KR102097174B1 - Polymerizable composition based on epoxy acryl compounds with improved storage stability and method of preparing optical material based on the epoxy acryl compounds - Google Patents

Abstract

(여기서 n = 0~15 이고, R₁은 H 또는 CH₃이며, R₂는 H 혹은 Br이다.)The present invention relates to a polymerizable composition for an epoxy acrylic-based optical material and a method for manufacturing the epoxy acrylic-based optical material, in particular, a polymerizable composition and an optical for an epoxy acrylic-based optical material with improved storage stability that can prevent color changes during long-term storage at room temperature. It relates to a method of manufacturing a material. In the present invention, a polymerizable composition for an epoxy acrylic optical material comprising a compound represented by the following Chemical Formula 1, diphenyl dodecyl phosphite, and a phosphoric acid ester compound is provided. According to the present invention, the optical properties such as high refractive index and excellent Abbe's water, transparency, light weight, and heat resistance are excellent, and the manufacturing cost is low. A high quality epoxy acrylic optical material can be easily obtained, and the epoxy acrylic optical material of the present invention can be widely used in various fields by replacing the existing optical material.
[Formula 1]

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

Description

Polymerizable composition for epoxy acrylic optical material with improved storage stability and method for preparing epoxy acrylic optical material {Polymerizable composition based on epoxy acryl compounds with improved storage stability and method of preparing optical material based on the epoxy acryl compounds}

The present invention relates to a polymerizable composition for an epoxy acrylic-based optical material and a method for manufacturing the epoxy acrylic-based optical material, in particular, a polymerizable composition and an optical for an epoxy acrylic-based optical material with improved storage stability that can prevent color changes during long-term storage at room temperature. It relates to a method of manufacturing a material.

The plastic optical lens was introduced as a replacement product that supplemented the high specific gravity and low impact characteristics of glass lenses. Representative examples include polyethylene glycol bisallyl carbonate, polymethyl methacrylate, diallyl phthalate, and the like. However, the optical lenses made of these polymers are excellent in physical properties such as moldability, dyeability, hard coat film adhesion, and impact resistance, but the refractive index is as low as 1.50 (nD) and 1.55 (nD), which makes the lens thicker. . Accordingly, various attempts have been made to develop an optical material having a high refractive index to reduce the thickness of the lens.

In the Republic of Korea Patent Registration No. 10-0136698, 10-0051275, 10-0051939, 10-0056025, 10-0040546, 10-0113627, a polyisocyanate compound and a polythiol compound are thermally cured to obtain a thiourethane-based optical lens. Thiourethane-based optical lenses have excellent optical properties such as dyeability, impact resistance, and transparency, but there is a problem that the Abbe number decreases as the refractive index increases, and the material is expensive, and the lens manufacturing process is sensitive to moisture. It is difficult, and there is a problem in the central deformation of the lens due to moisture in the air even when the lens is stored.

In Korea Patent Registration Nos. 10-0496911 and 10-0498896, unlike these thiourethane-based lenses, they have high refractive index, high Abbe number, excellent optical properties such as transparency, light weight, and heat resistance, and are cheap epoxy acrylic optical materials. The composition is disclosed. Such an epoxy acrylic optical material can produce a lens without requiring moisture management in the air even in an area with high temperature and humidity, and there is no central deformation of the lens due to moisture in the air when the lens is stored. However, these epoxy acrylic optical materials have a problem in that color changes occur when stored at room temperature for a long time. This storage stability is not only a problem in the process of storage and distribution after lens manufacture, but also a problem in the process of finally using the lens after the consumer purchases it.

Conventionally, a phosphorus-based heat stabilizer was used for the epoxy acrylic optical material (Republic of Korea Patent Registration No. 10-0498896). Examples of the phosphorus-based thermal stabilizer include triphenyl phosphite, diphenyl decyl phosphite, phenyl didecyl phosphite, diphenyl dodecyl phosphite, trinoryl phenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, tripropyl One or two or more compounds selected from phosphite, triethylphosphite, trimethylphosphite, tris (monodesilphosphite), and tris (monophenyl) phosphite were used. However, the conventional heat stabilizer was intended to prevent deformation such as discoloration on the lens at high temperatures during hard coating or multi-coating, and the heat stability at high temperatures and storage stability at room temperature are not in a proportional relationship.

In addition, Korean Patent Registration No. 10-0897407 discloses a lens composition using a phosphoric acid ester compound in order to prevent yellowing of a lens caused by heat during annealing when manufacturing a lens from an epoxy acrylic optical material. Examples of such phosphoric acid ester compounds include isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, dioctylic acid phosphate, and trioctyl acid phosphate , Isodecyl Acid Phosphate, Diisodecyl Acid Phosphate, Triisodecyl Acid Phosphate, Tridecanoic Acid Phosphate, Bis (tridecanoic acid) phosphate, Dimethyl Acid Phosphate, Trimethyl Acid Phosphate, Diethyl Acid Phosphate, Triethyl Acid Phosphate, Di Propyl acid ester, tripropyl acid ester, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, benzyl acid phosphate, dibenzyl acid phosphate, tribenzyl acid phosphate, polyoxyethylene nonyl phenol ether phosphate, tri polyoxyethylene nonyl phenol Ter phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene glycol monoethyl phosphate, diethylene glycol monobutyl triphosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate, isopropylene glycol mono Ethyl phosphate, diisopropylene glycol monoethyl phosphate, triisopropylene glycol monoethyl phosphate, and the like are used alone or in combination of two or more. However, this is also intended to solve the problem of severe yellowing caused by oxidation of organic or inorganic pigments by a catalyst during annealing after thermal curing, that is, discoloration triggered by a catalyst at a high temperature, and a phosphoric acid ester compound at room temperature. It has not solved the problem of storage stability.

Republic of Korea Registered Patent Publication 10-0496911 Republic of Korea Registered Patent Publication 10-0498896 Republic of Korea Registered Patent Publication 10-0897407

The present inventors unexpectedly found that the use of diphenyl dodecyl phosphite and a phosphoric acid ester compound as a phosphorus-based thermal stabilizer in an epoxy acrylic polymerizable composition can dramatically improve the storage stability of optical materials. The present invention has been confirmed and completed, and it is an object of the present invention to provide a polymerizable composition for an epoxy acrylic optical material that contains a diphenyl dodecyl phosphite and a phosphoric acid ester compound together in a polymerizable composition, and has significantly improved storage stability. .

In the present invention,

A polymerizable composition for an epoxy acrylic optical material comprising a compound represented by Formula 1, diphenyl dodecyl phosphite, and a phosphoric acid ester compound is provided. The polymerizable composition for an epoxy acrylic optical material of the present invention may further include a compound represented by Formula 2 below.

[Formula 1]

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

[Formula 2]

(Here R is H or CH ₃ , m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10.)

In addition, in the present invention,

When the polymerizable composition containing the epoxy acrylate-based compound represented by the formula (1) is mold-polymerized, an epoxy acrylic-based optical system comprising adding and polymerizing diphenyl dodecyl phosphite and a phosphate ester compound to improve storage stability A method of making a material is provided. At this time, the polymerizable composition may further include a compound represented by Formula 2 above.

In addition, in the present invention, there is provided an optical material obtained by casting polymerization of the polymerizable composition and an optical lens made of the optical material. The optical lens particularly includes a spectacle lens or a polarizing lens.

In the present invention, the storage stability of the epoxy acrylic optical material can be greatly improved by including the diphenyl dodecyl phosphite and phosphoric acid ester compounds in the composition. The optical material manufactured according to the present invention has a high refractive index, has a high Abbe number, has excellent optical properties such as transparency, light weight, and heat resistance, and has the advantage of an epoxy acrylic optical material that is inexpensive to manufacture and stores for a long time at room temperature. Even if used or used, a high quality epoxy acrylic optical material without discoloration can be easily obtained.

The polymerizable composition for an epoxy acrylic optical material of the present invention includes an epoxy acrylate-based compound represented by Formula 1 below, a diphenyl dodecyl phosphite, and a phosphoric acid ester compound, preferably represented by Formula 2 below. It may further include a compound.

[Formula 1]

Where n is 0-15, R ₁ is H or CH ₃ and R ₂ is H or Br. Preferably, n is 0 to 10, more preferably 0 to 5.

[Formula 2]

(Here R is H or CH ₃ , m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10.)

In the polymerizable composition of the present invention, diphenyl dodecyl phosphite, together with the phosphoric acid ester compound, imparts storage stability to the polymer so that the polymerized lens does not discolor even when stored at room temperature for a long time. This is different from the role of a heat stabilizer that prevents discoloration in the manufacturing process involving high temperatures such as hard coating or multi-coating. The use amount of diphenyl dodecyl phosphite is 0.5 to 8% by weight of the total composition. If the content is less than 0.5% by weight, the effect is negligible, and when it exceeds 8% by weight, the thermal stability and storage stability are reduced, and the physical properties of the lens are also adversely affected. More preferably, 1 to 5% by weight was good.

In the polymerizable composition of the present invention, the phosphoric acid ester compound is isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, dioctylic acid phosphate , Trioctyl acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, triisodecyl acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, dimethyl acid phosphate, trimethyl acid phosphate, diethyl acid phosphate, tri Ethyl acid phosphate, dipropyl acid ester, tripropyl acid ester, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, benzyl acid phosphate, dibenzyl acid phosphate, tribenzyl acid phosphate, polyoxyethylene nonyl phenol ether phosphate, tri poly jade Ethylene nonyl phenol ether phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene glycol monoethyl phosphate, diethylene glycol monobutyl triphosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate, iso propylene glycol monomethyl phosphate, di-isopropylene glycol mono ethyl phosphate, tri-iso-propylene glycol mono-ethyl phosphate, jelrek UN ^TM (Zelec UN ^TM) may be used alone or in combination with two or more of them.

The polymerizable composition of the present invention may further include a reactive diluent. Other reactive diluents include, for example, styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrenedimer, benzylmethacrylate, chlorostyrene, bromostyrene, methoxystyrene, monobenzylmaleate, dibenzylmaleate, monobenzyl Fumalate, dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl malate, dibutyl fumarate, monobutyl malate, monopentyl malate, dipentyl malate, monopentyl fumarate , Dipentyl fumarate, diethylene glycol bisaryl carbonate, or the like may be used alone or in combination of two or more. The ratio of the total reactive diluent to 100 parts by weight of the total epoxy acrylate-based compound further comprising a compound represented by Chemical Formula 1 or represented by Chemical Formula 2 in the polymerizable composition of the present invention, preferably 30 to 300 Parts by weight. When a reactive diluent is used in an amount of less than 30 parts by weight, the viscosity is high, so the moldability is difficult, and the workability is poor. When it is used in excess of 300 parts by weight, the polymerizable composition flows out of the mold when injected into a glass mold assembled with a gasket. Can come out.

The polymerizable composition of the present invention may further include an internal release agent, a heat stabilizer, an ultraviolet absorber, an organic dye, an inorganic pigment, an anti-coloring agent, an antioxidant, a light stabilizer, a catalyst, etc. according to a conventional method.

As the internal release agent, other phosphoric acid ester compounds, silicone-based surfactants, fluorine-based surfactants, etc. may be used alone or in combination of two or more, in addition to the phosphoric acid ester, preferably 0.001 to 10% by weight in the polymerizable composition. . As the internal release agent, preferably, a phosphoric acid ester compound other than the phosphoric acid ester can be used. Other phosphoric acid ester compounds used as the internal release agent include, for example, polyoxyethylene nonylphenol ether phosphate (5% by weight of 5 moles of ethylene oxide added, 80% by weight of 4 moles added, 10% by weight of 3 moles added), 1 mol added 5 wt%), polyoxyethylene nonylphenyl phosphate (9 mol ethylene oxide added 5 wt%, ethylene oxide 8 mol added 80 wt%, ethylene oxide 7 mol added 10 Weight%, ethylene oxide 6 mol or less added 5 wt%), polyoxyethylene nonylphenol ether phosphate (ethylene oxide 11 mol added 3 wt%, 10 mol added 80 wt%, 9 mol added 5 wt%, 7 mol added 6 wt%, 6 mol added 6 wt%), polyoxyethylene nonylphenol ether phosphate (13 mol added ethylene oxide 3 wt%, 12 mol added 80 wt%) , 11 mol added 8 wt%, 9 mol added 3 wt%, 4 mol 6% by weight of added), polyoxyethylene nonylphenol ether phosphate (3% by weight of 17 moles of ethylene oxide added, 79% by weight of 16 moles added, 10% by weight of 15 moles added, 14% of added) 4% by weight, 4% by weight of 13 moles added), polyoxyethylene nonylphenol ether phosphate (5% by weight of 21 moles of ethylene oxide added, 78% by weight of 20 moles added, 19% of added 7 Weight%, 18 mol added 6 wt%, 17 mol added 4 wt%) or the like may be used alone or in combination of two or more.

The heat stabilizer may be preferably included in the composition in an amount of 0.01 to 5.00% by weight. When the heat stabilizer is used at 0.01% by weight or less, the thermal stability effect is weak, and when it is used at 5.00% by weight or more, the polymerization failure rate is high during curing, and the heat stability of the cured product is lowered. Examples of the heat stabilizer include metal stearate, calcium stearate, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate, zinc octoate, etc. One or two or more compounds selected from the compounds can be used. Preferably, phosphorus-based triphenylphosphite, diphenyldecylphosphite, phenyl didecylphosphite, trinorylphenylphosphite, diphenylisooctylphosphite, tributylphosphite, tripropylphosphite, triethylphosphite , Trimethylphosphite, tris (monodecylphosphite), or tris (monophenyl) phosphite. In addition, one or more selected from compounds such as lead-based 3PbO.PbSO4.4H ₂ O, 2PbO.Pb (C ₈ H ₄ O ₄ ), 3PbO.Pb (C ₄ H ₂ O ₄ ) .H ₂ O Also available, organotin-based dibutyltin diaurate, dibutyltin maleate, dibutyltin bis (isooctyl maleate), dioctyl maleate, dibutyltin bis (monomethyl maleate), dibutyltin Bis (lauryl mercaptide), dibutyl bis (isooxyl mercaptoacetate), monobutyltin tris (isooctyl mercaptoacetate), dimethyltin bis (isooctyl mercaptoacetate), tris (isooctyl mercaptoacetate) ), Bioctylatin bis (isooctyl mercaptoacetate), dibutyltin bis (2-mercaptoethyl erorate), monobutyl tin tris (2-mercaptoethyrorate), dimethyltin bis (2-mercapto) Ethylate), monomethyltin tris (2-mercaptoethylolate), etc. Or two or more types can be used. In addition, it is also possible to use a mixture of two or more kinds of heat stabilizers having different series among the heat stabilizers illustrated above. Most preferably, by using a phosphorus-based thermal stabilizer, it is possible to greatly improve the thermal stability of the optical lens without deteriorating optical characteristics such as transparency, impact strength, heat resistance, and polymerization yield, as well as the initial color of the molded lens.

The method for producing the epoxy acrylic optical material of the present invention, when a template polymerization of an epoxy acrylate-based compound further comprising a compound represented by the formula (1) or represented by the formula (2), diphenyl dodecyl phosphite and phosphoric acid ester The compound is added and mixed, followed by template polymerization. According to a preferred embodiment, prior to preparation, the purity of all raw materials is checked to purify the compound with low purity and the compound with high purity is used without purification. Preferably, a high purity compound having a purity of 70 to 99.99% is used. According to a preferred embodiment, after mixing the epoxy acrylate compound and diphenyl dodecyl phosphite, a phosphoric acid ester compound and a reactive diluent, a reaction catalyst is added and stirred, followed by degassing under reduced pressure to inject the polymerizable composition into the mold. The mold into which the polymerizable composition is injected is placed in a forced-circulating oven and gradually cured from 30 ° C to 100 ° C, cooled to about 70 ± 10 ° C, and the mold is detached to obtain a lens.

[ Example ]

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

Epoxy Acrylate series  compound

1) Synthesis of Component (I) Compound

The component (I) compound is as in the formula (3). A compound having an equivalent weight of 259 was prepared by acrylated (prepared by reacting at 105 ° C for 20 hours) by adding acrylic acid to YD-128 epoxy resin of Kukdo Chemical with an equivalent weight of 187, and a mixture having an average molecular weight of 518.

[Formula 3]

(n = 0 ~ 15)

2) Component (II) compound

The component (II) compound is as in the formula (4). A compound having an equivalent weight of 273 was prepared by acrylated by adding methacrylic acid to an epoxy resin having an equivalent weight of 187 (prepared by reacting at 105 ° C for 20 hours), and a mixture having an average molecular weight of 546.

[Formula 4]

(n = 0 to 15)

3) Component (III) compound

The component (III) compound is as in formula (5). A compound having an equivalent weight of 472 was prepared by acrylated by adding acrylic acid to a YDB-400 epoxy resin of Kukdo Chemical (equivalent to reacting at 105 ° C. for 20 hours) having an equivalent weight of 400, and a mixture having an average molecular weight of 944.

[Formula 5]

(n = 0 to 15)

4) Component (IV) compound

The component (IV) compound is as in the formula (6). A compound having an equivalent weight of 486 was prepared by acrylated by adding methacrylic acid to an epoxy resin having an equivalent weight of 400 (prepared by reacting at 105 ° C for 20 hours), and a mixture having an average molecular weight of 972.

[Formula 6]

(n = 0 to 15)

5) Component (V) compound

Acrylic acid was added to the alcohol in which ethylene oxide was added to bisphenol A having an equivalent weight of 175 to acrylate (prepared by reacting at 105 ° C for 20 hours) to prepare a compound having an equivalent weight of 229. It is a mixture having an average molecular weight of 458, and the structural formula is as shown in Chemical Formula 7.

[Formula 7]

(m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10.)

6) Component (VI) compound

A compound having an equivalent weight of 243 was prepared by acrylated (prepared by reacting at 105 ° C for 20 hours) by adding methacrylic acid to an alcohol in which ethylene oxide was added to bisphenol A having an equivalent weight of 175. It is a mixture having an average molecular weight of 486, and the structural formula is as shown in Chemical Formula 8.

[Formula 8]

(m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10.)

Example  One

Among the epoxy acrylate-based compounds obtained above, component (I) 15g, component (III) 30g and component (V) 40 g of styrene, 2 g of methylstyrene dimer, 2 g of DPDP, 1 g of DOP, and 2 g of DBTM were added to 10 g, followed by stirring for about 30 minutes. After filtering with a filter paper of 0.45 µm or less, 0.05 g of V65 and 0.12 g of 3-M are added as catalysts, and 0.05 g of 4-PENPP and 0.2 g of 8-PENPP are mixed as an internal release agent to polymerize the composition for optical lenses. Made. The polymerizable composition for an optical lens thus prepared was stirred for 1 hour, defoamed under reduced pressure for 10 minutes, filtered, and then injected into a glass mold assembled with polyester adhesive tape. The glass mold in which the polymerizable composition was injected was heat-cured from 35 ° C to 110 ° C in a forced circulation oven over 20 hours, and then cooled to 70 ° C to detach the glass mold to obtain a lens. The obtained lens was processed to a diameter of 72 mm and then ultrasonically washed in an alkaline aqueous cleaning solution, and then annealed at 120 ° C for 2 hours. Table 1 shows the results of measuring the physical properties in the following manner.

Property test method

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

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

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

3) Releasability: When the optical lens was manufactured, the epoxy acrylic resin composition was thermally cured, and it was denoted by "○" and "x" depending on the breakage of the lens or mold when separating the optical lens from the mold when demolding at 70 ° C. "○" means that the lens or mold is not damaged at all during the separation process of 100 optical lenses and mold, or "x" means more than 4 lenses or molds during the separation process of 100 optical lenses and mold. It was shown as a broken case.

4) Thermal stability: The cured optical lens is maintained at 100 ° C. for 10 hours, and when the color change is measured, the APHA value is changed to less than 1, indicated as “◎”, and when changed to 1 or more and less than 2, indicated as “○”, 2 If it changes abnormally, it is indicated by "x". APHA used Hunterlab's ColorQuest XE and measured directly with a plastic lens. The concentration of the standard solution prepared by dissolving the reagents of platinum and cobalt was dataized, and the APHA value obtained from the comparison of the built-in program and the sample solution was used as a measurement value. The smaller the measured value, the better the color.

5) Low stability: When the cured optical lens is annealed at 120 ° C for 2 hours, stored at 20 ° C for 30 days, and the APHA value of the measured color change changes to less than 1, it is set to "◎", 1 to 2 If it changes, it is indicated by "○", and if it changes by 2 or more, it is indicated by "X".

6) Polymerization imbalance: 100 lenses obtained in the process are visually observed with a mercury arc lamp (USH10 USH-102D) and 3 or more optical distortions appear as “×”, and if the optical distortion is 3 or less It was written as "○".

7) Color: If the color of the cured optical lens is colorless, it is indicated as "○", and when it is colored, it is indicated as "x".

Example  2 ~ 6

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.

Comparative example  One

Among the epoxy acrylate-based compounds obtained above, 15 g of component (I), 29.4 g of component (IV) and 8 g of component (VI), 40 g of styrene, 5 g of alpha-methylstyrene, 2 g of methylstyrene dimer, DPDP 0.3 g, TDP 0.3 g and DPP 2 g was added and stirred for about 30 minutes. Then, filter with a filter paper of 0.45 µm or less, add 0.05 g of V65 and 0.13 g of 3-M as a catalyst, and mix 8-PENPP 0.1 g and 12-PENPP 0.1 g as an internal release agent to prepare a resin composition for optical lenses. After making, an optical lens was prepared in the following manner, and the physical properties of the lens were measured. A lens was prepared and the physical properties of the lens were measured, and the results are shown in Table 1 .

Comparative example  2-3

Comparative Example 1 Preparation of each composition and the optical lens according to the proportion described in Table 1 in the same way, and the physical properties it was experimental, and results thereof are illustrated in Table 1.

division
Example Comparative example One 2 3 4 5 6 One 2 3 basic
Suzy
(g)
Ingredient I 15 20 14.5 13 15 15 15 Ingredient II 14.5 13 Ingredient III 30 29 Ingredient IV 30 30 35 29.7 29.4 30 29 Ingredient V 10 6 8 Ingredient VI 5 5 8 8 diluent
(g)
Styrene 40 40 40 40 40 40 40 40 40 Alpha-methylstyrene 5 5 5 5 5 5 5 Methyl styrene dimer 2 2 One One 2 2 2 2 3 Save
stabilizator
(g) DPDP 2 One 3 4 5 2 0.3 8 Phosphoric acid ester compound (g) DOP One One 0.5 0.3 0.5 2 TDP
One 0.5 0.5 0.3 Heat stabilizer
(g) DBTM 2 TPP 2 One 2 2 DPP One 2 2 2 inside
Release agent
(g) 4-PENPP 0.05 0.1 0.15 0.1 8-PENPP 0.2 0.2 0.1 0.1 0.1 12-PENPP 0.2 0.1 0.1 16-PENPP 0.05 0.2 0.1 0.1 Radical initiator
(g) V65 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 3-M 0.12 0.11 0.13 0.13 0.13 0.13 0.13 0.13 0.13 lens
Properties Refractive index (nE, 20 ℃) 1.5971 1.5971 1.5970 1.5972 1.5970 1.5970 1.5970 1.5968 1.5970 Abbe 32 32 32 32 32 32 32 32 32 importance 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.29 1.29 Heterogeneity ○ ○ ○ ○ ○ ○ × ○ ○ Thermal stability ◎ ○ ◎ ○ ○ ◎ × ○ × Storage stability ◎ ○ ◎ ○ ○ ◎ × × × Transparency ○ ○ ○ ○ ○ ○ × × × Polymerization imbalance ○ ○ ○ ○ ○ ○ ○ ○ × color ○ ○ ○ ○ ○ ○ × × ×

[Abbreviation]

Storage stabilizer

DPDP: diphenyldodecyl phosphite

Phosphoric acid ester compound

DOP: dioctyl acid phosphate

TDP: Tridecanol acid phosphate

Heat stabilizer

DBTM: dibutyltinmaleate

TPP: triphenylphosphite

DPP: diphenylisodecylphosphite

Polymerization initiator

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

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

Internal release agent

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

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

12-PENPP: Polyoxyethylene nonylphenol ether phosphate (3 wt% with 13 mol added ethylene oxide, 80 wt% with 12 mol added, 8 wt% with 11 mol added, 3 wt% with 9 mol added) , 4 mol added 6 wt%)

16-PENPP: Polyoxyethylene nonylphenol ether phosphate (3 wt% with 17 mol ethylene oxide added, 79 wt% with 16 mol added, 10 wt% with 15 mol added, 4 wt% with 14 mol added) , 13 mol added 4% by weight)

According to the present invention, the optical properties such as high refractive index and excellent Abbe's number, transparency, light weight, and heat resistance are excellent, and the manufacturing cost is low. A high quality epoxy acrylic optical material can be easily obtained. The epoxy acrylic optical material manufactured according to the present invention can be widely used in various fields by replacing the existing optical material, and in particular, it can be used as an eyeglass lens or a camera lens. Specifically, the optical material of the present invention can be used as a plastic spectacle lens, a 3D polarized lens equipped with a polarizing film on the spectacle lens, and the like, as well as a recording medium substrate or color filter used in prisms, optical fibers, optical discs, etc. and absorbing ultraviolet rays. It can be used for various optical products such as filters.

Claims (13)

In the method for producing an epoxy acrylic optical material comprising a template polymerization of a polymerizable composition comprising a compound represented by Formula 1 below,
In order to improve the storage stability at room temperature of the epoxy acrylic optical material, diphenyl dodecyl phosphite and phosphoric acid ester compounds are simultaneously included in 0.5 to 8% by weight and 0.5 to 3% by weight in the polymerizable composition, and mold polymerization is performed. Characterized in, the manufacturing method of the epoxy acrylic optical material with improved storage stability.
[Formula 1]

(Where n = 0-15, R ₁ is H or CH ₃ , R ₂ is H or Br.) The method of claim 1, wherein the polymerizable composition further comprises a compound represented by Formula 2 below.
[Formula 2]

(Here R is H or CH ₃ , m = 0 ~ 5, n = 0 ~ 5, m and n are not 0 at the same time, m + n = 1 ~ 10.) delete According to claim 1 or claim 2, wherein the phosphoric acid ester compound is isopropyl acid phosphate, diisopropyl acid phosphate, triisopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, tributyl acid phosphate, octylic acid phosphate, Dioctylic acid phosphate, trioctylic acid phosphate, isodecyl acid phosphate, diisodecyl acid phosphate, triisodecyl acid phosphate, tridecanoic acid phosphate, bis (tridecanoic acid) phosphate, dimethyl acid phosphate, trimethyl acid phosphate, diethyl acid Phosphate, triethyl acid phosphate, dipropyl acid ester, tripropyl acid ester, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, benzyl acid phosphate, dibenzyl acid phosphate, tribenzyl acid phosphate, polyoxyethylene nonyl phenol ether phosphate , Tree poly Cyethylene nonyl phenol ether phosphate, ethylene glycol monoethyl phosphate, diethylene glycol monoethyl phosphate, triethylene glycol monoethyl phosphate, diethylene glycol monobutyl triphosphate, diethylene glycol monobutyl diphosphate, diethylene glycol monobutyl phosphate, isopropylene glycol monoethyl phosphate, di-isopropylene glycol monoethyl phosphate, tri isopropylene glycol monoethyl phosphate and jelrek UN ^TM (Zelec UN ^TM) epoxy acrylic optical material, characterized in that at least one or two selected from the group consisting of Method of manufacturing. The method according to claim 1 or 2, wherein the polymerizable composition is a reactive diluent, styrene, divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer, benzyl methacrylate, chlorostyrene, bromostyrene, methoxystyrene, mono Benzyl maleate, dibenzyl maleate, monobenzyl fumarate, dibenzyl fumarate, methylbenzyl maleate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl fumarate, monobutyl maleate, monophene Of epoxy acrylic optical material, characterized in that it further comprises one or two or more compounds selected from the group consisting of tilmalate, dipentyl malate, monopentyl fumarate, dipentyl fumarate and diethylene glycol bisaryl carbonate. Manufacturing method. The method of claim 5, wherein the polymerizable composition is triphenyl phosphite, diphenyl decyl phosphite, phenyl didecyl phosphite, trinorylphenyl phosphite, diphenyl isooctyl phosphite, tributyl phosphite, tri Epoxy acrylic system characterized in that it further comprises one or more compounds selected from the group consisting of propylphosphite, triethylphosphite, trimethylphosphite, tris (monodesilphosphite) and tris (monophenyl) phosphite. Method of manufacturing optical material. The method of claim 4, wherein the polymerizable composition further comprises another phosphoric acid ester compound as an internal release agent. delete delete delete An epoxy acrylic optical material with improved storage stability obtained by the method of claim 1 or 2. delete delete