JP6722085B2 - Thietanyl compound, polymerizable composition containing the compound and use thereof - Google Patents

Description

The present invention relates to a novel thietanyl compound, a polymerizable composition containing the thietanyl compound, a resin obtained by curing the polymerizable composition, a molded article made of the resin, and a plastic lens.

In recent years, plastic lenses have been attracting attention as optical materials. Compared to glass lenses, plastic lenses are lighter in weight, less prone to breakage, and easier to process such as dyeing and cutting. Among them, some proposals have been made such as a transparent resin obtained by polymerizing a compound having an episulfide group or a compound having a thietanyl group (Patent Documents 1 to 3).

Since polythioether, which is a polymer of polyepisulfide described in Patent Document 1 and Patent Document 2, has a high refractive index of 1.6 to 1.7 in the latter half of the range, and an Abbe number as high as 30 or more, an optical lens or It contributes to the thinning of prisms.

A polymer obtained from a compound having a thietanyl group and a metal atom, which is described in Patent Document 3, can improve the refractive index up to around 1.8, and is effective for thinning.

JP-A-9-110979 JP, 11-322930, A International Publication No. 2005/095490 Pamphlet JP, 2003-327583, A

However, the compound described in Patent Document 3 has a property of easily self-polymerizing because it has a metal atom in the molecule. Therefore, depending on the conditions, when the compound is mixed or when defoaming after mixing, the viscosity may increase, and there is room for improvement in handling.
In view of the above-mentioned conventional techniques, the present inventors have focused on the search for a raw material monomer for a resin having a high refractive index, and have found that a thietanyl compound having a specific structure can be used as a raw material monomer for a resin having a high refractive index, The present invention has been reached.

（Ｘは酸素原子または硫黄原子を表す）
［２］ ［１］記載の化合物を含む重合性組成物。
［３］ さらに、ポリチオール化合物、ポリイソ（チオ）シアナート化合物、ポリアミン化合物、（メタ）アクリレート化合物、アリルカーボネート化合物、（チオ）エポキシ化合物、オキセタン化合物、アルコキシシラン化合物、酸無水物、および一般式（１）で表される化合物以外のチエタン化合物から選択される少なくとも１種を含む、［２］記載の重合性組成物。
［４］ ［２］または［３］記載の重合性組成物を硬化させた成形体。
［５］ ［４］記載の成形体からなる光学材料。
［６］ ［４］記載の成形体からなるプラスチックレンズ
［７］ ３−チエタノールをハロゲン化剤と反応させ、３−ハロゲノチエタンを調製する工程と、
前記３−ハロゲノチエタンをチア化剤と反応させ、３−メルカプトチエタンを調製する工程と、
前記３−メルカプトチエタンを、ホスゲン誘導体またはチオホスゲンと反応させる工程と、を含む、一般式（１）で表されるチエタニル化合物の製造方法。

（Ｘは酸素原子または硫黄原子を表す） That is, the present invention can be shown as follows.
[1] A thietanyl compound represented by the following general formula (1).

(X represents an oxygen atom or a sulfur atom)
[2] A polymerizable composition containing the compound according to [1].
[3] Further, a polythiol compound, a polyiso(thio)cyanate compound, a polyamine compound, a (meth)acrylate compound, an allyl carbonate compound, a (thio)epoxy compound, an oxetane compound, an alkoxysilane compound, an acid anhydride, and the general formula (1 The polymerizable composition according to [2], containing at least one selected from thietane compounds other than the compound represented by the formula (1).
[4] A molded product obtained by curing the polymerizable composition according to [2] or [3].
[5] An optical material comprising the molded product according to [4].
[6] A plastic lens comprising the molded article according to [4] [7] A step of reacting 3-thiethanol with a halogenating agent to prepare 3-halogenothiethane.
Reacting the 3-halogenothiethane with a thiating agent to prepare 3-mercaptothietane;
And a step of reacting the 3-mercaptothietane with a phosgene derivative or thiophosgene, the method for producing a thietanyl compound represented by the general formula (1).

(X represents an oxygen atom or a sulfur atom)

The molded product obtained by polymerizing the novel thietanyl compound of the present invention has a high refractive index and can be suitably used as an optical material such as a plastic lens. Furthermore, thickening in the mixing step of the thietanyl compound is suppressed, and the handling property is excellent.

1 is a ¹ H-NMR chart of dithietanyl trithiocarbonate obtained in Example 1. 3 is a ¹ H-NMR chart of dithietanyl dithiocarbonate obtained in Example 2.

Hereinafter, the present invention will be described in detail.
The thietanyl compound of the present invention is represented by the above general formula (1).

In the general formula (1), X represents an oxygen atom or a sulfur atom. When the thietanyl compound of the present invention is used in combination with a compound having a thietanyl group and a metal described below, a compound in which X is a sulfur atom can give a molded article having a higher refractive index. preferable.
The thietanyl compound of the present invention represented by the general formula (1) is dithietanyl dithiocarbonate and dithietanyl trithiocarbonate.

The novel thietanyl compound of the present invention represented by the general formula (1) can be produced by the following production method.

The starting material, 3-thiethanol, can be easily synthesized by a known method. For example, epihalohydrin and alkali may be simultaneously charged into alcohol or water in which hydrogen sulfide is saturated and dissolved. The alcohol used here may be any alcohol as long as hydrogen sulfide can be dissolved therein, but methanol having high solubility is preferable. As the epihalohydrin, epichlorohydrin and epibromohydrin are preferable. The alkali may be any of inorganic and organic, alkali metal or alkaline earth metal hydroxide, alkali metal or alkaline earth metal carbonate, alkali metal or alkaline earth metal bicarbonate, ammonia, A tertiary amine, a secondary amine, a primary amine, a metal alkoxide and the like are preferable. In addition, there is also a method of reacting 1-chloro-3-mercaptopropan-2-ol with the alkali without solvent or in a solvent such as water or alcohol.

Step 1:
The obtained 3-thiethanol is converted into 3-halogenothiethane by a halogenating agent or the like. Preferred examples of the halogenating agent used here include thionyl chloride, phosphorus trichloride, hydrochloric acid, hydrogen chloride, phosphorus tribromide, hydrobromic acid, hydrogen bromide, chlorine, bromine, etc., but are limited to the exemplified compounds. It is not done. The solvent used in the reaction varies depending on the kind of the halogenating agent and cannot be generally stated, but any solvent may be used as long as it does not inhibit the halogenation or does not react with the halogenating agent. The reaction temperature also differs depending on the kind of the halogenating agent and cannot be generally specified, but usually, -30°C to 50°C may give good results, and -10°C to 30°C is preferable.

Process 2:
3-halogenothiethane can convert a halogen atom into a mercapto group by a substitution reaction. This substitution reaction includes thiocyanate-based reactions, thiourea-based reactions, triphenylphosphine sulfide-based reactions, sodium hydrosulfide, potassium hydrosulfide, sodium sulfide, potassium sulfide and other alkali metal hydrosulfides and alkali sulfides. Method using metal, method using metal polysulfide such as sodium polysulfide and potassium polysulfide, method using alkali metal trithiocarbonate such as sodium trithiocarbonate, potassium trithiocarbonate, method using potassium xanthate, Bunte salt Is a known reaction such as a method using.
A method using a thiating agent such as thiocyanates, thioureas, and triphenylphosphine sulfide, preferably thiocyanates and thioureas, is suitable for the step. As the method, an isothiuronium salt is formed by reacting with a thiating agent in at least one polar solvent selected from water, alcohols, ketones, esters and the like. 3-Mercaptothietane having a structure represented by the general formula (a) can be synthesized by adding the same alkali to the solution containing the isothiuronium salt or the taken-out isothiuronium salt and reacting.

In step 3, 3-mercaptothietane is reacted with a phosgene derivative or thiophosgene. The case of reacting 3-mercaptothietane with a phosgene derivative to obtain the compound (b) will be described as step (A), and the case of reacting 3-mercaptothietane with thiophosgene to obtain the compound (c) will be described as step (B).

Process (A):
The obtained compound (a), 3-mercaptothietane, is reacted with a phosgene derivative (phosgene or triphosgene) to produce compound (b), dithietanyldithiocarbonate. The amount of phosgene or triphosgene used is in the range of approximately 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents, and most preferably 1.0 to 1.2 equivalents, relative to compound (a). .. The reaction temperature is in the range of about -50°C to 200°C, preferably -10 to 100°C, more preferably 0 to 50°C. By the step, a reaction mixture containing the compound (b) is obtained.

For the purpose of improving the rate of this reaction, triethylamine, tributylamine, N,N-dimethylcyclohexylamine, N-methylpiperazine, 1,5-diazabicyclo[4.3.0]non-5-ene,1,8-diazabicyclo [5.4.0] Undecene-7, tertiary amines such as triphenylphosphine, pyridine, N,N-dimethylaniline and N,N-dimethylbenzylamine, phosphines such as tributylphosphine and triphenylphosphine, hydroxylation Known basic compounds such as inorganic bases such as sodium, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, calcium oxide, sodium methoxide, sodium and sodium hydride may be added. The amount of the basic compound added is approximately 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents, and most preferably 1.0 to 1.2 equivalents, relative to the compound (a).

Finally, the reaction solution obtained above is purified by a known purification method such as washing with water, distillation, or column chromatography to obtain the target compound (b) dithietanyldithiocarbonate.

Process (B):
The compound (c), dithietanyl trithiocarbonate, can be similarly prepared by changing phosgene or triphosgene in step (A) to thiophosgene.

In the step (A) and the step (B), a known solvent can be used, but it is inert to the raw material, the intermediate, and the final target product, and is a suitable solvent depending on the properties of the final target product. Is selected. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and cyclohexane, halogens such as dichloromethane, chloroform, dichloroethane, chlorobenzene and dichlorobenzene, and esters such as ethyl acetate and butyl acetate. , Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane and anisole, nitriles such as acetonitrile, adiponitrile and cyanobenzene, N,N-dimethylformamide, N,N-dimethylacetamide , N,N-dimethylimidozolidinone and other aprotic polar compounds.

[Polymerizable composition]
The polymerizable composition of the present invention contains a thietanyl compound represented by the general formula (1). The content is in the range of 0.1 to 100% by weight, preferably in the range of 1 to 100%, more preferably in the range of 10 to 100%, and further preferably in the range of 30 to 100%. Is.

The polymerizable composition of the present invention may contain, in addition to the thietanyl compound represented by the general formula (1), a polymerization reactive compound other than the thietanyl compound.
The thietanyl compound of the present invention can be used more suitably as a monomer for a high refractive index resin by using it in combination with another high refractive index monomer. Further, by using it in combination with another high refractive index monomer having a problem in handling, it is possible to stably produce a resin and a molded article having an extremely high refractive index by general cast polymerization.

Examples of other polymerization-reactive compounds include compounds having at least one functional group copolymerizable with the thietanyl compound represented by the general formula (1) or compounds having at least one functional group capable of being polymerized alone. ..

Specifically, for example, polythiol compounds, polyiso(thio)cyanate compounds, polyamine compounds, (meth)acrylate compounds, allyl carbonate compounds, (thio)epoxy compounds, oxetane compounds, alkoxysilane compounds, acid anhydrides, and general formulas Examples thereof include thietane compounds other than (1), and at least one of them can be used.

The polythiol compound is a compound having two or more mercapto groups in one molecule, and includes, for example, ethanedithiol, bis(2-mercaptoethyl)sulfide, 2,3-dimercapto-1-propanol, 1,2,3- Trimercaptopropane, tetrakis(mercaptomethyl)methane, diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropio) Nate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate) , Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide , Bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2- Bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio) ) Propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto- 3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-dimercapto-3,6,9-Trithiaundecane, 4,8-Dimercaptomethyl-1,11-dimercapto-3 6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercaptomethyl- 1,4-dithiane, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and their thioglycolic acid and mercaptopropionic acid esters , Hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxy Methyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl Ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), thiodiglycolic acid bis(2-mercaptoethyl ester), thiodipropionic acid bis(2-mercaptoethyl ester), Dithiodiglycolic acid bis(2-mercaptoethyl ester), dithiodipropionic acid bis(2-mercaptoethyl ester), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis Aliphatic polythiol compounds such as (mercaptomethylthio)ethane, tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane;
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4- Bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,3,5-trimercaptobenzene, 1,3,5-Tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 2,5-toluenedithiol, 3, Aromatic polythiol compounds such as 4-toluenedithiol, 1,5-naphthalenedithiol and 2,6-naphthalenedithiol;
3,4-dimercapto-1-thiophene, 2,5-bis(mercaptomethyl)-1-thiophene, bismuthiol, 2,5-zircapto-1,4-dithiane, 2,5-bis(mercaptomethylthio)-1, Heterocyclic polythiol compounds such as 4-dithiane, 4,6-bis(mercaptomethylthio)-1,3-dithiane and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane. , At least one kind can be used.

The above polyiso(thio)cyanate compound is a compound having two or more isocyanate groups or isothiocyanate groups alone or in combination in one molecule, and examples thereof include tetramethylene diiso(thio)cyanate and pentamethylene diiso( Thio)cyanate, hexamethylenediiso(thio)cyanate, pentamethylenediiso(thio)cyanate, octamethylenediiso(thio)cyanate, 2,2,4-trimethylhexamethylenediiso(thio)cyanate, 2,4 , 4-Trimethylhexamethylene diiso(thio)cyanate, lysine diisocyanatomethyl ester, lysine triiso(thio)cyanate, xylylene diiso(thio)cyanate and other aliphatic polyiso(thio)cyanate compounds;
Isophorone diiso(thio)cyanate, bis{iso(thio)cyanatomethyl}cyclohexane, dicyclohexylmethane diiso(thio)cyanate, dicyclohexyldimethylmethaneiso(thio)cyanate, 2,5-bis{iso(thio)cyanatomethyl}bicyclo- [2.2.1]-heptane, 2,6-bis{iso(thio)cyanatomethyl}bicyclo-[2.2.1]-heptane, 3,8-bis{iso(thio)cyanatomethyl}tricyclodecane, Fats such as 3,9-bis{iso(thio)cyanatomethyl}tricyclodecane, 4,8-bis{iso(thio)cyanatomethyl}tricyclodecane, and 4,9-bis{iso(thio)cyanatomethyl}tricyclodecane A cyclic polyiso(thio)cyanate compound;
Aromatic polyiso(thio)cyanate compounds such as tolylene diiso(thio)cyanate, 4,4′-diphenylmethane diiso(thio)cyanate, diphenyl sulfide-4,4-diiso(thio)cyanate, phenylene diiso(thio)cyanate;
2,5-diiso(thio)cyanatothiophene, 2,5-bis{iso(thio)cyanatomethyl}thiophene, 2,5-diiso(thio)cyanatotetrahydrothiophene, 2,5-bis{iso(thio)cyanatomethyl } Tetrahydrothiophene, 3,4-bis{iso(thio)cyanatomethyl}tetrahydrothiophene, 2,5-diiso(thio)cyanato-1,4-dithiane, 2,5-bis{iso(thio)cyanatomethyl}-1, Heterocyclic polyiso(thio)cyanate compounds such as 4-dithiane, 4,5-diiso(thio)cyanato-1,3-dithiolane, 4,5-bis{iso(thio)cyanatomethyl}-1,3-dithiolane, and These iso(thio)cyanurate body, dimer body, 1-nylon body, carbodiimide body, (thio)urea body, burette body, alohanate body, adduct body with polyhydric alcohol such as trimethylolpropane, and the like can be mentioned. One can be used.

The polyamine compound is a compound having two or more amino groups in one molecule, and includes, for example, phenylamine, 1,3-bis(3-aminophenyloxy)benzene, cyclohexylamine, pentane-1,5-diamine, Hexane-1,6-diamine, isophoronediamine, norbornanebis(aminemethyl), bis(4-aminecyclohexyl)methane, 1,3-xylylenediamine, 1,4-xylylenediamine, 1,3-bis(amine Methyl)cyclohexane, 1,4-bis(aminemethyl)crohexane and the like can be mentioned, and at least one can be used.

The above-mentioned (meth)acrylate compound is a compound having one or more groups selected from an acrylate group, a methacrylate group, a thioacrylate group, or a thiomethacrylate group in one molecule, or a combination thereof, for example, {(meth) Acryloylthio}benzene, {(meth)acryloylthiomethyl}benzene, 1,2-bis{(meth)acryloylthio}ethane, 1,5-bis{(meth)acryloylthio}-3-thiaheptane, 2,5- Bis{(meth)acryloylthio}-1,4-dithiane, 2,5-bis{(meth)acryloylthiomethyl}-1,4-dithiane,1,8-bis{(meth)acryloylthio}-4- {(Meth)acryloylthiomethyl}-3,6-dithiaoctane, 1,11-bis{(meth)acryloylthio}-4,8-bis{(meth)acryloylthiomethyl}-3,6,9-trithia Examples thereof include compounds having a thioacrylate group or a thiomethacrylate group such as undecane and 1,1,3,3-tetrakis{(meth)acryloylthiomethylthio)}propane, and at least one of them can be used.

For example, methyl (meth)acrylate, {(meth)acryloyloxy}benzene, {(meth)acryloyloxymethyl}benzene, ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1, 3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10- Decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth ) Acrylate, 1,2-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}ethane, 1,2-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}propane, 1 ,3-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}propane, 1,4-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}butane,1,6-bis {3-(meth)acryloyloxy-2-hydroxy-propyloxy}hexane;
Neopentyl glycol hydroxypivalic acid di(meth)acrylate;
Polyethylene glycol di(meth)acrylate, 1,2-polypropylene glycol di(meth)acrylate, 1,3-polypropylene glycol di(meth)acrylate, 1,4-polybutylene glycol di(meth)acrylate, polyethylene glycol-bis{ 3-(meth)acryloyloxy-2-hydroxy-propyl} ether, 1,2-polypropylene glycol-bis{3-(meth)acryloyloxy-2-hydroxy-propyl} ether, 1,2-polypropylene glycol-bis{ (Meth)acryloyl-poly(oxyethylene)} ether, 1,3-polypropylene glycol di(meth)acrylate, 1,4-polybutylene glycol di(meth)acrylate, 1,4-polybutylene glycol-bis{3- (Meth)acryloyloxy-2-hydroxy-propyl} ether and the like can be mentioned, and at least one kind can be used.

In addition, for example, bis{2-(meth)acryloylthio-ethyl}sulfide, bis{5-(meth)acryloylthio-3-thiapentyl}sulfide;
Cyclohexanediol di(meth)acrylate, bis{(meth)acryloyloxy-methyl}cyclohexane, bis{7-(meth)acryloyloxy-2,5-dioxaheptyl}cyclohexane, bis{(meth)acryloyloxy-poly( Ethyleneoxy)-methyl}cyclohexane, tricyclodecanedimethanol di(meth)acrylate, 2-propenoic acid {2-(1,1,-dimethyl-2-{(1-oxo-2-propenyl)oxy}} Ethyl)-5-ethyl-1,3-dioxan-5-yl}methyl ester (Nippon Kayaku Co., Ltd., trade name "KAYARAD R-604"), N,N',N"-tris{2-(meta ) Acryloyloxy-ethyl}isocyanurate, xylylenediol di(meth)acrylate, bis{7-(meth)acryloyloxy-2,5-dioxaheptyl}benzene, bis{(meth)acryloyloxy-poly(ethyleneoxy) )-Methyl}benzene, bisphenol A di(meth)acrylate, bis{(meth)acryloyl-oxyethyl}bisphenol A, bis{(meth)acryloyl-oxypropyl}bisphenol A, bis{(meth)acryloyl-poly(oxyethylene) )} Bisphenol A, bis{(meth)acryloyl-poly(oxy-1,2-propylene)}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl}bisphenol A, bis{3-( (Meth)acryloyloxy-2-hydroxy-propyl-oxyethyl}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-oxypropyl}bisphenol A, bis{3-(meth)acryloyloxy-2 -Hydroxy-propyl-poly(oxyethylene)}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-poly(oxy-1,2-propylene)}bisphenol A, bis{(meth)acryloyl -Oxyethyl-oxypropyl}bisphenol A, bis{(meth)acryloyl poly(oxyethylene)-poly(oxy-1,2-propylene)}bisphenol A, naphthalenediol di(meth)acrylate, bis{3-(meth) Acryloyloxy-2-hydroxy-propyl-oxy}naphthalene, 9,9-fluorenediol di(meth)acrylate, 9,9-bis{4- (2-(meth)acryloyloxy-ethyl-oxy)}fluorene, 9,9-bis{3-phenyl-4-(meth)acryloyloxy-poly(ethyleneoxy)}fluorene; and the like. Can be used.

Further, for example, phenol novolac type epoxy (meth)acrylate (manufactured by Shin-Nakamura Chemical, trade name “NK oligo EA-6320, EA-7120, EA-7420”), glycerin-1,3-di(meth)acrylate, 1 -Acryloyloxy-2-hydroxy-3-methacryloyloxy-propane, 2,6,10-trihydroxy-4,8-dioxaundecane-1,11-di(meth)acrylate, 1,3-bis{3- (Meth)acryloyloxy-2-hydroxy-propyl-oxy}-2-hydroxypropane, 1,2,3-tris{3-(meth)acryloyloxy-2-hydroxy-propyl-oxy}propane, 1,2,2 3-tris{2-(meth)acryloyloxy-ethyl-oxy}propane, 1,2,3-tris{2-(meth)acryloyloxy-propyl-oxy}propane, 1,2,3-tris{(meth ) Acryloyloxy-poly(1,2-ethyleneoxy)}propane, 1,2,3-tris{(meth)acryloyloxy-poly(1,2-propyleneoxy)}propane, 1,2,3-tris{ (Meth)acryloyloxy-poly(1,3-propyleneoxy)}propane trimethylolpropane tri(meth)acrylate, trimethylolpropane-tris{(meth)acryloyloxy-ethyl-oxy}ether, trimethylolpropane-tris{ 2-(meth)acryloyloxy-propyl-oxy} ether, trimethylolpropane-tris{(meth)acryloyloxy-poly(ethyleneoxy)} ether, trimethylolpropane-tris{(meth)acryloyloxy-poly(1, 2-propyleneoxy)} ether, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol-tetrakis{(meth)acryloyloxy-ethyl-oxy}ether, pentaerythritol-tetrakis{2-(meth) ) Acryloyloxy-propyl-oxy} ether, pentaerythritol-tetrakis {(meth)acryloyloxy-poly(ethyleneoxy)} ether, pentaerythritol-tetrakis {(meth)acryloyloxy-poly(1,2-propyleneoxy)} Ether, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane-tetrakis{(meth)a Cryloyloxy-ethyl-oxy} ether, ditrimethylol, propane-tetrakis{2-(meth)acryloyloxy-propyl-oxy} ether, ditrimethylolpropane-tetrakis{(meth)acryloyloxy-poly(ethyleneoxy)} ether , Ditrimethylolpropane-tetrakis{(meth)acryloyloxy-poly(1,2-propyleneoxy)} ether, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol-hexa{( (Meth)acryloyloxy-ethyl-oxy} ether, dipentaerythritol-hexa{2-(meth)acryloyloxy-propyl-oxy}ether, dipentaerythritol-hexa{(meth)acryloyloxy-poly(ethyleneoxy)} ether , Dipentaerythritol-hexa{(meth)acryloyloxy-poly(1,2-propyleneoxy)} ether; and the like, and at least one kind can be used.

In addition, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with hexamethylene diisocyanate Urethane reaction product,
A urethane reaction product of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate and isophorone diisocyanate,
Urethane reaction product of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate with bis(isocyanatomethyl)norbornane ,
Urethane of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate and norbis(4-isocyanatocyclohexyl)methane Reactant,
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate and 1,3-bis(isocyanatomethyl)cyclohexane Urethane reaction product of
Pentaerythritol tri(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth) Examples thereof include (thio)urethane reaction products of acrylate and the above polyiso(thio)cyanate compound, and at least one kind can be used.

The above allyl carbonate compound is a compound having one or more allyl carbonate groups, thioallyl carbonate groups, or dithioallyl carbonate groups in one molecule alone or in combination, and examples thereof include phenyl allyl carbonate, benzyl allyl carbonate, ethylene glycol- 1,2-diallyl carbonate, 1,2-bis(allylthiocarbonato)ethane, 1,2-bis(allyldithiocarbonato)ethane, diethylene glycol diallyl carbonate, 1,5-bis(allylthiocarbonato)-3 -Oxaheptane, 1,5-bis(allyldithiocarbonato)-3-oxaheptane, 1,5-bis(allylthiocarbonato)-3-thiasaheptane, 1,5-bis(allyldithiocarbonato)-3 -Thiaheptane, triethylene glycol diallyl carbonate, propylene glycol diallyl carbonate, dipropylene glycol diallyl carbonate, tripropylene glycol diallyl carbonate, etc., and at least one of them can be used.

The (thio)epoxy compound is a compound having one or more epoxy groups or thioepoxy groups alone or in combination in one molecule, and examples thereof include ethylene oxide, propylene oxide, ethylene sulfide, propylene sulfide,
For example, poly(thio)epoxy compounds such as bisphenol A diglycidyl ether;
Bis(2,3-(thio)epoxypropyl)sulfide, bis(2,3-(thio)epoxypropyl)disulfide, bis(2,3-(thio)epoxypropylthio)methane, 1,2-bis(2 ,3-(thio)epoxypropylthio)ethane, 1,2-bis(2,3-(thio)epoxypropylthio)propane, 1,3-bis(2,3-(thio)epoxypropylthio)propane, 1,3-bis(2,3-(thio)epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-(thio)epoxypropylthio)butane, 1,4-bis(2,2 3-(thio)epoxypropylthio)-2-methylbutane, 1,3-bis(2,3-(thio)epoxypropylthio)butane, 1,5-bis(2,3-(thio)epoxypropylthio) Pentane, 1,5-bis(2,3-(thio)epoxypropylthio)-2-methylpentane, 1,5-bis(2,3-(thio)epoxypropylthio)-3-thiapentane, 1,6 -Bis(2,3-(thio)epoxypropylthio)hexane, 1,6-bis(2,3-(thio)epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-( Thio)epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-(thio)epoxypropylthio)propane, 2,2-bis(2,3-(thio)epoxypropylthio )-1,3-Bis(2,3-(thio)epoxypropylthiomethyl)propane, 2,2-bis(2,3-(thio)epoxypropylthiomethyl)-1-(2,3-(thio ) Epoxypropylthio)butane, 1,5-bis(2,3-(thio)epoxypropylthio)-2-(2,3-(thio)epoxypropylthiomethyl)-3-thiapentane, 1,5-bis (2,3-(thio)epoxypropylthio)-2,4-bis(2,3-(thio)epoxypropylthiomethyl)-3-thiapentane, 1-(2,3-(thio)epoxypropylthio) -2,2-bis(2,3-(thio)epoxypropylthiomethyl)-4-thiahexane, 1,5,6-tris(2,3-(thio)epoxypropylthio)-4-(2,3 -(Thio)epoxypropylthiomethyl)-3-thiahexane, 1,8-bis(2,3-(thio)epoxypropylthio)-4-(2,3-(thio)epoxypropylthiomethyl)-3, 6-dithiaoctane, 1,8-bis(2,3-(thio ) Epoxypropylthio)-4,5-bis(2,3-(thio)epoxypropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-(thio)epoxypropylthio)-4 ,4-bis(2,3-(thio)epoxypropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-(thio)epoxypropylthio)-2,5-bis(2,2 3-(thio)epoxypropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-(thio)epoxypropylthio)-2,4,5-tris(2,3-(thio) Epoxypropylthiomethyl)-3,6-dithiaoctane, 1,1,1-tris[[2-(2,3-(thio)epoxypropylthio)ethyl]thiomethyl]-2-(2,3-(thio) Epoxypropylthio)ethane, 1,1,2,2-tetrakis[[2-(2,3-(thio)epoxypropylthio)ethyl]thiomethyl]ethane, 1,11-bis(2,3-(thio) Epoxypropylthio)-4,8-bis(2,3-(thio)epoxypropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(2,3-(thio)epoxypropylthio )-4,7-Bis(2,3-(thio)epoxypropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(2,3-(thio)epoxypropylthio)-5 , 7-bis(2,3-(thio)epoxypropylthiomethyl)-3,6,9-trithiaundecane and other linear aliphatic 2,3-(thio)epoxypropylthio compounds;
1,3-bis(2,3-(thio)epoxypropylthio)cyclohexane, 1,4-bis(2,3-(thio)epoxypropylthio)cyclohexane, 1,3-bis(2,3-(thio ) Epoxypropylthiomethyl)cyclohexane, 1,4-bis(2,3-(thio)epoxypropylthiomethyl)cyclohexane, 2,5-bis(2,3-(thio)epoxypropylthiomethyl)-1,4 -Dithiane, 2,5-bis[[2-(2,3-(thio)epoxypropylthio)ethyl]thiomethyl]-1,4-dithiane, 2,5-bis(2,3-(thio)epoxypropyl A cycloaliphatic 2,3-(thio)epoxypropylthio compound such as thiomethyl)-2,5-dimethyl-1,4-dithiane;
1,2-bis(2,3-(thio)epoxypropylthio)benzene, 1,3-bis(2,3-(thio)epoxypropylthio)benzene, 1,4-bis(2,3-(thio ) Epoxypropylthio)benzene, 1,2-bis(2,3-(thio)epoxypropylthiomethyl)benzene, 1,3-bis(2,3-(thio)epoxypropylthiomethyl)benzene, 1,4 -Bis(2,3-(thio)epoxypropylthiomethyl)benzene, bis[4-(2,3-(thio)epoxypropylthio)phenyl]methane, 2,2-bis[4-(2,3-) (Thio)epoxypropylthio)phenyl]propane, bis[4-(2,3-(thio)epoxypropylthio)phenyl]sulfide, bis[4-(2,3-(thio)epoxypropylthio)phenyl]sulfone , 4,4′-bis(2,3-(thio)epoxypropylthio)biphenyl and other aromatic 2,3-(thio)epoxypropylthio compounds; and the like.

The above-mentioned oxetane compound is a compound having one or more oxetanyl groups in one molecule, and examples thereof include 3-ethyl-3-hydroxymethyloxetane and 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy. ] Methyl}benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[1-ethyl-(3-oxetanyl)]methyl ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac Examples include oxetane.

The above-mentioned alkoxysilane compound is a compound having one or more alkoxysilyl groups in one molecule, and examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane and decyltrisilane. Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxy-propyltrimethoxysilane, p-styryltrimethoxysilane, 3-acryloyloxy- Propyltrimethoxysilane, 3-methacryloyloxy-propyltrimethoxysilane, 3-amino-propyltrimethoxysilane, N-2(aminoethyl)-3-amino-propyltrimethoxysilane, bis(trimethoxysilylpropyl)amine, 3-(2,2,6,6-tetramethylpiperidin-4-yloxypropyl)triethoxysilane, 3-trimethoxysilylpropylsuccinic acid, and their hydrolysis-condensation oligomers, and the like. Can be used.

The above-mentioned acid anhydride is a compound having one or more acid anhydride groups in one molecule, and examples thereof include succinic anhydride, phthalic anhydride, maleic anhydride, tetrabromophthalic anhydride, tetrahydrophthalic anhydride and hexahydroanhydride. Examples thereof include phthalic acid, methyl-hexahydrophthalic anhydride, trimellitic anhydride, and dodecyl succinic anhydride, and at least one of them can be used.

The thietane compound other than the above general formula (1) is a compound having one or more thietanyl groups in one molecule, for example, 3-mercapto-1-thietane, 1-{4-(6-mercaptomethylthio)-1. ,3-Dithianylthio}-3-{2-(1,3-dithietanyl)}methyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis{4 -(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2-(1,3-dithietanyl)}methyl-2,4-dithiapentane, 4,6-bis[3-{2-(1, 3-dithietanyl)}methyl-5-mercapto-2,4-dithiapentylthio]-1,3-dithiane, 3-{2-(1,3-dithietanyl)}methyl-7,9-bis(mercaptomethylthio) )-1,11-Dimercapto-2,4,6,10-tetrathiaundecane, 9-{2-(1,3-dithietanyl)}methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1 , 17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-{2-(1,3-dithietanyl)}methyl-7,9,13,15-tetrakis(mercaptomethylthio) -1,17-Dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis{2-(1,3-dithietanyl)}methyl-1,9-dimercapto-2, 4,6,8-Tetrathianonane, 4,5-bis[1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiolane, 4-[ 1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]-5-{1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio}-1,3 -Dithiolane, 4-{4-(5-mercaptomethylthio-1,3-dithiolanyl)thio}-5-[1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane Tris(thietanylthio)antimony, pentakis(thietanylthio)antimony, tris(thietanylthio)bismuth, tetrakis(thietanylthio)zirconium, pentakis(thietanylthio)tantalum, tetrakis(thietanylthio)tin, dithietanyl tetrasulfide, etc. And at least one kind can be used.
From the viewpoint of the effect of the present invention, the other polymerization-reactive compound used together with the thietanyl compound of the present invention is preferably the above compound having one or more thietanyl group in one molecule.

When another polymerization-reactive compound is used, the total amount of the thietanyl compound of the present invention and the other polymerization-reactive compound is 100% by weight, and the thietanyl compound of the present invention is 99 to 1% by weight, preferably 50 to 2% by weight. %, more preferably 20 to 2% by weight, and 1 to 99% by weight of other polymerization-reactive compounds, preferably 50 to 98% by weight, more preferably 80 to 98% by weight.

The above-mentioned polymerizable composition includes, for example, an infrared absorber, a radical scavenger, an antioxidant, a polymerization inhibitor, a dye, a binder in addition to the polymerization-reactive compound other than the compound represented by the general formula (1). , Various additives such as a dispersant, a leveling agent and a solvent may be contained.
The polymerizable composition of the present invention can be obtained by mixing the above components by a conventionally known method.

[Molded body]
By applying heat or radiation to the polymerizable composition of the present invention to polymerize and cure the polymerizable composition, the molded product of the present invention and an optical material such as a plastic lens made of the molded product can be obtained. When curing by heat, it is preferable to add a catalyst or a thermal polymerization initiator. When curing by radiation, for example, ultraviolet rays, it is preferable to add a catalyst or a photopolymerization initiator.

The catalyst used for the above purpose, for example, boron compounds such as boron trifluoride diethyl ether complex, dimethyltin dichloride, dibutyltin dichloride, dioctyltin dichloride, dibutyltin dilaurate, tin compounds such as dioctyltin dilaurate, 1, Tertiary and quaternary amine compounds such as 8-diazabicyclo[5.4.0]undec-7-ene, tributylamine, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraphenylammonium chloride, tetraphenylammonium bromide, tributyl Phosphine, triphenylphosphine, tetrabutylphosphine chloride, tetrabutylphosphine bromide, tetraphenylphosphine chloride, tetraphenylphosphine bromide and other phosphorus compounds, bis(3,5-di-t-butylsalicylidene)-1,2- Complex of diaminobenzene and chromium chloride, bis(3,5-di-t-butylsalicylidene)-1,2-diaminoethane and chromium chloride complex, bis(3,5-di-t-butylsalicylidene) )-1,2-diaminobenzene and chromium bromide complex, metal complex compounds such as bis(3,5-di-t-butylsalicylidene)-1,2-diaminobenzene and chromium iodide complex,
Triethylamine, tributylamine, N,N-dimethylcyclohexylamine, N-methylpiperazine, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undecene- 7, tertiary amines such as triphenylphosphine, pyridine, N,N-dimethylaniline, N,N-dimethylbenzylamine, phosphines such as tributylphosphine and triphenylphosphine, sodium hydroxide, potassium hydroxide, sodium carbonate, Known basic compounds such as sodium hydrogen carbonate, calcium oxide, sodium methoxide, sodium, and inorganic bases such as sodium hydride can be used.

The addition amount of the above-mentioned catalyst is not particularly limited, but the catalyst is usually 0.001 to 20% by weight with respect to the thietanyl compound of the present invention, or the total of the thietanyl compound and other polymerization reactive compounds. %, preferably 0.01 to 10% by weight, and the polymerization initiator is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight.

The molded article of the present invention is obtained by heating the above-mentioned polymerizable composition or irradiating it with radiation such as ultraviolet rays. In order to prevent the resin obtained by polymerizing the polymerizable composition of the present invention from deteriorating even when exposed to the outside for a long period of time, the polymerizable composition of the present invention is further provided with an ultraviolet absorber and a hindered amine light stabilizer. It is desirable to use a polymerizable composition to which an agent is added.

The ultraviolet absorber is not particularly limited, and examples thereof include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, propanedioic acid ester-based ultraviolet absorbers, and oxanilide-based ultraviolet absorbers. Various ultraviolet absorbers such as an ultraviolet absorber can be used.

For example, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-tert-butylphenol, 2-(2H-benzotriazol-2-yl). -4,6-Di-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2) -Yl)-4-(1,1,3,3-tetramethylbutyl)-6-(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-( 3-on-4-oxa-dodecyl)-6-tert-butyl-phenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4-(3-on-4-oxa-dodecyl) -6-tert-Butyl-phenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4-methyl-6-tert-butyl-phenol, 2-(2H-benzotriazol-2-yl )-4,6-Di-tert-pentylphenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4,6-di-tert-butylphenol, 2-(2H-benzotriazole-2) -Yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl)-4-methyl 6-n-dodecylphenol, methyl-3-{3-(2H-benzotriazol-2-yl) Benzotriazole-based UV absorbers such as -5-tert-butyl-4-hydroxyphenyl}propionate/polyethylene glycol 300 reactive organisms; 2-(4-phenoxy-2-hydroxy-phenyl)-4,6-diphenyl- 1,3,5-triazine, 2-(2-hydroxy-4-oxa-hexadecyloxy)-4,6-di(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-( 2-Hydroxy-4-oxa-heptadecyloxy)-4,6-di(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-iso-octyloxy-phenyl)- 4,6-di(2,4-dimethyl-phenyl)-1,3,5-triazine, trade name Tinuvin 326 (manufactured by BASF), trade name Tinuvin 400 (manufactured by BASF), trade name Tinuvin 405 (manufactured by BASF), Product name TINUVIN 460 (manufactured by BASF), Product name TINUVIN 479 (manufactured by BASF) ) And other triazine-based UV absorbers; 2-hydroxy-4-n-octoxybenzophenone and other benzophenone-based UV absorbers; 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4. -Benzoate ultraviolet absorbers such as hydroxybenzoate; propanediocic acid-{(4-methoxyphenyl)-methylene}-dimethyl ester, trade name Hostabine PR-25 (manufactured by Clariant Japan KK), trade name Hostabine B- Propanedioic acid ester-based UV absorbers such as CAP (manufactured by Clariant Japan Co., Ltd.); 2-ethyl-2′-ethoxy-oxanilide, oxanilide-based UV absorbers such as trade name Sanduvor VSU (manufactured by Clariant Japan Co., Ltd.) Agents and the like.

The hindered amine light stabilizer (Hindered Amin Light Stabilizers: HALS) is a general term for compounds having a 2,2,6,6-tetramethylpiperidine skeleton, and depending on the molecular weight, low molecular weight HALS, medium molecular weight HALS, It is roughly classified into high molecular weight HALS and reactive HALS. As the hindered amine light stabilizer, for example, trade name Tinuvin 111FDL (manufactured by BASF), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name Tinuvin 123 (manufactured by BASF)). ), trade name TINUVIN 144 (manufactured by BASF), trade name TINUVIN 292 (manufactured by BASF), trade name TINUVIN 765 (manufactured by BASF), trade name TINUVIN 770 (manufactured by BASF), N,N′-bis(3-aminopropyl) Ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate (trade name CHIMASSORB119FL (manufactured by BASF), trade name CHIMASSORB2020FDL (manufactured by BASF), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate succinate (trade name CHIMASSORB622LD). (Manufactured by BASF), poly[{6-(1,1,3,3-tetramethyl-butyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -Tetramethyl-4-piperidyl)imino}hexamethylene {(2,2,6,6-tetramethyllauryl-4-piperidyl)imino}] (trade name CHIMASSORB944FD (manufactured by BASF)), trade name Sanduvor 3050 Liq. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3052 Liq. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3058 Liq. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3051 Powder. (Manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3070 Powder. (Made by Clariant Japan Co., Ltd.), trade name VP Sandover PR-31 (made by Clariant Japan Co., Ltd.), trade name Hostabin N20 (made by Clariant Japan Co., Ltd.), trade name Hostabin N24 (made by Clariant Japan Co., Ltd.) Product name Hostabin N30 (manufactured by Clariant Japan Co., Ltd.), Product name Hostabin N321 (manufactured by Clariant Japan Co., Ltd.), Product name Hostabin PR-31 (manufactured by Clariant Japan Co., Ltd.), Product name Hostabin 845 (Clariant Japan Co., Ltd.) Manufactured by K.K., product name Nairostab S-EED (made by Clariant Japan K.K.), and the like.

The amount of the ultraviolet absorber and the hindered amine-based light stabilizer added is not particularly limited, but with respect to the thietanyl compound of the present invention, or the total of the thietanyl compound and other polymerization reactive compounds, ultraviolet absorption The agent is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, and the hindered amine light stabilizer is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. It is a range.

Further, for the purpose of imparting light controllability, a light control dye may be added. As a typical photochromic dye, for example, one kind or two or more kinds can be used from spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, and bisimidazole compounds, depending on the desired coloring. ..

Examples of the spiropyran-based compound, indolinospyrobenzopyran indole ring and benzene ring halogen, methyl, ethyl, methylene, ethylene, each substituent substituted with a hydroxyl group, indolinospyronaphthopyran indole ring and Each substitution product in which the naphthalene ring is substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc., Each substitution in which the indole ring of indinospiroquinolinopyran is substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. And indolinospiropyridopyran indole ring substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group and the like.

Examples of the spirooxazine-based compound include indolinospirobenzoxazine substituted with an indole ring and a benzene ring, halogen, methyl, ethyl, methylene, ethylene, each substituted product substituted with a hydroxyl group, indolinospironaphthoxazine. Substitutes in which the indole ring and naphthalene ring are substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc., the indole ring of indinospirophenanthroxazine is halogen, methyl, ethyl, methylene, ethylene, hydroxyl group, etc. Each substituted with, each indole ring of indolinospyroquinolinoxazine is substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group and the like, piperidine ring and naphthalene ring of piperidinospironaphthoxazine Examples include substituents substituted with halogen, methyl, ethyl, methylene, ethylene, hydroxyl group and the like.

Examples of the fulgide-based compound include N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzo[b]thiophenedicarboximide-7,2′-tricyclo[3. 3.1.1 ^3,7 ]decane], N-cyanomethyl-6,7-dihydro-2-(p-methoxyphenyl)-4-methylspiro(5,6-benzo[b]thiophenedicarboximide-7, 2′-tricyclo[3.3.1.1 ^3,7 ]decane), 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl-2-phenylspiro(5,6-benzo[b]thiophenedi carboxyimide -7,2'- tricyclo [3.3.1.1 ^{3, 7]} decane), 6,7 dihydro-4-methyl-2-(p-methylphenyl) -N- nitro methyl spiro (5 , 6-benzo[b]thiophenedicarboximide-7,2'-tricyclo[3.3.1.1 ^3,7 ]decane), N-cyanomethyl-6,7-dihydro-4-cyclopropyl-3- methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 ^{3, 7]} decane), N- cyanomethyl-6,7-dihydro-4-cyclopropyl spiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 ^{3, 7]} decane), N- cyanomethyl-6,7-dihydro-2-(p - methoxyphenyl) -4-cyclopropyl spiro (5,6-benzo [b] thiophene-dicarboximide -7,2'- tricyclo [3.3.1.1 ^{3, 7]} decane), and the like.

Examples of the naphthopyran compound include spiro[norbornane-2,2'-[2H]benzo[h]chromene], spiro[bicyclo[3.3.1]nonane-9,2'-[2H]benzo[ h]chromene], 7'-methoxyspiro[bicyclo[3.3.1]nonane-9,2'-[2H]benzo[h]chromene], 7'-methoxyspiro[norbornane-2,2'-[2H ] Benzo[f]chromene], 2,2-dimethyl-7-octoxy[2H]benzo[h]chromene, spiro[2-bicyclo[3.3.1]nonene-9,2′-[2H]benzo[ h]chromene], spiro[2-bicyclo[3.3.1]nonene-9,2′-[2H]benzo[f]chromene], 6-morpholino-3,3-bis(3-fluoro-4-). Methoxyphenyl)-3H-benzo(f)chromene, 5-isopropyl-2,2-diphenyl-2H-benzo(h)chromene, and the like.

The addition amount of these light control dyes is not particularly limited, but is about 0.01 to 10000 ppm (based on the thietanyl compound of the present invention or on the total of the thietanyl compound and other polymerization reactive compounds. Weight), preferably 0.1 to 1000 ppm (weight), more preferably 1 to 100 ppm (weight).

The polymerizable composition of the present invention containing the compound represented by the general formula (1) can be polymerized by heating or irradiation with radiation to form a resin. At this time, polymerization is performed in a molding mold (cavity) formed from a glass plate and a tape or gasket, and the cured resin is formed by a cast polymerization method in which the glass plate and the tape or gasket are peeled off after completion of the polymerization. Optical materials such as molded bodies and plastic lenses can be obtained.

An internal release agent may be used, if necessary, for the purpose of improving the releasability of the molded product and a glass plate such as a plastic lens. Examples of the internal mold release agent that is preferably used include phosphoric acid esters, and examples thereof include dibutyl phosphoric acid, dioctyl phosphoric acid, monobutoxyphosphoric acid, dibutoxyphosphoric acid, and monomethyl mono-3,6,9-trioxaundec-1-ylphosphoric acid. Acid, monomethyl mono-3,6,9-trioxaundec-1-yl sodium phosphate, monoethyl mono(14-hydroxy-3,6,9,12-tetraoxatetradec-1-yl)phosphoric acid, Mono(14-hydroxy-3,6,9,12-tetraoxatetradec-1-yl)monooctyl phosphate, monoethyl mono-3,6,9-trioxaphenicosa-1-yl phosphate, mono Butyl mono-3,6,9,12,15,18,21-heptaoxatetratriacomto-1-yl phosphate, monobutyl mono-3,6,9,12,15,18,21-heptaoxatetratria Conto-1-ylphosphate, monomethylmono(23-(nonylphenoxy)-3,6,9,12,15,18,21-heptaoxatricosa-1-yl)phosphate, monomethylmono(23-(nonyl Phenoxy)-3,6,9,12,15,18,21-heptaoxatricosa-1-yl) sodium phosphate, monomethylmono(29-(4-nonylphenoxy)-3,6,9,12, 15,18,21,24,27-Nonoxanonacosa-1-yl)phosphoric acid, monoethylmono(26-(isooctylphenoxy)-3,6,9,12,15,18,21,24- Octaoxahexacos-1-yl)phosphoric acid, monohexadecylmono(14-hydroxy-3,6,9,12-tetraoxatetradec-1-yl)phosphoric acid, monododecylmono(17-hydroxy-1) , 4,7,10-Tetramethyl-3,6,9,12,15-pentaoxaheptadec-1-yl)phosphoric acid and the like.

The addition amount of the internal mold release agent is not particularly limited, but is usually 0.0001 to 10 weight with respect to the thietanyl compound of the present invention or the total of the thietanyl compound and the other polymerization reactive compound. %, preferably 0.001 to 5% by weight, more preferably 0.01 to 3% by weight.

When producing a molded article and a plastic lens by cast polymerization by heating or irradiating the polymerizable composition of the present invention, if a large amount of residual solvent and water remain in the composition, during injection and polymerization curing. Since bubbles are likely to be generated and the bubbles are finally fixed (solidified) inside the molded body, it is preferable that the composition containing the polymerization-reactive compound does not contain solvent and water as much as possible. Therefore, the amount of the solvent and water contained in the polymerizable composition of the present invention immediately before injection into the cavity is preferably at least 20% by weight, more preferably 5% by weight or less, and further preferably 1% by weight or less. preferable.

When an optical material such as a molded product of the present invention or a plastic lens made of the molded product is produced by heating, heating is usually performed gradually from a low temperature for the purpose of preventing polymerization nonuniformity (stria) due to convection. Then, it is polymerized over several days. As a typical heating condition, for example, the temperature is gradually raised from a low temperature in the range of −25 to 200° C. for 64 hours, the range of 5 to 150° C. is 40 hours, and the range of 20 to 120° C. is 16 times. Conditions such as time are mentioned. Alternatively, conditions such as holding at a constant temperature of 60 to 80° C. for 2 to 80 hours can be mentioned.

Similarly, in the case of polymerizing by radiation such as UV, in order to prevent polymerization nonuniformity (stria) due to convection, the irradiation of radiation is usually divided and the illuminance is lowered to gradually polymerize. To be In order to prevent more convection, a uniform polymerizable reaction composition is injected into the cavity and then cooled once to form a state in which convection is hard to occur, and then weak radiation is applied to form a uniform gel state. In some cases, a dual cure method in which the formed semi-cured composition is completely cured by heating is used.

When the resin of the present invention, a molded product made of the resin, and an optical material such as a plastic lens are produced by radiation, energy rays having a wavelength range of 0.0001 to 800 nm are usually used as radiation. The radiation is classified into α-rays, β-rays, γ-rays, X-rays, electron beams, ultraviolet rays, visible light, etc., and can be appropriately selected and used according to the composition of the mixture. Among these radiations, ultraviolet rays are preferable, and the output peak of ultraviolet rays is preferably in the range of 200 to 450 nm, more preferably in the range of 230 to 445 nm, further preferably in the range of 240 to 430 nm, and particularly preferably in the range of 250 to 400 nm. .. When ultraviolet rays in the above output peak range are used, there are few problems such as yellowing and thermal deformation during polymerization, and the polymerization can be completed in a relatively short time even when an ultraviolet absorber is added.

In the present invention, molded products of various shapes can be obtained by changing the molding mold during polymerization. The molded product of the present invention can be used as various optical materials by forming it into a desired shape and including a coat layer and other members that are laminated as necessary.

The resin obtained from the polymerizable composition of the present invention and the molded product made of the resin have a higher refractive index than the episulfide resin, and can be suitably used for optical materials. Examples of the optical material include a plastic lens, a light emitting diode (LED), a prism, an optical fiber, an information recording substrate, a filter and a light emitting diode. In particular, it is suitable as a plastic lens.

The resin of the present invention thus obtained, a molded article made of the resin, and an optical material such as a plastic lens have a hard coat, an antireflection coat, an antifogging coat, an antifouling coat, a light control coat, and a sliding property on the surface thereof. Coat or slippery imparting treatment, functional coating layer such as antistatic coat, etc., dyeing treatment for imparting fashionability, surface and edge polishing treatment, etc. For the purpose of imparting it, the polarizing film may be put inside or attached to the surface, or processed to impart various functionalities.

Further, for the purpose of improving the adhesion between the functional coat layer and the substrate, the surface of the obtained resin of the present invention, the molded article made of the resin and the optical material such as a plastic lens is subjected to corona treatment, ozone. Physical or chemical treatment such as treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment with chemicals, flame treatment and the like can also be performed.

Further, instead of or in addition to these treatments, the resin of the present invention, the surface of the optical material such as a molded article and a plastic lens made of the resin, and the outermost layer formed by the above physical or chemical treatment ( A primer layer formed by a primer treatment, an undercoat treatment, an anchor coat treatment, or the like may be provided between the surface and the atmosphere contact surface).

Examples of the coating agent used for the primer layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth)acrylic resins, polyvinyl acetate resins, polyethylene and polypropylene. A coating agent containing a resin such as a polyolefin resin or a copolymer or modified resin thereof, or a cellulose resin as a main component of the vehicle can be used. The coating agent may be either a solvent type coating agent or an aqueous type coating agent.

Among these coating agents, modified polyolefin-based coating agents, ethyl vinyl alcohol-based coating agents, polyethyleneimine-based coating agents, polybutadiene-based coating agents, polyurethane-based coating agents, polyester-based polyurethane emulsion coating agents, polyvinyl chloride emulsion coating agents, retan Acrylic emulsion coating agent, silicone acrylic emulsion coating agent, vinyl acetate acrylic emulsion coating agent, acrylic emulsion coating agent;
Styrene-butadiene copolymer latex coating agent, acrylonitrile-butadiene copolymer latex coating agent, methyl methacrylate-butadiene copolymer latex coating agent, chloroprene latex coating agent, polybutadiene latex rubber-based latex coating agent, polyacrylic acid ester A latex coating agent, a polyvinylidene chloride latex coating agent, a polybutadiene latex coating agent, or a coating agent comprising a carboxylic acid-modified latex of a resin contained in these latex coating agents or a dispersion is preferable.

These coating agents can be applied by, for example, a dip coating method, a spin coating method, a spray coating method, etc., and the coating amount on the substrate is usually 0.005 g/m ^{2 to} 30 g in a dry state. / m ^2, preferably from ^{0.05g / m 2 ~10g / m 2} .

Among these coating agents, polyurethane coating agents are more preferable. The polyurethane type coating agent has a urethane bond in the main chain or side chain of the resin contained in the coating agent. The polyurethane coating agent is a coating agent containing polyurethane obtained by reacting a polyol such as polyester polyol, polyether polyol, or acrylic polyol with an isocyanate compound.

Among these polyurethane-based coating agents, polyurethane obtained by mixing a polyester polyol such as condensed polyester polyol and lactone-based polyester polyol with an isocyanate compound such as tolylene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate. A system coating agent is preferable because it has excellent adhesion.

The method of mixing the polyol compound and the isocyanate compound is not particularly limited. The compounding ratio is also not particularly limited, but when the isocyanate compound is too small, curing failure may occur, so that the OH group of the polyol compound and the NCO group of the isocyanate compound are in the range of 2/1 to 1/40 in equivalent. Preferably.
The resin of the present invention and a molded article made of the resin include molded articles, films and sheets.

The resin of the present invention and the molded product made of the resin may be applied to optical materials other than plastic lenses. Applications other than plastic lenses include, for example, light extraction materials such as LED sealing materials, and sheets and films manufactured using a flat mold in the same manner as plastic lenses. Sheets and films made of the resin of the present invention have their surfaces treated physically or chemically in the same manner as plastic lenses, or have a functional layer formed by the above-mentioned primer layer and physical or chemical treatment. The outermost layer (atmosphere contact surface) may be laminated.

The optical material such as a molded product and a plastic lens made of the resin of the present invention has the above-mentioned primer between the functional outermost layer (atmosphere contact surface) formed by the physical or chemical treatment and the surface of the cured resin. It may be a laminate including layers.

The molded product of the present invention thus obtained can be used for various lens applications such as a spectacle lens, a camera lens, a pickup lens, a Fresnel lens, a prism lens, and a lenticular lens. Among them, particularly preferable applications include plastic lenses such as eyeglass lenses, camera lenses, and pickup lenses.

Similarly obtained molded article, sheet, and film of the present invention are flat panel, display member such as smartphone panel, shatterproof film, specific wavelength cut film, film member such as decorative film, building material window glass, vehicle window. It can also be used for various flat member applications requiring transparency such as glass and glass substitute members.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. The cured resin and the plastic lens were evaluated by the following methods.
<Appearance (transparency)>
It was judged visually.
<Refractive index (ne), Abbe number (νe)>
It measured at 25 degreeC using Shimadzu digital precision refractometer KPR-30V.
<Heat resistance (glass transition temperature: Tg)>
It was measured by a TMA-60 thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (load of 50 g, pin tip 0.5 mmφ, heating rate 10° C./min).

[Example 1] Production of dithietanyl trithiocarbonate (DTT) In a reactor equipped with a stirrer and a thermometer, 190 g of thiourea, 253 g of 35% hydrochloric acid, and 250 g of water were charged, and the mixture was dropped while stirring. While charging 156 g of 3-thiethanol, the mixture was aged at 30° C. for 24 hours with stirring. Next, while maintaining the temperature at 30° C., 177 g of 24% ammonia water was added dropwise, and the mixture was aged at 30° C. for 15 hours while stirring. After standing still, 134 g of the lower layer which is an organic layer was taken out. The lower layer taken out was distilled under reduced pressure to collect a fraction at 40° C. at 106 Pa. The obtained fraction was 69 g and was 3-mercaptothietane.
To the obtained 3-mercaptothietane (42.3 g, 0.40 mol) was added and dissolved 470 ml of dichloromethane, and 44.4 g (0.44 mol) of triethylamine was added dropwise at an internal temperature of 5 to 15°C, and then thiophosgene. Similarly, 24.2 g (0.21 mol) was added dropwise in the range of 5 to 15°C, and the mixture was aged at 10°C for 3 hours. The obtained reaction solution was washed twice with 200 ml of water, then 200 ml of 5 wt% sodium hydrogen carbonate, and further 200 ml of water. 15 g of anhydrous magnesium sulfate was added to the separated lower organic layer, the mixture was stirred at room temperature for 2 hours, and the filtrate obtained by filtration was passed through a column filled with 150 cm3 of silica gel (WAKO GEL C-200). Further, 200 ml of dichloromethane was also passed. The liquid finally passed was concentrated by a rotary evaporator to obtain 47.3 g of the objective dithietanyl trithiocarbonate. The refractive index (D line 589 nm) of the obtained dithietanyl trithiocarbonate was 1.692, and the identification data ( ¹ H-NMR) is shown in FIG.

[Example 2] Production of dithietanyl dithiocarbonate (DTD) To 10.6 g (0.10 mol) of 3-mercaptothietane obtained in Example 1, 20 ml of dichloromethane and 5.44 g (0.018 mol) of triphosgene were added. The mixture was dissolved by mixing, and a mixed solution of 12.1 g (0.12 mol) of triethylamine and 40 ml of dichloromethane was added dropwise within an internal temperature range of 10 to 20°C, followed by aging at 10°C for 2 hours. The obtained reaction liquid was washed with 100 ml of water and 100 ml of 5 wt% sodium hydrogen carbonate, and further washed successively with 200 ml of water. Anhydrous magnesium sulfate was added to the separated lower organic layer, the mixture was stirred at room temperature for 1 hour, the filtrate obtained by filtration was concentrated with a rotary evaporator, and methanol was added to the obtained filter cake for sludging, The filter cake obtained by filtering again was dried under reduced pressure to obtain 7.5 g of the objective dithietanyl trithiocarbonate. Identification data ( ¹ H-NMR) is shown in FIG.

[Example 3] Production of plastic lens using DTT 0.5 g of dithietanyl trithiocarbonate obtained in Example 1, 3.0 g of dithietanyl tetrasulfide, 6.5 g of tetrakis(thietanylthio)tin, and dioctyl phosphorus 0.003 g of acid was mixed and dissolved at 65 to 70° C., and the filtrate obtained through a 3 μm Teflon filter was mixed and degassed under reduced pressure of <10 mmHg to obtain a uniform polymerizable composition.
The polymerizable composition thus obtained was poured into a cavity (curve shape: 2 curves for both concave and convex surfaces, center thickness: 1 mm) consisting of a glass mold and tape, sealed with tape, and placed in a polymerization oven at 65° C. for 3 hours. After the temperature was maintained, the temperature was raised to 110 over 11 hours, and the temperature was further maintained at 110° C. for 2 hours to polymerize and cure. After cooling, the glass mold and the tape were peeled off, and the molded body (plastic lens) made of the cured resin formed inside was taken out. The obtained plastic lens was transparent and had a refractive index Ne=1.80 and an Abbe number νe=25. The evaluation results are shown in Table-1.

[Example 4] Production of plastic lens using DTD The dithietanyl trithiocarbonate was changed to the dithietanyl dithiocarbonate obtained in Example 2 and the same test as in Example 3 was carried out. The evaluation results are shown in Table-1.

Example 5 Production of Plastic Lens Using DTD Dithietanyldithiocarbonate 2.0 g, tetrakis(thietanylthio)tin 8.0 g, and dibutylphosphoric acid 0.003 g were mixed and dissolved in a hot water bath at 80° C., Degassing was performed for 10 to 20 minutes under a reduced pressure of 10 mmHg to obtain a uniform polymerizable composition.
The polymerizable composition thus obtained was poured into a cavity (curve shape: 2 curves for both concave and convex surfaces, center thickness: 1 mm) consisting of a glass mold and tape, sealed with tape, and placed in a polymerization oven at 80° C. for 3 days. It was held and polymerized and cured to obtain a transparent plastic lens. The evaluation results are shown in Table-1.

[Comparative Example 1] Production of plastic lens using DTD The test was conducted in the same manner as in Example 5 without adding 2.0 g of dithietanyl dithiocarbonate, but the polymerizable composition was increased during dissolution and defoaming. It was viscous and could not be injected into a cavity composed of a glass mold and a tape (curve shape: both curved surfaces had 2 curves, central thickness: 1 mm).

The compounds listed in Table-1 are as follows.
DTT: dithietanyl trithiocarbonate DTD: dithietanyl dithiocarbonate TTS: dithietanyl tetrasulfide TMTS: tetrakis(thietanylthio) tin

Claims (7)

A thietanyl compound represented by the following general formula (1).

(X represents an oxygen atom or a sulfur atom) A polymerizable composition comprising the compound according to claim 1. Furthermore, a polythiol compound, a polyiso(thio)cyanate compound, a polyamine compound, a (meth)acrylate compound, an allyl carbonate compound, a (thio)epoxy compound, an oxetane compound, an alkoxysilane compound, an acid anhydride, and a compound represented by the general formula (1) The polymerizable composition according to claim 2, comprising at least one selected from thietane compounds other than the compound described above. A molded article obtained by curing the polymerizable composition according to claim 2 or 3. An optical material comprising the molded body according to claim 4. A plastic lens comprising the molded body according to claim 4. Reacting 3-thiethanol with a halogenating agent to prepare 3-halogenothiethane,
Reacting the 3-halogenothiethane with a thiating agent to prepare 3-mercaptothietane;
And a step of reacting the 3-mercaptothietane with a phosgene derivative or thiophosgene, the method for producing a thietanyl compound represented by the general formula (1).

(X represents an oxygen atom or a sulfur atom)

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