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    • 专利摘要:
    PURPOSE: To provide a new episulfide compound which is useful as the raw material of optical materials having a high refractive index and Abbe's number, and also provide a method for producing the compound efficiently. CONSTITUTION: The episulfide compound represented by general formula (1) (wherein n is an integer of 0 to 2) and the production method thereof in which the compound represented by general formula (1) is produced by the reaction of an episulfide compound having a mercapto group with 2,4,6-trimethylene-1,3,5- trithiane are provided.
    公开号:KR20030043661A
    申请号:KR1020020071104
    申请日:2002-11-15
    公开日:2003-06-02
    发明作者:오쿠보쓰요시；타카마쓰켄
    申请人:호야 가부시키가이샤；
    IPC主号:
    专利说明:

    Episulfide compound, preparation method thereof, and optical product comprising the same {EPISULFIDE COMPOUND, METHOD FOR PRODUCING THE SAME AND OPTICAL PRODUCT COMPRISING THE SAME}
    [1] The present invention relates to a novel episulfide compound, a method for producing the same, and an optical product comprising the same. More specifically, the present invention relates to a novel episulfide compound capable of providing an optical material having a high refractive index and Abbe number at the same time, and excellent in heat resistance, transparency, and the like, a method for efficiently producing the same, and an optical product including the same. .
    [2] Plastics have been used in various optical applications such as lenses in recent years because they are lighter than glass and are less likely to be broken and dyed. As the optical plastic material, poly (diethylene glycol bisallylcarbonate) (CR-39) and poly (methyl methacrylate) are generally used. However, these plastics have a refractive index of 1.50 or less. Thus, for example, when these are used for the lens material, the stronger the power, the thicker the lens, and the superiority of the plastic, which is advantageous in light weight, is impaired. In particular, a strong concave lens is not preferable because the lens periphery becomes thick and birefringence and chromatic aberration occur. Moreover, thick lenses tend to degrade aesthetics in eyeglass applications. In order to obtain a thin lens, it is effective to increase the refractive index of the material. Generally, glass and plastics have an Abbe number that decreases with increasing refractive index, and as a result, their chromatic aberration increases. Therefore, a plastic material having high refractive index and Abbe's number is desired.
    [3] As a plastic material having such a performance, for example, (1) polyurethane obtained by addition polymerization of a polyol having a bromine and a polyisocyanate (JP-A-164615 / 1983), (2) polythiol and polyisocyanate Polythiourethane (Japanese Unexamined Patent Publication No. 58489/1992, Japanese Patent Publication No. 148340/1993) obtained by addition polymerization of the above has been proposed. Particularly, as a polythiol as a raw material of the polythiourethane of (2), a branched polyol (Japanese Patent Publication No. 270859/1990, Patent Publication No. 148340/1993) or a sulfur atom having a high content of sulfur atoms is used. A polythiol (Japanese Patent Publication No. 5323/1994 and 118390/1995) which introduces a dithiane structure has been proposed to increase the height. Furthermore, (3) A polymer of alkyl sulfide having episulfide as a polymerization functional group has been proposed (Japanese Patent Laid-Open No. 71580/1997 and Japanese Patent Laid-Open No. 110979/1997).
    [4] However, although the refractive index is slightly improved, the polyurethane of (1) has the drawback that low Abbe number and low light resistance, high specific gravity, and light weight are impaired. In the polythiourethane of (2), the polythiourethane obtained by using polythiol having a high sulfur content rate as the polythiol as a raw material has, for example, a refractive index of 1.60 to 1.68, but an optical inorganic having an equivalent refractive index. Abbe number is lower than glass. Therefore, it has a subject that the Abbe number must be raised further. Moreover, the alkyl sulfide polymer of (3) has a high refractive index of 1.70 with an Abbe number of 36 as an example. Although the lens obtained using this polymer is remarkably thin and lightweight, the plastic material which raised the refractive index and Abbe's number further is desired.
    [5] SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and a novel compound capable of providing an optical material having both high refractive index and Abbe number, excellent heat resistance, transparency, and the like, a method of efficiently manufacturing the same, and an optical product comprising the same The purpose is to provide.
    [6] MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to achieve the said objective. As a result, compounds formed by the coupling of derivatives of episulfide to 1,3,5-trithiane (hereinafter abbreviated as trithiane) are novel and may be suitable for the above-mentioned purposes, and the compounds may be It was found that it is obtained efficiently by Based on this finding, the present invention has been completed.
    [7] That is, this invention is the novel episulfide compound represented by General formula (1):
    [8] (One)
    [9] Where EP is N represents an integer of 0 to 2)
    [10] And a method for producing a novel episulfide compound represented by the general formula (1) by reacting an episulfide compound having a mercapto group with 2,4,6-trimethylene-1,3,5-trithione. It is.
    [11] [Embodiment of the Invention]
    [12] The novel episulfide compound of the present invention is represented by the above general formula (1), and as can be seen from it, three identical episulfide-containing substituents are bonded to the tritian ring.
    [13] (One)
    [14] Where EP is N represents an integer of 0 to 2).
    [15] In the episulfide compound represented by the general formula (1), the tritian ring contains sulfur having a high atomic refractive index at a high rate, thereby greatly increasing the refractive index of the polymer obtained by using the novel episulfide compound of the present invention. Moreover, ethylene sulfide chains produced by ring-opening polymerization of episulfide compounds also contribute to an increase in the refractive index of the polymer. Usually, the Abbe's number of an amorphous material tends to decrease with the increase in its refractive index. One problem with polymers containing sulfur in high proportions is that the electron resonance of sulfur becomes remarkable, and a large drop in Abbe number is often observed. However, this is not the case with the novel episulfide compound of the present invention. Another factor of the increase in refractive index is the reduction of the molecular volume, and in the case of polymers, it is expressed by high crosslinking density or strong intermolecular force. The novel episulfide compound of the present invention has three polymerization functional groups, and the polymer thereof has a high refractive index due to the effect of electrons. In General formula (1), increase of n reduces sulfur content and crosslinking density, and provides the polymer which reduced the refractive index. Therefore, the range of n must be 0-2. Moreover, since the glass transition temperature (Tg) of the polymer obtained using the novel episulfide of the present invention decreases with the increase of n in the general formula (1), the range of n is 0 to obtain a polymer having good heat resistance. It must be -2.
    [16] As a novel episulfide compound represented by General formula (1) of this invention, specifically, 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5- tritiane, 2,4,6- Tris (ethiothiothiothio))-1,3,5-tritriane, 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-tritriane, etc. are mentioned.
    [17] These novel episulfide compounds of the present invention have an epitoxy group having a mercapto group in a 2,4,6-trimethylene-1,3,5-tritriane in which a methylene group is introduced at a 2,4,6 position. It can manufacture efficiently by the method of this invention which en-thiol-reacts a sulfide compound.
    [18] As an episulfide compound which has a mercapto group, 3-mercaptopropene sulfide, 4-mercaptobutene sulfide, 5-mercaptopentene sulfide, etc. are mentioned.
    [19] For example, 3-mercaptopropene sulfide can be prepared by the method described in F.P.Doyle et al., Journal of Chemical Society, 2660 pages, 1960.
    [20] The process for the preparation of the novel episulfide compounds of the present invention comprises the following steps:
    [21] (a) reacting chloroacetaldehyde with hydrogen sulfide to obtain 2,4,6-tris (chloromethyl) -1,3,5-trithiane,
    [22] (b) adding 2,4,6-trimethylene-1,3,5-trithiane by adding a base to the product obtained in step (a) and dehydrochlorination,
    [23] (c) 2,4,6-trimethylene-1,3,5-trithione in the presence of a radical generator with 3-mercaptopropene sulfide / 4-mercaptobutene sulfide / 5-mercaptopentene sulfide Reacting to obtain the episulfide compound described above.
    [24] Process for producing 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-trithiane (compound of n = 0 in general formula (1)) which is a novel episulfide compound of the present invention An example of general low is shown in Scheme 1 below. Dissolve 40% by weight aqueous solution of chloroacetaldehyde in 70% by weight sulfuric acid and pass hydrogen sulfide at -20 to 40 ° C for 2 to 100 hours to give 2,4,6-tris (chloromethyl) -1,3,5- Tritian is obtained. In addition to sulfuric acid, 60/40 (v / v) 95% by weight sulfuric acid-acetic acid and acetic acid saturated with hydrogen chloride, ether, 95% by weight ethanol and the like can be used. Potassium hydroxide is added to the methanol solution of the chlorine compound obtained, and dehydrochlorination is carried out at -10-40 degreeC for 0.5 to 10 hours, and 2,4,6- trimethylene- 1,3,5- trithiane is obtained. 2,4,6-tris (ethiothiomethylthiomethyl) -1,3 as the target product by heating and reacting 3-mercaptopropene sulfide with 6 to 100 hours at 0 to 100 ° C in the presence of a radical generator. , 5-trithiane is obtained.
    [25] As a radical generator, azobisbutylonitrile, benzoyl peroxide, bis (cyclohexyl carbonyl) peroxide, etc. are used.
    [26] Furthermore, in addition to 3-mercaptopropene sulfide as an episulfide compound having a mercapto group, 4-mercaptobutene sulfide and 5-mercaptopentene sulfide are used to give 2,4,6-tris (ethiothiothiothio)- 1,3,5-tritiane and 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-tritiane are obtained, respectively.
    [27] Scheme 1:
    [28]
    [29] In the formula, EP And Me is a methyl group.
    [30] Next, the optical material obtained using the novel episulfide compound of this invention is demonstrated. The novel episulfide compound represented by General formula (1) is an essential component, may be used 1 type, or may be used in combination of 2 or more type. Moreover, this novel episulfide compound may contain other episulfide compounds, epoxy compounds, and homopolymerizable vinyl monomers as optional components for appropriately improving physical properties and the like of the obtained polymer.
    [31] Examples of the above-mentioned optionally used episulfide compound include bis (β-epithiopropylthio) methane, 1,2-bis (β-ethiothiopropylthio) ethane, 1,3-bis (β-ethiothiopropylthio) Propane, 1,2-bis (β-ethiothiopropylthio) propane, 1- (β-ethiothiopropylthio) -2- (β-ethiothiopropylthiomethyl) propane, 1,4-bis (β-epi Thiopropylthio) butane, 1,3-bis (β-ethiothiopropylthio) butane, 1- (β-ethiothiopropylthio) -3- (β-ethiothiopropylthiomethyl) butane, 1,5-bis (β-epithiopropylthio) pentane, 1- (β-ethiothiopropylthio) -4- (β-ethiothiopropylthiomethyl) pentane, 1,6-bis (β-ethiothiopropylthio) hexane, 1 -(β-epithiopropylthio) -5- (β-ethiothiopropylthiomethyl) hexane, 1- (β-ethiothiopropylthio) -2-[(2-β-ethiothiopropylthioethyl) thio] Ethane, 1- (β-ethiothiopropylthio) -2-[[2- (2-β-ethiothiopropylthioethyl) thioe ] Such as chain-like organic compounds such as thio] ethane; Tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-ethiothiopropylthiomethyl) propane, 1,5-bis (β-ethiothiopropylthio) -2- (β- Epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-ethiothiopropylthio) -2,4-bis (β-ethiothiopropylthiomethyl) -3-thiapentane, 1- (β Epithiopropylthio) -2,2-bis (β-ethiothiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-ethiothiopropylthio) -4- (β-ethiothio Propylthiomethyl) -3-thiahexane, 1,8-bis (β-ethiothiopropylthio) -4- (β-ethiothiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis ( β-epithiopropylthio) -4,5-bis (β-ethiothiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-ethiothiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-ethiothiopropylthio) -2,4,5-tris (β-ethiothiopropylthiomethyl) -3 , 6-dithiaoctane, 1,8-bis (β -Epithiopropylthio) -2,5-bis (β-ethiothiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-ethiothiopropylthio) -5- (β-epi Thiopropylthiomethyl) -5-[(2-β-ethiothiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-ethiothiopropylthio) -5,6- Bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-ethiothiopropylthio) -4,8-bis (β-ethiothio Propylthiomethyl) -3,6,9-trithiaoundecan, 1,11-bis (β-ethiothiopropylthio) -5,7-bis (β-ethiothiopropylthiomethyl) -3,6,9 -Trithiaundane, 1,11-bis (β-ethiothiopropylthio) -5,7-[(2-β-ethiothiopropylthioethyl) thiomethyl] -3,6,9-trithiaoundecan And branched organic compounds such as 1,11-bis (β-ethiothiopropylthio) -4,7-bis (β-ethiothiopropylthiomethyl) -3,6,9-trithiaoundecan and the compounds At least one of the hydrogens of the episulfide group Compounds substituted with methyl groups; 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) cyclohexane, bis [4- (β-epi Thiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) cyclohexyl] propane, bis [4- (β-ethiothiopropylthio) cyclohexyl] sulfide, 2,5 Cyclic aliphatic organic compounds such as -bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-ethiothiopropylthioethylthiomethyl) -1,4-dithiane, and Compounds in which at least one of hydrogen of the episulfide group of these compounds is substituted with a methyl group; 1,3- and 1,4-bis (β-ethiothiopropylthio) benzene, 1,3- and 1,4-bis (β-ethiothiopropylthiomethyl) benzene, bis [4- (β-ethiothio Propylthio) phenyl] methane, 2,2-bis [4- (β-ethiothiopropylthio) phenyl] propane, bis [4- (β-ethiothiopropylthio) phenyl] sulfide, bis [4- (β- Epithiopropylthio) phenyl] aromatic organic compounds such as sulfone and 4,4'-bis (β-ethiothiopropylthio) biphenyl, compounds in which at least one of hydrogen of the episulfide group of these compounds is substituted with a methyl group, etc. Can be mentioned. You may use these individually or in combination of 2 or more types. The amount of these used is preferably 0.01 to 50 mol% based on the total amount of the novel episulfide compound represented by the general formula (1).
    [32] Examples of the epoxy compound suitably used include polyhydric phenol compounds such as hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A and novolak resin and epihalo. Phenolic epoxy compounds prepared by condensation of hydrin; 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 bisphenol A, bisphenol A-ethylene oxide addition Alcohol-based epoxy compounds produced by condensation of polyhydric alcohol compounds such as water and bisphenol A-propylene oxide adducts with epihalohydrin; Adipic acid, sebacic acid, decandicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, het acid , Polyhydric carboxylic acid compounds such as nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenone tetracarboxylic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and epihalo Glycidyl ester epoxy compounds prepared by condensation of hydrin; 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, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2'-dimethylpropane, 1,2-, 1,3- and 1,4-bisaminocyclohexane, 1,3- and 1,4- Bisaminomethylcyclohexane, 1,3- and 1,4-bisaminoethylcyclohexane, 1,3- and 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, iso Isophoronediamine, 1,4-bisaminopropylpiperazine, m- and p-phenylenediamine, 2,4- and 2,6-torylenediamine, m- and p-xylylenediamine, 1, 5- and 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2- (4,4'-diaminodiphenyl) propane Primary diamine, N, N'- Methylethylenediamine, 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- and 2,6-dimethylpipepe Razine, Homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane Amine epoxy compounds produced by condensation of secondary amines such as 1,4-di- (4-piperidyl) butane and epihalohydrin; 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexane dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3,4-epoxycyclohexanemeta Aliphatic ring epoxy compounds such as dioxane and bis (3,4-epoxycyclohexyl) adipate; Epoxy compounds produced by epoxidation of unsaturated compounds such as cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, and vinylcyclohexene epoxide; The urethane type epoxy compound manufactured from the above-mentioned polyhydric alcohol, a phenol compound, diisocyanate, glycidol, etc. are mentioned. You may use these individually or in combination of 2 or more types. The amount of these used is preferably 0.01 to 50 mol% with respect to the total amount of the novel episulfide compound represented by the general formula (1).
    [33] Examples of the homopolymerizable vinyl monomers suitably used include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate. , Diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1, 3-butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polypropylene glycol diacrylate Acrylate, polypropylene glycol dimethacrylate, 2,2-bis [4- (acryloxy Ethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [ 4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] Propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, bis (2,2,2-trimethylolethyl) ether hexaacrylate, bis (2 Compound which has ester structure of monohydric or polyhydric alcohol, acrylic acid, methacrylic acid, such as (2, 2- trimethylol ethyl) ether hexamethacrylate; Allyl compounds such as allyl sulfide, diallyl phthalate and diethylene glycol bisallylcarbonate; Vinyl compounds such as acrolein, acrylonitrile and vinyl sulfide; Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, methylvinylbenzene, ethylvinylbenzene, (alpha) -chlorostyrene, chlorovinylbenzene, vinylbenzyl chloride, paradivinylbenzene, and metadivinylbenzene, etc. are mentioned. You may use these individually or in combination of 2 or more types. The amount of these used is preferably 0.01 to 20 mol% relative to the total amount of the novel episulfide compound represented by the general formula (1).
    [34] In the polymerizable composition composed of the above-mentioned essential components and optional components, additives such as ultraviolet absorbers, antioxidants, anti-colorants, fluorescent dyes, etc., may be suitably used for the purpose of improving weather resistance within a range not impairing the object of the present invention. You may add it. In addition, a catalyst for improving the polymerization reaction may be appropriately used. For such catalysts, for example, amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodine salts, mineral acids, Lewis acids, organic acids and silicic acids And boron tetrafluoride are effective.
    [35] The optical material obtained using the novel episulfide compound of this invention can be manufactured, for example by the method shown below.
    [36] First, a uniform composition containing the polymerizable composition and various additives used as necessary is prepared, and the composition is combined with a mold made of glass or metal and a resinous gasket using a known mold polymerization method. It is injected into the mold and heated to cure. At this time, in order to easily take out the molded resin after molding, the mold may be released in advance, or the release agent may be mixed with the composition. Although polymerization temperature changes with the compound to be used, it is generally -20- + 150 degreeC, and polymerization time is about 0.5-72 hours. The polymer released after polymerization can be easily dyed in water or an organic solvent using a conventional disperse dye. At this time, in order to make dyeing easier, a carrier may be added to the dye dispersion and the dye bath may be heated. Although the optical material obtained in this way is not limited to this, It is used especially suitably as optical products, such as a plastic lens.
    [37] EXAMPLE
    [38] Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples. At this time, the physical properties of the novel episulfide compound obtained in the examples, and the physical properties of the polymer obtained from the application example and the comparative application heat were measured according to the method shown below.
    [39] Physical Properties of New Episulfide Compounds
    [40] The refractive index (n D ) and Abbe number (ν D ) were measured at 25 ° C. using an Abbe refractive index DR-M4 manufactured by Atago.
    [41] <Physical Properties of Polymer>
    [42] 1) Refractive index (n D ) and Abbe number (ν D ): Measured in the same manner as described above.
    [43] 2) Appearance: Observed by visual observation.
    [44] 3) Heat resistance: Measured by a TMA apparatus manufactured by Rigaku Corporation. TMA measurements were performed at a temperature of 10 ° C./min under a load of 98 mN (10 gf) using a pin with a diameter of 0.5 mm. The heat resistance of the sample was measured from the peak temperature of the chart.
    [45] 4) Transparency: It evaluated by the light transmittance at 550 nm using the ultraviolet spectrometer UV-330 by Hitachi.
    [46] Example 1:
    [47] Preparation example of 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-tritriane (T1) (n = 0 in general formula (1))
    [48] Hydrogen sulfide was bubbled into 70 wt% (v / v) sulfuric acid (100 mL) at 0 ° C. for 30 minutes, and 40 wt% chloroacetaldehyde (17.5 mL) was added dropwise at 7.5 ° C. in 7.5 hours. Again at this temperature, hydrogen sulfide was bubbled for 24 hours. The aqueous solution of the upper layer was decanted, the residue dichloromethane (150 mL) solubles were washed with water (25 mL × 3 times), dried over anhydrous magnesium sulfate, and filtered. The solvent was distilled off to obtain a pale yellow crude product (9.5 g). The crude product was washed with hexane (40 mL × 4 times), hexane / ether (6/1) (50 mL × 2 times), heated hexane (30 mL × 2 times) and vacuum dried to give 2,4,6-tris (chloromethyl) as white crystals. ) -1,3,5-tritriane (2.50 g) was obtained. To a methanol (25 mL) solution of this compound (0.3 g, 1.06 mmol) was added a methanol solution (5 mL) of potassium hydroxide (0.62 g, 11 mmol) at once with vigorous stirring at room temperature, followed by stirring at room temperature for 75 minutes. The dichloromethane (20 mL × 5 times) extract of the reaction mixture diluted with water (30 mL) was dried over anhydrous magnesium sulfate and filtered. The solvent was distilled off from the filtrate to obtain 2,4,6-trimethylene-1,3,5-trithione (150 mg) as a yellow oily residue. 3-mercaptopropene sulfide (1.14 g) and azobisbutylonitrile (0.2 mg) were added to a benzene (1 mL) solution of this compound (0.47 g), followed by stirring at 40 ° C for 2 hours in an argon atmosphere. The residue obtained by distilling off the solvent from the reaction mixture was recrystallized from chloroform / methanol to crystallize 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-tritriane (411 mg) (mp = 55∼). 56 ° C.).
    [49] The analysis results for the structure specification of this compound are shown below.
    [50] 1 H-NHR (solvent: CDC1 3 , internal standard: TMS): d2.27 (d, 3H), d2.59 (d, 3H), d2.76 (m, 3H), d3.19-3.29 ( m, 12H), d4.37-4.63 (t, t, m, 3H).
    [51] IR (KBr purification): 620, 660, 710, 740, 800, 860, 920, 1060, 1095, 1190, 1250, 1420, 1440 cm -1 .
    [52] Example 2:
    [53] Preparation example of 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-tritriane (T3) (n = 2 in general formula (1))
    [54] Example 1 except that 5-mercaptopentene sulfide (1.45 mg) and cyclohexylcarbonyl peroxide (0.3 mg) were used instead of 3-mercaptopropene sulfide and azobisbutylonitrile, respectively. 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-trithione (T3) (481 mg) was obtained by the same operation as 1. The refractive index (n D ) of this compound was 1.696 and the Abbe number (ν D ) was 30.1.
    [55] The analysis results for the structure specification of this compound are shown below.
    [56] 1 H-NMR (solvent: CDCl 3 , internal standard: TMS): d2.29 (d, 3H), d2.44-2.52 (m, 12H), d2.58 (d, 3H), d2.74 ( m, 3H), d3.12-3.16 (m, 6H), d3.25-3.31 (m, 6H), d4.39-4.66 (t, t, m, 3H).
    [57] IR (KBr purification method): 620, 658, 714, 738, 803, 861, 918, 1064, 1099, 1185, 1244, 1444, 1446 cm -1 .
    [58] Application Example 1:
    [59] Manufacture of Polymer Optical Materials
    [60] A mixture of T1 (0.05 mol) obtained in Example 1 and 2x10 -5 mol of tetra (n-butyl) phosphonium bromide (CT1), which is a polymerization catalyst, was uniformly stirred at 60 ° C, and injected into two lens molds. It was. In the mold, the mixture was heat-polymerized at 70 ° C. for 10 hours, then at 80 ° C. for 5 hours, and again at 100 ° C. for 3 hours to obtain a lens-shaped polymer. The physical properties of the obtained polymer are shown in Table 1. From Table 1, the polymer obtained in this application example 1 was colorless and transparent. Its refractive index (n D ) was very high at 1.796, Abbe's number (ν D ) was also high at 30 (meaning low dispersion of the polymer), and excellent in heat resistance (135 ° C.) and transparency (92%). . Therefore, the obtained polymer was preferable as an optical material.
    [61] Application Examples 2 to 5:
    [62] Manufacture of Polymer Optical Materials
    [63] The novel episulfide compound (component C1), the other episulfide compound, epoxy compound and / or vinyl monomer (component C2), and the polymerization catalyst of the present invention are used as shown in Table 1 to appropriately change the polymerization conditions. Except having performed the same operation as in Application Example 1, a lens-shaped polymer was obtained. The physical properties of these polymers are shown in Table 1. From Table 1, the polymers obtained in Examples 2 to 5 were also colorless and transparent. Its refractive index (n D ) is very high (1.709-1.778), Abbe number (ν D ) is also high (31-36) (meaning low dispersion of polymer), heat resistance (111-141 ° C.), transparency (89 -96%) was excellent.
    [64] Application Example 1:
    [65] Manufacture of Polymer Optical Materials
    [66] As shown in Table 1, pentaerythritol tetrakis mercaptopropionate (CE5) 0.1 mol, m- xylitol alkylene diimide SOCIETE Annette (CE6) and 0.2 moles of dibutyltin dichloride (CT5) mixture of 1.0X10 -4 mol The mixture was stirred uniformly and injected into two glass molds for lens molding. Inside the mold, the mixture was heat-polymerized at 50 ° C. for 10 hours, then at 60 ° C. for 5 hours, and again at 120 ° C. for 3 hours to obtain a lens-shaped polymer. The physical properties of the obtained polymer are shown in Table 1. From Table 1, the polymer of this Application Comparative Example 1 was colorless and had good transparency (92%), but had a low refractive index with n D / ν D of 1.59 / 36. Moreover, heat resistance also dropped to 86 degreeC.
    [67] Application Example 2, 3:
    [68] Manufacture of Polymer Optical Materials
    [69] Except having used the raw material composition shown in Table 1, operation similar to the application comparative example 1 was performed and the lens-shaped polymer was obtained. The physical properties of these polymers are shown in Table 1. From Table 1, the polymer of this Application Comparative Example 2 had a low n D / ν D of 1.67 / 28 and both its n D and ν D were low. Although heat resistance (94 degreeC) was comparatively favorable, coloring was seen and transparency (81%) was low. The polymer of this Application Comparative Example 3 had a relatively high n D of 36, excellent weather resistance, and colorlessness and good transparency (89%). However, the heat resistance (90 ° C.) fell, the n D was not as high as 1.70, and the polymer was weak.
    [70] TABLE 1
    [71] Application exampleC1 component (mol)C2 component (mol)Polymerization catalyst (mol)n D / v D ExteriorHeat resistance (℃)Transparency (%) OneT1 (0.05)-CT1 (2x10 -5 )1.796 / 30Colorless transparent hard11792 2T2 (0.04)CE1 (0.01)CT2 (1.8x10 -5 )1.766 / 32Colorless transparent hard11196 3T3 (0.047)CE2 (0.003)CT3 (3.9x10 -4 )1.764 / 35Colorless transparent hard14191 4T1 (0.035)CE3 (0.015)CT3 (3.1x10 -4 )1.709 / 36Colorless transparent hard13890 5T1 / T2 (0.03 / 0.013CE4 (0.0075)CT4 (9x10 -5 )1.778 / 31Colorless transparent hard11589 Application Comparative ExampleRaw material composition (mol)Polymerization catalyst (mol)n D / v D ExteriorHeat resistance (℃)Transparency (%) OneCE5 / CE6 (0.1 / 0.2)CT5 (1.0x10 -4 )1.59 / 36Colorless transparent hard8692 2CE7 / CE6 (0.2 / 0.3)CT5 (1.5x10 -4 )1.67 / 28Pale yellow and transparent hard9481 3CE1 (0.1)CT2 (1.0x10 -4 )1.70 / 36Colorless transparent fragrance9089
    [72] (Abbreviation of Table 1)
    [73] T1: 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-trithione
    [74] T2: 2,4,6-tris (ethiothioethylthiomethyl) -1,3,5-trithione
    [75] T3: 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-trithione
    [76] CE1: bis (ethiothiomethyl) sulfide
    [77] CE2: 2,2-bis (4- (2-glycidyloxy) ethoxyphenyl) propane
    [78] CE3: cyclohexene oxide
    [79] CE4: bis (2-acryloxyethyl) 1,4-xyrylcarbamate
    [80] CE5: pentaerythritol tetrakismercaptopropionate
    [81] CE6: m-xylene diisocyanate
    [82] CE7: 1,3,5-trimercaptobenzene
    [83] CT1: tetra (n-butyl) phosphonium bromide
    [84] CT2: triethylamine
    [85] CT3: 2,4,6-tridimethylaminophenol
    [86] CT4: boron trifluoride-pyridine complex
    [87] CT5: dibutyltin dichloride
    [88] The episulfide compound of the present invention is a novel compound in which three reactive substituents containing an episulfide group are bonded around a tritian ring, and is suitably used as a raw material of an optical material. Moreover, the optical material obtained using the novel episulfide compound of this invention is high in refractive index and Abbe's number, and is excellent in heat resistance and transparency. Therefore, it is suitable as a material for manufacturing optical products such as lenses, such as spectacle lenses, camera lenses, prisms, optical fibers, optical disks, magnetic disks, recording medium substrates, color filters, infrared absorption filters, and the like.
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] Episulfide compound represented by the general formula (1):
    (One)
    In the formula, EP And n represents the integer of 0-2.
    [2" claim-type="Currently amended] The method of claim 1,
    The episulfide compound represented by the general formula (1) is 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-trithione, 2,4,6-tris (ethiothioethylthiomethyl ), 1,3,5-trithione or 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-trithione.
    [3" claim-type="Currently amended] Method for preparing an episulfide compound represented by the general formula (1) by reacting an episulfide compound having a mercapto group with 2,4,6-trimethylene-1,3,5-trithione:
    (One)
    In the formula, EP And n represents the integer of 0-2.
    [4" claim-type="Currently amended] The method of claim 3, wherein
    The episulfide compound which has a mercapto group is 3-mercaptopropene sulfide, 4-mercaptobutene sulfide, or 5-mercaptopentene sulfide, The method of manufacturing the episulfide compound characterized by the above-mentioned.
    [5" claim-type="Currently amended] The method of claim 3, wherein
    The episulfide compound represented by the general formula (1) is 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-trithione, 2,4,6-tris (ethiothioethylthiomethyl ), 1,3,5-tritriane or 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-trithione.
    [6" claim-type="Currently amended] An optical product comprising a polymer obtained by using at least one episulfide compound represented by the general formula (1) as an essential monomer component:
    (One)
    In the formula, EP And n represents the integer of 0-2.
    [7" claim-type="Currently amended] The method of claim 6,
    The episulfide compound represented by the general formula (1) is 2,4,6-tris (ethiothiomethylthiomethyl) -1,3,5-trithione, 2,4,6-tris (ethiothioethylthiomethyl ), 1,3,5-tritriane or 2,4,6-tris (ethiothiopropylthiomethyl) -1,3,5-tritriane.
    [8" claim-type="Currently amended] The method of claim 6,
    The polymer comprises an episulfide compound represented by the general formula (1) and an episulfide compound other than that.
    [9" claim-type="Currently amended] The method of claim 6,
    The polymer is an optical product, characterized in that it comprises an episulfide compound and an epoxy compound represented by the general formula (1).
    [10" claim-type="Currently amended] The method of claim 6,
    The polymer is an optical article, characterized in that it comprises an episulfide compound represented by the general formula (1) and a vinyl monomer homopolymerizable.
    [11" claim-type="Currently amended] The method of claim 6,
    The polymer comprises an episulfide compound, a polyisocyanate compound and / or a polyisothiocyanate compound represented by the general formula (1), and a polythiol compound.
    [12" claim-type="Currently amended] The method according to any one of claims 6 to 11,
    The optical product is an optical product, characterized in that the plastic lens.
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    同族专利:
    公开号 | 公开日
    KR100538015B1|2005-12-21|
    AU2002301989B2|2004-04-22|
    EP1316555A1|2003-06-04|
    CN1239499C|2006-02-01|
    DE60202832D1|2005-03-10|
    US6696540B2|2004-02-24|
    AT288429T|2005-02-15|
    US20030144431A1|2003-07-31|
    JP4076760B2|2008-04-16|
    CA2406303A1|2003-05-28|
    JP2003160582A|2003-06-03|
    KR100495111B1|2005-06-14|
    EP1316555B1|2005-02-02|
    CN1421445A|2003-06-04|
    KR20050026455A|2005-03-15|
    DE60202832T2|2006-01-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-11-28|Priority to JP2001362375A
    2001-11-28|Priority to JPJP-P-2001-00362375
    2002-11-15|Application filed by 호야 가부시키가이샤
    2003-06-02|Publication of KR20030043661A
    2005-12-21|Application granted
    2005-12-21|Publication of KR100538015B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001362375A|JP4076760B2|2001-11-28|2001-11-28|Episulfide compound and method for producing the same|
    JPJP-P-2001-00362375|2001-11-28|
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