WO2013069964A1 - Procédé pour fabriquer une matière optique à base de (thio)uréthane - Google Patents

Procédé pour fabriquer une matière optique à base de (thio)uréthane Download PDF

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WO2013069964A1
WO2013069964A1 PCT/KR2012/009344 KR2012009344W WO2013069964A1 WO 2013069964 A1 WO2013069964 A1 WO 2013069964A1 KR 2012009344 W KR2012009344 W KR 2012009344W WO 2013069964 A1 WO2013069964 A1 WO 2013069964A1
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bis
added
weight
thio
optical material
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PCT/KR2012/009344
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Korean (ko)
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장동규
노수균
김문일
김종효
서진무
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주식회사 케이오씨솔루션
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Priority to CN201280054308.3A priority Critical patent/CN103917579A/zh
Publication of WO2013069964A1 publication Critical patent/WO2013069964A1/fr

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    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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 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.
  • 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.
  • 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.
  • striae, haze and the like may occur to deteriorate the quality of the lens.
  • 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.
  • thio polyiso (thio) cyanate compounds and thiourethane-based compounds.
  • 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.
  • 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.
  • "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, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylenediisocyanate, tolyl Rendiisocyanate
  • 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.
  • 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.
  • pouring into a mold are 21-40 degreeC
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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, ⁇ , ⁇ , ⁇ ', ⁇ '-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.
  • 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.
  • 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, cyclohexane
  • 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.
  • 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.
  • 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- Mercapto) -3
  • 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 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.
  • 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.
  • a phosphate ester compound 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.
  • 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.
  • 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).
  • 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
  • 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 °C. 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.
  • 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.
  • 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.
  • physical and chemical treatments such as hard coat treatment, anti-reflective coat treatment, dyeing treatment, and dimming treatment can be performed.
  • Injection temperature The injection temperature at the time of inject
  • 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.
  • 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
  • Example 1 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 1 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 1 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.
  • 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.
  • Example 1 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • IPDI isophorone diisocyanate
  • NBDI 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane (2,5-bis (isocyanatomethyl) bicyclo [2,2,1] hepthane
  • PETMP pentaerythritol tetrakis (3-mercaptopropionate) (pentaerythritol-tetrakis (3-mercaptopropionate))
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une matière optique à base de (thio)uréthane, et particulièrement un procédé de fabrication d'une matière optique de haute qualité, à rendement élevé sans formation de stries ou de turbidité blanche due à un déséquilibre de polymérisation, cette matière étant incolore, transparente et invariable. L'invention concerne également un procédé de fabrication d'une matière optique à base de (thio)uréthane dans laquelle un composite de polymérisation, comprenant un composé polythiol et un composé polyiso(thio)cyanate, est polymérisé dans un moule et est caractérisé en ce que le mélange, l'écumage et l'injection dans un moule sont effectués dans une plage de températures comprise entre 21 et 40 °C. La matière optique à base de (thio)uréthane fabriquée selon la présente invention peut remplacer la matière optique existante et être utilisée à grande échelle dans de nombreuses industries.
PCT/KR2012/009344 2011-11-07 2012-11-07 Procédé pour fabriquer une matière optique à base de (thio)uréthane WO2013069964A1 (fr)

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KR102448166B1 (ko) * 2020-09-22 2022-09-27 에스케이씨 주식회사 폴리티올 조성물 및 이를 포함하는 광학용 중합성 조성물

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KR20130050262A (ko) 2013-05-15
CN106220813B (zh) 2019-08-30
CN106220813A (zh) 2016-12-14
KR20140001808A (ko) 2014-01-07

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