to have a bispentaerythritol content of 5% by weight or less by heat treatment at 160 ° C. to 200 ° C., and further, pentaerythritol having a content of 98% by weight or more. It is known that it can be purified to a low temperature (see Patent Document 5). However, even when pentaerythritol purified in this way is used, the resulting pentaerythritol mercaptocarboxylic acid ester and the polyisocyanate compound are polymerized, and the resulting lens may become cloudy. Suppression was desired.

JP-A-60-199016 JP-A-60-217229, JP-A-63-46213 Japanese Examined Patent Publication No. 39-9071 JP-A-56-20530 JP-A-10-120646

  An object of the present invention is a pentaerythritol mercaptocarboxylic acid ester obtained by reacting pentaerythritol with a mercaptocarboxylic acid, which can obtain a polyurethane-based lens having no cloudiness when polymerized with poly (iso) thiocyanate. It is to provide.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that the cause of the polyurethane-based lens becoming cloudy is the pentaerythritol mercaptocarboxylic acid ester that is a monomer. As a result of further intensive investigations, surprisingly, a pentamer produced from pentaerythritol having a bispentaerythritol content of a specific amount or less and a total content of sodium and calcium of a specific amount or less is used as a raw material. It has been found that if erythritol mercaptocarboxylic acid ester is used, the above-mentioned problems are solved and a colorless and transparent polyurethane-based lens in which white turbidity is suppressed can be obtained, leading to the present invention.

That is, the present invention
1) Pentaerythritol mercaptocarboxylic acid ester in which pentaerythritol having a total content of sodium and calcium of 1.0% by weight or less and a content of bispentaerythritol of 5.0% by weight or less is reacted with mercaptocarboxylic acid It relates to the manufacturing method.
Further, the following 2 to 8) are each one of preferred embodiments of the present invention.
2) The method for producing a pentaerythritol mercaptocarboxylic acid ester according to 1), wherein the total content of alkali metal and alkaline earth metal in the pentaerythritol is 1.0% by weight or less.
3) Content of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn in the pentaerythritol The method for producing pentaerythritol mercaptocarboxylic acid ester according to 1), which is 1.0% by weight or less in total.
4) Pentaerythritol mercaptocarboxylic acid ester obtained by the production method according to any one of 1) to 3) above.
5) A polymerizable composition comprising the pentaerythritol mercaptocarboxylic acid ester described in 4) above and a polyiso (thio) cyanate compound. Here, “consisting of a pentaerythritol mercaptocarboxylic acid ester and a polyiso (thio) cyanate compound” means that a part of the polymerizable composition is composed of the pentaerythritol mercaptocarboxylic acid ester and a polyiso (thio) cyanate compound. In this case, and when a part of the polymerizable composition is composed of the pentaerythritol mercaptocarboxylic acid ester and the polyiso (thio) cyanate compound.
6) A resin obtained by curing the polymerizable composition as described in 5) above.
7) An optical element made of the resin described in 6) above.
8) A lens made of the resin described in 6) above.
In the above 7) and 8), “made of resin” means that the optical element or the lens is entirely made of the resin, and that a part of the optical element or the lens is made of the resin. If it is, it is intended to include both.

  The method for producing pentaerythritol mercaptocarboxylic acid ester of the present invention and the polyurethane-based lens obtained by this method solve the above-mentioned problems. Thereby, a colorless and transparent polyurethane-based lens in which white turbidity is suppressed is provided.

  The pentaerythritol used as the raw material of the ester compound of the present invention is specified by the content of bispentaerythritol and the total content of sodium and calcium. That is, pentaerythritol having a bispentaerythritol content of 5.0% by weight or less and a total content of sodium and calcium of 1.0% by weight or less is used.

  When bispentaerythritol is 5.0% by weight or less, it is possible to obtain a polyurethane-based lens that is excellent in releasability and does not generate bubbles. The content of bispentaerythritol can be measured, for example, by gas chromatography as described in Patent Document 5, or can be measured by high performance liquid chromatography as described in Patent Document 6. The content of bispentaerythritol can be reduced by appropriately adopting a conventionally known method. For example, heat treatment may be performed at 160 ° C. to 200 ° C. as described in Patent Document 5, or hydrolysis may be performed while heating under reflux in a nitrogen atmosphere as described in Patent Document 6. By appropriately applying these means, pentaerythritol having a bispentaerythritol content of 5.0% by weight or less can be obtained.

  Further, if the total content of sodium and calcium is 1.0% by weight or less, a polyurethane system obtained by polymerizing pentaerythritol mercaptocarboxylic acid ester and polyiso (thio) cyanate produced using the pentaerythritol The lens is a colorless and transparent polyurethane-based lens in which white turbidity is suppressed. From the viewpoint of suppression of white turbidity, the sodium and calcium contents of pentaerythritol used in the present invention are 1.0% by weight or less in total, preferably 0.5% by weight or less in total, and more preferably 0. 2% by weight or less. Similarly, from the viewpoint of suppressing white turbidity, the total content of alkali metals and alkaline earth metals is preferably 1.0% by weight or less, more preferably Li, Na, K, Rb, Cs, The total content of various metal elements of Be, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn is preferably 1.0% by weight or less. .

The method for measuring the content of the metal element is as follows. About light metals, such as Na, after making pentaerythritol into aqueous solution, it quantifies by the ion chromatography method. For heavy metals in general, pentaerythritol is incinerated and then dissolved in a coloring solution to develop color, and the content is quantified by an atomic absorption method for measuring absorbance, a plasma emission analyzer, or the like.
The content of sodium and calcium, and the content of various metals including alkali metals and alkaline earth metals is reduced by appropriately adopting conventionally known methods, and is 1.0% by weight or less. Can be. For example, it can be reduced by acid treatment with hydrochloric acid, sulfuric acid or the like, or can be reduced by an aqueous recrystallization method.

  The other raw material, mercaptocarboxylic acid, is a compound having one or more mercapto groups and one or more carboxyl groups in one molecule, and is not particularly limited in terms of quality, and ordinary industrial chemicals are preferably used. Is done. Specific examples include thioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, thiomalic acid, thiosalicylic acid and the like, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more with pentaerythritol.

  Examples of esterification catalysts usually used for reacting pentaerythritol with mercaptocarboxylic acid include mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and alumina, and p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and trichloroacetic acid. An acid catalyst typified by an organic acid such as dibutyltin dioxide is preferably used.

  For the production of pentaerythritol mercaptocarboxylic acid ester, the use of an azeotropic agent is not an essential condition, but a general method of removing by-product water from the system continuously under heating and reflux using an azeotropic agent is common. is there. Examples of commonly used azeotropic agents include benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichlorobenzene, anisole, diphenyl ether, methylene chloride, chloroform, dichloroethane and the like. These may be used as a mixture of two or more, or may be used as a mixture with other solvents.

  Examples of the pentaerythritol mercaptocarboxylic acid ester of the present invention obtained by the above method include the following compounds. Examples include pentaerythritol thioglycolic acid ester, pentaerythritol 3-mercaptopropionic acid ester, pentaerythritol thiolactic acid ester, and pentaerythritol thiosalicylic acid ester, but the present invention is not limited to these exemplified compounds. These ester compounds may be compounds in which the hydroxy group of pentaerythritol is completely esterified, or compounds in which only a part is esterified. Further, two or more of these ester compounds may be mixed.

  The polyiso (thio) cyanate compound of the present invention is a compound having at least two or more iso (thio) cyanate groups in one molecule and is not particularly limited. Specifically, hexamethylene diisocyanate, 2, 2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Narate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanato Ethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate Aliphatic polyisocyanate compounds such as diisocyanate,

  1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylpheny Range isocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4′-methylenebis (phenyl isocyanate), 4 , 4′-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4′-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatoethyl) benzene, bis Isocyanatopropyl) benzene, α, α, α ′, α′-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ether, bis ( Polyisocyanate compounds having an aromatic ring compound such as isocyanatoethyl) phthalate and 2,6-di (isocyanatomethyl) furan,

Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis ( Isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatomethylthio) ethane, 1, 5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1 , 2,6 7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithia-1,7-heptanediisocyanate, 2,5-diisocyanatomethylthiophene, 4-isocyanatoethylthio-2, Sulfur-containing aliphatic polyisocyanate compounds such as 6-dithia-1,8-octane diisocyanate,

  Aromatic isocyanate polyisocyanate compounds such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethylphenyl) sulfide,

  Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-6-isocyanatophenyl) Aromatic disulfide polyisocyanate compounds such as disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) disulfide,

  2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanate Natomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl A sulfur-containing alicyclic polyisocyanate compound such as -1,3-dithiolane,

  Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane, 1,6-diisothiocyanatohexane, alicyclic polyisothiocyanate compounds such as cyclohexanediisothiocyanate, 1,2-di Isothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, 4, 4'-methylenebis (phenylisothiocyanate), 4,4'-methylenebis (2-methylphenylisothiocyanate), 4,4'-methylenebis (3-methylphenylisothiocyanate), 4,4'-diisothi Oceanatobenzophenone, 4,4′-diisothiocyanato-3,3′-dimethylbenzophenone, bis (4 Isothiocyanatophenyl) aromatic poly isothiocyanate compounds such as ethers,

  Furthermore, carbonyl isothiocyanes such as 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4-dicarbonyldiisothiocyanate, etc. A sulfur-containing aliphatic isothiocyanate compound such as a nate compound, thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane),

  Sulfur-containing aromas such as 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene) Group polyisothiocyanate compounds, sulfur-containing alicyclic compounds such as 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane,

  1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2- Isocyanato groups such as isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanatophenyl sulfide, 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide And compounds having an isothiocyanato group, but are not limited to these exemplified compounds.

  Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products, and the like can also be used. These compounds may be used alone or in combination of two or more.

  The proportion of pentaerythritol mercaptocarboxylic acid ester and polyiso (thio) cyanate compound used is usually in the range of SH group / NCO group = 0.3 to 2.0, preferably in the range of 0.7 to 2.0. is there.

  For the purpose of improving various physical properties, operability, polymerization reactivity and the like of the polyurethane resin of the present invention, an active hydrogen typified by an amine or the like in addition to an ester compound and an iso (thio) cyanate compound forming a urethane resin. You may add 1 type (s) or 2 or more types other than urethane formation raw materials, such as a compound, an epoxy compound, an olefin compound, a carbonate compound, an ester compound, a metal, a metal oxide, an organometallic compound, and an inorganic substance.

  Also, depending on the purpose, as in known molding methods, chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, mold release agents, bluing agents, etc. Various substances may be added. In order to adjust to a desired reaction rate, a thiocarbamic acid S-alkyl ester or a known reaction catalyst used in the production of polyurethane can be appropriately added. A lens made of the polyurethane resin of the present invention is usually obtained by cast polymerization.

  Specifically, a pentaerythritol mercaptocarboxylic acid ester and a polyiso (thio) cyanate compound are mixed. If necessary, this mixed solution is defoamed by an appropriate method and then poured into a mold, and is usually gradually heated from a low temperature to a high temperature for polymerization.

  The polyurethane-based resin of the present invention thus obtained has a high refractive index and low dispersion, is excellent in heat resistance and durability, has light weight and excellent impact resistance, and is also cloudy. Occurrence is suppressed, and it is suitable as a material for optical elements such as eyeglass lenses and camera lenses.

Further, the polyurethane-based lens of the present invention is surface-polished in order to improve antireflection, imparting high hardness, improving wear resistance, improving chemical resistance, imparting cloud resistance, imparting fashionability, etc., as necessary. Physical and chemical treatments such as antistatic treatment, hard coat treatment, antireflective coat treatment, dyeing treatment, and light control treatment can be performed.

Hereinafter, the present invention will be specifically described by way of examples. The pentaerythritol used was analyzed by the following method. Further, among the performance of the obtained resin, refractive index, releasability, bubbles, and transparency were evaluated by the following test methods.
Bispentaerythritol content: Pentaerythritol was dissolved in water and measured by high performance liquid chromatography.
-Content of sodium and calcium: Pentaerythritol was dissolved in water and then measured by high performance liquid ion chromatography.
-Content of other metals: After ashing pentaerythritol, acidified with hydrochloric acid and then diluted with pure water was measured with an inductively coupled plasma emission spectrometer.
Refractive index (ne), Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
Evaluation of releasability: Evaluation was performed using a convex mold made of a glass mold and a tape having an outer diameter of 84 mm, a height of 17 mm, an outer diameter of 84 mm, and a height of 11 mm. 10 sets each were charged, and after completion of the polymerization, the mixture was allowed to cool to room temperature and no mold breakage or cracking was observed (◯), and the others were designated (x).
-Bubble evaluation: When a plastic lens was observed with a 100-fold microscope, the case where there was a bubble inside was (x), and the case where there was no bubble was marked as (o).
-Transparency: A circular flat plate having a thickness of 9 mm and a diameter of 75 mm was prepared and measured with a gray-scale image device. When the C luminance was 50 or less, (◯), and 51 or more was taken as (×).

[Example 1]
(Synthesis of pentaerythritol (3-mercaptopropionic acid) ester)
In a 1-liter four-necked reaction flask equipped with a stirrer, reflux-cooled moisture separator, nitrogen gas purge tube, and thermometer, 4.7% by weight of bispentaerythritol, 0.1% by weight of sodium (metal component is sodium only) ) Containing 143.0 parts by weight (1.0 mol) of pentaerythritol, 4.0 parts by weight of p-toluenesulfonic acid monohydrate, 172.0 parts by weight of toluene, 3-mercaptopropon 440.3 parts by weight (4.15 mol) of acid was added, and the reaction was carried out for 5 hours (internal temperature: 104 to 121 ° C.) while continuously removing water produced as a by-product under heating and refluxing, and then cooled to room temperature. . The amount of water extracted out of the system was 99.0% with respect to the theoretically generated water. The reaction solution was washed with a base and washed with water, and after removing toluene and a small amount of water under reduced pressure, filtration was performed to obtain 465.0 parts by weight of pentaerythritol-3-mercaptopropionic acid ester (hereinafter abbreviated as PEMP). It was. The obtained PEMP had an APHA of 10 and an SHV of 7.81 eq / g.

(Manufacture of plastic lenses)
87 parts by weight of m-xylylene diisocyanate, 0.01 parts by weight of dibutyltin dichloride as a curing catalyst, 0.18 parts by weight of Zelec UN (acidic phosphate ester), 0.10 parts by weight of Biosorb 583 (ultraviolet absorber), The mixture was dissolved at 20 ° C. 113 parts by weight of the obtained PEMP was charged and mixed to obtain a mixed homogeneous liquid. The uniform liquid was defoamed at 600 Pa for 1 hour, filtered through a 3 μm Teflon (registered trademark) filter, and then poured into a mold composed of a glass mold and a tape. The mold was put into an oven, gradually heated from 10 ° C. to 120 ° C., and polymerized in 18 hours. After completion of the polymerization, the mold was removed from the oven and released to obtain a resin. The obtained resin was further annealed at 120 ° C. for 3 hours. The obtained resin is colorless and highly transparent and has a good refractive index (ne) 1.600, Abbe number (νe) 35, releasability evaluation ○, bubble evaluation ○, and C luminance representing transparency is 20 It corresponded to ○.

[Example 2]
In place of pentaerythritol used in Example 1, pentaerythritol having a purity of 95.5% containing 4.0% by weight of bispentaerythritol and 0.02% by weight of calcium (the metal component is calcium only) was used. Prepared a pentaerythritol (3-mercaptopropionic acid) ester in the same manner as in Example 1. Using the obtained pentaerythritol (3-mercaptopropionic acid) ester, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

[Example 3]
Pentaerythritol thioglycolate was synthesized in the same manner as in Example 1 except that 382.3 parts by weight (4.15 mol) of thioglycolic acid was used instead of 3-mercaptopropionic acid. Using the obtained pentaerythritol thioglycolate, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 1]
Instead of pentaerythritol used in Example 1, pentaerythritol having a purity of 95.9% containing 1.0% by weight of bispentaerythritol and 3.1% by weight of sodium (metal component is sodium only) was used. Prepared a pentaerythritol (3-mercaptopropionic acid) ester in the same manner as in Example 1. Using the obtained pentaerythritol (3-mercaptopropionic acid) ester, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 2]
Instead of pentaerythritol used in Example 1, pentaerythritol having a purity of 94.8% containing 5.0% by weight of bispentaerythritol and 0.2% by weight of sodium (metal component is sodium only) was used. Prepared a pentaerythritol (3-mercaptopropionic acid) ester in the same manner as in Example 1. Using the obtained pentaerythritol (3-mercaptopropionic acid) ester, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 3]
Instead of pentaerythritol used in Example 1, pentaerythritol having a purity of 91.9% containing 5.0% by weight of bispentaerythritol and 3.1% by weight of sodium (metal component is sodium only) was used. Prepared a pentaerythritol (3-mercaptopropionic acid) ester in the same manner as in Example 1. Using the obtained pentaerythritol (3-mercaptopropionic acid) ester, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 4]
In place of pentaerythritol used in Example 1, pentaerythritol having a purity of 91.9% containing 5.0% by weight of bispentaerythritol and 3.1% by weight of calcium (metal component is calcium only) was used. Prepared a pentaerythritol (3-mercaptopropionic acid) ester in the same manner as in Example 1. Using the obtained pentaerythritol (3-mercaptopropionic acid) ester, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

[Comparative Example 5]
In place of pentaerythritol used in Example 3, pentaerythritol having a purity of 91.9% containing 5.0% by weight of bispentaerythritol and 3.1% by weight of calcium (the metal component is calcium only) was used. Prepared a pentaerythritol thioglycolate ester in the same manner as in Example 3. Using the obtained pentaerythritol thioglycolate, a plastic lens was produced and evaluated in the same manner as in Example 1. The evaluation results of the obtained plastic lens are shown in Table 1.

Claims (8)

A pentaerythritol mercaptocarboxylic acid ester in which pentaerythritol having a total content of sodium and calcium of 1.0% by weight or less and a content of bispentaerythritol of 5.0% by weight or less is reacted with mercaptocarboxylic acid Production method. The method for producing a pentaerythritol mercaptocarboxylic acid ester according to claim 1, wherein the total content of alkali metal and alkaline earth metal in the pentaerythritol is 1.0 wt% or less.   The total content of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn in the pentaerythritol The manufacturing method of the pentaerythritol mercaptocarboxylic acid ester of Claim 1 which is 1.0 weight% or less.         Pentaerythritol mercaptocarboxylic acid ester obtained by the production method according to any one of claims 1 to 3.   A polymerizable composition comprising the pentaerythritol mercaptocarboxylic acid ester according to claim 4 and a polyiso (thio) cyanate compound. A resin obtained by curing the polymerizable composition according to claim 5. An optical element made of the resin according to claim 6. A lens made of the resin according to claim 6.