WO2012112014A2 - Novel polythiol compound, preparation method therefor, and resin composition for urethane optical material using same - Google Patents
Novel polythiol compound, preparation method therefor, and resin composition for urethane optical material using same Download PDFInfo
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- WO2012112014A2 WO2012112014A2 PCT/KR2012/001276 KR2012001276W WO2012112014A2 WO 2012112014 A2 WO2012112014 A2 WO 2012112014A2 KR 2012001276 W KR2012001276 W KR 2012001276W WO 2012112014 A2 WO2012112014 A2 WO 2012112014A2
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- Prior art keywords
- bis
- diisocyanate
- isocyanatomethyl
- tris
- mercaptoethylthio
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
- C07C323/02—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/03—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- the present invention relates to a novel polythiol compound having usefulness for optical lens materials, a method for producing the same, and a resin composition for an optical material using the same, and particularly to a resin composition for a polythiourethane-based optical material having high refractive index and excellent heat resistance and reactivity. It is about.
- Urethane-based plastic optical lenses manufactured using mercapto compounds and isocyanates have been widely used as optical lens materials because of excellent optical properties, ie, transparency, Abbe number, and tensile strength.
- urethane-based plastic optical lenses have a low heat distortion temperature, which causes problems when the lens is hard and multi-coated (anti-reflective coating) on the surface of the lens after casting, causing deformation of the center of the lens. When exposed to heat, the thermal deformation of the lens is severe, causing a problem of severe cracking of the multi-film. This creates a cloudy film on the surface of the lens, which sharply degrades the transparency of the lens.
- urethane-based high refractive plastic optical lens manufactured as described above has a problem in that thermal deformation is severe when exposed to high temperature, so that the multi-film is easily cracked, and the lens center portion is deformed during hard and multi-coating on the lens surface.
- urethane-based ultrahigh refractive plastic optical lenses are manufactured by thermosetting xylylene diisocyanate and 2,3-bis (2-mercaptoethylthio) -propane-1-thiol.
- This lens has a high refractive index of 1.655, There is a problem in that the center portion of the lens is deformed during hard and multi-coating on the lens surface, and when the film is exposed to high temperature, the thermal deformation is severe and the multi-film easily breaks.
- Korean Patent Publication No. 1993-0006918 describes bis (isocyanatomethyl) triscyclo [5,2,1,02,6] decane and bis (isocyanato) in the production of urethane optical lenses.
- Thermosetting methyl) bicyclo [2,2,2] heptane compound and PETMP (pentaerythritol tetrakismercaptopropionate) or 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane To produce a urethane plastic optical lens.
- the urethane-based plastic optical lens thus prepared has a bis (isocyanatomethyl) triscyclo [5,2,1,02,6] decane, bis (isocyanatomethyl) bicyclo [2, 2,2] has a problem that is expensive to prepare heptane.
- a method of prepolymerizing a mercapto compound and an isocyanate compound to produce a resin composition for an optical material is disclosed in Korean Patent No. 10-0472837.
- the optical lens is manufactured by curing a compound having a dihydric alcohol added to a polyisocyanate and a polythiol compound, but the resin composition and optical lens for optical materials having a high Abbe number and high impact resistance It could not be manufactured.
- the resin for the optical material resin optical material introduced in this patent is difficult to inject, there is a problem that a large amount of polymerization failure occurs during curing of the resin composition.
- the manufactured lens has a refractive index of 1.545 to 1.556, which has a problem that the edge of the lens becomes thick due to its low refractive index.
- Korean Patent Registration Nos. 10-0237664 and 10-0241989 disclose that a component obtained by prepolymerizing a polythiol compound having a specific structure with a polyisocyanate compound comprises a component consisting of a (meth) acrylate compound and a compound copolymerizable with them. Polymerization curing with the composition provided an optical lens resin and an optical lens excellent in both physical properties and productivity of the lens.
- the prepolymer obtained by reacting the -SH / -NCO molar ratio of the resin composition for optical materials in the range of 3.0 to 7.0 can be blended with acrylic, but the viscosity is so high that it is directly blended with polyisocyanate, a urethane curing agent, and injected into the mold. Injecting is difficult, and there is a problem that a lot of polymerization failure occurs.
- the prepolymer having a -SH / -NCO molar ratio of 0.5 to 2.0 as disclosed in Japanese Patent Laid-Open No. 5-25240 has a higher viscosity and thus has the above problems in manufacturing a urethane-based optical lens.
- GST 2,3-bis (2-mercaptoethylthio) propane-1-thiol
- XDI xylylene diisocyanate
- the present inventors have developed a method of mixing isophorone diisocyanate or dicyclohexyl methane diisocyanate with 1,6-hexamethylene diisocyanate as a method of increasing the heat resistance of a lens while using a general-purpose isocyanate compound which is inexpensive. Has been elected.
- this method can achieve good heat resistance when the content of isophorone diisocyanate or dicyclohexyl methane diisocyanate in the isocyanate content is 40% by weight or more, in which case the reactivity with the mercapto compound decreases, resulting in high temperature.
- the present invention in order to solve the above problems, obtain a higher refractive index and increase the heat resistance, it is to provide a novel polythiol compound disulfide without using a thiol compound as it is.
- a higher refractive index can be obtained, and the heat resistance is increased to increase the viscosity, thereby reducing the solubility of the resin composition for optical materials, thereby solving the problem of tape whitening.
- R 1 and R 2 represent an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, a heterocyclic organic residue, an aromatic organic residue containing one or more sulfur atoms, an aliphatic organic residue containing one or more sulfur atoms, and one It is any one of the heterocyclic organic residue containing the above sulfur atom,
- x + y is an integer from 3 to 10
- n is an integer from 1 to 5.
- the resin composition for optical materials containing the polythiol compound of said Formula 1 is provided.
- the resin composition for an optical material of the present invention may further include an isocyanate compound or a thioisocyanate compound.
- the resin composition for an optical material of the present invention may further include other thiol compounds in addition to the polythiol compound of Formula 1.
- the resin composition for an optical material containing the polythiol compound of the present invention having disulfide had no problem of whitening or bubble generation during lens manufacture.
- the optical material resin obtained by hardening the said resin composition for optical materials and the optical product which consists of this optical material resin are provided.
- Optical products include spectacle lenses, 3D polarized lenses, polarized lenses, prismatic films, optical fibers, optical disks, magnetic disks, recording medium substrates, color filters, ultraviolet absorbing filters.
- the whitening phenomenon did not appear at the edges of the lens due to the adhesive elution of the adhesive tape by lowering the solubility and maintaining an appropriate viscosity. No bubble problems at the edges of the lens due to leakage.
- the polythiol compound having disulfide is used as a raw material for optical materials, and the optical material obtained by using the same can increase the refractive index, and has excellent heat resistance and reactivity, such as lenses of glasses, camera lenses, prisms, optical pipes, optical disks, It can be usefully used for optical products, such as recording medium engines, such as a magnetic disk, a coloring filter, and an infrared absorption filter.
- the novel polythiol compound provided by this invention has at least 1 or more disulfide, and is represented by following formula (1).
- R 1 and R 2 represent an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, a heterocyclic organic residue, an aromatic organic residue containing one or more sulfur atoms, an aliphatic organic residue containing one or more sulfur atoms, and one It is any one of the heterocyclic organic residue containing the above sulfur atom,
- x + y is an integer from 3 to 10
- n is an integer from 1 to 5.
- the polythiol compound of the present invention has at least one or more disulfide bonds formed in the reaction of the thiol compound and the oxidant, and is prepared by reacting the thiol compound and the oxidant.
- a halogen group compound, a radical catalyst, a peroxide such as sodium chlorite, etc. may be used, but is not limited thereto. More specific examples of the oxidizing agent may include oxygen, hydrogen peroxide, sodium hypochlorite, iodine, sulfyl chloride, iron (III) chloride, nitrogen oxide, and the like, but are not limited thereto.
- the amount of the chain extender to be used is preferably 0.05 to 1.5 moles with respect to the -SH molar ratio of the thiol compound, and preferably about 0.1 to 0.8 molar ratio.
- the use of less than 0.05 molar ratio did not help the problem of viscosity and tape whitening due to the small increase in viscosity and the equivalent, and the use of more than 1.5 molar ratio is too suitable for the resin composition for optical materials because the viscosity is too high to increase the molecular weight. Did not do it.
- thiol compound which may be used to prepare the polythiol compound of Chemical Formula 1, 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; Bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) disulfide; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,1,3,3-tetrakis (mercaptomethylthio) propane; 1,1,2,2-tetrakis (mercaptomethylthio) ethane; 4,6-bis (mercaptomethylthio) -1,3-dithiane; 2- (2,2-bis (mercaptomethylthio)
- thiol compounds that can be used include a thiol compound having an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, and a heterocyclic organic residue, including a halogen group and / or a hydroxy group or episulfide and thiethane. It may include.
- mercaptomethanol For example, mercaptomethanol; 2-mercaptoethanol; 1-chloro-3-mercapto-propan-2-ol; Thiethane-3-thiol; Oxylenyl methane thiol; Thylenyl methane thiol; 2-mercaptopropionic acid; 3-mercaptobutyric acid; 2-mercaptoisobutyric acid; 3-mercaptoisobutyric acid; Methanedithiol; 1,2-ethanedithiol; 1,1-propanedithiol, etc. can be used 1 or more types. However, it is not limited thereto.
- a resin composition for an optical material including the polythiol compound of Formula 1 is provided, and the resin composition for the optical material may further include an isocyanate compound or a thioisocyanate compound.
- the resin composition for an optical material of the present invention may further include other thiol compounds in addition to the polythiol compound of Formula 1.
- isocyanate compound or isothiocyanate compound examples include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4 -Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-iso Aliphatic polyisocyanate compounds such as cyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester and lysine triisocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diiso
- thiol compound which can be used in addition to the polythiol compound of Formula 1, 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 2,5-hexanedithiol; 1,6-hexanedithiol; 2,9-decanedithiol; 1,4-bis (1-mercaptoethyl) benzene; Cyclohexanedithiol; 1,2,3-propanethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercaptopropylmethyl ether; 2,3-dimercaptopropylmethyl ether; 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Bis (2-mercaptoethyl) ether; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethyl
- the resultant is purified using a purification method such as distillation under reduced pressure, washing, filtration, or the like, and more preferably, purified using high purity.
- a compound for controlling other reactions may be added, and as the compound to be added for this purpose, a compound such as a vinyl group, a compound having a thioepoxy group, an epoxy compound, thiethane, or the like may be used alone or in combination. Can be.
- the resin composition for optical materials of this invention may contain the additive for improving optical characteristics.
- Additives include in particular ultraviolet absorbers, stabilizers, internal mold release agents, color correctors (pigments, dyes), antioxidants, mold release agents and the like.
- any known ultraviolet absorbent surface usable for the optical lens can be used.
- any known ultraviolet absorbent surface usable for the optical lens can be used.
- 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole 2-hydroxy having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention.
- the stabilizer for improving the optical characteristic of the resin composition for optical materials in 0.01 to 5.00 weight% of all the compositions.
- the stabilizer is used at 0.01% by weight or less, the stability effect is weak, and when using at least 10.00% by weight, there is a problem in that the polymerization failure rate during curing is high and the stability of the cured product is lowered.
- calcium stearate which is a metal fatty acid salt type; Barium stearate; Zinc stearate; Cadmium stearate; Lead stearate; Magnesium stearate; Aluminum stearate; Potassium stearate;
- One or two or more of compounds such as zinc octoate can be used, and phosphorus-based triphenyl phosphite; Diphenyldecylphosphite; Phenyl didecyl phosphite; Diphenyldodecyl phosphite; Trinolylphenyl phosphite; Diphenylisooctylphosphite; Tributyl phosphite; Tripropyl phosphite; Triethyl phosphite; Trimethyl phosphite; Tris (monodecyl phosphite); One kind or two or more kinds of compounds such as
- a phosphorus stabilizer is used.
- the molded lens was able to greatly improve the stability of the optical lens without deteriorating the optical characteristics such as transparency, impact strength, heat resistance, and polymerization yield.
- Fluorine-type nonionic surfactant which has a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; Silicone nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt;
- the component selected from the acidic phosphate ester can be used individually or in combination of 2 or more types.
- acidic phosphate ester is used, and as acidic phosphate ester, isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof.
- ZELEC UN TM (Stepan), which is an acidic phosphate ester, was found to exhibit the best demolding when demolding the mold from the lens after curing.
- the internal mold release agent may be used in an amount of 0.0001 to 10% by weight based on the total weight of the reaction mixture. Preferably, 0.005 to 2% by weight of the mold release agent in the lens has a high polymerization yield. If the amount of the release agent is less than 0.005%, a phenomenon may occur in which the lens adheres to the surface of the glass mold when the molded optical lens is separated from the glass mold, and if more than 2% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that may cause stains on the surface.
- a hard coat coating may be provided on the outer surface of the cast resin to increase the wear resistance of the surface. Further, by inserting a primer layer between the surface of the resin and the hard coat film, the adhesion of the resin to the hard coat film can be improved.
- a completely cured and annealed resin is first coated with a primer solution, and then a conventional known method such as immersion method or spin-film method. And a hard coat agent according to the flow-coating method, the spraying method and other methods.
- an anti-reflection film can be installed on the surface of the cast resin to prevent surface reflection on the surface of the optical element, thereby increasing the transmittance of visible light.
- the resin composition for an optical material including the polythiol compound of the present invention having disulfide had no problem of whitening or bubble generation during lens manufacture.
- the optical material resin obtained by hardening the said resin composition for optical materials and the optical product which consists of this optical material resin are provided.
- Optical products include spectacle lenses, 3D polarized lenses, polarized lenses, prismatic films, optical fibers, optical disks, magnetic disks, recording medium substrates, colored filters, ultraviolet absorbing filters and the like.
- BDPS bis (2,3-dimercaptopropanyl) sulfide
- BDPSS bis (2,3-dimercaptopropanyl) disulfide
- optical lens obtained in (2) was processed to a diameter of 72 mm, ultrasonically washed with an alkaline aqueous washing solution, and then annealed at 120 ° C. for 2 hours.
- Refractive index It was measured using an Abbe refractometer of Atago Co., 1T and DR-M4 models.
- compositions and lens were prepared according to the composition described in Table 1 and the physical properties were tested in the same manner as in Example 1, and the results are shown in Table 1.
- IPDI isophorone diisocyanate
- PETMP pentaerythritol tetrakis (3-mercaptopropionate) (pentaerythritol-tetrakis (3-mercaptopropionate))
- GMTDS 2- (2-mercaptoethylthio-3- [3-mercapto-2- (2-mercaptoethylthio) -propyldithio) -propane-1-thiol (2- (2-mercaptoethylthio-3 Oligomeric Disulfide Polythiol Compounds of-[3-mercapto-2- (2-mercapto ethylthio) -propyldithio] propane-1-thiol)
- BDPSS 3- ⁇ 3- [3- (2,3-Dimercaptopropylthio) -2-mercaptopropylthio] -2-mercaptopropylthio ⁇ -propane-1,2-dithiol (3- ⁇ Oligomeric Disulfide Polythiol Compounds of 3- [3- (2,3-dimercaptopropylthio) -2-mercaptopropyldithio] -2-mercapto-propylthio ⁇ propane-1,2-dithiol)
- BDPSDS 3- ⁇ 2- [3- (2,3-dimercaptopropylthio) -2-mercaptopropyldithio] -3-mercaptopropyldithio ⁇ -propane-1,2-dithiol (3 Oligomeric Disulfide Polythiol Compounds of-(2- [3- (2,3-dimercaptopropyldithio) -2-mercaptopropyldithio] -3-mercapto-propyldithio ⁇ propane-1,2-dithiol)
- ZELEC UN An acidic phosphate ester compound manufactured by Stepan, trade name ZELEC UN TM
- HOPBT 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole
- the novel polythiol compound is used as a raw material of the optical material and the optical material obtained by using the same can increase the refractive index, and excellent in heat resistance and reactivity.
- the optical lens according to the present invention in particular, can be applied to the spectacle lens, and used in 3D polarized lenses equipped with a polarizing film on the spectacle lens, recording medium substrate, coloring used in prism, optical fiber, optical disk, magnetic disk, etc. in addition to the spectacle lens It can be usefully used as various optical products, such as a filter and an ultraviolet absorption filter.
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Abstract
The present invention relates to a novel polythiol compound having utility for optical lens material, a preparation method therefor, and a resin composition for an optical material using the novel polythiol. A resin composition for an optical material having the novel polythiol compound of the present invention has excellent heat resistance and reactivity while having high refractive index, and can thus be used for various optical products including lenses such as eyeglass lens and camera lens, prism, optical pipe, recording medium system such as optical disk and magnetic disk, colored filter, and infrared absorber filter.
Description
본 발명은 광학렌즈 재료에 유용성을 갖는 신규 폴리티올화합물과 그 제조 방법 및 이를 이용한 광학재료용 수지 조성물에 관한 것으로, 특히 굴절률이 높으면서도, 내열성 및 반응성이 우수한 폴리티오우레탄계 광학재료용 수지 조성물에 관한 것이다.The present invention relates to a novel polythiol compound having usefulness for optical lens materials, a method for producing the same, and a resin composition for an optical material using the same, and particularly to a resin composition for a polythiourethane-based optical material having high refractive index and excellent heat resistance and reactivity. It is about.
메르캅토화합물과 이소시아네이트를 사용하여 제조된 우레탄계 플라스틱 광학렌즈는 광학적 특성, 즉, 투명성, 아베수, 인장 강도 등이 우수하여 광학렌즈 소재로 널리 사용되고 있다. 그러나 우레탄계 플라스틱 광학렌즈는 열변형 온도가 낮아서, 캐스팅 후, 렌즈 표면에 하드 및 멀티코팅(반사방지막 코팅)을 할 경우 렌즈의 중심 변형이 발생하는 문제가 있고, 또 고온 다습한 지역이나 사우나 등의 열에 노출될 경우 렌즈의 열변형이 심하여 멀티막이 심하게 갈라지게 되는 문제가 된다. 이는 렌즈표면에 뿌연 막을 형성시켜서 렌즈의 투명도를 급격히 나빠지게 한다. Urethane-based plastic optical lenses manufactured using mercapto compounds and isocyanates have been widely used as optical lens materials because of excellent optical properties, ie, transparency, Abbe number, and tensile strength. However, urethane-based plastic optical lenses have a low heat distortion temperature, which causes problems when the lens is hard and multi-coated (anti-reflective coating) on the surface of the lens after casting, causing deformation of the center of the lens. When exposed to heat, the thermal deformation of the lens is severe, causing a problem of severe cracking of the multi-film. This creates a cloudy film on the surface of the lens, which sharply degrades the transparency of the lens.
한국 특허공고 특1987-0008928에서는 자일릴렌디이소시아네이트 0.05몰과 펜타에리트리톨테트라키스(메르캅토프로피오네이트) 0.025몰을 열경화시켜서 투명성, 아베수, 인장강도가 우수한 우레탄계 고굴절 플라스틱 광학렌즈를 제조하고 있다. 그러나 이렇게 제조된 우레탄계 고굴절 플라스틱 광학렌즈는 고온에 노출되었을 때 열변형이 심하여 멀티막이 쉽게 갈라지며, 또 렌즈 표면에 하드 및 멀티코팅시 렌즈 중심 부분이 변형되는 문제점이 있다. 한국 특허공고 특1992-0005708에서도 자일릴렌디이소시아네이트와 2,3-비스(2-메르캅토에틸티오)-프로판-1-티올을 열경화시켜 우레탄계 초고굴절 플라스틱 광학렌즈를 제조하고 있다. 이 렌즈는 굴절률ㅇ이 1.655로 높으나, 렌즈 표면에 하드 및 멀티코팅시 렌즈 중심 부분이 변형되는 문제점이 있고, 또 고온에 노출되었을 때 열변형이 심하여 멀티막이 쉽게 갈라지는 문제점이 있다.In Korea Patent Publication No. have. However, the urethane-based high refractive plastic optical lens manufactured as described above has a problem in that thermal deformation is severe when exposed to high temperature, so that the multi-film is easily cracked, and the lens center portion is deformed during hard and multi-coating on the lens surface. Also in Korean Patent Publication No. 1992-0005708, urethane-based ultrahigh refractive plastic optical lenses are manufactured by thermosetting xylylene diisocyanate and 2,3-bis (2-mercaptoethylthio) -propane-1-thiol. This lens has a high refractive index of 1.655, There is a problem in that the center portion of the lens is deformed during hard and multi-coating on the lens surface, and when the film is exposed to high temperature, the thermal deformation is severe and the multi-film easily breaks.
이러한 문제점을 해결하기 위하여, 한국 특허공고 특1993-0006918에서는 우레탄계 광학렌즈의 제조에 있어서, 비스(이소시아나토메틸)트리스시클로[5,2,1,02,6]데칸, 비스(이소시아나토메틸)비시클로[2,2,2]헵탄 화합물과 PETMP(펜타에리트리톨테트라키스메르캅토프로피오네이트) 혹은 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판을 열경화시켜서, 우레탄계 플라스틱 광학렌즈를 제조하고 있다. 이렇게 제조된 우레탄계 플라스틱 광학렌즈는 열변형 온도가 높아지기는 하였으나, 비스(이소시아나토메틸)트리스시클로[5,2,1,02,6]데칸, 비스(이소시아나토메틸)비시클로[2,2,2]헵탄을 제조하는데 많은 비용이 드는 문제점이 있다.In order to solve this problem, Korean Patent Publication No. 1993-0006918 describes bis (isocyanatomethyl) triscyclo [5,2,1,02,6] decane and bis (isocyanato) in the production of urethane optical lenses. Thermosetting methyl) bicyclo [2,2,2] heptane compound and PETMP (pentaerythritol tetrakismercaptopropionate) or 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane To produce a urethane plastic optical lens. The urethane-based plastic optical lens thus prepared has a bis (isocyanatomethyl) triscyclo [5,2,1,02,6] decane, bis (isocyanatomethyl) bicyclo [2, 2,2] has a problem that is expensive to prepare heptane.
또, 메르캅토 화합물과 이소시아네이트 화합물을 예비중합하여 광학재료용 수지 조성물을 제조하는 방법이 한국 특허 10-0472837에 소개되어 있다. 이 기술은 렌즈의 내충격성을 높이기 위하여 폴리이소시아네이트에 2가 알코올을 부가한 화합물과 폴리티올화합물을 경화시켜 안경렌즈를 제조하고 있으나, 아베수가 높고 내충격성이 좋은 광학재료용 수지 조성물 및 광학렌즈는 제조할 수 없었다. 또, 이 특허에서 소개한 광학재료용 수지광학재료용 수지 높아서 주입이 어렵고 수지조성물의 경화시 중합불량이 많이 발생하는 문제점이 있다. 또한, 제조한 렌즈는 굴절률이 1.545~1.556로 중굴절 안경렌즈로서 굴절률이 낮아 렌즈의 가장자리가 두꺼워지는 문제점이 있다. In addition, a method of prepolymerizing a mercapto compound and an isocyanate compound to produce a resin composition for an optical material is disclosed in Korean Patent No. 10-0472837. In order to increase the impact resistance of the lens, the optical lens is manufactured by curing a compound having a dihydric alcohol added to a polyisocyanate and a polythiol compound, but the resin composition and optical lens for optical materials having a high Abbe number and high impact resistance It could not be manufactured. In addition, the resin for the optical material resin optical material introduced in this patent is difficult to inject, there is a problem that a large amount of polymerization failure occurs during curing of the resin composition. In addition, the manufactured lens has a refractive index of 1.545 to 1.556, which has a problem that the edge of the lens becomes thick due to its low refractive index.
또한, 한국 특허등록 10-0237664와 10-0241989에서는 특정구조의 폴리티올화합물을 폴리이소시아네이트화합물로 예비중합화해서 얻어진 성분을, (메타)아크릴레이트화합물로 이루어진 성분 및 그들과 공중합이 가능한 화합물로 이루어진 조성물과 중합 경화하여 렌즈의 물성과 생산성이 모두 뛰어난 광학 렌즈용 수지 및 광학렌즈를 제공하였다. 그러나 이 광학재료용 수지 조성물의 -SH/-NCO몰 비가 3.0~7.0의 범위에서 반응시켜서 얻어진 프레폴리머는 아크릴과의 배합은 가능하나 점도가 너무 높아 우레탄 경화제인 폴리이소시아네이트와 직접 배합하여 몰드에 주입 시 주입이 어렵고, 또 중합불량이 많이 발생하는 문제점이 있다. 또한, 일본국 특개평 5-25240에서 제시한 -SH/-NCO몰비를 0.5~2.0로 한 프레폴리머는 점도가 더욱 높아 우레탄계 광학렌즈를 제조하기에는 상기와 같은 문제점이 있다.In addition, Korean Patent Registration Nos. 10-0237664 and 10-0241989 disclose that a component obtained by prepolymerizing a polythiol compound having a specific structure with a polyisocyanate compound comprises a component consisting of a (meth) acrylate compound and a compound copolymerizable with them. Polymerization curing with the composition provided an optical lens resin and an optical lens excellent in both physical properties and productivity of the lens. However, the prepolymer obtained by reacting the -SH / -NCO molar ratio of the resin composition for optical materials in the range of 3.0 to 7.0 can be blended with acrylic, but the viscosity is so high that it is directly blended with polyisocyanate, a urethane curing agent, and injected into the mold. Injecting is difficult, and there is a problem that a lot of polymerization failure occurs. In addition, the prepolymer having a -SH / -NCO molar ratio of 0.5 to 2.0 as disclosed in Japanese Patent Laid-Open No. 5-25240 has a higher viscosity and thus has the above problems in manufacturing a urethane-based optical lens.
2,3-비스(2-메르캅토에틸티오)프로판-1-티올(이하 "GST"라 함)와 XDI(자일릴렌디이소시아네이트)의 조합은 상용화되어 있는데, GST는 황함유율이 높으나 당량이 낮아 상대적으로 이소시아네이트에 비해 적게 투입되므로 전체적으로 굴절률 향상이 어렵고, 가교 밀도가 높지 않아 내열성이 떨어지는 문제점이 있다. 또한, GST는 다른 이소시아네이트와 작용시 점도가 낮아 테이프 배면에 점착제를 용해시켜 백화를 유발하는 원인이 되기도 하였다. A combination of 2,3-bis (2-mercaptoethylthio) propane-1-thiol (hereinafter referred to as "GST") and XDI (xylylene diisocyanate) is commercially available. GST has a high sulfur content but a low equivalent weight. It is relatively difficult to improve the refractive index because it is relatively less than the isocyanate, there is a problem that the heat resistance is poor because the crosslinking density is not high. In addition, GST has a low viscosity when working with other isocyanates, causing dissolution of the adhesive on the back of the tape, causing whitening.
본 발명자들은 가격이 저렴한 범용 이소시아네이트 화합물을 사용하면서도 렌즈의 내열성을 높일 수 있는 방법으로, 이소포론디이소시아네이트나 디시클로헥실메탄디이소시아네이트를 1,6-헥사메틸렌디이소시아네이트와 혼합하여 사용하는 방법을 개발하여 선출원한 바 있다. 그러나 이 방법은 이소시아네이트 함량 중 이소포론디이소시아네이트나 디시클로헥실메탄디이소시아네이트의 함량이 40 중량% 이상이 될 때 좋은 내열성을 얻을 수 있는데, 이 경우 메르캅토 화합물과의 반응시 반응성이 저하되어 높은 온도에서 반응이 진행되고, 이러한 높은 반응온도는 몰드를 고정시킨 점착테이프의 점착제가 용출되어 렌즈의 가장자리로 들어옴으로써 렌즈의 백화현상을 야기하는 문제점이 있다. 또, 온도의 증가에 따른 액상 조성물의 팽창으로 누액이 발생함으로써 렌즈의 가장자리에 기포가 발생하여 불량이 발생하는 문제점도 있다. 따라서 이소포론디이소시아네이트나 디시클로헥실메탄디이소시아네이트를 이소시아네이트 중에 40% 이상 혼합하여 사용하는 방법이 렌즈의 내열성을 높이는 방법으로 가장 좋으나, 현재 시판되고 있는 접착테이프의 이용에 문제가 있다. The present inventors have developed a method of mixing isophorone diisocyanate or dicyclohexyl methane diisocyanate with 1,6-hexamethylene diisocyanate as a method of increasing the heat resistance of a lens while using a general-purpose isocyanate compound which is inexpensive. Has been elected. However, this method can achieve good heat resistance when the content of isophorone diisocyanate or dicyclohexyl methane diisocyanate in the isocyanate content is 40% by weight or more, in which case the reactivity with the mercapto compound decreases, resulting in high temperature. In the reaction proceeds, such a high reaction temperature is a problem that causes the whitening of the lens by eluting the adhesive of the adhesive tape fixing the mold to the edge of the lens. In addition, due to the expansion of the liquid composition in accordance with the increase in the temperature of the liquid leakage caused by the bubble is generated at the edge of the lens there is also a problem that a defect occurs. Therefore, the method of mixing 40% or more of isophorone diisocyanate or dicyclohexyl methane diisocyanate in isocyanate is the best method for improving the heat resistance of the lens, but there is a problem in using commercially available adhesive tapes.
그리고 한국특허출원 10-2010-0038562에서는 폴리티올화합물에 이소시아네이트를 일부 미리 중합시켜 점도를 높게 하여 테이프 백화문제를 해결하려고 하였으나 이 경우는 미리 중합된 예비중합체가 굴절률 향상에 도움을 주지 못하였으며 또한 중합불균형 및 염색불균형을 일부 유발하였다.In addition, in Korean Patent Application No. 10-2010-0038562, a solution of tape whitening was solved by prepolymerizing some isocyanate to polythiol compound to increase the viscosity, but in this case, the prepolymerized prepolymer did not help to improve the refractive index. Some imbalance and staining imbalance were caused.
본 발명에서는, 상기와 같은 문제를 해결하고 보다 높은 굴절률을 얻고 내열성을 높이기 위해, 티올화합물을 그대로 사용하지 않고 디술피드화시킨 신규 폴리티올화합물을 제공하고자 한다. 본 발명의 디술피드화시킨 신규 폴리티올화합물을 사용하면, 보다 높은 굴절률을 얻을 수 있고, 내열성이 높아져 점도를 상승시키게 되므로 광학재료용 수지 조성물의 용해도를 떨어뜨려 테이프 백화 문제를 해결할 수 있다.In the present invention, in order to solve the above problems, obtain a higher refractive index and increase the heat resistance, it is to provide a novel polythiol compound disulfide without using a thiol compound as it is. When the new disulfide polythiol compound of the present invention is used, a higher refractive index can be obtained, and the heat resistance is increased to increase the viscosity, thereby reducing the solubility of the resin composition for optical materials, thereby solving the problem of tape whitening.
본 발명에서는,In the present invention,
아래 화학식 1로 표시되는 광학재료용 폴리티올화합물이 제공된다.Provided is a polythiol compound for an optical material represented by Formula 1 below.
식 중 R1, R2는 방향족유기잔기, 지환족유기잔기, 지방족유기잔기, 헤테로고리유기잔기, 한 개 이상의 황원자를 포함하는 방향족유기잔기, 한 개 이상의 황원자를 포함하는 지방족유기잔기, 한 개 이상의 황원자를 포함하는 헤테로고리유기잔기 중 어느 하나이고,Wherein R 1 and R 2 represent an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, a heterocyclic organic residue, an aromatic organic residue containing one or more sulfur atoms, an aliphatic organic residue containing one or more sulfur atoms, and one It is any one of the heterocyclic organic residue containing the above sulfur atom,
x+y는 3에서 10인 정수이고, x + y is an integer from 3 to 10,
n는 1에서 5인 정수이다. n is an integer from 1 to 5.
또한, 본 발명에서는, In the present invention,
티올화합물과 산화제를 반응시키는 것을 포함하는 상기 화학식 1의 폴리티올화합물의 제조방법이 제공된다.Provided is a method for preparing a polythiol compound of Chemical Formula 1, including reacting a thiol compound with an oxidizing agent.
또한, 본 발명에서는, 상기 식 1의 폴리티올화합물을 포함하는 광학재료용 수지조성물이 제공된다. 본 발명의 광학재료용 수지조성물은 이소시아네이트화합물 또는 티오이소시아네이트화합물을 더 포함할 수 있다. 또한, 본 발명의 광학재료용 수지조성물은 상기 식 1의 폴리티올화합물 외에 다른 티올화합물을 더 포함할 수 있다. 디설피드를 갖는 본 발명의 폴리티올화합물을 포함하는 광학재료용 수지 조성물은 렌즈 제조시 백화현상이나 기포 발생의 문제가 없었다. Moreover, in this invention, the resin composition for optical materials containing the polythiol compound of said Formula 1 is provided. The resin composition for an optical material of the present invention may further include an isocyanate compound or a thioisocyanate compound. In addition, the resin composition for an optical material of the present invention may further include other thiol compounds in addition to the polythiol compound of Formula 1. The resin composition for an optical material containing the polythiol compound of the present invention having disulfide had no problem of whitening or bubble generation during lens manufacture.
또한, 본 발명에서는 상기 광학재료용 수지 조성물을 경화시켜 얻은 광학재료용 수지와 이 광학재료용 수지로 이루어진 광학제품이 제공된다. 광학제품은, 특히 안경렌즈, 3D 편광렌즈, 편광렌즈, 프리즘필름, 광섬유, 광디스크, 자기디스크, 기록매체 기판, 착색 필터, 자외선 흡수 필터를 포함한다.Moreover, in this invention, the optical material resin obtained by hardening the said resin composition for optical materials, and the optical product which consists of this optical material resin are provided. Optical products include spectacle lenses, 3D polarized lenses, polarized lenses, prismatic films, optical fibers, optical disks, magnetic disks, recording medium substrates, color filters, ultraviolet absorbing filters.
본 발명의 디설파이드를 갖는 폴리티올화합물(화학식1)을 이용한 광학재료용 수지 조성물은, 용해도를 낮추어 줌으로 점착테이프의 점착제 용출에 따른 렌즈 가장자리에 백화 현상이 전혀 나타나지 않았으며 아울러 적절한 점도를 유지함으로 누액으로 인한 렌즈의 가장 자리의 기포 문제가 나타나지 않았다. 디설파이드를 갖는 폴리티올화합물은 광학재료의 원료로 사용되며, 이를 이용하여 얻어지는 광학재료는 굴절률을 높일 수 있고, 내열성 및 반응성이 우수하여 안경렌즈, 카메라 렌즈 등의 렌즈, 프리즘, 광파이프, 광디스크, 자기디스크 등의 기록매체 기관, 착색필트, 적외선 흡수필터 등의 광학제품에 유용하게 사용될 수 있다.In the resin composition for an optical material using the polythiol compound having the disulfide of the present invention (Formula 1), the whitening phenomenon did not appear at the edges of the lens due to the adhesive elution of the adhesive tape by lowering the solubility and maintaining an appropriate viscosity. No bubble problems at the edges of the lens due to leakage. The polythiol compound having disulfide is used as a raw material for optical materials, and the optical material obtained by using the same can increase the refractive index, and has excellent heat resistance and reactivity, such as lenses of glasses, camera lenses, prisms, optical pipes, optical disks, It can be usefully used for optical products, such as recording medium engines, such as a magnetic disk, a coloring filter, and an infrared absorption filter.
본 발명에서 제공하는 신규 폴리티올화합물은, 적어도 한 개 이상의 디설파이드를 가지며 아래 식 1로 표시된다. The novel polythiol compound provided by this invention has at least 1 or more disulfide, and is represented by following formula (1).
[식 1][Equation 1]
식 중 R1, R2는 방향족유기잔기, 지환족유기잔기, 지방족유기잔기, 헤테로고리유기잔기, 한 개 이상의 황원자를 포함하는 방향족유기잔기, 한 개 이상의 황원자를 포함하는 지방족유기잔기, 한 개 이상의 황원자를 포함하는 헤테로고리유기잔기 중 어느 하나이고,Wherein R 1 and R 2 represent an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, a heterocyclic organic residue, an aromatic organic residue containing one or more sulfur atoms, an aliphatic organic residue containing one or more sulfur atoms, and one It is any one of the heterocyclic organic residue containing the above sulfur atom,
x+y는 3에서 10인 정수이고, x + y is an integer from 3 to 10,
n는 1에서 5인 정수이다. n is an integer from 1 to 5.
본 발명의 폴리티올화합물은 티올화합물과 산화제의 반응에서 생성된 적어도 한 개 이상의 디설파이드 결합을 가지며, 티올화합물과 산화제를 반응시켜 제조한다. 티올화합물의 말단 티올기를 디설파이드로 연결을 하기 위한 산화제로, 할로겐족 화합물, 라디칼촉매제, 아염소산 나트륨 등의 과산화물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다. 보다 구체적인 산화제의 예로, 산소, 과산화수소, 치아염소산소다, 요오드, 염화설푸릴, 염화철(III), 산화질소 등을 사용할 수 있으며, 이에 한정되지는 않는다. 사슬연장제의 사용량은 티올화합물의 -SH 몰비에 대하여 0.05~1.5 몰의 사용이 적당하며, 바람직하게는 0.1~0.8 몰비 정도이다. 0.05 몰비 이하의 사용은 점도 상승 및 당량의 상승이 적어서 목적으로 하는 점도 및 테이프 백화문제에 도움이 되지 않았으며 1.5 몰비 이상의 사용은 점도가 상승이 너무 심하여 분자량이 커져서 광학재료용 수지 조성물로는 적합하지 않았다.The polythiol compound of the present invention has at least one or more disulfide bonds formed in the reaction of the thiol compound and the oxidant, and is prepared by reacting the thiol compound and the oxidant. As an oxidizing agent for connecting the terminal thiol group of the thiol compound with disulfide, a halogen group compound, a radical catalyst, a peroxide such as sodium chlorite, etc. may be used, but is not limited thereto. More specific examples of the oxidizing agent may include oxygen, hydrogen peroxide, sodium hypochlorite, iodine, sulfyl chloride, iron (III) chloride, nitrogen oxide, and the like, but are not limited thereto. The amount of the chain extender to be used is preferably 0.05 to 1.5 moles with respect to the -SH molar ratio of the thiol compound, and preferably about 0.1 to 0.8 molar ratio. The use of less than 0.05 molar ratio did not help the problem of viscosity and tape whitening due to the small increase in viscosity and the equivalent, and the use of more than 1.5 molar ratio is too suitable for the resin composition for optical materials because the viscosity is too high to increase the molecular weight. Did not do it.
상기 화학식1의 폴리티올화합물의 제조에 이용될 수 있는 티올화합물로는, 2,2-비스(메르캅토메틸)-1,3-프로판디티올; 테트라키스(메르캅토메틸)메탄; 2-(2-메르캅토에틸티오)프로판-1,3-디티올; 2,3-비스(2-메르캅토에틸티오)프로판-1-티올; 비스(2,3-디메르캅토프로판닐)설파이드; 비스(2,3-디메르캅토프로판닐)디설파이드; 2-(2,3-비스(2-메르캅토에틸티오)프로필티오)에탄티올; 1,1,3,3-테트라키스(메르캅토메틸티오)프로판; 1,1,2,2-테트라키스(메르캅토메틸티오)에탄; 4,6-비스(메르캅토메틸티오)-1,3-디티안; 2-(2,2-비스(메르캅토메틸티오)에틸)-1,3-디에탄; 트리스(메르캅토메틸티오)메탄; 1,1,5,5-테트라키스(메르캅토메틸티오)-2,4-디티아펜탄; 비스(4,4-비스(메르캅토메틸티오)-1,3-디티아부틸; 1,2,3-트리메르캅토벤젠; 1,3,5-트리스(메르캅토메틸)벤젠; 1,2,3-트리스(메르캅토메르캅토에틸)벤젠; 1,3,5-트리스(메르캅토에틸)벤젠; 1,2,3-트리스(메르캅토메틸티오)벤젠; 1,2,4-트리스(메르캅토메틸티오)벤젠; 1,3,5-트리스(메르캅토메틸티오)벤젠; 1,2,3-트리스(메르캅토에틸티오)벤젠; 1,2,4-트리스(메르캅토에틸티오)벤젠; 1,3,5-트리스(메르캅토에틸티오)벤젠; 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄; 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드; 2-(2-메르캅토에틸티오)-3-2-메르캅토-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]프로필티오-프로판-1-티올; 2,2-비스-(3-메르캅토-프로피오닐옥시메틸)-부틸 에스테르; 2-(2-메르캅토에틸티오)-3-(2-(2-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]에틸티오)에틸티오)프로판-1-티올; 트리메틸올프로판 트리스(메르캅토프로피오네이트); 트리메틸올에탄 트리스(메르캅토프로피오네이트); 글리세롤 트리스(메르캅토프로피오네이트); 트리메틸올클로로 트리스(메르캅토프로피오네이트); 트리메틸올프로판 트리스(메르캅토아세테이트); 트리메틸올에탄 트리스(메르캅토아세테이트); 펜타에리트리톨테트라키스(메르캅토프로피오네이트) (PETMP); 펜타에리트리톨테트라키스(메르캅토아세테이트)(PETMA); 비스펜타에리트리톨-에테르-헥사키스(메르캅토프로피오네이트)(BPEHMP); 비스펜타에리트리톨-에테르-헥사키스(2-메르캅토아세테이트)(BPEHMA); 비스펜타에리트리톨헥사(2-메르캅토아세테이트)(BPEMA); 비스트리메틸올프로판테트라키스(3-메르캅토프로피오네이트) (BTMPMP); 비스트리메틸올프로판테트라키스(2-메르캅토아세테이트)(BTMPMA)을 사용할 수 있으며, 위의 예시한 것에 한정되는 것은 아니다.As a thiol compound which may be used to prepare the polythiol compound of Chemical Formula 1, 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; Bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) disulfide; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,1,3,3-tetrakis (mercaptomethylthio) propane; 1,1,2,2-tetrakis (mercaptomethylthio) ethane; 4,6-bis (mercaptomethylthio) -1,3-dithiane; 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diene; Tris (mercaptomethylthio) methane; 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane; Bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl; 1,2,3-trimercaptobenzene; 1,3,5-tris (mercaptomethyl) benzene; 1,2 , 3-tris (mercaptomercaptoethyl) benzene; 1,3,5-tris (mercaptoethyl) benzene; 1,2,3-tris (mercaptomethylthio) benzene; 1,2,4-tris ( Mercaptomethylthio) benzene; 1,3,5-tris (mercaptomethylthio) benzene; 1,2,3-tris (mercaptoethylthio) benzene; 1,2,4-tris (mercaptoethylthio) Benzene; 1,3,5-tris (mercaptoethylthio) benzene; 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; 2- (2-mercaptoethylthio) -3- (2 -(2- [3-mercapto-2- (2-mercaptoethylthio) -prop Lofilo] ethylthio) ethylthio) propane-1-thiol; trimethylolpropane tris (mercaptopropionate); trimethylolethane tris (mercaptopropionate); glycerol tris (mercaptopropionate); trimethyl Allchloro tris (mercaptopropionate); trimethylolpropane tris (mercaptoacetate); trimethylolethane tris (mercaptoacetate); pentaerythritol tetrakis (mercaptopropionate) (PETMP); pentaerythritol Tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP); Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA) Bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); bistrimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); bistrimethylolpropanetet Kiss may be used. (2-mercaptoacetate) (BTMPMA), but is not limited to the examples above.
상기 화학식1의 제조에서, 사용될 수 있는 티올화합물로는 할로겐족 또는/그리고 히드록시기 또는 에피설파이드 및 티에탄을 포함한 방향족유기잔기, 지환족유기잔기, 지방족유기잔기, 헤테로고리유기잔기를 가진 티올화합물을 더 포함할 수 있다. 예를 들면, 메르캅토메탄올; 2-메르캅토에탄올; 1-클로로-3-메르캅토-프로판-2-올; 티에탄-3-티올; 옥시렌닐메탄티올; 티이렌닐메탄티올; 2-메르캅토프로피온산; 3-메르캅토부티르산; 2-메르캅토이소부티르산; 3-메르캅토이소부티르산; 메탄디티올; 1,2-에탄디티올; 1,1-프로판디티올 등을 1종 이상 사용할 수 있다. 그러나 이에 한정되는 것은 아니다. In the preparation of Chemical Formula 1, thiol compounds that can be used include a thiol compound having an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, and a heterocyclic organic residue, including a halogen group and / or a hydroxy group or episulfide and thiethane. It may include. For example, mercaptomethanol; 2-mercaptoethanol; 1-chloro-3-mercapto-propan-2-ol; Thiethane-3-thiol; Oxylenyl methane thiol; Thylenyl methane thiol; 2-mercaptopropionic acid; 3-mercaptobutyric acid; 2-mercaptoisobutyric acid; 3-mercaptoisobutyric acid; Methanedithiol; 1,2-ethanedithiol; 1,1-propanedithiol, etc. can be used 1 or more types. However, it is not limited thereto.
본 발명에서는, 상기 식 1의 폴리티올화합물을 포함하는 광학재료용 수지조성물이 제공되며, 광학재료용 수지조성물은 이소시아네이트화합물 또는 티오이소시아네이트화합물을 더 포함할 수 있다. 또한, 본 발명의 광학재료용 수지조성물은 상기 식 1의 폴리티올화합물 외에 다른 티올화합물을 더 포함할 수 있다. In the present invention, a resin composition for an optical material including the polythiol compound of Formula 1 is provided, and the resin composition for the optical material may further include an isocyanate compound or a thioisocyanate compound. In addition, the resin composition for an optical material of the present invention may further include other thiol compounds in addition to the polythiol compound of Formula 1.
상기 이소시아네이트화합물 또는 이소티오시아네이트화합물로는, 헥사메틸렌디이소시아네이트, 2,2-디메틸펜탄디이소시아네이트, 2,2,4-트리메틸헥산디이소시아네이트, 부텐디이소시아네이트, 1,3-부타디엔-1,4-디이소시아네이트, 2,4,4-트리메틸헥사메틸렌디이소시아네이트, 1,6,11-운데칸트리이소시아네이트, 1,3,6-헥사메틸렌트리이소시아네이트, 1,8-디이소시아네이토-4-이소시아네이토메틸옥탄, 비스(이소시아네이토에틸)카보네이트, 비스(이소시아네이토에틸)에테르, 리신디이소시아네이토메틸에스테르, 리신트리이소시아네이트 등의 지방족 폴리이소시아네이트 화합물; 1,2-디이소시아네이토벤젠, 1,3-디이소시아네이토벤젠, 1,4-디이소시아네이토벤젠, 2,4-디이소시아네이토톨루엔, 에틸페닐렌디이소시아네이트, 이소프로필페닐렌디이소시아네이트, 자일릴렌디이소시아네이트, 톨릴렌-2,4-디이소시아네이트, 디에틸페닐렌디이소시아네이트, 디이소프로필페닐렌디이소시아네이트, 트리메틸벤젠트리이소시아네이트, 벤젠트리이소시아네이트, 비페닐디이소시아네이트, 톨루이딘디이소시아네이트, 4,4'-메틸렌비스(페닐이소시아네이트), 4,4-메틸렌비스(2-메틸페닐이소시아네이트), 비벤질-4,4-디이소시아네이트, 비스(이소시아네이토페닐)에틸렌, 비스(이소시아네이토에틸)벤젠, 비스(이소시아네이토프로필)벤젠, α,α,α',α'-테트라메틸 크실릴렌디이소시아네이트, 비스(이소시아네이토부틸)벤젠, 비스(이소시아네이토메틸)나프탈린, 비스(이소시아네이토메틸페닐)에테르, 비스(이소시아네이토에틸)프탈레이트, 2,6-디(이소시아네이토메틸)푸란 등의 방향환 화합물을 가지는 폴리이소시아네이트 화합물; 이소포론디이소시아네이트, 3,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 3,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 2,5-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 비스(이소시아네이토메틸)시클로헥산, 디시클로헥실메탄디이소시아네이트, 시클로헥산디이소시아네이트, 메틸시클로헥산디이소시아네이트, 디시클로헥실디메틸메탄디이소시아네이트, 2,2′-디메틸디시클로헥실메탄디이소시아네이트, 비스(4-이소시아네이토-n-부틸리덴)펜타에리트리톨, 다이머산디이소시아네이트, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-5-이소시아네이토메틸비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-이소시아네이토메틸비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-5-이소시아네이토메틸-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-6-이소시아네이토메틸-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-5-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 1,3,5-트리스(이소시아네이토메틸)-시클로헥산, 디시클로헥실메탄-4,4-디이소시아네이트(H12MDI) 등의 지환족 화합물을 가지는 폴리이소시아네이트 화합물; 티오펜-2,5-디이소시아네이트, 메틸 티오펜-2,5-디이소시아네이트, 1,4-디티안-2,5-디이소시아네이트, 메틸 1,4-디티안-2,5-디이소시아네이트, 1,3-디티올란-4,5-디이소시아네이트, 메틸 1,3-디티올란-4,5-디이소시아네이트, 메틸 1,3-디티올란-2-메틸-4,5-디이소시아네이트, 에틸 1,3-디티올란-2,2-디이소시아네이트, 테트라히드로티오펜-2,5-디이소시아네이트, 메틸테트라히드로티오펜-2,5-디이소시아네이트, 에틸 테트라히드로티오펜-2,5-디이소시아네이트, 메틸 테트라히드로티오펜-3,4-디이소시아네이트, 1,2-디이소티오시아네이토에탄, 1,3-디이소티오시아네이토프로판, 1,4-디이소티오시아네이토부탄, 1,6-디이소티오시아네이토헥산, p-페닐렌디이소프로필리덴디이소티오시아네이트, 시클로헥산디이소티오시아네이트 등의 헤테로고리 디이소시아네이트 화합물; 비스(이소시아네이토메틸)설파이드, 비스(이소시아네이토에틸)설파이드, 비스(이소시아네이토프로필)설파이드, 비스(이소시아네이토헥실)설파이드, 비스(이소시아네이토메틸)설파이드, 비스(이소시아네이토메틸)디설파이드, 비스(이소시아네이토에틸)디설파이드, 비스(이소시아네이토프로필)디설파이드, 비스(이소시아네이토메틸티오)메탄, 비스(이소시아네이토에틸티오)메탄, 비스(이소시아네이토메틸티오)에탄, 비스(이소시아네이토에틸티오)에탄, 1,5-디이소시아네이토-2-이소시아네이토메틸-3-티아펜탄, 1,2,3-트리스(이소시아네이토메틸티오)프로판, 1,2,3-트리스(이소시아네이토에틸티오)프로판, 3,5-디티아-1,2,6,7-헵탄테트라이소시아네이트, 2,6-디이소시아네이토메틸-3,5-디티아-1,7-헵탄디이소시아네이트, 2,5-디이소시아네이토메틸티오펜, 4-이소시아네이토에틸티오-2,6-디티아-1,8-옥탄디이소시아네이트 등의 황함유 지방족 폴리이소시아네이트 화합물; 2-이소시아네이토페닐-4-이소시아네이토페닐설피드, 비스(4-이소시아네이토페닐)설피드, 비스(4-이소시아네이토메틸페닐)설피드 등의 방향족 설피드계 폴리이소시아네이트 화합물; 비스(4-이소시아네이토페닐)디설피드, 비스(2-메틸-5-이소시아네이토페닐)디설파이드, 비스(3-메틸-5-이소시아네이토페닐)디설파이드, 비스(3-메틸-6-이소시아네이토페닐)디설파이드, 비스(4-메틸-5-이소시아네이토페닐)디설파이드, 비스(4-메톡시-3-이소시아네이토페닐)디설파이드 등의 방향족 디설피드계 폴리이소시아네이트 화합물; 2,5-디이소시아네이토테트라히드로티오펜, 2,5-디이소시아네이토메틸테트라히드로티오펜, 3,4-디이소시아네이토메틸테트라히드로티오펜, 2,5-디이소시아네이토-1,4-디티안, 2,5-디이소시아네이토메틸-1,4-디티안, 4,5-디이소시아네이토-1,3-디티오란, 4,5-비스(이소시아네이토메틸)1,3-디티오란, 4,5-디이소시아네이토메틸-2-메틸-1,3-디티오란 등의 황함유 지환족 폴리이소시아네이트 화합물; 1,2-디이소티오시아네이토에탄, 1,6-디이소티오시아네이토헥산 등의 지방족 폴리이소티오시아네이트 화합물; 시클로헥산디이소티오시아네이트 등의 지환족 폴리이소티오시아네이트 화합물; 1,2-디이소티오시아네이토벤젠, 1,3-디이소티오시아네이토벤젠, 1,4-디이소티오시아네이토벤젠, 2,4-디이소티오시아네이토톨루엔, 2,5-디이소티오시아네이토-m-크실렌, 4,4-메틸렌비스(페닐이소티오시아네이트), 4,4-메틸렌비스(2-메틸페닐이소티오시아네이트), 4,4-메틸렌비스(3-메틸페닐이소티오시아네이트), 4,4-디이소티오시아네이토벤조페논, 4,4-디이소티오시아네이토-3,3-디메틸벤조페논, 비스(4-이소티오시아네이토페닐)에테르 등의 방향족 폴리이소티오시아네이트 화합물; 1,3-벤젠디카르보닐디이소티오시아네이트, 1,4-벤젠디카르보닐디이소티오시아네이트, (2,2-피리딘)-4,4-디카르보닐디이소티오시아네이트 등의 카르보닐 폴리이소티오시아네이트 화합물; 티오비스(3-이소티오시아네이토프로판), 티오비스(2-이소티오시아네이토에탄), 디티오비스(2-이소티오시아네이토에탄) 등의 황함유 지방족 폴리이소티오시아네이트 화합물; 1-이소티오시아네이토-4-[(2-이소티오시아네이토)티오]벤젠, 티오비스(4-이소티오시아네이토벤젠), 설포닐(4-이소티오시아네이토벤젠), 디티오비스(4-이소티오시아네이토벤젠) 등의 황함유 방향족 폴리이소티오시아네이트화합물; 2,5-디이소티오시아네이토티오펜, 2,5-디이소티오시아네이토-1,4-디티안 등의 황함유 지환족 폴리이소티오시아네이트 화합물; 1-이소시아네이토-6-이소티오시아네이토헥산, 1-이소시아네이토-4-이소티오시아네이토시클로헥산, 1-이소시아네이토-4-이소티오시아네이토벤젠, 4-메틸-3-이소시아네이토-1-이소티오시아네이토벤젠, 2-이소시아네이토-4,6-디이소티오시아네이토-1,3,5-트리아진, 4-이소시아네이토페닐-4-이소티오시아네이토페닐설피드, 2-이소시아네이토-에틸-2-이소티오시아네이토에틸디설피드 등의 이소시아네이토기와 이소티오시아네이토기를 가지는 화합물이 1종 혹은 2종 이상 혼합하여 사용될 수 있다.Examples of the isocyanate compound or isothiocyanate compound include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4 -Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-iso Aliphatic polyisocyanate compounds such as cyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester and lysine triisocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate , Xylylene diisocyanate, tolylene-2,4-diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4 '-Methylenebis (phenylisocyanate), 4,4-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatoethyl) Benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethyl xylylenediisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) Phthalic, bis (isocyanatomethyl phenyl) ether, bis (isocyanato ethyl) phthalate, 2,6-polyisocyanate compounds having an aromatic ring compound such as (isocyanatomethyl) furan; Isophorone diisocyanate, 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-bis (isocyanatomethyl) tricyclo [5,2 , 1,02,6] decane, 2,5-Bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, Bis (isocyanatomethyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane diisocyanate, 2,2'-dimethyldicyclohexyl methane diisocyanate, Bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2,2,1] -heptane , 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2 -(3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-iso Anatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -ratio Cyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 1 , 3,5-tris (isocyanatomethyl) -cyclohexane, dicyclohexylmethane-4,4-diisocyanate (H12Polyisocyanate compounds having an alicyclic compound such as MDI); Thiophene-2,5-diisocyanate, methyl thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, methyl 1,4-dithiane-2,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate, ethyl 1 , 3-dithiolane-2,2-diisocyanate, tetrahydrothiophene-2,5-diisocyanate, methyltetrahydrothiophene-2,5-diisocyanate, ethyl tetrahydrothiophene-2,5-diisocyanate , Methyl tetrahydrothiophene-3,4-diisocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, Heterocyclic diisocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenediisothiocyanate and cyclohexanediisothiocyanate; Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfide, Bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) Methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2, 3-tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptane tetraisocyanate, 2 , 6-Diisocyanatomethyl-3,5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanatomethylthiophene, 4-iso Sulfur-containing aliphatic polyisocyanate compounds such as isocyanato ethyl thio-2,6-thiazole-1,8-octane diisocyanate; Aromatic sulfide-based polys such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, and bis (4-isocyanatomethylphenyl) sulfide Isocyanate compounds; Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl Aromatic disulfide-based polys such as -6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, and bis (4-methoxy-3-isocyanatophenyl) disulfide Isocyanate compounds; 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato- 1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolan, 4,5-bis (isocyanato Sulfur-containing alicyclic polyisocyanate compounds such as methyl) 1,3-dithiolane and 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane; Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane; Alicyclic polyisothiocyanate compounds such as cyclohexanediisothiocyanate; 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2, 5-diisothiocyanato-m-xylene, 4,4-methylenebis (phenylisothiocyanate), 4,4-methylenebis (2-methylphenylisothiocyanate), 4,4-methylenebis ( 3-methylphenylisothiocyanate), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyanato-3,3-dimethylbenzophenone, bis (4-isothiocyanato Aromatic polyisothiocyanate compounds such as phenyl) ether; Carbonyl poly, such as 1, 3- benzenedicarbonyl diisothiocyanate, 1, 4- benzenedicarbonyl diisothiocyanate, and (2, 2-pyridine) -4, 4- dicarbonyl diisothiocyanate Isothiocyanate compounds; Sulfur-containing aliphatic polyisothiocyanate compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane) and dithiobis (2-isothiocyanatoethane); 1-isothiocyanato-4-[(2-isothiocyanato) thio] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), Sulfur-containing aromatic polyisothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene); Sulfur-containing alicyclic polyisothiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-diisothiocyanato-1,4-dithiane; 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4 -Methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocy Compounds having isocyanato groups and isothiocyanato groups such as anatotophenyl-4-isothiocyanatophenyl sulfide and 2-isocyanato-ethyl-2-isothiocyanatoethyl disulfide It can be used 1 type or in mixture of 2 or more types.
식 1의 폴리티올화합물에 첨가하여 사용할 수 있는 다른 티올화합물로는, 1,2-에탄디티올; 1,1-프로판디티올; 1,2-프로판디티올; 1,3-프로판디티올; 2,2-프로판디티올; 2,5-헥산디티올; 1,6-헥산디티올; 2,9-데칸디티올; 1,4-비스(1-메르캅토에틸)벤젠; 시클로헥산디티올; 1,2,3-프로판트리티올; 1,1-비스(메르캅토메틸시클로헥산); 1,2-디메르캅토프로필메틸에테르; 2,3-디메르캅토프로필메틸에테르; 2,2-비스(메르캅토메틸)-1,3-프로판디티올; 비스(2-메르캅토에틸)에테르; 테트라키스(메르캅토메틸)메탄; 2-(2-메르캅토에틸티오)프로판-1,3-디티올; 2,3-비스(2-메르캅토에틸티오)프로판-1-티올; 2-(2,3-비스(2-메르캅토에틸티오)프로필티오)에탄티올;비스(2,3-디메르캅토프로판닐)설파이드; 비스(2,3-디메르캅토프로판닐)디설파이드; 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판; 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄; 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드; 2-(2-메르캅토에틸티오)-3-2-메르캅토-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]프로필티오-프로판-1-티올; 2,2 -비스-(3-메르캅토-프로피오닐옥시메틸)-부틸 에스테르; 2-(2-메르캅토에틸티오)-3-(2-(2-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]에틸티오)에틸티오)프로판-1-티올; 트리메틸올프로판 트리스(메르캅토프로피오네이트); 트리메틸올에탄 트리스(메르캅토프로피오네이트); 글리세롤 트리스(메르캅토프로피오네이트); 트리메틸올클로로 트리스(메르캅토프로피오네이트); 트리메틸올프로판 트리스(메르캅토아세테이트); 트리메틸올에탄 트리스(메르캅토아세테이트); 펜타에리트리톨테트라키스(메르캅토프로피오네이트) (PETMP); 펜타에리트리톨테트라키스(메르캅토아세테이트)(PETMA); 비스펜타에리트리톨-에테르-헥사키스(메르캅토프로피오네이트)(BPEHMP); 비스펜타에리트리톨-에테르-헥사키스(2-메르캅토아세테이트)(BPEHMA); 비스펜타에리트리톨헥사(2-메르캅토아세테이트)(BPEMA); 비스트리메틸올프로판테트라키스(3-메르캅토프로피오네이트) (BTMPMP); 비스트리메틸올프로판테트라키스(2-메르캅토아세테이트)(BTMPMA) 등을 1종 또는 2종 이상 사용할 수 있다. As another thiol compound which can be used in addition to the polythiol compound of Formula 1, 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 2,5-hexanedithiol; 1,6-hexanedithiol; 2,9-decanedithiol; 1,4-bis (1-mercaptoethyl) benzene; Cyclohexanedithiol; 1,2,3-propanethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercaptopropylmethyl ether; 2,3-dimercaptopropylmethyl ether; 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Bis (2-mercaptoethyl) ether; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) 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; 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchloro tris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylolethane tris (mercaptoacetate); Pentaerythritol tetrakis (mercaptopropionate) (PETMP); Pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP); Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); Bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); Bistrimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); Bistrimethylol propane tetrakis (2-mercapto acetate) (BTMPMA) etc. can be used 1 type (s) or 2 or more types.
본 발명의 폴리티올화합물(식 1) 및 광학재료용 수지 조성물의 제조에 사용되는 모든 화학약품(원재료) 및 이를 합성하여 얻은 화합물은, 정제하지 않거나 혹은 정제하여 사용하였다. 바람직하게는, 감압증류, 세척, 여과 등의 정제방법으로 정제하여 사용하며, 더욱 바람직하게는 고순도로 정제하여 사용한다. All the chemicals (raw materials) used in the preparation of the polythiol compound (Formula 1) and the resin composition for an optical material of the present invention and the compound obtained by synthesizing the compound were used without purification or purification. Preferably, the resultant is purified using a purification method such as distillation under reduced pressure, washing, filtration, or the like, and more preferably, purified using high purity.
본 발명의 조성물에는, 기타 반응을 조절하기 위한 화합물이 첨가될 수 있으며, 이러한 목적으로 첨가되는 화합물로는 비닐기, 티오에폭시기를 갖는 화합물, 에폭시화합물, 티에탄 등의 화합물이 단독으로 또는 혼합 사용될 수 있다.In the composition of the present invention, a compound for controlling other reactions may be added, and as the compound to be added for this purpose, a compound such as a vinyl group, a compound having a thioepoxy group, an epoxy compound, thiethane, or the like may be used alone or in combination. Can be.
이밖에도 본 발명의 광학재료용 수지 조성물에는, 광학적인 특성을 향상시키기 위한 첨가제가 포함될 수 있다. 첨가제는, 특히 자외선흡수제, 안정제, 내부 이형제, 색상보정제(안료, 염료), 산화방지제, 이형제 등을 포함한다. In addition, the resin composition for optical materials of this invention may contain the additive for improving optical characteristics. Additives include in particular ultraviolet absorbers, stabilizers, internal mold release agents, color correctors (pigments, dyes), antioxidants, mold release agents and the like.
자외선 흡수제로는, 광학렌즈에 사용 가능한 공지의 자외선 흡수제면 제한 없이 사용될 수 있다. 예를 들면, 에틸-2-시아노-3,3-디페닐아크릴레이트; 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-아밀페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3',5'-디-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-부틸페닐)-2H-벤조트리아졸; 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸; 2,4-디히드록시벤조페논; 2-히드록시-4-메톡시벤조페논; 2-히드록시-4-옥틸옥시벤조페논; 4-도데실옥시-2-히드록시벤조페논; 4-벤족시-2-히드록시벤조페논; 2,2',4,4'-테트라히드록시벤조페논; 2,2'-디히드록시-4,4'-디메톡시벤조페논 등이 단독으로 또는 2종 이상 혼합 사용될 수 있다. 바람직하게는, 400㎚ 이하의 파장역에서 양호한 자외선 흡수능을 가지고, 본 발명의 조성물에 양호한 용해성을 갖는 2-(2'-히드록시-5-메틸페닐)-2H-벤조트리아졸, 2-히드록시-4-메톡시벤조페논; 에틸-2-시아노-3,3-디페닐아크릴레이트; 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸; 2,2'-디히드록시-4,4'-디메톡시벤조페논; 2-(2'-히드록시-3',5'-디-t-아밀페닐)-2H-벤조트리아졸; 2-(2'-히드록시-3,5'-디-t-부틸페닐)-5-클로로-2H-벤조트리아졸; 2-(2'-히드록시-3'-t-부틸-5'-메틸페닐)-5-클로로-2H-벤조트리아졸 및 2,2-디히드록시-4,4'-디메톡시벤조페논 등이 단독으로 또는 2종 이상 같이 사용될 수 있다.As the ultraviolet absorbent, any known ultraviolet absorbent surface usable for the optical lens can be used. For example, ethyl-2-cyano-3,3-diphenyl acrylate; 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-benzoxoxy-2-hydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone; 2,2'- dihydroxy-4,4'- dimethoxy benzophenone etc. can be used individually or in mixture of 2 or more types. Preferably, 2- (2'-hydroxy-5-methylphenyl) -2H-benzotriazole, 2-hydroxy having good ultraviolet absorption in the wavelength range of 400 nm or less and having good solubility in the composition of the present invention. -4-methoxybenzophenone; Ethyl-2-cyano-3,3-diphenylacrylate; 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -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 and 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like These may be used alone or in combination of two or more.
광학재료용 수지 조성물의 광학특성을 향상시키기 위한 안정제는, 전체 조성물 중 0.01~5.00 중량%로 첨가하여 주는 것이 바람직하다. 안정제는 0.01 중량% 이하 사용할 때에는 안정성 효과가 약하며, 10.00 중량% 이상을 사용할 때에는 경화시 중합불량률이 높고 경화물의 안정성이 도리어 낮아지는 문제점이 있다. 예를 들면, 금속 지방산염계인 칼슘 스테아레이트; 바륨 스테아레이트; 아연 스테아레이트; 카드뮴 스테아레이트; 납 스테아레이트; 마그네슘 스테아레이트; 알루미늄 스테아레이트; 칼륨스테아레이트; 아연 옥토에이트 등의 화합물 중 1종 혹은 2종 이상이 사용가능하며, 인계인 트리페닐 포스파이트; 디페닐데실포스파이트; 페닐디데실포스파이트; 디페닐도데실포스파이트; 트리노릴페닐포스파이트; 디페닐이소옥틸포스파이트; 트리부틸포스파이트; 트리프로필포스파이트; 트리에틸포스파이트; 트리메틸포스파이트; 트리스(모노데실포스파이트); 트리스(모노페닐)포스파이트 등의 화합물 중 1종 혹은 2종 이상이 사용가능하며, 납계인 3PbO.PbSO4.4H2O; 2PbO.Pb(C8H4O4); 3PbO.Ph(C4H2O4).H2O 등의 화합물 중 1종 혹은 2종 이상이 사용가능하며, 유기주석계인 디부틸틴 디아우레이트; 디부틸틴말리에이트; 디부틸틴 비스(이소옥틸말리에이트); 디옥틸말리에이트; 디부틸틴 비스(모노메틸말리에이트); 디부틸틴 비스(라우릴메르캅티드); 디부틸 비스(이소옥실메르캅토아세테이트); 모노부틸틴 트리스(이소옥틸메르캅토아세테이트); 디메틸틴비스(이소옥틸메르캅토아세테이트); 트리스(이소옥틸메르캅토아세테이트); 비옥틸틴비스(이소옥틸메르캅토아세테이트); 디부틸틴 비스(2-메르캅토에틸로레이트); 모노부틸틴트리스(2-메르캅토에티로레이트); 디메틸틴 비스(2-메르캅토에틸로이트); 모노메틸틴 트리스(2-메르캅토에틸로레이트) 등의 화합물 중 1종 혹은 2종 이상 사용가능한다. 또한, 상기 예시한 안정제를 2종 이상 혼합하여 사용하여도 좋다. 더욱 바람직하게는 인계의 안정제를 사용한다. 인계의 안정제를 사용할 경우 성형된 렌즈는 초기 색상뿐 아니라 투명성, 충격강도, 내열성 및 중합수율 등 광학특성의 저하 없이 광학렌즈의 안정성을 크게 향상시킬 수 있었다. It is preferable to add the stabilizer for improving the optical characteristic of the resin composition for optical materials in 0.01 to 5.00 weight% of all the compositions. When the stabilizer is used at 0.01% by weight or less, the stability effect is weak, and when using at least 10.00% by weight, there is a problem in that the polymerization failure rate during curing is high and the stability of the cured product is lowered. For example, calcium stearate which is a metal fatty acid salt type; Barium stearate; Zinc stearate; Cadmium stearate; Lead stearate; Magnesium stearate; Aluminum stearate; Potassium stearate; One or two or more of compounds such as zinc octoate can be used, and phosphorus-based triphenyl phosphite; Diphenyldecylphosphite; Phenyl didecyl phosphite; Diphenyldodecyl phosphite; Trinolylphenyl phosphite; Diphenylisooctylphosphite; Tributyl phosphite; Tripropyl phosphite; Triethyl phosphite; Trimethyl phosphite; Tris (monodecyl phosphite); One kind or two or more kinds of compounds such as tris (monophenyl) phosphite can be used, and lead-based 3PbO.PbSO4.4H 2 O; 2PbO.Pb (C 8 H 4 O 4 ); 3PbO.Ph (C 4 H 2 O 4 ) .H be one species or two or more kinds of the compounds, such as O 2 is used, and sealed organotin dibutyltin diahwoo rate; Dibutyl tin maleate; Dibutyltin bis (isooctyl maleate); Dioctyl maleate; Dibutyltin bis (monomethylmaleate); Dibutyltin bis (lauryl mercaptide); Dibutyl bis (isooxylmercaptoacetate); Monobutyl tin tris (isooctyl mercaptoacetate); Dimethyl tin bis (isooctyl mercaptoacetate); Tris (isooctyl mercaptoacetate); Bioctyl tin bis (isooctyl mercaptoacetate); Dibutyltin bis (2-mercaptoethylorate); Monobutyl tin tris (2-mercaptoethyrate); Dimethyltin bis (2-mercaptoethylate); One kind or two or more kinds of compounds such as monomethyl tin tris (2-mercaptoethyl laurate) can be used. Moreover, you may mix and use 2 or more types of stabilizers mentioned above. More preferably, a phosphorus stabilizer is used. When the phosphorus stabilizer was used, the molded lens was able to greatly improve the stability of the optical lens without deteriorating the optical characteristics such as transparency, impact strength, heat resistance, and polymerization yield.
본 발명에 사용되는 내부 이형제로는, 퍼플루오르알킬기, 히드록시알킬기 또는 인산에스테르기를 지닌 불소계 비이온계면활성제; 디메틸폴리실록산기, 히드록시알킬기 또는 인산에스테르기를 가진 실리콘계 비이온계면활성제; 알킬제 4급 암모늄염 즉, 트리메틸세틸 암모늄염, 트리메틸스테아릴, 디메틸에틸세틸 암모늄염, 트리에틸도데실 암모늄염, 트리옥틸메틸 암모늄염, 디에틸시클로헥사도데실 암모늄염; 산성 인산에스테르 중에서 선택된 성분이 단독으로 혹은 2종 이상 함께 사용될 수 있다. 바람직하게는 산성 인산에스테르를 사용하며, 산성 인산에스테르로는, 이소프로필산포스페이트; 디이소프로필산포스페이트; 부틸산포스페이트; 옥틸산포스페이트; 디옥틸산포스페이트; 이소데실산 포스페이트; 디이소데실산포스페이트; 트리데칸올산포스페이트; 비스(트리데칸올산)포스페이트 등이 단독으로 또는 2종 이상 혼합 사용될 수 있다. 본 발명의 실시예에서는 산성 인산에스테르계인 ZELEC UN™(Stepan 사)이 경화 후 몰드를 렌즈에서 탈형시킬 때의 탈형성이 가장 좋은 것으로 나타났다. 내부이형제는 상기 반응 혼합물 전체 중량에 대하여 0.0001~10 중량%로 사용할 수 있으나, 바람직하게는 0.005~2 중량%로 사용하는 것이 렌즈에서 몰드의 탈형성이 좋고 중합수율 또한 높았다. 이형제의 첨가량이 0.005% 이하이면 성형된 광학렌즈를 유리 몰드에서 분리시 유리몰드 표면에 렌즈가 부착되어 일어나는 현상이 발생할 수 있고, 2 중량% 이상이면 주형 중합 중 렌즈가 유리 몰드에서 분리되어 렌즈의 표면에 얼룩이 발생할 수 있는 문제점이 있다.As an internal mold release agent used for this invention, Fluorine-type nonionic surfactant which has a perfluoroalkyl group, a hydroxyalkyl group, or a phosphate ester group; Silicone nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphate ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; The component selected from the acidic phosphate ester can be used individually or in combination of 2 or more types. Preferably, acidic phosphate ester is used, and as acidic phosphate ester, isopropyl acid phosphate; Diisopropyl acid phosphate; Butyl phosphate; Octylic acid phosphate; Dioctyl acid phosphate; Isodecyl phosphate; Diisodecyl phosphate; Tridecanoic acid phosphate; Bis (tridecanoic acid) phosphate or the like may be used alone or in combination of two or more thereof. In the embodiment of the present invention, ZELEC UN ™ (Stepan), which is an acidic phosphate ester, was found to exhibit the best demolding when demolding the mold from the lens after curing. The internal mold release agent may be used in an amount of 0.0001 to 10% by weight based on the total weight of the reaction mixture. Preferably, 0.005 to 2% by weight of the mold release agent in the lens has a high polymerization yield. If the amount of the release agent is less than 0.005%, a phenomenon may occur in which the lens adheres to the surface of the glass mold when the molded optical lens is separated from the glass mold, and if more than 2% by weight, the lens is separated from the glass mold during the polymerization of the mold. There is a problem that may cause stains on the surface.
더 나아가, 표면의 내마모성 특성을 증가시키기 위해 하드코트피막을 주형성형수지의 외부표면에 설치할 수 있다. 더욱이 시발제(primer)층을 수지의 표면과 하드코트피막 사이에 삽입함으로써 하드코트피막에 대한 수지의 접착성을 향상시킬 수 있다. 하드코트피막을 표면에 설치하기 위해 수지외부 표면상에 하드코트제를 도포하기 위해서 완전히 경화되고 어닐링된 수지를 먼저 시발체 용액으로 피막하고, 다음에 통상의 알려진 방법, 예컨대 침지법, 스핀-피막법, 유동-피막법, 분무법 및 기타 방법에 따라서 하드코트제로 피막한다. 또한 반사-방지 필름을 주형성형수지 표면에 설치하여 광학적 요소표면상의 표면반사를 방지하고 이로 인해 가시광선의 투과율을 증가시킬 수 있다. Furthermore, a hard coat coating may be provided on the outer surface of the cast resin to increase the wear resistance of the surface. Further, by inserting a primer layer between the surface of the resin and the hard coat film, the adhesion of the resin to the hard coat film can be improved. In order to apply the hard coat agent on the outer surface of the resin for installing the hard coat film on the surface, a completely cured and annealed resin is first coated with a primer solution, and then a conventional known method such as immersion method or spin-film method. And a hard coat agent according to the flow-coating method, the spraying method and other methods. In addition, an anti-reflection film can be installed on the surface of the cast resin to prevent surface reflection on the surface of the optical element, thereby increasing the transmittance of visible light.
디설피드를 갖는 본 발명의 폴리티올화합물을 포함하는 광학재료용 수지 조성물은 렌즈 제조시 백화현상이나 기포 발생의 문제가 없는 것을 확인할 수 있었다. It was confirmed that the resin composition for an optical material including the polythiol compound of the present invention having disulfide had no problem of whitening or bubble generation during lens manufacture.
또한, 본 발명에서는 상기 광학재료용 수지 조성물을 경화시켜 얻은 광학재료용 수지와 이 광학재료용 수지로 이루어진 광학제품이 제공된다. 광학제품에는, 특히 안경렌즈, 3D 편광렌즈, 편광렌즈, 프리즘필름, 광섬유, 광디스크, 자기디스크, 기록매체 기판, 착색 필터, 자외선 흡수 필터 등이 포함된다. Moreover, in this invention, the optical material resin obtained by hardening the said resin composition for optical materials, and the optical product which consists of this optical material resin are provided. Optical products include spectacle lenses, 3D polarized lenses, polarized lenses, prismatic films, optical fibers, optical disks, magnetic disks, recording medium substrates, colored filters, ultraviolet absorbing filters and the like.
[실시예]EXAMPLE
이하 구체적인 실시예들을 통해 본 발명을 보다 상세히 설명한다. 그러나 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these examples are only for illustrating the present invention in more detail, the scope of the present invention is not limited by these examples.
합성예 1 Synthesis Example 1
GSTDS의 제조Manufacture of GSTDS
4구 1L의 플라스크에 GST(2,3-비스(2-메르캅토에틸티오)프로판-1-티올)를 1몰 넣고 아세톤 200g에 희석한 후, 과산화수소 0.5몰을 30℃ 이하에 유지하면서 천천히 적가한다. 발열의 온도를 30℃ 이하에 8시간 유지한 후, 50℃에서 2시간 숙성시킨 후, 60℃에서 2시간 더 숙성하고 용매를 감압에서 제거하여 올리고머 디설파이드 폴리티올화합물을 얻는다. 수율은 정량적이며 얻은 액상의 굴절률은 1.655 (nD, 20℃)을 얻었다.1 mole of GST (2,3-bis (2-mercaptoethylthio) propane-1-thiol) was added to a 4-necked 1 L flask, diluted in 200 g of acetone, and slowly added dropwise while maintaining 0.5 mole of hydrogen peroxide at 30 ° C or lower. do. The temperature of the exotherm is maintained at 30 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 60 ° C. for 2 hours, and the solvent is removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.655 (nD, 20 ° C).
합성예 2Synthesis Example 2
GMTDS의 제조Manufacture of GMTDS
4구 1L의 플라스크에 GMT(2-(2-메르캅토에틸티오)프로판-1,3-디티올) 1몰 넣고 아세톤 200g에 희석한 후, 과산화수소 0.5몰을 30℃이하를 유지하면서 천천히 첨가한다. 발열의 온도를 30℃ 이하에 8시간 유지한 후, 50℃에서 2시간 숙성시킨 후, 60℃에서 2시간 더 숙성하고 용매를 감압에서 제거하여 올리고머 디설파이드 폴리티올화합물을 얻는다. 수율은 정량적이며 얻은 액상의 굴절률은 1.648 (nD, 20℃)을 얻었다.1 mole of GMT (2- (2-mercaptoethylthio) propane-1,3-dithiol) was added to a 4-necked 1 L flask, diluted with 200 g of acetone, and 0.5 mole of hydrogen peroxide was slowly added while maintaining the temperature below 30 ° C. . The temperature of the exotherm is maintained at 30 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 60 ° C. for 2 hours, and the solvent is removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.648 (nD, 20 degreeC).
합성예 3Synthesis Example 3
BDPSS의 제조Manufacturing of BDPSS
4구 1L의 플라스크에 BDPS(비스(2,3-디메르캅토프로판닐)설피드)를 1몰 넣고, 아세톤 200g에 희석한 후, 과산화수소를 0.5몰을 10℃ 이하에 유지하면서 천천히 첨가한다. 발열의 온도를 15℃ 이하에 8시간 유지한 후, 50℃에서 2시간 숙성시킨 후, 60℃에서 2시간 더 숙성하고 용매를 감압에서 제거하여 올리고머 디설파이드 폴리티올화합물을 얻는다. 수율은 정량적이며 얻은 액상의 굴절률은 1.662 (nD, 20℃)을 얻었다.One mole of BDPS (bis (2,3-dimercaptopropanyl) sulfide) is added to a four-necked 1 L flask, and diluted with 200 g of acetone, and then slowly added while keeping 0.5 mole of hydrogen peroxide at 10 ° C or lower. The temperature of the exotherm is maintained at 15 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 60 ° C. for 2 hours, and the solvent is removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.662 (nD, 20 degreeC).
합성예 4Synthesis Example 4
BDPSDS의 제조Preparation of BDPSDS
4구 1L의 플라스크에 BDPSS(비스(2,3-디메르캅토프로판닐)디설피드)를 1몰 넣고, 아세톤 200g에 희석한 후, 과산화수소를 10℃ 이하를 유지하면서 천천히 첨가한다. 발열의 온도를 15℃ 이하를 8시간 유지한 후, 50℃에서 2시간 숙성시킨 후, 50℃에서 2시간 더 숙성하고 용매를 감압에서 제거하여 올리고머 디설파이드 폴리티올화합물을 얻는다. 수율은 정량적이며 얻은 액상의 굴절률은 1.695 (nD, 20℃)을 얻었다.One mole of BDPSS (bis (2,3-dimercaptopropanyl) disulfide) is added to a four-necked 1-L flask, and diluted with 200 g of acetone, and then hydrogen peroxide is slowly added while maintaining 10 ° C or less. The temperature of exotherm was kept at 15 ° C. or lower for 8 hours, then aged at 50 ° C. for 2 hours, then further aged at 50 ° C. for 2 hours, and the solvent was removed at reduced pressure to obtain an oligomeric disulfide polythiol compound. The yield was quantitative and the refractive index of the obtained liquid phase was 1.695 (nD, 20 degreeC).
실시예 1Example 1
광학렌즈 제조Optical lens manufacturers
(1) 자일릴렌디이소시아네이트 2070g, 이소포론디이소시아네이트 1656g, 1,6-헥사메틸렌디이소시아네이트 370g에 GSTDS 5702g을 진공 탈포 교반이 가능한 혼합용기에 넣고 15℃을 유지하면서 여기에 Zelec UN 10g, HOPBT 150g 및 HTAQ 20 ppm, PRD 10ppm 및 BTC 10g을 넣어 질소 기류하에서 20분간 교반하여 안경렌즈용 수지조성성물을 얻은 후, 0.1 torr 이하로 1시간 30분간 감압탈포하고 질소로 채운후, 질소압력을 이용하여 폴리에스테르 점착테이프로 교정된 유리몰드에 주입하였다(디옵타 -5.00).(1) 2070 g of xylylene diisocyanate, 1656 g of isophorone diisocyanate, and 370 g of 1,6-hexamethylene diisocyanate are placed in a mixing vessel capable of vacuum defoaming stirring and kept at 15 ° C., while maintaining 15 ° C., Zelec UN 10 g, HOPBT 150 g 20 ppm of HTAQ, 10 ppm of PRD and 10 g of BTC were stirred for 20 minutes under a nitrogen stream to obtain a resin composition for the spectacle lens, and then degassed under 0.1 torr for 1 hour and 30 minutes, filled with nitrogen, and then charged with nitrogen. The glass mold was calibrated with polyester adhesive tape (Diopta -5.00).
(2) 안경 렌즈용 수지조성물이 주입된유리몰드를 강제순환식 오븐에 35℃로 유지, 40℃로 3시간 승온, 120℃로 12시간 승온, 120℃로 2시간 유지, 70℃로 2시간에 걸쳐서 냉각시켜 가열 경화시킨 후, 고형물에서 몰드를 이형시켜 중심 두께 1.2 mm인 광학렌즈를 얻었다.(2) The glass mold in which the resin composition for the spectacle lens was injected was kept at 35 ° C. in a forced circulation oven, heated at 40 ° C. for 3 hours, heated at 120 ° C. for 12 hours, held at 120 ° C. for 2 hours, and at 70 ° C. for 2 hours. After cooling and heat curing, the mold was released from the solid to obtain an optical lens having a center thickness of 1.2 mm.
(3) (2)에서 얻은 광학렌즈를 지름 72mm로 가공한 후, 알칼리 수성 세척액에 초음파 세척한 다음, 120℃에서 2시간 어닐링 처리하였다.(3) The optical lens obtained in (2) was processed to a diameter of 72 mm, ultrasonically washed with an alkaline aqueous washing solution, and then annealed at 120 ° C. for 2 hours.
(4) (3)에서 얻은 렌즈를 KOH 5% 용액에 표면 에칭 후, (주)화인코팅 하드액에 함침한 후 열경화시키고, 양면에 산화규소, 산화지르코늄, 산화규소, ITO, 산화지로코늄, 산화규소, 산화지르코늄, 수막(불화수지)을 진공 증착하여 하드코팅 및 멀티 코팅된 안경렌즈를 얻었다. (4) The surface of the lens obtained in (3) was etched in KOH 5% solution, impregnated in fine coating hard solution, and then thermally cured, and silicon oxide, zirconium oxide, silicon oxide, ITO, and zirconium oxide on both surfaces. , Silicon oxide, zirconium oxide, water film (resin fluoride) was vacuum deposited to obtain a hard-coated and multi-coated spectacle lens.
물성실험방법Property test method
물질 분석 및 특성은 아래의 방법에 따라 측정하여 실시예에 나타내었다.Material analysis and properties were measured in the following manner and shown in the examples.
1) 굴절률: Atago Co., 1T 및 DR-M4 모델인 아베 굴절계를 사용하여 측정하였다.1) Refractive index: It was measured using an Abbe refractometer of Atago Co., 1T and DR-M4 models.
2) 백화 현상 : (2)공정에서 얻은 렌즈 100개를 육안으로 관찰하여 3 개 이상 렌즈의 가장자리에 백화 현상이 나타나면 ‘X’, 나타나지 않으면 ‘O’로 표기하였다.2) Whitening phenomenon: 100 lenses obtained in step (2) were visually observed and marked with 'X' if whitening phenomenon appeared at the edges of three or more lenses.
3) 가장자리 기포 : (2)공정에서 얻은 렌즈 100개를 육안 관찰하여 3 개 이상 렌즈의 가장자리에 누액에 의한 기포가 나타나면 ‘X’, 나타나지 않으면 ‘O’로 표기하였다.3) Edge bubble: When 100 lenses obtained in the process (2) were visually observed, bubbles appeared due to leakage at the edges of three or more lenses were marked as 'X', and if not, 'O' was indicated.
실험예 2~3Experimental Examples 2-3
실시예 1과 같은 방법으로 표1에 기재된 조성에 따라 각각의 조성물 및 렌즈를 제조하고 물성을 실험하여, 그 결과를 표1에 나타내었다.Each composition and lens were prepared according to the composition described in Table 1 and the physical properties were tested in the same manner as in Example 1, and the results are shown in Table 1.
비교예1Comparative Example 1
자일릴렌디이소시아네이트 2617g, 이소포론디이소시아네이트 2094g, 1,6-헥실메틸렌디이소시아네이트 467g에 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 4823g을 혼합하여 광학재료용 수지 조성물을 제조하는 것 이외에는 실시예 1과 동일한 방법으로 실시하여 그 특성을 표1에 나타내었다.2617 g of xylylene diisocyanate, 2094 g of isophorone diisocyanate, and 467 g of 1,6-hexyl methylene diisocyanate were mixed with 4823 g of 2,3-bis (2-mercaptoethylthio) propane-1-thiol to prepare a resin composition for an optical material. Except for the preparation, it was carried out in the same manner as in Example 1 and its properties are shown in Table 1.
[약어][Abbreviation]
모노머Monomer
IPDI: 이소포론디이소시아네이트(isophorone diisocyanate)IPDI: isophorone diisocyanate
HDI: 1,6-헥사메틸렌디이소시아네이트(1,6-hexamethylene diisocyanate)HDI: 1,6-hexamethylene diisocyanate
XDI: 자일릴렌디이소시아네이트(xylylene diisocyanate)XDI: xylylene diisocyanate
GST: 2,3-비스(2-메르캅토에틸티오)프로판-1-티올 (2,3-bis(2-mercaptoethylthio)propane-1-thiol)GST: 2,3-bis (2-mercaptoethylthio) propane-1-thiol (2,3-bis (2-mercaptoethylthio) propane-1-thiol)
PETMP: 펜타에리트리톨테트라키스(3-메르캅토프로피오네이트) (pentaerythritol-tetrakis(3-mercaptopropionate))PETMP: pentaerythritol tetrakis (3-mercaptopropionate) (pentaerythritol-tetrakis (3-mercaptopropionate))
GSTDS: 2-(2-메르캅토에틸티오)-3-(2-{2-[2-메르캅토-1-(2-메르캅토에틸티오메틸)에틸티오]에틸티디티오}에틸티오)-프로판-1-티올(2-(2-Mercaptoethylthio)-3-(2-{2-[2-mercapto-1-(2-mercaptoethylthiomethyl)-ethylthio]-ethyldithio} ethylthio)propane-1-thiol)의 올리고머 디설파이드 폴리티올화합물GSTDS: 2- (2-mercaptoethylthio) -3- (2- {2- [2-mercapto-1- (2-mercaptoethylthiomethyl) ethylthio] ethyltidithio} ethylthio)- Oligomer of propane-1-thiol (2- (2-Mercaptoethylthio) -3- (2- {2- [2-mercapto-1- (2-mercaptoethylthiomethyl) -ethylthio] -ethyldithio} ethylthio) propane-1-thiol) Disulfide Polythiol Compounds
GMTDS: 2-(2-메르캅토에틸티오-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필디티오)-프로판-1-티올(2-(2-mercaptoethylthio-3-[3-mercapto-2-(2-mercapto ethylthio)-propyldithio]propane-1-thiol)의 올리고머 디설파이드 폴리티올화합물GMTDS: 2- (2-mercaptoethylthio-3- [3-mercapto-2- (2-mercaptoethylthio) -propyldithio) -propane-1-thiol (2- (2-mercaptoethylthio-3 Oligomeric Disulfide Polythiol Compounds of-[3-mercapto-2- (2-mercapto ethylthio) -propyldithio] propane-1-thiol)
BDPSS: 3-{3-[3-(2,3-디메르캅토프로필티오)-2-메르캅토프로필티오]-2-메르캅토프로필티오}-프로판-1,2-디티올(3-{3-[3-(2,3-dimercaptopropylthio)-2-mercaptopropyldithio]-2-mercapto-propylthio}propane-1,2-dithiol)의 올리고머 디설파이드 폴리티올화합물BDPSS: 3- {3- [3- (2,3-Dimercaptopropylthio) -2-mercaptopropylthio] -2-mercaptopropylthio} -propane-1,2-dithiol (3- { Oligomeric Disulfide Polythiol Compounds of 3- [3- (2,3-dimercaptopropylthio) -2-mercaptopropyldithio] -2-mercapto-propylthio} propane-1,2-dithiol)
BDPSDS: 3-{2-[3-(2,3-디메르캅토프로필티오)-2-메르캅토프로필디티오]-3-메르캅토프로필디티오}-프로판-1,2-디티올(3-{2-[3-(2,3-dimercaptopropyldithio)-2-mercaptopropyldithio]-3-mercapto-propyldithio}propane-1,2-dithiol)의 올리고머 디설파이드 폴리티올화합물BDPSDS: 3- {2- [3- (2,3-dimercaptopropylthio) -2-mercaptopropyldithio] -3-mercaptopropyldithio} -propane-1,2-dithiol (3 Oligomeric Disulfide Polythiol Compounds of-(2- [3- (2,3-dimercaptopropyldithio) -2-mercaptopropyldithio] -3-mercapto-propyldithio} propane-1,2-dithiol)
이형제Release agent
ZELEC UN: Stepan 사에서 제조하는 산성 인산에스테르화합물로 상품명 ZELEC UNTM
ZELEC UN: An acidic phosphate ester compound manufactured by Stepan, trade name ZELEC UN TM
자외선 흡수제UV absorbers
HOPBT: 2-(2'-히드록시-5'-t-옥틸페닐)-2H-벤조트리아졸HOPBT: 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole
(2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole)(2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole)
유기염료Organic dyes
HTAQ:1-히드록시-4-(p-톨루딘)엔트로퀴논HTAQ: 1-hydroxy-4- (p-toludine) entroquinone
[1-hydroxy-4-(p-toluidin)anthraquinone][1-hydroxy-4- (p-toluidin) anthraquinone]
PRD: 퍼리논 염료(perinone dye)PRD: perinone dye
중합개시제Polymerization initiator
BTC: 디부틸틴디클로라이드BTC: dibutyl tin dichloride
본 발명에 따르면, 신규폴리티올화합물은 광학재료의 원료로 사용되며 이를 이용하여 얻어지는 광학재료는 굴절률을 높일 수 있고, 내열성 및 반응성이 우수하다. According to the present invention, the novel polythiol compound is used as a raw material of the optical material and the optical material obtained by using the same can increase the refractive index, and excellent in heat resistance and reactivity.
본 발명에 따른 광학렌즈는, 특히, 안경렌즈에 적용될 수 있으며, 안경렌즈에 편광필름을 장착한 3D 편광렌즈 등에 사용되고, 안경렌즈 외에도 프리즘, 광섬유, 광디스크, 자기디스크 등에 사용되는 기록매체 기판, 착색 필터, 자외선 흡수 필터 등의 다양한 광학제품으로 유용하게 사용할 수 있다. The optical lens according to the present invention, in particular, can be applied to the spectacle lens, and used in 3D polarized lenses equipped with a polarizing film on the spectacle lens, recording medium substrate, coloring used in prism, optical fiber, optical disk, magnetic disk, etc. in addition to the spectacle lens It can be usefully used as various optical products, such as a filter and an ultraviolet absorption filter.
Claims (13)
- 아래 식 1로 표시되는 광학재료용 폴리티올화합물.Polythiol compound for optical materials represented by the following formula 1.[식 1][Equation 1]식 중 R1, R2는 방향족유기잔기, 지환족유기잔기, 지방족유기잔기, 헤테로고리유기잔기, 한 개 이상의 황원자를 포함하는 방향족유기잔기, 한 개 이상의 황원자를 포함하는 지방족유기잔기, 한 개 이상의 황원자를 포함하는 헤테로고리유기잔기 중 어느 하나이고,Wherein R 1 and R 2 represent an aromatic organic residue, an alicyclic organic residue, an aliphatic organic residue, a heterocyclic organic residue, an aromatic organic residue containing one or more sulfur atoms, an aliphatic organic residue containing one or more sulfur atoms, and one It is any one of the heterocyclic organic residue containing the above sulfur atom,x+y는 3에서 10인 정수이고, x + y is an integer from 3 to 10,n는 1에서 5인 정수이다. n is an integer from 1 to 5.
- 티올화합물과 산화제를 반응시키는 것을 포함하는 제1항의 폴리티올화합물의 제조방법.A method for producing a polythiol compound according to claim 1, comprising reacting a thiol compound with an oxidizing agent.
- 제2항에 있어서, 상기 티올화합물은, 2,2-비스(메르캅토메틸)-1,3-프로판디티올; 테트라키스(메르캅토메틸)메탄; 2-(2-메르캅토에틸티오)프로판-1,3-디티올; 2,3-비스(2-메르캅토에틸티오)프로판-1-티올; 비스(2,3-디메르캅토프로판닐)설파이드; 비스(2,3-디메르캅토프로판닐)디설파이드; 2-(2,3-비스(2-메르캅토에틸티오)프로필티오)에탄티올; 1,1,3,3-테트라키스(메르캅토메틸티오)프로판; 1,1,2,2-테트라키스(메르캅토메틸티오)에탄; 4,6-비스(메르캅토메틸티오)-1,3-디티안; 2-(2,2-비스(메르캅토메틸티오)에틸)-1,3-디에탄; 트리스(메르캅토메틸티오)메탄; 1,1,5,5-테트라키스(메르캅토메틸티오)-2,4-디티아펜탄; 비스(4,4-비스(메르캅토메틸티오)-1,3-디티아부틸; 1,2,3-트리메르캅토벤젠; 1,3,5-트리스(메르캅토메틸)벤젠; 1,2,3-트리스(메르캅토메르캅토에틸)벤젠; 1,3,5-트리스(메르캅토에틸)벤젠; 1,2,3-트리스(메르캅토메틸티오)벤젠; 1,2,4-트리스(메르캅토메틸티오)벤젠; 1,3,5-트리스(메르캅토메틸티오)벤젠; 1,2,3-트리스(메르캅토에틸티오)벤젠; 1,2,4-트리스(메르캅토에틸티오)벤젠; 1,3,5-트리스(메르캅토에틸티오)벤젠; 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄; 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드; 2-(2-메르캅토에틸티오)-3-2-메르캅토-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]프로필티오-프로판-1-티올; 2,2-비스-(3-메르캅토-프로피오닐옥시메틸)-부틸 에스테르; 2-(2-메르캅토에틸티오)-3-(2-(2-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]에틸티오)에틸티오)프로판-1-티올; 메르캅토메탄올; 2-메르캅토에탄올; 1-클로로-3-메르캅토-프로판-2-올; 티에탄-3-티올; 옥시렌닐메탄티올; 티이렌닐메탄티올; 2-메르캅토프로피온산; 3-메르캅토부티르산; 2-메르캅토이소부티르산; 3-메르캅토이소부티르산; 메탄디티올; 1,2-에탄디티올; 1,1-프로판디티올트리메틸올프로판 트리스(메르캅토프로피오네이트); 트리메틸올에탄 트리스(메르캅토프로피오네이트); 글리세롤 트리스(메르캅토프로피오네이트); 트리메틸올클로로 트리스(메르캅토프로피오네이트); 트리메틸올프로판 트리스(메르캅토아세테이트); 트리메틸올에탄 트리스(메르캅토아세테이트); 펜타에리트리톨테트라키스(메르캅토프로피오네이트) (PETMP); 펜타에리트리톨테트라키스(메르캅토아세테이트)(PETMA); 비스펜타에리트리톨-에테르-헥사키스(메르캅토프로피오네이트)(BPEHMP); 비스펜타에리트리톨-에테르-헥사키스(2-메르캅토아세테이트)(BPEHMA); 비스펜타에리트리톨헥사(2-메르캅토아세테이트)(BPEMA); 비스트리메틸올프로판테트라키스(3-메르캅토프로피오네이트) (BTMPMP); 및 비스트리메틸올프로판테트라키스(2-메르캅토아세테이트)(BTMPMA)으로 구성된 군으로부터 선택된 1종 또는 2종 이상인 것을 특징으로 하는 폴리티올화합물의 제조방법.The method of claim 2, wherein the thiol compound is 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; Bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) disulfide; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; 1,1,3,3-tetrakis (mercaptomethylthio) propane; 1,1,2,2-tetrakis (mercaptomethylthio) ethane; 4,6-bis (mercaptomethylthio) -1,3-dithiane; 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-diene; Tris (mercaptomethylthio) methane; 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane; Bis (4,4-bis (mercaptomethylthio) -1,3-dithiabutyl; 1,2,3-trimercaptobenzene; 1,3,5-tris (mercaptomethyl) benzene; 1,2 , 3-tris (mercaptomercaptoethyl) benzene; 1,3,5-tris (mercaptoethyl) benzene; 1,2,3-tris (mercaptomethylthio) benzene; 1,2,4-tris ( Mercaptomethylthio) benzene; 1,3,5-tris (mercaptomethylthio) benzene; 1,2,3-tris (mercaptoethylthio) benzene; 1,2,4-tris (mercaptoethylthio) Benzene; 1,3,5-tris (mercaptoethylthio) benzene; 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; 2- (2-mercaptoethylthio) -3- (2 -(2- [3-mercapto-2- (2-mercaptoethylthio) -prop Lofilthio] ethylthio) ethylthio) propane-1-thiol; mercaptomethanol; 2-mercaptoethanol; 1-chloro-3-mercapto-propan-2-ol; thiethane-3-thiol; oxenylmethane Thiols; tyrenylmethanethiol; 2-mercaptopropionic acid; 3-mercaptobutyric acid; 2-mercaptoisobutyric acid; 3-mercaptoisobutyric acid; methanedithiol; 1,2-ethanedithiol; 1,1 Propanedithioltrimethylolpropane tris (mercaptopropionate), trimethylolethane tris (mercaptopropionate), glycerol tris (mercaptopropionate), trimethylolchloro tris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptopropionate) (PETMP); pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether- Sakis (mercaptopropionate) (BPEHMP); bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); bis Trimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); And bistrimethylolpropanetetrakis (2-mercaptoacetate) (BTMPMA). 1.
- 제2 또는 제3항에 있어서, 상기 산화제는, 할로겐족 화합물, 라디칼촉매제, 과산화물 중 어느 하나인 것을 특징으로 하는 폴리티올화합물의 제조방법.The method for producing a polythiol compound according to claim 2 or 3, wherein the oxidizing agent is any one of a halogen group compound, a radical catalyst, and a peroxide.
- 제2 또는 제3항에 있어서, 상기 산화제는, 산소, 과산화수소, 치아염소산소다, 요오드, 염화설푸릴, 염화철(III), 산화질소 중 어느 하나인 것을 특징으로 하는 폴리티올화합물의 제조방법.The method for producing a polythiol compound according to claim 2 or 3, wherein the oxidizing agent is any one of oxygen, hydrogen peroxide, sodium hypochlorite, iodine, sulfuryl chloride, iron (III) chloride and nitrogen oxide.
- 제1항의 폴리티올화합물을 포함하는 광학재료용 수지조성물.A resin composition for an optical material, comprising the polythiol compound of claim 1.
- 제6항에 있어서, 이소시아네이트화합물 또는 티오이소시아네이트화합물을 더 포함하는 광학재료용 수지조성물. The resin composition for an optical material according to claim 6, further comprising an isocyanate compound or a thioisocyanate compound.
- 제7항에 있어서, 상기 이소시아네이트화합물 또는 이소티오시아네이트화합물은, 헥사메틸렌디이소시아네이트, 2,2-디메틸펜탄디이소시아네이트, 2,2,4-트리메틸헥산디이소시아네이트, 부텐디이소시아네이트, 1,3-부타디엔-1,4-디이소시아네이트, 2,4,4-트리메틸헥사메틸렌디이소시아네이트, 1,6,11-운데칸트리이소시아네이트, 1,3,6-헥사메틸렌트리이소시아네이트, 1,8-디이소시아네이토-4-이소시아네이토메틸옥탄, 비스(이소시아네이토에틸)카보네이트, 비스(이소시아네이토에틸)에테르, 리신디이소시아네이토메틸에스테르, 리신트리이소시아네이트 등의 지방족 폴리이소시아네이트 화합물; 1,2-디이소시아네이토벤젠, 1,3-디이소시아네이토벤젠, 1,4-디이소시아네이토벤젠, 2,4-디이소시아네이토톨루엔, 에틸페닐렌디이소시아네이트, 이소프로필페닐렌디이소시아네이트, 자일릴렌디이소시아네이트, 톨릴렌-2,4-디이소시아네이트, 디에틸페닐렌디이소시아네이트, 디이소프로필페닐렌디이소시아네이트, 트리메틸벤젠트리이소시아네이트, 벤젠트리이소시아네이트, 비페닐디이소시아네이트, 톨루이딘디이소시아네이트, 4,4'-메틸렌비스(페닐이소시아네이트), 4,4-메틸렌비스(2-메틸페닐이소시아네이트), 비벤질-4,4-디이소시아네이트, 비스(이소시아네이토페닐)에틸렌, 비스(이소시아네이토에틸)벤젠, 비스(이소시아네이토프로필)벤젠, α,α,α',α'-테트라메틸 크실릴렌디이소시아네이트, 비스(이소시아네이토부틸)벤젠, 비스(이소시아네이토메틸)나프탈린, 비스(이소시아네이토메틸페닐)에테르, 비스(이소시아네이토에틸)프탈레이트, 2,6-디(이소시아네이토메틸)푸란 등의 방향환 화합물을 가지는 폴리이소시아네이트 화합물; 이소포론디이소시아네이트, 3,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 3,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,8-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 4,9-비스(이소시아나토메틸)트리시클로[5,2,1,02,6]데칸, 2,5-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 2,6-비스(이소시아나토메틸)비시클로[2,2,1]헵탄, 비스(이소시아네이토메틸)시클로헥산, 디시클로헥실메탄디이소시아네이트, 시클로헥산디이소시아네이트, 메틸시클로헥산디이소시아네이트, 디시클로헥실디메틸메탄디이소시아네이트, 2,2′-디메틸디시클로헥실메탄디이소시아네이트, 비스(4-이소시아네이토-n-부틸리덴)펜타에리트리톨, 다이머산디이소시아네이트, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-5-이소시아네이토메틸비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-이소시아네이토메틸비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-5-이소시아네이토메틸-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-6-이소시아네이토메틸-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-3-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-5-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 2-이소시아네이토메틸-2-(3-이소시아네이토프로필)-6-(2-이소시아네이토에틸)-비시클로[2,2,1]-헵탄, 1,3,5-트리스(이소시아네이토메틸)-시클로헥산, 디시클로헥실메탄-4,4-디이소시아네이트(H12MDI) 등의 지환족 화합물을 가지는 폴리이소시아네이트 화합물; 티오펜-2,5-디이소시아네이트, 메틸 티오펜-2,5-디이소시아네이트, 1,4-디티안-2,5-디이소시아네이트, 메틸 1,4-디티안-2,5-디이소시아네이트, 1,3-디티올란-4,5-디이소시아네이트, 메틸 1,3-디티올란-4,5-디이소시아네이트, 메틸 1,3-디티올란-2-메틸-4,5-디이소시아네이트, 에틸 1,3-디티올란-2,2-디이소시아네이트, 테트라히드로티오펜-2,5-디이소시아네이트, 메틸테트라히드로티오펜-2,5-디이소시아네이트, 에틸 테트라히드로티오펜-2,5-디이소시아네이트, 메틸 테트라히드로티오펜-3,4-디이소시아네이트, 1,2-디이소티오시아네이토에탄, 1,3-디이소티오시아네이토프로판, 1,4-디이소티오시아네이토부탄, 1,6-디이소티오시아네이토헥산, p-페닐렌디이소프로필리덴디이소티오시아네이트, 시클로헥산디이소티오시아네이트 등의 헤테로고리 디이소시아네이트 화합물; 비스(이소시아네이토메틸)설파이드, 비스(이소시아네이토에틸)설파이드, 비스(이소시아네이토프로필)설파이드, 비스(이소시아네이토헥실)설파이드, 비스(이소시아네이토메틸)설파이드, 비스(이소시아네이토메틸)디설파이드, 비스(이소시아네이토에틸)디설파이드, 비스(이소시아네이토프로필)디설파이드, 비스(이소시아네이토메틸티오)메탄, 비스(이소시아네이토에틸티오)메탄, 비스(이소시아네이토메틸티오)에탄, 비스(이소시아네이토에틸티오)에탄, 1,5-디이소시아네이토-2-이소시아네이토메틸-3-티아펜탄, 1,2,3-트리스(이소시아네이토메틸티오)프로판, 1,2,3-트리스(이소시아네이토에틸티오)프로판, 3,5-디티아-1,2,6,7-헵탄테트라이소시아네이트, 2,6-디이소시아네이토메틸-3,5-디티아-1,7-헵탄디이소시아네이트, 2,5-디이소시아네이토메틸티오펜, 4-이소시아네이토에틸티오-2,6-디티아-1,8-옥탄디이소시아네이트 등의 황함유 지방족 폴리이소시아네이트 화합물; 2-이소시아네이토페닐-4-이소시아네이토페닐설피드, 비스(4-이소시아네이토페닐)설피드, 비스(4-이소시아네이토메틸페닐)설피드 등의 방향족 설피드계 폴리이소시아네이트 화합물; 비스(4-이소시아네이토페닐)디설피드, 비스(2-메틸-5-이소시아네이토페닐)디설파이드, 비스(3-메틸-5-이소시아네이토페닐)디설파이드, 비스(3-메틸-6-이소시아네이토페닐)디설파이드, 비스(4-메틸-5-이소시아네이토페닐)디설파이드, 비스(4-메톡시-3-이소시아네이토페닐)디설파이드 등의 방향족 디설피드계 폴리이소시아네이트 화합물; 2,5-디이소시아네이토테트라히드로티오펜, 2,5-디이소시아네이토메틸테트라히드로티오펜, 3,4-디이소시아네이토메틸테트라히드로티오펜, 2,5-디이소시아네이토-1,4-디티안, 2,5-디이소시아네이토메틸-1,4-디티안, 4,5-디이소시아네이토-1,3-디티오란, 4,5-비스(이소시아네이토메틸)1,3-디티오란, 4,5-디이소시아네이토메틸-2-메틸-1,3-디티오란 등의 황함유 지환족 폴리이소시아네이트 화합물; 1,2-디이소티오시아네이토에탄, 1,6-디이소티오시아네이토헥산 등의 지방족 폴리이소티오시아네이트 화합물; 시클로헥산디이소티오시아네이트 등의 지환족 폴리이소티오시아네이트 화합물; 1,2-디이소티오시아네이토벤젠, 1,3-디이소티오시아네이토벤젠, 1,4-디이소티오시아네이토벤젠, 2,4-디이소티오시아네이토톨루엔, 2,5-디이소티오시아네이토-m-크실렌, 4,4-메틸렌비스(페닐이소티오시아네이트), 4,4-메틸렌비스(2-메틸페닐이소티오시아네이트), 4,4-메틸렌비스(3-메틸페닐이소티오시아네이트), 4,4-디이소티오시아네이토벤조페논, 4,4-디이소티오시아네이토-3,3-디메틸벤조페논, 비스(4-이소티오시아네이토페닐)에테르 등의 방향족 폴리이소티오시아네이트 화합물; 1,3-벤젠디카르보닐디이소티오시아네이트, 1,4-벤젠디카르보닐디이소티오시아네이트, (2,2-피리딘)-4,4-디카르보닐디이소티오시아네이트 등의 카르보닐 폴리이소티오시아네이트 화합물; 티오비스(3-이소티오시아네이토프로판), 티오비스(2-이소티오시아네이토에탄), 디티오비스(2-이소티오시아네이토에탄) 등의 황함유 지방족 폴리이소티오시아네이트 화합물; 1-이소티오시아네이토-4-[(2-이소티오시아네이토)티오]벤젠, 티오비스(4-이소티오시아네이토벤젠), 설포닐(4-이소티오시아네이토벤젠), 디티오비스(4-이소티오시아네이토벤젠) 등의 황함유 방향족 폴리이소티오시아네이트화합물; 2,5-디이소티오시아네이토티오펜, 2,5-디이소티오시아네이토-1,4-디티안 등의 황함유 지환족 폴리이소 티오시아네이트 화합물; 1-이소시아네이토-6-이소티오시아네이토헥산, 1-이소시아네이토-4-이소티오시아네이토시클로헥산, 1-이소시아네이토-4-이소티오시아네이토벤젠, 4-메틸-3-이소시아네이토-1-이소티오시아네이토벤젠, 2-이소시아네이토-4,6-디이소티오시아네이토-1,3,5-트리아진, 4-이소시아네이토페닐-4-이소티오시아네이토페닐설피드 및 2-이소시아네이토-에틸-2-이소티오시아네이토에틸디설피드로 구성된 군으로부터 선택된 1종 또는 2종 이상인 것을 특징으로 하는 광학재료용 수지 조성물.The said isocyanate compound or the isothiocyanate compound of Claim 7 is hexamethylene diisocyanate, 2, 2- dimethylpentane diisocyanate, 2, 2, 4- trimethyl hexane diisocyanate, butene diisocyanate, 1, 3- Butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate Aliphatic polyisocyanate compounds such as iso-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester and lysine triisocyanate; 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate , Xylylene diisocyanate, tolylene-2,4-diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4 '-Methylenebis (phenylisocyanate), 4,4-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatoethyl) Benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethyl xylylenediisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) Phthalic, bis (isocyanatomethyl phenyl) ether, bis (isocyanato ethyl) phthalate, 2,6-polyisocyanate compounds having an aromatic ring compound such as (isocyanatomethyl) furan; Isophorone diisocyanate, 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-bis (isocyanatomethyl) tricyclo [5,2 , 1,02,6] decane, 2,5-Bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, Bis (isocyanatomethyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl dimethyl methane diisocyanate, 2,2'-dimethyldicyclohexyl methane diisocyanate, Bis (4-isocyanato-n-butylidene) pentaerythritol, dimer acid diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl Bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethylbicyclo [2,2,1] -heptane , 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2 -(3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-iso Anatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -ratio Cyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2, 1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 1 , 3,5-tris (isocyanatomethyl) -cyclohexane, dicyclohexylmethane-4,4-diisocyanate (H12Polyisocyanate compounds having an alicyclic compound such as MDI); Thiophene-2,5-diisocyanate, methyl thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, methyl 1,4-dithiane-2,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-4,5-diisocyanate, methyl 1,3-dithiolane-2-methyl-4,5-diisocyanate, ethyl 1 , 3-dithiolane-2,2-diisocyanate, tetrahydrothiophene-2,5-diisocyanate, methyltetrahydrothiophene-2,5-diisocyanate, ethyl tetrahydrothiophene-2,5-diisocyanate , Methyl tetrahydrothiophene-3,4-diisocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, Heterocyclic diisocyanate compounds such as 1,6-diisothiocyanatohexane, p-phenylenediisopropylidenediisothiocyanate and cyclohexanediisothiocyanate; Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfide, Bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) Methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2, 3-tris (isocyanatomethylthio) propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptane tetraisocyanate, 2 , 6-Diisocyanatomethyl-3,5-dithia-1,7-heptane diisocyanate, 2,5-diisocyanatomethylthiophene, 4-iso Sulfur-containing aliphatic polyisocyanate compounds such as isocyanato ethyl thio-2,6-thiazole-1,8-octane diisocyanate; Aromatic sulfide-based polys such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, and bis (4-isocyanatomethylphenyl) sulfide Isocyanate compounds; Bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl Aromatic disulfide-based polys such as -6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, and bis (4-methoxy-3-isocyanatophenyl) disulfide Isocyanate compounds; 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato- 1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolan, 4,5-bis (isocyanato Sulfur-containing alicyclic polyisocyanate compounds such as methyl) 1,3-dithiolane and 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane; Aliphatic polyisothiocyanate compounds such as 1,2-diisothiocyanatoethane and 1,6-diisothiocyanatohexane; Alicyclic polyisothiocyanate compounds such as cyclohexanediisothiocyanate; 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2, 5-diisothiocyanato-m-xylene, 4,4-methylenebis (phenylisothiocyanate), 4,4-methylenebis (2-methylphenylisothiocyanate), 4,4-methylenebis ( 3-methylphenylisothiocyanate), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyanato-3,3-dimethylbenzophenone, bis (4-isothiocyanato Aromatic polyisothiocyanate compounds such as phenyl) ether; Carbonyl poly, such as 1, 3- benzenedicarbonyl diisothiocyanate, 1, 4- benzenedicarbonyl diisothiocyanate, and (2, 2-pyridine) -4, 4- dicarbonyl diisothiocyanate Isothiocyanate compounds; Sulfur-containing aliphatic polyisothiocyanate compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane) and dithiobis (2-isothiocyanatoethane); 1-isothiocyanato-4-[(2-isothiocyanato) thio] benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), Sulfur-containing aromatic polyisothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene); Sulfur-containing alicyclic polyiso thiocyanate compounds such as 2,5-diisothiocyanatothiophene and 2,5-diisothiocyanato-1,4-dithiane; 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4 -Methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocy Optical, characterized in that one or more selected from the group consisting of anatotophenyl-4-isothiocyanatophenylsulfide and 2-isocyanato-ethyl-2-isothiocyanatoethyldisulfide Resin composition for materials.
- 제7항에 있어서, 상기 식 1의 폴리티올화합물 외에 다른 티올화합물을 더 포함하며, 다른 티올화합물은, 1,2-에탄디티올; 1,1-프로판디티올; 1,2-프로판디티올; 1,3-프로판디티올; 2,2-프로판디티올; 2,5-헥산디티올; 1,6-헥산디티올; 2,9-데칸디티올; 1,4-비스(1-메르캅토에틸)벤젠; 시클로헥산디티올; 1,2,3-프로판트리티올; 1,1-비스(메르캅토메틸시클로헥산); 1,2-디메르캅토프로필메틸에테르; 2,3-디메르캅토프로필메틸에테르; 2,2-비스(메르캅토메틸)-1,3-프로판디티올; 비스(2-메르캅토에틸)에테르; 테트라키스(메르캅토메틸)메탄; 2-(2-메르캅토에틸티오)프로판-1,3-디티올; 2,3-비스(2-메르캅토에틸티오)프로판-1-티올; 2-(2,3-비스(2-메르캅토에틸티오)프로필티오)에탄티올;비스(2,3-디메르캅토프로판닐)설파이드; 비스(2,3-디메르캅토프로판닐)디설파이드; 1,2-비스(2-메르캅토에틸티오)-3-메르캅토프로판; 1,2-비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필티오)에탄; 비스(2-(2-메르캅토에틸티오)-3-메르캅토프로필)술피드; 2-(2-메르캅토에틸티오)-3-2-메르캅토-3-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]프로필티오-프로판-1-티올; 2,2 -비스-(3-메르캅토-프로피오닐옥시메틸)-부틸 에스테르; 2-(2-메르캅토에틸티오)-3-(2-(2-[3-메르캅토-2-(2-메르캅토에틸티오)-프로필티오]에틸티오)에틸티오)프로판-1-티올; 트리메틸올프로판 트리스(메르캅토프로피오네이트); 트리메틸올에탄 트리스(메르캅토프로피오네이트); 글리세롤 트리스(메르캅토프로피오네이트); 트리메틸올클로로 트리스(메르캅토프로피오네이트); 트리메틸올프로판 트리스(메르캅토아세테이트); 트리메틸올에탄 트리스(메르캅토아세테이트); 펜타에리트리톨테트라키스(메르캅토프로피오네이트) (PETMP); 펜타에리트리톨테트라키스(메르캅토아세테이트)(PETMA); 비스펜타에리트리톨-에테르-헥사키스(메르캅토프로피오네이트)(BPEHMP); 비스펜타에리트리톨-에테르-헥사키스(2-메르캅토아세테이트)(BPEHMA); 비스펜타에리트리톨헥사(2-메르캅토아세테이트)(BPEMA); 비스트리메틸올프로판테트라키스(3-메르캅토프로피오네이트) (BTMPMP); 및 비스트리메틸올프로판테트라키스(2-메르캅토아세테이트)(BTMPMA)로 구성된 군으로부터 선택된 1종 또는 2종 이상인 것을 특징으로 하는 광학재료용 수지 조성물.The method according to claim 7, further comprising a thiol compound other than the polythiol compound of Formula 1, wherein the other thiol compound is 1,2-ethanedithiol; 1,1-propanedithiol; 1,2-propanedithiol; 1,3-propanedithiol; 2,2-propanedithiol; 2,5-hexanedithiol; 1,6-hexanedithiol; 2,9-decanedithiol; 1,4-bis (1-mercaptoethyl) benzene; Cyclohexanedithiol; 1,2,3-propanethiol; 1,1-bis (mercaptomethylcyclohexane); 1,2-dimercaptopropylmethyl ether; 2,3-dimercaptopropylmethyl ether; 2,2-bis (mercaptomethyl) -1,3-propanedithiol; Bis (2-mercaptoethyl) ether; Tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol; 2,3-bis (2-mercaptoethylthio) propane-1-thiol; 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol; bis (2,3-dimercaptopropanyl) sulfide; Bis (2,3-dimercaptopropanyl) 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; 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio) propane-1-thiol ; Trimethylolpropane tris (mercaptopropionate); Trimethylolethane tris (mercaptopropionate); Glycerol tris (mercaptopropionate); Trimethylolchloro tris (mercaptopropionate); Trimethylolpropane tris (mercaptoacetate); Trimethylolethane tris (mercaptoacetate); Pentaerythritol tetrakis (mercaptopropionate) (PETMP); Pentaerythritol tetrakis (mercaptoacetate) (PETMA); Bispentaerythritol-ether-hexakis (mercaptopropionate) (BPEHMP); Bispentaerythritol-ether-hexakis (2-mercaptoacetate) (BPEHMA); Bispentaerythritol hexa (2-mercaptoacetate) (BPEMA); Bistrimethylolpropanetetrakis (3-mercaptopropionate) (BTMPMP); And bistrimethylolpropane tetrakis (2-mercaptoacetate) (BTMPMA).
- 제7항에 있어서, 이형제, 안정제(열안정제), 산화방지제, 촉매, 자외선흡수제, 색상보정제(안료, 염료)를 1종 또는 2종 이상 사용하는 것을 특징으로 하는 광학재료용 수지 조성물.8. The resin composition for an optical material according to claim 7, wherein one or two or more release agents, stabilizers (heat stabilizers), antioxidants, catalysts, ultraviolet absorbers, color correctors (pigments, dyes) are used.
- 제7항의 광학재료용 수지 조성물을 경화시켜 얻은 광학재료용 수지.Resin for optical materials obtained by hardening | curing the resin composition for optical materials of Claim 7.
- 제11항의 광학재료용 수지로 이루어진 광학제품. An optical product comprising the resin for optical materials according to claim 11.
- 제12항에 있어서, 상기 광학제품은 안경렌즈, 3D 편광렌즈, 편광렌즈, 프리즘필름, 광섬유, 광디스크, 자기디스크, 기록매체 기판, 착색 필터, 자외선 흡수 필터 중 어느 하나인 것을 특징으로 하는 광학제품. The optical product according to claim 12, wherein the optical product is any one of an eyeglass lens, a 3D polarizing lens, a polarizing lens, a prism film, an optical fiber, an optical disk, a magnetic disk, a recording medium substrate, a coloring filter, and an ultraviolet absorption filter. .
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CN105601549A (en) * | 2015-12-25 | 2016-05-25 | 四川大学 | Simulated sensitive diisocyanate |
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WO2023167262A1 (en) * | 2022-03-01 | 2023-09-07 | 三井化学株式会社 | Resin, molded article, optical material, lens, 2,5-bis(isocyanatomethyl)furan, and polymerizable composition |
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