Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
  • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
  • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols

Definitions

• the present invention relates to a resin for epoxy acrylic optical lenses, and more particularly, to a molding polymerization method of an epoxy acrylic optical lens resin which can be easily separated from a mold, and a resin composition for epoxy acrylic optical lenses including an internal release agent.
• Plastic optical lenses were introduced as a replacement for the high specific gravity and low impact of glass lenses.
• Representative examples thereof include polyethylglycol bisallylcarbonate, polymethyl methacrylate, polyethylglycol bisallylcarbonate and diallyl phthalate.
• 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 by Urethane optical lenses are obtained.
• Urethane-based optical lenses have excellent optical properties such as dyeability, impact resistance, Abbe's number and transparency, but have a problem in that materials are expensive and the manufacturing process of the lens is difficult. That is, since the urethane resin composition is sensitive to moisture, it is necessary not only at the time of assembling the mold, but also at the time of injecting the resin composition into the mold, so that the water is blocked until the injection is completed.
• Humidity control of air is necessary. If the mold inner surface and the resin composition are exposed to moisture in the air, clouding occurs on the lens surface, thereby degrading the transparency of the lens. In addition, not only the raw material but also the finished lens that has completed the hard multi-coating may cause a problem that the lens absorbs moisture and deforms the central portion of the lens, which is the thinnest part, when stored in a warehouse or a store for a long time.
• Korean Patent Application No. 10-2003-0018653 unlike urethane lenses, has excellent optical properties and low price of materials, and it is possible to produce lenses without requiring water management in air even in high temperature and high humidity areas.
• the epoxy acrylic resin composition for optical lenses which does not have the center strain of the lens by heavy water is disclosed.
• the lens is manufactured from an epoxy acrylic resin composition, there is a problem that it is more difficult to separate the lens from the mold than when the lens is manufactured from another resin composition.
• the internal mold release agent is incorporated into the lens resin composition to reduce the adhesive force between the mold and the molded article to facilitate mold release, and has an effect of increasing the productivity of the lens.
• Internal mold release agents currently used include fluorine based nonionic surfactants, silicone based nonionic surfactants, alkyl quaternary ammonium salts, phosphate ester compounds, liquid paraffins, waxes, higher fatty acids and their metal salts, higher fatty acid esters, higher aliphatic alcohols, and bisamies.
• Drewes, polysiloxanes, aliphatic ethylene ethylene oxide adducts and the like are known, and these internal release agents are mainly applied to urethane-based lenses.
• An object of the present invention is to provide a mold polymerization method which can be improved to a level that satisfies the releasability of an epoxy acrylic resin, that is, there is no difficulty in detaching a lens from a mold during molding polymerization and there is little damage.
• the use of general purpose phosphate ester compounds known as internal release agents in the production of epoxy acrylic optical lenses helps to separate the cured optical lenses from the glass mold.
• the "satisfactory level" means a degree of almost no breakage of the lens from the mold). There is still a need for improvement.
• the present invention aims to solve such a problem, and an object of the present invention is to provide a casting polymerization method in which the releasability is improved to a satisfactory level after casting polymerization of an epoxy acrylic optical lens.
• an object of the present invention to provide a mold polymerization method capable of easily separating a lens from a mold after curing, even in a lens with a thin edge (low lens of the lens, + lens).
• an object of the present invention is to provide a resin composition for epoxy acrylic optical lens containing a release agent to facilitate the production of epoxy acrylic optical lens.
• the present invention unexpectedly improves the releasability of the resin composition for an optical lens containing epoxy acrylate as a main component when a compound having a polar group (hydroxy group and / or carboxylic acid group) is used as an internal mold release agent. Based on not finding it. Compounds having a polar group (hydroxy group and / or carboxylic acid group) may be used alone as an internal release agent, but even when used as an internal release agent together with a known general-purpose phosphate ester compound, the release property of the epoxy acrylate resin is satisfactory. Can be improved.
• the present invention unexpectedly found that when the phosphate ester compound represented by the following Chemical Formula 3 is used as an internal mold release agent, the releasability of the resin composition for an optical lens containing epoxy acrylate as a main component can be improved to a satisfactory level. Based.
• R represents hydrogen, carbon, alkyl group, alkyl group containing unsaturated group, aromatic group, alkylphenyl group, phenylalkyl group, alicyclic moiety, X represents hydroxy group or carboxylic acid group or both.
• N represents 1 Is an integer of ⁇ 6.
• R is an alkyl group having 3 to 20 carbon atoms, n is 0 to 10, and m is 1 to 2)
• an epoxy acrylate compound including one or two or more compounds represented by Formula 1, a reactive diluent 15 to 75% by weight, and a compound having a polar group represented by Formula 2 as an internal mold release agent or
• a resin composition for epoxy acrylate-based optical lens containing 0.001 to 10% by weight of the phosphate ester compound represented by the formula (3).
• the optical material obtained by adding a catalyst and thermosetting to the said resin composition for epoxy acrylate type optical lenses is provided.
• the optical material may be used in particular as a plastic spectacle lens or a polarizing lens.
• a compound having a polar group represented by the formula (2) or a phosphate ester compound represented by the formula (3) is added as an internal mold release agent to a composition in which a reactive diluent, an additive, and the like are mixed with the epoxy acrylic compound represented by the formula (1).
• the resin composition for an optical lens of the present invention can be manufactured at a lower cost than a urethane-based high refractive lens, and it is possible to produce the lens without a separate dehumidification facility even in a region of high temperature and humidity due to less reaction to moisture. Since there is no center deformation of the lens due to moisture, release property from the mold, which is an existing problem while solving the advantages of the epoxy acrylic lens, can be widely used in place of a urethane-based lens.
• the optical material obtained by hardening the resin composition of this invention can be used widely as an eyeglass lens, a camera lens, etc.
• the epoxy acrylic resin of the present invention can be used as a plastic glasses lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, and in addition to the recording media substrates, color filters and ultraviolet absorbing filters used in prisms, optical fibers, optical disks, etc. It can also be used for various optics.
• Mold polymerization method of the present invention is a polymer polymerization composition for an optical lens comprising 20 to 80% by weight of an epoxy acrylate compound containing one or two or more compounds represented by Formula 1 and 15 to 75% by weight of a reactive diluent
• the compound having a polar group represented by the formula (2) or the phosphate ester compound represented by the formula (3) is added in advance as an internal mold release agent.
• the resin composition for an optical lens of the present invention is mixed with 20 to 80% by weight of the resin represented by the formula (1) 15 to 75% by weight of the reactive diluent, and at least one compound having a polar group represented by the formula (2) or formula (3) It is a resin composition for optical lenses obtained by mixing 1 or more types of phosphate ester compounds represented by 0.001-10 weight%.
• the composition may further include a ultraviolet absorber, a phosphate ester compound, a reaction rate regulator, a heat stabilizer, a dye, a catalyst, and the like.
• the composition preferably has a liquid viscosity of 25 to 1000 cps at 25 ° C. suitable for mold polymerization, a liquid refractive index (nE, 20 ° C.) of 1.50 to 1.58, and a solid phase refractive index (nE, 20 ° C.) of 1.57 to 1. 1.63.
• R represents hydrogen, carbon, alkyl group, alkyl group containing unsaturated group, aromatic group, alkylphenyl group, phenylalkyl group, alicyclic moiety, X represents hydroxy group or carboxylic acid group or both.
• N represents 1 Is an integer of ⁇ 6.
• R is an alkyl group having 3 to 20 carbon atoms, n is 0 to 10, and m is 1 to 2)
• the intramolecular -OH group has a bonding force with the glass mold, which causes a lot of difficulty in separating the cured lens from the mold.
• the present invention in order to solve this problem, by improving the release property of the epoxy acrylic lens to a satisfactory level by adding a compound having a polar group represented by the formula (2) or a phosphate ester compound represented by the formula (3) to the optical resin composition as an internal mold release agent. In particular, even lenses with thin edges can be manufactured without edge drift when separated.
• a general-purpose phosphate ester internal mold release agent may be mixed with a compound having a polar group as an internal mold release agent, and a compound having a polar group represented by Formula 2 to the phosphate ester compound represented by Formula 3 as an internal mold release agent. It was good to mix and use.
• Examples of the compound having a polar group represented by the formula (2) include compounds having a carboxylic acid group such as acetic acid, formic acid, oxalic acid, propionic acid, acrylic acid and methacrylic acid; Compounds having a hydroxyl group such as water (ground water, rainwater, distilled water, deionized water, etc.), methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, allyl alcohol; And hydroxyl such as 2-hydroxypropionic acid, 3-hydroxypropionic acid, 2,2-dimethylolpropionic acid, 3- (para-hydroxyphenyl) propionic acid, beta-lactic acid, lactic acid, tartaric acid, malic acid, salicylic acid, phenolic acid and the like.
• the compound which has time and a carboxylic acid group can be used 1 type or in mixture of 2 or more types.
• the phosphate ester compound represented by the formula (3) is preferably polyoxyethylene nonyl phenol ether phosphate (5% by weight of 5 mol ethylene oxide added, 80% by weight 4 mol added, 10 parts by 3 mol added %, 1 mole added 5% by weight), polyoxyethylene nonylphenol etofate (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 8% by weight added, 9% by weight added 3% by weight, 4% by weight added 6% by weight, polyoxyethylene nonylphenol ether phosphate (3% by weight with 17 moles of ethylene oxide, 16 mole added 79 weight%, 15 mol added 10 weight%, 14 mol added 4 weight%, 13 mol added 4 weight%)
• the compound having a polar group represented by the formula (2) or the phosphate ester compound represented by the formula (3) used as the internal mold release agent is preferably added to the composition in 0.001 to 10% by weight.
• a compound having a polar group it is more preferably added in an amount of 0.01 to 5% by weight. When the amount is less than 0.01% by weight, the releasability is considerably decreased. When 5% by weight or more is used, whitening occurs in the lens or during polymerization. In this case, a problem may occur between the lens and the mold in advance.
• the phosphate ester compound of the formula (3) is more preferably included 0.03 to 1.0% by weight, particularly preferably from 0.05 to 0.5% by weight. Experimental results showed that the use of 0.08 wt% resulted in good mold deformability in the lens and high polymerization yield.
• the composition of the present invention may further include a heat stabilizer in order to improve the optical properties of the resin composition for an optical lens.
• the heat stabilizer may preferably be included in the composition at 0.01 to 5.00% by weight. When the thermal stabilizer is used at 0.01 wt% or less, the thermal stability effect is weak. When the thermal stabilizer is used at 5.00 wt% or more, the polymerization failure rate during curing is high and the thermal stability of the cured product is lowered.
• thermal stabilizer examples include compounds such as calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate and zinc octoate, which are metal fatty acid salts. One or two or more compounds selected from among them can be used.
• triphenyl phosphite diphenyldecyl phosphite, phenyl diddecyl phosphite, diphenyl dodecyl phosphite, trinolyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, and tripropyl
• phosphite triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite) and tris (monophenyl) phosphite can be used.
• heat stabilizers from which the series differs among the heat stabilizers illustrated above.
• a phosphorus-based heat stabilizer not only the initial color of the molded lens but also the thermal stability of the optical lens can be greatly improved without deteriorating optical properties such as transparency, impact strength, heat resistance and polymerization yield.
• Reactive diluent for viscosity control of the resin composition for an optical lens of the present invention is contained in 15 to 75% by weight in the composition.
• a resin composition for epoxy acrylic high refractive optical lens having a liquid viscosity of 20 to 1,000 cps at 25 ° C. which is suitable for injecting into a glass mold assembled with a tape or a synthetic resin gasket, can be obtained. If the liquid viscosity is 20 cps or less, the composition flows out of the mold when the liquid resin composition is injected into a glass mold assembled with a synthetic resin gasket. When the viscosity of the liquid is 1,000 cps or more, it is difficult to inject the composition into the mold.
• Reactive diluents for viscosity adjustment of the resin composition for optical lenses are, for example, styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrenedimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, mono Benzyl maleate, dibenzyl maleate, monobenzyl fumarate, dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monophene
• One or two or more selected from compounds such as tilmaleate, dipentyl maleate, monopentyl fumarate, dipentyl fumarate, and diethylene glycol bisaryl carbonate may be used. It is not limited. All reactive diluents
• the present invention preferably, prior to the preparation of the epoxy acrylic resin compound and the reactive diluent compound used in the resin composition for the optical lens to check the purity of all raw materials to refine the low purity compounds and high purity compounds without purification use.
• a high purity compound having a purity of 70 to 99.99% is used.
• a known ultraviolet absorber, organic dye, inorganic pigment, color inhibitor, heat stabilizer, antioxidant, light stabilizer, catalyst, and the like may be included in a conventional method in order to improve optical properties.
• a general-purpose phosphate ester compound, a silicone-based surfactant and a fluorine-based surfactant known as an auxiliary internal mold release agent may be used together.
• a phosphate ester compound can be used.
• General purpose phosphoric acid ester compounds which can be used at this time include, for example, (mono, di) methyl phosphoric acid, (mono, di) ethyl phosphoric acid, (mono, di) (n-propyl) phosphoric acid, (mono, di) iso Propylphosphate, (mono, di) (n-butyl) phosphate, (mono, di) (n-pentyl) phosphate, (mono, di) (n-hexyl) phosphate, (mono, di) (n-heptyl) phosphate , (Mono, di) (n-octyl) phosphate, (mono, di) (2-ethylhexyl) phosphate, (mono, di) (n-nonyl) phosphate, (mono, di) (n-decyl) phosphate, (Mono, di) (isodecyl) phosphate, (mono, di)
• the phosphate ester compound represented by the formula (3) when using the phosphate ester compound represented by the formula (3) as the internal mold release agent may be used together with a compound having a polar group represented by the formula (2) as an auxiliary internal mold release agent for further improving the release properties .
• the component (I) compound is represented by the formula (4), and a compound having an equivalent weight of 259 by acrylated (prepared by reacting at 105 ° C. for 20 hours) by adding acrylic acid to KD Chemical's YD-128 epoxy resin having an equivalent weight of 187. And a mixture having an average molecular weight of 518.
• Component (II) compound is the same as the compound shown in formula (3), but is the same mixture as component (I) except that it is aged by adding 0.1% by weight of oxalic acid for 30 minutes at 100 ° C after completion of acrylated.
• Component (III) compound is represented by the formula (5), and the equivalent weight of 201 epoxy resin was added to acrylic acid and acrylated (prepared by reacting at 105 ° C for 20 hours) to prepare a compound having the equivalent weight of 273. This is a mixture which is 546.
• the component ( IV ) compound is represented by the formula (6), and the compound is equivalent to 472 by acrylated (prepared by reacting at 105 DEG C for 20 hours) by adding acrylic acid to the equivalent YDB-400 epoxy resin of Kukdo Chemical. And a mixture having an average molecular weight of 944. Equivalent to 472, with an average molecular weight of 944.
• Component ( V ) compound is shown in Chemical Formula (7), and the compound having the equivalent weight of 486 was prepared by acrylatelation (prepared by reaction at 105 ° C. for 20 hours) by adding acrylic acid to an epoxy resin having an equivalent weight of 414. This is a mixture of 972.
• styrene, 2 g of methylstyrene dimer, and 0.05 g of oxalic acid were added to 21 g of component (I) and 35 g of component ( IV ) in the epoxy acrylic compound obtained above, followed by stirring for about 30 minutes. Then, filtered with a filter paper of 0.45 ⁇ m or less, V65 0.05g, 3-M 0.12g is added to the catalyst, and Zelec UN TM 0.2g is mixed with an internal release agent to prepare a resin composition for the optical lens, and then An optical lens was prepared and the physical properties of the lens were measured.
• Refractive index and Abbe number It was measured using an Abbe refractometer, a DR-M4 model of Atago.
• the resin composition (Example) in which the internal releasing agent of the present invention was added to the epoxy acrylate resin and the reactive diluent had less polymerization imbalance and good release property when compared with the comparative example.
• the internal mold release agent of the present invention was added in advance, and then the reactive diluent was mixed and the resin composition for the optical lens was prepared. Therefore, in the case of using the internal mold release agent of the present invention, the polymerization imbalance is small and the demolition is excellent, so that the efficiency of optical lens manufacturing can be improved, and also the yield of the lens is reduced due to the small damage of the lens during mold release, and the transparency and thermal stability The optical characteristic of was excellent.
• Zelec UN TM Phosphate ester compound manufactured by Stapan, trade name Zelec UN
• 4-PENPP polyoxyethylene nonylphenyl phosphate (5% by weight of 5 mol of ethylene oxide added, 80% by weight of 4 mol of ethylene oxide added, 10% by weight of 3 moles of ethylene oxide added, 5% by weight of 1 mole of ethylene oxide added)
• 8-PENPP polyoxyethylene nonylphenyl phosphate (5% by weight of 9 mol of ethylene oxide added, 80% by weight of 8 mol of ethylene oxide, 10% by weight of 7 mol of ethylene oxide, ethylene oxide 5 mole% added by 6 mol or less)
• 12-PENPP polyoxyethylene nonyl phenol ether phosphate (3% by weight of 13 mol of ethylene oxide added, 80% by weight of 12 mol added, 8% by weight of 11 mol added, 3% by weight 9 mol added , 4 mol added 6 wt%)
• 16-PENPP polyoxyethylene nonylphenol ether phosphate (3% by weight of 17 moles of ethylene oxide added, 79% by weight of 16 moles added, 10% by weight of 15 moles added, 4% by weight 14 moles added) , 13 mol added 4 wt%)
• 20-PENPP polyoxyethylene nonylphenol ether phosphate (5% by weight of 13 moles of ethylene oxide, 76% by weight of 12 moles added, 7% by weight of 11 moles added, 6% by weight of 10 moles added , 9 mole added 4 wt%)
• KF96 A silicone release agent manufactured by Shin-Etsu Co., Ltd.
• V65 2,2'-azobis (2,4-dimethylbarrenonitrile) (2,2'-azobis (2,4-dimethylvaleronitrile)
• the resin for epoxy acrylic spectacle lens of the present invention can overcome the problem of separation with the mold after polymerization, which is a conventional problem, excellent optical properties such as light weight, moldability, dyeing property, transparency, and the like, are less affected by moisture. It can be widely used in the optical field as a useful resin utilizing the advantages of having excellent thermal stability.
• Resin prepared according to the present invention can be applied to optical lenses, in particular spectacle lenses and camera lenses, can be used as a 3D polarizing lens equipped with a polarizing film on the spectacle lens, in addition to the spectacle lens, prism, optical fiber, optical disk, magnetic disk It can be used as various optical products, such as a recording medium substrate, a coloring filter, an ultraviolet absorbing filter, etc. used for the present invention.

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• Compositions Of Macromolecular Compounds (AREA)
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• 2012
  • 2012-06-13 WO PCT/KR2012/004673 patent/WO2013187539A1/fr not_active Ceased
  • 2012-06-13 CN CN201280003139.0A patent/CN103635497A/zh active Pending

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