WO2018216901A1 - Resin composition for epoxy acrylic middle-refractive optical lens and preparation method therefor - Google Patents

Abstract

The present invention relates to an epoxy acrylic optical lens and, especially, to a resin composition for an epoxy acrylic middle-refractive optical lens having favorable moldability, thermal stability, light resistance, and compressive strength, together with a solid-state refractive index of 1.53-1.58, and to a preparation method for the resin composition. Provided in the present invention is a resin composition for an epoxy acrylic middle-refractive optical lens having a solid-state refractive index of 1.53-1.58, the resin composition containing: 50-70 wt% of bisphenol A epoxyacrylate having an acid value of 0.01-2.5; 21-45 wt% of methyl methacrylate; and 1-17 wt% of a reactive diluent. According to the present invention, an epoxy acrylic middle-refractive optical lens having excellent moldability, thermal stability, and light resistance as well as high compressive strength, while maintaining transparency and Abbe's number in good condition can be produced at a low production cost, by controlling the acid value of epoxy acrylate and allowing a large amount of MMA to be contained in the composition. The epoxy acrylic middle-refractive optical lens according to the present invention can be widely used in various fields by substituting for an existing middle-refractive optical lens.

Description

Resin composition for epoxy acrylic mid-refractive optical lens and method of manufacturing same

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy acrylic optical lens, and more particularly, to a resin composition for an epoxy acrylic medium refractive optical lens having excellent releasability, compressive strength, thermal stability, transparency, and color of a refractive index of 1.53 to 1.58, and a method of manufacturing the same.

Lenses made of PMMA (polymethyl-methacrylate), an acrylic resin introduced in 1936, are also called acrylic lenses and have a high transparency with Abbe number 57, but have a low refractive index of 1.49 and heat resistance compared to CR-39 with similar refractive index. And there is a disadvantage of low surface strength.

Japan's DISO Co., Ltd. developed acrylic high refractive resin for the first time in 1992 by mixing a reactive diluent such as styrene with dibromobisphenol A diacrylate. It didn't work.

Later, Japanese Patent Laid-Open Nos. Hei 6-49133 and Hei 7-206974 have suggested a method of manufacturing a lens by mixing divinylbenzene, styrene, benzyl methacrylate, isocyanate and the like with tetrabromobisphenol A diacrylate. These optical lenses have improved light resistance and heat resistance, but have low thermal stability, causing color change during hard coating.

In order to solve this problem, Korean Patent Publication No. 10-2004-0083942 discloses thermal stability and light resistance of spectacle lenses by mixing a reactive diluent such as styrene and methyl styrene to tetrabromobisphenol A diacrylate and adding an acidic phosphate ester thereto. The lens of the refractive index 1.58-1.61 is greatly improved. Such an epoxy acrylic lens has advantages of high refractive index and high Abbe's number, excellent optical properties such as transparency, light weight, and heat resistance, and low cost of materials.

However, when manufacturing an epoxy acrylate type lens, the release property, thermal stability, and light resistance may be inferior for the unknown reason. In addition, reactive diluents are needed to control the viscosity and reaction rate. Such reactive diluents are conventionally styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrenedimer, benzyl methacrylate, chlorostyrene, bromostyrene, Toxy styrene, dibenzyl maleate, etc. are used individually or in mixture of 2 or more types. The choice of diluent affects the productivity and optical properties of the lens and also the production cost. For example, styrene, which is frequently contained at present and in a high content in the resin, causes a decrease in strength.

Meanwhile, various optical resins such as polyethylene glycol bisallylcarbonate, polymethyl methacrylate, diallyl phthalate, polystyrene, and polycarbonate are conventionally used as optical lenses in the medium refractive index range.

In European Patent 06905 A2, 5 to 40 parts by weight of acrylic acid and bisphenol A type epoxy resin reactant, 15 to 50 parts by weight of styrene, 5 to 40 parts by weight of acrylic acid and bis-tetra-bromo bisphenol A type epoxy resin reactant, There is provided an optical resin composition in which 5 to 20 parts by weight of divinylbenzene, diallyl diphenate, vinyltoluene, and chlorostyrene are mixed, but there is a problem of insufficient thermal stability.

Japanese Patent Laid-Open No. 53-7787 provides an optical lens in which 85% by weight of diallyl isophthalate and 15% by weight of diethylene glycol bisallylcarbonate are polymerized. In the case of this lens, the lens has been successfully thinned. There is still a problem of weak impact resistance.

In Japanese Patent Laid-Open No. 62-235901 and No. 64-45412 and Japanese Patent Hei 1-60494, a plastic lens made of a copolymer of modified diallyl phthalate and dibenzyl fumarate and made of diallyl phthalate and methyl acrylate To provide a plastic lens produced by the copolymer, these also have a problem of low impact resistance.

Republic of Korea Patent Publication 10-0431434 discloses a monomer composition for a medium refractive lens in the range of 1.53 ~ 1.55, consisting of diallyl ester oligomer, dialkyl maleate, diethylene glycol bisallylcarbonate and diallyl adipate. This has improved properties in light stability and impact resistance compared to the existing mid-refractive lens, but has a problem of low transparency and low heat resistance with Abbe's number.

In the case of epoxy acrylic lenses, optical properties such as transparency and Abbe's number are good, so if the quality can be improved in terms of release property, compressive strength, thermal stability, and light resistance, and the production cost can be lowered, the lens of other material in the refractive index of about 1.53 ~ 1.58 It can be competitive.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Japanese Laid-Open Patent Digestion 53-7787

(Patent Document 2) Japanese Patent Laid-Open No. 62-235901

(Patent Document 3) Japanese Patent Laid-Open No. 64-45412

(Patent Document 4) Japanese Patent Publication No. 1-60494

(Patent Document 5) European Patent 06905

(Patent Document 6) Republic of Korea Patent Publication 10-0431434

(Patent Document 7) Republic of Korea Patent Registration 10-0496911

(Patent Document 8) Republic of Korea Patent Registration 10-0498896

(Patent Document 9) Republic of Korea Patent Publication 10-2015-0071170

In the present invention, when the epoxy acrylate lens is manufactured, the problem of release, thermal stability and light resistance which are often unknown cause is found to be related to the acid number of the epoxy acrylate and solves this problem. It aims to do it.

Methyl methacrylate is conventionally used as a reactive diluent together with styrene, divinylbenzene, alphamethylstyrene, and alphamethylstyrene dimer, but when used in more than 20% by weight of resin, there are problems in physical properties in many aspects such as whitening and polymerization imbalance. It is only used in small quantities. However, when the methyl methacrylate is used in a large amount, the compressive strength is improved as compared with the case of using styrene, and thus the compressive strength can be improved without the addition of the production cost. In the present invention, while containing a large amount of methyl methacrylate in the lens resin composition of 20% by weight or more, the transparency, Abbe number, thermal stability, light resistance and release properties are all excellent, excellent in compressive strength and economical resin composition for epoxy acrylic mid-refraction optical lens It aims to provide.

In the present invention to achieve the above object,

50 to 70% by weight of bisphenol A epoxy acrylate represented by the following Chemical Formula 1 and having an acid value of 0.01 to 2.5,

With 21-45 weight% of methyl methacrylates,

It provides the resin composition for epoxy acryl-type medium refractive optical lenses of the solid-state refractive index 1.53-1.58 containing 1-17 weight% of reactive diluents.

[Formula 1]

Where n = 0-15.

The resin composition for the epoxy acrylic mid-refraction optical lens may further comprise an internal release agent in 0.001 to 10% by weight of the composition.

In addition, the resin composition for the epoxy acrylic medium refractive optical lens may further comprise a heat stabilizer in 0.01 to 5% by weight of the composition.

In the present invention,

50 to 70% by weight of bisphenol A epoxy acrylate represented by the following Chemical Formula 1 and having an acid value of 0.01 to 2.5,

With 21-45 weight% of methyl methacrylates,

An epoxy acrylic medium refractive optical lens having a solid-state refractive index of 1.53 to 1.58 obtained by polymerizing a resin composition for an optical lens containing 1 to 17 wt% of a reactive diluent in a mold is provided.

[Formula 1]

Where n = 0-15.

In the present invention,

Provided is a method of manufacturing an acrylic mesopore optical lens comprising the step of polymerizing the resin composition for epoxy acrylic mesopore optical lens into a mold.

In the present invention, by controlling the acid value of the bisphenol A diglycidyl ether and containing a large amount of MMA in the composition of more than 20% by weight in the medium refractive lens of the solid-state refractive index of 1.53 ~ 1.58 to significantly improve the compressive strength and release property, heat Stability, light resistance, transparency, and Abbe's number can also provide a resin composition for an epoxy acrylic medium refractive optical lens.

The resin composition for the epoxy acrylic medium refractive optical lens of the present invention,

Bisphenol A epoxy acrylate (BPDA) represented by the formula (1) below; Methylmethacrylate (MMA) and reactive diluents.

[Formula 1]

Where n = 0-15.

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

[Formula 2]

Where n = 0-15.

Scheme 1

Thus prepared bisphenol A epoxy acrylate has a difference in acid value depending on the manufacturing process. The present inventors have found that the problem of release property, thermal stability and light resistance deterioration, which is often unknown when manufacturing an epoxy acrylate lens, is related to the acid value of bisphenol A epoxy acrylate. In the present invention, the acid value of bisphenol A epoxy acrylate is preferably 0.01 to 2.5, more preferably 0.05 to 2.4. The acid value can be controlled by adjusting the equivalent of acrylic acid in the preparation of bisphenol A epoxyacrylate. As a result of confirming in the present invention, when the epoxy equivalent and the acrylic equivalent in the reaction of the epoxy compound (YD128) and acrylic acid in a ratio of 1: 0.9 ~ 1.0, the oligomer is generated or deteriorated into a polymer during some reactions, thereby causing a problem in reactivity. However, by controlling the epoxy equivalent and acrylic equivalent in a ratio of 1: 1.005 to 1.06, there is no such problem and a bisphenol A epoxy acrylate having an acid value of 0.01 to 2.5 can be obtained. Moreover, the optical lens manufactured using this bisphenol A epoxy acrylate was excellent in mold release property, thermal stability, light resistance, transparency, and color.

In the present invention, the acid value of bisphenol A epoxy acrylate is measured by the following method.

Acid number  Measure

Wash thoroughly and add 100 mL of a mixture of ethanol and toluene in a volume ratio of 1: 1 in a 200 mL beaker and dry. Three drops of phenolphthalein (prepared to 1% concentration in ethanol) were added to this solution, and two drops of 0.5 N KOH (aq.) Was added thereto. The solution turns pale pink and loses color when 3.0g of sample is added. The solution is completely dissolved by heating, cooled, and titrated with 0.5N KOH (aq.) Solution.

[Equation 1]

The bisphenol A epoxy acrylate (BPDA) is contained in the resin composition for epoxy acrylic mid-refraction optical lens of the present invention 50 to 70% by weight, preferably 55 to 65% by weight.

Methyl methacrylate (MMA) included 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, alphamethylstyrene, and alphamethylstyrene dimer. However, unlike styrene and divinylbenzene, MMA is not included in a large amount and is usually used in a small amount of 3% or less but less than 20%. This is because when MMA is contained in an optical lens resin of 20% by weight or more, there are problems in the physical properties of the lens in various aspects such as whitening and polymerization imbalance. However, in the present invention, while containing a large amount of MMA in the resin of 20% by weight or more, the acid value of the bisphenol A epoxy acrylate used together is limited to 0.01 to 2.5, while the content of bisphenol A epoxy acrylate in the resin 50 to 70 weight By setting it as%, both mold release property, thermal stability, and light resistance can be improved. In addition, by containing a large amount of MMA instead of styrene can also significantly increase the compressive strength without adding production costs. MMA in the resin composition of the present invention is preferably included in 21 to 45% by weight, more preferably may be included in 25 to 40% by weight.

The reactive diluent included in the resin composition of the present invention serves to appropriately control the viscosity and polymerization rate of the composition, and can be used as long as it is used as a reactive diluent in the resin for epoxy acrylic optical lens, and is not particularly limited. .

Preferably, the reactive diluent is styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzylmaleate, monobenzyl fumalate, di Benzyl maleate, dibenzyl fumarate, methyl benzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monopentyl maleate, dipentyl maleate, monopentyl fumal Compounds selected from the group consisting of latex, dipentylfumalate and diethylene glycol bisaryl carbonate may be used alone or in combination of two or more. More preferably, the reactive diluent is one or two or more compounds selected from the group consisting of styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer.

Since MMA, which is essentially included in the resin composition of the present invention, serves as a reactive diluent, it is preferable that other reactive diluents are contained in a small amount of 1 to 17 wt%. If the total content of reactive diluents including MMA and other reactive diluents exceeds 60% by weight, the viscosity of the composition may be too low to melt the tape adhesive, which may lead to tape bleaching and leakage during curing after injection. As a result, whitening and stria may occur in the lens.

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

The resin composition of the present invention may further include an internal mold release agent. By adding an internal mold release agent in a resin composition before mold polymerization, mold release property after superposition | polymerization can be improved significantly. The internal mold release agent may preferably be included in an amount of 0.001 to 10% by weight in the polymerizable composition.

As an internal mold release agent, a phosphate ester compound, a silicone type surfactant, a fluorine type surfactant, an alkyl quaternary ammonium salt, etc. can be used individually or in combination of 2 or more types, respectively.

Fluorine-based nonionic surfactants are compounds having a perfluoroalkyl group in the molecule, such as Eudin DS-401 ™ (Japan, Daishin Industrial Co., Ltd.), Unidin DS-403 ™ (Japan, Daikin Industrial Co., Ltd.), Eftop EF. 122A ™ (Japan, Shin-Avada Chemical Co., Ltd.), Effope EF 126 ™ (Japan, Shin-Avada Chemical Co., Ltd.), and Eftop EF 301 ™ (Japan, Shin-Avada Chemical Co., Ltd.).

Silicone-based nonionic surfactants are compounds having a dimethylpolysiloxane group in a molecule, such as Q2-120A ™ of Dow, USA.

Alkyl quaternary ammonium salts are commonly known as cationic surfactants, and include halogen salts, phosphates, sulfates, and the like. Among these chloride salts, trimethylcetyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethylethylcetyl ammonium chloride, tri Ethyldecylammonium chloride, trioctylmethyl ammonium chloride, decylammonium chloride, and the like.

 Preferably, a phosphate ester compound can be used as an internal mold release agent. The phosphate ester compound is a compound having a phosphate ester group, and is, for example, isopropyl acid phosphate, diisopropyl acid phosphate, butylic acid phosphate, dibutyl phosphate, octylic acid phosphate, dioctyl acid phosphate, isodecyl acid phosphate or diisode. Carboxylic acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, and mixtures of two or more thereof. As the phosphate ester compound, preferably, polyoxyethylene nonylphenol ether phosphate (5% by weight of 5 mole of ethylene oxide added, 80% by weight of 4 mole added, 10% by weight of 3 mole added, 1 mole added) 5% by weight), polyoxyethylenenonylphenyl 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 5% by weight of oxide added up to 6 mol), polyoxyethylenenonylphenol ether phosphate (3% by weight of 11 moles of ethylene oxide added, 80% by weight of 10 moles added, 5% by weight of 9 moles added, 7 mole added 6% by weight, 6 mole added 6% by weight), polyoxyethylene nonylphenol ether phosphate (13 mole added by ethylene oxide 3% by weight, 12 mole added by 80% by weight, 11 mole added 8% by weight, 9% by weight added 3% by weight, 4% by weight added 6% by weight), poly Cyethylene nonylphenol ether phosphate (3% by weight of 17 mole of ethylene oxide added, 79% by weight of 16 mole added, 10% by weight 15 mole added, 4% by weight 14 mole added, 13 moles added 4 wt%), polyoxyethylenenonylphenol ether phosphate (21 wt% added ethylene oxide 5 wt%, 20 mol added 78 wt%, 19 mol added 7 wt%, 18 mol added 6 Weight%, 17 mole added 4% by weight), dioctyl acid phosphate and Zelec UN ™ can be used one or two or more compounds selected from the group consisting of.

The resin composition of the present invention may further include a heat stabilizer. Heat stabilizer, Preferably it may be included in 0.01 to 5.00% by weight in the resin composition of the present invention. When the thermal stabilizer is used at less than 0.01% by weight, the thermal stability effect is weak. When the thermal stabilizer is used at more than 5.00%, the polymerization failure rate during curing may be high and the thermal stability of the cured product may be lowered.

Examples of the thermal stabilizer include 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 the compounds can be used.

Preferably, triphenyl phosphite, diphenyldecyl phosphite, phenyldidecyl phosphite, diphenyldodecyl phosphite, diphenylisodecyl phosphate, trinolylphenyl phosphite, diphenylisooctyl phosphite, tri One or two or more compounds selected from butyl phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite) and tris (monophenyl) phosphite can be used. Especially preferably diphenylisodecyl phosphate can be used.

In addition, one or two selected from compounds such as lead-based 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 The above can also be used.

In addition, organotin-based dibutyltin diaurate, dibutyltin maleate, dibutyltin bis (isooctyl maleate), dioctyl maleate, dibutyltin bis (monomethyl maleate), dibutyltin bis (la Uryl mercaptide), dibutyl bis (isooxyl mercaptoacetate), monobutyl tin tris (isooctyl mercapto acetate), dimethyl tin bis (isooctyl mercapto acetate), tris (isooctyl mercapto acetate), fertility Tiltin bis (isooctyl mercaptoacetate), dibutyl tin bis (2-mercapto ethyl laurate), monobutyl tin tris (2- mercapto ethyl laurate), dimethyl tin bis (2- mercapto ethylate) And 1 type, or 2 or more types selected from compounds, such as a monomethyltin tris (2-mercapto ethyl laurate), can also be used.

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, the thermal stability of the optical lens can be greatly improved without deteriorating not only the initial color of the molded lens but also optical properties such as transparency, impact strength, heat resistance and polymerization yield.

The resin composition of the present invention may further include ultraviolet absorbers, organic dyes, inorganic pigments, anti-colorants, antioxidants, light stabilizers, catalysts, and the like, in addition to conventional techniques in the field of plastic optical lenses.

The epoxy acrylic mid-refraction optical lens according to the present invention can be produced by putting the resin composition of the present invention into a mold and polymerizing the same. According to a preferred embodiment, after injecting the resin composition into the mold, the mold is placed in a forced circulation oven and gradually heat-cured from 30 ℃ to 120 ℃, and then cooled to 70 ± 10 ℃ to remove the mold to obtain a lens. In this case, all the raw materials are preferably high purity compounds with a purity of 70 to 99.99%. Preferably, the purity of all raw materials is checked to purify low purity compounds and use high purity compounds without purification.

The acryl-based medium refractive optical lens obtained by the above manufacturing method may be used in various fields as a medium refractive lens having a solid-state refractive index of 1.53-1.58, replacing the existing medium refractive lens. Specifically, it can be used as a plastic glasses lens, a 3D polarizing lens equipped with a polarizing film on the spectacle lens, a camera lens, etc. In addition to a variety of optical, such as recording media substrates, color filters and ultraviolet absorption filters used in prisms, optical fibers, optical disks, etc. Can be used in the product.

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.

Acid number  Measure

100 mL of a mixture of ethanol and toluene in a volume ratio of 1: 1 was added to the 200 mL beaker, which was washed cleanly, and stirred. Three drops of phenolphthalein (prepared to 1% concentration in ethanol) were added to this solution, and two drops of 0.5 N KOH (aq.) Was added thereto. The solution turns pale pink and loses color when 3.0g of sample is added. The solution was heated to complete dissolution and cooling, then titrated with 0.5N KOH (aq.) Solution. The acid value was determined according to Equation 1 below.

[Equation 1]

Epoxy Acrylate  compound( BPDA ) Synthesis

Synthesis Example  One

Kukdo Chemical BPDE equivalent to 187 To (561g) was added acrylic acid (436g, 6.06 mol.), Dibenzylmethylamine (5g) and 2,6-di-t-butyl-4-methylphenol (4g) and reacted from 60 ° C to 105 ° C. Slowly raise the temperature to react for 20 hours to acrylate the compound of Chemical Formula 1 ( BPDA 1 ) was obtained. The acid value was 0.11.

Scheme 1

Synthesis Example  2

Kukdo Chemical BPDE equivalent to 187 To (561g) compound was added the same as in Synthesis Example 1 except adding acrylic acid (440g, 6.10 mol.), Dibenzylmethylamine (5g) and 2,6-di-t-butyl-4-methylphenol (4g) Reacted by the method to acrylate the compound ( BPDA 2 ) was obtained. The acid value was 0.63.

Synthesis Example  3

Kukdo Chemical BPDE equivalent to 187 To (561g) compound was added the same as in Synthesis Example 1 except adding acrylic acid (445 g, 6.17 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g). Reacted by the method to acrylate the compound ( BPDA 3 ) was obtained. The acid value was 1.32.

Synthesis Example  4

Kukdo Chemical BPDE equivalent to 187 To the compound of (561 g) was the same as in Synthesis Example 1 except adding acrylic acid (451 g, 6.25 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g). Reacted by the method to acrylate the compound ( BPDA 4 ) was obtained. The acid value was 2.16.

Synthesis Example  5

Kukdo Chemical BPDE equivalent to 187 To (561g) compound was added the same as in Synthesis Example 1 except adding acrylic acid (455g, 6.31 mol.), Dibenzylmethylamine (5g) and 2,6-di-t-butyl-4-methylphenol (4g) Reacted by the method to acrylate the compound ( BPDA 5 ) was obtained. The acid value was 2.38.

Comparative Synthesis Example  One

Kukdo Chemical BPDE equivalent to 187 To (561g) compound was added the same as in Synthesis Example 1 except adding acrylic acid (459 g, 6.36 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g). Reacted by the method to acrylate the compound ( BPDA 6 ) was obtained. The acid value was 2.63.

Comparative Synthesis Example  2

Kukdo Chemical BPDE equivalent to 187 (561 g) to the compound of the same as Synthesis Example 1 except adding acrylic acid (465 g, 6.45 mol.), Dibenzylmethylamine (5 g) and 2,6-di-t-butyl-4-methylphenol (4 g) Reacted by the method to acrylate the compound ( BPDA 2 ) was obtained. The mountain was 2.95.

Example  One

To 60 g of epoxy acrylate compound ( BPDA 1 ), 0.5 g of alpha methyl styrene dimer as a polymerization regulator was added, 5 g of styrene and 35 g of methyl methacrylate as a reaction diluent were added, 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 as a catalyst, and 4-PENPP 0.05g and 8-PENPP 0.2g as an internal release agent was added and mixed for the optical lens After the resin composition was prepared, an optical lens was manufactured by the following method, and the physical properties of the optical lens were measured.

(1) After stirring the resin composition for optical lenses prepared as 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

Physical properties of the optical lens manufactured in Example was measured by the following experimental method, and the results are shown in Table 1 .

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.

3) Release property: "◎", "○", "Δ" and "×" depending on the breakage of the lens or mold when the optical acrylic and the mold is heat-set during optical lens manufacture and demolding at 70 ° C. Marked as. "◎" means that the lens or mold is not broken at all or one is broken during the separation of 100 optical lenses and the mold, and "○" means 2 to 3 lenses or molds are separated during the separation of 100 optical lenses and the mold. If broken, "Δ" means 4 to 5 lenses or molds are broken during the separation of 100 optical lenses and molds, and "x" means 6 lenses or molds during separation of 100 optical lenses and molds. It was shown as a case where the abnormality was broken.

4) Compressive strength: The spectacle lens has a diameter of 75mm, a center thickness of 1.2mm, and a degree of 8.00 degrees. The LR5K-Plus universal material tester of LLOYD Instruments can break the spectacle lens according to the method of ISO 14889 and JIS T57331. Until measured and expressed as N (Newton).

5) Thermal stability: The cured optical lens was kept at 100 ° C for 10 hours, and when the APHA value changed to less than 1 in the measurement of color change, "◎" was displayed. When the APHA value changed to 1 ~ 2, "○" ", And when the APHA value is changed by 3 or more," x ".

6) Transparency: 100 eyes are visually observed under the Mercury Arc Lamp (USHIO USH-10D). If the haze of the optical lens is found to be less than one, mark "◎". If two are found, It marked with "(circle)" and if it is three or more, it marked with "x".

7) Light resistance: Q-Lab. QUV / SE model Accelerated Weathering Tester was used. QUV test was conducted with 48 mm thick flat lens under UVA-340 (340nm), light 0.76W / m2, 4 hours Black Panel Temperature (60 ℃), 4 hours condensation (50 ℃). After that, in the measurement of color change, if the APHA value is changed to less than 0 ~ 2, "◎" is displayed. If the APHA value is changed to 2 ~ 4, "○" is displayed. Marked as.

Example  2 ~ 5

In the same manner as in Example 1 , an optical lens was manufactured according to the composition shown in Table 1 , the physical properties thereof were measured, and the results are shown in Table 1 .

Comparative example  One

To 60 g of the epoxy acrylate compound ( BPDA 6 ), 0.5 g of alpha methyl styrene dimer as a polymerization regulator was added, 5 g of styrene and 35 g of methyl methacrylate as a reaction diluent were added, 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 as a catalyst, and 4-PENPP 0.05g and 8-PENPP 0.2g as an internal release agent was added and mixed for the optical lens After the resin composition was prepared, an optical lens was manufactured in the same manner as in Example 1 . The physical properties were measured and the results are shown in Table 1 .

Comparative example  2 ~ 3

An optical lens was manufactured according to the composition of Table 1 in the same manner as in Comparative Example 1 , the physical properties thereof were measured, and the results are shown in Table 1 .

TABLE 1

[Abbreviation]

MMA : Methyl methacrylate

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 mol of ethylene oxide added, ethylene oxide 1 mole added 5% by weight)

8- PENPP : polyoxyethylene nonylphenyl phosphate (5% by weight of 9 mol of ethylene oxide added, 80% by weight of 8 mol of ethylene oxide added, 10% by weight of 7 mol of ethylene oxide added, ethylene oxide 5% by weight of 6 mol or less)

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

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

According to the present invention, by adjusting the acid value of the epoxy acrylate, while maintaining a good amount of transparency and Abbe number while containing a large amount of MMA in the composition, an epoxy acrylic medium refractive optical lens having excellent release properties, thermal stability, light resistance and high compressive strength It can be manufactured at low production cost. The optical lens according to the present invention can be widely used in the related art by replacing the existing medium refractive lens. In particular, it can be used in the field of plastic glasses, 3D polarizing lens with polarizing film on the spectacle lens, camera lens, and various optical products such as recording media substrates, coloring filters and ultraviolet absorbing filters used for prism, optical fiber, optical disk, etc. It can be used to.

Claims (12)

1. 50 to 70% by weight of bisphenol A epoxy acrylate represented by the following Chemical Formula 1 and having an acid value of 0.01 to 2.5,

   With 21-45 weight% of methyl methacrylates,

   The resin composition for epoxy acryl-type medium refractive optical lenses of the solid-state refractive index 1.53-1.58 containing 1-17 weight% of reactive diluents.

   [Formula 1]

   

   Where n = 0-15.
2. The method of claim 1,

   The reactive diluents include styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxy styrene, monobenzyl maleate, monobenzyl fumalate, dibenzyl maleate, Dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monopentyl maleate, dipentyl maleate, monopentyl fumarate, dipentyl Resin composition, characterized in that one or two or more compounds selected from the group consisting of fumarate and diethylene glycol bisaryl carbonate.
3. The method of claim 1,

   The reactive diluent is a resin composition, characterized in that one or two or more compounds selected from the group consisting of styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer.
4. The method of claim 1,

   The resin composition further comprises an internal mold release agent at 0.001 to 10% by weight of the composition.
5. The method according to any one of claims 1 to 4,

   The resin composition further comprises a heat stabilizer at 0.01 to 5% by weight of the composition.
6. The method of claim 5,

   The thermal stabilizer is triphenyl phosphite, diphenyldecyl phosphite, phenyldidecyl phosphite, diphenyldodecyl phosphite, diphenylisodecyl phosphate, trinorylphenyl phosphite, diphenylisooctyl phosphite, tributyl phosphate Resin composition characterized in that one or two or more compounds selected from the group consisting of phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite), tris (monophenyl) phosphite .
7. 50 to 70% by weight of bisphenol A epoxy acrylate represented by the following Chemical Formula 1 and having an acid value of 0.01 to 2.5,

   With 21-45 weight% of methyl methacrylates,

   Epoxy acryl-type medium refractive optical lens of the solid-state refractive index 1.53-1.58 obtained by superposing | polymerizing in resin mold the resin composition for optical lenses containing 1 to 17 weight% of a reactive diluent.

   [Formula 1]

   

   Where n = 0-15.
8. The method of claim 7, wherein

   The reactive diluent is an epoxy acrylic medium refractive optical lens, characterized in that one or two or more compounds selected from the group consisting of styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer.
9. The method according to claim 7 or 8,

   Epoxy acryl-based medium refractive optical lens further comprises a heat stabilizer in 0.01 to 5% by weight in the resin composition.
10. 10. The method of claim 9, wherein the heat stabilizer is triphenyl phosphite, diphenyldecyl phosphite, phenyldidecyl phosphite, diphenyldodecyl phosphite, diphenylisodecyl phosphate, trinolylphenyl phosphite, diphenylisooctyl One or two or more compounds selected from the group consisting of phosphite, tributyl phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite), tris (monophenyl) phosphite Epoxy acryl-based medium refractive optical lens, characterized in that.
11. The method of claim 9,

    Epoxy acryl-based medium refractive optical lens further comprises an internal release agent in 0.001 to 10% by weight in the resin composition.
12. The method of manufacturing an acrylic mid-refractive optical lens comprising the step of polymerizing the resin composition of claim 1 in a mold.