WO2013069964A1

WO2013069964A1 - Method for manufacturing thiourethane-based optical material

Info

Publication number: WO2013069964A1
Application number: PCT/KR2012/009344
Authority: WO
Inventors: 장동규; 노수균; 김문일; 김종효; 서진무
Original assignee: 주식회사 케이오씨솔루션
Priority date: 2011-11-07
Filing date: 2012-11-07
Publication date: 2013-05-16
Also published as: CN106220813A; KR20140001808A; CN106220813B; KR20130050262A; CN103917579A

Abstract

The present invention relates to a method for manufacturing thiourethane-based optical material, and particularly to a method for manufacturing high-quality optical material having high yield without developing striae or white turbidity due to imbalanced polymerization, and is colorless, transparent and changeless. Provided is a method for manufacturing thiourethane-based optical material in which a polymerization composite, comprising a polythiol compound and a polyiso(thio)cyanate compound, is in-mold polymerized, and is characterized in that mixing, defoaming and injection into a mold are performed within the 21- 40℃ temperature range. The thiourethane-based optical material manufactured according to the present invention can replace existing optical material and be widely used in a variety of industries.

Description

Method for manufacturing thiourethane optical material

The present invention relates to a method for producing a thiourethane-based optical material, and in particular, to a method for producing a high-quality optical material that is colorless, transparent and without deformation without occurrence of stria and turbidity due to polymerization imbalance.

Plastic optical lenses were introduced as a replacement for the high specific gravity and low impact of glass lenses. Representative examples thereof include polyethylene glycol bisallylcarbonate, polymethyl methacrylate, diallyl phthalate, and the like. However, optical lenses made of these polymers are excellent in physical properties such as moldability, dyeability, hard coat coating adhesion, impact resistance, etc., but the refractive index is about 1.50 (nD) and 1.55 (nD), resulting in a problem of thickening the lens. . Therefore, various attempts have been made to develop optical materials having high refractive indexes to reduce the thickness of lenses.

In Korean Patent Nos. 10-0136698, 10-0051275, 10-0051939, 10-0056025, 10-0040546, 10-0113627, and the like, a polyisocyanate compound and a polythiol compound are thermally cured to manufacture a thiourethane optical lens. Thiourethane-based optical materials are widely used as optical lens materials because of excellent optical properties such as transparency, Abbe number, transmittance, and phosphorus strength. However, when hardening the polymerizable composition containing a polythiol compound and a general-purpose isocyanate compound to produce an optical material, striae, haze and the like may occur to deteriorate the quality of the lens. 3,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 3,9-bis (isocyanato) having isoisocyanate compound and excellent blendability with polythiol compound Methyl) tricyclo [5,2,1,02,6] decane, 4,8-bis (isocyanatomethyl) tricyclo [5,2,1,02,6] decane, 4,9-bis (iso Cyanatomethyl) tricyclo [5,2,1,02,6] decane, 2,5 - bis (isocyanatomethyl) bicyclo [2,2,1] heptane, 2,6-bis (isocyanato In the case of using methyl) bicyclo [2,2,1] heptane, such a phenomenon is less, but there is a problem in that the production cost increases due to the use of expensive isocyanate compounds. On the other hand, isophorone diisocyanate, dicyclohexyl methane-4,4'-diisocyanate (H ₁₂ MDI), 1,6-hexamethylene diisocyanate, etc. are inexpensive general-purpose polyiso (thio) cyanate compounds and thiourethane-based compounds. Although the production cost of the optical material can be lowered, there is a problem of occurrence of turbidity due to the stria due to the polymerization imbalance and tape adhesive when the lens is manufactured due to poor mixing with the polythiol compound. Since the occurrence of stria and turbidity degrade the quality of the lens, improvement has been required in the meantime. In addition, the production cost reduction has been a major concern in the recent lens field, the occurrence of striae, turbidity, etc. is a factor that increases the production cost by lowering the lens yield, the improvement is also urgently required in terms of production cost reduction.

The present invention solves the problems of polymerization imbalance and turbidity when polymerizing a polythiol compound and a general-purpose polyiso (thio) cyanate compound to produce a thiourethane-based optical material, while using a general-purpose polyisocyanate compound. It is an object of the present invention to provide a high-quality thiourethane optical material that is free from white turbulence due to adhesive elution of the tape and tape due to polymerization imbalance. "Stria" refers to a phenomenon that is locally different from the surrounding normal refractive index due to a difference in composition. "Cloudy" means that when the polymerizable composition for an optical lens is cured, turbidity appears in the optical lens due to polymerization heterogeneity. In the present invention, "general purpose polyiso (thio) cyanate compound" refers to a polyiso (thio) cyanate compound, which is mass-produced and inexpensive because it is used for other purposes besides optical lenses, in particular, isophorone di Isocyanate, dicyclohexylmethane-4,4'-diisocyanate (H ₁₂ MDI), 1,6-hexamethylene diisocyanate, 1,3,5-tris (6-isocyanatohexyl)-[1,3 , 5] -triziane-2,4,6-trione (HDI trimer), o, m, p-xylylenediisocyanate, α, α, α ', α'-tetramethylxylylenediisocyanate, tolyl Rendiisocyanate (TDI) and the like. In the present invention, "stress" includes polymerization heterogeneity caused by poor reactivity with a polythiol compound and consequently stria, especially when a general purpose polyiso (thio) cyanate compound is used. In addition, in the present invention, "clouding" includes, in particular, the use of a general-purpose polyiso (thio) cyanate compound, which elutes the tape adhesive of the mold, causing cloudiness to the polymerized lens. The striae and turbidity generated during the lens polymerization degrade the product yield and adversely affect the quality and performance of the final optical material.

The inventors have unexpectedly found that the temperature in the process of blending, defoaming and injecting the polymerizable composition has a significant correlation with the occurrence of striae and haze of the finally obtained lens. That is, when the polymerizable composition is blended, degassed at a specific temperature, and injected into a mold to polymerize, even if a general purpose polyiso (thio) cyanate compound is used, the polymerization is uniform and the adhesive of the tape is not eluted, thereby finally obtaining the polymerized composition. Almost no stria and turbidity occurred in the lens. The present invention has been confirmed and completed, the present invention, using a polymerizable composition comprising a polythiol compound and a general-purpose polyiso (thio) cyanate compound, colorless transparent high-quality thio without the occurrence of striae and turbidity It is an object to provide a method for producing a urethane-based optical material.

In the present invention,

In the manufacturing method of the optical material which mold-polymerizes the polymerizable composition containing a polythiol compound and a polyiso (thio) cyanate compound, the said polymerizable composition mix | blended, defoaming, and injection | pouring into a mold are 21-40 degreeC Provided is a method for producing a thiourethane-based optical material, which is made in a range.

Further, in the present invention, an optical material obtained by the above manufacturing method and an optical lens composed of the optical material are provided. The optical lens in particular comprises an spectacle lens or a polarizing lens.

In the present invention, by mixing, defoaming, and molding the polymerizable composition in a specific temperature range, a colorless, transparent, high-quality lens is used, which is inexpensive due to polymerization imbalance while using a general-purpose polyiso (thio) cyanate compound which is inexpensive. It can manufacture. In particular, the optical material obtained in accordance with the present invention is colorless and transparent, has a high refractive index, low dispersion, excellent impact properties, stainability, processability, etc., and has the optimum conditions for plastic lenses. Production costs can also be significantly reduced due to improved use and yield. The optical material obtained according to the present invention can be widely used in various fields in place of the conventional thiourethane optical material.

In the method for producing a thiourethane-based optical material of the present invention, the polymerization is carried out by maintaining the temperature in a specific range in the process of compounding, defoaming, and mold injection of a polymerizable composition containing a polythiol compound and a polyiso (thio) cyanate compound.

As a result of earnest examination, the present inventors have found that the occurrence of polymerization unevenness and turbidity of an optical lens made of a polyurethane-based resin has a close correlation with the polymerization rate of the polymerizable composition, that is, the blending and injection temperature of the polymerizable composition. Also, conventionally, expensive isocyanate compounds (isocyanate 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane, etc.) and polythiol compounds having properties excellent in compatibility with polythiol compounds When manufacturing a lens by polymerizing a polymerizable composition consisting of, the temperature was maintained at 10 ~ 20 ℃ during the compounding defoaming process and injection process, in this case, when the temperature is 20 ℃ or more, the reaction occurs rapidly, the viscosity of the composition Elevation prevented injection of the composition into the mold. However, polymerizable compositions composed of polyiso (thio) cyanate compounds and polythiol compounds such as hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, etc., which are general-purpose polyiso (thio) cyanates, Compounding and injecting in the range of ˜20 ° C. resulted in polymerization unevenness and clouding problems in the optical lens. In the present invention, such a polymerization non-uniformity and turbidity problem was solved by adjusting the blending and injection temperature of the polymerizable composition to 21-40 ° C. In the present invention, the blending and injection temperature of the polymerizable composition comprising a polythiol compound and a polyiso (thio) cyanate compound is preferably 21 to 40 ° C, more preferably 28 to 36 ° C. The correlation between polymerization heterogeneity and turbidity with respect to this temperature has not been recognized in the prior art. Conventionally, in order to solve the problem of polymerization unevenness and turbidity, a method of using an expensive isocyanate compound having excellent miscibility with a polythiol compound is selected, but in the present invention, a general purpose polyiso (thio) cyanate compound is used. Solve the problem.

In the present invention, the blending and injection temperature of the polymerizable composition containing the polythiol compound and the polyiso (thio) cyanate compound is preferably 21 to 40 ° C, more preferably 28 to 36 ° C. If the mixing defoaming and the injection temperature of the polymerizable composition is adjusted to 40 ° C. or more, the pot life is shortened, which causes difficulty in injection, and causes striae in the manufactured optical lens. In addition, if the mixing defoaming and the injection temperature of the polymerizable composition is adjusted to 21 ° C. or lower, the reaction rate may be slow, and white turbidity may occur in the manufactured optical lens. When the blending, defoaming and injection temperature of the polymerizable composition was in the range of 21 to 40 ° C., high performance high refractive index polyurethane optical lenses without streaks or white turbidity, colorless transparency, and no deformation were produced, and more preferably 28 When the temperature was in the range of -36 ° C., the most excellent high refractive index polyurethane optical lens could be manufactured.

The polyiso (thio) cyanate compound included in the polymerizable composition of the present invention is preferably a general purpose polyiso (thio) cyanate compound. The general purpose polyiso (thio) cyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, 1,3,5-tris (6-isocyanatohexyl)- [1,3,5] -triziane-2,4,6-trione, o, m, p-xylylenediisocyanate, α, α, α ', α'-tetramethylxylylenediisocyanate, tolylenedi It is 1 or more types of isocyanate (TDI).

The polymerizable composition of the present invention may further include one kind or two or more kinds of compounds having an iso (thio) cyanate group, that is, polyisocyanate or polyisothiocyanate, in addition to the general-purpose polyiso (thio) cyanate compound. have. The compound which has the iso (thio) cyanate group further contained is, for example, an alicyclic polyisocyanate compound; Polyisocyanate compounds having an aromatic ring compound; Sulfur-containing aliphatic polyisocyanate compounds; Aromatic sulfide-based polyisocyanate compounds; Aromatic disulfide polyisocyanate compounds; Sulfur-containing alicyclic polyisocyanate compounds; Aliphatic polyisothiocyanate compounds; Alicyclic polyisothiocyanate compounds; Aromatic polyisothiocyanate compounds; Carbonyl polyisothiocyanate compounds; Sulfur-containing aliphatic polyisothiocyanate compounds; Sulfur-containing aromatic polyisothiocyanate compounds; Sulfur-containing alicyclic polyisothiocyanate compounds; Polyiso (thio) cyanate compound etc. which have an isocyanato group and an iso thio cyanato group are all possible. In addition, halogen substituents such as chlorine substituents and bromine substituents, alkyl substituents, alkoxy substituents, prepolymer-type modifications with nitro substituents and polyhydric alcohols, carbodiimide modifications, urea modifications, biuret modifications, dimerization or Trimerization reaction products, etc. can also be used. Each of the above exemplary compounds may be used alone or in combination of two or more thereof. Preferably, the compound having an iso (thio) cyanate group further included is 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexanediisocyanate, butene diisocyanate, 1,3-butadiene-1,4 -Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undectriisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanato Aliphatic isocyanate compounds such as methyl octane, bis (isocyanatoethyl) carbonate and bis (isocyanatoethyl) ether; 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, cyclohexanediisocyanate, Alicyclic isocyanate compounds such as methylcyclohexanediisocyanate, dicyclohexyldimethylmethane isocyanate and 2,2-dimethyldicyclohexylmethane isocyanate; Bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylenedi Isocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzenetriisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenyl Methane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzenediisocyanate Aromatic isocyanate compounds such as hexahydrodiphenylmethane-4,4-diisocyanate and bis (isocyane) Toethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (Isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethyl Sulfur-containing aliphatic isocyanate compounds such as thio) ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyane Itomethylbenzene) sulfide, 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyldiphenyldisulfide-5,5 -Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4-dimethyldiphenyldisulfide-5, Sulfur-containing aromatic isocyanate compounds such as 5-diisocyanate, 3,3-dimethoxy diphenyldisulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyldisulfide-3,3-diisocyanate; 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) Tetrahydrothiophene, 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiorane, 4,5-bis (isocyanatomethyl) -1,3-dithiorane, 4,5-bis ( One or two or more iso (thio) cyanate compounds selected from the group consisting of sulfur-containing heterocyclic isocyanate compounds such as isocyanatomethyl) -2-methyl-1,3-dithiolane.

In the polymerizable composition of the present invention, the polythiol compound is not particularly limited, and may be used alone or in combination of two or more if it is a compound having at least one thiol group. For example, aliphatic polythiol compounds; Aromatic polythiol compounds; Aromatic polythiol compounds containing sulfur atoms; Aliphatic polythiol compounds containing sulfur atoms and esters of thioglycolic acid and mercaptopropionic acid; Aliphatic polythiol compounds containing a sulfur atom and an ester bond in addition to the mercapto group; Heterocyclic compounds containing a sulfur atom; A compound containing a hydroxy group; Compounds having a dithioacetal or dithioketal skeleton; A compound having an orthotrithioformate ester skeleton; The compound etc. which have an ortho tetrathio carbonate ester frame | skeleton can be used. The polythiol compound which can be used is not limited to each above-mentioned exemplified compound, Moreover, each above-mentioned exemplified compound may be used individually or in mixture of 2 or more types. Preferably, the polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) -3-propane-1 -Thiol, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) 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-propionyloxy Methyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio Propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12-tetrathiatetradecane-1,14-dithiol, (S) -3- ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4 R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mer Capto-2-((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2-((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane -1,2-dithiol), (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R , 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1, 11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropio Nate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate) , 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1 1 or 2 or more types of compounds selected from the group consisting of, 3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane. The polythiol compound is particularly preferably 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 2-[(2-mercaptoethyl) thio] propane-1,3-dithi All or one selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane and 2-mercaptoethanol The above compound.

The use ratio of a polythiol compound and a polyiso (thio) cyanate compound is SH group / NCO group = 0.5-3.0, Preferably it is 0.6-2.0, More preferably, it exists in the range of 0.8-1.3.

The polymerizable composition of the present invention is, in addition, as necessary, similar to a thiourethane-based polymerizable composition for optical materials, such as an internal mold release agent, an ultraviolet absorber, a dye, a stabilizer, a blueing agent, a chain extender, a crosslinking agent, a light stabilizer, and an antioxidant. And optional components such as a filler may be further included. Moreover, in order to adjust reaction rate, the well-known reaction catalyst used in manufacture of thiocarbamic acid S-alkyl ester or a polyurethane can also be added suitably. It is also possible to further include an epoxy compound, a thioepoxy compound, a compound having a vinyl group or an unsaturated group, a metal compound, or the like, which is copolymerizable with the urethane resin composition.

As said internal mold release agent, a phosphate ester compound, a silicone type surfactant, a fluorine type surfactant, etc. can be used individually or in combination of 2 or more types, respectively. Preferably, a phosphate ester compound is used as an internal mold release agent. Phosphoric acid ester compound is prepared by adding 2-3 mol alcohol compound to phosphorus pentoside (P ₂ O ₅ ), and there may be various forms of acidic phosphoric acid ester compound depending on the type of alcohol used. Typical examples include those in which ethylene oxide or propylene oxide is added to the aliphatic alcohol, or ethylene oxide or propylene oxide is added to the nonylphenol group. When the acidic phosphate ester compound added with ethylene oxide or propylene oxide is included in the polymerizable composition of the present invention as an internal mold release agent, an optical material having good release property and excellent quality can be obtained. The phosphate ester compound used as the internal mold release agent is preferably polyoxyethylene nonylphenol ether phosphate (5 wt% with 5 mol of ethylene oxide added, 80 wt% with 4 mol added, 10 wt with 3 mol added). %, 1 mole added 5% by weight), polyoxyethylenenonylphenol ether phosphate (3% by weight 9 mole of ethylene oxide added, 80% by weight 8 mole added, 5% by weight 9 mole added, 7 mole added 6% by weight, 6 mole added 6% by weight), polyoxyethylene nonylphenol ether phosphate (13 mole added by ethylene oxide 3% by weight, 12 mole added by 80% by weight, 11 mole added 8% by weight, 9% by weight, 3% by weight, 4% by weight, 6% by weight of polyoxyethylenenonylphenol ether phosphate (3% by weight, 17% by weight of ethylene oxide) 79 weight%, 15 mol added 10 weight%, 14 mol added 4 weight%, 13 mol added 4 weight%), polyoxyethyl Nonylphenol ether phosphate (21% added ethylene oxide 5% by weight, 20 moles added 76% by weight, 19 moles added 7% by weight, 18 moles added 6% by weight, 17 moles added 4 Wt%), acidic phosphate ester compounds added with ethylene oxide or propylene oxide, such as Zelec UN ™, may be used alone or in combination of two or more thereof. The internal mold release agent is preferably included at 0.001 to 10% by weight in the total polymerizable composition.

The thiourethane-based optical material of the present invention can be produced by molding a polymerizable composition comprising a polythiol compound and a polyiso (thio) cyanate compound as described above. Specifically, first, a polythiol compound and a polyiso (thio) cyanate compound are mixed, and then the mixed solution (polymerizable composition) is subjected to vacuum degassing by a suitable method as necessary, and then injected into an optical material mold. At this time, mixing (blending), defoaming, injection into the mold is to be made in the temperature range of 21 ~ 40 ℃. After injection into a mold, a thiourethane-based optical material is usually obtained by gradually heating from low temperature to high temperature to polymerize and demolding.

The optical material obtained in accordance with the present invention has a high refractive index, low dispersion, excellent heat resistance and durability, light weight and excellent impact resistance, and good color. Therefore, the optical material obtained according to the present invention is suitable for the use of lenses, prisms, and the like, and is particularly suitable for the use of lenses such as spectacle lenses and camera lenses.

In addition, the optical lens obtained according to the present invention may be subjected to surface polishing and antistatic treatment for the purpose of improving antireflection, high hardness, improving wear resistance, improving chemical resistance, providing weather resistance, or imparting fashion as necessary. And physical and chemical treatments such as hard coat treatment, anti-reflective coat treatment, dyeing treatment, and dimming treatment can be performed.

[실시예]EXAMPLE

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.

시험방법Test Methods

Injection temperature : The injection temperature at the time of inject | pouring a polymeric composition into a mold was measured with the thermometer Fluke 62 Mini Infrared Thermometer (made in China).

Refractive index : The refractive index was measured at 20 ° C. using an Abe refractometer of Atago Co., 1T and DR-M4.

Streak rate : 100 lenses were visually observed under a Mercury Arc Lamp, which is a USHIO USH-10D.

White cloud occurrence rate : 100 lenses were visually observed under a Mercury Arc Lamp, which is a USHIO USH-10D, and it was determined that a lens with variable or middle turbidity was found to have white cloud, and the white cloud occurrence rate was calculated.

Example 1

(1) Measurement of Polymerizable Composition Injection Temperature

50 parts by weight of isophorone diisocyanate, 0.05 parts by weight of dibutyltin dichloride as a curing catalyst, 0.08 parts by weight of phosphate ester (trade name Gelek UN ™) and 0.15 parts by weight of an ultraviolet absorber (SEESORB 709) were mixed and dissolved at 30 ° C. . 49 parts by weight of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane was charged and mixed (mixed) to obtain a mixed homogeneous liquid (polymerizable composition). This mixed homogeneous liquid was defoamed at 1.0 torr for 1 hour and then injected into the lens mold. The temperature at the time of mixing (mixing), defoaming and injecting was measured, and the results are shown in Table 1.

(2) manufacture of plastic lenses

Following the mold injection in (1), the mold was placed in an oven, held at 25 ° C for 4 hours, heated to 50 ° C over 4 hours, heated to 70 ° C over 3 hours, and held for 4 hours. did. Then, it heated up to 80 degreeC over 3 hours, heated up to 130 degreeC over 3 hours, and hold | maintained for 2 hours. Cool down to 80 ° C. over 1 hour. As mentioned above, it superposed | polymerized for 24 hours in the temperature range of 25 degreeC-130 degreeC. After the completion of the polymerization, the mold was taken out of the oven and released to obtain a lens. The obtained lens was annealed further at 130 degreeC for 2 hours. In this way, 100 lenses were produced and the striae generation rate and the turbidity occurrence rate were calculated. The results are shown in Table 1.

Example 2

Except that the type and ratio of the polyisocyanate and polythiol compound in Example 1 were different, the injection temperature of the polymerizable composition and the manufacture of the plastic lens were carried out in the same manner as in Example 1. 30 parts by weight of isophorone diisocyanate and 20 parts by weight of hexamethylene diisocyanate were used as the polyisocyanate, and 40 weights of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane as the polythiol compound. 9 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) was used. The results are shown in Table 1.

Example 3

Except that the kind and ratio of the polyisocyanate and the mercapto compound in Example 1 were different, the injection temperature of the polymerizable composition and the preparation of the plastic lens were carried out in the same manner as in Example 1. 40 parts by weight of isophorone diisocyanate and 10 parts by weight of dicyclohexylmethane diisocyanate were used as the polyisocyanate, and 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane as the polythiol compound. 40 parts by weight and 9 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) were used. The results are shown in Table 1.

Example 4

Except for the different kinds of polyisocyanate and mercapto compound in Example 1, the injection temperature of the polymerizable composition and the preparation of the plastic lens were carried out in the same manner as in Example 1. 50 parts by weight of dicyclohexylmethane diisocyanate was used as the polyisocyanate, and 49 parts by weight of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane was used as the mercapto compound. The results are shown in Table 1.

Comparative Example 1

Except for the different kinds of polyisocyanate in Example 1, the injection temperature of the polymerizable composition and the manufacture of the plastic lens were carried out in the same manner as in Example 1. As the polyisocyanate, 50 parts by weight of xylylene diisocyanate was used. The results are shown in Table 1.

Comparative Example 2

Except that the kind and ratio of polyisocyanate and mercapto compound in Example 1 were different, the injection temperature of the polymerizable composition and the manufacture of the plastic lens were carried out in the same manner as in Example 1. 50 parts by weight of 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane was used as the polyisocyanate, and 1,2-bis [(2-mercaptoethyl) was used as the mercapto compound. 26 parts by weight of thio] -3-mercaptopropane and 23 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) were used. The results are shown in Table 1.

Comparative Example 3

The manufacturing method of the plastic lens was performed similarly to Example 1 except having injected the polymeric composition into the mold at 15 degreeC. The type and ratio of the polyisocyanate and polythiol compound were the same as in Example 2. The results are shown in Table 1.

[Comparative Example 4]

The manufacturing method of the plastic lens was performed similarly to Example 1 except having injected the polymeric composition into the mold at 15 degreeC. The kind and ratio of the polyisocyanate and polythiol compound were the same as in Example 3. The results are shown in Table 1.

[Comparative Example 5]

The manufacturing method of the plastic lens was performed similarly to Example 1 except having injected the polymeric composition into the mold at 55 degreeC. The kind and ratio of the polyisocyanate and polythiol compound were the same as in Example 2. The results are shown in Table 1.

Comparative Example 6

The manufacturing method of the plastic lens was performed similarly to Example 1 except having injected the polymeric composition into the mold at 55 degreeC. The kind and ratio of the polyisocyanate and polythiol compound were the same as in Example 3. The results are shown in Table 1.

Table 1

Abbreviation

IPDI: isophorone diisocyanate

HDI: hexamethylene diisocyanate

H ₁₂ MDI: dicyclohexylmethane-4,4-diisocyanate

XDI: xylylene diisocyanate

NBDI: 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane (2,5-bis (isocyanatomethyl) bicyclo [2,2,1] hepthane

GST: 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane (1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane)

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

According to the present invention, it is possible to easily prepare a thiourethane-based optical material having excellent quality without striae and turbidity, and the thiourethane-based optical material prepared according to the present invention can be widely used in various fields in place of existing optical materials. Specifically, it can be used as a plastic glasses lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, a camera lens, etc. In addition to a variety of optical, such as recording media substrates, color filters and ultraviolet absorption filters used in prisms, optical fibers, optical disks, etc. Can be used in the product.

Claims

In the manufacturing method of the optical material which mold-polymerizes the polymerizable composition containing a polythiol compound and a polyiso (thio) cyanate compound, the said polymerizable composition mix | blended, defoaming, and injection | pouring into a mold are 21-40 degreeC The manufacturing method of the thiourethane type optical material characterized by the above-mentioned.
The method of claim 1, wherein the poly-iso (thio) cyanate compound, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate (H 12 MDI), hexamethylene diisocyanate, 1,3,5- Tris (6-isocyanatohexyl)-[1,3,5] -trizian-2,4,6-trione, o, m, p-xylylene diisocyanate, α, α, α ′, α A method for producing a thiourethane-based optical material, characterized in that it is one or two or more compounds selected from the group consisting of '-tetramethylxylylene diisocyanate and tolylene diisocyanate (TDI).
The polythiol compound according to claim 1, wherein the polythiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) -3- Propane-1-thiol, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane; 2- (2-mercaptoethylthio) propane-1,3-dithiol, 2- (2,3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2,3-dimercapto Propaneyl) 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-propionyloxy Methyl) -butyl ester, 2- (2-mercaptoethylthio) -3- (2- (2- [3-mercapto-2- (2-mercaptoethylthio) -propylthio] ethylthio) ethylthio Propane-1-thiol, (4R, 11S) -4,11-bis (mercaptomethyl) -3,6,9,12-tetrathiatetradecane-1,14-dithiol, (S) -3- ((R-2,3-dimercaptopropyl) thio) propane-1,2-dithiol, (4 R, 14R) -4,14-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptan-1,17-dithiol, (S) -3-((R-3-mer Capto-2-((2-mercaptoethyl) thio) propyl) thio) propyl) thio) -2-((2-mercaptoethyl) thio) propane-1-thiol, 3,3'-dithiobis (propane -1,2-dithiol), (7R, 11S) -7,11-bis (mercaptomethyl) -3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R , 12S) -7,12-bis (mercaptomethyl) -3,6,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1, 11-dimercapto-3,6,9-trithiaoundecan, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, 4,8-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaoundecan, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropio Nate), pentaerythritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis (3-mercaptopropionate) , 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1 Thio urethane-based optical material, characterized in that one or two or more compounds selected from the group consisting of 3-dithiane and 2- (2,2-bis (mercaptodimethylthio) ethyl) -1,3-dithiane Manufacturing method.
The method for producing a thiourethane-based optical material according to claim 2, wherein the polymerizable composition further comprises a compound having an iso (thio) cyanate group.
The method for producing a thiourethane-based optical material according to any one of claims 1 to 4, wherein the polymerizable composition further comprises a phosphate ester compound as an internal mold release agent.
The method of claim 5, wherein the phosphate ester compound, polyoxyethylene nonyl phenol ether phosphate (5% by weight of 5 mol ethylene oxide added, 80% by weight 4 mol added, 10% by weight 3 mol added, 1 mole added 5% by weight), polyoxyethylene nonylphenol ether phosphate (9% added by 9 moles of ethylene oxide, 80% added by 8 moles added, 5% by weight 9 moles added, 7 moles added 6 wt%, 6 mol added 6 wt%), polyoxyethylene nonylphenol ether phosphate (13 wt% added ethylene oxide 3 wt%, 12 wt% added 80 wt%, 11 mol added 8 Wt%, 9 mol added 3 wt%, 4 mol added 6 wt%), polyoxyethylene nonylphenol ether phosphate (17 mol added ethylene oxide 3 wt%, 16 mol added 79 wt% , 15 mole added 10% by weight, 14 mole added 4% by weight, 13 mole added 4% by weight), polyoxyethylene nonylphenol ether 5% by weight of 21 mole of ethylene oxide added, 76% by weight of 20 mole added, 7% by weight of 19 mole added, 6% by weight 18 mole added, 4% by weight 17 mole added ) And one or two or more compounds selected from the group consisting of Zelec UN ™.
An optical material produced by the manufacturing method of any one of claims 1 to 3.
An optical lens made of the optical material of claim 7.
The optical lens of claim 8, wherein the optical lens is an eyeglass lens or a polarizing lens.