JPH08271702A - Lens and its production - Google Patents

Abstract

PURPOSE: To obtain a colorless, transparent and lightweight plastic lens with high refractive index and low dispersion and excellent in weather resistance, shock resistance and heat resistance by allowing a specific mercapto compound to react with an ester compound selected from a polyisocyanates or the like. CONSTITUTION: The plastic lens is obtained by allowing the mercapto compounds expressed by formula I to react with at least one kind of the ester compound selected from polyisocyanate compounds, polyisothiocyanate compounds and isothiocyanate compounds having an isocyanate group. The mercapto compound expressed by formula I is obtained, for example, by allowing a glycerine derivative such as 1,3-dichloro-2-propanol or an epihalohydrine such as an epichlorohydrine to react with 2-mercaptoethanol in the presence of an alkali under cooling or heating to obtain a triol expressed by formula II and after allowing the obtained triol to react with thiourea in a mineral acid, modifying with -SH by alkali hydrolysis. In this time, the 1-,2-position rearrangement occurs to make the mercapto compound expressed by formula 1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sulfur-containing urethane resin lens using a novel mercapto compound and a method for producing the same.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight and less susceptible to cracking than inorganic lenses and can be dyed, so that they have rapidly become popular in optical elements such as spectacle lenses and camera lenses in recent years.

Resins widely used for these purposes are those obtained by radically polymerizing diethylene glycol bis (allyl carbonate) (hereinafter referred to as D.A.C.). This resin has various characteristics such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. There is.

However, the refractive index of the inorganic lens (n _D =
N _D = 1.50, which is smaller than that of 1.52), and in order to obtain the same optical characteristics as a glass lens, the center thickness of the lens,
It is necessary to increase the edge thickness and the curvature, and it is inevitable that the edge becomes thick as a whole. Therefore, a resin for lenses having a higher refractive index is desired.

Furthermore, as one of the lens resins which give a high refractive index, a reaction between an isocyanate compound and a hydroxy compound such as diethylene glycol (JP-A-57-1).
36601) or a reaction with a hydroxy compound containing a halogen atom such as tetrabromobisphenol A (JP-A-58-164615) or a reaction with a hydroxy compound containing a diphenylsulfide skeleton (JP-A-60-194401). A plastic lens made of a polyurethane resin or the like obtained is known.

Further, the applicant of the present invention, as a resin for a high-refractive index lens, reacts an isocyanate compound with a hydroxy compound containing a sulfur atom (JP-A-60-217229),
Furthermore, a reaction with a polythiol compound (JP-A-60-1)
99016, JP-A-62-267316, JP-A-63-
A plastic lens made of a polyurethane-based resin or the like obtained from No. 46213) was previously proposed.

[0007]

However, the lenses made of these known resins are disclosed in D.I. A. C. Although the refractive index is improved compared to the lens using, the refractive index is still insufficient, and in order to improve the refractive index, a compound having many halogen atoms or aromatic rings is used in the molecule. Therefore, it has the drawback of poor weather resistance or large specific gravity.

Further, even in the plastic lens proposed by the present inventors, it cannot be said that the refractive index is still high, and there is a problem in heat resistance in post-processing such as dyeing and coating. Further improvement is desired such that the sulfur odor has a discomfort to an operator at the time of manufacturing a lens or at the time of post-processing.

[0009]

[Means for Solving the Problems] In view of such a situation,
As a result of further investigations, the present inventors have found a novel mercapto compound of the present invention, and arrived at the present invention.

That is, the present invention relates to the formula (I)

[0011]

Embedded image The present invention relates to a lens obtained by reacting a mercapto compound represented by the following formula with at least one ester compound selected from polyisocyanate compounds, polyisothiocyanate compounds and isothiocyanate compounds having an isocyanate group. More specifically, the present invention is a colorless and transparent lens using a mercapto compound having a low sulfur odor, a high refractive index, low dispersion, lightweight, excellent weather resistance, impact resistance, and a lens having excellent heat resistance, and The present invention relates to a manufacturing method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The mercapto compound (formula (I)) of the present invention comprises, for example, a glycerin derivative such as 1.3-dichloro-2-propanol, an epihalohydrin such as epichlorohydrin, and 2-mercaptoethanol in the presence of an alkali. The reaction is carried out while cooling or heating, and the formula (II)

[0013]

[Chemical 4] The triol represented by is reacted with thiourea in a mineral acid and then subjected to SH by an alkali hydrolysis method. At that time, rearrangement occurs at the 1- and 2-positions to give the mercapto compound of the formula (I).

As another method, 2,3-dibromo-
A glycerin derivative such as 1-propanol and 2-mercaptoethanol were prepared in the same manner as in formula (III).

[0015]

Embedded image It is also synthesized by obtaining a triol represented by the formula (1), reacting it with thiourea in a mineral acid, and then subjecting it to SH by an alkali hydrolysis.

For example, 2-mercaptoethanol and a base are added to water or a lower alcohol solvent such as methanol or ethanol, and then epichlorohydrin is added dropwise. At this time, the reaction temperature is preferably 0 ° C to 120 ° C.

The amount of 2-mercaptoethanol used should be 2 equivalents or more with respect to epichlorohydrin,
Equivalent weights are preferred. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, and tertiary amines such as triethylamine and tributylamine. From the aspect, sodium hydroxide is most preferable, and the amount used is 1 equivalent or more with respect to epichlorohydrin, but 2
-It is preferable that it is less than or equal to the number of moles of mercaptoethanol used.

The reaction is preferably carried out in two steps in order to control the coloration of the product. That is, 1 to 3 equivalents of 2-mercaptoethanol with respect to epichlorohydrin and a catalytic amount of preferably 0.001 to
Epichlorohydrin was added dropwise to a solution of 0.1 equivalent of the above base in water or a lower alcohol such as methanol or ethanol to obtain the compound of formula (IV)

[0019]

[Chemical 6] And then add 2-mercaptoethanol to the equivalent amount of epichlorohydrin, if any, so that 2-mercaptoethanol is added to the equivalent amount, and further add 1-2 equivalents to epichlorohydrin. The triol represented by the formula (II) can be obtained by adding the deficiency of When a strong base such as sodium hydroxide is used in the synthesis of the diol represented by the formula (IV), the reaction temperature is appropriately 0 to 50 ° C. When the reaction temperature is 50 ° C. or higher, the base added in a catalytic amount is consumed in the reaction for producing triol from the diol, and the yield of the diol body decreases. When a tertiary amine is used in the synthesis of diol, such a problem does not occur even at 50 to 120 ° C.

Next, the triol represented by the formula (II) is mixed with 3
Equivalent or more, preferably 3 to 6 equivalents of thiourea are reacted in 3 or more, preferably 3 to 12 equivalents of an aqueous mineral acid solution in the range of room temperature to reflux temperature. Hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid and the like can be used as the mineral acid, but hydrochloric acid is preferable because a sufficient reaction rate can be obtained and the coloration of the product can be controlled.

In the subsequent hydrolysis reaction, 3 equivalents or more, preferably 3 to 12 equivalents, of a metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine such as triethylamine is added to the above reaction solution to give an alkaline solution. And from the room temperature to the reflux temperature. The temperature at the time of adding the base is preferably 0 to 50 ° C, and 5
If the temperature is higher than 0 ° C, the product tends to be colored.

The mercapto compound represented by the formula (I) thus produced can be purified by a general method such as extraction with an organic solvent such as toluene, acid washing, washing with water, concentration and filtration, and if necessary, distillation purification. It is possible.

Although the present invention can be carried out in the atmosphere,
Preference is given to carrying out the whole under nitrogen.

The sulfur-containing urethane resin of the present invention comprises a mercapto compound represented by the formula (I) and a polyisocyanate compound,
It is obtained by reacting at least one ester compound selected from a polyisothiocyanate compound and an isothiocyanate compound having an isocyanate group.

In the present invention, as the polyisocyanate compound used as the raw material for the sulfur-containing urethane resin, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene are used. Diisocyanate,
Nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-
1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, l, 6,11-undecatriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate Nato-4-isocyanatomethyloctane, 2,5,7-trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-
Butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine diisocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-diisocyanato hexanoate, 2-
Isocyanatopropyl-2,6-diisocyanate hexanoate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ′, α′-tetramethylxylylenediene Isocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitylenetriisocyanate, 2,6-di (isocyanatomethyl) Aliphatic polyisocyanate such as furan,

Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2 '
-Dimethyldicyclohexylmethane diisocyanate,
Bis (4-isocyanate-n-butylidene) pentaerythritol, diisocyanate dimer, 2-isocyanatomethyl-3- (3-isocyanatopropyl)
-5-Isocyanatomethyl-bicyclo [2.2.1]
-Heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-
Bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-
Isocyanatomethyl-bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2.2.1] -heptane, 2- Isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-
Isocyanatoethyl) -bicyclo [2.2.1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1]. -Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl)
-5- (2-isocyanatoethyl) -bicyclo [2.
2.1] -Heptane, 2-isocyanatomethyl-2-
An alicyclic polyisocyanate such as (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2.2.1] -heptane,

Phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate,
Isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate , Toluidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) Ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, Phenyl methane-2,4,
4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyl-
Diphenylmethane-3,5,2'4 ', 6'-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthylenediisocyanate, hexahydrobenzenediisocyanate, hexahydrodiphenylmethane-4 , 4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate Aroma such as nato, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, etc. Group polyisocyanate, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, etc. Sulfur-containing aliphatic isocyanate,

Diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylthioether, bis (4-) Isocyanatomethylbenzene) sulfide, aromatic sulfide-based isocyanate such as 4,4′-methoxybenzenethioethylene glycol-3,3′-diisocyanate, diphenyldisulfide-4,4′-diisocyanate, 2,2 '-Dimethyldiphenyldisulfide-
5,5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-5,5'-diisocyanate,
3,3'-Dimethyldiphenyldisulfide-6,6 '
-Diisocyanate, 4,4'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-
Aromatic disulfide-based isocyanates such as dimethoxydiphenyldisulfide-4,4'-diisocyanate and 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate,

Diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinesulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate , 4-methyldiphenylsulfone-2,4'-
Diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyldiphenylsulfone- 3,3 '
-Diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4'-methoxybenzene ethylenedisulfone-3,
Aromatic sulfone-based isocyanates such as 3'-diisocyanate and 4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol Ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester-based sulfonate isocyanate,

4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,
Such as 4'-diisocyanate, 4,4'-methoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3'-isocyanate Aromatic sulfonic acid amides, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and 1,4-dithian-2,5-diisocyanate can be used.

Further, these chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds,
A nitro-substituted product, a prepolymer modified product with a polyhydric alcohol, a carbodiimide modified product, a urea modified product, a buret modified product, a dimerization or trimerization reaction product and the like can also be used.

The polyisothiocyanate compound used in the present invention is a compound containing two or more -NCS groups in one molecule, and may further contain a sulfur atom in addition to the isothiocyanate group. Specifically, for example, 1,2-diisothiocyanatoethane, 1,3-isothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane,
Aliphatic isothiocyanates such as p-phenylene diisopropylidene diisothiocyanate, alicyclic isothiocyanates such as cyclohexane diisothiocyanate,

1,2-diisothiocyanatobenzene,
1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, 4,4′-diisothiene Oceanate-l, 1'-
Biphenyl, 1,1'-methylenebis (4-isothiocyanatobenzene), 1,1'-methylenebis (4-isothiocyanato-2-methylbenzene), 1,1'-
Methylenebis (4-isothiocyanato-3-methylbenzene), 1,1 '-(1,2-ethanediyl) bis (4-isothiocyanatobenzene), 4,4'-diisothiocyanatobenzophenone, 4,4 '-Diisothiocyanate-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenylether-4,4'-diisothiocyanate, diphenylamine-4,4'-diisothiocyanate Aromatic isothiocyanate,

2,4,6-triisothiocyanate-
Heterocyclic ring-containing isothiocyanates such as 1,3,5-triazine, and further hexanedioil diisothiocyanate, nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate , 1,4-benzenedicarbonyldiisothiocyanate, (2,2'-bipyridine)-
Carbonyl isothiocyanates such as 4,4′-dicarbonyl diisothiocyanate can be mentioned.

Examples of the bifunctional or higher polyisothiocyanate containing at least one sulfur atom in addition to the isothiocyanate group used as a raw material in the present invention include, for example, thiobis (3-isothiocyanatopropane), Thiobis (2-isothiocyanatoethane), dithiobis (2-
Sulfur-containing aliphatic isothiocyanate such as isothiocyanatoethane), 1-isothiocyanato-4-{(2-isothiocyanato) sulfonyl} benzene, thiobis (4
-Isothiocyanatobenzene), sulfonylbis (4
-Isothiocyanatobenzene), sulfinylbis (4-isothiocyanatobenzene), dithiobis (4
-Isothiocyanatobenzene), 4-isothiocyanato-1-{(4-isothiocyanatophenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-
Sulfur-containing aromatic isothiocyanates such as isothiocyanate benzenesulfonyl-4'-isothiocyanatophenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate, thiophenone Examples thereof include sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate and 1,4-dithiane-2,5-diisothiocyanate.

Further, these polyisothiocyanates include halogen-substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-type modified products with polyhydric alcohols, and carbodiimides. Modified products, urea modified products, burette modified products, dimerization or trimerization reaction products and the like can also be used.

The isothiocyanate compound having an isocyanate group used as a raw material in the present invention is
For example, 1-isothiocyanato-3-isothiocyanatopropane, 1-isothiocyanato-5-isothiocyanatopentane, 1-isothiocyanato-6-isothiocyanatohexane, isothiocyanatocarbonylisothiocyanate, 1 -Isothiocyanate-4
An aliphatic or alicyclic compound such as isothiocyanatocyclohexane,

Aromatic compounds such as 1-isothiocyanato-4-isothiocyanatobenzene, 4-methyl-3-isothiocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,5-diisocyanate −
Heterocyclic compounds such as 1,3,5-triazine, and further other than isothiocyanate groups such as 4-isocyanato-4'-isothiocyanate diphenyl sulfide and 2-isocyanato-2'-isocyanate diethyl disulfide. Also, a compound containing a sulfur atom can be mentioned.

Further, halogen-substituted compounds such as chlorine-substituted compounds, bromine-substituted compounds, etc., alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer modified products with polyhydric alcohols, carbodiimide modified products, and urea modified products of these compounds. body,
A modified burette, a dimerized or trimerized reaction product, etc. can also be used.

These ester compounds may be used alone or in admixture of two or more.

The ratio of the ester compound to the mercapto compound represented by the formula (I) is (NCO + NC).
The S) / SH (functional group) molar ratio is usually within the range of 0.5 to 3.0, preferably within the range of 0.5 to 1.5.

The plastic lens of the present invention is made of a thiocarbamic acid S-alkyl ester resin or a dithiourethane resin, and has a thiocarbamic acid S-alkyl ester bond or an isothiocyanate bond formed by an isocyanate group and a mercapto group. The main group is a dithiourethane bond by a group and a mercapto group, but depending on the purpose,
Other than that, it may of course contain an alohanate bond, a urea bond, a thiourea bond, a biuret bond and the like.

For example, it may be preferable to increase the crosslinking density by reacting the thiocarbamic acid S-alkyl ester bond with an isocyanate group or by reacting the dithiourethane bond with an isothiocyanate group. Many. In this case, the reaction temperature is raised to at least 100 ° C. or higher and a large amount of isocyanate component or isothiocyanate component is used. Alternatively, a urea bond or a biuret bond can be used by partially using an amine or the like. When using a compound other than a mercapto compound that reacts with an isocyanate compound or an isothiocyanate compound, it is necessary to pay particular attention to coloring.

Depending on the purpose, various kinds of internal release agents, chain extenders, cross-linking agents, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, etc. can be used in the same manner as in known molding methods. The substance may be added.

In order to adjust the reaction rate to a desired value, a known reaction catalyst used in the production of polyurethane can be added appropriately.

The lens of the present invention is usually obtained by cast polymerization. Specifically, the ester compound and the mercapto compound represented by the formula (I) are mixed, the mixture is defoamed by an appropriate method as necessary, and then poured into a mold to polymerize. At this time, in order to facilitate the releasability after polymerization, the mold may be subjected to a known releasing treatment.

The sulfur-containing urethane resin of the present invention obtained in this manner has no discomfort due to the sulfur odor during handling of the monomer or the sulfur odor during post-processing, and has an extremely low physical property dispersion. It has a high refractive index, excellent heat resistance, is colorless and transparent, is lightweight, has excellent weather resistance, impact resistance, etc., and is an optical element material such as spectacle lenses, camera lenses, glazing materials, and paints. Suitable as a material for adhesives.

Further, the lens made of the sulfur-containing urethane resin of the present invention can be used for antireflection, high hardness, abrasion resistance improvement, chemical resistance improvement, antifogging property addition, fashionability addition, etc. In order to improve the above, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment and light control treatment can be applied.

[0049]

The present invention will be described below in more detail with reference to examples and comparative examples. In the performance test of the obtained lens, the refractive index, Abbe number and weather resistance were evaluated by the following test methods.

Refractive index, Abbe number: Measured at 20 ° C. using a Pulfrich refractometer.

Weather resistance: The lens resin was set in a weatherometer equipped with a sunshine carbon arc lamp, and after 20 hours, the lens was taken out and compared with the hue of the lens resin before the test. The evaluation criteria were no change (◯), slight yellowing (Δ), and yellowing (x).

Appearance: Visual observation.

Odor: The one having a strong sulfur odor at the time of mixing the monomers was designated as (x), the one having almost no sulfur odor was designated as (◯), and the one having a little odor was designated as (Δ).

Heat resistance: 5 g on a test piece using a thermomechanical analyzer [Perkin Elmer (USA)]
It was weighted and heated at 2.5 ° C./min to measure the thermal deformation start temperature.

Example 1 5-Mercaptoethanol 53.2 g (0.681 mol), sodium hydroxide 27.2 g (0.680 mol)
Was dissolved in 200 ml of ethanol to make a uniform solution, and then 30.0 g of epichlorohydrin while maintaining the internal temperature at 15 ° C.
(0.324 mol) was added dropwise.

After completion of dropping, the reaction solution was heated to 50 ° C. and stirred for 1 hour, then cooled to room temperature, and a 36% hydrochloric acid aqueous solution 40.
5 g (0.399 mol) was added. Precipitated sodium chloride was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude intermediate which was a colorless viscous liquid. 1,3-bis (2-hydroxyethylthio) -2-propanol (II) was obtained from NMR data. 70.
It was identified as 6 g.

Next, (II) is added with 203 g of 36% hydrochloric acid aqueous solution
(2.0 mol) and dissolved in 92.6 g (1.
(22 mol) was added and the mixture was heated with stirring at 110 ° C. for 6 hours. Then, it is cooled to room temperature and 50% sodium hydroxide aqueous solution 1
95 g (2.44 mol) was added while keeping it at 20 to 40 ° C., and the mixture was further heated and stirred at 110 ° C. for 30 minutes.

The reaction solution was cooled to room temperature, and toluene 100 was added.
The mixture was extracted with ml, and the organic layer was washed with 100 ml of a 5% hydrochloric acid aqueous solution and 100 ml of water successively twice, and then dried with sodium sulfate. The organic layer was concentrated under reduced pressure to obtain 75.6 g (0.290 mol) of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) as a viscous liquid of APHA15.

The results of elemental analysis and NMR analysis are shown below.

Example 2 50.4 g (0.567) of 45% aqueous sodium hydroxide solution
88.7 g of 2-mercaptoethanol (1.1 mol)
(4 mol) was added dropwise to form a uniform solution, and then 50.5 g (0.546 mol) of epichlorohydrin was added dropwise over 1.5 hours, followed by heating and stirring at 112 ° C. for 0.5 hours.

After cooling to room temperature, 270 g of 36% hydrochloric acid
(2.66 mol) and 154 g (2.02 mol) of thiourea
Was added and the mixture was stirred at 112 ° C. for 1.5 hours.

Next, while maintaining the temperature at 20 to 35 ° C., 288 g (3.24 mol) of 45% sodium hydroxide solution was added to 0.5
The mixture was added dropwise over a period of time and heated with stirring at 110 ° C. for 1.5 hours. After cooling to room temperature, 200 ml of water and 250 ml of toluene were added for extraction, and the organic layer was separated. This is 36% hydrochloric acid 50m
After washing with 1, washed with 200 ml of water three times, concentrated under reduced pressure,
Distilled under reduced pressure (boiling point 185 to 205 ° C./0.4 Torr) and APHA10 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) 105.8.
g (0.406 mol) was obtained. The results of elemental analysis and NMR analysis were the same as in Example 1.

Example 3 8-Mercaptoethanol 84.4 g (1.08 mol)
0.8 g of a 48.7% aqueous sodium hydroxide solution (0.0
(01 mol) was added and homogenized, then kept under cooling at 40 ° C. or below, and 50.0 g (0.540 mol) of epichlorohydrin was added.
Was added dropwise over 0.5 hour and stirring was continued for another 0.5 hour.

Next, the temperature was kept at 40 to 70 ° C. under cooling and 48.7%.
Aqueous sodium hydroxide solution 44.4 g (0.541 mol)
Was added dropwise over 0.5 hour, and the mixture was stirred for 0.5 hour while cooling, then cooled to room temperature and 313 g of 36% hydrochloric acid.
(3.09 mol) and 123.4 g (1.62 mol) of thiourea were added, and the mixture was heated with stirring at 112 ° C. for 1.5 hours.

The mixture was cooled to room temperature again, and kept at 25 to 35 ° C., 254 g of 48.7% sodium hydroxide aqueous solution (3.
(09 mol) was added, and the mixture was heated with stirring at 110 ° C. for 1.5 hours.

After cooling to room temperature, 150 g of water and 1 of toluene
80 g was added and extracted, and the toluene layer was separated. This one
It was washed with 150 g of 8% hydrochloric acid and then with 30 g of water three times.

After the toluene was distilled off under reduced pressure, 120 ° C / 2
129 g (0.495 g of 0.495 of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA10 was obtained by distilling off low-boiling components with Torr for 2 hours and filtering with a 1-micron filter. Mol) was obtained. The results of elemental analysis and NMR analysis were the same as in Example 1.

Example 4 84.4 g (1.08 mol) of 2-mercaptoethanol
After adding 1.0 g (0.005 mol) of tributylamine to the above, 50.0 g (0.540 mol) of epichlorohydrin was added dropwise over 0.5 hour, and the mixture was further stirred for 0.5 hour.

Next, the temperature was kept at 40 to 70 ° C. under cooling and 48.7%.
Aqueous sodium hydroxide solution 44.4 g (0.541 mol)
Was added dropwise over 0.5 hour and after stirring for 0.5 hour,
After cooling to room temperature, the reaction solution was added with 36% hydrochloric acid (313.1 g).
(3.09 mol) and 123.4 g (1.62 mol) of thiourea were added, and the mixture was heated with stirring at 112 ° C. for 1.5 hours.

The mixture was cooled to room temperature again, and kept at 25 to 35 ° C., 254 g of a 48.7% sodium hydroxide aqueous solution (3.
(09 mol) was added, and the mixture was heated with stirring at 110 ° C. for 1.5 hours.

After cooling to room temperature, 150 g of water and 1 of toluene
80 g was added and extracted, and the toluene layer was separated. This one
It was washed with 150 g of 8% hydrochloric acid and then with 30 g of water three times.

After the toluene was distilled off under reduced pressure, 120 ° C / 2
125 g (0.480) of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA10 was obtained by distilling off low-boiling components with Torr for 2 hours and filtering with a 1-micron filter. Mol) was obtained. The results of elemental analysis and NMR analysis were the same as in Example 1.

Example 5 84.4 g (1.08 mol) of 2-mercaptoethanol
While maintaining the temperature at room temperature to 60 ° C, 44.4 g (0.541 mol) of 48.7% sodium hydroxide aqueous solution was added dropwise to a mixture of 50.0 g (0.540 mol) of epichlorohydrin and 1 hour, and further 0.5 hour. Stir at 80 ° C. After cooling to room temperature, 313 g (3.09 mol) of 36% hydrochloric acid and 123.4 g (1.62 mol) of thiourea were added, and the temperature was 112 ° C.
It was heated and stirred for 1.5 hours.

The mixture was cooled to room temperature again, and kept at 25 to 35 ° C., 254 g of 48.7% sodium hydroxide aqueous solution (3.
(09 mol) was added, and the mixture was heated with stirring at 110 ° C. for 1.5 hours. After cooling to room temperature, 150 g of water and 180 g of toluene were added for extraction, and the organic layer was washed successively with 150 g of 18% hydrochloric acid and 30 g of water three times.

After the toluene was distilled off under reduced pressure, 120 ° C./2To
122 g (0.468) of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA15 was obtained by distilling off the low boiling point for 2 hours with rr and filtering with a 1 micron filter. Mol) was obtained. The results of elemental analysis and NMR analysis were the same as in Example 1.

Example 6 270 g (2.66 mol) of 36% hydrochloric acid in Example 2
Was replaced with 735 g (1.50 mol) of 20% sulfuric acid and the same reaction was carried out to obtain 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) 1 of APHA10.
02 g (0.392 mol) were obtained. Elemental analysis and NMR
The results of the analysis were the same as in Example 1.

Example 7 270 g (2.66 mol) of 36% hydrochloric acid in Example 2
Was changed to 327 g (1.00 mol) of 30% phosphoric acid and the same reaction was carried out to obtain 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA10.
100 g (0.384 mol) were obtained. Elemental analysis and NM
The results of the R analysis were the same as in Example 1.

Example 8 2-Mercaptoethanol (53.2 g, 0.680 mol) and caustic soda (27.2 g, 0.680 mol) were dissolved in 200 ml of ethanol to homogenize the mixture.
While maintaining the temperature at 5 ° C, 70.0 g (0.324 mol) of 2,3-dibromo-1-propanol was added dropwise.

After completion of the dropping, the system was heated to 50 ° C. and stirred for 1 hour, then cooled to room temperature, the precipitated salt was removed by suction filtration, and the filtrate was concentrated under reduced pressure to obtain a colorless viscous liquid. Certain 1.3-bis [(2-mercaptoethyl) thio] -2-
Mixture 7 of propanol (II) and 1,2-bis [(2-hydroxyethyl) thio] -3-propanol (III) 7
1.3 g was obtained.

Next, the mixture of (II) and (III) was dissolved in 203 g (2.00 mol) of 36% hydrochloric acid aqueous solution, 92.6 g (1.22 mol) of thiourea was added, and the mixture was heated at 110 ° C. for 6 hours. It was stirred. Then cool to room temperature, 20 to 4
Keeping at 0 ℃, 50% sodium hydroxide solution 195
After adding g (2.44 mol), the mixture was heated with stirring at 110 ° C. for 30 minutes.

The system is cooled to room temperature and 100 ml of toluene
Liquid separation extraction is performed, and the toluene layer is mixed with a 5% hydrochloric acid aqueous solution 10
After washing once with 0 ml and twice with 100 ml of water, 1,2-bis [(2-mercaptoethyl) thio] -3- of APHA15, which is a colorless viscous liquid after drying with sodium sulfate and concentration, is obtained.
75.6 g (0.290 mol) of mercaptopropane (I) was obtained.

The results of elemental analysis and NMR analysis are shown.

Example 9 Represented by the formula (I) synthesized in Example 1

[0084]

[Chemical 7] 1,2-bis [(2-mercaptoethyl) thio] -3-
After 87 g of mercaptopropane and 94 g of m-xylylene diisocyanate were mixed and made uniform, they were poured into a mold composed of a glass mold and a gasket, and then cured by heating. The lens thus obtained is colorless and transparent and has excellent impact resistance, a refractive index n _D = 1.66 and an Abbe number ν _D = 3.
3. The thermal deformation starting temperature was 98 ° C.

Examples 10 to 28, Comparative Examples 1 to 11 Lenses having the compositions shown in Table 1 were produced in the same manner as in Example 9,
The results are also shown in Table-1.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

Claims (2)

[Claims] 1. Formula (I): A lens obtained by reacting a lucapto compound represented by the following formula with at least one ester compound selected from a polyisocyanate compound, a polyisothiocyanate compound and an isothiocyanate compound having an isocyanate group. 2. Formula (I): The production of a lens characterized by casting polymerization of at least one ester compound selected from a lucapto compound represented by and a polyisocyanate compound, a polyisothiocyanate compound and an isothiocyanate compound having an isocyanate group. Method.