KR100529369B1 - Resin composition for producing optical lens having low density and medium refraction index, and optical lens produced with the same - Google Patents

Abstract

A resin composition for producing a plastic lens having a refractive index of 1.55 or more, a low specific gravity of 1.20 or less, and a high Abbe number of 40 or more, excellent in impact resistance, moldability, dyeing, and the like, and particularly excellent in light stability. The resin composition may comprise (A) 10 to 60% by weight of a bifunctional or higher epoxydiacrylate compound having a bisphenol A skeleton represented by the following formula;

(Wherein R 1 is a methyl group and n is an integer from 1 to 4).

(B) 0.1 to 10% by weight of an aliphatic acrylic acid compound having at least one functional group; (C) 10 to 35% by weight of an aromatic allyl compound having at least one functional group; And (D) 5 to 35% by weight of an aliphatic compound having two or more functional groups and three or more ether groups.

Description

Resin composition for producing optical lens having low density and medium refraction index, and optical lens produced with the same}

 The present invention relates to a resin composition for a low specific gravity, medium refractive index plastic lens, more specifically, having a refractive index of 1.55 or more, low specific gravity of 1.20 or less, Goabe number of 40 or more, and excellent in impact resistance, moldability, dyeability, etc. In particular, the present invention relates to a resin composition for plastic lenses having excellent light stability and a plastic lens manufactured using the same.

As the main resin for producing plastic lenses for eyeglasses, a polymer of diethylene glycol bisallylcarbonate (commercially available under the trade name CR-39 of PPG Industries Co.) was used, but now diacrylate derived from bisphenol-A. Or dimethacrylates [Japanese Patent Laid-Open No. 116,301 / 83], combinations of halogenated styrene monomers and polyfunctional methacrylates [Japanese Patent Laid-Open Nos. 104,101 / 82, 28,118 / 82 and 28,116]. / 82] and diallyl phthalate monomers [Japanese Patent Laid-Open No. 212,401 / 82 and 15,513 / 83]. However, such resins tend to be discolored in the polymerization process by the polymerization inhibitor contained in the polymeric material, and are not only satisfactory in weather resistance and visible light transmittance, but also have disadvantages of poor coloring and thermal stability.

The inventors have conducted extensive research to develop plastic lenses that do not have the drawbacks described above. That is, it basically has a refractive index of 1.55 or more and low specific gravity of 1.2 or less, and is excellent in all of heat resistance, low water absorption, impact resistance, moldability, dyeing, and the like. In particular, it is excellent in light stability and capable of high-speed polymerization by radicals. In order to manufacture a plastic lens, a bisphenol-based epoxy resin having excellent heat resistance is used as a base resin, and in order to complement impact resistance and moldability, extensive research has been conducted on a material well crosslinked with the base resin. It came to invention.

It is therefore an object of the present invention to provide a resin composition for producing an optical lens having a refractive index of at least 1.55, a low specific gravity of at most 1.2 and a high Abbe number of at least 40.

Another object of the present invention is to optimize the type and content of each component used to reduce or eliminate the defects (common name, striae, locust; bad type) inside the lens that can occur after polymerization, low specific gravity It is to provide a resin composition for producing a medium refractive index optical lens and an optical lens produced therefrom.

Still another object of the present invention is to provide a resin composition for producing a low specific gravity, medium refractive index optical lens excellent in heat resistance, impact resistance, transparency, moldability, colorability, chemical resistance, and coating properties, and an optical lens manufactured therefrom.

In order to achieve the above object, the present invention is (A) 10 to 60% by weight of a bifunctional or more epoxy diacrylate compound having a bisphenol A skeleton represented by the following formula (1);

[Formula 1]

(Wherein R 1 is a methyl group and n is an integer from 1 to 4).

      (B) 0.1 to 10% by weight of an aliphatic acrylic acid compound having at least one functional group; (C) 10 to 35% by weight of an aromatic allyl compound having at least one functional group; And (D) 5 to 35% by weight of an aliphatic compound having two or more functional groups and three or more ether groups, to provide a low specific gravity, medium refractive index optical resin composition.

The component (B) is methacrylic acid, and the component (C) is styrene, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, m-diisopropenylbenzene, p-diiso Propylene benzene, alpha methyl styrene, etc., (D) component is trimethylol propane tri (meth) acrylate, the trimethylol propane tri (meth) acrylate to which alkylene oxide was added, alkylene glycol di (meth) acrylate, It is preferable that it is a pentaerythritol acrylate compound, a mixture thereof, etc.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a resin composition for producing a medium refractive index plastic lens having a bisphenol-A epoxy-based diacrylate derivative having excellent heat resistance as a basic skeleton, wherein the resin composition for an optical lens according to the present invention is (A) And bifunctional or higher epoxydiacrylate compounds having a bisphenol A skeleton represented by formula (1).

Wherein R 1 is a methyl group and n is an integer from 1 to 4.

The bisphenol A-based epoxy diacrylate component is obtained by reacting epichlorohydrin with acrylic acid in an equivalent weight equivalent, and then adding this to bisphenol A, or reacting n bisphenol-A with n epichlorohydrin, It can be obtained by reacting one epichlorohydrin with two acrylic acids, specifically 4,4- (1-methylethylidene) bisphenol polymer combined with chloromethyloxirane and 2-propenoate (4, 4- (1-methylethylidene) Bisphenol Polymer with (chloromethyloxirane, 2-propenoate)) can be illustrated. The component (A) functions to impart high refractive index, low water absorption, excellent heat resistance and surface precision. The content of the bisphenol A-based epoxy diacrylate component is 10 to 60% by weight, preferably 20 to 50% by weight based on the total resin composition, and when the content of the component is less than 10% by weight, the refractive index, low absorption, and heat resistance , The physical properties such as surface precision is insufficient, and if more than 60% by weight may cause a problem that the Abbe number greatly decreases due to excessive increase in the refractive index.

The resin composition for an optical lens according to the present invention contains 0.1 to 10% by weight, preferably 1 to 5% by weight of an aliphatic acrylic acid compound having one or more functional groups as the component (B). The aliphatic acrylic acid compound plays an important role in improving the mechanical strength of the polymerized lens, and specifically, methacrylic acid may be exemplified. When the content of the aliphatic acrylic acid compound exceeds 10% by weight, there is a risk of mold breakage due to the decrease in refractive index and strong adhesion to the mold, and in the case of less than 0.1% by weight, the mechanical strength of the polymerized lens may be lowered.

        Component (C) used in the present invention is an aromatic allyl compound containing at least one functional group. The aromatic allyl compound containing one or more functional groups improves the refractive index of the optical lens and functions to dilute other components, and those capable of radical copolymerization with other components are used. Specific examples of the aromatic allyl compound include styrene monomer, o-divinyl benzene, m-divinylbenzene, p-divinylbenzene, m-diisopropenylbenzene, and p-diisopropenyl. Benzene, alphamethylstyrene, mixtures thereof and the like can be exemplified, and styrene, o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene can be used particularly preferably. The content of the aromatic allyl compound is 10 to 35% by weight, preferably 15 to 25% by weight based on the total resin composition. If the content of the aromatic allyl compound exceeds 35% by weight, the Abbe number decreases due to the increase in the refractive index and When the lens is molded, the lens may be too hard to cause a problem of damage to the lens due to the impact, if less than 10% by weight may reduce the refractive index of the polymerized optical lens.

         Component (D) used in the present invention is an aliphatic (meth) acrylate compound having two or more functional groups and three or more ether groups, and such component (D) is easily crosslinked with other components of the resin composition, Not only does it function as a crosslinking agent for improving the heat resistance, Abbe's number and impact resistance of the polymerized lens, but also serves as a diluent because of its low viscosity. Specific examples of the component (D) include trimethylolpropane tri (meth) acrylate, trimethylolpropane (EO) 15 mole triacrylate added with 15 mol of ethylene oxide, and trimethylolpropane (EO) added with 6 mol added ethylene oxide. Trimethylolpropane tri-added with alkylene oxide such as 6 mole triacrylate, trimethylolpropane (PO) added with 3 mol of propylene oxide, trimethylolpropane (EO) triacrylate added with ethylene oxide ( Alkylene glycol di (meth) acrylates, such as meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate, and propylene oxide are added. Pentaerythritol triacrylate, pentaerythritol triacrylate with ethylene oxide added, ethylene jade Pentaerythritol acrylate compounds, such as pentaerythritol tetraacrylate with a side added, a mixture thereof, etc. can be illustrated, The content is 5-35 weight% with respect to the total resin composition, Preferably it is 10-30 weight %to be. At this time, if the content of the component exceeds 35% by weight, the lens is very soft, workability during demolding, there is a problem of mold damage, if the content of the component is less than 10% by weight, the heat resistance of the polymerized lens, Abbe There exists a possibility that water and impact resistance may fall.

If necessary, radical copolymerization may also be carried out by post-adding a thiol compound of 0 to 10% by weight, more preferably 0.1 to 10% by weight, to the resin composition for an optical lens according to the present invention. The thiol compound included in the post-treatment improves the heat resistance of the resin and, since it contains sulfur atoms in the molecule, serves to increase the refractive index of the lens, it is preferable to use a bifunctional or higher thiol compound. In addition, the thiol compound may be used together with other components of the present invention to promote crosslinking between resins, and have an additional effect of improving impact resistance and transparency of the polymerized lens. Specific examples of such thiol compounds include dimercaptodiethyl sulfide, ethanedithiol, trimethylolpropane trimercaptopropionate, bis (mercaptomethyl) sulfide, bis (mercaptopropyl) sulfide, and 2-mercapto Polythiol compounds, such as ethyl ether bis (3-mercapto propionate) and mixtures thereof, can be illustrated. Moreover, the composition for plastic lenses of this invention may also contain various additives, such as antioxidant, a yellowing agent, a ultraviolet absorber, dye, as needed in the range which does not impair the effect of this invention.

In the composition for plastic lenses of the present invention, in the presence of a polymerization initiator, the components (A) to (D) are mixed and stirred in a conventional manner, a thiol compound is added as a post-addition as necessary, and then radical copolymerized to provide an optical lens. It can be used to prepare, and if necessary, various additives may be combined. As a polymerization initiator used for hardening of the composition for optical lenses which concerns on this invention, Organic peroxides, such as benzoyl peroxide, t-butylperoxy isobutylate, t-butylperoxy-2-ethylhexanoate; Azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); Photoinitiators, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, methylphenylglyoxylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, can be illustrated. The blending ratio of such a polymerization initiator is usually 0.01 to 5 parts by weight based on 100 parts by weight of the components (A) to (D). In the polymerization curing method, the composition of the present invention including the polymerization initiator is injected into a mirror polished two glass plate molds through a gasket made of ethylene-vinyl acetate copolymer, and the mixture is heated at a temperature of 35 to 100 ° C. for about 20 hours. The polymerization can be carried out by heating from one or both sides of the mold. As the mold, glass and glass, glass and plastic plates, glass and metal plates, or a combination thereof may be used. As the gasket, a polyester adhesive tape may be used in addition to the thermoplastic resin. When the curing of the polymer is complete, annealing is performed at a temperature of 100 ° C. or higher according to a conventional method. In addition, if necessary, the surface of the optical lens may be polished, or may be further subjected to physical and chemical treatments such as antistatic treatment, hard coat treatment, anti-reflective coating treatment, and dyeing treatment.

The optical lens obtained by curing the resin composition for an optical lens according to the present invention is polymerized in a short time, so that the productivity is high, the refractive index (n ^D ₂₀ ) is 1.55 or more, usually 1.595 or less, specific gravity is 1.20 or less, Abbe number Is 40 or more, and has excellent physical properties such as transparency, optical uniformity, impact resistance, visible light transmittance, polishing processability, colorability, heat resistance, and low absorption. In addition, the optical lens obtained by curing the resin composition according to the present invention is a lightweight three-dimensional crosslinking, mainly made of a polyvinyl bond by a reactive unsaturated group, excellent productivity, low viscosity, which is an advantage of the conventional aryl and acrylic resin, And low water absorption and the advantages of the conventional urethane resin has a medium refractive index, high Abbe water, heat resistance, surface precision, excellent surface hardness and impact resistance at the same time, the specific gravity can be reduced to reduce the weight of the lens. In addition, unlike the existing CR-39, which requires a long time for synthesis and production, the compounding and processing process can be shortened to prevent productivity loss and reduce production costs.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples the units of each component content are in weight percent.

[Example 1-6, Comparative Example 1-2]

After uniformly mixing and stirring the compounds of the contents and ingredients shown in Table 1 below, dimercaptodiethylsulfide, a thiol compound, was added as a post addition as necessary, followed by 2,2'-azobis (2,4 0.3 parts by weight of dimethylvaleronitrile) and stirred again. The mixture was poured into two glass molds, heat cured for 20 hours at a temperature of 35 to 100 ° C. according to a conventional method, and then cooled to 65 ° C. when curing was completed, and then the cured molding was taken out of the mold, and then at 110 ° C. Annealing for 1 hour to remove residual stress to prepare a plastic lens. Evaluation of physical properties of the prepared optical plastic lens is shown in Table 1 below.

Raw material name Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 BPA-EDA 47 47 47 47 47 55 56 BP-2-EMA 54 TMPTMA 10 5 9 TEGDMA 8 9 PTTA 28 TMP (EO) 15mol TA 28 TMP (EO) 6 mol TA 28 TMP (EO) TA 28 TMP (PO) 3 mol TA 28 MAA One One One One One One MMA 15 15 HEMA 6 HDDA 18 SM 23 23 23 23 23 25 5 5 a -MSD One DVB 1.5 DMDS (Referral) One One One One One One 0.5 Refractive index ( n D20) 1.5594 1.5531 1.5558 1.5535 1.5508 1.5609 1.5490 1.5480 Abbe number ( v D20) 41 42 42 42 43 41 41 40 Specific gravity (g / cm3) 1.14 1.14 1.14 1.14 1.14 1.15 1.17 1.18 Impact resistance O O O O O O O O Weather resistance O O O O O O Ⅹ Ⅹ Dyeability O O O O O O Ⅹ O Heat resistance O O O O O O Ⅹ O Optical distortion O O O O O O O Ⅹ

In Table 1, BPA-EDA chloromethyloxirane and 2-propenoate are bonded to 4,4- (1-methylethylidene) bisphenol polymer, and BP-2-EMA is diethylene oxide added. Diethyleneoxide added Dimethacylate of Bisphenol A, TMPTMA stands for trimethylolpropane trimethacrylate, TEGDMA stands for triethyleneglycol dimethacrylate, PTTA stands for petaerythritol triacrylate ( Pentaerythritol Triacrylate), TMP (EO) 15 mol TA is trimethylolpropane (EO) 15 mole triacrylate with 15 mol ethylene oxide added, TMP (EO) 6 mol TA is trimethylol propane (6 mol ethylene oxide added) EO) 6mole triacrylate, TMP (EO) TA is trimethylolpropane (EO) triacrylate with ethylene oxide added, TMP (PO) 3mol TA is trimethyl with 3 mol propylene oxide added Propane (PO) 3mole tree represents an acrylate. MAA stands for methacrylic acid, MMA stands for methyl methacrylate, HEMA stands for hydroxyethyl methacrylate, HDDA stands for hexanediol diacrylate, SM stands for styrene monomer, a-MSD stands for a-MethylStyrene Dimonomer, m-DVB-57 stands for m-divinylbenzene (57%), and DMDS stands for dimercaptodiethyl Represents sulfide.

In addition, the evaluation method of each physical property shown in Table 1 is as follows.

(1) Refractive index, Abbe's number: It measured at 20 degreeC using the Folfrihi refractometer.

(2) Specific gravity: The ratio of the weight and the volume of the plastic lens was determined by an underwater substitution method.

(3) Impact resistance: The lens was manufactured with a center thickness of 1.8mm and a diameter of 80mm and subjected to a falling ball test using steel balls of 68g at a height of 127cm (according to the FDA standard). It was set as x.

(4) Heat resistance: The lens was kept at 130 ° C. for 2 hours, and if there was no change in deformation, cracking, yellowing, etc., it was indicated as ○, and if the change was severe, ×.

(5) Dyeing property: In the dyeing bath, dyeing was performed simultaneously with the diethylene glycol bisallylcarbonate resin, and the thing dyed equally or more by visual observation was ○, and the thing falling was ×.

(6) Weather resistance: The lens was set in a weather resistance tester equipped with a sunshine carbon discharge lamp, and the lens was taken out after 200 hours and the color was compared with the lens before the test. When there was no change of color, it changed into (triangle | delta), (triangle | delta), and yellow when it changed to yellow slightly.

From the above Table 1, the medium refractive index optical lens obtained by curing the resin composition for an optical lens according to the present invention has a refractive index, impact resistance, weather resistance, heat resistance, dyeing resistance, optical distortion, etc., unlike a resin comprising a conventional epoxy and acrylic acid reaction. In addition to good physical properties, it can be seen that there is an advantage that the light weight of the lens is low density.

As described above, the resin composition for an optical lens according to the present invention not only has a medium refractive index and a high Abbe number, but also has a lightweight three-dimensional crosslinking bond, and has weather resistance, heat resistance, dyeing property, light safety, visible light transmittance, and polishing property. Etc. It can be used to manufacture a medium refractive index optical lens with good physical properties.

Claims (7)

(A) 10 to 60% by weight of a bifunctional or higher epoxydiacrylate compound having a bisphenol A skeleton represented by the following formula (1); [Formula 1] (Wherein R 1 is a methyl group and n is an integer from 1 to 4). (B) 0.1 to 10% by weight of an aliphatic acrylic acid compound having at least one functional group; (C) 10 to 35% by weight of an aromatic allyl compound having at least one functional group; And (D) A low specific gravity, medium refractive index optical lens resin composition comprising 5 to 35% by weight of an aliphatic compound having two or more functional groups and three or more ether groups. The resin composition of claim 1, wherein the compound represented by Chemical Formula 1 is a 4,4- (1-methylethylidene) bisphenol polymer having chloromethyloxirane and 2-propenoate bonded thereto. The component (B) is methacrylic acid, and the component (C) is styrene, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, and m-diisopropenylbenzene. , p-diisopropenylbenzene, alphamethyl styrene, and mixtures thereof. According to claim 1, wherein the component (D) is trimethylolpropane tri (meth) acrylate, trimethylol propane tri (meth) acrylate to which alkylene oxide is added, alkylene glycol di (meth) acrylate, pentaeryte A resin composition for an optical lens, which is selected from the group consisting of a lithol acrylate compound, and a mixture thereof. (A) 10 to 60% by weight of a bifunctional or higher epoxydiacrylate compound having a bisphenol A skeleton represented by the following formula (1); [Formula 1] (Wherein R 1 is a methyl group and n is an integer from 1 to 4). (B) 0.1 to 10% by weight of an aliphatic acrylic acid compound having at least one functional group; (C) 10 to 35% by weight of an aromatic allyl compound having at least one functional group; (D) 5 to 35% by weight of an aliphatic compound having two or more functional groups and three or more ether groups; And (E) A low specific gravity, medium refractive index optical lens resin composition containing 0.1 to 10% by weight of a thiol compound. 6. The thiol compound according to claim 5, wherein the thiol compound is dimercaptodiethyl sulfide, ethanedithiol, trimethylolpropane trimercaptopropionate, bis (mercaptomethyl) sulfide, bis (mercaptopropyl) sulfide, 2- A resin composition for a low specific gravity, medium refractive index optical lens, selected from the group consisting of mercaptoethyl ether bis (3-mercaptopropionate) and mixtures thereof. The optical lens manufactured by radically polymerizing the resin composition for optical lenses of any one of Claims 1-6.