JP3048929B2 - Sulfur-containing urethane resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Plastic lenses are lighter and harder to break than inorganic lenses, and can be dyed. Therefore, plastic lenses have recently been rapidly used in optical elements such as spectacle lenses and camera lenses.

[0003] As a resin widely used at present for these purposes, there is a resin obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter, referred to as DAC). This resin has various characteristics, such as being excellent in impact resistance, being lightweight, being excellent in dyeability, being excellent in workability such as cutting property and polishing property. I have.

However, the refractive index of an inorganic lens (n _D =
1.52) is smaller than n _D = 1.50, and in order to obtain optical characteristics equivalent to a glass lens, the center thickness of the lens must be
It is necessary to increase the edge thickness and the curvature, and it is unavoidable that the entire thickness is increased. Therefore, a lens resin having a higher refractive index is desired.

Further, as one of the lens resins giving 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 having a diphenylsulfide skeleton (JP-A-60-194401). A plastic lens made of a polyurethane-based resin or the like obtained is known.

Further, the present applicant has proposed a reaction between an isocyanate compound and a sulfur-containing hydroxy compound as a resin for a high refractive index lens (JP-A-60-217229).
Further, a reaction with a polythiol compound (JP-A-60-1)
99016, JP-A-62-267316, JP-A-63-267
46213), a plastic lens made of a polyurethane-based resin or the like has been previously proposed.

[0007]

However, these lenses made of known resins are disclosed in D.A. A. C. Although the refractive index is higher than that of a lens using, a compound having a large number of halogen atoms or aromatic rings in the molecule is used in order to improve the refractive index because the refractive index is still insufficient. For this reason, it has the disadvantage that the weather resistance is poor or the specific gravity is large.

Further, the plastic lenses proposed by the present inventors cannot be said to have a high refractive index yet, and have a problem in heat resistance in post-processing such as dyeing and coating. Further improvement is desired, for example, such that the sulfur odor contained in the lens gives a worker an unpleasant sensation during the production or post-processing of the lens.

[0009]

In view of such a situation,
As a result of further studies, the present inventors have found a novel mercapto compound of the present invention, and have reached the present invention.

That is, the present invention provides a compound of the formula (I)

[0011]

Embedded image And a at least one compound selected from a polyisocyanate compound, a polyisothiocyanate compound and an isothiocyanate compound having an isocyanate group in a molar ratio (NCO + NCS) / SH of 0.5 to TECHNICAL FIELD The present invention relates to a method for producing a sulfur-containing urethane-based resin obtained by allowing a reaction to be 3.0, and a substantially colorless and transparent sulfur-containing urethane-based resin obtained by this method. Furthermore, the present invention relates to a mercapto compound having a low sulfur odor and a colorless and transparent high refractive index, low dispersion, lightweight, excellent weather resistance, impact resistance,
The present invention relates to a sulfur-containing urethane resin having excellent heat resistance and a method for producing the same.

[0012]

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

[0013]

Embedded image Is obtained, reacted with thiourea in a mineral acid, and then subjected to SH conversion by alkali hydrolysis. At that time, rearrangement occurs at the 1- and 2-positions, resulting in a mercapto compound of the formula (I).

As another method, 2,3-dibromo-
From a glycerin derivative such as 1-propanol and 2-mercaptoethanol in a similar manner, formula (III)

[0015]

Embedded image Is obtained by reacting it with thiourea in a mineral acid, followed by SH conversion by alkali hydrolysis.

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

The amount of 2-mercaptoethanol used must be at least 2 equivalents to epichlorohydrin,
Equivalents 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 viewpoint of sodium hydroxide, sodium hydroxide is most preferred, and the amount used is at least 1 equivalent to epichlorohydrin.
It is preferable that the number of moles of the mercaptoethanol is not more than the used mole number.

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

[0019]

Embedded image Then, if there is a deficiency such that 2-mercaptoethanol is used in an amount of 2 to 3 equivalents relative to epichlorohydrin, it is added, and further, a base is added so that the amount becomes 1 to 2 equivalents relative to epichlorohydrin. The triol represented by the formula (II) can be obtained by adding the shortage 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 suitably from 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 a diol from a diol, and the yield of the diol is reduced. When a tertiary amine is used in the synthesis of the diol, such a problem does not occur even at 50 to 120 ° C.

Next, 3 is added to the triol represented by the formula (II).
The equivalent or more, preferably 3 to 6 equivalents of thiourea is reacted in an aqueous solution of mineral acid of 3 or more equivalents, preferably 3 to 12 equivalents, at a temperature ranging from room temperature to reflux temperature. As the mineral acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid and the like can be used, but hydrochloric acid is preferable because a sufficient reaction rate can be obtained and coloration of the product is controlled.

In the subsequent hydrolysis reaction, at least 3 equivalents, preferably 3 to 12 equivalents, preferably 3 to 12 equivalents of a metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine such as ammonia or triethylamine are added to the above reaction solution. The reaction is carried out in the range from room temperature to reflux temperature. The temperature at the time of adding the base is preferably 0 to 50 ° C., preferably 5 to 50 ° C.
When the temperature is 0 ° C. or higher, coloring of the product easily occurs.

The resulting mercapto compound represented by the formula (I) can be purified by a general method such as acid washing, concentration, and filtration after extraction with an organic solvent such as toluene, and can be purified by distillation if necessary. is there.

Although the present invention can be carried out in the atmosphere,
Preferably, the whole is carried out 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.

The polyisocyanate compound used as a raw material of the sulfur-containing urethane resin in the present invention includes ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and octamethylene. 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, 1,6,11-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-diisocyanate hexanoate, 2-
Isocyanatopropyl-2,6-diisocyanatohexanoate, xylylenediisocyanate, 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, mesitylene triisocyanate, 2,6-di (isocyanatomethyl) Aliphatic polyisocyanates such as furan,

Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2 ′
-Dimethyldicyclohexylmethane diisocyanate,
Bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate dimerate, 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 isocyanate,
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 4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandisocyanate, carbazole diisocyanate Aroma such as nathate, ethyl carbazole diisocyanate, dichlorocarbazole diisocyanate Group polyisocyanate,

Sulfur-containing compounds such as thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, and dithiodipropyl diisocyanate. Aliphatic isocyanate, diphenylsulfide-2,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis ( 4-isocyanatomethylbenzene) sulfide, 4,4'-
Methoxybenzenethioethylene glycol-3,3'-
Aromatic sulfide isocyanates such as diisocyanates,

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'-dimethoxydiphenyl disulfide-4,4'-
Aromatic disulfide isocyanates such as diisocyanate and 4,4'-dimethoxydiphenyl disulfide-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'-diisocyanatodibenzylsulfone, 4,4'-dimethyldiphenylsulfone 3,3 '
-Diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4′-methoxybenzeneethylenedisulfone-3,
Aromatic sulfone isocyanates such as 3'-diisocyanate and 4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol Esters, sulfonic acid ester isocyanates such as 4-methoxy-3-isocyanatobenzenesulfonyl-4′-isocyanate phenol ester,

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; Examples thereof include a sulfur-containing heterocyclic compound such as aromatic sulfonic acid amide and thiophene-2,5-diisocyanate, and 1,4-dithian-2,5-diisocyanate.

Halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products,
Nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, buret-modified products, dimerization or trimerization reaction products, and the like can also be used.

The polyisothiocyanate compound used as a raw material in the present invention is a compound containing two or more -NCS groups in one molecule, and may contain a sulfur atom in addition to the isothiocyanate group. Good. Specifically, for example, 1,2-diisothiocyanatoethane,
Aliphatic isothiocyanates such as 1,3-isothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, and p-phenylenediisopropylidenediisothiocyanate; cyclohexanediisothiane Alicyclic isothiocyanate such as ocyanate, 1,2-diisothiocyanatobenzene, 1,3
-Diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, 4,4'-diisothiocyanate- 1,1'-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'-diisothiocyanato-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenylether-4 Aromatic isothiocyanates such as 4,4'-diisothiocyanate, diphenylamine-4,4'-diisothiocyanate, and heterocyclic rings such as 2,4,6-triisothiocyanate-1,3,5-triazine Containing isothiocyanate, furthermore, hexanedioilodiisothiocyanate, nonanedioildiisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate Nate, (2,2'-bipyridine) -4,4'-dicarbonyl Carbonyl isothiocyanate, such as isothiocyanate, and the like.

Examples of the bifunctional or higher polyisothiocyanate containing one or more sulfur atoms in addition to the isothiocyanate group used as a raw material in the present invention include 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 isothiocyanatobenzenesulfonyl-4'-isothiocyanate phenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate, and thiophenone Sulfur-containing heterocyclic compounds such as -2,5-diisothiocyanate and 1,4-dithiane-2,5-diisothiocyanate are exemplified.

Furthermore, halogen-substituted, alkyl-, alkoxy-, and nitro-substituted polyisothiocyanates, such as chlorine-substituted and bromine-substituted polyisothiocyanates, prepolymer-modified polyhydric alcohols, and carbodiimides A modified product, a urea modified product, a buret modified product, a dimerization or trimerization reaction product, and the like can also be used.

The isothiocyanate compound having an isocyanate group used as a raw material in the present invention includes:
For example, 1-isocyanate-3-isothiocyanate propane, 1-isocyanate-5-isothiocyanate pentane, 1-isocyanate-6-isothiocyanate hexane, isothiocyanate carbonyl isocyanate, 1-isocyanate- Aliphatic or alicyclic compounds such as 4-isothiocyanatocyclohexane;
-Isocyanato-4-isothiocyanatobenzene,
Aromatic compounds such as 4-methyl-3-isocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and the like; Is 4-isocyanato-4′-isothiocyanatodiphenyl sulfide,
Compounds containing a sulfur atom in addition to the isothiocyanate group, such as 2-isocyanate-2'-isothiocyanate diethyl disulfide, may be mentioned.

Further, halogen-substituted, alkyl-substituted, alkoxy-substituted or nitro-substituted compounds of these compounds, such as chlorine- or bromine-substituted compounds, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, and urea-modified products body,
Bullet modified products, dimerization or trimerization reaction products, and the like can also be used.

These ester compounds may be used alone or in combination 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 in the range of 0.5 to 3.0, preferably in 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 formed by an isocyanate group and a mercapto group. Is mainly a dithiourethane bond by a group and a mercapto group, but depending on the purpose,
In addition, it is of course possible to include an allohanate bond, a urea bond, a thiourea bond, a biuret bond, and the like.

For example, increasing the crosslink density by reacting an S-alkyl thiocarbamate bond with an isocyanate group or reacting a dithiourethane bond with a further isothiocyanate group may give favorable results. Many. In this case, the reaction temperature is increased to at least 100 ° C. or higher, and a large amount of an isocyanate component or an isothiocyanate component is used. Alternatively, an urine 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, as in the case of the known molding method, various kinds of materials such as an internal release agent, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler and the like can be used. May be added.

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

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, and the mixed solution is defoamed by an appropriate method if necessary, and then is injected into a mold and polymerized. At this time, a known release treatment may be applied to the mold in order to facilitate the release property after the polymerization.

The sulfur-containing urethane-based resin of the present invention obtained as described above has no discomfort due to sulfur odor at the time of handling the monomer or sulfur odor at the time of post-processing. It has a high refractive index, excellent heat resistance, is colorless and transparent, is lightweight, has features such as weather resistance and impact resistance, and is used for optical element materials such as spectacle lenses and camera lenses, glazing materials, and paints. It is suitable as a material for an adhesive.

The lens made of the sulfur-containing urethane-based resin of the present invention may be provided with anti-reflection, high hardness, improved abrasion resistance, improved chemical resistance, anti-fogging property, or fashionability as required. Physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, light control treatment and the like can be carried out in order to improve the quality.

[0047]

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 and 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 (△), and yellowing (x).

Appearance: Observed visually.

Odor: When the monomer was mixed, those with a strong sulfur odor were rated as (x), those with almost no smell were rated as (o), and those with a little were rated as (Δ).

Heat resistance: 5 g was applied to the test piece using a thermomechanical analyzer [PerkinElmer (USA)].
The sample was heated under a load of 2.5 ° C./min, and the thermal deformation onset temperature was measured.

Example 1 53.2 g (0.681 mol) of 2-mercaptoethanol and 27.2 g (0.680 mol) of sodium hydroxide
Was dissolved in 200 ml of ethanol to obtain a homogeneous solution, and 30.0 g of epichlorohydrin was maintained while maintaining the internal temperature at 15 ° C.
(0.324 mol) was added dropwise.

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

Next, (II) was treated with 203 g of a 36% hydrochloric acid aqueous solution.
(2.00 mol), and 92.6 g of thiourea (1.
22 mol) and heated and stirred at 110 ° C. for 6 hours. Thereafter, the mixture is cooled to room temperature, and 50% aqueous sodium hydroxide solution 1
95 g (2.44 mol) was added 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
The organic layer was washed twice with 100 ml of a 5% hydrochloric acid aqueous solution and 100 ml of water 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. _{^{1 H NMR (CDCl 3) δppm}} = 1.74~1.91 (3H, m, S H) 2.70~3.00 (13H, m, C H) 13 C NMR (in CDCl 3) δppm = 24 _{.7 -S-CH 2 C H 2} SH 24.9 -S-CH 2 C H 2 SH 28.6 -S-CH 2 CH (S-) C H 2 SH 35.4 -S C H 2 CH 2 _{SH 36.0 -S C H 2 CH 2} SH 36.8 -S- C H 2 CH (S-) CH 2 SH 48.7 -S-CH 2 C H (S-) CH 2 SH

Example 2 50.4 g of a 45% aqueous sodium hydroxide solution (0.567 g)
88.7 g (1.1 mol) of 2-mercaptoethanol
4 mol) was added dropwise to make a homogeneous 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 hour.

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 stirred at 112 ° C. for 1.5 hours.

Next, while maintaining the temperature at 20 to 35 ° C., 288 g (3.24 mol) of a 45% sodium hydroxide solution was added in 0.5 part.
The mixture was added dropwise over time, and heated and stirred 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 36m hydrochloric acid 50m
After washing with water, wash three times with 200 ml of water and concentrate under reduced pressure.
Distillation under reduced pressure (boiling point: 185 to 205 ° C / 0.4 Torr) was performed, and APHA10 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) 105.8.
g (0.406 mol) were obtained. The results of elemental analysis and NMR analysis were the same as in Example 1.

Example 3 84.4 g (1.08 mol) of 2-mercaptoethanol
0.8 g of a 48.7% aqueous sodium hydroxide solution (0.0
After addition, the mixture was kept uniform at 40 ° C. or less under cooling, and epichlorohydrin 50.0 g (0.540 mol) was added.
Was added dropwise over 0.5 hour, and stirring was continued for another 0.5 hour.

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

After cooling to room temperature again and keeping the temperature at 25 to 35 ° C., 254 g of a 48.7% aqueous sodium hydroxide solution (3.
09 mol), and the mixture was heated and stirred at 110 ° C for 1.5 hours.

After cooling to room temperature, 150 g of water and 1 part of toluene
80 g was added for extraction, and the toluene layer was separated. This one
After washing with 150 g of 8% hydrochloric acid, it was washed three times with 30 g of water.

After the toluene was distilled off under reduced pressure, the mixture was heated at 120 ° C./2
The low boiling point was distilled off at Torr for 2 hours, and the mixture was filtered through a 1-micron filter to obtain 129 g (0.495) of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA10. Mol). 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 mixture, 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 is maintained at 40 to 70 ° C. under cooling, and 48.7%
44.4 g (0.541 mol) of aqueous sodium hydroxide solution
Was added dropwise in 0.5 hour, and after stirring for another 0.5 hour,
After cooling to room temperature, 313.1 g (3.09 mol) of 36% hydrochloric acid and 123.4 g (1.62 mol) of thiourea were added, and 1
The mixture was heated and stirred at 12 ° C. for 1.5 hours.

Cool to room temperature again, and maintain 254 g of an aqueous 48.7% sodium hydroxide solution (3.
09 mol), and the mixture was heated and stirred at 110 ° C for 1.5 hours.

After cooling to room temperature, 150 g of water and 1 part of toluene
80 g was added for extraction, and the toluene layer was separated. This one
After washing with 150 g of 8% hydrochloric acid, it was washed three times with 30 g of water.

After the toluene was distilled off under reduced pressure, the mixture was heated at 120 ° C./2
The low-boiling components were distilled off for 2 hours with Torr, and the solution was filtered through a 1-micron filter to give 125 g (0.480) of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA10. Mol). 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
And a mixture of 50.0 g (0.540 mol) of epichlorohydrin and 44.4 g (0.541 mol) of a 48.7% aqueous sodium hydroxide solution added dropwise over 1 hour while maintaining the temperature at room temperature to 60 ° C., and further for 0.5 hour Stirred 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 112 ° C.
For 1.5 hours.

Cool again to room temperature and maintain 254 g of 48.7% sodium hydroxide aqueous solution (3.
09 mol), and the mixture was heated and stirred 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. The organic layer was washed with 150 g of 18% hydrochloric acid, and then sequentially washed with 30 g of water three times.

After the toluene was distilled off under reduced pressure, the mixture was heated at 120 ° C./2To.
The low-boiling components were distilled off at rr for 2 hours, and the mixture was filtered through a 1-micron filter to give 122 g (0.468) of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (I) of APHA15. Mol). The results of elemental analysis and NMR analysis were the same as in Example 1.

Example 6 In Example 2, 270 g (2.66 mol) of 36% hydrochloric acid was used.
Was changed to 735 g (1.50 mol) of 20% sulfuric acid, and the reaction was carried out in the same manner 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 In Example 2, 270 g (2.66 mol) of 36% hydrochloric acid was used.
Was changed to 327 g (1.00 mol) of 30% phosphoric acid, and the reaction was carried out in the same manner 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 53.2 g (0.680 mol) of 2-mercaptoethanol and 27.2 g (0.680 mol) of caustic soda were dissolved in 200 ml of ethanol to make the mixture uniform, and the internal temperature was raised to 1%.
While keeping the temperature at 5 ° C, 70.0 g (0.324 mol) of 2,3-dibromo-1-propanol was added dropwise.

After completion of the dropwise addition, the system was heated to 50 ° C., stirred for 1 hour, cooled to room temperature, the precipitated salts were removed by suction filtration, and the filtrate was concentrated under reduced pressure to give 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)
1.3 g were obtained.

Next, the mixture of (II) and (III) was dissolved in 203 g (2.00 mol) of a 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. Stirred. Then, cool to room temperature,
While maintaining the temperature at 0 ° C.,
After adding g (2.44 mol), the mixture was heated and stirred at 110 ° C. for 30 minutes.

Cool the system to room temperature and add 100 ml of toluene.
, And the mixture was subjected to liquid separation extraction.
After washing once with 0 ml and twice with 100 ml of water, drying and concentrating on sodium sulfate, 1,2-bis [(2-mercaptoethyl) thio] -3-APHA15 which is a colorless viscous liquid is performed.
75.6 g (0.290 mol) of mercaptopropane (I) were obtained.

The results of elemental analysis and NMR analysis are shown. _{^{1 H NMR (CDCl 3) δppm}} = 1.74~1.91 (3H, m, S H) 2.70~3.00 (13H, m, C H) 13 C NMR (in CDCl 3) δppm = 24 _{.7 -S-CH 2 C H 2} SH 24.9 -S-CH 2 C H 2 SH 28.6 -S-CH 2 CH (S-) C H 2 SH 35.4 -S C H 2 CH 2 _{SH 36.0 -S C H 2 CH 2} SH 36.8 -S- C H 2 CH (S-) CH 2 SH 48.7 -S-CH 2 C H (S-) CH 2 SH

Example 9 Formula (I) synthesized in Example 1

[0082]

Embedded image 1,2-bis [(2-mercaptoethyl) thio] -3-
After 87 g of mercaptopropane and 94 g of m-xylylene diisocyanate were mixed and made uniform, the mixture was 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, has excellent impact resistance, a refractive index n _D = 1.66 and an Abbe number ν _D = 3.
3. The thermal deformation onset temperature was 98 ° C.

Examples 10 to 28 and Comparative Examples 1 to 11 In the same manner as in Example 9, lenses were manufactured with the compositions shown in Table 1,
The results are also shown in Table 1.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

Claims (2)

(57) [Claims] 1. A compound of the formula (I) And a at least one compound selected from a polyisocyanate compound, a polyisothiocyanate compound and an isothiocyanate compound having an isocyanate group in a molar ratio (NCO + NCS) / SH of 0.5 to A method for producing a sulfur-containing urethane-based resin, which is performed by heat-curing to 3.0. 2. A skeleton represented by the formula (V) in a structure: (Wherein, X represents an oxygen atom or a sulfur atom) .