KR20170018305A - Novel thiol compound and polymerizable composition containing same - Google Patents

Abstract

The present invention relates to novel thiol compounds and polymerizable compositions comprising them. In the present invention, a thiol compound and a polymerizable composition containing the same are provided. The thiol compound and the polymerizable composition containing the thiol compound of the present invention are suitable for the production of urethane-based plastic materials satisfying both quality and economical efficiency, and are particularly suitable for the production of urethane-based plastic materials which require colorless transparency and high refractive index or heavy refraction.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel thiol compound and a polymerizable composition containing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to novel thiol compounds and polymerizable compositions comprising them.

The plastic optical material is lighter and easier to break than an optical material made of an inorganic material, and can be dyed. In recent years, plastic materials of various resins have been used in optical materials, and the required properties thereof are also increasing day by day.

In Korean Patent Nos. 10-0136698, 10-0051275, 10-0051939, 10-0056025, 10-0040546, 10-0113627, etc., urethane-based optical lenses are obtained by thermosetting a polyisocyanate compound and a polythiol compound. Compared with other optical materials, urethane-based optical materials have excellent optical properties such as moldability, transparency, abbe number, heat resistance, light resistance, weather resistance, transmittance and tensile strength, and are excellent in coating and processability. However, urethane-based optical materials have a higher production cost than other plastic optical materials and are mainly used for high-priced high-refractive-index lenses.

Particularly, 2,3-bis (2-mercaptoethylthio) -3-propane-1-thiol (GST), 2- (2-mercaptoethylthio) Thiol compounds such as dithiol (GMT) and pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) are expensive and cause a rise in the production cost of optical materials. Such a thiol compound is also preferably used as an isocyanate compound, such as 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanatomethyl ) Tricyclo [5,2,1,02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,9- NATO methyl) tricyclo [5,2,1,02,6] decane, 2,5-bis (isocyanato methyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl- ) Bicyclo [2,2,1] heptane or the like can be used to form a polymerizable composition, a high-quality optical material can be obtained without any problem, but isocyanate compounds such as isophorone diisocyanate, dicyclohexylmethane- diisocyanate (H ₁₂ MDI), the low quality, such as 1,6-hexamethylene off during polymerization reactivity when using an isocyanate compound such as isocyanate for inexpensive multipurpose striae, birch, microbubbles This phenomenon often occurs.

The reduction of production cost with the improvement of the quality of the lens is a major concern in the recent lens field. From this point of view, a new thiol compound which can be used for a transparent plastic material having a high refractive index such as an optical material is one of the continuously required tasks in this field.

Korean Patent Publication No. 10-0136698 Korean Patent Publication No. 10-0051275 Korean Patent Publication No. 10-0051939 Korean Patent Publication No. 10-0056025 Korean Patent Publication No. 10-0040546

The present invention aims to provide a novel thiol compound, a polymerizable composition containing the novel thiol compound, and a method for producing the same, which can be used instead of conventional thiol compounds in urethane optical materials.

In the present invention,

A thiol compound represented by the following formula (1) is provided.

[Chemical Formula 1]

Further, in the present invention,

There is provided a process for preparing a thiol compound represented by the above formula (1), comprising the step of introducing malic acid and 2-mercaptoethanol into a reactor and performing an esterification reaction under elevated temperature and reduced pressure.

Further, in the present invention,

There is provided a polymerizable composition comprising a thiol compound represented by the above formula (1).

Further, in the present invention,

A plastic material obtained by polymerizing the polymerizable composition and an optical lens made of the plastic material are provided. The optical lens particularly includes a spectacle lens.

The thiol compound of the present invention can be used instead of a conventional thiol compound in an urethane-based optical material or the like. By using the thiol compound of the present invention, it is possible to obtain a plastic material which is clear and transparent, has high initial heat distortion temperature and excellent heat resistance, and in particular, has a medium refractive index and high refractive index, which satisfy both quality and economical efficiency. Particularly, the polymerizable composition containing the thiol compound of the present invention can obtain a urethane-based optical material having a high colorless transparency with high yield even if a general-purpose isocyanate compound having low reactivity with an isocyanate compound is used, .

The thiol compound of the present invention is represented by the following formula (1).

[Chemical Formula 1]

The thiol compound of the present invention can be prepared according to the preferred embodiment by the method shown in the following reaction formula (1).

According to a preferred embodiment,

In the reactor, malic acid, 2-mercaptoethanol, toluene, and p-toluenesulfonic acid were added and esterification reaction was carried out under elevated temperature and reduced pressure to give bis (2-mercaptoethyl) -2- Bis (2-mercaptoethyl) -2-hydroxysuccinate.

The final product thus obtained contains, in addition to bis (2-mercaptoethyl) -2-hydroxysuccinate, a monoclonal product of the main product, a polynuclear species represented by the following formula (2) . Polynuclear species (Formula 2) can be prepared by a method in which some thioesterification reaction occurs in the esterification reaction when bis (2-mercaptoethyl) -2-hydroxysuccinate is prepared It is the side products that are produced.

[Reaction Scheme 1]

(2)

(A, B, C, D is H or OH, X, Y is O or S, and m is an integer of 1 to 10.)

The polymerizable composition of the present invention includes the thiol compound represented by the above formula (1). This thiol compound makes it possible to obtain plastic materials which are clear and transparent, have high heat distortion temperature and excellent heat resistance. The thiol compound is particularly excellent in compatibility with a general-purpose isocyanate compound having a low reactivity, so that a colorless transparent urethane-based optical material can be obtained even if a general-purpose isocyanate compound is used in the polymerizable composition. The polymerizable composition of the present invention may further contain a thiol compound other than the thiol compound represented by the general formula (1). The other thiol compound is not particularly limited, and a compound having two or more thiol groups in one molecule may be used. For example, the other thiol compound is a compound represented by the above formula (2); 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane; 2,3-bis (2-mercaptoethylthio) -3-propane-1-thiol; 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Bis (2-mercaptoethyl) sulfide; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; Bis (2,3-dimercaptopropanel) sulfide; Bis (2,3-dimercaptopropanel) disulfide; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) ethane; Bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide; 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio-propane-1-thiol; 2,2-bis- (3-mercapto-propionyloxymethyl) -butyl ester; Ethylthio) propane-1-thiol (2-mercaptoethylthio) -3- (2- (2- [ ; (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12-tetrathiatetradecane-1,14-dithiol; (S) -3 - ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol; (S) -3 - ((R-3- (4-methylpiperazin-1-yl) Mercapto-2 - ((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2 - ((2-mercaptoethyl) thio) propane-1-thiol; 3,3'-dithiobis (propane-l, 2-dithiol); (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentaterehexane-1,17-dithiol; (7R, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13,16-hexatiaoctadecane-1,18-dithiol; 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane; 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane; 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane; Pentaerythritol tetrakis (3-mercaptopropionate); Trimethylolpropane tris (3-mercaptopropionate); Pentaerythritol tetrakis (2-mercaptoacetate); Bispentaerythritol-ether-hexakis (3-mercaptopropionate); 1,1,3,3-tetrakis (mercaptomethylthio) propane; 1,1,2,2-tetrakis (mercaptomethylthio) ethane; Dithiane selected from the group consisting of 4,6-bis (mercaptomethylthio) -1,3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) Or two or more compounds. Preferably, the thiol compound is 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane; 1,2-bis (2- (2-mercaptoethylthio) -3-mercaptopropylthio) -ethane; Bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide; 2- (2-mercaptoethylthio) -3-2-mercapto-3- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] propylthio-propane-1-thiol; 2,2'-thiodiethanethiol; 4,14-bis (mercaptomethyl) -3,6,9,12,15-pentatiahectadecane-1,17-dithiol; 2- (2-mercaptoethylthio) -propoxy] -phenyl} -1-methylethyl (2-mercaptoethylthio) -3- [4- ) -Phenoxy] -propane-1-thiol; Pentaerythritol tetrakis (3-methapropropionate); Pentaerythritol methaptoacetate; Trimethiolpropane trismeptopropionate; Glycerol trimepctpropionate; Dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate and dipentaerythritol hexamethacrylate.

The polymerizable composition of the present invention may further comprise an isocyanate compound. The isocyanate compound is preferably a general-purpose isocyanate compound which is supplied at low cost. For example, the isocyanate compound can be 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane (NBDI); Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate (H ₁₂ MDI); Hexamethylene diisocyanate; Methylcyclohexane diisocyanate; Tolylene diisocyanate; Phenylenediisocyanate; 1,3,5-tris (6-isocyanato-hexyl) - [1,3,5] -triazanan-2,4,6-trione (HDI trimer); one or more isocyanates selected from the group consisting of o, m, p-xylylene diisocyanate and tetramethyl xylylene diisocyanate (TMXDI) may be used singly or in combination.

However, the isocyanate compound usable in the polymerizable composition of the present invention is not limited to the general-purpose isocyanate compound as described above, and any compound having at least one isocyanate and / or iso (thio) cyanate group can be used. That is, instead of the general-purpose isocyanate compound, one or more iso (thio) cyanate compounds together with the general-purpose isocyanate compound may be included. For example, such other iso (thio) cyanate compounds include 2,2-dimethylpentane diisocyanate; 2,2,4-trimethylhexane diisocyanate; Butane diisocyanate; 1,3-butadiene-1,4-diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 1,6,11-undecatriisocyanate; 1,3,6-hexamethylene triisocyanate; 1,8-diisocyanate-4-isocyanatomethyloctane; Bis (isocyanatoethyl) carbonate; An aliphatic isocyanate compound containing bis (isocyanatoethyl) ether,

1,2-bis (isocyanatomethyl) cyclohexane; 1,3-bis (isocyanatomethyl) cyclohexane; 1,4-bis (isocyanatomethyl) cyclohexane; Cyclohexane diisocyanate; Methylcyclohexane diisocyanate; Dicyclohexyldimethylmethane isocyanate; An alicyclic isocyanate compound containing 2,2-dimethyldicyclohexylmethane isocyanate,

Bis (isocyanatobutyl) benzene; Bis (isocyanatomethyl) naphthalene; Bis (isocyanatomethyl) diphenyl ether; Phenylenediisocyanate; Ethylphenylenediisocyanate; Isopropylphenylenediisocyanate; Dimethylphenylenediisocyanate; Diethylphenylenediisocyanate; Diisopropylphenylenediisocyanate; Trimethylbenzene triisocyanate; Benzene triisocyanate; Biphenyl diisocyanate; Toluidine diisocyanate; 4,4-diphenylmethane diisocyanate; 3,3-dimethyldiphenylmethane-4,4-diisocyanate; 4-diisocyanate; Bis (isocyanatophenyl) ethylene; 3,3-dimethoxybiphenyl-4,4-diisocyanate; Hexahydrobenzene diisocyanate; An aromatic isocyanate compound containing hexahydrodiphenylmethane-4,4-diisocyanate,

Bis (isocyanatoethyl) sulfide; Bis (isocyanatopropyl) sulfide; Bis (isocyanatohexyl) sulfide; Bis (isocyanatomethyl) sulfone; Bis (isocyanatomethyl) disulfide; Bis (isocyanatopropyl) disulfide; Bis (isocyanatomethylthio) methane; Bis (isocyanatoethylthio) methane; Bis (isocyanatoethylthio) ethane; Bis (isocyanatomethylthio) ethane; A sulfur-containing aliphatic isocyanate compound containing 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane,

Diphenyl sulfide-2,4-diisocyanate; Diphenylsulfide-4, 4-diisocyanate; 3,3-dimethoxy-4, 4-diisocyanatodibenzyl thioether; Bis (4-isocyanatomethylbenzene) sulfide; 4,4-methoxybenzenethioethylene glycol-3, 3-diisocyanate; Diphenyl disulfide-4, 4-diisocyanate; 2,2-dimethyl diphenyldisulfide-5,5-diisocyanate; 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate; 3,3-dimethyl diphenyldisulfide-6,6-diisocyanate; 4,4-dimethyl diphenyldisulfide-5,5-diisocyanate; 3,3-dimethoxy diphenyl disulfide-4, 4-diisocyanate; A sulfur aromatic isocyanate compound including 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate, and

2,5-diisocyanatothiophene; 2,5-bis (isocyanatomethyl) thiophene; 2,5-diisocyanato tetrahydrothiophene; 2,5-bis (isocyanatomethyl) tetrahydrothiophene; 3,4-bis (isocyanatomethyl) tetrahydrothiophene; 2,5-diisocyanato-1,4-dithiane; 2,5-bis (isocyanatomethyl) -1,4-dithiane; 4,5-diisocyanato-1,3-dithiolane; 4,5-bis (isocyanatomethyl) -1,3-dithiolane; A sulfated heterocyclic isocyanate compound comprising 4,5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane

(Thio) cyanate compound selected from the group consisting of an isocyanate compound and an isocyanate compound.

The polymerizable composition of the present invention may be composed of a thiephene clock polymerizable composition by further containing a thioepoxy compound. The thioepoxy compound is not particularly limited. The thioepoxy compound is, for example, bis (2,3-epithiopropyl) sulfide; Bis (2,3-epithiopropyl) disulfide; 2,3-epithiopropyl (2,3-epithiopropyl) disulfide; 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide; 1,3 and 1,4-bis (? - epithiopropylthio) cyclohexane; 1,3 and 1,4-bis (? - epithiopropylthiomethyl) cyclohexane; Bis [4- (beta -epithiopropylthio) cyclohexyl] methane; 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane; Episulfide compounds having an alicyclic skeleton such as bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene; Bis [4- (beta -epithiopropylthio) phenyl] methane; 2,2-bis [4- (β-epithiopropylthio) phenyl] propane; Bis [4- (beta -epithiopropylthio) phenyl] sulfide; Bis [4- (beta -epithiopropylthio) phenyl] sulfine; An episulfide compound having an aromatic skeleton such as 4,4-bis (β-epithiopropylthio) biphenyl, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane; 2,5-bis (? - epithiopropylthioethylthiomethyl) -1,4-dithiane; 2,5-bis (? - epithiopropylthioethyl) -1,4-dithiane; An episulfide compound having a dithiane chain skeleton such as 2,3,5-tri (β-epithiopropylthioethyl) -1,4-dithiane, an episulfide compound having a dithiane chain skeleton such as 2- (2-β-epithiopropylthioethylthio) -1,3-bis (? - epithiopropylthio) propane; 1,2-bis [(2 -? - epithiopropylthioethyl) thio] -3- (? - epithiopropylthio) propane; Tetrakis ([beta] -epithiopropylthiomethyl) methane; 1,1,1-tris (beta -epithiopropylthiomethyl) propane; And an episulfide compound having an aliphatic skeleton such as bis- (beta -epithiopropyl) sulfide. As the thioepoxy compound, there can also be used a chlorine substituent of a compound having an episulfide group, a halogen substituent such as a bromine substituent, an alkyl substituent, an alkoxy substituent, or a prepolymer type modified form with a nitro substituent or a polythiol.

The polymerizable composition of the present invention is a polymerizable composition comprising, as a main component, a compound such as an isocyanate compound capable of undergoing a polymerization reaction with the thiol compound of the present invention. The polymerizable composition may contain an internal mold release agent, ultraviolet absorber, polymerization initiator, , A bluing agent, and the like.

The inner mold release agent may preferably include a phosphoric acid ester compound. Phosphoric esters are prepared by adding 2 to 3 moles of alcohol compound to phosphorus pentoxide (P ₂ O ₅ ). Depending on the type of alcohol used, various types of phosphoric acid ester compounds may be present. Representative examples are those in which ethylene oxide or propylene oxide is added to an aliphatic alcohol, or ethylene oxide or propylene oxide is added to a nonylphenol group or the like. When a phosphoric acid ester compound to which ethylene oxide or propylene oxide is added is included in the composition of the present invention as an internal mold release agent, an optical material having good releasability and excellent quality can be obtained.

The ultraviolet absorber may be included in the polymerizable composition of the present invention for improving the light resistance of the optical material and ultraviolet blocking. As the ultraviolet absorber, known ultraviolet absorbers may be used without limitation. Ethyl-2-cyano-3, 3-diphenylacrylate; 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-butylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-4-octyloxybenzophenone; 4-dodecyloxy-2-hydroxybenzophenone; 4-benzooxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and the like, or a mixture of two or more thereof. More preferably, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -methanone having a good ultraviolet ray absorbing ability in a wavelength range of 400 nm or less and having good solubility in the composition of the present invention 5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole and the like. When such an ultraviolet absorber is used in an amount of 0.6 g or more per 100 g of the optical resin composition, blocking of 400 nm or more is possible.

The polymerization initiator may be an amine-based or tin-based compound. As the tin compound, butyl tin dilaurate; Dibutyl tin dichloride; Dibutyl tin diacetate; Stannous octoate; Dibutyl tin dilaurate; Tetrafluoro-tin; Tetrachlorotin; Tetrabromoquite; Tetraiodide tin; Methyl tin trichloride; Butyltin trichloride; Dimethyl tin dichloride; Dibutyltin dichloride; Trimethyltin chloride; Tributyltin chloride; triphenyltin chloride; Dibutyltin sulfide; Di (2-ethyl sec-butyl) tin oxide, etc. may be used alone or in combination of two or more.

The optical material of the present invention can be produced, for example, by injecting a polymerizable composition comprising a thiol compound of the present invention and an isocyanate compound, and optionally selected optional components into a mold for a lens and curing. Further, it is also possible to further polymerize the epoxy compound, the thioepoxy compound, the compound having a vinyl group or an unsaturated group, the metal compound and the like which can be copolymerized with the urethane resin composition. The urethane-based optical material produced in the present invention, for example, a urethane-based lens, is produced by casting polymerization. Specifically, various additives and a catalyst are dissolved in an isocyanate compound, a thiol compound is added, and a vacuum degassing is carried out while cooling. After a suitable period of time, it is poured into a glass mold molded with a tape, and cured by gradually heating at a low temperature and a high temperature for about 24 to 48 hours.

The urethane-based optical material produced by the present invention has low refractive index, low dispersion, excellent heat resistance, durability, light weight, excellent impact resistance, and good color. Therefore, it is suitable for the use of the urethane-based optical lens or prism according to the present invention, and is particularly suitable for lenses such as spectacle lenses and camera lenses.

 The urethane-based optical material of the present invention has very little tape whitening and bubbles, and can be produced at a good yield. The optical material of the present invention can be used for surface polishing, antistatic treatment, hard coat treatment, surface hardening treatment or the like for the purpose of improving antireflection, hardness impartation, abrasion resistance improvement, chemical resistance improvement, antifouling property, It is possible to perform physical and chemical treatments such as an anti-reflection coat treatment, a dyeing treatment, and a dimming treatment.

Hereinafter, the present invention will be described in detail with reference to specific examples. However, these embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

Assessment Methods

Refractive indices (nd and nE) and Abbe numbers: Measured at 20 캜 using an Abbe refractometer, model of IT and DR-M4 from Atago.

Initial heat distortion temperature (Tg): TMA was measured under a high purity nitrogen at a temperature of 5 ° C / min with a load of 0.5N, a tip of 0.5 mm Φ and a tip temperature of 5 ° C / min using a penetration probe of TMAQ400 (TA instruments).

Synthesis Example 1

BMHS1 (Bis (2-mercaptoethyl) -2-hydroxysuccinate)) (bis (2-mercaptoethyl)

A Dean-stark apparatus equipped with a thermostatable 1 L reactor was charged with malic acid (134.09 g, 1.00 mol), 2-mercaptoethanol (156.26 g, 2.00 mol), toluene 130 g, p-toluenesulfonic acid (11.41 g, 0.06 mole) was added and the reaction was carried out for 7 hours while maintaining the internal temperature at 50 캜 under a reduced pressure of 100 torr while stirring. The water produced in the reaction was reacted while removing water using a Dean-stark apparatus. The reaction was terminated when the amount of the theoretical product produced was 36 g and the starting material, 2-mercaptoethanol, was eliminated on the HPLC. When the reaction was completed, the temperature of the reactor was lowered. When the temperature reached room temperature, the catalyst was slowly neutralized with 200 g of 5 wt% NaHCO ₃ (aq) to remove residual p-toluenesulfonic acid. (Pure) 100 g. The organic layer was separated by layer separation and concentrated under reduced pressure to obtain 203 g of a thiol compound. The yield was 80%, and the refractive index (nd, 20 캜) was 1.527.

Synthesis Example 2

BMHS2 (Bis (2-mercaptoethyl) -2-hydroxysuccinate)) (bis (2-mercaptoethyl)

A Dean-stark apparatus equipped with a thermostatable 1 L reactor was charged with malic acid (134.09 g, 1.00 mol), 2-mercaptoethanol (160.20 g, 2.05 mol), toluene 200 g, p- toluenesulfonic acid (11.41 g, 0.06 mole) was added and the reaction was carried out for 7 hours while maintaining the internal temperature at 50 캜 under a reduced pressure of 100 torr while stirring. The water produced in the reaction was reacted while removing from the reactants using a Dean-stark apparatus. The reaction was terminated when the amount of the theoretical value and the starting material, 2-mercaptoethanol, disappeared on the HPLC. When the reaction was completed, the temperature of the reactor was lowered. When the temperature reached room temperature, the catalyst was slowly neutralized with 200 g of 5 wt% NaHCO ₃ (aq) to remove residual p-toluenesulfonic acid. (Pure) 100 g. The organic layer was separated by layer separation and concentrated under reduced pressure to obtain 212 g of a thiol compound. The yield was 83%, and the refractive index (nd, 20 캜) was 1.527.

[Example]

The thiol compound, the isocyanate compound, and the additive prepared in the above Synthesis Example were mixed in the composition as shown in Table 1 and subjected to template polymerization to prepare a urethane optical lens, and the refractive index and the Abbe number were evaluated.

Example 1

53.37 g of the compound (BMHS1), 2,5 (6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI) prepared in the above Synthesis Example 1, 0.12 g of the release agent Gelek UN, 1.50 g of 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole as a polymerization initiator, 0.05 of dibutyl tin dichloride as a polymerization initiator, and 1-hydroxy-4-paridoluidane) anthraquinone ) And 10 ppm of perynone dye were placed in a mixing container equipped with a stirrer and replaced with nitrogen to remove air in the mixing container. This mixed solution was defoamed at 1 torr for 1 hour. Thereafter, filtration was performed with a 1 mu m PTFE filter, and the solution was injected into a glass mold fixed with a tape. The mold was placed in a polymerization oven, and the temperature was gradually elevated to 25 ° C to 130 ° C over 21 hours to polymerize. After completion of the polymerization, the mold was taken out of the oven. The release from the mold was good, and the obtained resin was annealed at 130 캜 for 4 hours. The physical properties of the obtained resin were 1.559 in refractive index (nE), Abbe number (? E) 44, and initial thermal deformation temperature (Tg) of 120 占 폚.

Examples 2 to 3

The compositions and optical lenses were prepared and evaluated in the same manner as in Example 1, except that the composition shown in Table 1 below was used. The results are shown in Table 1 below.

<Abbreviation>

BMHS : bis (2-mercaptoethyl) -2-hydroxysuccinate) (bis (2-mercaptoctoethyl)

PETMP: pentaerythritol tetra (3-mercaptopropionate) (pentaerythritol tetra (3-mercaptopropionate)

H ₁₂ MDI: dicyclohexyl methane-4,4'-diisocyanate (dicyclohexyl methane-4,4'-diisocyanate)

HDI: Hexamethylene diisocyanate

NBDI: 2,5 (6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (2,5 (6) -Bis (isocyanatomethyl) bicyclo [2.2.1] heptane)

HOPBT: 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole) 2- (2'-

HTAQ: 1-hydroxy-4- (p-toluidine) anthraquinone.

PRD: Perinone dye

As can be seen from the above Table 1, the plastic material obtained from the polymerizable composition containing the thiol compound of the present invention was clear and transparent in color, had high initial heat distortion temperature and excellent heat resistance. These results indicate that when the thiol compound of the present invention is used as the main component of the polymerizable composition for a urethane-based optical lens, an optical lens having excellent optical characteristics can be produced at a low cost. INDUSTRIAL APPLICABILITY The thiol compound of the present invention can be widely applied as a transparent plastic material having a refractive index including an inexpensive urethane-based optical lens.

The thiol compound and the polymerizable composition containing the thiol compound of the present invention are suitable for the production of urethane-based plastic materials satisfying both quality and economical efficiency, and are particularly suitable for the production of urethane-based plastic materials which require colorless transparency and high refractive index or heavy refraction. More specifically, the present invention relates to various optical materials such as a spectacle lens, a polarizing lens, a camera lens, a prism, an optical fiber, a recording medium substrate used for an LCD, an optical disk, a magnetic disk, And a surface protective cover for an electronic product.

Claims (12)

A thiol compound represented by the following formula (1).
[Chemical Formula 1]

A process for producing a thiol compound represented by the following general formula (1), comprising the step of subjecting malic acid and 2-mercaptoethanol to a reaction in an esterification reaction under elevated temperature and reduced pressure.
[Chemical Formula 1]

A polymerizable composition comprising a thiol compound represented by the following formula (1).
[Chemical Formula 1]

The polymerizable composition according to claim 3, further comprising an isocyanate compound. 4. The polymerizable composition of claim 3, further comprising a thioepoxy compound. 5. The method of claim 4, wherein the isocyanate compound is selected from the group consisting of 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, isophorone diisocyanate, dicyclohexylmethane- Hexamethylene diisocyanate, methylcyclohexane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, 1,3,5-tris (6-isocyanatohexyl) - [1,3,5] , 6-trione, o, m, p-xylylene diisocyanate, and tetramethyl xylylene diisocyanate. The polymerizable composition according to any one of claims 3 to 5, further comprising a thiol compound other than the thiol compound represented by the formula (1). 8. The method according to claim 7,
A thiol compound represented by the following general formula (2) 3-propane-1-thiol, 2,2-bis (2-mercaptoethylthio) Mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane; (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Bis (2- (2-mercaptoethyl) thiophene) sulfide, bis (2,3-dimercaptopropanyl) disulfide, 1,2- Mercaptoethylthio) -3-mercaptopropylthio) ethane, bis (2- (2-mercaptoethylthio) -3-mercaptopropyl) sulfide, 2- (2-mercaptoethylthio) (3-mercaptoethylthio) propylthio] propylthio-propane-1-thiol, 2,2-bis- (3-mercaptoethylthio) Methyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) ) Propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12-tetrathiatetradecane- ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4 R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15-pentatihaheptane-1,17-dithiol, (S) -3- Thio) propyl) thio) -2 - ((2-mercaptoethyl) thio) propane-1-thiol, 3,3'- (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentaterehexane-1,17-dithiol, 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13,16-hexatiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11 -Dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,8-dimer Mercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate ), Pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate), 1,1, Tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) And 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane.
(2)

(A, B, C, D is H or OH, X, Y is O or S, and m is an integer of 1 to 10.) 6. The polymerizable composition according to any one of claims 3 to 5, further comprising an ultraviolet absorber. A plastic material obtained by polymerizing the polymerizable composition of any one of claims 3 to 5. An optical lens made of the plastic material of claim 10. The optical lens according to claim 11, wherein the optical lens is a spectacle lens.