KR101920164B1 - A method of preparing epoxy acryl based optical material - Google Patents

Abstract

The present invention relates to an epoxy acrylic optical lens, More specifically, the present invention relates to a resin composition for high quality epoxy acrylic middle refractive optical lenses, ensuring excellent thermal stability, light resistance, transparency, color, deformation, and compression strength at a solid-state refractive index of 1.53 to 1.58. The present invention further relates to a production method thereof. To this end, the resin composition for epoxy acrylic middle refractive optical lenses with solid-state refractive index of 1.53 to 1.58 is composed of 50-70 wt% of bisphenol A epoxy acrylate having hydrolyzable chlorine content of 0.01 to 0.11 wt%, 21-45 wt% of methyl methacrylate, and 1-17 wt% of a reactive diluent. According to the present invention, by controlling the content of hydrolyzable chlorine of bisphenol A diglycidyl ether to 0.11 wt% or less and containing a large amount of methyl-methacrylate(MMA) in the composition, it is possible to improve the compressive strength in a medium refractive lens having the refractive index of 1.53 to 1.58. It is also possible to obtain a resin composition for epoxy acrylic middle refractive optical lenses having good thermal stability, light resistance, transparency, color, and deformation. The epoxy acrylic medium refractive optical lens, according to the present invention, can be widely used in various fields in place of the conventional middle refractive optical lenses.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin composition for an epoxy acrylic middle refractive optical lens,

TECHNICAL FIELD The present invention relates to an epoxy acrylic optical lens, and more particularly to a resin composition for a high-quality epoxyacrylic medium refractive index lens having a refractive index of 1.53 to 1.58 and excellent in thermal stability, light resistance, transparency, color, will be.

The lens using PMMA (polymethyl-methacrylate), which was introduced in 1936, is also referred to as an acrylic lens, and has a high transparency of Abbe number 57. However, it has a low refractive index of 1.49 and is more heat resistant than comparable refractive index CR- And the surface strength is low.

DISO Corporation in Japan developed the acrylic high refractive index resin first by mixing a reactive diluent such as styrene with diacrylate of tetrabromobisphenol A in 1992. However, since the lens using the acrylic high refractive index resin lacks thermal stability and light resistance, .

Japanese Patent Laid-Open Nos. 6-49133 and 7-206974 disclose a method for producing a lens by mixing divinyl benzene, styrene, benzyl methacrylate, isocyanate, etc. with tetrabromobisphenol A diacrylate. These optical lenses have improved light resistance and heat resistance, but have a low thermal stability and cause a color change during hard coating.

In order to solve such a problem, Korean Patent Laid-Open Publication No. 10-2004-0083942 discloses a thermosetting resin composition which is obtained by mixing a reactive diluent such as styrene and methylstyrene with tetrabromobisphenol A diacrylate and adding an acidic phosphate ester thereto, And a refractive index of 1.58-1.61. Such an epoxy acrylic lens has a high refractive index and a high Abbe's number, and is excellent in optical properties such as transparency, light weight, and heat resistance, and has an advantage of low cost of materials.

However, when manufacturing an epoxy acrylate-based lens, thermal stability, light resistance, transparency, releasability, and the like are sometimes deteriorated for reasons unknown. In addition, a reactive diluent is required to control the viscosity and the reaction rate. Examples of such a reactive diluent include styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer, benzylmethacrylate, chlorostyrene, bromostyrene, Ethoxy styrene, dibenzyl malate, and the like, or a mixture of two or more thereof. The choice of such a diluent influences the productivity and optical properties of the lens and also affects the production cost. For example, styrene presently present at high and in the resin frequently causes a decrease in strength.

On the other hand, various resins such as polyethylene glycol bisallyl carbonate, polymethylmethacrylate, diallyl phthalate, polystyrene and polycarbonate have been conventionally used as optical lenses having a medium refractive index range.

In EP 06905 A2, 5 to 40 parts by weight of acrylic acid and bisphenol A type epoxy resin reactant and 5 to 40 parts by weight of acrylic acid and bis-tetra-bromobisphenol A type epoxy resin reactant are added to 15 to 50 parts by weight of styrene, And 5 to 20 parts by weight of divinylbenzene, diallyl diphenate, vinyltoluene, and chlorostyrene. However, the optical resin composition has a problem of insufficient thermal stability.

Japanese Laid-Open Patent Publication No. 53-7787 discloses an optical lens obtained by polymerizing 85 wt% of diallyl isophthalate and 15 wt% of diethylene glycol bisallyl carbonate. This lens succeeded in reducing the thickness of the lens The impact resistance is still weak.

Japanese Patent Laid-Open No. 62-235901 and Digest 64-45412 and Japanese Patent Publication No. 1-60494 also disclose a plastic lens made of a copolymer composed of modified diallyl phthalate and dibenzyl fumarate, and a lens made of diallyl phthalate and methyl acrylate There is a problem that a plastic lens made by a copolymer is low in impact resistance.

Korean Patent Publication No. 10-0431434 discloses a monomer composition for a mid-refracting lens in the range of 1.53 to 1.55, which comprises a diallyl ester oligomer, dialkyl maleate, diethylene glycol bisallyl carbonate and diallyl adipate. It has improved physical properties in light stability and impact resistance as compared with conventional medium refractive lenses, but has a problem of low transparency and low heat resistance.

Epoxy acrylic lenses have good optical properties such as transparency and Abbe number. Therefore, if it is possible to raise the quality in terms of heat stability, light resistance, releasability, color, and compressive strength and to lower the production cost, the refractive index of the medium refractive lens having a refractive index of about 1.53 to 1.58 The lens can be competitive with the lens.

Japanese Unexamined Patent Publication No. 53-7787 Japanese Patent Application Laid Open No. 62-235901 Japanese Unexamined Patent Publication No. 64-45412 Japanese Patent Publication No. Hei 1-60494 European patent 06905 Korean Patent Publication No. 10-0431434 Korean Patent Publication No. 10-0496911 Korean Patent Publication No. 10-0498896 Korean Patent Publication No. 10-2015-0071170

In the present invention, when manufacturing an epoxy acrylate-based lens, problems of thermal stability, light resistance, and transparency deteriorate, which are often unknown, are caused by the hydrolyzable chlorine generated in the process of producing bisphenol A diglycidyl ether (BPDE) And to solve the problem by controlling it below a certain level.

Methylmethacrylate is conventionally used as a reactive diluent together with styrene, divinylbenzene, alphamethylstyrene, alpha methylstyrene dimer and the like, but when it is used in a resin in an amount of 20 wt% or more, there are problems in physical properties in many aspects such as whitening and polymerization imbalance, It is used only in small quantities. However, when methyl methacrylate is used in a large amount, the compression strength is improved as compared with the case of using styrene, so that the compression strength can be improved without adding the production cost. In the present invention, a resin composition for an epoxyacrylic medium refractive optical lens having excellent transparency, Abbe's number, thermal stability, light resistance and releasability, excellent compression strength, and economical efficiency while containing a large amount of methyl methacrylate in a lens resin composition in an amount of 20% The purpose is to provide.

In order to achieve the above object, according to the present invention,

50 to 70% by weight of bisphenol A epoxy acrylate represented by the following formula (1) and having a hydrolyzable chlorine content of 0.01 to 0.11% by weight,

21 to 45% by weight of methyl methacrylate,

Based refractive index optical lens having a solid refractive index of 1.53 to 1.58, wherein the refractive index is 1 to 17% by weight of a reactive diluent.

[Chemical Formula 1]

Where n = 0 to 15.

The resin composition for an epoxyacrylic medium refractive optical lens may further contain an internal mold release agent in an amount of 0.001 to 10% by weight based on the composition.

The resin composition for an epoxyacrylic medium refractive optical lens may further contain a heat stabilizer in an amount of 0.01 to 5% by weight based on the composition.

In the present invention,

50 to 70% by weight of bisphenol A epoxy acrylate represented by the following formula (1) and having a hydrolyzable chlorine content of 0.01 to 0.11% by weight,

21 to 45% by weight of methyl methacrylate,

Based refractive index optical lens having a solid-phase refractive index of 1.53 to 1.58 obtained by polymerizing a resin composition for an optical lens containing 1 to 17% by weight of a reactive diluent in a mold.

[Chemical Formula 1]

Where n = 0 to 15.

In the present invention,

There is provided a process for producing an acrylic-based refraction optical lens comprising a step of polymerizing a resin composition for an epoxy-acrylic-based medium refractive index optical lens in a mold.

In the present invention, by controlling the hydrolyzable chlorine content of bisphenol A diglycidyl ether to 0.11% by weight or less and containing a large amount of MMA in the composition of 20% by weight or more, It is possible to provide a resin composition for a high-quality epoxyacrylic medium refractive optical lens which can greatly improve the strength and is excellent in heat stability, light resistance, transparency, color and releasability.

INDUSTRIAL APPLICABILITY The resin composition for an epoxyacrylic medium refractive index optical lens of the present invention,

A bisphenol A epoxy acrylate (BPDA) represented by the following formula (1); Methyl methacrylate (MMA) and a reactive diluent.

[Chemical Formula 1]

Where n = 0 to 15.

The bisphenol A epoxy acrylate is usually obtained by reacting bisphenol A diglycidyl ether represented by the following formula (2) and acrylic acid as shown in the following reaction formula (2).

(2)

Where n = 0 to 15.

[Reaction Scheme 1]

The present inventors have found that the problems of thermal stability, light resistance, and transparency deterioration, which are often unexplained in the production of epoxy acrylate-based lenses, are caused by the hydrolyzable chlorine generated in the course of the production of bisphenol A diglycidyl ether (BPDE) And the content of In the present invention, the preferred hydrolyzable chlorine content of the bisphenol A diglycidyl ether (BPDE) is 0.01 to 0.11% by weight, more preferably 0.03 to 0.08% by weight. The hydrolyzable chlorine content in the BPDE can be removed or reduced by vacuum removal and washing with water and ammonia water. The hydrolyzable chlorine content in the BPDE may be less than 0.01% by weight, but it is not easy to reduce it to less than 0.01% by weight, while less than 0.01% by weight and 0.01 to 0.05% by weight have little difference in lens quality. Therefore, when considering the lens quality and the production cost, the preferable chlorine content of BPDE is 0.01 to 0.11 wt%, more preferably 0.03 to 0.08 wt%.

In the present invention, the hydrolyzable chlorine content of bisphenol A diglycidyl ether (BPDE) is measured by the following method.

The content of hydrolyzable chlorine (Cl,%)  How to measure

The epoxy acrylic compound was weighed and thoroughly dissolved in toluene (15 mL), dissolved in about 50 mL of pure water with 0.1N KOH (methyl Cellosolve) solution (KOH (85%)) and dissolved in methyl Cellosolve 1 L) is added. Attach the air cooling tube to the water bath set at 70 ℃ ± 5 ℃. After 30 minutes, take out from the water bath, cool to room temperature, clean the cooler with about 5 mL of methyl Cellosolve (Me-OH), and mix this solution in the flask. Add 5 to 6 drops of a mixture indicator (1 part of Cresol Red 0.1% alcohol solution and 3 parts of Thymol Blue 0.1% alcohol solution) and add 0.1 N HCl standard solution (9 mL of 35% concentrated hydrochloric acid to methanol to make 1 L) . The end point is defined as the point at which it changes from blue to yellow.

[Formula 1]

A: Amount (mL) of 0.1N HCl standard solution consumed.

B: Amount (mL) of 0.1 N HCl standard solution consumed in Blank Test.

F: Factor of 0.1 N HCl standard solution

W: Amount of sample (g)

The bisphenol A epoxy acrylate (BPDA) is contained in an amount of 50 to 70% by weight, preferably 55 to 65% by weight in the resin composition for an epoxyacrylic medium refractive optical lens of the present invention.

Methyl methacrylate (MMA) contained in the resin composition of the present invention has been used as a reactive diluent in conventional epoxy acrylic optical resins together with styrene, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer and the like. However, unlike styrene and divinylbenzene, MMA is not included in large amounts and is usually used in a small amount of about 3% and at most 20%. This is because when the MMA is contained in the resin for the optical lens in an amount of 20 wt% or more, there are problems in physical properties of the lens in various aspects such as whitening and polymerization imbalance. However, in the present invention, the content of hydrolyzable chlorine in bisphenol A diglycidyl ether (BPDE) is controlled to 0.01 to 0.11% by weight, and the content of bisphenol A epoxy acrylate in the resin composition for an all- 50 to 70% by weight, it is possible to contain a large amount of MMA in an amount of 20% by weight or more in the whole resin composition. By containing a large amount of MMA in an amount of 20 wt% or more, the compression strength can be greatly increased without adding production cost. In the resin composition of the present invention, MMA is preferably contained in an amount of 21 to 45% by weight, more preferably 25 to 40% by weight.

The reactive diluent contained in the resin composition of the present invention plays a role of appropriately controlling the viscosity and the polymerization rate of the composition and is not particularly limited as long as it is used as a reactive diluent in a resin for an epoxy acrylic optical lens .

Preferably, the reactive diluent is selected from the group consisting of styrene, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzyl maleate, monobenzyl fumarate, di Benzyl maleate, dibenzyl fumarate, methyl benzyl maleate, dimethyl malate, diethyl malate, dibutyl malate, dibutyl fumarate, monobutyl malate, monopentyl malate, dipentyl malate, A compound selected from the group consisting of dibutyl phthalate, dipentyl fumarate, and diethylene glycol bisaryl carbonate may be used singly or in combination of two or more thereof. More preferably, the reactive diluent is one or more compounds selected from the group consisting of styrene, divinylbenzene, alpha methyl styrene, and alpha methyl styrene dimer.

Since MMA, which is essentially contained in the resin composition of the present invention, serves as a reactive diluent, other reactive diluents are preferably contained in a small amount of 1 to 17 wt%. If the total reactive diluent content, including MMA and other reactive diluents, exceeds 60% by weight, the viscosity of the composition will be too low to melt the tape adhesive, which will result in tape bleaching and leakage during the curing process after injection This may result in white pigmentation and fogging on the lens.

The resin composition of the present invention comprising MMA and the reactive diluent has a liquid phase viscosity of 20-200 cps at 25 캜 suitable for casting polymerization and a liquid phase refractive index (nD, 20 캜) of 1.48-1.55, a solid refractive index (nE, 20 < 0 > C) is 1.53-1.58. If the viscosity of the liquid phase is less than 20 cps, there is a problem that the composition flows out of the mold when the liquid resin composition is injected into the glass mold assembled with the synthetic resin gasket. When the viscosity of the liquid phase exceeds 200 cps, There is a difficult problem. A more preferable viscosity is 30 to 100 cps.

The resin composition of the present invention may further contain an internal release agent. By adding an internal effervescent material to the resin composition before the casting polymerization, the releasability after polymerization can be greatly improved. The inner blowing agent is preferably contained in an amount of 0.001 to 10% by weight in the polymerizable composition.

As the internal release agent, a phosphoric acid ester compound, a silicone surfactant, a fluorinated surfactant, an alkyl quaternary ammonium salt, etc. may be used alone or in combination of two or more thereof

The fluorine-based nonionic surfactant is a compound having a perfluoroalkyl group in the molecule, and includes a combination of Unidyne DS-401 122A ™ (Shin-Aichi Kasei Co., Ltd., Japan), Eftof EF 126 ™ (Shin Akitagase Co., Ltd., Japan) and Eftof EF 301 ™ (Shin-Etsu Chemical Co., Ltd., Japan).

The silicone-based nonionic surfactant is a compound having a dimethylpolysiloxane group in the molecule, such as Q2-120A of U.S. Dow.

The alkyl quaternary ammonium salt is generally known as a cationic surfactant and includes halogen salts, phosphates and sulfates. Examples of the chloride type include trimethylcetylammonium chloride, trimethylstearylammonium chloride, dimethylethylcetylammonium chloride, Triethyldecylammonium chloride, trioctylmethylammonium chloride, diethylcyclohexyl, decylammonium chloride, and the like.

 Preferably, a phosphoric acid ester compound can be used as an inner mold release agent. The phosphate ester compound is a compound having a phosphoric acid ester group, and examples thereof include isopropyl acid phosphate, diisopropyl acid phosphate, butylate phosphate, dibutylate phosphate, octylate phosphate, dioctylate phosphate, isodecylate phosphate, Tricarboxylic acid phosphate, tridecanolic acid phosphate, bis (tridecanolic acid) phosphate, and mixtures of two or more thereof. As the phosphoric acid ester compound, preferably polyoxyethylene nonylphenol ether phosphate (5 mol% of ethylene oxide, 5 mol% of ethylene oxide, 80 mol% of 4 mol of ethylene oxide, 10 mol% of 3 mol of ethylene oxide, (5 wt% of ethylene oxide, 9 wt% of ethylene oxide, 8 wt% of ethylene oxide, 80 wt% of ethylene oxide, 10 wt% of ethylene oxide of 7 mol of ethylene oxide, 5 wt% of oxide having 6 mol or less added thereto), polyoxyethylene nonylphenol ether phosphate (3 mol% of ethylene oxide, 11 mol of ethylene oxide, 80 wt% of ethylene oxide, 5 wt% of 9 mol of ethylene oxide, 6 mol% of 7 mol%, 6 wt% of 6 mol%), polyoxyethylene nonylphenol ether phosphate (3 mol% of ethylene oxide 13 mol, 12 mol% of 80 mol% 8% by weight, 9% by mole of 3% by weight, and 4% by mole of 6% by weight), polyoxy Ethylene nonylphenol ether phosphate (having 3 parts by weight of 17 mol of ethylene oxide, 79 parts by weight of 16 parts by mole, 10 parts by weight of 15 parts by mol, and 4 parts by weight of 13 parts by mol of 14 parts by mol of ethylene oxide, 4% by weight), polyoxyethylene nonylphenol ether phosphate (21% by mole of ethylene oxide, 5% by weight, 20% by mole of 78% by weight, 19% by mole of 7% , 4% by weight of 17 mol%), dioctyl acid phosphate, and Zelec UN (TM).

The resin composition of the present invention may further comprise a heat stabilizer. The heat stabilizer may preferably be contained in an amount of 0.01 to 5.00% by weight in the resin composition of the present invention. When the heat stabilizer is used in an amount of less than 0.01% by weight, the heat stabilizing effect is weak. When the heat stabilizer is used in an amount exceeding 5.00% by weight, the polymerization defective rate upon curing is high and the thermal stability of the cured product may be lowered.

Examples of the thermal stabilizer include metal stearate such as calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate and zinc octoate Or a combination thereof.

Preferably, phosphorus compounds such as triphenylphosphite, diphenyldecylphosphite, phenyldodecylphosphite, diphenyldodecylphosphite, diphenyl isodecylphosphate, trinorylphenylphosphite, diphenyl isooctylphosphite, tri It is possible to use one or more compounds selected from butyl phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite), and tris (monophenyl) phosphite. Particularly preferably, diphenyl isodecyl phosphate can be used.

Further, the sealed lead _{3PbO.PbSO 4 .4H 2 O, 2PbO.Pb (} C 8 H 4 O 4), 3PbO.Pb (C 4 H 2 O 4) .H ₂ O 1 selected from compounds, such as species or two kinds of Or more.

The organic tin compounds such as dibutyl tin diarouate, dibutyl tin maleate, dibutyl tin bis (isooctyl maleate), dioctyl maleate, dibutyl tin bis (monomethyl maleate), dibutyl tin bis (Isooctyl mercaptoacetate), tris (isooctyl mercaptoacetate), dibutyl tin (isooctyl mercaptoacetate), dibutyl tin (isooctyl mercaptoacetate), monobutyl tin tris (2-mercaptoethylolate), dibutyltin bis (2-mercaptoethylolate), monobutyltin (2-mercaptoethanolate), dimethyltin bis (2-mercaptoethylolate) , Monomethyltin tris (2-mercaptoethylolate), and the like can be used.

It is also possible to use a mixture of two or more kinds of heat stabilizers different in the series among the above-exemplified heat stabilizers. Most preferably, by using a thermal stabilizer of phosphorus, 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 as well as the initial color of the formed lens.

The resin composition of the present invention may further contain an ultraviolet absorber, an organic dye, an inorganic pigment, a coloring inhibitor, an antioxidant, a light stabilizer, a catalyst and the like according to a conventional technique in addition to conventional techniques in the field of plastic optical lenses .

The epoxy acryl-based medium refractive optical lens according to the present invention can be produced by putting the above resin composition of the present invention into a mold and polymerizing. According to a preferred embodiment, after the resin composition is injected into a mold, the mold is placed in a forced circulation oven and slowly cured by heating from 30 ° C to 120 ° C, followed by cooling to about 70 ° C to 10 ° C to desorb the mold to obtain a lens. In this case, all the raw materials preferably use a high purity compound having a purity of 70 to 99.99%. Preferably, the purity of all the raw materials is checked to purify the compounds with low purity, and the compounds with high purity are used without purification.

The acrylic-based refractive-index optical lens obtained by the above-described method can be used in various fields as a medium-refractive-index lens having a solid-state refractive index of 1.53-1.58 in place of the conventional middle-refractive-index lens. Specifically, it can be used as a plastic spectacle lens, a 3D polarized lens in which a polarizing film is attached to a spectacle lens, a camera lens, etc. In addition, a recording medium substrate used for a prism, an optical fiber, Products.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, these embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

Hydrolytic  The chlorine content (Cl, % )

The hydrolyzable chlorine content (%) of the obtained bisphenol A diglycyl ether compound was measured by the following method.

The epoxy acrylic compound was weighed and thoroughly dissolved in toluene (15 mL), dissolved in about 50 mL of pure water with 0.1N KOH (methyl Cellosolve) solution (KOH (85%)) and dissolved in methyl Cellosolve 1 L) is added. Attach the air cooling tube to the water bath set at 70 ℃ ± 5 ℃. After 30 minutes, take out from the water bath, cool to room temperature, clean the cooler with about 5 mL of methyl Cellosolve (Me-OH), and mix this solution in the flask. Add 5 ~ 6 drops of 0.1 N HCl standard solution (9 mL of 35% concentrated hydrochloric acid in methanol to make 1 L). Add 1 part of Cresol Red 0.1% alcohol solution and 3 parts of Thymol Blue 0.1% alcohol solution. ). The end point is defined as the point at which it changes from blue to yellow.

[Formula 1]

A: Amount (mL) of 0.1N HCl standard solution consumed.

B: Amount (mL) of 0.1 N HCl standard solution consumed in Blank Test.

F: Factor of 0.1 N HCl standard solution

W: Amount of sample (g)

Epoxy Acrylate  compound( BPDA ) Synthesis of

Synthesis Example 1

Acrylic acid (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to a compound of National Chemical Industry BPDE (561 g) The reaction temperature was lowered to 60 ° C, and 1.12 g of 35% concentrated hydrochloric acid was added. The reaction temperature was gradually raised to 105 ° C. and further reacted for 2 hours to obtain an acrylated chemical reaction formula Compound ( BPDA 1 ). The hydrolyzable chlorine content was 0.03%.

[Reaction Scheme 1]

Synthesis Example 2

Route Chemistry BPDE of equivalent 187 (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to 561 g of the compound The reaction was carried out for 18 hours. The temperature was lowered at 60 DEG C and 1.55 g of 35% concentrated hydrochloric acid was added. The reaction temperature was gradually raised to 105 DEG C and further reacted for 2 hours to obtain an acrylated compound ( BPDA 2 ). The hydrolyzable chlorine content was 0.05%.

Synthesis Example 3

Route Chemistry BPDE of equivalent 187 (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to 561 g of the compound The reaction was carried out for 18 hours. The temperature was lowered, 2.02 g of 35% concentrated hydrochloric acid was added at 60 DEG C, the reaction temperature was gradually raised to 105 DEG C and further reacted for 2 hours to obtain acrylate compound ( BPDA 3 ). The hydrolyzable chlorine content was 0.07%.

Synthesis Example 4

Route Chemistry BPDE of equivalent 187 (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to 561 g of the compound The reaction was carried out for 18 hours. The temperature was lowered, and 2.52 g of 35% concentrated hydrochloric acid was added at 60 캜. The reaction temperature was gradually raised to 105 캜 and further reacted for 2 hours to obtain an acrylated compound represented by BPDA 4 ). The hydrolyzable chlorine content was 0.08%.

Synthesis Example 5

Route Chemistry BPDE of equivalent 187 (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to 561 g of the compound The reaction was carried out for 18 hours. The temperature was lowered, 3.08 g of 35% concentrated hydrochloric acid was added at 60 DEG C, the reaction temperature was gradually raised to 105 DEG C and further reacted for 2 hours to obtain acrylated compound ( BPDA 5 ). The hydrolyzable chlorine content was 0.10%.

Comparative Synthesis Example 1

Route Chemistry BPDE of equivalent 187 (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to 561 g of the compound The reaction was carried out for 18 hours. The temperature was lowered, 4.03 g of 35% concentrated hydrochloric acid was added at 60 DEG C, the reaction temperature was gradually raised to 105 DEG C and further reacted for 2 hours to obtain acrylate compound ( BPDA 6 ). The hydrolyzable chlorine content was 0.14%.

Comparative Synthesis Example 2

Route Chemistry BPDE of equivalent 187 (436 g, 6.06 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) were added to 561 g of the compound The reaction was carried out for 18 hours, and the temperature was lowered. Then, 5.14 g of 35% concentrated hydrochloric acid was added at 60 DEG C, the reaction temperature was gradually raised to 105 DEG C and further reacted for 2 hours to obtain acrylated compound ( BPDA 7 ). The hydrolyzable chlorine content was 0.18%.

Example 1

0.5 g of alpha methylstyrene dimer as a polymerization regulator was added to 60 g of the epoxy acrylate compound ( BPDA 1 ), 5 g of styrene as a reaction diluent and 35 g of methyl methacrylate were added, and the mixture was stirred for about 30 minutes. Thereafter, 0.05 g of V65 and 0.12 g of 3-M were added as a catalyst, 0.05 g of 4-PENPP and 0.2 g of 8-PENPP were added to the resulting solution, After making the resin composition, an optical lens was manufactured by the following method and the physical properties of the optical lens were measured.

(1) The resin composition for an optical lens prepared as described above was stirred for 1 hour, defoamed under reduced pressure for 10 minutes, filtered, and then 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 cured by heating in a forced circulation oven from 35 ° C to 110 ° C over 20 hours, and then cooled to 70 ° C to desorb the glass mold to obtain a lens. The obtained lens was processed to a diameter of 72 mm, ultrasonically washed with an aqueous alkaline washing solution, and annealed at 120 ° C for 2 hours. The physical properties were measured in the following manner, and the results are shown in Table 1 .

Physical properties test method

The physical properties of the optical lens prepared in the examples were measured by the following experimental methods, and the results are shown in Table 1 .

1) Refractive index and Abbe number: Measured using an Abbe refractometer, a model of Atago's DR-M4.

2) Specific gravity: An analytical balance was used and measured by an underwater substitution method.

3) Dissimilarity: "⊚", "◯", "Δ", and "×" in the case of separating the optical lens and the mold when the epoxy acrylic resin composition was thermally cured at 70 ° C., Respectively. "◎" means that when the lens or mold is not damaged or damaged in the process of separating 100 optical lenses and mold, "○" means that there are 2 or 3 lenses or molds in the process of separating 100 optical lenses and molds In case of breakage, "Δ" means that when 4 or 5 lenses or molds are broken in the process of separating 100 optical lenses and molds, "×" means 6 lenses or molds in the process of separating 100 optical lenses and molds Or more is broken.

4) Compressive Strength: LR5K-Plus universal material testing machine of LLOYD Instruments has a spectacle lens of 75 mm in diameter, center thickness of 1.2 mm, and a water depth of 8.00, according to the method of ISO 14889 and JIS T57331 And the measured value was expressed as N (Newton).

5) Thermal Stability: The cured optical lens was maintained at 100 ° C for 10 hours. When the APHA value was changed to less than 1 in the color change measurement, it was indicated as "⊚". When the APHA value was changed from 1 to 2, "And the value of" × "if the APHA value was changed by 3 or more.

6) Transparency: 100 lenses were observed with the naked eye under a USHIO USH-10D Mercury Arc Lamp, and when the turbidity of the optical lens was found to be less than 1, it was marked as "Quot;, and " x " if three or more were found.

7) Light fastness: QUV / SE Model Accelerated Weathering Tester from Q-Lab. Was used. The QUV test was conducted by irradiating a flat lens having a thickness of 1.2 mm for 48 hours under conditions of UVA-340 (340 nm), 0.76 W / m2 light intensity, 4 hours BPT (Black Panel Temperature) Quot; when the APHA value changes from 2 to 4, and " X " when the APHA value changes by 5 or more from the measurement of the color change, Respectively.

Examples 2 to 5

Optical lenses were produced in the same manner as in Example 1 , according to the composition shown in Table 1 , and their physical properties were measured.

Comparative Example 1

0.5 g of alpha methylstyrene dimer as a polymerization controlling agent was added to 60 g of an epoxy acrylate compound ( BPDA 6 ), 5 g of styrene as a reaction diluent and 35 g of methyl methacrylate were added, and the mixture was stirred for about 30 minutes. Thereafter, 0.05 g of V65 and 0.12 g of 3-M were added as a catalyst, 0.05 g of 4-PENPP and 0.2 g of 8-PENPP were added to the resulting solution, After preparing the resin composition, an optical lens was prepared in the same manner as in Example 1. [ The properties were measured and the results are shown in Table 1 .

Comparative Examples 2 to 3

In the same manner as in Comparative Example 1 , an optical lens was produced in accordance with the composition shown in Table 1 , and the properties thereof were measured.

[Abbreviation]

MMA : methyl methacrylate

4-PENPP : polyoxyethylene nonylphenyl phosphate (5 mol% of ethylene oxide, 5 mol% of ethylene oxide, 80 mol% of ethylene oxide, 3 mol of ethylene oxide and 10 mol% of ethylene oxide, 1 mole added 5% by weight)

8-PENPP : polyoxyethylene nonylphenyl phosphate (5 mol% of ethylene oxide, 9 mol% of ethylene oxide, 80 mol% of ethylene oxide, 10 mol% of ethylene oxide, 7 mol of ethylene oxide, 5 mol% or less added thereto)

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

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

According to the present invention, by controlling the amount of hydrolyzable chlorine of the epoxy acrylate, it is possible to provide a composition which contains a large amount of MMA but retains transparency and Abbe's number in a good state and is excellent in heat stability, light resistance, transparency, color and releasability, An acrylic-based refracting optical lens can be manufactured at a low production cost. The optical lens according to the present invention can be widely used in related fields by replacing the conventional middle refractive lens. In particular, it can be used in the fields of plastic spectacle lenses, 3D polarized lenses in which polarizing films are attached to spectacle lenses, and camera lenses. In addition, various optical products such as recording medium substrates used for prisms, optical fibers, optical discs, Lt; / RTI >

Claims (12)

50 to 70% by weight of bisphenol A epoxy acrylate represented by the following formula (1) and having a hydrolyzable chlorine content of 0.01 to 0.11% by weight,
21 to 45% by weight of methyl methacrylate,
1 to 17% by weight of a reactive diluent, and a solid-refractive index of 1.53 to 1.58.
[Chemical Formula 1]

Where n = 0 to 15. The method according to claim 1,
The reactive diluent may be selected from the group consisting of styrene, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzyl maleate, monobenzyl fumarate, Dibenzyl maleate, dibutyl maleate, dibenzyl maleate, dibenzyl fumarate, methyl benzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, Wherein the resin is at least one compound selected from the group consisting of fumarate and diethylene glycol bisaryl carbonate. The method according to claim 1,
Wherein the reactive diluent is one or more compounds selected from the group consisting of styrene, divinylbenzene, alphamethylstyrene, and alpha methylstyrene dimer. The method according to claim 1,
Wherein the resin composition further comprises an internal mold release agent in an amount of 0.001 to 10% by weight of the composition. 5. The method according to any one of claims 1 to 4,
Wherein the composition further comprises a heat stabilizer in an amount of 0.01 to 5% by weight of the composition. 6. The method of claim 5,
The thermal stabilizer may be selected from the group consisting of triphenyl phosphite, diphenyldecyl phosphite, phenyldodecyl phosphite, diphenyldodecyl phosphite, diphenyl isodecyl phosphate, trinolyl phenyl phosphite, diphenyl isooctyl phosphite, tributylphosphate Wherein the resin composition is at least one compound selected from the group consisting of tripolyphosphate, triethylphosphite, trimethylphosphite, tris (monodecylphosphite), and tris (monophenyl) phosphite. . 50 to 70% by weight of bisphenol A epoxy acrylate represented by the following formula (1) and having a hydrolyzable chlorine content of 0.01 to 0.11% by weight,
21 to 45% by weight of methyl methacrylate,
1 to 17% by weight of a reactive diluent obtained by polymerizing a resin composition for an optical lens in a mold, and having a solid-phase refractive index of 1.53 to 1.58.
[Chemical Formula 1]

Where n = 0 to 15. 8. The method of claim 7,
Wherein the reactive diluent is at least one compound selected from the group consisting of styrene, divinyl benzene, alpha methyl styrene, and alpha methyl styrene dimer. 9. The method according to claim 7 or 8,
Wherein the resin composition further comprises a heat stabilizer in an amount of 0.01 to 5% by weight. The method of claim 9, wherein the heat stabilizer is selected from the group consisting of triphenyl phosphite, diphenyldecyl phosphite, phenyldodecyl phosphite, diphenyldodecyl phosphite, diphenyl isodecyl phosphate, trinolyl phenyl phosphite, diphenyl isooctyl At least one compound selected from the group consisting of phosphite, tributyl phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite), and tris (monophenyl) phosphite Wherein the refractive index of the epoxy-acrylic-based medium-refractive- 10. The method of claim 9,
Wherein the resin composition further contains an internal mold release agent in an amount of 0.001 to 10% by weight. A process for producing an acrylic-based refractive optical lens, comprising the step of polymerizing the resin composition of claim 1 in a mold.