JP2849067B2 - Thiocarbamic acid S-alkyl ester lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to thiocarbamic acid S
A plastic lens made of an alkyl ester resin; More particularly, the present invention relates to a method for producing a resin for thiocarbamic acid S-alkyl ester-based lenses in which a polyisocyanate is reacted with a thiol compound having a hydroxyl group and having a sulfur atom in addition to a mercapto group, and a plastic lens comprising the resin. It is.

[0002] Plastic lenses are lighter and harder to break than inorganic lenses, and can be dyed. Therefore, plastic lenses have been rapidly spread in optical elements such as spectacle lenses and camera lenses in recent years.

[0003]

2. Description of the Related Art Diethylene glycol bis (allyl carbonate) (hereinafter referred to as DA) is widely used for these purposes.
C) is radically polymerized. This resin has various characteristics such as being excellent in impact resistance, being lightweight, being excellent in dyeing properties, 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), which is as small as n _D = 1.50, and in order to obtain the same optical characteristics as a glass lens, it is necessary to increase the center thickness, edge thickness, and curvature of the lens. Thickening is inevitable. Therefore, a lens resin having a higher refractive index is desired. 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-57-136601) or a reaction with a hydroxy compound containing a halogen atom such as tetrabromobisphenol A Reaction (JP-A-58-164615) and reaction with a sulfur-containing hydroxy compound (JP-A-60-164615).
194401, 60-217229), and a reaction with a polythiol compound (JP-A-60-19901).
5, a plastic lens made of a polyurethane-based resin or the like obtained from JP-A-62-267316 is known.

[0005] However, although the lenses made of these known resins have a higher refractive index than lenses using DAC, they are still insufficient in refractive index, and a large number of molecules in the molecule are required to improve the refractive index. The use of a compound having a halogen atom or an aromatic compound has disadvantages such as large dispersion of refractive index, poor weather resistance, and large specific gravity. An object of the present invention is to provide a method for producing a novel resin for thiocarbamic acid S-alkyl ester-based lenses that solves the above problems, and to provide a plastic lens made of the resin.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have studied a resin for a high refractive index polyurethane-based lens, and reacted polyisocyanate with a thiol compound having a hydroxyl group and containing a sulfur atom in addition to a mercapto group. The thiocarbamic acid S-alkyl ester-based resin obtained by the above-mentioned method solves the disadvantages of the above-mentioned known resin for a lens, such as insufficient refractive index, dispersibility of refractive index, and weather resistance specific gravity. The inventors have found that the polyisocyanate has excellent optical properties, and when the polyisocyanate contains a sulfur atom, it has found that the polyisocyanate has more excellent optical properties, leading to the present invention.

That is, the present invention relates to a process for producing a thiocarbamic acid S-alkyl ester-based resin obtained by reacting a polyisocyanate with a thiol compound having a hydroxyl group and having a sulfur atom in addition to a mercapto group, and a method for producing the same. The present invention relates to a lens made of resin. Further, the present invention relates to a resin obtained by using a polyisocyanate containing a sulfur atom and a lens made of the resin.

A thiocarbamic acid S-alkyl ester-based resin obtained by reacting a polyisocyanate with a thiol compound having a hydroxyl group and having a sulfur atom in addition to a mercapto group, and a plastic lens made of the resin are not disclosed. unknown.

In the present invention, the term "polyisocyanate" includes those containing a sulfur atom.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Among the polyisocyanates used as raw materials in the present invention, those containing no sulfur atom include, for example, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, Methylene 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-hexamethylene triisocyanate, 1,
8-diisocyanate-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis (isocyanateethyl) carbonate, bis (isocyanateethyl) 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-diisocyanate hexanoate, xylylenediene Isocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene,
α, α, α ′, α′-tetramethylxylylenediisocyanate, bis (isocyanatebutyl) benzene, bis (isocyanatemethyl) naphthalene, bis (isocyanatemethyl) diphenylether, bis (isocyanateethyl) phthalate, mesitylene triisocyanate, 2, Aliphatic polyisocyanate such as 6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate , Bis (4-isocyanate-n-butylidene) pentaerythritol , Dimer diisocyanate, 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) -6- (2-isocyanatoethyl) -bicyclo [2 2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2-isocyanatomethyl-2- (3 -Isocyanatopropyl) -5- (2-isocyanatoethyl)
-Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6
-(2-isocyanatoethyl) -bicyclo [2,2,
1]-aliphatic polyisocyanates such as heptane, phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropylene phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate , Methyl naphthalenediisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane
4,4'-diisocyanate, bibenzyl-4,4'-
Diisocyanate, bis (isocyanatephenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-
Diisocyanate, triphenylmethane triisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-
Triisocyanate, 4-methyl-diphenylmethane-
3,5,2 ', 4', 6'-pentaisocyanate, phenyl isocyanate methyl isocyanate, phenyl isocyanate ethyl ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-
Aromatic polyisocyanates such as 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, ethylcarbazole diisocyanate, and dichlorocarbazole diisocyanate. Is mentioned.

Examples of the polyisocyanate containing a sulfur atom include thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, and dithiodipropyl diisocyanate. 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 isocyanates such as 4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate; Nildisulfide-
4,4′-diisocyanate, 2,2′-dimethyldiphenyldisulfide-5,5′-diisocyanate,
3,3'-dimethyldiphenyl disulfide-5,5 '
-Diisocyanate, 3,3'-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-
Aromatic disulfide-based isocyanates such as dimethyldiphenyldisulfide-5,5′-diisocyanate, 3,3′-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-methyldiphenylmethanesulfone-2,4 '-Diisocyanate, 4,4'-dimethoxydiphenylsulfone-
3,3′-diisocyanate, 3,3′-dimethoxy-
4,4′-diisocyanate dibenzyl sulfone, 4,
4'-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-
Aromatic sulfone isocyanates such as methoxybenzene ethylene disulfone-3,3'-diisocyanate, 4,4'-dichlorodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatebenzenesulfonyl-4'-isocyanate phenol Esters, sulfonic acid ester-based isocyanates such as 4-methoxy-3-isocyanate benzenesulfonyl-4′-isocyanate phenol ester, 4-methyl-
3-isocyanatobenzenesulfonylanilide-3 '
-Methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate,
4,4'-methoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-
Aromatic sulfonic acid amides such as isocyanate benzenesulfonylanilide-4-methyl-3'-isocyanate, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and other 1,4-dithiane-2,5-diisocyanates. No.

In addition, halogen-substituted or alkyl-substituted polyisocyanates such as chlorine-substituted or bromine-substituted products,
An alkoxy-substituted product, a nitro-substituted product, a modified prepolymer with a polyhydric alcohol, a carbodiimide-modified product, a urea-modified product, a puret-modified product, a dimerization or trimerization reaction product, and the like can also be used.

Among these polyisocyanates, those which are liquid at room temperature and have a low vapor pressure are preferred. Further, aliphatic polyisocyanates are more preferable in view of yellowing to heat and light. These may be used alone or in combination of two or more.

Examples of the thiol compound having a hydroxy group and containing at least one sulfur atom in addition to the mercapto group include, for example, hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthio Benzene, 4-hydroxy-4'-mercaptodiphenylsulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethylsulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl- Tris (mercaptoethylthiomethyl) methane and the like can be mentioned.

Further, a halogen-substituted product such as a chlorine-substituted product or a bromine-substituted product of a thiol compound having at least one sulfur atom in addition to the mercapto group having a hydroxy group may be used. These may be used alone or in combination of two or more.

The ratio of the polyisocyanate to the thiol compound having a hydroxy group and containing at least one sulfur atom in addition to the mercapto group is NCO /
The functional group molar ratio of (SH + OH) 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-based resin, and mainly comprises a thiocarbamic acid S-alkyl ester bond and a urethane bond by an isocyanate group, a mercapto group and a hydroxy group. However, depending on the purpose, of course, other than the above-mentioned bond, an allohanate bond, a urea bond, a biuret bond or the like may be contained.

For example, it is often desirable to increase the crosslink density by further reacting an isocyanate group with a thiocarbamic acid S-alkyl ester bond and a urethane bond to give a favorable result. In this case, the reaction temperature is increased to at least 100 ° C., and a large amount of isocyanate component is used. Alternatively, an amine or the like is partially used in combination,
Urea bonds and biuret bonds can also be used, but when reacting a compound other than a thiol compound containing a sulfur atom in addition to a mercapto group with a hydroxy group with an isocyanate compound, particularly in terms of coloring, It is necessary to keep in mind.

The lens of the present invention is usually obtained by a casting polymerization method. Specifically, a polyisocyanate and a thiol compound having a hydroxyl group and having a sulfur atom in addition to a mercapto group are mixed. This mixed solution is defoamed by an appropriate method if necessary, and then poured into a mold to be polymerized.

The S-alkyl thiocarbamate resin used in the present invention thus obtained is characterized by high refraction, low dispersion, colorless and transparent, light weight and excellent weather resistance and impact resistance. It is suitable as a material for optical elements such as spectacle lenses and camera lenses.

Further, when polymerizing the resin,
Various substances such as a chain extender, a cross-linking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, and a filler may be added according to the purpose as in the known molding method.

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 polymerization temperature and time vary depending on the type of monomer and additives such as a release agent, but are usually from -50 ° C to 200 ° C.
° C, preferably from room temperature to 150 ° C, suitably from 50 to 12 ° C.
0.5-72 hours at 0 ° C. The polymerized lens may be annealed as needed.

The lens of the present invention made of a thiocarbamic acid S-alkyl ester resin obtained by reacting a polyisocyanate with a thiol compound having a hydroxyl group and having a sulfur atom in addition to a mercapto group, Surface polishing, antistatic treatment, hard coat treatment, non-reflective coat to improve anti-reflection, high hardness, abrasion resistance, chemical resistance, anti-fogging or fashionability as required Physical or chemical treatment such as treatment, dyeing treatment, and light control treatment can be performed.

[0025]

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 and Abbe number were measured by the following test methods. Refractive index, Abbe number: Measured at 20 ° C. using a Pulfrich refractometer. A weather resistance test was performed on the obtained lens resin in the following manner. Weather resistance: The lens resin was set in a weather meter equipped with a sunshine carbon arc lamp, and after 200 hours, the lens was taken out and the hue was compared with the lens resin before the test. The evaluation criteria were no change (○), slight yellowing (△), and yellowing (x).

Example 1 13.8 g (0.08 mol) of thiodiethyl diisocyanate and 17.0 g (0.04 mol) of hydroxyethylthiomethyl-tris (mercaptoethylthiomethyl) methane were mixed, and a glass mold and a gasket were mixed. Into the mold. Next, the temperature was gradually raised from room temperature to 120 ° C., and the composition was cured by heating for 48 hours. The lens made of the resin thus obtained was colorless and transparent, had excellent weather resistance, and had a refractive index n ²⁰ _D = 1.64 and an Abbe number ν ²⁰ _D = 37.

Examples 2 to 6, Comparative Examples 1 to 3 Lenses were formed in the same manner as in Example 1 with the compositions shown in Table 1.
Table 1 shows the results of the performance test.

Comparative Examples 1 to 3 are conventional resins which do not have a sufficient refractive index and Abbe's number, and Comparative Example 3 is slightly yellowish.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

The resin for thiocarbamic acid S-alkyl ester-based lens thus obtained has high surface accuracy and excellent optical properties, is lightweight and excellent in impact resistance, and is used for eyeglass lenses, camera lenses and the like. It is suitable as an optical element material.

Continuing from the front page Examiner Eika Hashimoto (56) References Patent 2615183 (JP, B2) (58) Field investigated (Int. Cl. ⁶ , DB name) G02B 1/04 C08G 18/00-18/87

Claims (2)

(57) [Claims] 1. Thiocarbamic acid S obtained by reacting one or more polyisocyanates with a thiol compound having one or more hydroxy groups and containing at least one sulfur atom in addition to a mercapto group
A plastic lens made of an alkyl ester resin. 2. The S-alkyl thiocarbamate plastic lens according to claim 1, wherein the polyisocyanate is a polyisocyanate containing a sulfur atom.