JP2000053761A - Optical resin composition, optical resin and plasic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical resin composition having a high refractive index, a high Abbe number, heat resistance, optical distortion, brittleness, strength, etc., in a good balance by adding an epoxy compound having a specific trithiocarbonate skeleton, etc., as a main component. SOLUTION: This optical resin composition contains an epoxy or/or thioepoxy compound having a trithiocarbonate skeleton of formula I [X1-X4 are each S or O; (m) and (n) are each 0-6] as a main component. The compound of formula I is obtained by reacting a thiocarbonate, etc., with a halogenated alkyl alcohol, etc., to obtain a dihydroxy compound of formula II, reacting the obtained compound with a dimercapto compound and an epihalohydrin preferably in an amount of 2-30 times that of the compound of formula II in the presence of an alkali preferably at -10 to 60 deg.C for <=10 hr to obtain the structure of formula III, and subsequently reacting the obtained epoxy compound with a thia compound-producing agent such as a thiocyanate salt, preferably the thiocyanate salt or thiourea, preferably at 20-70 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical resin composition containing an epoxy or thioepoxy compound having a trithiocarbonate skeleton as a main component, an optical resin obtained therefrom, and a plastic lens comprising the optical resin. Things.

[0002]

2. Description of the Related Art Plastic lens materials are lightweight, tough, and easy to dye. Therefore, plastic lens materials have been widely used in various optical materials, especially for spectacle lenses in recent years.

[0003] The diethylene glycol bis (allyl carbonate) resin lens in the prior art is superior in safety, workability, fashionability and the like as compared with a glass lens, and furthermore has anti-reflection technology, hard coating technology, and hard coating + reflection. It has spread rapidly due to the development of prevention technology. However, since the refractive index of diethylene glycol bis (allyl carbonate) resin is 1.50, which is lower than that of a glass lens, the outer peripheral portion of a near-sighted spectacle lens and the central portion of a far-sighted lens are thicker than a glass lens. There is a disadvantage that.

For this reason, in the field of plastic lenses for spectacles, technical development for reducing the thickness by using a high-refractive-index plastic lens material has been actively carried out. The performance required for optical materials, particularly spectacle lenses, is a high refractive index and a high Abbe number as optical performance in addition to low specific gravity, and high heat resistance and high strength as physical performance. A high-refractive-index lens reduces chromatic aberration of the lens, and high heat resistance and high strength are important from the viewpoint of safety and the like, as well as facilitating secondary processing.

[0005] Developments with a refractive index of 1.6 or higher have been made. Proposals have already been made of polymers of methacrylate compounds containing chloro and bromine atoms, and thermosetting optical materials having a urethane structure obtained by the reaction of hydroxy compounds containing bromo atoms with isocyanate compounds (JP-A-58-164615, etc.). Have been.
However, when a compound containing a chloro or bromo atom was used, the specific gravity was large, and in this case also, the lightness was impaired. Therefore, a thermosetting optical material having a thiourethane structure obtained by reacting a polythiol compound with a polyisocyanate compound is disclosed in Japanese Patent Publication No. 4-584.
89 and JP-A-5-148340. That is, JP-A-5-148340 discloses a branched polythiol compound having four sulfur atoms in one molecule, and JP-A-2-27059 discloses a branched polythiol compound having five sulfur atoms in one molecule. However, JP-A-6-192250 proposes a polythiol compound having a dithiane ring structure in the molecule. Although the refractive index and Abbe number have been improved to some extent by these optical materials having a thiourethane structure, they have been still insufficient. Further, a technique of polymerizing an epoxy group or a thioepoxy group with a compound having two or more functionalities to obtain a lens is disclosed in
-96815 and JP-A-3-83320. The refractive index of the optical material obtained by curing and polymerizing these conventional epoxy and thioepoxy compounds was not sufficient, and the Abbe number was low, and the refractive index and Abbe number were unsatisfactory. In any case, the problems of thinner thickness and lighter weight have been solved to some extent by these conventional sulfur-containing compounds and the like, but it goes without saying that a higher refractive index is desirable. On the other hand, another important performance required for the optical material is low chromatic aberration. Since the chromatic aberration becomes better as the Abbe number becomes higher, a material having a higher Abbe number is desired. However, the Abbe number generally shows a tendency to decrease with an increase in the refractive index, and in the case of plastic materials made from diethylene glycol bisallyl carbonate and conventional compounds represented by polythiol compounds and polyisocyanate compounds, epoxy and thioepoxy compounds, , Refractive index 1.5 to 1.5
In the case of 5, the Abbe number is about 50 to 55, and the refractive index is 1.60.
In the case of the above, the Abbe number is limited to about 30 when the refractive index is 1.66, and the Abbe number is limited to about 30 in the case of the refractive index of 1.66. Further, in the case of the prior art, particularly in the case of a thiourethane material or the like, the molecular weight of the raw material sulfur compound becomes large in order to exhibit a high refractive index, so that the crosslink density is reduced, which causes problems such as reduced heat resistance. In order to solve these problems, JP-A-9-71580 and JP-A-9-110797 have been proposed.
In the publication, a branched alkyl sulfide type episulfide compound and a linear alkyl sulfide type episulfide compound are respectively proposed. However, this branched, straight-chain alkyl sulfide type episulfide compound has an improved refractive index and Abbe number, but has insufficient heat resistance, easily breaks brittlely, and is damaged during framing processing and use in spectacle lenses. Has disadvantages. Japanese Patent Application Laid-Open No. 9-255781 discloses an episulfide compound having a cyclic skeleton. However, when an aromatic is used as the cyclic skeleton, optical distortion occurs. In addition, the alicyclic group described in the above publication still has insufficient brittle strength.

[0006]

An object of the present invention is to obtain a high refractive index, a high Abbe number, heat resistance, optical distortion, brittle strength, and the like in a well-balanced manner.

[0007]

Means for Solving the Problems The present inventors have made intensive studies in order to achieve the above object, and as a result, have found that an epoxy or thioepoxy compound having a trithiocarbonate skeleton represented by the general formula (1) is mainly used. It has been found that the object of the present invention can be achieved by using it as a component, and the present invention has been completed.

[0008]

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(X ₁ , X ₂ , X ₃ and X ₄ are S or O;
(m and n represent 0 to 6) Hereinafter, the present invention will be described in more detail.

X ₁ , X ₂ , X ₃ , and X ₄ represent S or O. When the refractive index is required to be 1.70 or more, the number of S is 50% or more of the sum of S and O. It is. When m and n exceed 6, the heat resistance of the optical material obtained by polymerization and curing decreases, and the sulfur content decreases, so that a high refractive index cannot be achieved.

The most characteristic feature of the present invention is that the basic skeleton has a trithiocarbonate skeleton.
The sulfur atom makes it possible to increase the refractive index and the carbonate skeleton to maintain the brittle strength.

The epoxy and / or thioepoxy compound having a trithiocarbonate skeleton according to the present invention starts from thiocarbonic acid, sodium thiocarbonate, potassium thiocarbonate or calcium thiocarbonate, and comprises a halogenated alkyl alcohol, a halogenated alkyl thiol, a halogenated alkyl thiol, The structure (2) can be obtained by a reaction with a glycol or a halogenated thioglycol.

[0013]

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(X ₃ and X ₄ are S or O, m and n are 0
Then, the dihydroxy compound of formula (2), the dimercapto compound and epihalohydrin are reacted in the presence of an alkali to obtain a structure of formula (3).

[0015]

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(X ₃ and X ₄ are S or O, m and n are 0
The epoxy compound is used as a thiocyanate such as thiocyanate, thiourea, triphenylphosphine sulfide, or 3-methylbenzothiazol-2-thione, and preferably a thiocyanate or thiourea. And produced. Equation (3)
In the production of the epoxy compound represented by the formula, epichlorohydrin is preferred as the epihalohydrin compound.

The epihalohydrin compound is used stoichiometrically twice as much as the dihydroxy compound of formula (2) and the dimercapto compound. However, if importance is attached to the purity of the product, the reaction rate, the economic efficiency, etc. Less or more may be used. Preferably, the reaction is carried out using 2 to 30 times mol. The reaction may be carried out without solvent or in a solvent. When a solvent is used, epihalohydrin, a dihydroxy compound of formula (3), a dimercapto compound, a metal salt of a dihydroxy compound, or a metal salt of a dimercapto compound may be used. It is desirable to use a soluble one. Specific examples include water, alcohols, ethers, aromatic hydrocarbons, halogenated hydrocarbons, and the like. The reaction proceeds easily in the presence of more than stoichiometric base. As the base, pyridine, triethylamine,
Tertiary amines such as diazabicycloundecene and the like, and alkali or alkaline earth metal hydroxides are preferred. Preferred are alkali or alkali metal hydroxides, and more preferred is sodium hydroxide. , Potassium hydroxide and the like. Reaction temperature is usually -10 to 100 ° C
, Preferably at -10 to 60 ° C. The reaction time may be any time as long as the reaction is completed under the above-mentioned various conditions, but is usually usually 10 hours or less. When a thiocyanate is used as a thiocyanate in a method for producing an episulfide compound of the formula (1) from an epoxy compound represented by the formula (3), preferred thiocyanates are amine, alkali or alkaline earth metal salts. And more preferred are potassium thiocyanate and sodium thiocyanate. The thiocyanate is used stoichiometrically in an amount of 1 or 2 times the mole of the epoxy compound of the formula (3). Larger amounts can be used. Preferably, the reaction is carried out using 1 to 10 times mol. The reaction may be carried out without a solvent or in a solvent. When a solvent is used, it is preferable to use one in which a thiocyanate or a thiourea or an epoxy compound of the formula (3) is soluble. . Specific examples include alcohols such as water, methanol, ethanol, and isopropanol; ethers such as diethyl ether, tetrahydrofuran, and dioxane; hydroxy ethers such as methyl cellosolve; and aromatic hydrocarbons such as benzene, toluene, and xylene. And halogenated hydrocarbons such as dichloroethane, chloroform, chlorobenzene and the like, and the combined use thereof, for example, a combination of ethers, hydroxyethers, halogenated hydrocarbons, aromatic hydrocarbons and alcohols It is effective. Addition of an acid, an acid anhydride and the like as a polymerization inhibitor to the reaction solution is an effective means from the viewpoint of improving the reaction results. Specific examples of acids and acid anhydrides include nitric acid, hydrochloric acid, sulfuric acid, fuming sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid , Maleic acid, benzoic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, acetic anhydride, propionic anhydride, butyric anhydride,
Examples include succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, silica gel, silica alumina, aluminum chloride and the like, and some of them can be used in combination. The amount of addition is usually 0.00
1 to 10 wt%. The reaction is usually carried out at a temperature of 0 to 100 ° C, preferably 20 to 70 ° C. The reaction product can be washed with an acidic aqueous solution to improve the stability of the obtained compound. Specific examples of the acid used for the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, and maleic acid. These may be used alone or in combination of two or more. Aqueous solutions of these acids usually have an effect at pH 6 or lower, but more effectively at pH 3 or lower.

As another production method, an unsaturated compound of the formula (4) corresponding to an epoxy compound of the formula (1) or a thioepoxy compound is produced by oxidation with an organic peracid, an alkyl peroxide, hydrogen peroxide or the like, There is also a method of converting this into the epoxy compound or thioepoxy compound of the formula (1) by the above-mentioned method.

[0019]

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(X ₃ and X ₄ are S or O, m and n are 0
To 6) The epoxy or / and thioepoxy compound having a trithiocarbonate skeleton of the present invention can be heated and polymerized in the presence or absence of a curing catalyst to produce a resin. A preferred method is a method using a curing catalyst. As the curing catalyst, amines, phosphines, sulfonium salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid and the like are used. Specific examples include (1) ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, lauryl. Amine, mystyrilamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, aminohexanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine , 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, amino Methylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine,
Primary amines such as naphthylamine and furfurylamine; ethylenediamine, 1,2-diaminopropane, 1,3-
Diaminopropane, 1,2-diaminobutane, 1,3-
Diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-
Diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopropyl) ether, 1,2-
Bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, aminoethylethanolamine, 1,2-, 1-
3 or 1,4-bisaminocyclohexane, 1,3
-Or 1,4-bisaminomethylcyclohexane,
1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4 -Aminomethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, methanediamine, 1,4-bisaminopropylpiperazine, o-, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, 2,4-toluenediamine, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylenediamine, 4- Methoxy-6-methyl-m-phenylene Amines, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, benzidine, 4,4'-bis (0-toluidine), dianidin, 4,4'-diaminodiphenylmethane, 2, 2- (4,4'-diaminodiphenyl) propane, 4,4'-diaminodiphenyl ether, 4,4 '
-Thiodiamine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminoditolylsulfone, methylenebis (0-chloroaniline), 3,9-bis (3-aminopropyl) 2,4,8,10-tetra Kisaspiro [5,
5] undecane, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, 1,4-bis (aminoethylpiperazine), 1, 4
Primary polyamines such as -bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) sulfone; diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, isobutyl Amine, di-n-pentylamine, di-
3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl) amine, methylhexylamine, diallylamine, pyrrolidine, piperidine,
-, 6-, 3,5-lupedin, diphenylamine, N-
Secondary amines such as methylaniline, N-ethylaniline, dibenzylamine, dinaphthylamine, pyrrole, indoline, indole, and morpholine; N, N′-dimethylethyleneamine, N, N′-dimethyl-1, 2-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane, N, N '-Dimethyl-1,4-diaminobutane, N, N'-dimethyl-1,5-diaminopentane, N, N'-dimethyl-1,6-diaminohexane,
N, N′-dimethyl-1,7-diaminoheptane,
N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1,3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N'-diethyl-
1,3-diaminobutane, N, N′-diethyl-1,
3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N′-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,
5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2
-Di- (4-piperidyl) ethane, 1,3-di- (4-
Secondary polyamines such as piperidyl) propane, 1,4-di- (4-piperidyl) butane, and tetramethylguanidine; trimethylamine, triethylamine, tri-n-
Propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n-butylamine, tri-i
so-propylamine, tri-sec-butylamine,
Tri-pentylamine, tri-n-hexylamine, tri-dodecylamine, tri-laurylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N -Methyldicyclohexylamine, triethanolamine, tribenzylamine,
N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N-dimethylaminomethyl)
Phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2- Tertiary amines such as dioxabornane; tetramethylethylenediamine, piperazine, N, N'-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ', N'-tetramethyl-1,3- Butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-
Tris (N, N-dimethylaminomethyl) phenol,
Tertiary polyamines such as heptamethylisobiguanide; imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N-butylimidazole, 2-butyl Imidazole, N-undecylimidazole, 2-undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-
Benzylimidazole, 1-benzyl-2-methylimidazole, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2 -Undecyl imidazole, N- (2'-cyanoethyl) -2
Various imidazoles such as -phenylimidazole, 3,3-bis- (2-ethyl-4-methylimidazolyl) methane, and condensates of alkylimidazole and formaldehyde; 1,8-diazabicyclo (5,4,0) undecene-7 , 1,5-diazabicyclo (4,3,0) nonene-
Amidines such as 5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; amine compounds represented by the above.

(2) Quaternary ammonium salts of the amines of (1) with halogens, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acid, and the like.

(3) Complexes of the amines of (1) with borane and boron trifluoride.

(4) trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-cyclohexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, Tris (3-methylphenyl) phosphine, tris (diethylamino) phosphine, dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethylphenylphosphine,
Phosphines such as diphenylcyclohexylphosphine and chlorodiphenylphosphine (5) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid and half esters thereof (6) Boron trifluoride and boron trifluoride etherate Representative Lewis acids (7) Organic acids represented by carboxylic acids and their half esters (8) Silicic acid, tetrafluoroboric acid and the like.

Among these, preferred are those having less coloring of the cured product, such as primary monoamine, secondary monoamine, tertiary polyamine, imidazoles, amidines, quaternary ammonium salts, and phosphines. More preferred are secondary monoamines, tertiary monoamines, tertiary polyamines, imidazoles, amidines, quaternary ammonium salts, and phosphines having one or less groups capable of reacting with an episulfide group. These may be used alone or in combination of two or more. The above curing catalyst is usually used in an amount of 0.0001 mol to 1.0 mol, preferably 0.0001 mol to 0.5 mol, more preferably 0.0001 mol, per 1 mol of the epoxy or thioepoxy compound. To less than 0.1 mole, most preferably 0.0001 to 0.05 mole. If the amount of the curing catalyst is larger than the above range, the refractive index and heat resistance of the cured product are reduced, and the cured product is colored.
If it is less than this, the composition will not be cured sufficiently and the heat resistance will be insufficient.

The epoxy or / and thioepoxy compound having a trithiocarbonate skeleton according to the present invention may be a compound having at least one functional group capable of reacting with an epoxy group or / and a thioepoxy group, or a compound having at least one of these functional groups. An optical material can also be produced by curing polymerization with a compound having at least one functional group capable of homopolymerization. Examples of the compound having a functional group capable of reacting with the epoxy group or the thioepoxy group include an epoxy compound, a known thioepoxy compound, a polycarboxylic acid, a polycarboxylic anhydride, a mercaptocarboxylic acid, a polymercaptan, and a mercaptoalcohol. , Mercaptophenol, polyphenol, amines, amides and the like. On the other hand, compounds having at least one functional group capable of reacting with an epoxy group or / and an episulfide group and at least one other functional group capable of being homopolymerized include vinyl,
Aromatic vinyl, methacrylic, acrylic, epoxy compound having an unsaturated group such as allyl, thioepoxy compound, carboxylic acid, carboxylic anhydride, mercaptocarboxylic acid,
Examples include mercaptans, phenols, amines, amides and the like. Hereinafter, specific examples of the compound having two or more functional groups capable of reacting with an epoxy group and / or a thioepoxy group will be described.

Specific examples of epoxy compounds include hydroquinone, catechol, resorcin, bisphenol A,
Bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, a phenolic epoxy compound produced by condensation of a polyphenol compound such as a novolak resin and epihalohydrin; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- And 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated Alcoholic epoxy compounds produced by condensing epihalohydrin with polyhydric alcohol compounds such as sphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct; adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid , Phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, heptic acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenone tetracarboxylic acid Glycidyl ester epoxy compounds produced by condensation of polyhalocarboxylic acid compounds such as acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and epihalohydrin; ethylenediamine, 1,2-diamine Propane,
1,3-diaminopropane, 1,2-diaminobutane,
1,3-diaminobutane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis- (3-aminopropyl) ether, 1,2
-Bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,
4-bisaminopropylcyclohexane, hydrogenated 4,4 '
-Diaminodiphenylmethane, isophoronediamine,
1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-
Tolylenediamine, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine,
Primary diamines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2- (4,4'-diaminodiphenyl) propane, N, N'-
Dimethylethylenediamine, N, N'-dimethyl-1,
2-diaminopropane, N, N'-dimethyl-1,3-
Diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane,
N, N'-dimethyl-1,5-diaminopentane, N,
N'-dimethyl-1,6-diaminohexane, N, N '
-Dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2
-Diaminopropane, N, N'-diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane, N, N ' -Diethyl-1,4-diaminobutane,
N, N'-diethyl-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,
6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane, 1,2-di- (4-piperidyl) -ethane, 1,3-di- (4-piperidyl)
An amine-based epoxy compound produced by condensation of a secondary diamine such as propane, 1,4-di- (4-piperidyl) -butane and epihalohydrin; 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate; Vinylcyclohexanedioxide, 2-
Alicyclic epoxy compounds such as (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) adipate; cyclopentadiene epoxide, epoxidation Epoxy compounds produced by epoxidation of unsaturated compounds such as soybean oil, epoxidized polybutadiene and vinylcyclohexene epoxide; urethane epoxy compounds produced from the above-mentioned polyhydric alcohols, phenol compounds and diisocyanates and glycidol, etc. Can be done.

Specific examples of known thioepoxy compounds include thioepoxy compounds obtained by thioepoxidizing some or all of the epoxy groups of the above epoxy compounds.

Polycarboxylic acids, polycarboxylic anhydrides,
Specific examples of polyphenols, amines, and the like include those described above as the raw materials of the partner to be reacted with epihalohydrin described in the above epoxy compound.

Specific examples of the polymercaptan include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, and di (2-mercaptoethyl). ) Sulfide, linear dimercaptan compounds such as 1,2- [bis (2-mercaptoethylthio)] ethane; 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-di Mercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis [(2-mercaptoethylthio)]-
Branched aliphatic polymercaptan compounds such as 3-mercaptopropane, 1,1,1-tris (mercaptomethyl) propane and tetrakismercaptomethylmethane; ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, 1,4-butane Diol dithioglycolate, 1,4-butanediol dithiopropionate, trimethylolpropane tris (β-thioglycolate), trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (β-thioglycolate) ), Pentaerythritol tetrakis, ester-containing aliphatic polymercaptan compounds such as (β-thiopropionate); 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane,
1,4-dimercaptomethylcyclohexane, 1,3-
Dimercaptomethylcyclohexane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptoethyl-1,4-dithiane, 2,5-dimercaptomethyl-1-thiane, 2,5-di And aliphatic cyclic dimercaptan compounds such as mercaptoethyl-1-thiane.

The following are representative specific examples of compounds having at least one functional group capable of reacting with an epoxy group and / or a thioepoxy group and at least one other functional group capable of homopolymerization. As the epoxy compound having an unsaturated group,
Examples thereof include vinyl phenyl glycidyl ether, vinyl benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. As the thioepoxy compound having an unsaturated group, a compound obtained by thioepoxidizing the epoxy group of the epoxy compound having an unsaturated group described above, for example, vinyl phenyl thioglycidyl ether, vinyl benzyl thioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, ant And luthioglycidyl ether.

Examples of the carboxylic acid compound having an unsaturated group include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and fumaric acid. Examples of the amide having an unsaturated group include amides of the above α, β-unsaturated carboxylic acids.

Further, a functional group capable of reacting with an epoxy group and / or a thioepoxy group and capable of being homopolymerized has one or more functional groups.
Preferred examples of the compound having one compound include a compound having one epoxy group or one thioepoxy group. More specifically, monoepoxy compounds such as ethylene oxide and propylene oxide, glycidyl esters of monocarboxylic acids such as acetic acid, propionic acid and benzoic acid, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether and ethylene sulfide Thioglycidyl esters having a structure derived from the above-mentioned monocarboxylic acid and thioglycidol (1,2-epithio-3-hydroxypropane), methylthioglycidyl ether (1,2-epi) Thiopropyloxymethane), ethylthioglycidylether, propylthioglycidylether, butylthioglycidylether and the like. Among these, more preferred are compounds having one thioepoxy group.

Compounds having at least two functional groups capable of reacting with the epoxy group and / or thioepoxy group of the present invention, compounds having at least one of these functional groups and at least one other functional group capable of homopolymerization, The compound having one functional group capable of reacting with a thioepoxy group and being homopolymerizable can be produced by curing and polymerization in the presence of a curing polymerization catalyst. As the curing catalyst, the above-mentioned amines, phosphines, acids and the like are used. As specific examples, those described above are also used here.

Further, when a compound having an unsaturated group is used, it is preferable to use a radical polymerization initiator as a polymerization accelerator. The radical polymerization initiator is not particularly limited as long as it generates a radical by heating or ultraviolet light or an electron beam. For example, cumyl peroxy neodecanoate, diisopropyl peroxy dicarbonate, diallyl peroxy dicarbonate, di-n- Propyl peroxy dicarbonate, dimyristyl peroxy dicarbonate, cumyl peroxy neohexanoate, ter-hexyl peroxy neodecanoate,
ter-butyl peroxy neodecanoate, ter-
Hexylperoxyneohexanoate, ter-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide,
Peroxides such as dicumyl peroxide and di-tert-butyl peroxide; hydroperoxides such as cumene hydroperoxide and ter-butyl hydroperoxide; 2,2′-azobis (4-methoxy-2,4 -Dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2
2′-azobis (2,4-dimethylvaleronitrile),
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-
[(1-cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile 2,2′-azobis (2-methylpropane), 2,2′-azobis Known thermal polymerization catalysts such as azo compounds such as (2,4,4-trimethylpentane),
Known photopolymerization catalysts such as benzophenone and benzoin benzoin methyl ether are exemplified. Of these, preferred are peroxides, hydroperoxides and azo compounds, more preferred are peroxides and azo compounds, and most preferred are 2,2′-azobis ( 4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'- Azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-
1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2′-azobis (2-methylpropane) 2
2'-azobis, (2,4,4-trimethylpentane)
And the like. These can all be mixed and used. The amount of the radical polymerization initiator varies depending on the components of the composition and the curing method, and thus cannot be unconditionally determined, but is usually 0.01 wt% based on the total amount of the composition.
% To 5.0 wt%, preferably 0.1 wt% to 2.0 wt%
% Range.

In addition, when an epoxy or / and thioepoxy compound having a trithiocarbonate skeleton of the present invention is polymerized and cured to obtain an optical material, it is obtained by adding known additives such as antioxidants and ultraviolet absorbers. Of course, it is possible to further improve the practicality of the material. It is also possible to use or add a known external and / or internal release agent to improve the releasability of the obtained cured material from the mold. The internal release agent referred to herein is a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, a phosphate, an acidic phosphate, an alkali metal salt of an acidic phosphate, or a metal of a higher fatty acid. Examples include salts, higher fatty acid esters, paraffin, wax, higher fatty acid amides, higher fatty acid alcohols, polysiloxanes, and aliphatic amine ethylene oxide adducts.

When an epoxy or / thioepoxy compound having a trithiocarbonate skeleton of the present invention is polymerized and cured to obtain an optical material, an epoxy or / and thioepoxy compound as a raw material and, if desired, the aforementioned curing catalyst When used in combination with a thioepoxy group having an unsaturated group, for example, glycidyl methacrylate, thioglycidyl methacrylate (episulfided glycidyl methacrylate epoxy group) or the like, a radical polymerization initiator, a radical polymerizable monomer, Further, after mixing additives such as a release agent, an antioxidant, and an ultraviolet absorber, the mixture is polymerized and cured as described below to obtain an optical material such as a lens. That is, after the raw materials after mixing are poured into a glass or metal mold and the polymerization and curing reaction is advanced by heating,
It is manufactured out of the mold. The curing time is 0.1 to 100 hours, usually 1 to 48 hours, and the curing temperature is -10 to 16
0 ° C, usually -10 to 140 ° C. After the curing is completed, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for preventing distortion of the optical material of the present invention. Further, if necessary, a surface treatment such as hard coating, antireflection, imparting anti-fogging property can be performed. The method for producing the cured resin optical material of the present invention is described below in more detail. As described above, the main raw material and the auxiliary raw material are mixed and then injected and cured in a mold. The main raw material is an epoxy or / and thioepoxy compound having a trithiocarbonate skeleton and an epoxy group or / Or a compound having two or more functional groups capable of reacting with an episulfide group, or a compound having one or more functional groups capable of reacting with one or more other homopolymerizable functional groups and capable of reacting and homopolymerizing with an episulfide group The compound having one functional group, and the curing catalyst, the radical polymerization initiator, the releasing agent, the stabilizer, and the like, which are used as desired, can be mixed in the same container simultaneously with stirring. Alternatively, each raw material may be added and mixed stepwise, or several components may be separately mixed and then remixed in the same container. Upon mixing, the set temperature, the time required for the mixing, and the like may be basically set as long as the components are sufficiently mixed, but an excessive temperature and time may cause an undesired reaction between the raw materials and additives, Furthermore, it is not appropriate because the viscosity increases and the casting operation becomes difficult. The mixing temperature should be in the range of about −10 ° C. to 100 ° C., and the preferred temperature range is −10 ° C. to 50 ° C.
° C, more preferably -5 ° C to 30 ° C. The mixing time is 1 minute to 5 hours, preferably 5 minutes to 2 hours, more preferably 5 minutes to 30 minutes, and most preferably about 5 minutes to 15 minutes. Performing a degassing operation under reduced pressure before, during or after the mixing of the raw materials and additives is a preferred method from the viewpoint of preventing the formation of bubbles during the subsequent casting and curing. The degree of pressure reduction at this time is 0.1 mm
Hg to about 700 mmHg, preferably 1
It is 0 mmHg to 300 mmHg. Further, it is preferable to remove impurities by filtering them with a microfilter or the like at the time of injection into a mold from the viewpoint of improving the quality of the optical material of the present invention.

[0037]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The performance of the obtained polymer was measured by the following measurement method, and the results are shown in Table 2.

Refractive index, Abbe number (e-line): Measured at 20 ° C. using an Abbe refractometer. Specific gravity: Measured at 20 ° C. using an electronic hydrometer and corrected by a conventional method. Heat resistance: those having a Vicat softening point of 120 ° C. or higher
A sample having a temperature of less than 20 ° C and a temperature of 80 ° C or more was evaluated as Δ, and a sample less than 80 ° C was evaluated as ×. Bending strength: In a three-point bending test measurement using an autograph, those having a strain of 0.2 or more were evaluated as ○, and less than 0.2 as 0.1.
The above was evaluated as Δ, and the one less than 0.1 was evaluated as ×. Falling ball strength: A lens having a center thickness of 1.0 mm was evaluated according to the FDA standard. The maximum weight (g) of the steel ball that did not break the lens when the steel ball was dropped from a height of 127 cm was determined.

Example 1 In the above formula (1), 100 parts by weight of bis (β-epithiopropyl) trithiocarbonate in which X ₁ and X ₂ are S and m and n are 0 are used as catalysts with N, N-diethanolamine as a catalyst. In an amount of 2,6-di-ter as an antioxidant.
After mixing 0.1 part by weight of -butyl-4-methylphenol and 0.1 part by weight of 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole as an ultraviolet absorber, the mixture was stirred at room temperature and mixed with a homogeneous liquid. And Further, deaeration was sufficiently performed under a reduced pressure of 10 mmHg. Then, the temperature was raised in a glass mold at 30 ° C. for 10 hours, from 30 ° C. to 100 ° C. over 10 hours, and further polymerized and cured at 100 ° C. for 2 hours. After polymerization, release from glass mold at room temperature
Annealing was performed at 0 ° C. for 1 hour. The resulting material was colorless and transparent, had a good surface condition, and hardly any striae or surface deformation. Table 2 shows the evaluation results of the physical properties.

Examples 2 to ₄ The same procedures as in Example 1 were carried out except that the atoms of X ₁ , X ₂ , X ₃ and X ₄ and m and n were changed to Table 1, and the evaluation results of the physical properties were shown in Table 1. 2 is shown.

[0041]

[Table 1]

Comparative Example 1 The procedure of Example 1 was repeated except that the main raw material was changed to bis- (β-epithiopropyl) sulfide.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the main raw material was changed to 1,4-bis- (β-epithiopropylthioethyl) cyclohexane, and the evaluation results of the physical properties are shown in Table 2. .

Comparative Example 3 The procedure of Example 1 was repeated except that the main raw material was changed to 2,5-bis (β-epithiopropylthioethyl) -1,4-dithiane. 2 is shown.

Comparative Example 4 The main raw material was 1,2-bis (β-epithiopropyloxy)
Except for changing to ethane, all the procedures were performed in the same manner as in Example 1, and the evaluation results of the physical properties are shown in Table 2.

[0046]

[Table 2]

[0047]

The cured resin optical material obtained by polymerizing and curing the epoxy or / and thioepoxy compound having a trithiocarbonate skeleton according to the present invention has a sufficiently high refraction which has been difficult as long as the compound of the prior art is used as a raw material. And a resin optical material having a good balance between the refractive index and the Abbe number. That is, the novel compound of the present invention has made remarkable progress in reducing the weight and thickness of the resin optical material and reducing chromatic aberration. This has made it possible to produce a material that is preferable for use in lenses such as spectacles.
Further, the novel resin cured material of the present invention has excellent heat resistance and strength and can be used for various applications.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shuji Naito 3-3-5 Yamato, Suwa-shi, Nagano Seiko Epson Corporation F-term (reference) 4J005 AA09 AA11 4J030 BA03 BA04 BA20 BB03 BB06 BB07 BB13 BB21 BB46 BB52 BB62 BB67 BC05 BC06 BC08 BC09 BC13 BC14 BC17 BC18 BC32 BC33 BC34 BC36 BC37 BC38 BG25

Claims (3)

[Claims] 1. An optical resin composition comprising an epoxy or thioepoxy compound having a trithiocarbonate skeleton represented by the general formula (1) as a main component. Embedded image (X ₁ , X ₂ , X ₃ , and X ₄ are S or O, and m and n are 0 to 0.
6) 2. An optical resin obtained by polymerizing and curing the optical resin composition according to claim 1. 3. A plastic lens comprising the optical resin according to claim 2.