WO2017175407A1

WO2017175407A1 - Optical element production method

Info

Publication number: WO2017175407A1
Application number: PCT/JP2016/076848
Authority: WO
Inventors: 幸夫影山; 上坂　昌久; 山本　明典
Original assignee: ホヤレンズタイランドリミテッド; 幸夫影山; 上坂　昌久; 山本　明典
Priority date: 2016-04-06
Filing date: 2016-09-12
Publication date: 2017-10-12
Also published as: JPWO2017175407A1

Abstract

The present invention provides an optical element production method by which an optical element having excellent heat resistance can be obtained and provides a polythiol mixture production method. The optical element production method comprises: a step 1 for obtaining a polymerizable composition by mixing mixture 1 containing a compound 1-1, a compound 1-2, and a compound 1-3 and a polyiso(thio)cyanate compound; and a step 2 for obtaining an optical element by polymerizing the polymerizable composition obtained in step 1, wherein the measured value of the thiol equivalent amount of mixture 1 in step 1 is 102 g/eq or less.

Description

Manufacturing method of optical member

The present invention relates to a method for producing an optical member and a method for producing a polythiol mixture.

The plastic spectacle lens is lighter and has better impact durability than the glass spectacle lens. In the current spectacle lens market, plastic spectacle lenses are the mainstream.
Patent Document 1 describes a method of manufacturing a plastic lens that can stabilize the dyeability of a thiourethane plastic lens. Here, in a plastic lens manufacturing method for manufacturing a plastic lens from a polymer obtained by polymerizing a thiol compound containing a thiol group and an isocyanate compound containing an isocyanate group, the thiol group and the isocyanate group are predetermined. And a method for producing a plastic lens, characterized in that a thiol compound and an isocyanate compound are used so that the fluctuation of the functional group molar ratio falls within a predetermined range. .

JP 2000-47003 A

When a plastic lens is produced using a specific thiol compound, depending on the production lot, the glass transition temperature (hereinafter also referred to as “Tg”) is low, and sufficient heat resistance may not be obtained.
Patent Document 1 states that stabilization of the dyeability of a plastic lens is an issue, and it is described that the dispersion of the dyeability has a great influence on the thiol equivalent representing the purity of the raw material thiol compound, but the heat resistance is evaluated. It has not been.
An object of one embodiment of the present invention is to provide a method for producing an optical member from which an optical member having excellent heat resistance is obtained, and a method for producing a polythiol mixture.

When using a mixture of specific thiol compounds as the monomer of the polymerization composition, the inventor obtains an optical member having excellent heat resistance by setting the measured value of the thiol equivalent of the mixture within a predetermined range. I found out that

One example is
Step 1: A step of mixing a mixture 1 of the following compound 1-1, the following compound 1-2 and the following compound 1-3 with a polyiso (thio) cyanate compound to obtain a polymerization composition;
Step 2: a step of polymerizing the polymerization composition obtained in Step 1 to obtain an optical member;
With
It is a manufacturing method of the optical member whose measured value of the thiol equivalent of the mixture 1 of the process 1 is 102 g / eq or less.

One example is
Step A: 2-Mercaptoethanol and epichlorohydrin are reacted in the presence of an amine catalyst to obtain a compound represented by the formula (1):

Obtaining a compound represented by:
Step B: By reacting the compound obtained in Step A with sodium sulfide, the formula (2):

Obtaining a compound represented by:
Step C: reacting the compound obtained in Step B with thiourea in the presence of a mineral acid to obtain an isothiuronium salt;
Step D: a step of hydrolyzing the isothiuronium salt obtained in Step C with a basic substance to obtain a mixture of Compound 1-1, Compound 1-2, and Compound 1-3;
Step E: washing the mixture obtained in Step D with mineral acid and water and purifying the mixture,
It is a manufacturing method of the polythiol mixture which makes the measured value of the thiol equivalent of the mixture obtained at the process E below 102 g / eq.

According to the above-described embodiment, it is possible to provide an optical member manufacturing method and a polythiol mixture manufacturing method for obtaining an optical member having excellent heat resistance.

[Method for producing optical member]
The manufacturing method of the optical member of one example is as follows:
Step 1: Mixture 1 of Compound 1-1, Compound 1-2 and Compound 1-3 (hereinafter also referred to as “polythiol mixture” or “mixture 1”) and a polyiso (thio) cyanate compound are mixed to form a polymerization composition. Obtaining
Step 2: a step of polymerizing the polymerization composition obtained in Step 1 to obtain an optical member;
With
The measured value of the thiol equivalent of the mixture 1 in step 1 is 102 g / eq or less.
According to the manufacturing method of one Example, Tg of the optical member obtained can be raised by using the mixture of the measured value of the thiol equivalent of the above-mentioned range, and the optical member which has the outstanding heat resistance is obtained.

[Step 1]
<Polythiol mixture>
The polythiol mixture includes the following compound 1-1, the following compound 1-2, and the following compound 1-3.

In order to obtain excellent heat resistance, the measured value of the thiol equivalent of the polythiol mixture is 102 g / eq or less, preferably 100 g / eq or less, more preferably 99 g / eq or less.
The measured value of the thiol equivalent of the polythiol mixture is preferably 95 g / eq or more, more preferably 96 g / eq or more, still more preferably 97 g / eq or more, and further preferably 98 g / eq or more in order to obtain excellent heat resistance. In this range, in addition to excellent heat resistance, there are also effects of suppressing striae and cloudiness.
In this specification, a thiol equivalent means the mass (g) per unit quantity (eq) of the mercapto group contained in a polythiol mixture.
The measuring method of the measured value of thiol equivalent is based on the method described in the Examples.

The polythiol mixture is not particularly limited, but is preferably obtained by a production method including the following steps A to E for adjustment of the measured value of the thiol equivalent.

[Process A]
In step A, 2-mercaptoethanol and epichlorohydrin are reacted in the presence of an amine catalyst to obtain the formula (1):

To obtain a compound represented by:

The molar ratio of 2-mercaptoethanol to epichlorohydrin is preferably 60/40 to 40/60, more preferably 60/40 to 50/50, and still more preferably 55/45 to 50/50.

Examples of the amine catalyst include triethylamine, trimethylamine, tripropylamine, and the like.
The compounding amount of the amine catalyst is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and further preferably 0 to 100 parts by mass of the total of 2-mercaptoethanol and epichlorohydrin. .5 to 5 parts by mass.

In Step A, the reaction temperature is preferably 0 to 60 ° C., more preferably 10 to 55 ° C., and still more preferably 20 to 50 ° C.
In step A, the reaction time is, for example, 30 minutes to 2 hours.

[Process B]
In step B, the compound obtained in step A is reacted with sodium sulfide to give the formula (2):

To obtain a compound represented by:

The amount of sodium sulfide used is preferably more than 50.0 mol%, more preferably, in order to adjust the measured value of thiol equivalent and obtain excellent heat resistance with respect to 100 mol% of the compound obtained in Step A. 51.0 mol% or more, more preferably 52.0 mol% or more.
The amount of sodium sulfide used is preferably 55.0 mol% or less, more preferably, in order to adjust the measured value of the thiol equivalent with respect to 100 mol% of the compound obtained in Step A and to obtain excellent heat resistance. It is 54.0 mol% or less, More preferably, it is 53.0 mol% or less, More preferably, it is 52.0 mol% or less, More preferably, it is 51.5 mol% or less.
Sodium sulfide is preferably added as an aqueous solution. In this case, the concentration of the aqueous sodium sulfide solution is preferably 40 to 80% by mass, more preferably 45 to 70% by mass, and further preferably 50 to 60% by mass.

In Step B, the reaction temperature is preferably 0 to 60 ° C., more preferably 10 to 55 ° C., and still more preferably 20 to 50 ° C.
In step B, the reaction time is, for example, about 30 minutes to 2 hours.

[Process C]
In Step C, the compound obtained in Step B is reacted with thiourea in the presence of a mineral acid to obtain an isothiuronium salt.
Examples of the mineral acid include hydrochloric acid, nitric acid, sulfuric acid and the like.
The mineral acid is preferably added as an aqueous solution. In this case, the concentration of the mineral acid aqueous solution is preferably 10 to 50% by mass, more preferably 20 to 45% by mass, and further preferably 30 to 40% by mass.
The blending amount of the mineral acid is preferably 100 to 300 mol%, more preferably 110 to 200 mol%, still more preferably with respect to 100 mol% of the total blending amount of 2-mercaptoethanol and epichlorohydrin in Step A. Is 130 to 180 mol%.

In Step C, the reaction temperature is preferably 80 to 130 ° C, more preferably 90 to 120 ° C, and still more preferably 100 to 115 ° C.
In step C, the reaction time is, for example, about 5 to 15 hours.

[Process D]
In Step D, the isothiuronium salt obtained in Step C is hydrolyzed with a basic substance to obtain a mixture of Compound 1-1, Compound 1-2, and Compound 1-3.
Examples of the basic substance include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferable.
The basic substance is preferably added as an aqueous solution. In this case, the concentration of the basic substance aqueous solution is preferably 10 to 50% by mass, more preferably 20 to 45% by mass, and still more preferably 25 to 45% by mass. is there.

In Step D, the reaction temperature is preferably 40 to 100 ° C, more preferably 50 to 90 ° C, and still more preferably 55 to 80 ° C.
In step D, the reaction time is, for example, about 1 to 8 hours.

[Process E]
In step E, the mixture obtained in step D is washed with mineral acid and water to purify the mixture.
Suitable examples of the mineral acid are the same as those exemplified in Step C.
Washing with water is carried out by a conventional method. In addition, you may remove the organic solvent used by washing | cleaning or the previous process as needed.
The mixture obtained in step E is preferably used as mixture 1 in step 1.

As described above, in the production method described above, by adjusting the amount of sodium sulfide used for the compound obtained in step A, and adjusting various conditions in consideration of technical common sense, measurement of the thiol equivalent of the resulting thiol mixture You can adjust the value.

<Polyiso (thio) cyanate compound>
The polyiso (thio) cyanate compound means at least one selected from a polyisocyanate compound and a polyisothiocyanate compound. The polyiso (thio) cyanate compound is preferably a polyisocyanate compound.
Examples of the polyiso (thio) cyanate compound include a polyiso (thio) cyanate compound having one or more aromatic rings, an alicyclic polyiso (thio) cyanate compound, and a linear or branched aliphatic polyiso (thio) cyanate compound. Can be mentioned.

Examples of the polyiso (thio) cyanate compound having one or more aromatic rings include diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene. Diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4'-diisocyanate Bis (isocyanatophenyl) ethylene, xylylene diisocyanate, bis (iso Anatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ) Ether, 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) disulfide, bis (4-methyl-5-isocyanatophenyl) ) Disulf Bis (3-methoxy-4-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) disulfide, 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′-diisothiocyanatobenzophenone, 4,4′-diisothiocyanato-3,3′-dimethylbenzophenone, bis (4-isothiocyanatophenyl) ether, and the like.

Examples of alicyclic polyiso (thio) cyanate compounds include diisocyanatocyclohexane, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, bis (isocyanatomethyl) bicycloheptane, 2,5-diisocyanato-1, 4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, Examples include 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane.

Examples of linear or branched aliphatic polyiso (thio) cyanate compounds include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, and 1,3-butadiene-1. , 4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, Bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) Rufide, 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 (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-pentane, 1,2,3-tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptanetetraisocyanate, 2,6 -Diisocyanatomethyl- , 5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanatomethylthiophene, 4-isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate, 1,2-diisothiocyanato Examples include ethane and 1,6-diisothiocyanatohexane.
One or more polyiso (thio) cyanate compounds may be used.

The polyiso (thio) cyanate compound is preferably selected from xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, and bis (isocyanatomethyl) bicycloheptane in order to improve heat resistance. At least one.

The mixing ratio of the polyiso (thio) cyanate compound and the polythiol mixture is such that the molar ratio of iso (thio) cyanate group / mercapto group is usually 0.5 to 2.0, preferably 0.95 to 1.05. is there.

In Step 1, in addition to a polyiso (thio) cyanate compound and a polythiol mixture, a polymerization catalyst such as organic tin such as dimethyltin dichloride, a release agent such as butoxyethyl acid phosphate, an antioxidant, an ultraviolet stabilizer, and coloring prevention You may mix | blend various additives, such as an agent, a blueing agent, and a fluorescent whitening agent.

A polymerization composition can be obtained by mixing the above-mentioned various components by a usual method.

[Step 2]
In step 2, the polymerization composition obtained in step 1 is polymerized to obtain an optical member.
When the optical member is a spectacle lens, the polymerization is preferably a cast polymerization method. The spectacle lens can be obtained, for example, by performing polymerization by injecting a polymerization composition into a mold die in which a glass or metal mold and a tape or gasket are combined.

The polymerization conditions can be appropriately set according to the polymerization composition.
The polymerization initiation temperature is usually 0 to 50 ° C., preferably 20 to 40 ° C. It is preferable to raise the temperature from the polymerization start temperature and then heat to form a cured film. For example, the temperature rise is usually 110 to 130 ° C.
After the polymerization, the spectacle lens may be released and an annealing process may be performed. The temperature of the annealing treatment is preferably 100 to 150 ° C.

[Optical member]
An example of the optical member is a spectacle lens.
The surface shape of the spectacle lens is not particularly limited, and may be any of a flat surface, a convex surface, a concave surface, and the like.
The spectacle lens may be any of a single focus lens, a multifocal lens, a progressive power lens, and the like. For example, as an example, for a progressive-power lens, normally, the near portion region (near portion) and the progressive portion region (intermediate region) are included in the lower region, and the far portion region (distance portion) is the upper portion. Included in the region.
The spectacle lens may be a finish spectacle lens or a semi-finish spectacle lens.

The thickness and diameter of the spectacle lens are not particularly limited, but the thickness is usually about 1 to 30 mm and the diameter is usually about 50 to 100 mm.
The refractive index ne of the spectacle lens is preferably 1.53 or more, more preferably 1.55 or more, more preferably 1.58 or more, still more preferably 1.60 or more, still more preferably 1.67 or more, still more preferably. 1.70 or more, preferably 1.80 or less.

In the present invention, the examples, contents, and various physical properties of each component described above may be arbitrarily combined with the matters described in the detailed description of the invention as examples or preferred ranges.
Moreover, if the composition described in the Example is adjusted to the composition described in the detailed description of the invention, the invention can be carried out in the same manner as in the Example over the entire composition range claimed.

Specific examples will be described below, but the scope of the claims is not limited by the following examples.
In the examples, various physical properties were measured and evaluated by the following methods.

[Heat-resistant]
The glass transition temperature (Tg) of the spectacle lenses obtained in Examples and Comparative Examples was measured by a penetration method using a thermal instrument analyzer “TMA8310” manufactured by Rigaku Corporation. The heating rate during measurement was 10 K / min, and an indenter having a diameter of 0.5 mm was used as an indenter for the penetration method.

[Striath]
Projection inspection was performed using an appearance inspection apparatus “Optical Modex SX-UI251HQ” manufactured by USHIO INC. Using a high-pressure UV lamp “USH-102D” as the light source, a white screen is installed at a distance of 1 m, the test resin is inserted between the light source and the screen, the projected image on the screen is observed, and judgment is made according to the following criteria. It was.
A: The projected image has no linear irregularity.
B: The projected image has a very thin linear irregularity.
C: The projected image has thin thin irregularities.
D: The projected image has a linear dark irregularity.
E: The projected image has a linear irregularity.

[White turbidity]
The test resin was observed under a fluorescent lamp in a dark box and judged according to the following criteria.
A: The resin has no cloudiness at all.
B: The resin has a very thin cloudiness.
C: The resin has a thin cloudiness.
D: The resin has a dark cloudiness.
E: The resin has significant cloudiness.

[Measured value of thiol equivalent]
Measurement was performed using an automatic potentiometric titrator “AT-610” (manufactured by Kyoto Electronics Co., Ltd.).
0.1 g of the polythiol mixture is weighed, dissolved in a mixed solvent of 20 mL of chloroform and 10 mL of isopropyl alcohol, titrated with a 0.05 mol / L iodine solution, and the thiol equivalent (g / eq) is determined by the following formula.
Thiol equivalent (g / eq) = [[sample amount (g)] × [iodine solution factor] × 100 × 100] / [titration amount]

Example 1
(Synthesis of polythiol mixture)
92.5 g (1.000 mol) of epichlorohydrin was added dropwise to a mixed solution of 78.1 g (1.000 mol) of 2-mercaptoethanol and 2.0 g of triethylamine over 1 hour while maintaining the internal temperature at 35 to 40 ° C. Aging was performed at 40 ° C. for 1 hour (step A). An aqueous solution in which 125.0 g (0.520 mol) of sodium sulfide nonahydrate was previously dissolved in 100 g of pure water was added dropwise to this reaction solution over 1 hour while maintaining the internal temperature at 40 to 45 ° C., and further at 45 ° C. for 1 hour. Aging was performed (step B).
Next, 303.8 g (3.0 mol) of 36 mass% hydrochloric acid aqueous solution and 190.3 g (2.50 mol) of thiourea were added to the reaction solution, and the mixture was heated and stirred at 110 ° C. for 9 hours (Step C).
After cooling to room temperature, 400 mL of toluene was added, 600.4 g (4.5 mol) of a 30% by mass aqueous sodium hydroxide solution was gradually added, and hydrolysis was performed at 60 ° C. for 4 hours (Step D).
After completion of hydrolysis, 130 mL of 36 mass% hydrochloric acid aqueous solution was added, and washing was performed at 40 ° C for 1 hour.
Subsequently, it was washed twice with 100 mL of water, the organic layer was recovered, and toluene was removed with a rotary evaporator to obtain a target polythiol mixture (Step E).

(Production of spectacle lenses)
50.6 parts by mass of xylylene diisocyanate (hereinafter also referred to as “XDI”), 0.01 parts by mass of dimethyltin dichloride as a curing catalyst, and acidic phosphate ester “JP-506h” (manufactured by Johoku Chemical Industry Co., Ltd.) as a release agent 0.20 part by mass and 0.5 part by mass of an ultraviolet absorber “Seesorb 701” (manufactured by Sipro Kasei Co., Ltd.) were mixed and dissolved.
Furthermore, 49.4 parts by mass of the above polythiol mixture was added and mixed to obtain a polymerization composition.
The measured value of the thiol equivalent of the polythiol mixture was 98 g / eq.
This polymerized composition was defoamed at 200 Pa for 1 hour, and then filtered through a PTFE (polytetrafluoroethylene, filtration accuracy: 5.0 μm) filter. Next, the mixture was poured into a lens mold composed of a glass mold having a diameter of 75 mm and −4.00 D and a tape. After completion of the polymerization, the mold was removed from the electric furnace and released to obtain a spectacle lens. The obtained spectacle lens was further annealed at 120 ° C. for 3 hours.
The obtained polymer had a heat resistance (Tg) of 103 ° C. Furthermore, striae and cloudiness were evaluated. The results are summarized in Table 1.

Examples 2-3 and Comparative Examples 1-2
In Example 2, the amount of sodium sulfide nonahydrate used is 0.515 mol, in Example 3, the amount of sodium sulfide nonahydrate used is 0.510 mol, and in Comparative Example 1, the amount of sodium sulfide nonahydrate used is In 0.500 mol, in Comparative Example 2, the amount of sodium sulfide nonahydrate was changed to 0.490 mol, and polymerization was performed in the same manner as in Example 1 except that polythiol mixtures having different thiol equivalents were used. Prepared and measured heat resistance. Furthermore, striae and cloudiness were evaluated. The results are summarized in Table 1. In addition, the thiol equivalent in a table | surface is a measured value.

Examples 4-6
Polymerization was carried out in the same manner as in Example 3 except that the type and amount of the polyisocyanate compound and the amount of polythiol were changed as shown in Table 2, and the heat resistance was measured. Furthermore, striae and cloudiness were evaluated. The results are summarized in Table 2. In addition, the thiol equivalent in a table | surface is a measured value.

Comparative Examples 3-5
Polymerization was performed in the same manner as in Comparative Example 1 except that the type and amount of the polyisocyanate compound and the amount of polythiol were changed as shown in Table 2, and the heat resistance was measured. Furthermore, striae and cloudiness were evaluated. The results are summarized in Table 2. In addition, the thiol equivalent in a table | surface is a measured value.

Various materials in the table are as follows.
XDI: xylylene diisocyanate H6XDI: bis (isocyanatomethyl) cyclohexane H12MDI: bis (isocyanatocyclohexyl) methane NBDI: bis (isocyanatomethyl) bicycloheptane

Finally, the embodiments of the present invention will be summarized.

One embodiment is:
Step 1: A step of mixing a mixture 1 of the following compound 1-1, the following compound 1-2 and the following compound 1-3 with a polyiso (thio) cyanate compound to obtain a polymerization composition;
Step 2: a step of polymerizing the polymerization composition obtained in Step 1 to obtain an optical member;
With
It is a manufacturing method of the optical member whose measured value of the thiol equivalent of the mixture 1 of the process 1 is 102 g / eq or less.

According to the manufacturing method of one embodiment, by using a mixture of thiol equivalents in the above range, the Tg of the obtained optical member can be increased, and an optical member having excellent heat resistance can be obtained.

One embodiment is:
Step A: 2-Mercaptoethanol and epichlorohydrin are reacted in the presence of an amine catalyst to obtain a compound represented by the formula (1):

According to the manufacturing method of one embodiment, when it is used for manufacturing an optical member by using a mixture of thiol equivalents in the above range, the Tg of the obtained optical member can be increased, and excellent heat resistance can be obtained. The optical member which has is obtained.

The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Claims

Step 1: A step of mixing a mixture 1 of the following compound 1-1, the following compound 1-2 and the following compound 1-3 with a polyiso (thio) cyanate compound to obtain a polymerization composition;
Step 2: Polymerizing the polymerization composition obtained in Step 1 to obtain an optical member;
With
The manufacturing method of the optical member whose measured value of the thiol equivalent of the mixture 1 of the said process 1 is 102 g / eq or less.
2. The polyiso (thio) cyanate compound is at least one selected from xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, bis (isocyanatocyclohexyl) methane, and bis (isocyanatomethyl) bicycloheptane. The manufacturing method of the optical member of description.
Step A: 2-Mercaptoethanol and epichlorohydrin are reacted in the presence of an amine catalyst to obtain a compound represented by the formula (1):

Obtaining a compound represented by:
Step B: By reacting the compound obtained in Step A with sodium sulfide, the formula (2):

Obtaining a compound represented by:
Step C: reacting the compound obtained in Step B with thiourea in the presence of a mineral acid to obtain an isothiuronium salt;
Step D: Hydrolyzing the isothiuronium salt obtained in Step C with a basic substance to obtain a mixture of Compound 1-1, Compound 1-2, and Compound 1-3;
Step E: washing the mixture obtained in Step D with mineral acid and water, and further purifying the mixture,
The method for producing an optical member according to claim 1, wherein the mixture obtained in the step E is used as the mixture 1 in the step 1.
The method for producing an optical member according to claim 3, wherein in the step B, the sodium sulfide is used in an amount of more than 50.0 mol% with respect to 100 mol% of the compound obtained in the step A.
The method for producing an optical member according to any one of claims 1 to 4, wherein the optical member is a spectacle lens.
Step A: 2-Mercaptoethanol and epichlorohydrin are reacted in the presence of an amine catalyst to obtain a compound represented by the formula (1):

Obtaining a compound represented by:
Step B: By reacting the compound obtained in Step A with sodium sulfide, the formula (2):

Obtaining a compound represented by:
Step C: reacting the compound obtained in Step B with thiourea in the presence of a mineral acid to obtain an isothiuronium salt;
Step D: a step of hydrolyzing the isothiuronium salt obtained in Step C with a basic substance to obtain a mixture of the following Compound 1-1, the following Compound 1-2, and the following Compound 1-3;
Step E: washing the mixture obtained in Step D with mineral acid and water and purifying the mixture,
The manufacturing method of the polythiol mixture which makes the measured value of the thiol equivalent of the mixture obtained at the said process E 102 g / eq or less.
The method for producing a polythiol mixture according to claim 6, wherein in the step B, the sodium sulfide is used in an amount of more than 50.0 mol% based on 100 mol% of the compound obtained in the step A.