JP2849065B2 - High refractive index plastic lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-refractive index plastic lens, and more particularly to a sulfur-containing aliphatic polyisocyanate excluding an adduct modified with polythiol, a sulfur-free polyol and a hydroxyl-free polyol. And, obtained by reaction with an active hydrogen compound selected from the group consisting of a polythiol containing no sulfur atom other than the mercapto group and a hydroxy group, and having a polythiol containing at least one sulfur atom other than the mercapto group. The present invention relates to a high refractive index plastic lens made of a resin to be used.

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

[0003]

2. Description of the Related Art Diethylene glycol bis (allyl carbonate) (hereinafter referred to as DAC) is used as a material for these lenses.
) Is radically polymerized. These resins have 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. ing.

However, the lens obtained from the DAC has a refractive index n _D = n _D compared to an inorganic lens (n _D = 1.52).
In order to obtain an optical characteristic equivalent to that of a glass lens, which is as small as 1.50, it is necessary to increase the center thickness, the edge thickness, and the curvature of the lens. Therefore, a lens resin having a higher refractive index is desired.

[0005] Further, as one of 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 tetrabromobisphenol A
Such as a polyurethane resin obtained by a reaction with a hydroxy compound having a halogen atom (Japanese Patent Application Laid-Open No. 58-164615) or a reaction with a hydroxy compound having a diphenyl sulfide skeleton (Japanese Patent Application Laid-Open No. 60-194401). Plastic lenses are known.

The present inventors have also proposed a reaction between an isocyanate compound and a sulfur-containing hydroxy compound as a resin for a high refractive index plastic lens (Japanese Patent Application Laid-Open No. Sho 60-2).
17229) and a reaction with a polythiol compound (JP-A-60-199016, JP-A-62-26731).
A plastic lens made of a polyurethane-based resin or the like obtained in 6) was previously proposed.

[0007]

However, although the lenses made of these known resins have a higher refractive index than lenses using DAC, they are still inadequate or have a molecular structure in order to improve the refractive index. Since a compound having a large number of halogen atoms or aromatic rings is used, it has disadvantages such as large dispersion, poor weather resistance, and large specific gravity.

[0008]

Means for Solving the Problems The inventors of the present invention obtain a compound obtained by reacting an aliphatic polyisocyanate containing a sulfur atom excluding an adduct modified product with polythiol and an active hydrogen compound having two or more functional groups. The present inventors have found that the resin has solved the above-mentioned problems and has excellent optical properties, and has completed the present invention.

That is, the present invention relates to an aliphatic polyisocyanate containing one or more sulfur atoms excluding a modified product of an adduct with polythiol, a polyol containing no sulfur atom, a hydroxyl group-free polyol, and Characterized by reacting a polythiol containing no sulfur atom other than the mercapto group and having no hydroxy group, and an active hydrogen compound selected from the group consisting of polythiols containing at least one sulfur atom other than the mercapto group, The present invention relates to a method for producing a resin for a high refractive index plastic lens, and a plastic lens made of the resin obtained by the method.

[0010] One or more kinds of aliphatic polyisocyanates containing sulfur atoms excluding adduct modified products with polythiols, polyols containing no sulfur atoms, polythiols containing no hydroxyl groups and containing no sulfur atoms Alternatively, a resin for a high refractive index plastic lens obtained by reacting a polythiol having no hydroxy group and containing at least one sulfur atom other than the mercapto group, and a plastic lens made of the resin obtained by the manufacturing method Was not known at all.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the aliphatic polyisocyanate containing a sulfur atom other than the adduct modified with polythiol used as a raw material in the present invention include thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, and dimethyl sulfone. Acyclic sulfur-containing aliphatic isocyanates such as diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, and dithiodipropyl diisocyanate; aliphatic sulfur-containing isocyanates containing an aromatic ring such as bis [(4-isocyanatomethyl) phenyl] sulfide; Examples include cyclic sulfur-containing aliphatic isocyanates such as 4-dithiane-2,5-diisocyanate, and aliphatic sulfur-containing isocyanates containing a heterocycle.

Further, these halogen-substituted compounds such as chlorine-substituted and bromine-substituted products, as well as their buret-forming reaction products, adduct-reaction products with trimethylolpropane, dimerization- or trimerization-reaction products, and the like are also included. Can be used. These may be used alone or as a mixture of two or more.

Examples of the active hydrogen compound used as a raw material include a polyol containing no sulfur atom, a polythiol containing no hydroxyl group and containing no sulfur atom other than a mercapto group, a polythiol containing no hydroxy group, and a mercapto group. And polythiols containing at least one sulfur atom.

Examples of the polyol containing no sulfur atom include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside,
Pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycerose, digliperol, triethylene glycol, polyethylene glycol , Tris (2
-Hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0
^2,6 ] decane-dimethanol, bicyclo [4,3,0]
-Nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5
3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol,
Cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol , Di (2-hydroxyethoxy) benzene, bisphenol A-bis-
(2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis-
(2-hydroxyethyl ether), dibromoneopentyl glycol, polyols such as epoxy resins, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid , Isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, a condensation reaction product of the above polyol with an organic polybasic acid such as bromophthalic acid, and the polyol Reaction products of an alkylene oxide with an alkylene oxide such as ethylene oxide or propylene oxide; and addition products of an alkylene polyamine with an ethylene oxide or an alkylene oxide such as propylene oxide. That. Further, a halogen-substituted product such as a chlorine-substituted product or a bromine-substituted product may be used.

The polythiol having no hydroxy group and containing no sulfur atom other than the mercapto group includes:
For example, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol,
2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol,
2,2-dimethylpropane-1,3-dithiol, 3,
4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,1] pepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl ) Cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3- Dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercapto Propyl methyl ether, 2,2-bis Mercaptomethyl) -1,3
Propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropanebis (2-mercaptoacetate), trimethylolpropanebis ( Aliphatic polythiols such as 3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate); 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,
4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl)
Benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,
3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis ( Mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercapto Benzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3
-Tris (mercaptomethyl) benzene, 1,2,4-
Tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,3 5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4-
Tris (mercaptomethyleneoxy) benzene, 1,
3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy)
Benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5- Tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3 1,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3
4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5- Tetrakis (mercaptoethyleneoxy) benzene, 1,
2,4,5-tetrakis (mercaptoethyleneoxy)
Benzene, 2,2′-dimercaptobiphenyl, 4,
4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-
Toluene dithiol, 1,4-naphthalenedithiol,
1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-
Dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiols such as 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di (p-mercaptophenyl) pentane;
5-dichlorobenzene-1,3-dithiol, 1,3-
Di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene Halogen-substituted aromatic polythiol such as chlorine-substituted or bromine-substituted, 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-
Triazine, 2-amino-4,6-dithiol-sym
-Triazine, 2-morpholino-4,6-dithiol-
sym-triazine, 2-cyclohexylamino-4,
6-dithiol-sym-triazine, 2-methoxy-
4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-
Polythiols containing a heterocycle such as thiobenzeneoxy-4,6-dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine, and their chlorine-substituted and bromine-substituted products. And halogen-substituted compounds.

Examples of the polythiol having no hydroxy group and containing at least one sulfur atom in addition to the mercapto group include 1,2-bis (mercaptomethylthio) benzene and 1,3-bis (mercaptomethylthio) Benzene, 1,4-bis (mercaptomethylthio)
Benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene,
1,2,3-tris (mermercaptomethylthio) benzene, 1,2,4-tris (mermercaptomethylthio) benzene, 1,3,5-tris (mermercaptomethylthio) benzene, 1,2,3-tris ( Mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1 , 2,3,5
-Tetrakis (mercaptomethylthio) benzene, 1,
2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4 , 5-tetrakis (mercaptoethylthio) benzene, etc., and aromatic polythiols such as alkylated nuclei thereof, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptoethylthio) ) Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (mercaptoethylthio) ethane, 1,2- Bis (mercaptopropylthio) ethane, 1,3-bis (meth Mercaptomethyl thio) propane,
1,3-bis (2-mercaptoethylthio) propane,
1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptoethylthio) propane, tetrakis (mercaptomethylthio) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc., and esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis 2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2- Mercapto acetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate),
Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-
Mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate), hydroxypropyldisulfidebis (3-mercaptopropionate), 2-mercaptoethyletherbis (2-mercaptoacetate), 2-mercaptoethyletherbis ( 3-mercaptopropionate), 1,4-dithiane-2,5-diolbis (2-mercaptoacetate), 1,4-dithiane-2,5-diolbis (3
-Mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutylic acid bis (2-mercaptoethyl ester),
Bis (2-mercaptoethyl ester) dithiodiglycolate, bis (2-mercaptoethyl ester) dithiodipropionate, bis (2-mercaptoethyl ester) 4,4-dithiodibutylate
Mercaptoethyl ester), bis (2,3-dimercaptopropyl ester) thiodiglycolate, bis (2,3-dimercaptopropyl ester) thiodipropionate, bis (2,3-dimercaptopropyl ester) dithioglycolate ), Bis (2,2-dithiodipropionate)
Aliphatic polythiols such as 3-dimercaptopropyl ester); heterocyclic compounds such as 3,4-thiophenedithiol, bismuthiol, and 2,5-dimercapto-1,3,4-thiadiazole; and the like. Further, a halogen-substituted product such as a chlorine-substituted product or a bromine-substituted product may be used.

These active hydrogen compounds may be used alone or in combination of two or more.

The use ratio of these polyisocyanates to active hydrogen compounds is such that the NCO / (SH + OH) (functional group molar ratio) is usually in the range of 0.5 to 3.0, preferably 0.5 to 1. 5 is within the range.

The plastic lens of the present invention is made of a urethane resin or a thiocarbamic acid S-alkyl ester resin as a raw material. The plastic lens is a urethane bond formed by an isocyanate group and a hydroxy group, or a thiocarbamic acid S-alkyl group formed by an isocyanate group and a mercapto group. Although it is mainly composed of an alkyl ester bond, depending on the purpose, other than the above two kinds of bonds, an allohanate bond, a urethane 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 urethane bond or an S-alkyl thiocarbamate bond. In this case, the reaction temperature is increased to at least 100 ° C. or higher, and a large amount of the isocyanate component is used. Alternatively, an urine bond or a biuret bond can be used by partially using an amine or the like.

When a compound other than the hydroxy compound or the mercapto compound that reacts with the isocyanate compound is used, it is necessary to pay particular attention to coloring.

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 are added according to the purpose, as in the known molding method. May be.

In order to adjust the reaction rate to a desired one, a known reaction catalyst used in the production of polyurethane and S-alkyl thiocarbamate may be appropriately added.

The resin for lenses of the present invention is usually obtained by cast polymerization. Specifically, a sulfur-containing aliphatic polyisocyanate excluding an adduct modified product with polythiol,
An active hydrogen compound is mixed, injected into a mold and polymerized.

The polymerization temperature and time vary depending on the type of the monomer, but are usually from -20 ° C to 200 ° C, preferably from room temperature to 150 ° C, and preferably from 0.5 to 72 ° C at 50 to 120 ° C.
Time. The polymerized lens may be annealed as needed.

The surface of the plastic lens of the present invention is polished to improve antireflection, high hardness, high abrasion resistance, high chemical resistance, high antifogging property, or high fashion, if necessary. And physical or chemical treatments such as antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, and light control treatment.

[0027]

The present invention will be described below in more detail with reference to examples and comparative examples. The refractive index, Abbe number, weather resistance, releasability, and appearance of the obtained lens resin and lens performance test were measured by the following test methods. Refractive index, Abbe number: 2 using a Pulfrich refractometer
It was measured at 0 ° C. 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). Appearance: Observed visually.

Example 1 18.4 g of dithiodiethyl diisocyanate (0.09
Mol) and 8.0 g of 1,2,6-hexanetriol
(0.06 mol) was injected into a mold composed of a glass mold and a gasket. Next, the temperature was gradually raised from room temperature to 120 ° C., and the composition was cured by heating for 28 hours.
The lens thus obtained is colorless and transparent and has excellent weather resistance, a refractive index n ²⁰ _D = 1.57, an Abbe number ν ²⁰ _D = 44, and a specific gravity d ^20.
= 1.32.

Examples 2 to 18 and 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.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

The plastic lens of the present invention obtained as described above has excellent optical properties of high refraction, low dispersion and colorless transparency, is lightweight and excellent in impact resistance, and is used for eyeglass lenses.
It is suitable for use as an optical element material such as a camera lens.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 63-37515 (32) Priority date February 22, 1988 (33) Priority claim country Japan (JP) (31) Priority Claim number Japanese Patent Application No. 63-37523 (32) Priority date February 22, 1988 (33) Country claiming priority Japan (JP) (31) Priority claim number Japanese Patent Application No. 63-37525 (32) Priority (1988) February 22 (1988) Priority claiming country Japan (JP) Examiner Eika Hashimoto (56) References Patent 2615182 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , (DB name) G02B 1/04 C08G 18/00-18/87

Claims (1)

(57) [Claims] An aliphatic polyisocyanate containing one or more sulfur atoms excluding an adduct modified product with a polythiol, a polyol containing no sulfur atom, a hydroxyl group-free polyol and a mercapto group. By reacting a polythiol containing no sulfur atom and having no hydroxy group, and one or more active hydrogen compounds selected from the group consisting of polythiols containing at least one sulfur atom other than the mercapto group High refractive index plastic lens made of the obtained resin.