HK1159667B - Polymerizable composition for optical materials, optical material, and method for producing optical materials - Google Patents

Abstract

Disclosed is a polymerizable composition for optical materials, which is characterized by containing a tolylene diisocyanate, a C4-8 aliphatic polyisocyanate, and one or more polythiol selected from pentaerythritol tetrakis(mercaptoacetate) and pentaerythritol tetrakis(mercaptopropionate).

Description

Polymerizable composition for optical material, and method for producing optical material

Technical Field

The present invention relates to a polymerizable composition for an optical material, and particularly to a polymerizable composition for an optical material containing a specific polyisocyanate and a specific polythiol compound. The present invention also relates to an optical material obtained from the polymerizable composition for an optical material and a method for producing the optical material.

Background

Conventionally, plastic materials have been used as an alternative material to inorganic materials for optical parts. The plastic material is preferably used because it is lightweight, less likely to break, and dyeable, as compared with inorganic materials that have been used so far. In particular, as an optical member such as a lens, a plastic material having a high refractive index is expected, and as such a plastic material having a high refractive index, for example, a sulfur-containing urethane (thiourethane) resin described in patent documents 1 to 5 is proposed.

Patent document 1: japanese laid-open patent publication No. H02-153302

Patent document 2: japanese patent laid-open publication No. H01-295202

Patent document 3: japanese laid-open patent publication No. H02-000802

Patent document 4: japanese laid-open patent publication No. 63-046213

Patent document 5: japanese laid-open patent publication No. Sho 64-045611

Disclosure of Invention

However, in the prior art, although the aromatic thiocarbamate resin is a material with a high refractive index, it is difficult to put it into practical use from the viewpoint of color tone, and the aromatic thiocarbamate resin can be put into practical use by developing additives such as bluing agents. On the other hand, in recent years, it is also desired to use a plastic material for an optical member for use in applications requiring high durability. Such plastic materials are also required to have optical properties, particularly properties of small change in color tone with time, that is, high light resistance.

On the other hand, plastic materials having a high refractive index are often materials having low dyeability of the base material, and the dyeability is not sufficient in the application of optical parts requiring high dyeability, and improvement of the dyeability is increasingly required. Further, there is an increasing demand for higher refractive index and higher heat resistance, but since heat resistance and dyeability are in a trade-off relationship, generally, when heat resistance is high, dyeability is lowered.

The present inventors have found that a material having a high refractive index and simultaneously achieving high heat resistance and high dyeability can be obtained by using a specific polyisocyanate composed of a specific isocyanate and a specific polythiol compound in combination, and have completed the present invention.

Namely, the present invention is as follows.

(1) A polymerizable composition for optical materials, characterized by containing toluene diisocyanate, an aliphatic polyisocyanate having 4 to 8 carbon atoms, and 1 or more polythiols selected from pentaerythritol tetramercaptoacetate and pentaerythritol tetramercaptopropionate.

(2) The polymerizable composition for optical materials according to (1), wherein the aliphatic polyisocyanate having 4 to 8 carbon atoms is at least 1 polyisocyanate selected from 1, 6-hexamethylene diisocyanate and 1, 5-pentamethylene diisocyanate.

(3) The polymerizable composition for optical materials according to (1) or (2), further comprising an active hydrogen compound having 2 or more active hydrogen groups in the molecule.

(4) An optical material obtained by curing the polymerizable composition for an optical material according to any one of (1) to (3).

(5) A method for producing an optical material, which comprises curing the polymerizable composition for an optical material according to any one of (1) to (3).

(6) A method for producing an optical material, characterized in that in the method for producing an optical material according to (5), the polymerizable composition for an optical material is molded by cast polymerization.

According to the present invention, a polymerizable composition for an optical material having a high refractive index, high heat resistance and good dyeability, and an optical material obtained from the polymerizable composition can be provided.

Detailed Description

The following describes embodiments of the present invention.

The polymerizable composition for optical materials of the present embodiment is characterized by containing toluene diisocyanate, an aliphatic polyisocyanate having 4 to 8 carbon atoms, and 1 or more polythiols selected from pentaerythritol tetramercaptoacetate and pentaerythritol tetramercaptopropionate.

In the present invention, any one of 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate or a mixture thereof may be used as tolylene diisocyanate. When a mixture of 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate is used, the content of 2, 4-tolylene diisocyanate is preferably 60% or more, more preferably 75% or more. In addition, in the case where a mixture is not used, 2, 4-tolylene diisocyanate is preferable. Commercially available toluene diisocyanate includes CosmonateT-100 and CosmonateT-80 available from Mitsui chemical Co., Ltd.

The aliphatic polyisocyanate having 4 to 8 carbon atoms in the present invention is a linear or branched aliphatic polyisocyanate having 4 to 8 carbon atoms, preferably a linear diisocyanate. Specific examples of the aliphatic polyisocyanate having 4 to 8 carbon atoms include tetramethylene diisocyanate, 1, 5-pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate and 1, 8-octamethylene diisocyanate, and 1, 6-hexamethylene diisocyanate and 1, 5-pentamethylene diisocyanate are preferable from the viewpoint of obtaining, handling and heat resistance of the obtained resin.

In addition, other isocyanate compounds can be used in addition to toluene diisocyanate and aliphatic polyisocyanates having 4 to 8 carbon atoms (hereinafter, isocyanate compounds other than toluene diisocyanate and aliphatic polyisocyanates having 4 to 8 carbon atoms are referred to as "other isocyanate compounds"). Examples of the other isocyanate compounds include, but are not limited to, the following compounds:

aliphatic polyisocyanate compounds such as 2, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2, 4, 4-trimethyl-1, 6-hexamethylene diisocyanate, lysine methyl ester diisocyanate (lysine diisocyanate) and lysine triisocyanate;

alicyclic polyisocyanate compounds such as isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, dicyclohexyldimethyl methane isocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isocyanatomethyl) tricyclodecane, 3, 9-bis (isocyanatomethyl) tricyclodecane, 4, 8-bis (isocyanatomethyl) tricyclodecane, 4, 9-bis (isocyanatomethyl) tricyclodecane and the like (for example, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane and 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, can be produced by the production methods described in International publication No. 2008/001490, Japanese patent application laid-open No. H03-095151, Japanese patent application laid-open No. 2003-055327, Japanese patent application laid-open No. 2003-055328, Japanese patent application laid-open No. H03-081255, Japanese patent application laid-open No. H03-109361, Japanese patent application laid-open No. H03-181446, Japanese patent application laid-open No. 2001-089424, and Japanese patent application laid-open No. H07-309827, and can be used alone or as a mixture. When used as a mixture, the mixing ratio thereof may be arbitrary. ) (ii) a

Aromatic polyisocyanate compounds such as 4, 4' -diphenylmethane diisocyanate, diphenylsulfide-4, 4-diisocyanate, and phenylene diisocyanate;

and heterocyclic polyisocyanate compounds such as 2, 5-diisocyanatothiophene, 2, 5-bis (isocyanatomethyl) thiophene, 2, 5-diisocyanatotetrahydrothiophene, 2, 5-bis (isocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isocyanatomethyl) tetrahydrothiophene, 2, 5-diisocyanato-1, 4-dithiane, 2, 5-bis (isocyanatomethyl) -1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, and 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane.

Further, in addition to tolylene diisocyanate and aliphatic polyisocyanates having 4 to 8 carbon atoms, isocyanate groups of the above-listed isocyanate compounds may be partially converted to isothiocyanate groups.

Examples of such isothiocyanate compounds include, but are not limited to, the following:

aliphatic polyisothiocyanate compounds such as 1, 6-hexamethylene diisothiocyanate, lysine methyl ester diisothiocyanate, lysine triisothiocyanate, m-xylylene diisothiocyanate, bis (isothiocyanatomethyl) sulfide, bis (isothiocyanatoethyl) disulfide and the like;

alicyclic polyisothiocyanate compounds such as isophorone diisothiocyanate, bis (isothiocyanatomethyl) cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2, 5-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isothiocyanatomethyl) tricyclodecane, 3, 9-bis (isothiocyanatomethyl) tricyclodecane, 4, 8-bis (isothiocyanatomethyl) tricyclodecane, 4, 9-bis (isothiocyanatomethyl) tricyclodecane and the like;

aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4-diphenylmethane diisothiocyanate, diphenyl disulfide-4, 4-diisothiocyanate and the like;

sulfur-containing heterocyclic polyisothiocyanate compounds such as 2, 5-diisothiocyanatothiophene, 2, 5-bis (isothiocyanatomethyl) thiophene, 2, 5-isothiocyanattetrahydrothiophene, 2, 5-bis (isothiocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isothiocyanatomethyl) tetrahydrothiophene, 2, 5-diisothiocyanato-1, 4-dithiane, 2, 5-bis (isothiocyanatomethyl) -1, 4-dithiane, 4, 5-diisothiocyanato-1, 3-dithiolane, 4, 5-bis (isothiocyanatomethyl) -1, 3-dithiolane and the like.

Further, as other isocyanate compounds, halogen substituted compounds such as chlorine substituted compounds and bromine substituted compounds of the above isocyanate compounds, alkyl substituted compounds, alkoxy substituted compounds, nitro substituted compounds, prepolymer type modified products formed with polyhydric alcohols, carbodiimide modified products, urea modified products, biuret modified products, dimerization reaction products, or the like can be used. The isocyanate compounds may be used alone or in combination of two or more.

The weight ratio of the toluene diisocyanate (A) to the aliphatic polyisocyanate (B) having 4 to 8 carbon atoms is not particularly limited, and the weight ratio (A/B) is 58 to 98/42 to 2, preferably 58 to 90/42 to 10, and more preferably 58 to 85/42 to 15. When the amount is within the above range, an optical material having an excellent balance between heat resistance and dyeing properties can be obtained.

In the present invention, an active hydrogen compound may be further added. The active hydrogen compound used in the present invention means a compound having at least 2 or more active hydrogen groups. Examples of the active hydrogen group include a hydroxyl group and a mercapto group. The active hydrogen compound is preferably an aliphatic or aromatic active hydrogen compound having 1 to 12 carbon atoms, more preferably an aliphatic or aromatic active hydrogen compound having 1 to 8 carbon atoms, and still more preferably an aliphatic active hydrogen compound having 1 to 8 carbon atoms. The active hydrogen compound may contain an ether bond, an ester bond, a thioether bond, or a disulfide bond in its molecule.

Specifically, the following substances may be mentioned: mercapto group-and hydroxyl group-containing compounds such as 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, 7-mercaptoheptanol, 8-mercaptooctanol, 3-mercapto-1, 2-propanediol, glycerol di (mercaptoacetate), 4-mercaptophenol, and 2, 3-dimercapto-1-propanol; ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 4-pentanediol, 1, 3-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 1, 3-hexanediol, 1, 2-cyclohexanediol, hydroxyl group-containing compounds such as 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 7-heptanediol, 1, 8-octanediol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, xylitol, 1, 2-dihydroxybenzene, 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, m-benzenedimethanol, p-benzenedimethanol, and o-benzenedimethanol;

methyldithiol, 1, 2-ethanedithiol, 1, 2, 3-propanetrithiol, 1, 2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 1, 2-bis (3-mercaptopropylthio) ethane, and mixtures thereof, Mercapto group-containing compounds such as 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, and 1, 4-bis (mercaptoethyl) benzene.

From the viewpoint of high refractive index, high heat resistance, and high dyeability of the resulting resin, ethylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, 2-mercaptoethanol, 3-mercaptopropanol, 1, 2-ethanedithiol, 1, 3-bis (mercaptomethyl) benzene, and the like are preferred, and ethylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, and 2-mercaptoethanol are more preferred. The active hydrogen compounds can be used alone, or can be mixed with 2 or more kinds of use. The active hydrogen compound may be in the form of an oligomer.

In addition, other polythiol compounds (hereinafter, a polythiol compound other than pentaerythritol tetramercaptoacetate and pentaerythritol tetramercaptopropionate is referred to as "other polythiol compound") may be used in addition to pentaerythritol tetramercaptoacetate and pentaerythritol tetramercaptopropionate. Examples of the other polythiol compounds include, but are not limited to, the following compounds:

trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), 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, 2, 5-dimercaptomethyl-2, 5-dimethyl-1, 4-dithiane, And mercaptoacetates, mercaptopropionates, hydroxymethylthioether bis (2-mercaptoacetate), hydroxymethylthioether bis (3-mercaptopropionate), hydroxyethylthioether bis (2-mercaptoacetate), hydroxyethylthioether bis (3-mercaptopropionate), hydroxymethyldisulfide bis (2-mercaptoacetate), hydroxymethyldisulfide bis (3-mercaptopropionate), hydroxyethyldisulfide bis (2-mercaptoacetate), hydroxyethyldisulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), Aliphatic polythiol compounds such as bis (2-mercaptoethyl) dithiodipropionate, 1, 3, 3-tetrakis (mercaptomethylthio) propane, 1, 2, 2-tetrakis (mercaptomethylthio) ethane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, tris (mercaptomethylthio) methane, and tris (mercaptoethylthio) methane;

1, 3, 5-trimercaptobenzene, 1, 3, 5-tris (mercaptomethyl) benzene, 1, 3, 5-tris (mercaptomethyleneoxy) benzene, 1, 3, 5-tris (mercaptoethyleneoxy) benzene, 2, 5-methanebenzenedithiol, 3, 4-methanebenzenedithiol, 1, 5-naphthalenedithiol, aromatic polythiol compounds such as 2, 6-naphthalenedithiol, 2-methylamino-4, 6-dithiol-s-triazine, 3, 4-thiophenedithiol, 2, 5-dimercapto-1, 3, 4-thiadiazole (bismuthiol), 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, and 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiacyclobutane;

heterocyclic polythiol compounds such as 2-methylamino-4, 6-dithiol-s-triazine, 3, 4-thiophenedithiol, 2, 5-dimercapto-1, 3, 4-thiadiazole, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, and 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiane.

Further, a halogen-substituted compound such as pentaerythritol tetramercaptoacetate, pentaerythritol tetramercaptopropionate, an active hydrogen compound, an oligomer or a chlorine-substituted compound or a bromine-substituted compound of another polythiol compound may be added to the polymerizable composition for an optical material of the present invention. The above compounds may be used alone, or 2 or more kinds thereof may be mixed and used.

The tolylene diisocyanate, the aliphatic polyisocyanate having 4 to 8 carbon atoms, and another isocyanate compound (hereinafter referred to as "isocyanate compound") added as necessary, which are used in the present embodiment, may be reacted with the polythiol, and the active hydrogen compound and a part of another polythiol compound added as necessary in advance. The polythiols used in the present invention may be reacted with a part of the isocyanate compounds in advance.

Examples of the epoxy compound that can be added as the resin modifier include, but are not limited to, the following:

phenolic epoxy compounds obtained by condensation reaction of polyhydric phenol compounds such as bisphenol a glycidyl ether and epihalohydrin compounds;

alcohol epoxy compounds obtained by condensation of a polyhydric alcohol compound such as hydrogenated bisphenol a glycidyl ether and an epihalohydrin compound;

glycidyl ester epoxy compounds obtained by condensation of a polyvalent organic acid compound such as 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate and an epihalohydrin compound;

amine epoxy compounds obtained by condensation of primary and secondary diamine compounds and epihalohydrin compounds;

aliphatic polyepoxy compounds such as vinylcyclohexene diepoxy compounds, and the like.

Examples of episulfide compounds that can be added as a resin modifier include, but are not limited to, the following:

chain aliphatic 2, 3-epithiopropylthio compounds such as bis (2, 3-epithiopropylthio) sulfide, bis (2, 3-epithiopropylthio) disulfide, bis (2, 3-epithiopropylthio) methane, 1, 2-bis (2, 3-epithiopropylthio) ethane and 1, 5-bis (2, 3-epithiopropylthio) -3-thiapentane;

cyclic aliphatic compounds such as 1, 3-bis (2, 3-epithiopropylthio) cyclohexane, 2, 5-bis (2, 3-epithiopropylthiomethyl) -1, 4-dithiane and 2, 3-epithiopropylthio compounds having a heterocyclic ring;

aromatic 2, 3-epithiopropylthio compounds such as 1, 3-bis (2, 3-epithiopropylthio) benzene and 1, 4-bis (2, 3-epithiopropylthio) benzene.

Examples of the organic acid and the acid anhydride thereof which can be added as the resin modifier include, but are not limited to, the following compounds:

thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.

Examples of the olefin compound that can be added as the resin modifier include, but are not limited to, the following:

benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol diglycidyl acrylate, ethylene glycol diglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, trimethylolpropane triacrylate, bisphenol A diacrylate, bisphenol F diacrylate, propylene glycol diacrylate, styrene, (meth) acrylate compounds such as trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, xylylene thiol diacrylate, xylylene thiol dimethacrylate, mercaptoethylsulfide diacrylate and mercaptoethylsulfide dimethacrylate;

allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, and diethylene glycol diallyl carbonate;

vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, and 3, 9-divinylspirobis (m-dioxane).

The resin modifier may be used alone, or 2 or more kinds thereof may be mixed and used.

The isocyanate compound and the active hydrogen compound used in the present invention are used in a proportion that is usually within a range of 0.8 to 1.5, preferably within a range of 0.8 to 1.2, more preferably within a range of 0.8 to 1.1, and still more preferably within a range of 0.85 to 1.05 in terms of a molar ratio of (NCO + NCS)/(SH + OH) functional groups in the polymerizable composition for optical materials.

The present invention also provides an optical material obtained by curing the polymerizable composition for an optical material.

The refractive index of the optical material can be adjusted as needed by the kind and composition ratio of the isocyanate compound and the active hydrogen compound in the polymerizable composition. In particular, the optical material of the present embodiment is required to have a high refractive index, and from this viewpoint, a combination of isocyanate compounds and active hydrogen compounds which can give a resin having a refractive index of usually 1.55 or more, preferably 1.59 or more, measured by e-ray, for example, and a composition ratio thereof are preferable.

In addition, the optical material of the present invention is also excellent in light resistance. The light resistance can be evaluated by measuring the change in yellowness (hereinafter referred to as "YI") measured by a QUV tester after 48 hours of light irradiation (hereinafter referred to as "Δ YI"). From the viewpoint of excellent light resistance, the Δ YI value of the optical material is preferably as small as possible, and is usually 10.0 or less, preferably 7.0 or less, and more preferably 6.0 or less. The lower limit is not particularly limited, and is, for example, 0.1 or more.

The heat resistance of the optical material of the present invention is preferably 90 ℃ or higher, more preferably 95 ℃ or higher, and still more preferably 100 ℃ or higher.

The optical material of the present invention has excellent dyeability. The dyeing property in the present invention refers to ease of dyeing when an optical material is immersed in a dye dispersion prepared by adding a dyeing agent to pure water and then dyeing. Specifically, the lens sheet after dyeing was scanned with a UV spectrometer (UV-1600 manufactured by Shimadzu corporation) at a wavelength of 400 to 800nm, and the light transmittance (% T) at 565nm, which is the maximum absorption wavelength, was small.

The optical material of the present invention herein has a dyeability of preferably 60% T or less, more preferably 50% T or less, and even more preferably 45% T or less, as a value of light transmittance (% T) described below.

From another viewpoint, the present invention provides a method for producing an optical material by curing a polymerizable composition, for example, a method for producing an optical material by molding the polymerizable composition by cast polymerization using a mold for lens casting.

When a mixture of isocyanate compounds and active hydrogen compounds as the polymerizable composition for optical materials is cured and molded, a polymerization catalyst described in the following international publication No. 2010/001550, a catalyst (hereinafter, also referred to as "curing catalyst") such as dialkyltin dichloride (specifically, dialkyltin dichloride having an alkyl group of 1 to 4 carbon atoms, for example, dimethyltin dichloride or dibutyltin dichloride), an ultraviolet absorber such as benzotriazole, an internal mold release agent such as an acid phosphate, a light stabilizer, an antioxidant, a reaction initiator such as a radical reaction initiator, a chain extender, a crosslinking agent, an anti-coloring agent, an oil-soluble dye, a filler, and the like may be added as necessary in the same manner as in a known molding method.

When the reaction catalyst, the release agent, and other additives are mixed with the isocyanate compounds and the active hydrogen compounds to prepare the injection liquid, the addition of the catalyst, the release agent, and other additives is also affected by the solubility in the isocyanate compounds and the active hydrogen compounds, but the catalyst, the release agent, and other additives may be added to and dissolved in the isocyanate compounds, the active hydrogen compounds, or the mixture of the isocyanate compounds and the active hydrogen compounds. Alternatively, the isocyanate compound or the active hydrogen compound may be dissolved in a part of the isocyanate compound or the active hydrogen compound to prepare a mother solution, and then the mother solution may be added. The order of addition is not limited to the method listed, and may be selected appropriately based on the operability, safety, simplicity, and the like.

The mixing is usually carried out at a temperature of 30 ℃ or lower. From the viewpoint of pot life of the mixture, it is sometimes preferable to carry out at a lower temperature. In addition, when additives such as a catalyst and a release agent do not have good solubility in isocyanate compounds and active hydrogen compounds, they may be dissolved in isocyanate compounds, active hydrogen compounds, or a mixture thereof by heating in advance.

Further, depending on the physical properties required for the plastic lens to be obtained, it is usually preferable to carry out, if necessary, a defoaming treatment under reduced pressure, a filtration treatment under pressure, reduced pressure, or the like.

Then, the lens casting mold into which the mixture of isocyanate compounds and active hydrogen compounds and the polarizing film are injected is placed in a heating apparatus such as an oven or water, and is heated for several hours to several tens of hours at a predetermined temperature program (program) to be cured and molded.

The conditions vary depending on the composition of the mixture, the kind of the catalyst, the shape of the mold, etc., and therefore the temperature of the polymerization and curing is not limited, but the polymerization and curing is carried out at a temperature of about-50 to 200 ℃ for 1 to 100 hours.

Typically, it is started at a temperature in the range of 5 ℃ to 40 ℃ and then slowly warmed to a temperature in the range of 80 ℃ to 130 ℃, typically heated at this temperature for 1 hour to 4 hours.

After the completion of the curing molding, the molded article is taken out from the lens casting mold, whereby a plastic lens can be obtained.

In order to alleviate the deformation caused by polymerization, the plastic lens obtained from the optical material of the present embodiment is preferably subjected to annealing treatment by heating the lens after mold release. The annealing temperature is usually in the range of 80 to 150 ℃, preferably in the range of 100 to 130 ℃, and more preferably in the range of 110 to 130 ℃. The annealing time is usually in the range of 0.5 to 5 hours, preferably in the range of 1 to 4 hours.

The plastic lens obtained from the optical material of the present embodiment is used by providing a coating layer on one surface or both surfaces as necessary. Examples of the coating layer include an undercoat layer, a hard coat layer, an antireflection film layer, an antifogging coating film layer, an antifouling layer, and a waterproof layer. The coating layers may be used individually, or a plurality of coating layers may be multilayered. When the coatings are provided on both surfaces, the same coating may be provided on each surface, or different coatings may be provided.

These coatings may be formed using an ultraviolet absorber for the purpose of protecting the lens and eyes from ultraviolet rays, an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer or an antioxidant for the purpose of improving the weatherability of the lens, a dye or a pigment for the purpose of improving the fashionability of the lens, a photosensitive dye or a photosensitive pigment, an antistatic agent, or a combination of known additives for the purpose of improving the performance of the lens. Various leveling agents may also be used for the purpose of improving coatability.

In general, an undercoat layer is formed between a lens substrate (optical material obtained from the polymerizable composition of the present embodiment) and a hard coat layer for the purpose of improving the adhesion of the hard coat layer and the impact resistance of a plastic lens, and the film thickness of the undercoat layer is usually about 0.1 to 10 μm.

The undercoat layer is formed, for example, by a coating method or a dry method. As for the coating method, a known coating method such as spin coating or dip coating is used to coat the primer composition and then the composition is cured to form a primer layer. The dry method is a known dry method such as a CVD method or a vacuum deposition method. In the formation of the primer layer, the lens surface may be subjected to pretreatment such as alkali treatment, plasma treatment, or ultraviolet treatment as necessary for the purpose of improving adhesion.

As the primer composition, a material having high adhesion between the cured primer and the lens substrate (optical material obtained from the polymerizable composition of the present embodiment) is preferable, and a primer composition containing a urethane resin, an epoxy resin, a polyester resin, a melamine resin, or a polyvinyl acetal as a main component is generally used. The primer composition may be used without solvent, but an appropriate solvent that does not affect the lens may be used for the purpose of adjusting the viscosity of the composition.

The hard coat layer is a layer for imparting functions such as scratch resistance, abrasion resistance, moisture resistance, hot water resistance, heat resistance, weather resistance, etc. to the surface of the lens, and the film thickness is usually about 0.3 to 30 μm.

The hard coat layer is usually formed by applying a hard coat composition by a known coating method such as spin coating or dip coating and then curing the composition. Examples of the curing method include thermal curing and a curing method using irradiation with energy rays such as ultraviolet rays and visible light. In the formation of the hard coat layer, the coated surface (lens base material or primer layer) may be subjected to pretreatment such as alkali treatment, plasma treatment, or ultraviolet treatment as necessary for improving adhesion.

As the hard coat composition, a mixture of an organosilicon compound having curability and fine oxide particles (including composite oxide particles) of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, and the like is generally used In many cases. Further, in addition to the above-mentioned substances, amines, amino acids, metal acetylacetonate complexes, organic acid metal salts, perchloric acids, salts of perchloric acids, metal chlorides, polyfunctional epoxy compounds, and the like can be used. The hard coat composition may be used without a solvent, but an appropriate solvent which does not affect the lens may also be used.

An antireflection layer is usually formed on the hard coat layer as needed. The antireflection layer includes inorganic and organic, and when inorganic, SiO is generally used in many cases₂、TiO₂And the like, and is formed by a dry method such as a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, and the like. In the case of organic materials, a composition containing an organosilicon compound and silica-based fine particles having a cavity therein is generally used in many cases and formed by a wet process.

The antireflection layer may be a single layer or a plurality of layers, and when used as a single layer, the refractive index is preferably at least 0.1 lower than that of the hard coat layer. In order to effectively exhibit an antireflection function, a multilayer antireflection film is preferable, and in this case, a low refractive index film and a high refractive index film are generally alternately laminated. In this case, the difference in refractive index between the low refractive index film and the high refractive index film is preferably 0.1 or more. Examples of the high refractive index film include ZnO and TiO₂、CeO₂、Sb₂O₅、SnO₂、ZrO₂、Ta₂O₅Etc. As the low refractive index film, SiO can be mentioned₂Films, and the like. The film thickness is usually about 50 to 150 nm.

Further, the plastic lens obtained from the optical material of the present embodiment may be subjected to back grinding, antistatic treatment, dyeing treatment, light control treatment, and the like as necessary.

The plastic lens can be made thin, and is useful as a spectacle lens, particularly a vision correction lens, and is fashionable because of its excellent dyeability.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The lenses obtained by polymerization were subjected to performance tests and evaluated. The performance test was evaluated by the following test methods using color tone, refractive index, abbe number, heat resistance, specific gravity, and dyeability as indices.

Color tone: a resin flat plate having a thickness of 9mm was prepared, and the Yellowness (YI) was measured with a color difference meter (CR-200 manufactured by Minolta).

Refractive index (ne) abbe number (ve): the measurement was carried out at 20 ℃ using a Pohl refractometer KPR-30 manufactured by Shimadzu corporation.

Heat resistance: using TMA-60 manufactured by Shimadzu corporation, the TMA penetration method (load: 50g, tip)0.5mm) as heat resistance.

Specific weight: the measurement was carried out by the Archimedes method at 20 ℃.

Dyeing property: a dye dispersion was prepared by adding 1.5g of "MLP-Blue" dispersion dye for spectacle lens manufactured by Mitsui chemical Co., Ltd, "2.0 g of" MLP-Yellow "and" 1.5g of "MLP-Red" as coloring agents to 995g of pure water. After heating to 90 ℃, a plastic lens sheet having a thickness of 9mm was immersed at 90 ℃ for 5 minutes to dye the sheet. The dyed lens sheet was scanned at a wavelength of 400 to 800nm using a UV spectrometer (UV-1600 manufactured by Shimadzu corporation), and the light transmittance (% T) at 565nm, which is the maximum absorption wavelength, was measured.

Light resistance test: a resin plate having a thickness of 2mm was prepared, irradiated in a QUV tester (Q-Lab) for 48 hours, and then the Δ YI was measured from the resin color tone before and after the irradiation. (as QUV test conditions, as lightThe source used UVB-340 at an illumination of 0.35W/m²And blackboard (BlackPanel) at 50 ℃. )

(example 1)

26.4g of toluene diisocyanate (Cosmonatet T-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 13.7g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 59.9g of pentaerythritol tetramercaptopropionate was added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 7.9, the refractive index (ne) was 1.595, the Abbe number (ve) was 32, the heat resistance was 98 ℃, the specific gravity of the resin was 1.34, and the light resistance (. DELTA.YI value in 48 hours) was 6.6. Further, the light transmittance at 565nm after dyeing of the obtained resin was 29% T.

(examples 2 to 8, comparative examples 1 to 3)

The curing catalyst, the ultraviolet absorber and the internal mold release agent were polymerized in the monomer composition shown in table 1 in the same manner as in example 1. The physical properties of the obtained resin are summarized in Table 1.

(example 9)

The kind and amount of the internal mold release agent and curing conditions were the same as in example 1 except that 0.01g of dibutyltin dichloride was used as a curing catalyst, and polymerization was carried out in the monomer composition shown in table 1. As the toluene diisocyanate, CosmonateT-100 (batch No. K09B04505) manufactured by Mitsui chemical Co., Ltd. The physical properties of the obtained resin are summarized in Table 1.

[ Table 1]

(examples 10 to 15)

The curing catalyst, the ultraviolet absorber and the internal mold release agent were polymerized in the monomer composition shown in Table 2 in the same manner as in example 1, except for the kinds and amounts of the added curing catalyst, ultraviolet absorber and internal mold release agent and the curing conditions. The physical properties of the obtained resin are summarized in Table 2.

[ Table 2]

(example 16)

As the curing catalyst, the curing catalyst (polymerization catalyst) described in example A1 of International publication No. 2010/001550 was used. Specifically, a mixture of 26.4g of toluene diisocyanate (Cosmonatet-80 (batch No. K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 13.7g of 1, 6-hexamethylene diisocyanate was mixed and dissolved, and 0.20g of a mixture of 0.17g of an isopropyl alcohol solution of tri-n-octylmethyl ammonium chloride (containing 25% isopropyl alcohol) (manufactured by LIONAKKO) and 0.03g of methanesulfonic acid (manufactured by Tokyo Kagaku Co., Ltd.) and 0.02g of zinc dibutyldithiocarbamate (manufactured by Kakoku Co., Ltd.) were added as a curing catalyst, and the kind and the addition amount of an ultraviolet absorber and an internal mold release agent and curing conditions were the same as those of example 1, and polymerization was carried out in a monomer composition shown in Table 3. The physical properties of the obtained resin are summarized in Table 3.

(examples 17 to 20)

The ultraviolet absorber and the internal mold release agent were used in the same kinds and amounts as those of example 1 except that 0.01g of dibutyltin dichloride was used as a curing catalyst, and polymerization was carried out under the same curing conditions with the monomer composition shown in Table 3. The physical properties of the obtained resin are summarized in Table 3.

[ Table 3]

(example 21)

20.0g of toluene diisocyanate (CosmonateT-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 20.0g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber, and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal mold release agent were further added and mixed and dissolved at 20 ℃. After dissolution, 60.0g of pentaerythritol tetramercaptopropionate was added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 7.7, the refractive index (ne) was 1.587, the Abbe number (. nu.e) was 34, the heat resistance was 91 ℃, the specific gravity of the resin was 1.33, and the light resistance (. DELTA.YI value in 48 hours) was 4.2. Further, the light transmittance at 565nm after dyeing of the obtained resin was 17% T.

(example 22)

24.1g of toluene diisocyanate (Cosmonatet T-80 (K09B 26302) manufactured by Mitsui chemical Co., Ltd.) and 16.1g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate ester: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 59.8g of pentaerythritol tetramercaptopropionate was added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 7.9, the refractive index (ne) was 1.593, the Abbe number (. nu.e) was 32, the heat resistance was 98 ℃, the specific gravity of the resin was 1.34, and the light resistance (. DELTA.YI value in 48 hours) was 4.5. Further, the light transmittance at 565nm after dyeing of the obtained resin was 22% T.

(example 23)

28.2g of toluene diisocyanate (Cosmonatet T-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 12.1g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 59.7g of pentaerythritol tetramercaptopropionate was added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 8.1, the refractive index (ne) was 1.598, the Abbe number (. nu.e) was 31, the heat resistance was 104 ℃, the specific gravity of the resin was 1.35, and the light resistance (. DELTA.YI value in 48 hours) was 4.6. Further, the light transmittance at 565nm after dyeing of the obtained resin was 36% T.

(example 24)

51.1g of toluene diisocyanate (Cosmonatet T-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 2.7g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 31.7g of pentaerythritol tetramercaptopropionate and 14.5g of 2-mercaptoethanol were added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 7.5, the refractive index (ne) was 1.620, the Abbe number (. nu.e) was 28, the heat resistance was 117 ℃ and the specific gravity of the resin was 1.35. Further, the light transmittance at 565nm after dyeing of the obtained resin was 59% T.

(example 25)

48.4g of toluene diisocyanate (CosmonateT-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 5.4g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 31.7g of pentaerythritol tetramercaptopropionate and 14.5g of 2-mercaptoethanol were added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 7.1, the refractive index (ne) was 1.617, the Abbe number (. nu.e) was 28, the heat resistance was 111 ℃ and the specific gravity of the resin was 1.35. Further, the light transmittance at 565nm after dyeing of the obtained resin was 45% T.

(example 26)

45.7g of toluene diisocyanate (CosmonateT-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 8.1g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 31.7g of pentaerythritol tetramercaptopropionate and 14.5g of 2-mercaptoethanol were added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 6.9, the refractive index (ne) was 1.604, the Abbe number (. nu.e) was 29, the heat resistance was 109 ℃ and the specific gravity of the resin was 1.34. Further, the light transmittance at 565nm after dyeing of the obtained resin was 41% T.

(example 27)

32.1g of toluene diisocyanate (Cosmonatet T-80 (batch: K09B26302) manufactured by Mitsui chemical Co., Ltd.) and 21.4g of 1, 6-hexamethylene diisocyanate were mixed and dissolved, and 0.01g of dimethyltin dichloride as a curing catalyst, 1.50g of VIOSORB583 as an ultraviolet absorber and 0.10g of ZelecUN (acid phosphate: registered trademark, manufactured by Stepan Co., Ltd.) as an internal releasing agent were further added and mixed and dissolved at 20 ℃. After dissolution, 31.9g of pentaerythritol tetramercaptopropionate and 14.6g of 2-mercaptoethanol were added and mixed and dissolved to prepare a uniform solution. The homogeneous solution was degassed at 600Pa for 1 hour, filtered using a 1. mu. mTeflon (registered trademark) filter, and then injected into an injection mold composed of a glass mold and a tape. The above injection mold was put into an oven and polymerization was carried out by slowly raising the temperature from 25 ℃ to 120 ℃ over about 24 hours. After the polymerization is finished, the injection mold is taken out of the oven and demolded to obtain the resin. The resulting resin was further annealed at 120 ℃ for 4 hours. The YI value of the obtained resin was 6.6, the refractive index (ne) was 1.597, the Abbe number (ve) was 31, the heat resistance was 96 ℃ and the specific gravity of the resin was 1.32. Further, the light transmittance at 565nm after dyeing of the obtained resin was 13% T.

The physical properties of the resins obtained in examples 21 to 27 are summarized in Table 4.

[ Table 4]

The abbreviations used in the monomer compositions of tables 1 to 4 represent the following.

A-1: toluene diisocyanate (CosmonateT-80 (batch: K09B26302, manufactured by Mitsui chemical Co., Ltd.))

A-1-1: toluene diisocyanate (CosmonateT-100 (batch: K09B04505) manufactured by Mitsui chemical Co., Ltd.)

A-2: mixtures of 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane

A-3: m-xylylene diisocyanate

B-1: 1, 6-hexamethylene diisocyanate

B-2: 1, 5-Pentanediisocyanate

C-1: pentaerythritol Tetramercaptopropionate

C-2: pentaerythritol Tetramercaptoacetate

C-3: 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane

D-1: 2-mercaptoethanol

D-2: diethylene glycol

D-3: triethylene glycol

D-4: ethylene glycol

D-5: trimethylolpropane

From tables 1 to 4, the materials of examples 1 to 27 have a high refractive index, high heat resistance, and high dyeability, and can be said to be materials having a good balance.

On the other hand, in comparative example 1, although it has a high refractive index and high heat resistance, the dyeing property is inferior to that of the material of the present invention. That is, comparative example 1 is excellent in heat resistance but poor in dyeing property. More specifically, when compared with examples having similar glass transition temperatures as an index of heat resistance, example 5 was superior to comparative example 1 in heat resistance, though it was higher by 2 ℃ as compared with comparative example 1, whereas example 5 was lower by 26% T than comparative example 1 in dyeability, and example 5 was good.

Claims (13)

1. A polymerizable composition for optical materials, comprising (a) toluene diisocyanate, (b) 1 or more aliphatic polyisocyanates selected from 1, 6-hexamethylene diisocyanate and 1, 5-pentamethylene diisocyanate, and (c) 1 or more polythiols selected from pentaerythritol tetramercaptoacetate and pentaerythritol tetramercaptopropionate,

optionally further (d) a compound selected from the group consisting of 2, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2, 4, 4-trimethyl-1, 6-hexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine triisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, dicyclohexyldimethyl methane isocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isocyanatomethyl) tricyclodecane, 3, 9-bis (isocyanatomethyl) tricyclodecane, 4, 8-bis (isocyanatomethyl) tricyclodecane, 4, 9-bis (isocyanatomethyl) tricyclodecane, 4, 4' -diphenylmethane diisocyanate, diphenylsulfide-4, 4-diisocyanate, phenylene diisocyanate, 2, 5-diisocyanatothiophene, 2, 5-bis (isocyanatomethyl) thiophene, 2, 5-diisocyanatotetrahydrothiophene, 2, 5-bis (isocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isocyanatomethyl) tetrahydrothiophene, 2, 5-diisocyanato-1, 4-dithiane, 2, 5-bis (isocyanatomethyl) -1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, and at least one other isocyanate compound in the 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane ring, and/or at least one isocyanate compound selected from the group consisting of 1, 6-diisothiocyanate, lysine methyl diisothiocyanate, triisolysine thiocyanate, isophthalylene diisothiocyanate, bis (isothiocyanatomethyl) sulfide, Bis (isothiocyanatoethyl) sulfide, bis (isothiocyanatoethyl) disulfide, isophorone diisothiocyanate, bis (isothiocyanatomethyl) cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2, 5-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isothiocyanatomethyl) tricyclodecane, 3, 9-bis (isothiocyanatomethyl) tricyclodecane, 4, 8-bis (isothiocyanatomethyl) tricyclodecane, 4, 9-bis (isothiocyanatomethyl) tricyclodecane, toluene diisothiocyanate, 4-diphenylmethane diisothiocyanate, diphenyldisulfide-4, 4-diisothiocyanate, 2, 5-diisothiocyanatothiophene, 2, 6-bis (isothiocyanatomethyl) tricyclodecane, At least one isothiocyanate compound selected from the group consisting of 2, 5-bis (isothiocyanatomethyl) thiophene, 2, 5-isothiocyanatotetrahydrothiophene, 2, 5-bis (isothiocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isothiocyanatomethyl) tetrahydrothiophene, 2, 5-diisothiocyanato-1, 4-dithiane, 2, 5-bis (isothiocyanatomethyl) -1, 4-dithiane, 4, 5-diisothiocyanato-1, 3-dithiolane, 4, 5-bis (isothiocyanatomethyl) -1, 3-dithiolane,

optionally further containing (e) an active hydrogen compound having 2 or more active hydrogen groups in the molecule other than (c), the active hydrogen compound being a mercapto group-and hydroxyl group-containing compound, a hydroxyl group-containing compound, or a mercapto group-containing compound,

so that the molar ratio of the functional groups expressed by (NCO + NCS)/(SH + OH) is 0.8 to 1.5,

and the weight ratio of the (a) toluene diisocyanate to the (b) aliphatic polyisocyanate is 58-98/42-2.

2. The polymerizable composition for optical materials according to claim 1, wherein the aliphatic polyisocyanate (b) is 1, 5-pentamethylene diisocyanate.

3. The polymerizable composition for optical materials according to claim 1, wherein the polymerizable composition for optical materials contains at least one other isocyanate compound selected from the group consisting of: 2, 2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 2, 4, 4-trimethyl-1, 6-hexamethylene diisocyanate, lysine methyl ester diisocyanate, lysine triisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, dicyclohexyldimethyl methane isocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2, 6-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 3, 8-bis (isocyanatomethyl) tricyclodecane, 3, 9-bis (isocyanatomethyl) tricyclodecane, 4, 8-bis (isocyanatomethyl) tricyclodecane, 4, 9-bis (isocyanatomethyl) tricyclodecane, 4, 4' -diphenylmethane diisocyanate, diphenylsulfide-4, 4-diisocyanate, Phenylene diisocyanate, 2, 5-diisocyanatothiophene, 2, 5-bis (isocyanatomethyl) thiophene, 2, 5-diisocyanatotetrahydrothiophene, 2, 5-bis (isocyanatomethyl) tetrahydrothiophene, 3, 4-bis (isocyanatomethyl) tetrahydrothiophene, 2, 5-diisocyanato-1, 4-dithiane, 2, 5-bis (isocyanatomethyl) -1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, and 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane.

4. The polymerizable composition for optical materials according to claim 1, which contains an active hydrogen compound having 2 or more active hydrogen groups in the molecule other than (c).

5. The polymerizable composition for optical materials as claimed in claim 4, wherein the active hydrogen compound is a mercapto group-and hydroxyl group-containing compound, a hydroxyl group-containing compound, or a mercapto group-containing compound.

6. The polymerizable composition for optical materials according to claim 5, wherein the active hydrogen compound is at least one selected from the group consisting of: 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, 7-mercaptoheptanol, 8-mercaptooctanol, 3-mercapto-1, 2-propanediol, glycerol di (mercaptoacetate), 4-mercaptophenol, 2, 3-dimercapto-1-propanol, ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 4-pentanediol, 1, 3-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 1, 3-hexanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 7-heptanediol, 1, 8-octanediol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, trimethylolpropane, sorbitol, xylitol, 1, 2-dihydroxybenzene, 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, m-benzenedimethanol, p-xylylene glycol, o-xylylene glycol, methanedithiol, 1, 2-ethanedithiol, 1, 2, 3-propanetrithiol, 1, 2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 1, 2-bis (3-mercaptopropylthio) ethane, 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, and 1, 4-bis (mercaptoethyl) benzene.

7. The polymerizable composition for optical materials according to claim 3, which contains an active hydrogen compound having 2 or more active hydrogen groups in the molecule other than (c).

8. The polymerizable composition for optical materials according to claim 7, wherein the active hydrogen compound is a compound containing a mercapto group and a hydroxyl group, a compound containing a hydroxyl group, or a compound containing a mercapto group.

9. The polymerizable composition for optical materials according to claim 8, wherein the active hydrogen compound is at least one selected from the group consisting of: 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, 7-mercaptoheptanol, 8-mercaptooctanol, 3-mercapto-1, 2-propanediol, glycerol di (mercaptoacetate), 4-mercaptophenol, 2, 3-dimercapto-1-propanol, ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 4-pentanediol, 1, 3-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 1, 3-hexanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 7-heptanediol, 1, 8-octanediol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, trimethylolpropane, sorbitol, xylitol, 1, 2-dihydroxybenzene, 1, 3-dihydroxybenzene, 1, 4-dihydroxybenzene, m-benzenedimethanol, p-xylylene glycol, o-xylylene glycol, methanedithiol, 1, 2-ethanedithiol, 1, 2, 3-propanetrithiol, 1, 2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 1, 2-bis (3-mercaptopropylthio) ethane, 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, and 1, 4-bis (mercaptoethyl) benzene.

10. The polymerizable composition for optical materials according to claim 2, which contains an active hydrogen compound having 2 or more active hydrogen groups in the molecule other than (c).

11. An optical material obtained by curing the polymerizable composition for optical materials according to any one of claims 1 to 10.

12. A method for producing an optical material, which comprises curing the polymerizable composition for an optical material according to any one of claims 1 to 10.

13. A method for producing an optical material, according to claim 12, wherein the optical material is molded from the polymerizable composition by cast polymerization.