KR20200109779A - Composition for improving thermal stability and releasability of optical lenses and composition for Epoxy Acryl Based Optical Lens comprising same - Google Patents

Abstract

The present invention relates to a composition for improving the heat stability and releasability of an optical lens, and a composition for an epoxy acryl-based optical lens including the same. The composition for improving the heat stability and releasability of an optical lens includes: at least one heat stabilizer selected from metal fatty acid salt-, phosphorus- and organotin-based heat stabilizers; at least one internal releasing agent selected from phosphate compounds, fluorinated surfactants and alkyl quaternary ammonium salts; 2,2′-methylene bis(6-tert-butyl-4-methylphenol); and 2-tert-butyl-4,6-dimethylphenol. The composition for improving the heat stability and releasability of an optical lens according to the present invention can significantly improve the heat stability and releasability of a lens, and thus can be used widely for manufacturing optical lenses, and particularly, for manufacturing epoxy acryl-based optical lenses.

Description

Composition for improving thermal stability and releasability of optical lenses and composition for Epoxy Acryl Based Optical Lens comprising same}

The present invention relates to a composition for improving thermal stability and releasability of an optical lens, and a composition for an epoxy acrylic optical lens comprising the same.

Plastic optical lenses were introduced as an alternative to complement the high specific gravity and low impact resistance, which are the problems of glass lenses. Representative examples thereof include polyethyl glycol bisallyl carbonate, polymethyl methacrylate, polyethyl glycol bisallyl carbonate and diallyl phthalate. However, optical lenses made of these polymers are excellent in physical properties such as moldability, dyeing property, adhesion to hard coat film, and impact resistance, but there is a problem that the lens is thickened because the refractive index is low about 1.50 (nD) and 1.55 (nD). . Accordingly, various attempts have been made to develop optical materials having a high refractive index to reduce the thickness of the lens.

In Korean Patent Publications 10-1990-0007871, 10-1992-001650, 10-1992-0001245, 10-1996-0013389, 10-1992-0006006, and Patent Publication 10-0136698, a polyisocyanate compound and a polythiol compound are heated. By curing, a thiourethane-based optical lens is obtained. Thiourethane-based optical lenses have the advantage of excellent optical properties such as dyeing property, impact resistance, Abbe number and transparency. On the other hand, there is a problem in that the manufacturing process of the lens is difficult because the material is expensive and requires blocking of moisture.

Korean Patent Registration No. 10-0498896 discloses an epoxy acrylic resin composition for an optical lens having excellent optical properties and low material cost. Epoxy acrylic lenses have a lower refractive index than thiourethane-based optical lenses, but have very good transparency and can produce lenses without separate moisture management in the air even in hot and humid areas, and the center of the lens due to moisture in the air when storing the lens. It has the advantage of no deformation. However, the stability against moisture is excellent, but there is a problem in that the color changes at high temperature, so improvement in thermal stability is required. In addition, since epoxy acrylic lenses have poor releasability, it is more difficult to separate the lens from the mold than other resins such as thiourethane during manufacture, and defects occur.

Korean Patent Publication 10-1990-0007871 Korean Patent Publication 10-1992-001650 Korean Patent Publication 10-1992-0001245 Korean Patent Publication 10-1996-0013389 Korean Patent Publication 10-1992-0006006 Republic of Korea Patent Registration 10-0136698 Korean Patent Registration 10-0498896

An object of the present invention is to provide a composition capable of simultaneously improving thermal stability and releasability of an optical lens.

In addition, it is an object of the invention to provide a composition for an epoxy acrylic optical lens having good thermal stability and releasability, including the composition.

In the present invention to achieve the above object,

At least one thermal stabilizer selected from metal fatty acid salts, phosphorus, and organotin;

At least one type of internal releasing agent selected from a phosphate ester compound, a fluorine-based surfactant, and an alkyl quaternary ammonium salt;

2,2'-methylenebis(6-tert-butyl-4-methylphenol); And

It provides a composition for improving thermal stability and releasability of an optical lens containing 2-tert-butyl-4,6-dimethylphenol.

Also, in the present invention.

Bisphenol A epoxy acrylate;

Reactive diluents;

At least one thermal stabilizer selected from metal fatty acid salts, phosphorus, and organotin;

At least one type of internal releasing agent selected from a phosphate ester compound, a fluorine-based surfactant, and an alkyl quaternary ammonium salt;

2,2'-methylenebis(6-tert-butyl-4-methylphenol); And

It provides a composition for an epoxy acrylic optical lens containing 2-tert-butyl-4,6-dimethylphenol.

Also, in the present invention.

There is provided a method of manufacturing an acrylic medium refractive optical lens comprising the step of polymerizing the epoxy acrylic optical lens composition into a mold.

The composition of the present invention for improving the thermal stability and releasability of an optical lens can greatly improve the thermal stability and releasability of the lens when only an existing thermal stabilizer and a release agent are used. The composition for an optical lens of the present invention including the same has good thermal stability, so that a lens without color change at high temperature can be obtained, and because of its good releasability and low defect rate during demolding after polymerization, production efficiency and production yield can be improved, You can get a transparent quality lens.

The composition of the present invention for improving thermal stability and releasability of an optical lens,

At least one thermal stabilizer selected from metal fatty acid salts, phosphorus, and organotin; At least one type of internal releasing agent selected from a phosphate ester compound, a fluorine-based surfactant, and an alkyl quaternary ammonium salt; 2,2'-methylenebis(6-tert-butyl-4-methylphenol); And 2-tert-butyl-4,6-dimethylphenol.

The heat stabilizer in the composition is at least one selected from metal fatty acid salt, phosphorus, and organotin.

As the metal fatty acid salt system, for example, calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate, zinc octoate, and the like can be used. .

As a phosphorus system, for example, triphenyl phosphite, diphenyldecyl phosphite, phenyl didecyl phosphite, diphenyl dodecyl phosphite, diphenyl isodecyl phosphite, trinorylphenyl phosphite, diphenyl isoctyl phosphite Pite, tributyl phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite), tris (monophenyl) phosphite, tris (nonylphenyl) phosphite, and the like can be used.

As an organotin type, for example, dibutyltin diaurate, dibutyltin maleate, dibutyltin bis (isooctyl maleate), dioctyl maleate, dibutyltin bis (monomethyl maleate), dibutyl Tin bis (lauryl mercaptide), dibutyl bis (isooxyl mercaptoacetate), monobutyl tin tris (isooctyl mercaptoacetate), dimethyl tin bis (isooctyl mercapto acetate), tris (isooctyl mercapto) Acetate), fertyl tin bis (isooctyl mercaptoacetate), dibutyl tin bis (2-mercaptoethyloleate), monobutyl tin tris (2-mercaptoethyrorate), dimethyl tin bis (2-mer Captoethyloate), monomethyltin tris (2-mercaptoethylorate), and the like can be used.

As the heat stabilizer, preferably, a phosphorus-based heat stabilizer may be used, and particularly preferably, at least one of diphenylisodecylphosphite, diphenyldecylphosphite, and tris(nonylphenyl)phosphite may be used. By using a phosphorus-based thermal stabilizer, the thermal stability of the optical lens can be greatly improved without deteriorating optical properties such as initial color, transparency, impact strength, heat resistance, and polymerization yield of the molded lens.

The thermal stabilizer may preferably be included in an amount of 0.01 to 5.00% by weight in the composition for an optical lens. When the thermal stabilizer is used in an amount of less than 0.01% by weight, the thermal stability effect is weak, and when it is used in an amount exceeding 5.00% by weight, the polymerization defect rate is high during curing and the thermal stability of the cured product may be lowered.

In the composition, the internal release agent is at least one selected from a phosphate ester compound, a fluorine-based surfactant, and an alkyl quaternary ammonium salt.

As the fluorine-based nonionic surfactant, a compound having a perfluoroalkyl group in the molecule may be used. For example, Unidyne DS-401™ (Japan, Daigin Industrial Co., Ltd.), UNIDAIN DS-403™ (Japan, Daigin Industrial Co., Ltd.) Kein Industries Co., Ltd.), Ftop EF 122A™ (Japan, Shin-Aki Tagase Co., Ltd.), Ftop EF 126™ (Japan, Shin-Aki Tagase Co., Ltd.), Ftop EF 301™ (Japan, Shin-Aki Tagase Co., Ltd.) ), etc.

The alkyl quaternary ammonium salt is generally known as a cationic surfactant, and includes halogen salts, phosphates, sulfates, and the like. Preferably, among these, trimethylcetyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethylethylcetyl ammonium chloride, triethyldecylammonium chloride, trioctylmethyl ammonium chloride, diethylcyclohexide, decylammonium chloride, etc. can be used. have.

Preferably, a phosphoric acid ester compound may be used as the internal mold release agent. The phosphate ester compound is a compound having a phosphate ester group, and is preferably represented by Formula 1 below.

[Formula 1]

In the equation,

R ₁ and R ₂ are either an alkyl group, an alkylphenyl, or a phenylalkyl group, and R ₁ and R ₂ are independently the same or different from each other.

X ₁ and X ₂ are alkyl groups, and X ₁ and X ₂ are independently the same or different from each other.

m and n are 0-40, y and z are 0-2, and y+z is 2.

The phosphoric acid ester compound is more preferably,

(Mono, di)methyl phosphoric acid; (Mono, di) ethyl phosphoric acid; (Mono, di) (n-propyl) phosphoric acid; (Mono, di) isopropyl phosphoric acid; (Mono, di) (n-butyl) phosphoric acid; (Mono, di) (n-pentyl) phosphoric acid; (Mono, di) (n-hexyl) phosphoric acid; (Mono, di) (n-heptyl) phosphoric acid; (Mono, di)(n-octyl)phosphoric acid; (Mono, di) (2-ethylhexyl) phosphoric acid; (Mono, di)(n-nonyl)phosphoric acid; (Mono, di) (n-decyl) phosphoric acid; (Mono, di) (isodecyl) phosphoric acid; (Mono, di) (n-undecyl) phosphoric acid; (Mono, di) (n-dodecyl) phosphoric acid; (Mono, di) (tridecyl) phosphoric acid; (Mono, di) (n-tetradecyl) phosphoric acid; (Mono, di) (n-pentadecyl) phosphoric acid; (Mono, di) (n-hexadecyl) phosphoric acid; (Mono, di) (n-octadecyl) phosphoric acid; (Mono, di)(o-methyldecyl)phosphoric acid; (Mono, di) (p-methylphenyl) phosphoric acid; (Mono, di) (p-ethylphenyl) phosphoric acid; (Mono, di) (p-propylphenyl) phosphoric acid; (Mono, di) (p-butylphenyl) phosphoric acid; (Mono, di) (p-nonylphenyl) phosphoric acid; (Mono, di) (p-methylmethyl) phosphoric acid; (Mono, di) (2-phenylethyl) phosphoric acid; (Mono, di) (4-phenylbutyl) phosphoric acid; (Mono, di) (3-oxabutyl) phosphoric acid; (Mono, di) (3-oxapentyl) phosphoric acid; (Mono, di) (3-oxahexyl) phosphoric acid; (Mono, di)(3-oxaheptyl)phosphoric acid; (Mono, di) (3-oxacylsyl) phosphoric acid; (Mono, di)(3-oxanonyl)phosphoric acid; (Mono, di) (3-oxaundecyl) phosphoric acid; (Mono, di) (3-oxatridecyl) phosphoric acid; (Mono, di)(3-oxapentadecyl)phosphoric acid; (Mono, di)(3-oxaheptadecyl)phosphoric acid; (Mono, di)(3-oxanoadecyl)phosphoric acid; (Mono, di) (3-oxahenosyl) phosphoric acid; (Mono, di)(1-methyl-3-oxabutyl)phosphoric acid; (Mono, di)(1-methyl-3-oxapentyl)phosphoric acid; (Mono, di)(1-methyl-3-oxaheptyl)phosphoric acid; (Mono, di)(1,2-dimethyl-3-oxaheptyl)phosphoric acid; (Mono, di)(1-methyl-3-oxatridecyl)phosphoric acid; (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, di)(3, 6-dioxaheptyl)phosphoric acid; (mono, di)(3,6-dioxaoctyl)phosphoric acid; (mono, di)(3,6-dioxadecyl)phosphoric acid; (mono, di)(3,6- Dioxatetradecyl)phosphoric acid; (mono, di)(3,6-dioxahexadecyl)phosphoric acid; (mono, di)(3,6-dioxaoctadecyl)phosphoric acid; (3,6-dioxycosyl) Phosphoric acid; (3,6-dioxadocosyl)phosphoric acid; (mono, di)(3,6-dioxatetracosyl)phosphoric acid; (mono, di)(1,4-dimethyl-3,6-dioxadecyl ) Phosphoric acid; (mono, di) (3,6,9-trioxadecyl) phosphoric acid; (mono, di) (3,6,9-trioxaundecyl) phosphoric acid; (mono, di) (3,6, 9-trioxatridecyl)phosphoric acid; (mono, di)(3,6,9-trioxaheptadecyl)phosphoric acid; (mono, di)(3,6,9-trioxahenicosyl)phosphoric acid; (mono, Di)(3,6,9-trioxaheptacosyl)phosphoric acid; (mono, di)(1,4,7-trimethyl-3,6,9-trioxatridecyl)phosphoric acid; (mono, di)( 3,6,9,12-tetraoxaheptyldecyl)phosphoric acid; (mono, di)(3,6,9,12-tetraoxaoctyldecyl)phosphoric acid; (mono, di)(3,6,9, 12-tetraoxycosyl)phosphoric acid; (mono, di)(3,6,9,12-tetraoxadocosyl)phosphoric acid; (mono, di)(3,6,9,12-tetraoxatetracosyl)phosphoric acid ; (Mono, di)(1,4,7,10-tetramethyl-3,6,9,12-tetraoxahexadecyl)phosphoric acid; triisopropyl acid phosphate; tributyl acid phosphate; trioctylic acid phosphate; trioctylic acid phosphate; Isodecylic acid phosphate; tridecanoic acid phosphate; bis(tridecanoic acid) phosphate; trimethyl acid phosphate; triethyl acid phosphate; tripropyl acid ester; benzylic acid phosphate; dibenzyl acid phosphate; tribenzyl acid phosphate; polyoxyethylene nonyl Phenol ether phosphate; tripolyoxyethylene nonyl phenol ether phosphate; bis(tridecanoic acid) phosphate; ethylene glycol monoethyl phosphate; diethylene glycol monoethyl phosphate; triethylene glycol mono ethyl phosphate; diethylene glycol monobutyl diphosphate; diethylene glycol monobutyl diphosphate; Ethylene Glycol monobutyl phosphate; Isopropylene glycol monoethyl phosphate; Diisopropylene glycol monoethyl phosphate; And triisopropylene glycol monoethyl phosphate; It is one type selected from the group consisting of polyoxyethylene nonylphenol ether phosphate, or a mixture of two or more thereof.

As the phosphate ester compound, particularly preferably, polyoxyethylene nonylphenol ether phosphate represented by the following formula (2) may be used, wherein the polyoxyethylene nonylphenol ether phosphate is not a single compound, but a compound in which an ethylene oxide group is added in various moles. Military.

[Formula 2]

(In the above formula, m is 1 to 10)

For example, polyoxyethylene nonylphenol ether phosphate (5 wt% of ethylene oxide added by 5 mol, 80 wt% of added 4 mol, 10 wt% of 3 mol added, 5 wt% of 1 mol added) ), polyoxyethylene nonylphenyl phosphate (5 wt% of ethylene oxide added by 9 mol, 80 wt% of ethylene oxide added by 8 mol, 10 wt% of ethylene oxide added by 7 mol, and 6 mol of ethylene oxide) 5% by weight of those added below), polyoxyethylene nonylphenol ether phosphate (3% by weight of those with 11 moles of ethylene oxide, 80% by weight of those with 10 moles, 5% by weight of 9 moles) 6% by weight, 6% by weight of added 6 mol), polyoxyethylene nonylphenol ether phosphate (3% by weight of 13 mol of ethylene oxide added, 80% by weight of 12 mol added, 8% by 11 mol added) %, 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 wt%, 15 mol added 10 wt%, 14 mol added 4 wt%, 13 mol added 4 wt%), polyoxyethylene nonylphenol ether phosphate (21 mol ethylene oxide added 5 wt%, 20 mol Group consisting of added 78% by weight, 19 mol added 7% by weight, 18 mol added 6 wt%, 17 mol added 4 wt%), dioctylic acid phosphate, and Zelec UN™ It is 1 type or 2 or more types of compounds selected from

The internal release agent may preferably be included in 0.001 to 10% by weight in the composition.

2,2'-methylenebis(6-tert-butyl-4-methylphenol) and 2-tert-butyl-4,6-dimethylphenol are preferably contained in the present composition at the same time from the viewpoint of improving heat stability and releasability. When only 2,2'-methylenebis (6-tert-butyl-4-methylphenol) is included, the thermal stability is poor and the releasability is lower than the case of including both. When only 2-tert-butyl-4,6-dimethylphenol is included, the releasability is inferior, and the thermal stability is also lower than when both are included.

In the present composition, the 2,2'-methylenebis(6-tert-butyl-4-methylphenol) and 2-tert-butyl-4,6-dimethylphenol are preferably contained in an amount of 0.0005 to 3% by weight, respectively. The total amount of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) and 2-tert-butyl-4,6-dimethylphenol is preferably contained in 0.001 to 5% by weight in the composition. And, particularly preferably, it may be included in 0.01 to 0.5% by weight. By including a small amount of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) and 2-tert-butyl-4,6-dimethylphenol in the composition, it is possible to release the product after polymerization and curing in the mold with thermal stability. Releasability can be greatly improved.

In addition, in the present invention,

Bisphenol A epoxy acrylate; Reactive diluents; At least one thermal stabilizer selected from metal fatty acid salts, phosphorus, and organotin; At least one type of internal releasing agent selected from a phosphate ester compound, a fluorine-based surfactant, and an alkyl quaternary ammonium salt; 2,2'-methylenebis(6-tert-butyl-4-methylphenol); And it discloses a composition for an epoxy acrylic optical lens containing 2-tert-butyl-4,6-dimethylphenol.

The bisphenol A epoxy acrylate preferably includes bisphenol A epoxy acrylate (BPDA) represented by Formula 3 below. The bisphenol A epoxy acrylate compound of Formula 3 has advantages such as high refractive index, excellent optical properties, and no deformation during storage, and is therefore used in the manufacture of high refractive lenses in the range of 1.53 to 1.63.

[Formula 3]

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

The reactive diluent plays a role of appropriately controlling the viscosity and polymerization rate of the composition, and any one used as a reactive diluent in an epoxy acrylic optical lens resin may be used, and is not particularly limited.

Preferably, the reactive diluent is styrene, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer, methyl methacrylate, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzyl maleate, mono Benzyl fumalate, dibenzyl maleate, dibenzyl fumalate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumalate, monobutyl maleate, monopentyl maleate, dipentyl male A compound selected from the group consisting of rate, monopentyl fumalate, dipentyl fumalate 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, and alphamethylstyrene dimer.

Description of the remaining components constituting the composition for the epoxy acrylic optical lens is the same as above.

The composition for an epoxy acrylic optical lens may further include other acrylate monomer components in addition to the bisphenol A epoxy acrylate compound. As other acrylate monomer components, preferably, methanediol diacrylate, methanediol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3 -Propanediol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-butyl-2-ethyl -1,3-propanediol diacrylate Rate, 2-butyl-2-ethyl-1,3-propanediol dimethacrylate, trimethylolpropane diacrylate or trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacryl Rate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentatriolerythritol hexamethacrylate, dipentatriolerythritol pentamethacrylate, pentaerythritol tetraacrylate, polyalkylene glycol Diacrylate, polyalkylene glycol dimethacrylate, polyethylene 400 diacrylate, polyethylene 400 dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylol Propane trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate , Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, 1,4- Butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6- Hexanediol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,7-heptanediol diacrylate, 1,7- Heptanediol dimethac Relate, 1,8-octanediol diacrylate and/or 1,8-octanediol dimethacrylate, 1,9-nonandiol diacrylate, 1,9-nonandiol dimethacrylate, 2-methyl -1,8-octanediol diacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, 1,11 -Undecanediol diacrylate, 1,11-undecandiol dimethacrylate, 1,12-dodecanediol diacrylate and 1,12-dodecanediol dimethacrylate, etc., either alone or in two Can be used together with the above.

The composition for an epoxy-acrylic optical lens of the present invention, in addition to a UV absorber, an organic dye, an inorganic pigment, an anti-coloring agent, an antioxidant, a light stabilizer, a catalyst, etc., in accordance with a conventional technique in the field of plastic optical lenses Can include.

The composition for an epoxy acrylic optical lens of the present invention has a liquid viscosity of 30-1,000 cps at 25° C. suitable for template polymerization, a liquid refractive index (nD, 20° C.) of the resin composition is 1.50-1.58, and a solid refractive index (nE, 20° C.) ) Is 1.53-1.63. If the viscosity of the liquid phase is less than 30 cps, there is a problem that the composition flows out of the mold when molding by injecting the liquid resin composition into the glass mold assembled with a synthetic resin gasket.If the viscosity of the liquid phase exceeds 1,000 cps, the composition is injected into the mold. There is a difficult problem. A more preferable viscosity is 50 to 500 cps.

By putting the composition for an optical lens into a mold and polymerizing it, an epoxy acrylic medium refractive optical lens according to the present invention can be manufactured. According to a preferred embodiment, after injecting the resin composition into a mold, the mold is placed in a forced circulation oven and gradually heat-cured from 30°C to 120°C, and then cooled to about 70±10°C to detach the mold to obtain a lens. At this time, all raw materials are preferably high purity compounds of up to 70 to 99.99% of purity. Preferably, the purity of all raw materials is checked to purify the low purity compound and the high purity compound is used without purification.

The acrylic optical lens obtained by the above method is a medium refractive to high refractive lens having a solid refractive index of 1.53-1.63 and can be used in various fields by replacing the existing lens. Specifically, it can be used as a plastic spectacle lens, a 3D polarizing lens equipped with a polarizing film on a spectacle lens, a camera lens, etc. In addition, various optics such as a recording medium substrate used for prism, optical fiber, optical disk, colored filters and ultraviolet absorption filters. Can be used for products.

[Example]

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

Synthesis example One

Epoxy Acrylate system Compound: Synthesis of component (I) compound

Component (I) The compound is the same as the formula (4). It has an equivalent weight of 259 and an average molecular weight of 518.

[Formula 4]

(n = 0~15)

Synthesis example 2

Epoxy Acrylate system Compound: Synthesis of component (II) compound

Component (II) The compound is the same as the formula (5). It has an equivalent weight of 472 and an average molecular weight of 944.

[Formula 5]

(n = 0~15)

Example 1

Resin composition for optical lens

600 g of epoxy acrylic resin component (I) obtained in Synthesis Example 1, 0.11 g of antioxidant TBNP, 0.22 g of BMP and 350 g of MMA, 5 g of polymerization regulator alpha methyl styrene dimer, 50 g of reaction diluent styrene, 10.2 g of heat stabilizer DPP, release agent Zelec UN ^TM 1.95g, 0.5g of V65, and 1.2g of 3-M were added to prepare a resin composition for an optical lens.

Optical lens manufacturing

(1) The resin composition for an optical lens prepared as above was stirred for 1 hour, then degassed under reduced pressure for 10 minutes, and then injected into a glass mold assembled with polyester adhesive tape.

(2) The glass mold into which the resin composition for optical lenses was injected was gradually heat-cured from 35°C to 100°C in a forced circulation oven, and then cooled to 70°C to detach the glass mold to obtain a lens. The obtained lens was measured for physical properties in the following manner, and the results are shown in Table 1 .

(3) After processing the optical lens obtained in (2) to a diameter of 72 mm, it was ultrasonically washed in an alkaline aqueous cleaning solution, and then annealed at 120° C. for 2 hours.

(4) After surface etching the lens obtained in (3) in 5% KOH solution, it was impregnated with Fine Coater's hard solution and then thermally cured, and silicon oxide, zirconium oxide, silicon oxide, ITO, zirconium oxide, Silicon oxide, zirconium oxide, and a water film (fluorine resin) were vacuum deposited to obtain a hard-coated and multi-coated optical lens.

Physical property test method

The physical properties of each optical lens were measured by the following physical property test method, and the results are recorded in Table 1 below.

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

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

3) Thermal stability: The cured optical lens is maintained at 100°C for 10 hours, and when the APHA value changes from 0 to 2 in the measurement of color change, "◎" is displayed, and when the APHA value changes to 3 to 4, "○" When the APHA value changes from 5 to 6, it is indicated by "Δ", and when the APHA value changes to 7 or more, it is indicated by "x".

4) Deformation: When the epoxy acrylic resin composition is thermally cured and demolded at 80°C, the plastic lens and the mold are easily separated. If no mold breaks out of 100 glass molds, "◎", 1~2 out of 100 glass molds "○" when broken, "Δ" when 3-4 out of 100 glass molds are broken, "x" when 5 or more out of 100 glass molds are broken (a mold of -0.00 diopter was used for uniform evaluation. )

Example 2~5

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

Example 6

410 g of epoxy acrylic resin component (I) and 220 g of epoxy acrylic resin component (II) obtained in Synthesis Examples 1 and 2, antioxidant TBNP 0.11 g, BMP 0.22 g and alpha methyl styrene 15 g, polymerization regulator 5 g of alpha methyl styrene dimer, reaction diluent Styrene 350g, heat stabilizer DPP 10.2g, release agent Zelec UN ^TM 1.95g, V65 1.42g, 3-M 0.45g were added to prepare a resin composition for an optical lens. Example 1 and prepared for each composition and the optical lens according to the proportion described in Table 1 in the same way, and the physical properties were experimental, and results thereof are illustrated in Table 1.

Example 7-10

In the same manner as in Example 6, compositions and optical lenses were prepared according to the compositions shown in Tables 1 and 2 , respectively, and physical properties were tested, and the results are described in Tables 1 and 2 .

Comparative Examples 1 to 3

Example 1 and prepared for each composition and the optical lens according to the proportion described in Table 2 in the same way, and the physical properties were experimental, and results thereof are illustrated in Table 2.

Comparative Examples 4-6

Example 6 In the same manner as that in accordance with the composition shown in Table 2, each of the compositions prepared and the physical properties of optical lenses were experimental, and results thereof are illustrated in Table 2.

division Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Basic resin (g) Component I 600 620 600 580 650 410 415 420 Component II 220 225 230 Supplementary ingredient (g) TBNP 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 BMP 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 MMA 350 280 380 400 300 Alpha methyl styrene 15 15 15 Polymerization regulator (g) Alpha methyl styrene dimer 5 5 5 5 5 5 5 5 Diluent (g) Styrene 50 100 20 20 50 350 340 330 Heat stabilizer (g) DPP 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 Internal release agent (g) Zelec UN ^TM 1.95 1.95 1.95 1.95 1.95 1.95 1.95 1.95 Polymerization initiator (g) V65 0.5 0.5 0.5 0.5 0.5 1.42 1.42 1.42 3-M 1.2 1.2 1.2 1.2 1.2 0.45 0.45 0.45 Optical lens properties Refractive index
(nE, 20℃) 1.5473 1.5546 1.5433 1.5427 1.5478 1.5967 1.5969 1.5971 Abbesu
(νE, 20℃) 39 38 39 39 39 32 32 32 importance 1.21 1.22 1.20 1.19 1.21 1.29 1.29 1.30 Dysplasia ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Thermal stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

division Example Comparative example Example 9 Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 basic
Suzy
(g) Component I 425 410 650 600 500 415 410 420 Component II 235 220 230 230 220 230 assistant
ingredient
(g) TBNP 0.11 0.11 0.33 0.33 0 BMP 0.22 0.22 0.33 0.33 BHT 0.33 0.33 MMA 230 350 480 Alpha methyl styrene 15 15 15 15 15 Polymerization regulator (g) Alpha methyl styrene dimer 5 5 5 5 5 5 5 5 Diluent (g) Styrene 320 350 120 50 20 335 350 350 Heat stabilizer (g) DPP 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 Internal release agent (g) Zelec UN ^TM 1.95 1.95 1.95 1.95 1.95 1.95 1.95 1.95 Polymerization initiator (g) V65 1.42 1.42 0.5 0.5 0.5 1.42 1.42 1.42 3-M 0.45 0.45 1.2 1.2 1.2 0.45 0.45 0.45 Optical lens properties Refractive index
(nE, 20℃) 1.5975 1.5967 1.5591 1.5465 1.5357 1.5969 1.5967 1.5971 Abbesu
(νE, 20℃) 32 32 38 39 40 32 32 32 importance 1.31 1.29 1.24 1.21 1.18 1.29 1.29 1.30 Dysplasia ◎ ◎ ○ Δ × ○ Δ × Thermal stability ◎ ◎ Δ ○ Δ Δ ○ ×

[Abbreviation]

Auxiliary ingredients

MMA: methyl methacrylate

TBNP: 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (2,2'-methylenebis(6-tert-butyl-4-methylphenol))

BMP: 2-tert-butyl-4,6-dimethylphenol

BHT: 2,6-di-tert-butylphenol

Internal release agent

Zelec UN ^TM _: Phosphoric acid ester compound manufactured by Stapan

Heat stabilizer

DPP: diphenylisodecylphoshite

Polymerization initiator

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

3-M: 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane (1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane)

The composition of the present invention for improving the thermal stability and releasability of an optical lens can greatly improve the thermal stability and releasability of the lens, so it can be widely used in the manufacture of an optical lens, and in particular, it can be used in the manufacture of an epoxy acrylic optical lens. I can.

The composition for an epoxy acrylic optical lens of the present invention containing this composition has good thermal stability, does not change color at high temperatures, has good releasability, has a low defect rate during demolding after polymerization, and can produce lenses of transparent quality without clouding. It can be widely used by replacing the acrylic optical lens composition. In particular, it can be used in the field of plastic spectacle lenses, 3D polarizing lenses with polarizing films attached to spectacle lenses, and camera lenses. In addition, various optical products such as recording media substrates used for prisms, optical fibers, optical disks, colored filters and ultraviolet absorption filters. Can be used for

Claims (8)

At least one thermal stabilizer selected from metal fatty acid salts, phosphorus, and organotin;
At least one type of internal release agent selected from phosphate ester compounds, fluorine-based surfactants, and alkyl quaternary ammonium salts;
2,2'-methylenebis(6-tert-butyl-4-methylphenol); And
A composition for improving thermal stability and releasability of an optical lens, comprising 2-tert-butyl-4,6-dimethylphenol. The method of claim 1,
The heat stabilizer is triphenyl phosphite, diphenyldecyl phosphite, phenyl didecyl phosphite, diphenyl dodecyl phosphite, diphenyl isodecyl phosphite, trinorylphenyl phosphite, diphenyl isoctyl phosphite, tributyl Phosphite, tripropyl phosphite, triethyl phosphite, trimethyl phosphite, tris (monodecyl phosphite), tris (monophenyl) phosphite, tris (nonylphenyl) phosphite selected from at least one phosphorus-based thermal stabilizer A composition for improving thermal stability and releasability of an optical lens, characterized in that. The method of claim 1,
A composition for improving thermal stability and releasability of an optical lens, characterized in that the release agent is a phosphate ester compound represented by Formula 1 below.
[Formula 1]

(In the equation,
R ₁ and R ₂ are either an alkyl group, an alkylphenyl, or a phenylalkyl group, and R ₁ and R ₂ are independently the same or different from each other.
X ₁ and X ₂ are alkyl groups, and X ₁ and X ₂ are independently the same or different from each other.
m and n are 0~40, y and z are 0~2, and y+z is 2.) The method of claim 3,
The release agent is (mono, di) methyl phosphoric acid; (Mono, di) ethyl phosphoric acid; (Mono, di) (n-propyl) phosphoric acid; (Mono, di) isopropyl phosphoric acid; (Mono, di) (n-butyl) phosphoric acid; (Mono, di) (n-pentyl) phosphoric acid; (Mono, di) (n-hexyl) phosphoric acid; (Mono, di) (n-heptyl) phosphoric acid; (Mono, di)(n-octyl)phosphoric acid; (Mono, di) (2-ethylhexyl) phosphoric acid; (Mono, di)(n-nonyl)phosphoric acid; (Mono, di) (n-decyl) phosphoric acid; (Mono, di) (isodecyl) phosphoric acid; (Mono, di) (n-undecyl) phosphoric acid; (Mono, di) (n-dodecyl) phosphoric acid; (Mono, di) (tridecyl) phosphoric acid; (Mono, di) (n-tetradecyl) phosphoric acid; (Mono, di) (n-pentadecyl) phosphoric acid; (Mono, di) (n-hexadecyl) phosphoric acid; (Mono, di) (n-octadecyl) phosphoric acid; (Mono, di)(o-methyldecyl)phosphoric acid; (Mono, di) (p-methylphenyl) phosphoric acid; (Mono, di) (p-ethylphenyl) phosphoric acid; (Mono, di) (p-propylphenyl) phosphoric acid; (Mono, di) (p-butylphenyl) phosphoric acid; (Mono, di) (p-nonylphenyl) phosphoric acid; (Mono, di) (p-methylmethyl) phosphoric acid; (Mono, di) (2-phenylethyl) phosphoric acid; (Mono, di) (4-phenylbutyl) phosphoric acid; (Mono, di) (3-oxabutyl) phosphoric acid; (Mono, di) (3-oxapentyl) phosphoric acid; (Mono, di) (3-oxahexyl) phosphoric acid; (Mono, di)(3-oxaheptyl)phosphoric acid; (Mono, di) (3-oxacylsyl) phosphoric acid; (Mono, di)(3-oxanonyl)phosphoric acid; (Mono, di) (3-oxaundecyl) phosphoric acid; (Mono, di) (3-oxatridecyl) phosphoric acid; (Mono, di)(3-oxapentadecyl)phosphoric acid; (Mono, di)(3-oxaheptadecyl)phosphoric acid; (Mono, di)(3-oxanoadecyl)phosphoric acid; (Mono, di) (3-oxahenosyl) phosphoric acid; (Mono, di)(1-methyl-3-oxabutyl)phosphoric acid; (Mono, di)(1-methyl-3-oxapentyl)phosphoric acid; (Mono, di)(1-methyl-3-oxaheptyl)phosphoric acid; (Mono, di)(1,2-dimethyl-3-oxaheptyl)phosphoric acid; (Mono, di)(1-methyl-3-oxatridecyl)phosphoric acid; (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, di)(3, 6-dioxaheptyl)phosphoric acid; (mono, di)(3,6-dioxaoctyl)phosphoric acid; (mono, di)(3,6-dioxadecyl)phosphoric acid; (mono, di)(3,6- Dioxatetradecyl)phosphoric acid; (mono, di)(3,6-dioxahexadecyl)phosphoric acid; (mono, di)(3,6-dioxaoctadecyl)phosphoric acid; (3,6-dioxycosyl) Phosphoric acid; (3,6-dioxadocosyl)phosphoric acid; (mono, di)(3,6-dioxatetracosyl)phosphoric acid; (mono, di)(1,4-dimethyl-3,6-dioxadecyl ) Phosphoric acid; (mono, di) (3,6,9-trioxadecyl) phosphoric acid; (mono, di) (3,6,9-trioxaundecyl) phosphoric acid; (mono, di) (3,6, 9-trioxatridecyl)phosphoric acid; (mono, di)(3,6,9-trioxaheptadecyl)phosphoric acid; (mono, di)(3,6,9-trioxahenicosyl)phosphoric acid; (mono, Di)(3,6,9-trioxaheptacosyl)phosphoric acid; (mono, di)(1,4,7-trimethyl-3,6,9-trioxatridecyl)phosphoric acid; (mono, di)( 3,6,9,12-tetraoxaheptyldecyl)phosphoric acid; (mono, di)(3,6,9,12-tetraoxaoctyldecyl)phosphoric acid; (mono, di)(3,6,9, 12-tetraoxycosyl)phosphoric acid; (mono, di)(3,6,9,12-tetraoxadocosyl)phosphoric acid; (mono, di)(3,6,9,12-tetraoxatetracosyl)phosphoric acid ; (Mono, di)(1,4,7,10-tetramethyl-3,6,9,12-tetraoxahexadecyl)phosphoric acid; triisopropyl acid phosphate; tributyl acid phosphate; trioctylic acid phosphate; trioctylic acid phosphate; Isodecylic acid phosphate; tridecanoic acid phosphate; bis(tridecanoic acid) phosphate; trimethyl acid phosphate; triethyl acid phosphate; tripropyl acid ester; benzylic acid phosphate; dibenzyl acid phosphate; tribenzyl acid phosphate; polyoxyethylene nonyl Phenol ether phosphate; tripolyoxyethylene nonyl phenol ether phosphate; bis(tridecanoic acid) phosphate; ethylene glycol monoethyl phosphate; diethylene glycol monoethyl phosphate; triethylene glycol mono ethyl phosphate; diethylene glycol monobutyl diphosphate; diethylene glycol monobutyl diphosphate; Ethylene Glycol monobutyl phosphate; Isopropylene glycol monoethyl phosphate; Diisopropylene glycol monoethyl phosphate; And at least one phosphate ester compound selected from the group consisting of triisopropylene glycol monoethyl phosphate. A composition for improving thermal stability and releasability of an optical lens. Bisphenol A epoxy acrylate;
Reactive diluents;
At least one thermal stabilizer selected from metal fatty acid salts, phosphorus, and organotin;
At least one type of internal release agent selected from phosphate ester compounds, fluorine-based surfactants, and alkyl quaternary ammonium salts;
2,2'-methylenebis(6-tert-butyl-4-methylphenol); And
A composition for an epoxy acrylic optical lens containing 2-tert-butyl-4,6-dimethylphenol. The method of claim 5,
In the composition for an epoxy acrylic optical lens, the total amount of the 2,2'-methylenebis (6-tert-butyl-4-methylphenol) and 2-tert-butyl-4,6-dimethylphenol combined is 0.001 to 5% by weight Epoxy acrylic-based optical lens composition, characterized in that included as. The method of claim 5,
The reactive diluent is styrene, methyl methacrylate, divinylbenzene, alpha methyl styrene, alpha methyl styrene dimer, benzyl methacrylate, chloro styrene, bromo styrene, methoxy styrene, monobenzyl maleate, monobenzyl fumalate, Dibenzyl maleate, dibenzyl fumalate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumalate, monobutyl maleate, monopentyl maleate, dipentyl maleate, monopentyl Epoxy acrylic optical lens composition, characterized in that one or more compounds selected from the group consisting of fumalate, dipentyl fumalate and diethylene glycol bisaryl carbonate. A method of manufacturing an epoxy acrylic medium refractive optical lens comprising the step of polymerizing the composition of claim 5 in a mold.