JP2010018592A - New tetrathiaspiro compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material having high refractive index and exhibiting heat resistance and impact resistance at the same time. <P>SOLUTION: There are provided a tetrathiaspiro compound expressed by formula (1), formula (2), etc., a composition containing the compound of formula (1), formula (2), etc., an optical material obtained by curing the composition, and a method for producing the optical material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is suitably used for optical materials such as plastic lenses, prisms, optical fibers, information recording boards, filters, and especially plastic lenses. In addition, it has a wide range of uses such as synthetic resin raw materials, cross-linking materials, and curing agents.

In recent years, plastic materials have been widely used in various optical materials, particularly eyeglass lenses, because they are light and tough and easy to dye. The performance particularly required for optical materials, particularly spectacle lenses, is that both the refractive index and the Abbe number are high and the impact resistance is high. Since the high refractive index enables the lens to be thinned, the weight can be reduced, and at the same time, the appearance is good. The high Abbe number reduces the chromatic aberration of the lens, thereby reducing the burden on the eyes and making it less likely to get tired.
Conventionally, diethylene glycol diallyl carbonate resin, which has been widely used as a spectacle lens material, has a high Abbe number of 58 but a low refractive index of 1.50. For this reason, when used as a lens, the lens thickness becomes thick, the appearance is poor, and it becomes heavy, and the impact strength is also weak.
In order to improve the refractive index, introduction of sulfur atoms into the molecule is an effective means, and so high refractive index using sulfur atoms has been proposed so far. Examples thereof include thiourethane materials composed of polythiols and polyisocyanates of Patent Documents 1 to 4, and episulfide materials of Patent Documents 5 to 7. However, when aiming to increase the refractive index by these methods, thiourethane materials showed a decrease in heat resistance and episulfide materials showed a decrease in impact strength, and it was not sufficient to achieve both heat resistance and impact strength. .
Therefore, a material having a high refractive index and having both heat resistance and impact resistance has been desired.

JP-A-60-199016 Japanese Patent Laid-Open No. 2-270859 JP-A-5-208950 JP 7-252207 A Japanese Patent Laid-Open No. 9-110979 Japanese Patent Laid-Open No. 9-255781 JP-A-9-71580

  The problem to be solved by the present invention is to provide a material having a high refractive index and having both heat resistance and impact resistance.

（１）
２．ヒドロキシピバルアルデヒドとペンタエリスリチオールを反応させて得られる（１）式の化合物。
３．下記（２）式の化合物。

（２）
４．下記（３）式の化合物。

（３）
５．下記（４）式の化合物。

（４）
６．第３項記載の（２）式または第４項記載の（３）式の化合物と、ポリイソシアネート化合物、ポリイソチオシアネート化合物、イソシアネート基を有するイソチオシアネート化合物、およびエピスルフィド化合物から選択される少なくとも１種の化合物を含む樹脂用組成物。
７．第５項記載の（４）式の化合物を含む樹脂用組成物。
８．第５項記載の（４）式の化合物とポリチオール化合物を含む樹脂用組成物。
９．第５項記載の（４）式の化合物と（４）式以外のエピスルフィド化合物を含む樹脂用組成物。
１０．第６項〜第９項に記載の樹脂用組成物を硬化して得られる光学材料。
１１．第１０項記載の光学材料からなる光学レンズ。
１２．第６項〜第９項に記載の樹脂用組成物を硬化して得られる光学材料の製造方法。 In view of such a situation, the present inventors have intensively studied, and as a result, solved the problem and arrived at the present invention. Specifically, this problem was solved by the following novel tetrathiaspiro compound, and the present invention was achieved.
That is, the present invention is as follows.
1. A compound of the following formula (1).

(1)
2. A compound of the formula (1) obtained by reacting hydroxypivalaldehyde with pentaerythritol.
3. Compound of the following formula (2).

(2)
4). A compound of the following formula (3):

(3)
5). Compound of the following formula (4).

(4)
6). The compound represented by the formula (2) or the formula (3) according to the item 3, and at least one selected from a polyisocyanate compound, a polyisothiocyanate compound, an isothiocyanate compound having an isocyanate group, and an episulfide compound The resin composition containing the compound of these.
7). The resin composition containing the compound of Formula (4) of Claim 5.
8). A resin composition comprising a compound of formula (4) according to item 5 and a polythiol compound.
9. A resin composition comprising the compound of formula (4) according to item 5 and an episulfide compound other than formula (4).
10. An optical material obtained by curing the resin composition according to any one of Items 6 to 9.
11. An optical lens made of the optical material according to Item 10.
12 The manufacturing method of the optical material obtained by hardening | curing the resin composition of Claims 6-9.

  The compound of the present invention, the composition containing them, and the optical material obtained by polymerizing and curing them have high refractive index, high heat resistance and impact resistance, which were difficult as long as the compounds of the prior art were used as raw materials. It became possible to impart high physical properties.

  The tetrathiaspiro compound referred to in the present invention is a compound represented by the above formulas (1) to (4).

The compound of the formula (1) of the present invention is obtained by reacting hydroxypivalaldehyde obtained from isobutyraldehyde and formaldehyde and pentaerythritol. It is preferable to use an acid catalyst for the reaction, specifically, a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid such as p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid or tosylic acid, TiCl ₄ , Lewis acids such as AlCl ₃ , FeCl ₃ , ZnCl ₃ , and BF ₃ . The amount used depends on the type of catalyst, but is usually 0.01 to 0.5 mol, preferably 0.1 to 0.3 mol, relative to pentaerythritol.
The reaction is carried out by dissolving in water or a solvent inert to the reaction. Specific examples thereof include alcohols, aliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, and acetonitrile, preferably water, methanol, Isopropyl alcohol, butyl alcohol, amyl alcohol, cyclohexanol, hexane, heptane, chloroform, dichloromethane, acetonitrile, benzene and toluene. These may be used alone or in combination.
The amount of pentaerythritol used is 0.20 to 1.0, preferably 0.30 to 0.60 in terms of molar ratio to hydroxypivalaldehyde. If it exceeds 1.0, the amount of by-products produced is undesirably increased, and if it is less than 0.2, the unreacted amount of hydroxypivalaldehyde becomes large and purification in the subsequent step becomes difficult. .
The amount of the solvent used in the reaction is preferably adjusted so that the slurry concentration of the compound of the formula (1) to be produced is 5 to 50% by weight, preferably 10 to 30% by weight. If the slurry concentration exceeds 50% by weight, it is difficult to sufficiently stir and the yield is lowered, and if it is less than 5% by weight, the productivity is lowered.
The reaction time is 0.5 to 20 hours, usually 2 to 10 hours. The reaction pressure is not particularly limited, but it can also be performed under high pressure.
The reaction temperature is 10 to 120 ° C, preferably 40 to 100 ° C. If it is less than 10 ° C., the reaction time becomes longer, and if it exceeds 120 ° C., hydroxypivalaldehyde is altered and the yield is lowered.
The obtained compound of the formula (1) can be produced by a purification method such as recrystallization, reprecipitation, column separation operation, adsorbent treatment, ion exchange resin treatment and the like. In addition, although these manufacture can be implemented also in air | atmosphere, it is preferable to carry out in nitrogen atmosphere, in order to ensure prevention of oxidation and coloring of a raw material, a product, etc.
Moreover, it is possible to obtain the compounds of the formulas (2), (3) and (4) by using, as a starting material, a compound in which the OH group of the compound of the formula (1) is halogenated or thialated.

Methods for obtaining the compound of formula (2) include a method of reacting the compound of formula (1) with hydrogen sulfide and a method of reacting with thiourea, preferably a method of reacting with thiourea.
As a method of reacting thiourea, a compound of formula (1) and thiourea are reacted to form isothiuronium chloride and hydrolyzed, or after OH group of the compound of formula (1) is halogenated, There is a method of reacting urea to make isothiuronium chloride and hydrolyzing it, but preferably it is a method of reacting the compound of formula (1) with thiourea to make isothiuronium chloride and hydrolyzing it.
As the halogenation method, a method of reacting a hydrogen halide such as hydrochloric acid, hydrobromic acid or hydroiodic acid, a method using the hydrogen halide and a metal halide such as zinc chloride, potassium iodide, bromide or the like. Methods using alkali metal salts such as sodium and acids such as sulfuric acid and phosphoric acid, methods using halogen and phosphorus, thionyl chloride, phosphorus tribromide, phosphorus pentachloride, methanesulfonyl chloride, benzenesulfonyl chloride, p-toluenesulfonic acid There is a method using chloride or the like.
In the isothiuronium chloride reaction, 2 to 6 equivalents, preferably 2 to 4 equivalents of thiourea are reacted with respect to the OH group of the compound of formula (1), or halogenated when halogenated. When making it react with OH group, 1-10 equivalent with respect to OH group, Preferably 1-5 equivalent of mineral acid is added and it reacts. As the mineral acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid and the like can be used, and hydrochloric acid and hydrobromic acid are preferable.
In the subsequent hydrolysis reaction, an inorganic base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium acetate or potassium phosphate, or an organic base such as ammonia, triethylamine or hydrazine is added to the above reaction solution (1). ) 1 to 10 equivalents, preferably 1 to 5 equivalents, of the compound of the formula is subjected to hydrolysis to obtain the compound of formula (2).
(2) The reaction temperature until obtaining the compound is not limited because it varies depending on the selected method, catalyst, etc., but is preferably 0 to 200 ° C, more preferably 20 to 120 ° C.
The pressure may be any of reduced pressure, normal pressure and increased pressure, but normal pressure is preferred. The thus obtained compound (2) can be produced by purification methods such as recrystallization, reprecipitation, column separation operation, adsorbent treatment, ion exchange resin treatment and the like. In addition, although these manufacture can be implemented also in air | atmosphere, it is preferable to carry out in nitrogen atmosphere, in order to ensure prevention of oxidation and coloring of a raw material, a product, etc.

Furthermore, compounds of formula (3) and formula (4) can be obtained from the compound of formula (2).
As a method for obtaining the compound of formula (3), first, the compound of formula (2) is reacted with epichlorohydrin to obtain a halohydrin compound, which is then reacted with thiourea to obtain an isothiuronium salt, which is then hydrolyzed. There is a method of decomposing, or a method in which a halohydrin compound is converted to a tetrachloro compound with thionyl chloride or the like and then reacted with thiourea to form an isothiuronium salt which is hydrolyzed.
In synthesizing the halohydrin compound, 0.3 to 4 equivalents, preferably 0.4 to 3 equivalents, more preferably 0.5 to 2 equivalents of epichlorohydrin is added to the SH group of the compound of the formula (2). React. In the reaction, a basic substance is preferably used as a catalyst, more preferably an alkali metal or alkaline earth metal hydroxide or amine, and specific examples thereof include sodium hydroxide and potassium hydroxide. And triethylamine. The reaction temperature is usually -10 to 100 ° C, preferably 0 to 80 ° C, more preferably 10 to 60 ° C. The pressure may be any of reduced pressure, normal pressure and increased pressure, but normal pressure is preferred.
In the case where the produced halohydrin compound is a tetrachloro compound, thionyl chloride is preferably used.
The reaction in which a halohydrin compound or a tetrachloro compound is converted to a compound of formula (3) with thiourea is in accordance with the method shown in paragraph [0009]. At this time, a transfer reaction takes place, resulting in the structure of formula (3). (3) The formula compound can be produced by purification methods such as recrystallization, reprecipitation, column separation operation, adsorbent treatment, ion exchange resin treatment, and the like. In addition, although these manufacture can be implemented also in air | atmosphere, it is preferable to carry out in nitrogen atmosphere, in order to ensure prevention of oxidation and coloring of a raw material, a product, etc.

(4) As a method for obtaining the compound of the formula, first, the compound of the formula (2) is reacted with epichlorohydrin to obtain a halohydrin compound, which is then converted into an epoxy compound with a base, and then a thiaurea or the like is obtained. There is a method of reacting with an agent.
The method for obtaining the halohydrin compound is in accordance with the method shown in paragraph [0010].
The epoxy compound is produced by reacting a halohydrin compound with a basic substance. The reaction is carried out in the presence of a basic substance in a stoichiometric amount or more, and is usually 1 to 5 equivalents, preferably 1 to 2.5 equivalents, more preferably 1 to 1.5 equivalents. The reaction temperature is usually -10 to 100 ° C, preferably 0 to 80 ° C, more preferably 10 to 60 ° C.
In the case of thialation, thiocyanate or thiourea is used as a thiazing agent. Preferred are potassium thiocyanate, sodium thiocyanate, and thiourea, and more preferred is thiourea. In the case of thialation, the reaction is carried out in the presence of a stoichiometric agent of a stoichiometric amount or more, and is usually 1 to 5 equivalents, preferably 1 to 2.5 equivalents. The reaction temperature is usually -10 to 100 ° C, preferably 0 to 80 ° C, more preferably 10 to 60 ° C.
The pressure may be any of reduced pressure, normal pressure and increased pressure, but normal pressure is preferred. The thus obtained compound (4) can be produced by a purification method such as recrystallization, reprecipitation, column separation operation, adsorbent treatment, ion exchange resin treatment and the like. In addition, although these manufacture can be implemented also in air | atmosphere, it is preferable to carry out in nitrogen atmosphere, in order to ensure prevention of oxidation and coloring of a raw material, a product, etc.

In the present invention, a resin composition is a mixture of a polyisocyanate compound, a polyisothiocyanate compound, an isothiocyanate compound having an isocyanate group, or the like as a compound capable of reacting with the compound of formula (2) or (3). Specific examples of these reactive compounds include diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate). Methyl) cyclohexane, isophorone diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4,4 ′ -Diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 3- (2'-isocyanatocyclohexyl) propyl isocyanate , Tris (phenylisocyanate) thiophosphate, isopropylidenebis (cyclohexylisocyanate), 2,2′-bis (4-isocyanatophenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4 , 4 ′, 4 ″ -triisocyanate-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4, 4'-diisocyanatobiphenyl, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, dicyclohexylmethane-4,4'-diisocyanate, 1,1'-methylenebis (4-isocyanatobenzene), 1 , 1′-methylenebis (3- Til-4-isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,4-bis (1-isocyanate- 1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) benzene, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, bis (isocyanatomethyl) tetrahydro Dicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) tetrahydrothiophene, bis (isocyanatomethyl) norbornene, bis (isocyanatomethyl) adamantane, dimer acid diisocyanate, 1,3,5-tri (1-I Sosocyanatohexyl) isocyanuric acid, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, bis [(4-isocyanatomethyl) phenyl] sulfide, 2,5-diisocyanate-1,4-dithiane, 2,5-di Polyisocyanates such as isocyanatomethyl-1,4-dithiane, 2,5-diisocyanatomethylthiophene, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, and all or part of the isocyanate groups of the above isocyanates are isolated. The compound etc. which changed to the thiocyanate group can be mentioned. Among the above, polyisocyanates include isocyanates such as dimers, cyclized trimers and adducts of alcohols or thiols by burette type reaction.
Specific examples are shown above, but the present invention is not limited to these examples. These may be used alone or in combination of two or more. Among these, preferred compounds are 1,3-bis (isocyanatomethyl) cyclohexane, m-xylylene diisocyanate, bis (isocyanatomethyl) norbornene, 2,5-diisocyanatomethyl-1,4-dithiane, 1, In the present invention, which is 3-bis (1-isocyanato-1-methylethyl) benzene, a compound of formula (2) or (3), a polyisocyanate compound, a polyisothiocyanate compound, an isothiocyanate compound having an isocyanate group The compounding ratio of (2) or (3) is the total number of moles of SH groups and the number of moles of NCO groups and NCS groups in polyisocyanate compounds, polyisothiocyanate compounds, and isothiocyanate compounds having isocyanate groups. (SH group) / (NCO group) + NCS group) is in the range of 0.3 to 2, preferably in the range of 0.6 to 1.5.

Curing catalyst for resin composition comprising compound of formula (2) or (3) and at least one compound selected from polyisocyanate compound, polyisothiocyanate compound, and isothiocyanate compound having isocyanate group As such, it is possible to use a known urethanization catalyst.
Specific examples thereof include amines and organotin compounds, but preferably dimethyltin dichloride, methyltin trichloride, dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyltin trichloride, dibutyltin dilaurate, dibutyltin dimalate, dibutyltin. Distearate, dibutyltin diacetate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin distearate, and dioctyltin dimaleate, more preferably dibutyltin dichloride and dibutyltin dilaurate.
The addition amount is usually 0.0001 to 5.0 wt%, preferably 0.0005 to 3.0 wt%, more preferably 0.001 to 2.0 wt% with respect to 100 wt% of the total composition. It is.

（５）
(式中、ｍは０〜４の整数、ｎは０〜２の整数を示す。)
（５）式で表される化合物の具体例としてはビス（β−エピチオプロピル）スルフィド、ビス（β−エピチオプロピル）ジスルフィド、ビス（β−エピチオプロピル）トリスルフィド、ビス（β−エピチオプロピルチオ）メタン、１，２−ビス（β−エピチオプロピルチオ）エタン、１，３−ビス（β−エピチオプロピルチオ）プロパン、１，４−ビス（β−エピチオプロピルチオ）ブタン、ビス（β−エピチオプロピルチオエチル）スルフィド、などがあげられる。以上具体例を示したが、これらに限定されるわけではなく、またこれらは単独でも２種以上を混合して使用しても構わない。中でも好ましい化合物は、ビス（β−エピチオプロピル）スルフィド、ビス（β−エピチオプロピル）ジスルフィドであり、最も好ましい化合物は、ビス（β−エピチオプロピル）スルフィドである。
（２）式、（３）式の化合物と、エピスルフィド化合物の配合比率は、（２）式、（３）式の化合物中ＳＨ基のモル数とエピスルフィド化合物中のエピチオ基のモル数合計の比で表した場合、（ＳＨ基）／（エピチオ基）が０．３〜３の範囲内、好ましくは０．６〜２の範囲内である。
（４）式の化合物と、エピスルフィド化合物の配合比率は任意であるが、好ましくは（４）式の化合物中エピチオ基のモル数とエピスルフィド化合物中のエピチオ基のモル数合計の比で表した場合、（（４）式化合物中エピチオ基）／（エピチオ基）が０．３〜３の範囲内、より好ましくは０．６〜２の範囲内である。 In the present invention, specific examples of the episulfide compound that can be mixed with the compound represented by the formula (2), (3), or (4) include the episulfide compound represented by the formula (5). Form.

(5)
(In the formula, m represents an integer of 0 to 4, and n represents an integer of 0 to 2.)
Specific examples of the compound represented by the formula (5) include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, and bis (β-epi Thiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,4-bis (β-epithiopropylthio) butane Bis (β-epithiopropylthioethyl) sulfide, and the like. Specific examples are shown above, but the present invention is not limited to these examples. These may be used alone or in combination of two or more. Among them, preferred compounds are bis (β-epithiopropyl) sulfide and bis (β-epithiopropyl) disulfide, and the most preferred compound is bis (β-epithiopropyl) sulfide.
The compounding ratio of the compound of formula (2) and formula (3) and the episulfide compound is the ratio of the number of moles of SH groups in the compounds of formula (2) and formula (3) to the total number of moles of epithio groups in the episulfide compound. (SH group) / (epithio group) is in the range of 0.3 to 3, preferably in the range of 0.6 to 2.
The compounding ratio of the compound of formula (4) and the episulfide compound is arbitrary, but preferably expressed as a ratio of the number of moles of epithio group in the compound of formula (4) and the total number of moles of epithio group in the episulfide compound ((4) epithio group in formula compound) / (epithio group) is in the range of 0.3 to 3, more preferably in the range of 0.6 to 2.

As a curing catalyst for a resin composition comprising a compound of formula (2), formula (3) or formula (4) and an episulfide compound, or a resin composition comprising a compound of formula (4) alone, a known episulfide is used. A polymerization catalyst can be used, and specific examples include quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, and phosphine compounds. Of these, quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds are more preferable, and quaternary phosphonium salts are more preferable. Specific examples of more preferable compounds include tetra-n-methylammonium chloride, tetra-n-ethylammonium chloride, tetra-n-butylammonium chloride, tetraoctylammonium chloride, tetraphenylammonium chloride, and tetra-n-methylammonium bromide. , Quaternary such as tetra-n-ethylammonium bromide, tetra-n-butylammonium bromide, tetraoctylammonium bromide, tetraphenylammonium bromide, triethylbenzylammonium chloride, cetyldimethylbenzylammonium chloride, 1-n-dodecylpyridinium chloride Ammonium salt, tetra-n-methylphosphonium chloride, tetra-n-ethylphosphonium chloride , Tetra-n-butylphosphonium chloride, tetraoctylphosphonium chloride, tetraphenylphosphonium chloride, tetra-n-methylphosphonium bromide, tetra-n-ethylphosphonium bromide, tetra-n-butylphosphonium bromide, tetraoctylphosphonium bromide, tetra Examples include quaternary phosphonium salts such as phenylphosphonium bromide and phosphine compounds such as triphenylphosphine. Among these, further preferred compounds are triethylbenzylammonium chloride, tetra-n-butylphosphonium bromide and triphenylphosphine, and the most preferred compound is tetra-n-butylphosphonium bromide.
The amount of the polymerization catalyst added varies depending on the components of the composition, the mixing ratio, and the polymerization curing method, but is not generally determined, but is usually 0.001 wt% or more and 5 wt% or less, preferably 100 wt% of the total composition. Is used in an amount of 0.01 wt% to 1 wt%, most preferably 0.01 wt% to 0.5 wt%. When the addition amount of the polymerization catalyst is more than 5 wt%, the refractive index and heat resistance of the cured product may be lowered and coloring may occur. On the other hand, if it is less than 0.001 wt%, it may not be cured sufficiently and heat resistance may be insufficient.

In the present invention, specific examples of the polythiol compound in the resin composition of the polythiol compound capable of reacting with the compound of the formula (4) include methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, 1,2-bis (2 -Mercaptoethylthio) ethane, 1,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxy Butane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl 1,4- Mercaptopropane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 1,1,1-tris (mercaptomethyl) Propane, tetrakis (mercaptomethyl) methane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6 , 9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, ethylene glycol bis ( 2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4- Tandiol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,4- Dimercaptocyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (mercapto) Ethyl) -1,4-dithiane, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide Bis (4-mercaptophenyl) ether, 2,2-bis (4-mercaptophenyl) propane, bis (4-mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4 -Mercaptomethylphenyl) propane, o-dimercaptobenzene, m-dimercaptobenzene, p-dimercaptobenzene, 1,3,5-trimercaptobenzene and the like. Among them, preferred are bis (2-mercaptoethyl) sulfide, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 2,5-bis (mercaptomethyl) -1,4- Dithiane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercapto Methyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 1,1,3,3- Tetrakis (mercaptomethylthio) propane, 1,3-bis (mercaptomethyl) benzene, 1,4- Scan (mercaptomethyl) benzene. Specific examples of the most preferred compounds include bis (2-mercaptoethyl) sulfide, 2,5-bis (mercaptomethyl) -1,4-dithiane, 1,2-bis (2-mercaptoethylthio) -3- Mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane Examples include 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane.
The compounding ratio of the compound of the formula (4) and the polythiol compound is expressed by the ratio of the number of moles of the epithio group in the compound of the formula (4) and the total number of moles of the SH group in the polythiol compound. (Epithio group) is in the range of 0.01 to 0.5, preferably in the range of 0.01 to 0.3.

  Moreover, when combining the compound of Formula (4) and a polythiol compound, it is possible to use the curing catalyst described in paragraph [0015] as the curing catalyst.

  Although the composition of the present invention has been described above, it is also possible to mix a polyol, an epoxy compound, or the like as a resin modifier.

In addition, when the composition of the present invention is polymerized and cured to obtain a resin, it is possible to add additives such as known antioxidants, ultraviolet absorbers and bluing agents to further improve the practicality of the resulting material. Of course it is possible.
Preferable examples of the antioxidant include phenol derivatives. Among them, preferred compounds are polyhydric phenols and halogen-substituted phenols, more preferred compounds are catechol, pyrogallol, and alkyl-substituted catechols, and most preferred compounds are catechol and pyrogallol. A preferred example of the ultraviolet absorber is a benzotriazole-based compound. Among them, preferred compounds are benzotriazole compounds, and specific examples of particularly preferred compounds are 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-tert. -Butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di -Tert-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octyl) Oxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) A -2H- benzotriazole. Preferable examples of the bluing agent include anthraquinone compounds. These antioxidants, ultraviolet absorbers and bluing agents are usually added in amounts of 0.000001 to 5 wt% with respect to 100 wt% of the total composition.
Further, when the composition of the present invention is easily peeled off from the mold during polymerization, a known external and / or internal adhesion improver may be used or added to improve the adhesion between the obtained cured product and the mold. Is possible. Examples of the adhesion improving agent include known silane coupling agents and titanate compounds, and these may be used alone or in combination of two or more. The addition amount is usually 0.0001 to 5 wt% with respect to 100 wt% of the total composition. Conversely, when the composition of the present invention is difficult to peel off from the mold after polymerization, a known external and / or internal mold release agent may be used or added to improve the mold releasability from the mold of the resulting cured product. Is also possible. Release agents include fluorine-based nonionic surfactants, silicon-based nonionic surfactants, phosphate esters, acidic phosphate esters, oxyalkylene-type acidic phosphate esters, alkali metal salts of acidic phosphate esters, and alkalis of oxyalkylene-type acidic phosphate esters. Examples include metal salts, metal salts of higher fatty acids, higher fatty acid esters, paraffins, waxes, higher aliphatic amides, higher aliphatic alcohols, polysiloxanes, and aliphatic amine ethylene oxide adducts. May be mixed and used. The addition amount is usually 0.0001 to 5 wt% with respect to 100 wt% of the total composition.

  The method for producing a resin by polymerizing and curing the composition of the present invention will be described in detail as follows. Additives such as the above-mentioned composition components, antioxidants, ultraviolet absorbers, polymerization catalysts, radical polymerization initiators, adhesion improvers, mold release agents, etc., all mixed together in the same container under stirring, Each raw material may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container. Each raw material and auxiliary raw material may be mixed in any order.

  In mixing, the set temperature, the time required for this, and the like may basically be the conditions under which each component is sufficiently mixed.

In the present invention, the resin composition is degassed in advance, so that high transparency of the resin may be achieved. The deaeration treatment is performed under reduced pressure before, during or after mixing the compound capable of reacting with some or all of the composition components, the polymerization catalyst, and the additive. Preferably, it is performed under reduced pressure during or after mixing. The treatment conditions are 0 to 100 ° C. under reduced pressure of 0.001 to 50 torr for 1 minute to 24 hours. The degree of decompression is preferably 0.005 to 25 torr, more preferably 0.01 to 10 torr, and the degree of decompression may be varied within these ranges. The deaeration time is preferably 5 minutes to 18 hours, more preferably 10 minutes to 12 hours. The temperature at the time of deaeration is preferably 5 ° C. to 80 ° C., more preferably 10 ° C. to 60 ° C., and the temperature may be varied within these ranges. In the deaeration process, renewing the interface of the resin composition by stirring, blowing of gas, vibration by ultrasonic waves, or the like is a preferable operation for enhancing the deaeration effect. The components removed by the degassing treatment are mainly dissolved gas, low-boiling substances having a low molecular weight, and the like are not particularly limited as long as the effects of the present invention are exhibited.
Furthermore, filtering and purifying impurities and the like with a filter having a pore size of about 0.05 to 10 μm from these resin compositions and / or raw materials before mixing further enhances the quality of the optical material of the present invention. Is also preferable.

  The resin composition thus obtained is produced by pouring it into a glass or metal mold, proceeding with a polymerization and curing reaction by irradiation with active energy rays such as heating or ultraviolet rays, and then removing it from the mold. Preferably, it is polymerized and cured by heating. In this case, the curing time is 0.1 to 200 hours, usually 1 to 100 hours, and the curing temperature is −10 to 160 ° C., usually −10 to 140 ° C. The polymerization can be carried out at a predetermined polymerization temperature by holding for a predetermined time, raising the temperature by 0.1 ° C. to 100 ° C./hour, lowering the temperature by 0.1 ° C. to 100 ° C./hour, and combinations thereof. In addition, after the polymerization is completed, annealing the cured product at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing distortion of the optical material of the present invention. Furthermore, surface treatments such as dyeing, hard coating, impact resistant coating, antireflection and imparting antifogging properties can be performed as necessary.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Evaluation was performed by the following method.
¹ H and ¹³ C-NMR: Measured using a JEOL NMR apparatus LA-500.
Heat resistance: Using a thermomechanical analyzer TMA / SS6000 manufactured by Seiko Instruments Inc., place a pin with a diameter of 1 mm on the sample, apply a load of 10 g, raise the temperature from 30 ° C., perform TMA measurement, and determine the softening point temperature. Measurement was made and the heat resistance was evaluated.
Refractive index, Abbe number: The Abbe refractive index measuring machine NAR-4T manufactured by Atago Co., Ltd. was used to measure the refractive index and Abbe number at d-line at 25 ° C.
Impact strength: A ball drop test was performed by dropping a 500 g iron ball from a height of 127 cm onto a lens having a center thickness of 1.0 mm.

Example 1
(1) Synthesis of Formula Compound 3.3 g of triethylamine was added dropwise while stirring 59.5 g of isobutyraldehyde and 65.7 parts by weight of 37% formalin under a nitrogen stream at 40 ° C. After the dropping, the reaction temperature was gradually increased to 90 ° C. Thereafter, the reaction was gradually cooled to 60 ° C. to stop the reaction. Subsequently, unreacted low-boiling fractions such as isobutyraldehyde, triethylamine and methanol were removed at 70 ° C. and 53 kPa to obtain crude hydroxypivalaldehyde. As a result of GC analysis, 62% of hydroxypivalaldehyde was contained.
45.0 g of pentaerythritol was mixed with 290 g of chloroform, 86.4 g of crude hydroxypivalaldehyde and 2.5 g of hydrochloric acid were added thereto, and reacted at 90 ° C. for 5 hours. After completion of the reaction, reprecipitation was carried out in methanol to obtain 59.5 g of the compound of formula (12).
¹ H-NMR measurement results are shown. (CDCl ₃ , TMS)
1.11 (CH ₃ , 12H), 2.00 (OH, 2H), 2.36 (CH ₂ , 8H), 3.45 (CH ₂ , 4H), 3.55 (CH, 2H)
^The result of ¹³ C-NMR measurement is shown. (CDCl ₃ , TMS)
18.8 (CH ₃ ), 38.2 (CH ₂ ), 41.3 (C), 43.3 (C), 59.5 (CH), 71.4 (CH ₂ )

Example 2
(2) Synthesis of Formula Compound (1) 48.7 g of 36% hydrochloric acid, 30.5 g of thiourea and 100 g of water were added to 36.9 g of the compound of the formula, and the mixture was heated and stirred at 110 ° C. for 12 hours. After cooling to room temperature, 200 ml of toluene was added, and 49.1 g of 25% aqueous ammonia was gradually added, followed by hydrolysis at 60 ° C. for 3 hours. The obtained organic layer was washed twice with 36% hydrochloric acid, water, aqueous ammonia and water successively, and then toluene was distilled off to obtain 32.3 g of the compound of formula (2).
¹ H-NMR measurement results are shown. (CDCl ₃ , TMS)
1.11 (CH ₃ , 12H), 1.50 (SH, 2H), 2.36 (CH ₂ , 8H), 2.48 (CH ₂ , 4H), 3.55 (CH, 2H)
^The result of ¹³ C-NMR measurement is shown. (CDCl ₃ , TMS)
21.4 (CH ₃ ), 34.3 (CH ₂ ), 38.2 (CH ₂ ), 42.6 (C), 43.3 (C), 62.1 (CH)

Example 3
(3) Synthesis of Formula Compound (2) 0.8 g of triethylamine and 200 ml of toluene as a solvent were added to 20.0 g of the compound of the formula, and 10.0 g of epichlorohydrin was added dropwise and reacted at 50 ° C. for 3 hours. Next, 40.0 g of thionyl chloride was added dropwise to the reaction solution and reacted at 60 ° C. for 2 hours. After cooling to room temperature, 50 g of water was added to decompose excess thionyl chloride, and then the organic layer was extracted. The solvent was removed to obtain a tetrachloro product.
Next, 30.0 g of thiourea and 100 ml of water were added to the tetrachloro compound and reacted at 100 ° C. for 5 hours. After completion of the reaction, the temperature was returned to room temperature, and a 10% aqueous sodium hydroxide solution was added, followed by hydrolysis at 80 ° C for 1 hour. Thereafter, the mixture was extracted with toluene and washed with water, and then toluene was distilled off to obtain 17.7 g of the compound of the formula (3).
¹ H-NMR measurement results are shown. (CDCl ₃ , TMS)
1.11 (CH ₃ , 12H), 1.50 (SH, 4H), 2.36 (CH ₂ , 12H), 2.89 (CH ₂ , 8H), 3.16 (CH, 2H), 3. 55 (CH, 2H)
^The result of ¹³ C-NMR measurement is shown. (CDCl ₃ , TMS)
21.7 (CH ₃ ), 31.2 (CH ₂ ), 37.9 (CH ₂ ), 38.2 (CH ₂ ), 40.7 (C), 43.3 (C), 51.0 ( CH), 62.4 (CH)

Example 4
(4) Synthesis of Formula Compound (2) 1.2 g of 10% aqueous sodium hydroxide solution and 200 ml of toluene as a solvent are added to 20.0 g of the compound of formula, and 10.0 g of epichlorohydrin is added dropwise and reacted at 50 ° C. for 3 hours. I let you. Next, 20 g of 40% aqueous sodium hydroxide solution was added dropwise at 10 ° C. and reacted for 5 hours. After extraction with 100 ml of toluene, the solvent was removed to obtain an epoxy compound. Next, 30.0 g of thiourea, 100 ml of toluene and 100 ml of methanol were added to this epoxy compound, and reacted at 30 ° C. for 8 hours. After completion of the reaction, the mixture was extracted with toluene, washed with a 10% aqueous sulfuric acid solution and water, and then the toluene was distilled off to obtain 15.5 g of the compound of the formula (4).
¹ H-NMR measurement results are shown. (CDCl ₃ , TMS)
1.11 (CH ₃ , 12H), 2.23 (CH ₂ , 4H), 2.36 (CH ₂ , 12H), 2.54 (CH, 2H), 2.77 (CH ₂ , 4H), 3 .55 (CH, 2H)
^The result of ¹³ C-NMR measurement is shown. (CDCl ₃ , TMS)
21.7 (CH ₃ ), 24.8 (CH ₂ ), 33.0 (CH), 38.2 (CH ₂ ), 40.4 (C), 43.3 (C), 41.1 (CH ₂ ), 44.8 (CH ₂ ), 62.4 (CH)

Example 5
To 38.0 parts by weight of m-xylylene diisocyanate and 62.0 parts by weight of the compound of the formula (3), 0.1 part by weight of dibutyltin dichloride as a catalyst and 0.1 part by weight of butoxyethyl acid phosphate as a release agent are added and stirred. And made uniform. After deaeration, it was poured into a 4D lens glass mold (diameter 80 mm, center thickness 1 mm) and heated from 20 ° C. to 120 ° C. to cure. Table 1 shows the physical properties of the obtained resin.

Example 6
(4) To 100 parts by weight of the compound of the formula, 0.1 part by weight of tetrabutylphosphonium bromide was added as a catalyst and stirred to make it uniform. After deaeration, it was poured into a 4D lens glass mold (diameter 80 mm, center thickness 1 mm) and heated from 20 ° C. to 120 ° C. to cure. Table 1 shows the physical properties of the obtained resin.

Comparative Example 1
52.0 parts by weight of m-xylylene diisocyanate, 48.0 parts by weight of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 0.1 parts by weight of dibutyltin dichloride as a catalyst, and butoxyethyl acid as a release agent 0.1 parts by weight of phosphate was added and stirred until uniform. After deaeration, it was poured into a 4D lens glass mold (diameter 80 mm, center thickness 1 mm) and heated from 20 ° C. to 120 ° C. to cure. Table 1 shows the physical properties of the obtained resin.

Comparative Example 2
49.4 parts by weight of a mixture of 50.6 parts by weight of m-xylylene diisocyanate and 4,8-, 4,7- or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane To the part, 0.1 part by weight of dibutyltin dichloride as a catalyst and 0.1 part by weight of butoxyethyl acid phosphate as a release agent were added and stirred to make uniform. After deaeration, it was poured into a 4D lens glass mold (diameter 80 mm, center thickness 1 mm) and heated from 20 ° C. to 120 ° C. to cure. Table 1 shows the physical properties of the obtained resin.

Comparative Example 3
To 100 parts by weight of 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 0.1 part by weight of tetrabutylphosphonium bromide was added as a catalyst and stirred to make it uniform. After degassing, it was poured into a mold and heated from 20 ° C. to 120 ° C. to be cured. Table 1 shows the physical properties of the obtained resin.

Claims (12)

A compound of the following formula (1).

(1)   A production method of the formula (1) obtained by reacting hydroxypivalaldehyde with pentaerythritol. Compound of the following formula (2).

(2) A compound of the following formula (3):

(3) Compound of the following formula (4).

(4)   The compound of the formula (2) according to claim 3 or the formula (3) according to claim 4, and at least one selected from a polyisocyanate compound, a polyisothiocyanate compound, an isothiocyanate compound having an isocyanate group, and an episulfide compound The resin composition containing the compound of these.   A resin composition comprising the compound of formula (4) according to claim 5.   A resin composition comprising the compound of formula (4) according to claim 5 and a polythiol compound.   A resin composition comprising the compound of the formula (4) according to claim 5 and an episulfide compound other than the formula (4).   An optical material obtained by curing the resin composition according to claim 6.   An optical lens made of the optical material according to claim 10.   The manufacturing method of the optical material obtained by hardening | curing the resin composition of Claims 6-9.