JP2003020320A - Low specific gravity urethane based plastic lens composition, lens obtained therefrom, resin for lens, and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin having excellent optical properties and a low specific gravity of <=1.22. SOLUTION: The low specific gravity urethane based plastic lens composition gives a resin having a crosslinked structure to be obtained by selecting an iso(thio)cyanate compound and an active hydrogen compound so as to meet formula (1) (wherein A1 is a ratio of the molecular weight of the iso(thio) cyanate compound to the number of functional groups of the active hydrogen compound; A2 is a ratio of the molecular weight of the active hydrogen compound to the number of functional groups of the active hydrogen compound; D1 is a specific gravity of the iso(thio)cyanate compound; D2 is a specific gravity of the active hydrogen compound; and k is a ratio (molar ratio) of active hydrogen groups to iso(thio)cyanate groups).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low specific gravity urethane resin plastic lens having good optical properties and excellent impact resistance required for various optical lenses such as spectacle lenses, and the like. Regarding manufacturing method.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight and less prone 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. Currently, a resin widely used for these purposes is diethylene glycol bis (allyl carbonate).
(Hereinafter referred to as D.A.C.) radical polymerized. This resin has various characteristics such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. .

However, this resin has a small refractive index of nd = 1.50 as compared with the inorganic lens (nd = 1.52), and in order to obtain the optical characteristics equivalent to those of the glass lens,
It is necessary to increase the center thickness, the edge thickness, and the curvature of the lens, and it is inevitable that the lens becomes thick overall. For this reason, D. A. C. A plastic lens having excellent physical properties equivalent to that of the above and having a higher refractive index than the inorganic lens (nd = 1.52) has been desired.

Polyurethane type plastic lenses are known as lenses which satisfy this requirement. The inventors of the present invention have proposed, as the polyurethane lens, for example, in JP-A-63-46213, a polyurethane lens composed of a polymer of a xylylene diisocyanate compound and a polythiol compound. It is widely used as an optical lens.

However, in recent years, in addition to these physical properties, it has been required to reduce the specific gravity. In order to meet this further demand, the present inventors have disclosed in JP-A-2-270859, isophorone diisoanato (hereinafter referred to as IPDi).
Abbreviated. ) And 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane (hereinafter abbreviated as GST).

The specific gravity of the plastic lens made of IPDi and GST is 1.23, which is considerably smaller than that of the conventional urethane plastic lens, but it cannot fully meet the requirement for a further lower specific gravity. It was Therefore, the development of urethane plastic lenses with even lower specific gravity has been strongly desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to improve the specific gravity of a urethane plastic lens having excellent optical properties and to provide a urethane plastic lens having a low specific gravity.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have surprisingly found that a urethane-based composition obtained by polymerizing a composition satisfying the following formula (1) is obtained. The present invention has been accomplished by finding that a plastic lens has excellent optical properties and has a low specific gravity of 1.22 or less.

That is, in the present invention, an iso (thio) anato compound and an active hydrogen compound are represented by the formula (1)

[0010]

[Equation 2]

[In the formula (1), A1 = molecular weight of iso (thio) cyanate compound / number of functional groups of iso (thio) cyanate compound A2 = molecular weight of active hydrogen compound / number of functional groups of active hydrogen compound D1 = iso (thio) Cyanate The specific gravity of the compound D2 = the specific gravity of the active hydrogen compound k = the active hydrogen group / iso (thio) cyanato group (molar ratio). ]

A composition which gives a resin having a cross-linked structure selected so as to satisfy the above conditions, a method for producing a low specific gravity urethane resin plastic lens characterized by mixing the composition and heating and curing, and a method for producing the same. (However, in the case of a mixture of two or more iso (thio) cyanate compounds and active hydrogen compounds,
A1, D1, A2, D2 are their weighted averages. ).

The present invention will be described in detail below. The lens composition of the present invention comprises one or more iso (thio) cyanate compounds selected from an isocyanate compound, an isothiocyanate compound, and an isothiocyanate compound having an isocyanato group, a hydroxy compound, and a mercapto compound. The compound contains one or more active hydrogen compounds selected from a compound and a mercapto compound having a hydroxy group.

The iso (thio) cyanate compound used in the present invention is a monoisocyanate compound,
Examples include monoisothiocyanate compounds, polyisocyanate compounds, polyisothiocyanate compounds, and isocyanate compounds having an isocyanato group. Examples of the monoisocyanate compound include phenyl isocyanate, butyl isocyanate, cyclohexyl isocyanate and the like, and examples of the mono isothiocyanate compound include phenyl isothiocyanate, butyl isothiocyanate, cyclohexyl isothiocyanate and the like. Can be mentioned. Furthermore, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds and nitro-substituted compounds of these compounds can also be used. These may be used alone or in combination of two or more.

Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and 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-diisocyanato-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 di Isocyanatomethyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6-
Diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α,
α, α ', α'-Tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesitilerent Lysocyanate,
Aliphatic polyisocyanates such as 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl Dimethyl methane diisocyanate, 2,
2'-Dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate 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] -Alicyclic polyisocyanates such as heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, phenylenediene Isocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene Diisocyanate Methylnaphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Diisocyanate, bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) 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, Phenylisocyanatomethylisocyanate, Phenylisocyanatoethylisocyanate, Tetrahydronaphthylenediisocyanate, Hexahydrobenzenediisocyanate, Hexahydrodiphenylmethane-4,4'-di Isocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate,
Aromatic polyisocyanates such as diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, thiodiethyl diisocyanate,
Thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate,
Sulfur-containing aliphatic isocyanate such as dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, dicyclohexyl sulfide-4,4'-diisocyanate, diphenyl sulfide-2,4'-diisocyanate , Diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzyl thioether, bis (4-isocyanatomethylbenzene) sulfide, 4,4'-methoxybenzene Aromatic sulfide-based isocyanates such as thioethylene glycol-3,3′-diisocyanate, diphenyl disulfide-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 Nato, 3,3'-dimethoxydiphenyl disulfide-
Aromatic disulfide-based isocyanates such as 4,4'-diisocyanate and 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone- 3,3′-diisocyanate, benzidine sulfone-4,4′-diisocyanate, diphenylmethanesulfone-4,4′-diisocyanate, 4-methyldiphenylmethanesulfone-2,4′-diisocyanate, 4 , 4'-dimethoxydiphenyl sulfone-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'-methoxybenzeneethylenedisulfone-3,3 ' -Diisocyanate, 4,4'-dichlorodiphenyl sulfone-
Aromatic sulfone-based isocyanates such as 3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester,
4-methoxy-3-isocyanatobenzenesulfonyl-
Sulfonate-based isocyanates such as 4'-isocyanatophenol ester, 4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-
4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-
Methoxybenzenesulfonyl-ethylenediamine-3,
Aromatic sulfonic acid amides such as 3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3'-isocyanate, thiophene-2,5-diisocyanate, thiophene-2, 5-
Diisocyanatomethyl, 1,4-dithiane-2,5-diisocyanate, 4,5-bis (isocyanatomethyl)
Examples include sulfur-containing heterocyclic compounds such as -1,3-dithiolane, bis (isocyanatomethyl) tetrahydrothiophene, and 2,5-bis (isocyanatomethyl) -1,4-dithian.

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 isothiocyanato group.

Specifically, for example, 1,2-diisothiocyanatoethane, 1,3-isothiocyanatopropane,
Aliphatic isothiocyanates such as 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylene diisopropylidene diisothiocyanate, and cycloaliphatic isothiocyanates such as cyclohexane diisothiocyanate Nato, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato -M-xylene, 4,4'-diisothiocyanato-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, diphenyl ether-
4,4'-diisothiocyanate, diphenylamine-
Aromatic isothiocyanates such as 4,4′-diisothiocyanate, 2,4,6-triisothiocyanato-1,
Heterocyclic ring-containing isothiocyanates such as 3,5-triazine, and further hexanedioyl diisothiocyanate,
Nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2′-bipyridine) -4,
Carbonyl isothiocyanates such as 4'-dicarbonyl diisothiocyanate can be mentioned.

Examples of the bifunctional or higher polyisothiocyanate having at least one sulfur atom in addition to the isothiocyanato group used as a raw material in the present invention include, for example, thiobis (3-isothiocyanatopropane) and thiobis (2 −
Isothiocyanatoethane), sulfur-containing aliphatic isothiocyanate such as dithiobis (2-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-isothiocyanatobenzenesulfonyl-4'-isothiocyanato Phenyl ester,
4-Methyl-3-isothiocyanatobenzenesulfonylanilide-3'-methyl-4'-isothiocyanate and other sulfur-containing aromatic isothiocyanates, thiophenone-
2,5-diisothiocyanate, 1,4-dithiane-
Examples thereof include sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate.

Furthermore, halogen substitution products such as chlorine substitution products and bromine substitution products of these polyisothiocyanates, alkyl substitution products, alkoxy substitution products, nitro substitution products, prepolymer 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. Examples of the isothiocyanate compound having an isocyanato group used as a raw material in the present invention include 1-isocyanato-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, and 1-isocyanato-6-isothiocyanate. Aliphatic or alicyclic compounds such as isocyanatohexane, isocyanatocarbonylisothiocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato- Aromatic compounds such as 1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and further 4-isocyanato-4′-isothiocyana Todiphenyl sulfide, 2
In addition to the isothiocyanato group such as -isocyanato-2'-isothiocyanatodiethyldisulfide, compounds 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.

Among these iso (thio) cyanate compounds, in particular, isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, α, α, α ', α'- In the case of using tetramethylxylylene diisoanato, and the buret modified product and trimer modified product of these isoanaates, preferable results are often obtained. These iso (thio) cyanate compounds may be used alone or in combination of two or more.

Examples of the active hydrogen compound used in the present invention include a hydroxy compound, a mercapto compound and a mercapto compound having a hydroxy group.

Examples of the hydroxy compound include methanol, ethanol, isopropyl alcohol, butanol, benzyl alcohol, phenol, phenylphenol, ethoxyethanol, methoxypropanol,
Ethoxypropanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene 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, diglycerol,
Triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,2]
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 ′ -Aliphatic polyols such as bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyroga Roll, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) benzene, bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis- In addition to aromatic polyols such as (2-hydroxyethyl ether), halogenated polyols such as dibromoneopentyl glycol, polymer 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
-A condensation reaction product of an organic acid such as bromopropionic acid, 2-bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, bromophthalic acid and the polyol, alkylene oxide such as the polyol and ethylene oxide or propylene oxide. Addition reaction product with alkylene polyamine and ethylene oxide, addition reaction product with alkylene oxide such as propylene oxide, further bis-
[4- (hydroxyethoxy) phenyl] sulfide,
Bis- [4- (2-hydroxypropoxy) phenyl]
Sulfide, bis- [4- (2,3-dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl] sulfide,
Bis- [2-methyl-4- (hydroxyethoxy) -6
-Butylphenyl] sulfide and compounds obtained by adding an average of 3 molecules or less of ethylene oxide and / or propylene oxide per hydroxyl group to these compounds, di-
(2-hydroxyethyl) sulfide, 1,2-bis-
(2-hydroxyethylmercapto) ethane, bis (2
-Hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-)
Thiabutyl) methane, bis (4-hydroxyphenyl)
Sulfone (trade name bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,
4'-thiobis (6-tert-butyl-3-methylphenol), 3,6-dithiaoctane-1,8-diol, 1,3-bis (2-hydroxyethylthioethyl)
Examples thereof include polyols containing a sulfur atom such as cyclohexane.

Examples of the mercapto compound include methyl mercaptan, ethyl mercaptan, thiophenol, benzylthiol, methanedithiol, 1,
2-ethanedithiol, 1,1-propanedithiol,
1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol (trithioglycerin), tetrakis (mercaptomethyl) methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-
1,3-dithiol, 3,4-dimethoxybutane-1,
2-dithiol, 3,6-dioxaoctane-1,8-
Dimercaptan, 2-methylcyclohexane-2,3-
Dithiol, bicyclo [2,2,1] pepta-exo-
cis-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3- Dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-
Mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis ( Mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercapto) Acetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
-Aliphatic polythiols such as -mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, butanediol bis (3-mercaptopropionate), 1,2-dimercaptobenzene,
1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene (o-xylylenedithiol), 1,3-bis (mercaptomethyl) benzene (m-xylylenedithiol ),
1,4-bis (mercaptomethyl) benzene (p-xylylenedithiol), 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene ,
1,2-bis (mercaptomethoxy) benzene, 1,3
-Bis (mercaptomethoxy) benzene, 1,4-bis (mercaptomethoxy) benzene, 1,2-bis (mercaptoethoxy) benzene, 1,3-bis (mercaptoethoxy) benzene, 1,4-bis (mercaptoethoxy) Benzene, 1,2,3-Trimercaptobenzene, 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, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2 , 4-tris (mercaptomethoxy) benzene, 1,3,5-tris (mercaptomethoxy) benzene, 1,2,3-tris (mercaptoethoxy) benzene, 1,2,4-tris (mercaptoethoxy) benzene, 1 , 3,5-Tris (mercaptoethoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1, , 3,5-tetra-mercapto benzene, 1,2,4,5-mercapto benzene, 1,
2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene
Benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2 , 4,5-Tetrakis (mercaptoethyl) benzene, 1,2,3,4
-Tetrakis (mercaptoethyl) benzene, 1,2,
3,5-tetrakis (mercaptomethoxy) benzene,
1,2,4,5-tetrakis (mercaptomethoxy) benzene, 1,2,3,4-tetrakis (mercaptoethoxy) benzene, 1,2,3,5-tetrakis (mercaptoethoxy) benzene, 1,2,4 , 5-tetrakis (mercaptoethoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl,
4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 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-anthracene dimethanethiol, 1 , 3
-Di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-
Aromatic polythiols such as di (p-mercaptophenyl) pentane, and 2,5-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 and other chlorine-substituted compounds, bromine-substituted and other halogen-substituted aromatic polythiols, and 2-methyl Amino-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-s
ym-triazine, 2-thiobenzeneoxy-4,6-
Heterocyclic ring-containing polythiols such as dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine, 1,2-bis (mercaptomethylthio) benzene, and 1,3-bis (mercapto). Methylthio) 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 (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercapto) Ethylthio) 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, bis (4-mercaptophenyl) sulfide, etc., and aromatic polythiols containing a sulfur atom in addition to the mercapto group such as their nuclear alkylated products, bis (mercaptomethyl) sulfide, bis (Mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-
Bis (mercaptomethylthio) ethane, 1,2- (2-
Mercaptoethylthio) ethane, 1,2- (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3 -Mercaptopropylthio) propane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3
-Tris (mercaptomethylthio) propane, 1,2,
3-tris (2-mercaptoethylthio) propane,
1,2,3-Tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) 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 their thioglycolic acid and mercaptopropionic acid esters, hydroxymethylsulfide bis (2-mercaptoacetate), hydroxymethylsulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3 -Mercaptopropionate), hydroxymethyl disulfide bis (2-
Mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate) ), Hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (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-thiodibutyric acid bis (2-mercaptoethyl ester),
Dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-
Mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester) ), Dithiodipropionic acid (2,3-
Aliphatic polythiol containing sulfur atom in addition to mercapto group such as dimercaptopropyl ester), 3,4-thiophenedithiol, 2,5-bis (mercaptomethyl) tetrahydrothiophene, bis (mercaptomethyl) -1,3-dithiolane , 2,5-dimercapto-
1,3,4-thiadiazole, 2,5-dimercapto-
1,4-dithiane, 2,5-dimercaptomethyl-1,
Heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as 4-dithiane and the like can be mentioned.

Examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol and 3
-Mercapto-1,2-propanediol (thioglycerin), glycerin di (mercaptoacetate), 1-
Hydroxy-4-mercaptocyclohexane, 2,4-
Dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol (dithioglycerin), 1,2-dimercapto-1,3-butanediol , Pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol penta Kiss (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-mercaptoethylthiobenzene, 4-hydroxy-4'-mercap Todiphenyl sulfone, 2-
(2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate), dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane and the like can be mentioned.

Further, a chlorine-substituted product or a bromine-substituted product of these active hydrogen compounds may be used.

Among these active hydrogen compounds, particularly,
Glycerin, thioglycerin, dithioglycerin, trithioglycerin, 3,6-dioxaoctane-1,8-
Dimercaptan, bis (2-mercaptoethyl) sulfide, xylylenedithiol, trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), butanediol bis (3-mercaptopropionate) In many cases, favorable results are often obtained. These active hydrogen compounds may be used alone or in combination of two or more.

The compounding ratio of the active hydrogen compound and the iso (thio) cyanate compound is such that the functional group molar ratio (SH + O
H) / (NCO + NCS) is preferably within the range of 0.9 to 1.1. If it is less than 0.9 or exceeds 1.1, a resin having a low specific gravity may not be obtained, or the heat resistance of the resin may be impaired, which may give an unfavorable result.

The plastic lens of the present invention is made of urethane resin as a material, and mainly has a urethane bond by an iso (thio) cyanato group and an active hydrogen group, but depending on the purpose, other than that, an alohanate bond, a urea bond, or the like. A bond, a thiourea bond, a burette bond or the like may be contained, of course.

For example, it is often the case that the urethane bond is further reacted with an isocyanato group or the dithiourethane bond is further reacted with an isothiocyanato group to increase the crosslink density. In this case, the reaction rate is increased 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 may be used by partially using an amine or the like. When using a compound other than the active hydrogen compound that reacts with the iso (thio) cyanate compound, it is necessary to pay particular attention to the coloring point.

In addition, olefin compounds and epoxy compounds may be blended for the purpose of modifying the resin.

Examples of the olefin compound include methyl methacrylate, styrene, divinylbenzene, 5-vinylbicyclo [2,2,1] hept-2-ene, diethylene glycol bis (allyl carbonate), dicyclopentadiene, diallyl phthalate and triethyl phthalate. Examples include allyl isocyanurate, allyl methacrylate, glycerol diallyl ether, bisphenol A bis (methacryloxyethyl), glycerin dimethacrylate, butadiene, isoprene, 3-isopropenyl-α, α-dimethylbenzyl isocyanate.

Examples of the epoxy compound include vinyl cyclohexene dioxide and 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy).
Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-epoxy-p-vinylcyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate, triglycidyl isocyanurate. , Bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, N, N, N ', N'-tetraglycidyl diaminodiphenylmethane, N, N, N' , N′-tetraglycidyl xylylenediamine, N, N, N ′, N′-tetraglycidyl diaminodicyclohexylmethane, N,
N, N ', N'-tetraglycidylisophoronediamine, N, N-diglycidylaniline, N, N-diglycidylcyclohexylamine, trimethylolpropane triglycidyl ether, diglycidyl phthalate, diglycidyl hexahydrophthalate and the like can be mentioned. .

Further, as these modifiers, chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds, prepolymer-modified compounds and the like can also be used.

Depending on the purpose, as in the known molding method, various internal release agents, chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, etc. can be used. The substance may be added.

In order to adjust the reaction rate to a desired value, a known urethane reaction catalyst, radical polymerization catalyst, epoxy curing catalyst, epoxy curing agent, etc. may be added appropriately.

The lens of the present invention is usually obtained by cast polymerization. Specifically, a combination of an iso (thio) cyanate compound satisfying the formula (1) and an active hydrogen compound are mixed, the mixture is defoamed by an appropriate method as needed, and then the mixture is placed in a mold. It is injected, and polymerization is usually performed while gradually increasing the temperature from a low temperature of about 0 to 50 ° C to a high temperature of about 100 to 180 ° C. At this time, in order to facilitate the releasability after polymerization, the mold may be subjected to a known releasing treatment.

The urethane resin according to the present invention thus obtained is colorless and transparent, has a low specific gravity of 1.22 or less, a high refractive index, and a low dispersion. It is suitable as a material for optical elements such as camera lenses, glazing materials, paints, and adhesives. In addition, the lens made of the urethane resin according to the present invention may be improved in antireflection, high hardness, abrasion resistance, chemical resistance, antifogging property, or fashionability as required. Therefore, physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, anti-reflection coat treatment, dyeing treatment, light control treatment can be applied.

[0040]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The refractive index, Abbe number, specific gravity and appearance of the obtained lens were evaluated by the following test methods. ● Refractive index, Abbe number; 20 using Pulfrich refractometer
It was measured at ° C. ● Specific gravity: Measured by Archimedes method. ● Appearance: Visual observation.

Example 1 Isophorone diisocyanate (hereinafter abbreviated as IPDi) 4
6.6 parts (0.210 mol), thioglycerin (hereinafter T
G (abbreviated as G) 8.0 parts (0.074 mol), bis (2-mercaptoethyl) sulfide (hereinafter abbreviated as MES) 1
After 2.0 parts (0.078 mol) and 0.4% by weight of dibutyltin dichloride (based on the whole mixture) were mixed and defoamed to form a uniform solution, the glass mold and gasket were subjected to a mold release treatment. It was poured into a mold mold. Then 3
The temperature was gradually raised from 0 ° C. to 130 ° C., and the mixture was heated and cured for 24 hours. After completion of the polymerization, the lens was cooled and the lens was taken out of the mold. The obtained plastic lens is colorless and transparent, and has a refractive index nd = 1.545 and an Abbe number ν
d = 46 and specific gravity d = 1.17. The value of k in the formula (1) was 0.900. The calculated value of the composition according to the formula (1) was 1.105, which was 1.136 or less. The results are also shown in Table 1.

Examples 2 to 28, Comparative Examples 1 to 7 In the same manner as in Example 1, urethane type plastic lenses were manufactured. The results of Examples are shown in Table 1, and the results of Comparative Examples are shown in Table 2.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

IPDi; isophorone diisocyanate HMDi; dicyclohexylmethane-4,4'-diisocyanate HDi; hexamethylene diisocyanate TMDi; trimethylhexamethylene diisocyanate TMXDi; α, α, α ', α'-tetra Methyl xylylene diisocyanate XDi; Xylylene diisocyanate G; Glycerin TG; Thioglycerin DTG; Dithioglycerin TTG; Trithioglycerin MES; Bis (2-mercaptoethyl) sulfide TMP; Trimethylolpropane tris (3-mercaptopropionate) ) DOM: 3,6-dioxaoctane-1,8-dimercaptan EGTP; ethylene glycol bis (3-mercaptopropionate) BDTP; butanediol bis (3-mercaptoprone) Pionate) PEMP; Pentaerythritol tetrakis (3-mercaptopropionate) GST; 1,2-bis (2-mercaptoethylthio)
-3-propanethiol EDT; 1,2-ethanedithiol XDT; xylylenedithiol

[0049]

The urethane plastic lens obtained by the method of the present invention has excellent optical properties and a low specific gravity of 1.22 or less.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29K 105: 24 B29K 105: 24 B29L 11:00 B29L 11:00 (72) Inventor Teruyuki Nagata Omuta City, Fukuoka Prefecture 30 Asmutacho Mitsui Chemicals In-house F-term (reference) 4F204 AA42 AH74 EA03 EA04 EB01 EF01 EK13 EK17 4J034 CA05 CA32 CB01 CB03 CB04 CB07 CB08 CC08 CC09 CC10 CC12 CC35 CC62 CC65 CD06 HA04 HA07 HC08 HC08 HA02 HA08 HA08 HA11 HA13 HA13 HA02 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA02 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA08 HA02 HA08 HA08 HA08 HA08 HA08 HA08 HA02 HA08 HA08 HA08 HA11 HA13 HA02 HA08 HA02 HA08 HA02 HA08 HA02 HA08 HA08 HA08 HA02 HA08 HA02 HA08 HA02 HA08 HA02 HA08 HA08 HA02 HA08 HA08 HA02 HA08 HA02 HA08 HA07 HA08 HA08 HA07 HA08 HA02 HA08 HA02 HA08 HA than HC09 HC12 HC13 HC22 HC32 HC35 HC45 HC61 HC64 HC67 HC68 HC71 HC73 QA03 QB08 QB19 QC10 QD03 RA07 RA08 RA13

Claims (6)

[Claims] 1. An iso (thio) cyanate compound and an active hydrogen compound are represented by the formula (1): [In Formula (1), A1 = molecular weight of iso (thio) cyanate compound / functional group number of iso (thio) cyanate compound A2 = molecular weight of active hydrogen compound / functional group number of active hydrogen compound D1 = iso (thio) cyanate compound Specific gravity D2 = Specific gravity of active hydrogen compound k = Active hydrogen group / iso (thio) cyanato group (molar ratio) ] A low specific gravity urethane-based plastic lens composition which gives a resin having a crosslinked structure which is obtained by selecting 2. The method according to claim 1, wherein k = 0.9 to 1.1.
A composition for low specific gravity urethane plastic lenses, characterized in that 3. The low specific gravity urethane plastic lens according to claim 1, wherein the active hydrogen compound is one or more selected from a hydroxy compound, a mercapto compound, and a mercapto compound having a hydroxy group. Composition. 4. The iso (thio) cyanate compound is isophorone diisocyanate, dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, α, α,
α ′, α′-tetramethylxylylene diisocyanate, and a Burette modified product of these isocyanates,
One or more selected from trimer modified products or active hydrogen compounds are glycerin, thioglycerin, dithioglycerin, trithioglycerin, 3,6-dioxaoctane-1,8-dimercaptan, bis (2 -Mercaptoethyl) sulfide, xylylenedithiol, trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), butanediol bis (3-mercaptopropionate) The low specific gravity urethane-based plastic lens composition according to claim 1, comprising at least one of one kind or two or more kinds. 5. A method for producing a low specific gravity urethane plastic lens, which comprises polymerizing the composition according to claim 1 in a mold. 6. A low specific gravity urethane plastic lens obtained by the method according to claim 5.