WO2013187539A1 - Method for polymerizing resin casting for use as epoxy acrylic optical lens and resin composition containing internal releasing agent for use in epoxy acrylic optical lens - Google Patents

Description

Resin composition for epoxy acrylic optical lens including mold polymerization method of resin for epoxy acrylic optical lens and internal release agent

BACKGROUND OF THE INVENTION 1. Field of the Invention 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. 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 Application Nos. 10-1987-0001768, 10-1987-014268, 10-1989-001686, 10-1989-001865, 10-1989-001913, and 10-1993-015515, 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. However, when 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.

As described above, many internal mold release agents are known in relation to the urethane-based lens. However, epoxy acrylic resins are difficult to obtain satisfactory releasability by simply applying an internal mold release agent used in the production of a urethane-based lens because the properties of the urethane resin and the resin are different.

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. However, even when a general-purpose phosphate ester compound known as an internal release agent is used, the release property does not reach a satisfactory level (hereinafter, the "satisfactory level" means a degree of almost no breakage of the lens from the mold). There is still a need for improvement. Particularly in the case of a thin edge lens (low lens of the lens, + lens), even if the phosphate ester compound is used, separation of the lens from the mold after curing is still difficult, which not only lowers the production efficiency but also lowers the production yield.

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. In particular, it is 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). In addition, 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.

In addition, 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.

Under this recognition, in the present invention,

When molding a polymer composition for an optical lens containing 20 to 80% by weight of an epoxy acrylate compound containing one or two or more compounds represented by the following Formula 1 and a reactive diluent 15 to 75% by weight, Provided is a 0.001 to 10% by weight of a compound having a polar group represented by the formula or a phosphate ester compound represented by the following formula (3) in advance as an internal mold release agent is provided a casting polymerization method of a resin for epoxy acrylate-based optical lens.

[Formula 1]

[Revision 16.07.2012 under Rule 91]

(Where n = 0-15, R ₁ is H or CH ₃ and R ₂ is H or Br)

[Formula 2]

Wherein 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.)

[Formula 3]

(Where R is an alkyl group having 3 to 20 carbon atoms, n is 0 to 10, and m is 1 to 2)

In the present invention,

20 to 80% by weight of 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 There is provided 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).

Moreover, in this invention, 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.

In the present invention, 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). By molding the resin, the problem of mold release, demolding or separation can be solved without polymerization imbalance. In particular, according to the method of the present invention, since the lens having a thin edge can be separated from the mold after curing without being damaged, the production yield can be increased. 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. In particular, 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 In this case, 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.

In addition, 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.

[Formula 1]

[Revision 16.07.2012 under Rule 91]

(Where n = 0-15, R ₁ is H or CH ₃ and R ₂ is H or Br)

[Formula 2]

Wherein 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.)

[Formula 3]

(Where R is an alkyl group having 3 to 20 carbon atoms, n is 0 to 10, and m is 1 to 2)

When the epoxy acrylic optical lens composition having the formula (1) as a main component is injected into a glass mold and thermally cured, 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. In 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. In this case, 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%), polyjade Ethylenenonylphenol ether phosphate (21% added ethylene oxide 5% by weight, 20 mol added 76% by weight, 19 mol added 7% by weight, 18 mol added 6% by weight, 17 mol added 4% by weight) and Zelec UN ™, at least one compound selected from the group consisting of:

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. In the case of 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. In the case of 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. Examples of the thermal stabilizer 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. Preferably, triphenyl phosphite, diphenyldecyl phosphite, phenyl diddecyl phosphite, diphenyl dodecyl phosphite, trinolyl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, and tripropyl One or two or more compounds selected from phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite) and tris (monophenyl) phosphite can be used. In addition, one or two or more selected from compounds such as lead-based 3PbO.PbSO4.4H ₂ O, 2PbO.Pb (C ₈ H ₄ O ₄ ), 3PbO.Ph (C ₄ H ₂ O ₄ ) .H ₂ O and the like Dibutyltin diaurate, dibutyltin maleate, dibutyltin bis (isooctyl maleate), dioctyl maleate, dibutyltin bis (monomethyl maleate), dibutyl tin Bis (lauryl mercaptide), dibutyl bis (isooxyl mercaptoacetate), monobutyltin tris (isooctyl mercaptoacetate), dimethyltinbis (isooctyl mercaptoacetate), tris (isooctyl mercaptoacetate ), Dioctyl tin bis (isooctyl mercaptoacetate), dibutyl tin bis (2-mercapto ethyl laurate), monobutyl tin tris (2- mercapto ethyl laurate), dimethyl tin bis (2- mercapto 1 type selected from compounds such as ethylate) and monomethyltin tris (2-mercaptoethylorate) 2 may also be used or more. Moreover, it is also possible to mix and use 2 or more types of heat stabilizers from which the series differs among the heat stabilizers illustrated above. Most preferably, by using 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. When the reactive diluent is included 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. There is a difficult problem. More preferable viscosity is 30-500 cps. 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 used in the composition are preferably purified and obtained in high purity before use in the composition.

In 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. In the present invention, preferably, a high purity compound having a purity of 70 to 99.99% is used.

In the resin composition for an optical lens of the present invention, 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. .

In the polymerization method or the composition of the present invention, when using the compound having a polar group represented by the formula (2) as the internal mold release agent, 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. . Especially as an auxiliary internal mold release agent, Preferably, 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) (n-undecyl) phosphate, (mono, di) (n-dodecyl) phosphate, (mono, di) (tridecyl) phosphate, (mono , Di) (n-tetradecyl) phosphate, (mono, di) (n-pentadecyl) phosphate, (mono, di) (n-hexadecyl) phosphate, (mono, di) (n-octadecyl) phosphate, (Mono, di) (o-methyldecyl) phosphate, (mono, di) (p-methylphenyl) phosphate, (mono, di) (p-ethylphenyl) phosphate, (mono, di) (p-propylphenyl) phosphate , (Mono, di) (p-butylphenyl) phosphate, (mono, di) (p-nonylphenyl) phosphate, (mono, di) (p-meth Methylmethyl) phosphate, (mono, di) (2-phenylethyl) phosphate, (mono, di) (4-phenylbutyl) phosphate, (mono, di) (3-oxabutyl) phosphate, (mono, di) ( 3-oxapentyl) phosphoric acid, (mono, di) (3-oxahexyl) phosphoric acid, (mono, di) (3-oxaheptyl) phosphoric acid, (mono, di) (3-oxactylsil) phosphoric acid, (mono, Di) (3-oxanonyl) phosphate, (mono, di) (3-oxoundecyl) phosphate, (mono, di) (3-oxatridecyl) phosphate, (mono, di) (3-oxapentadecyl) Phosphoric acid, (mono, di) (3-oxaheptadecyl) phosphoric acid, (mono, di) (3-oxanonadecyl) phosphoric acid, (mono, di) (3-oxahenicosyl) phosphoric acid, (mono, di) ( 1-methyl-3-oxabutyl) phosphate, (mono, di) (1-methyl-3-oxapentyl) phosphoric acid, (mono, di) (1-methyl-3-oxaheptyl) phosphoric acid, (mono, di) (1,2-dimethyl-3-oxaheptyl) phosphate, (mono, di) (1-methyl-3-oxatridecyl) phosphate, (mono, di) (1-methyl-2- (o-methylphenoxy ) Ethyl) phosphoric acid, (mono, di) (1-methyl2- (p-nonylphenoxyethyl) phosphoric acid, (mono, di) (1-methyl-4-phenyl-3-oxabutyl) phosphoric acid, (mono, D) (3,6 -Dioxheptyl) phosphate, (mono, di) (3,6-dioxaoctyl) phosphate, (mono, di) (3,6-dioxadecyl) phosphate, (mono, di) (3,6-di Oxatetradecyl) phosphate, (mono, di) (3,6-dioxahexadecyl) phosphate, (mono, di) (3,6-dioxaoctadecyl) phosphate, (3,6-dioxycosyl) phosphate , (3,6-dioxadocosyl) phosphate, (mono, di) (3,6-dioxatetracosyl) phosphate, (mono, di) (1,4-dimethyl-3,6-dioxadecyl) Phosphoric Acid, (mono, di) (3,6,9-trioxadecyl) phosphate, (mono, di) (3,6,9-trioxoundecyl) phosphate, (mono, di) (3,6,9 Trioxatridecyl) phosphate, (mono, di) (3,6,9-trioxaheptadecyl) phosphate, (mono, di) (3,6,9-trioxahenicosyl) phosphate, (mono, di ) (3,6,9-trioxaheptacosyl) phosphate, (mono, di) (1,4,7-trimethyl-3,6,9-trioxatridecyl) phosphate, (mono, di) (3 , 6,9,12-tetraoxahepsadecyl) phosphate, (mono, di) (3,6,9,12-tetraoxaoctyldecyl) phosphate, (mono, di) (3,6,9,12 Tetraoxycosyl) phosphate, (mono, di) (3,6, 9,12-tetraoxadodocyl) phosphate, (mono, di) (3,6,9,12-tetraoxatetracosyl) phosphate, (mono, di) (1,4,7,10-tetramethyl-3 , 6,9,12-tetraoxahexadecyl) phosphate, triisopropyl acid phosphate, tributyl acid phosphate, trioctylic acid phosphate, triisodecyl acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, trimethyl Acid phosphate, triethyl phosphate, tripropyl acid ester, benzyl phosphate, dibenzyl phosphate, tribenzyl phosphate, bis (tridecanoic acid) phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene Glycol Monoethyl Phosphate, Diethylene Glycol Monobutyl Diphosphate, Diethylene Glycol Monobutyl Phosphate, Isopropylene Glycol Monoethyl Phosphate, Diisopropylene Glycol Noethyl phosphate, triisopropylene glycol monoethyl phosphate, Zelec UN ™ and the like can be used alone or in combination of two or more thereof. Usable phosphate ester compounds are not limited to the compounds exemplified above, and are not specified as compounds having a single composition.

In addition, in the polymerization method or the composition of the present invention, 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 .

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.

Epoxy acrylic compounds

1) Synthesis of Component (I) Compound

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.

[Formula 4]

[Revision 16.07.2012 under Rule 91]

(n = 0 to 15)

2) Component (II) Compound

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.

3) Component (III) Compound

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.

[Formula 5]

[Revision 16.07.2012 under Rule 91]

                                          (n = 0 to 15)

4) Component (IV) Compound

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.

[Formula 6]

[Revision 16.07.2012 under Rule 91]

                                (n = 0 to 15)

5) Component (V) Compound

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.

[Formula 7]

[Revision 16.07.2012 under Rule 91]

                          (n = 0 to 15)

Example 1

40 g of 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㎛ or less, V65 0.05g, 3-M 0.12g is added to the catalyst, and Zelec UN ™ 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.

(1) After stirring the resin composition for an optical lens prepared above for 1 hour, degassing under reduced pressure for 10 minutes and filtered, it was injected into a glass mold assembled with a polyester adhesive tape.

(2) The glass mold into which the resin composition for spectacle lens was injected was heat-cured in a forced circulation oven from 35 ° C to 110 ° C over 20 hours, and then cooled to 70 ° C to detach and remove the glass mold. The resulting lens was processed to a diameter of 72 mm and then ultrasonically washed with an alkaline aqueous washing solution, followed by annealing at 120 ° C. for 2 hours. The physical properties were measured by the following method, and the results are shown in Table 1 .

Property test method

The physical properties of the optical lenses manufactured by the following physical property test methods were measured and the results are reported in Table 1 below.

1) Refractive index and Abbe number: It was measured using an Abbe refractometer, a DR-M4 model of Atago.

2) Specific gravity: It was measured by an underwater substitution method using an analytical balance.

2) Release property: When the epoxy acrylic resin composition was thermoset and demolded at 70 ° C., it was marked as O, Δ, or X depending on the degree of breakage of the lens or mold when the plastic lens and the mold were separated. In this case, the lens has 100 diopters of -1.00 and 100 100 of 0.00 and 100 of +1.00, respectively.

O: If the lens or mold is broken at all or one is broken

Δ: 2 to 3 lenses or molds are broken

X: The case where four or more lenses or molds are broken is indicated.

3) Polymerization imbalance: 100 lenses obtained in the process are observed with the naked eye and a Mercury Arc Lamp of USH10 USH-102D. If 3 or more optical distortions appear, it is 'X' and if the optical distortion is 3 or less It is indicated by 'O'.

Examples 2-20

According to the composition described in Tables 1 to 3 in the same manner as in Example 1 to prepare a composition and an optical lens, and to test the physical properties, the results are shown in Tables 1 to 3 .

Comparative Example 1

40 g of styrene, 2 g of methylstyrene dimer and 2 g of DBTM were added to 21 g of component (I) and 35 g of component ( IV ) in the epoxy acrylic compound, followed by stirring for about 30 minutes. Thereafter, the resultant was filtered with a filter paper of 0.45 μm or less, and thereto was added 0.05 g of V65 as a catalyst and 0.12 g of 3-M, and 0.2 g of Zelec UN ™ was mixed as an internal release agent, and the resin composition for an optical lens was manufactured in the same manner as in Example 1. Made. An optical lens was produced from this composition, and the physical properties of the lens were measured, and the results are shown in Table 3 .

Comparative Examples 2-4

According to the composition shown in Table 3 in the same manner as in Comparative Example 1 to prepare a composition and an optical lens, and tested the physical properties, the results are shown in Table 3 .

Table 1 division Example One 2 3 4 5 6 7 8 Basic resin (g) Component I 21 20 20 20 20 20 20 20 Component II Component III Component IV 35 35 35 35 35 35 35 35 Component Ⅴ Thinner (g) Styrene 40 41 37 37 36 36 36 36 Alpha-methylstyrene 5 5 5 5 5 5 Methylstyrene dimer 2 2 One One 3 2 2 2 Heat stabilizer (g) DBTM 2 DOTM 2 ZnST 2 TBP 2 TPP 2 2 DPP 2 2 Internal Release Agent (g) Oxalic acid 0.05 0.1 0.15 Acetic acid 0.05 0.15 Deionized water 0.05 0.1 Malic acid 0.1 Zelec UN ™ 0.2 0.2 0.1 0.1 DOP 0.2 0.1 8-PENPP 0.2 0.1 KF-96 Radical initiator (g) V-65 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 3-M 0.12 0.11 0.13 0.13 0.13 0.13 0.13 0.13 Lens property Refractive index (nE, 20 ℃) 1.5972 1.5972 1.5972 1.5972 1.5972 1.5972 1.5972 1.5972 Abbesu 32 32 32 32 32 32 32 32 importance 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.29 Heterogeneity (-1.00) O O O O O O O O Dysplasia (0.00) O O O O O O O O Dysplasia (+1.00) O O O O O O O O Polymerization imbalance O O O O O O O O

TABLE 2 division Example 9 10 11 12 13 14 15 16 Basic resin (g) Component I 20 20 20 20 20 Component II 20 20 Component III 20 Component IV 35 35 35 35 35 Component Ⅴ 35 35 Thinner (g) Styrene 36 36 37 36 32 32 32 33 Alpha-methylstyrene 5 5 3 5 Methylstyrene dimer 2 2 3 2 3 3 3 2 Dibenzylmaleate 8 8 8 8 Heat stabilizer (g) DBTM 2 2 DOTM ZnST 2 TPP 2 TBP 2 2 2 DPP 2 Internal Release Agent (g) Oxalic acid 0.1 water 0.15 0.1 Deionized water 0.1 Zelec UN ™ 0.2 DOP 0.2 4-PENPP 0.2 0.2 8-PENPP 0.2 12-PENPP 0.2 16-PENPP 0.2 Radical initiator (g) V-65 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 3-M 0.12 0.15 0.12 0.11 0.12 0.12 0.12 0.12 Lens property Refractive index (nE, 20 ℃) 1.5968 1.5972 1.5972 1.5972 1.5932 1.5934 1.5931 1.594 Abbesu 33 32 32 32 34 34 34 33 importance 1.30 1.30 1.30 1.29 1.30 1.30 1.30 1.31 Heterogeneity (-1.00) O O O O O O O O Dysplasia (0.00) O O O O O O O O Dysplasia (+1.00) O O O O O O O O Polymerization imbalance O O O O O O O O

TABLE 3 division Example Comparative example 17 18 19 20 One 2 3 4 Basic resin (g) Component I 20 21 20 20 20 Component II 20 20 20 Component III 20 Component IV 35 35 35 35 35 Component Ⅴ 35 35 35 Thinner (g) Styrene 32 32 37 36 40 36 36 36 Alpha-methylstyrene 3 5 5 5 5 Methylstyrene dimer 3 3 3 2 2 2 2 2 Dibenzylmaleate 8 Divinylbenzene 8 Heat stabilizer (g) DBTM 2 2 DOTM ZnST 2 TPP 2 TBP 2 2 2 DPP 2 Internal Release Agent (g) Oxalic acid water Deionized water Zelec UN ™ 0.2 DOP 0.2 8-PENPP 0.18 0.16 0.16 0.2 16-PENPP 0.2 20-PENPP 0.2 Radical initiator (g) V-65 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 3-M 0.12 0.15 0.12 0.11 0.12 0.12 0.12 0.12 Lens property Refractive index (nE, 20 ℃) 1.5931 1.5935 1.5972 1.5972 1.5972 1.5972 1.5972 1.5972 Abbesu 33 32 32 32 32 32 32 32 importance 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.29 Heterogeneity (-1.00) O O O O △ X △ X Dysplasia (0.00) O O O O △ X X X Dysplasia (+1.00) O O O O X X X X Polymerization imbalance O O O O O O O X

From Tables 1 to 3, 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. In addition, in the case of preparing the epoxy acrylate compound, 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.

Abbreviation

Internal release agent

Zelec UN ™: Phosphate ester compound manufactured by Stapan, trade name Zelec UN

DOP: dioctyl acid phosphate

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.

Thermal stability

DBTM: dibutyltinmaleate

DOTM: dioctyltinmaleate

ZnST: zinc stearate

TPP: triphenylphosphite

TBP: tributylphosphite

DPP: diphenylisodecylphosphite

Polymerization initiator

V65: 2,2'-azobis (2,4-dimethylbarrenonitrile) (2,2'-azobis (2,4-dimethylvaleronitrile)

3-M: 1,1-bis (t-butylperoxy) -3,3-5-trimethyl cyclohexane, (1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane)

Since 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.

Claims (17)

[Revision 16.07.2012 under Rule 91]
When molding a polymer composition for an optical lens containing 20 to 80% by weight of an epoxy acrylate compound containing one or two or more compounds represented by the following Formula 1 and a reactive diluent 15 to 75% by weight, 0.001 to 10% by weight of a compound having a polar group represented by the formula or a phosphate ester compound represented by the following formula (3) is added in advance as an internal mold release agent, the mold polymerization method of the resin for epoxy acrylate-based optical lens. [Formula 1]

(Where n = 0-15, R ₁ is H or CH ₃ and R ₂ is H or Br) [Formula 2]

(Where 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.) [Formula 3]

(Where R is an alkyl group having 3 to 20 carbon atoms, n is 0 to 10, and m is 1 to 2) The compound having the polar group is acetic acid, formic acid, oxalic acid, propionic acid, acrylic acid, methacrylic acid, water, methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, allyl alcohol, 2- 1 selected from the group consisting of 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 It is a species or 2 or more types of compounds, The casting polymerization method of resin for epoxy acrylate type optical lenses. According to claim 1, 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 etofate (9 mole added ethylene oxide 3% by weight, 8 mole added 80% by weight, 9 mole added 5% by weight, 7 6% by weight added, 6% by weight added 6% by weight, polyoxyethylenenonylphenol ether phosphate (3% by weight, 13 moles added by ethylene oxide, 80% by weight added by 12 moles, 11 moles added by 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 Weight%, 15 mol added 10 wt%, 14 mol added 4 wt%, 13 mol added 4 wt%), polyoxyethylenenonylphenol Le phosphate (21% added ethylene oxide 5%, 20 mol added 76%, 19 mol added 7%, 18 mol added 6%, 17 mol added 4% by weight And a compound of one or two or more compounds selected from the group consisting of Zelec UN ™ and an epoxy acrylate-based optical lens resin. The method of claim 1, wherein the reactive diluent is styrene, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxy styrene, monobenzyl maleate, dibenzyl maly Eight, monobenzyl fumarate, dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monopentyl maleate, dipentyl maleate, 1. It is a 1 type, or 2 or more types of compound chosen from the group which consists of a monopentyl fumarate, a dipentyl fumalate, and a diethylene glycol bisaryl carbonate, The mold polymerization method of resin for epoxy acrylate type optical lenses. The method according to claim 1, wherein the optical lens composition further comprises a heat stabilizer. According to any one of claims 1, 2, 4 and 5, wherein the internal release agent is a compound having a polar group represented by the formula (2), wherein the optical lens composition is a phosphoric acid ester compound as an internal release agent. Mold polymerization method of a resin for epoxy acrylate optical lens, characterized in that it further comprises. The internal mold release agent is a phosphate ester compound represented by Formula 3, and the optical lens composition has a polar group represented by Formula 2 as an internal mold release agent. Mold polymerization method of the resin for epoxy acrylate optical lens, characterized in that it further comprises a compound. [Formula 2]

Wherein 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.) [Revision 16.07.2012 under Rule 91]
20 to 80% by weight of an epoxy acrylate compound containing 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 the following Formula 2 as an internal mold release agent, or Resin composition for an epoxy acrylate optical lens containing 0.001 to 10% by weight of the phosphate ester compound represented by the formula (3). [Formula 1]

(Where n = 0-15, R ₁ is H or CH ₃ and R ₂ is H or Br) [Formula 2]

(Where 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.) [Formula 3]

(Where R is an alkyl group having 3 to 20 carbon atoms, n is 0 to 10, and m is 1 to 2) The liquid composition of claim 8, wherein the resin composition for optical lenses has a liquid viscosity of 20 to 1,000 cps at 25 ° C, a liquid refractive index (nE, 20 ° C) of 1.50 to 1.58, and a solid state refractive index (nE, 20 ° C) of 1.54. It is -1.63, The resin composition for epoxy acrylate type optical lenses. The compound having the polar group is acetic acid, formic acid, oxalic acid, propionic acid, acrylic acid, methacrylic acid, water, methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, allyl alcohol, 2- 1 selected from the group consisting of 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 It is a species or 2 or more types of compound, The resin composition for epoxy acrylate type optical lenses. The method of claim 8, 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 etofate (9 mole added ethylene oxide 3% by weight, 8 mole added 80% by weight, 9 mole added 5% by weight, 7 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 Weight%, 9 mol added 3 weight%, 4 mol added 6 weight%), polyoxyethylene nonylphenol ether phosphate (3 mol% added 17 mol ethylene oxide, 79 weight added 16 mol added , 15 mole added 10% by weight, 14 mole added 4% by weight, 13 mole added 4% by weight), polyoxyethylene nonylphenol ether force Pate (5% by weight of 21 mole added ethylene oxide, 76% by weight 20 mole added, 7% by weight 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 ™. The method of claim 8, wherein the reactive diluent is styrene, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer, benzyl methacrylate, chlorostyrene, bromo styrene, methoxy styrene, monobenzyl maleate, dibenzyl maly Eight, monobenzyl fumarate, dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monopentyl maleate, dipentyl maleate, A resin composition for epoxy acrylate-based optical lenses, characterized in that one or two or more compounds selected from the group consisting of monopentyl fumarate, dipentyl fumarate, diethylene glycol bisaryl carbonate. The resin composition according to claim 8, further comprising a heat stabilizer. According to any one of claims 8 to 10, 12 and 13, wherein the internal release agent is a compound having a polar group represented by the formula (2), characterized in that it further comprises a phosphate ester compound as an internal release agent The resin composition for epoxy acrylate type optical lenses. The compound according to any one of claims 8, 9 and 11 to 13, wherein the internal mold release agent is a phosphate ester compound represented by the formula (3), and a compound having a polar group represented by the following formula (2) as the internal mold release agent. A resin composition for an epoxy acrylate optical lens, further comprising. [Formula 2]

Wherein 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.) An optical material obtained by adding a catalyst to the composition of claim 8 and thermosetting. A plastic spectacle lens or polarizing lens made of the optical material of claim 16.