KR20070089601A - Resin composition for producing optical lens having improved physical and chemical character, and optical lens produced with the same - Google Patents

Abstract

Provided are a resin composition for an optical lens which is excellent in dyeing property, weather resistance, heat resistance, impact resistance and lightweightness, and an optical lens prepared by polymerizing the composition. A resin composition comprises 18-50 parts by weight of a bisphenol epoxy compound represented by the formula(1) (wherein R1 and R2 are independently H or CH3; and n is an integer of 0-5); 5-40 parts by weight of a (meth)acrylate aliphatic compound having at least two functional groups; 20-50 parts by weight of an aromatic allyl compound having at least one functional group; and 30-60 parts by weight of a brominated bisphenol epoxy compound represented by the formula(2) (wherein R1 are independently H or CH3).

Description

Resin composition for producing optical lens having improved physical and chemical character, and optical lens produced with the same}

The present invention relates to a resin composition for an optical lens, and more particularly, a resin composition capable of producing optical lenses having good physical properties such as dyeing, elasticity, impact resistance, weather resistance, heat resistance, light weight, transparency, and the like by high-speed polymerization; It relates to an optical lens manufactured using the same.

Plastic lenses are lighter and less fragile than inorganic glass lenses, so they are not only advantageous for wearing and protecting the eyes, but also have the function of accessories in a modern society where fashion is important because they are easily molded and colored. The plastic lens overcomes the problems of weak impact resistance and high specific gravity of the glass lens, and was manufactured using polystyrene, polyethylene glycol bis aryl carbonate, polycarbonate, and modified diaryl phthalate as the main raw materials. Lenses have low scratch resistance and low resistance to organic solvents, and their use has been limited. In particular, the plastic lens made of polyethylene glycol bis aryl carbonate is excellent in light weight, moldability, dyeing, impact resistance, but has a disadvantage that the edge thickness of the lens becomes thick due to low refractive index of 1.50. In European Patent EP # 06905A2, 15 to 50 parts by weight of styrene, 10 to 50 parts by weight of an epoxy resin reactant of acrylic acid and bisphenol-A, 5 to 40 parts by weight of acrylic acid and bistetrabromobisphenol-A type epoxy resin reactant and divinylbenzene , Diaryl diphenylate, vinyl toluene, chlorostyrene, etc. discloses a resin composition for manufacturing a lens containing 5 to 20 parts by weight, but the lens made of the resin has a disadvantage of poor thermal stability.

In the case of spectacle lenses, the total weight of the lens is preferably as light as possible from a physical and optical standpoint. Such light weight has become an important reason for the widespread use of plastic lenses, but in general, plastic lenses have a low refractive index, which has the disadvantage of increasing the center thickness, peripheral thickness, and curvature of the lens compared to inorganic glass lenses. Currently, the resin mainly used as a lens for spectacles is diethylene glycol bisallylcarbonate polymer (PPG Industries Co., trade name CR-39), but the lens made of the resin is also lower than 1.52, which is the refractive index (n ^D ) of the inorganic glass lens. It has a refractive index of 1.50. Therefore, the resin is widely used in lenses having a thin edge thickness of less than -3.00, but it is difficult to use in more than that. Polycarbonates (n ^D = 1.58), polystyrenes (n ^D = 1.60), and the like are known as polymers capable of manufacturing lenses having a relatively high refractive index, but lenses made of these polymers have poor polishing processability and high surface hardness. Low scratch resistance is low, and resistance to organic solvents is weak. In order to overcome these disadvantages, various methods have been developed for producing stereocrosslinked plastic lenses having excellent wear resistance and high refractive index, such examples being (1) diacrylate or dimetha derived from bisphenol-A as a main component. Method of using methacrylate (Japanese Patent Laid-Open No. 116,301 / 83), (2) Method of using diacrylate or dimethacrylate derived from halogenated bisphenol-A (Japanese Patent Laid-Open No. 10,491 / 82), (3) a method using a combination of a halogenated styrene monomer and a polyfunctional methacrylate (Japanese Patent Publication Nos. 104,101 / 82, 28,118 / 82 and 28,116 / 82) and (4) diallylphthalate monomers Known methods (Japanese Patent Laid-Open Nos. 212,401 / 82 and 15,513 / 83) and the like are known. However, the resins have a high strength, so the workability is poor, there is a problem that the dyeability is not good, there is room for improvement.

Currently, thermosetting optical monomers practically used for spectacle lenses are roughly classified into polycondensation monomers represented by thiourethane resins and radical monomers represented by acrylic and vinyl compounds. The thiourethane resin has the advantage of manufacturing a lens having high refractive index and impact resistance, but is widely used as an optical resin such as for spectacle lenses, but the resin is produced by producing a urethane bond by condensation reaction of thiol and isocyanate. In order to perform the polymerization while maintaining the optical uniformity, not only a polymerization time of 24 hours or more is required, but the thiourethane resin is sensitive to moisture, and thus has a very difficult working condition. Therefore, the thiourethane resin is excellent in terms of performance as a resin, but there is room for improvement in terms of productivity. Meanwhile, a method of adding an alcohol to a reaction product of bisphenol A epoxy and acrylic acid as an acryl or vinyl compound, and mixing a styrene or an acrylic monomer thereto to form a plastic lens (Korean Patent Publication No. 1998-23955) is disclosed. However, the resin has a problem of poor dyeability. Therefore, the physical properties such as light weight, impact resistance, moldability, heat resistance, weather resistance and the like are excellent at the same time, in particular, the research on the production of plastic lens raw material and plastic lens excellent in dyeing is continuously performed.

Accordingly, an object of the present invention is to provide a resin composition for producing an optical lens having a three-dimensional crosslinking bond excellent in physical properties such as dyeability, light weight, impact resistance, heat resistance, light safety, visible light transmittance, polishing processability.

Another object of the present invention is to provide a resin composition for producing an optical lens capable of high-speed polymerization by radicals.

In order to achieve the above object, the present invention (A) 18 to 50 parts by weight of the bisphenol-type epoxy compound represented by the formula (1);

[Formula 1]

(Wherein R ₁ and R ₂ are each independently H or CH ₃ and n is an integer from 0 to 5).

(B) 5 to 40 parts by weight of (meth) acrylate aliphatic compound having two or more functional groups;

(C) 20 to 50 parts by weight of an aromatic allyl compound having at least one functional group; And

(D) It provides the resin composition for optical lenses containing 30-60 weight part of bromine type bisphenol-type epoxy compounds represented by following formula (2).

[Formula 2]

Wherein R ₁ is independently H or CH ₃ .

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

The present invention relates to a resin composition based on an epoxy derivative having a high refractive index as a basic skeleton, and has a high refractive index, light weight and impact resistance by replacing bromine in an epoxy compound, and having two or more functional groups (meth). By using the acrylate compound, disadvantages such as heat resistance, weather resistance, dyeing property, elasticity, polishing processability, etc., which are disadvantages of the epoxy resin, are improved, and in particular, the dye composition is significantly improved in the resin composition.

The resin composition for optical lenses which concerns on this invention contains the bisphenol-type epoxy compound represented by following formula (A) as a main component.

[Formula 1]

In the above formula, R ₁ and R ₂ are each independently hydrogen or a methyl group, and n is an integer of 0 to 5. When n is 0, the bisphenol-type epoxy compound may be prepared by reacting acrylic acid with epichlorohydrin, and then adding bisphenol, and when n is 1 or more, reacting epoxy and acrylic acid in n: 1 equivalent weight. , Epichlorohydrin and bisphenol can be added. Specific examples of the compound include 4,4- (1-methylethylidene) bisphenol A (chloromethyl oxirane and 2-propenoate added 4,4- (1-methylethylidene) to which chloromethyloxirane and 2-propenoate are added. ) bisphenol A). The component serves to improve the refractive index, impact resistance, heat resistance, light weight and the like of the optical lens, the content is 18 to 50 parts by weight. If the content of the component is less than 18 parts by weight, impact resistance, refractive index and dyeing property is lowered, if it exceeds 50 parts by weight there is a problem that the heat resistance is lowered. In addition, when the content of the component exceeds 60 parts by weight, the refractive index is improved but the viscosity is increased, so that the liquid injection into the mold during casting operation is not smooth, productivity is reduced, and even if the lens is molded after casting • The appearance is poor, and the impact resistance may be rather deteriorated.

The (meth) acrylate aliphatic compound having two or more functional groups (B) contained in the resin composition for an optical lens according to the present invention improves heat resistance, transparency, dyeing and impact resistance of the optical lens, and dilutes other components. Do it. Specific examples of the compound include 2-hexanediol diacrylate, 2-hexanediol dimethacrylate, trimethol triacrylate added with 3 mol of propylene oxide, and trimethol triacryl added with 3 mol of ethylene oxide. And trimethol triacrylate added with 6 moles of ethylene oxide, trimethol triacrylate added with 10 moles of ethylene oxide, and the like. The content of the component is 5 to 40 parts by weight, if the content of the component is less than 5 parts by weight, the heat resistance, dyeing resistance is lowered, if the content exceeds 40 parts by weight there is a problem that the impact resistance, transparency, refractive index is lowered.

The aromatic allyl compound containing (C) at least one functional group included in the resin composition for an optical lens according to the present invention improves the refractive index of the optical lens, and functions to dilute other components. Use what is possible. Specific examples of the compound include styrene, alpha methyl styrene, alpha methyl styrene dimer, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, m-diisopropenylbenzene and p-diisopropenyl Benzene and the like, and particularly preferably styrene, alphamethylstyrene dimer and p-diisopropenylbenzene can be used. The content of the component is 20 to 50 parts by weight, preferably 20 to 35 parts by weight, and if the content of the component is less than 20 parts by weight, the viscosity is high, so that it is difficult to inject the liquid during casting, resulting in a decrease in productivity, exceeding 50 parts by weight. If the refractive index is lowered, the lens is too hard when the lens is molded, and the lens may be damaged by the impact.

The resin composition for an optical lens according to the present invention includes (D) a bromine bisphenol type epoxy compound represented by the following general formula (2).

[Formula 2]

In the above formula, R ₁ is independently hydrogen or a methyl group. The bromine bisphenol-type epoxy compound may be prepared by reacting acrylic acid with epichlorohydrin and then adding bromine bisphenol. Specific examples of the compound include tetrabromo bisphenol A diglycidyl ether diacrylate to which tetrabromo bisphenol A and acrylic acid are added. The component serves to improve the refractive index, impact resistance, solvent resistance, light weight and the like of the optical lens, the content is 30 to 60 parts by weight. If the content of the component is less than 30 parts by weight, it does not reach the refractive index of the lens, which leads to a large frequency deviation, which is not preferable for the optical, it is difficult to obtain a sufficient effect in terms of heat resistance. In addition, if the content exceeds 60 parts by weight, the surface strength is too strong to reduce the impact resistance and solvent resistance, and the refractive index is improved, but the viscosity is increased. However, even if the lens is molded after casting, the lens internal and external appearance is poor, and impact resistance may be rather deteriorated.

The resin composition for optical lenses of this invention can contain various conventional additives, such as antioxidant, a yellowing inhibitor, a ultraviolet absorber, and dye as needed, within the range which does not impair the effect of this invention. The optical lens composition of the present invention can be prepared by mixing and stirring (A), (B), (C) and (D) components in a conventional manner in the presence of a polymerization initiator, and radical copolymerizing the optical lens. In this case, various additives may be blended as necessary. As a polymerization initiator used for hardening of the composition for optical lenses of 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- dimethyl valeronitrile); 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 1 part by weight based on 100 parts by weight of the sum of the components (A), (B), (C) and (D). The polymerization curing method is, for example, injecting the composition of the present invention including a polymerization initiator into a mirror polished two glass plate molds through a gasket made of ethylene-vinyl acetate copolymer, and at a temperature of 34 to 100 ° C. for 21 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. Upon completion of curing of the polymer, annealing treatment is carried out for 1 hour and 30 minutes at a temperature of 110 ° 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 coating treatment, antireflective coating treatment, and dyeing treatment.

The resin composition for an optical lens according to the present invention contains, as a main component, a bisphenol epoxy compound in which bromine is not substituted in an appropriate ratio, and includes a bromine bisphenol epoxy compound, a (meth) acrylate aliphatic compound having two or more functional groups, and an aromatic compound. By achieving an optimal composition using a certain amount of allyl compound, the optical lens obtained by curing the resin composition has a low specific gravity of 1.20 or less, excellent physical properties such as transparency, optical uniformity and impact resistance, and particularly excellent dyeing property. Since the resin composition according to the present invention forms a polyvinyl bond by a reactive unsaturated group during curing, it is polymerized in a short time unlike conventional urethane resins, and thus has high productivity, and has water resistance unlike conventional urethane-based optical lenses sensitive to moisture. And process productivity can be improved by simplifying the process. Therefore, the resin composition according to the present invention has excellent productivity, low viscosity and low water absorption, which are advantages of the conventional aryl and acrylic resins, and high refractive index, high Abbe's number, heat resistance, surface precision, and surface which are advantages of the conventional urethane resin. There is an effect having hardness and impact resistance.

Hereinafter, the present invention through examples and comparative examples in more detail, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, the unit of each component content is parts by weight.

[Example 1-2, Comparative Example 1-4]

The compounds were uniformly mixed and stirred according to the ingredients and contents shown in Table 1 below, and 0.28 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added and stirred again. The mixture was poured into two glass molds and heat cured in a conventional manner at a temperature of 34 to 100 ° C. for 21 hours, then cooled to 60 ° C. after curing was completed, and then the cured molding was taken out of the mold, and 110 Annealing for 1 hour 30 minutes at ℃ to remove the 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 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 BPA-Polymer (A) Ingredient 25 18 40 45 TPA-GMA 22.4 22.4 BPA-4-EDA (B) Component 5 10 HDDA (B) ingredient 32 20 TMP-10-ETA (B) Component 5 5 DBMA 18 m-DVB (57%) (C) component 18 SM (C) component 22 22 29 29 28 25 TBBPA-Polymer (D) Ingredients 48 50 31.5 31.5 Refractive Index (n ^D ₂₀ ) 1.5960 1.5965 1.6100 1.5800 1.5560 1.5570 Abbe number (v ^D ₂₀ ) 35 35 38 39 40 39 Specific gravity (g / cm ³ ) 1.16 1.15 1.27 1.26 1.16 1.16 Molding state O O X O O O Impact resistance O O X O O O Weather resistance O O O O O O Dyeability O O X X O O Heat resistance O O O X O O Light transmittance 95% 95% 92% 93% 95% 96% UV cut 100% 100% 100% 100%

In Table 1, BPA-Polymer represents 4,4- (1-methylethylidene) bisphenol polymer to which chloromethyloxirane and 2-propenoate are added, and TPA-GMA represents thiopropyl acid (thiopropanoic acid). ) And glycidyl methacrylate with triethylamine, and BPA-4-EDA represents bisphenol A diacrylate with 4 moles of epoxy, and HDDA represents 2-hexanediol diacrylate. TMP-10-ETA represents trimetholpropanetriacrylate with 10 moles of epoxy added, DBMA represents dibenzyl methacrylate, and m-DVB-57 represents m-divinylbenzene (57% by weight solution). ), SM stands for styrene monomer, and TBBPA-Polymer stands for tetrabromo bisphenol A diglycidyl ether diacrylate.

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) Molding state (appearance): When there is no abnormality in color, stripes, etc., it is regarded as satisfactory.

(4) Impact resistance: The lens was manufactured with a center thickness of 1.8 mm and a diameter of 80 mm, and a lens (0.00 degree of power) was made and subjected to a falling ball test using a steel ball of 68 g at a height of 127 cm (according to the FDA standard). .

(5) Weather resistance: The lens was set in a weather resistance tester equipped with a sunshine carbon discharge lamp, the lens was taken out after 200 hours, and the color was compared with the lens before the test. If there was no change in color, the color was changed to O and yellow.

(6) Dyeing property: Dyeing was performed simultaneously with diethylene glycol bisallylcarbonate resin in a dyeing bath, and the dyeing of the same or more dyes by visual observation was O and falling.

(7) Heat resistance: The lens was kept at 130 ° C. for 2 hours. If there was no change in deformation, cracking or yellowing, O was indicated and Ｘ when the change was severe.

(8) Light transmittance and ultraviolet (UV) blocking rate: It measured using the spectrophotometer.

In Table 1, Examples 1 to 2 according to the composition of the present invention, while the overall physical properties are all excellent, in the case of Comparative Examples 1 to 2 that do not contain component (A) and component (B), respectively, the molding state, The impact resistance, heat resistance, and the like were poor, and among them, the dyeability was commonly poor, and Comparative Examples 3 to 4, which did not contain the component (D), had a problem of low refractive index. In addition, Examples 1 to 2 according to the present invention, unlike the resin (comparative examples 1 to 2) consisting of a conventional epoxy and acrylic acid reaction, it is found that the gelation does not occur during molding, the specific gravity is low, the lens has the advantage of light weight. Can be.

Experimental Example: Dyeing Test

The resin composition of Example 1 was colored for 2.5 minutes and 10 minutes at 95 ° C. using BPI colorant, and the transmittance was measured. The results are shown in Table 2 below.

Looking at the Table 2, the resin composition according to the present invention was found that the transmittance after coloring is significantly lower than the initial transmittance, the dyeing power is very excellent. On the other hand, in Comparative Examples 1 and 2, the difference in transmittance before and after coloring is about 10% at 95 ° C and 2.5 minutes, and about 20% at 10 minutes, which is very low compared to the resin composition of the present invention. Force.

As described above, the resin composition for an optical lens according to the present invention is effective in producing an optical lens having good physical properties such as light weight, weather resistance, heat resistance, impact resistance, light safety, visible light transmittance, polishing processability, as well as excellent dyeing properties. Can be used.

Claims (4)

(A) 18 to 50 parts by weight of the bisphenol-type epoxy compound represented by the formula (1); [Formula 1]

(Wherein R ₁ and R ₂ are each independently H or CH ₃ and n is an integer from 0 to 5). (B) 5 to 40 parts by weight of (meth) acrylate aliphatic compound having two or more functional groups; (C) 20 to 50 parts by weight of an aromatic allyl compound having at least one functional group; And (D) The resin composition for optical lenses containing 30-60 weight part of bromine type bisphenol-type epoxy compounds represented by following General formula (2). [Formula 2]

Wherein R ₁ is independently H or CH ₃ . According to claim 1, wherein the bisphenol-type epoxy compound of formula (A) is a 4,4- (1-methylethylidene) bisphenol polymer combined with chloromethyl oxirane and 2-propenoate, B) (meth) acrylate aliphatic compounds include 2-hexanediol dimethacrylate, 2-hexanediol diacrylate, trimethol triacrylate added with 3 moles of propylene oxide, and trimeth added with 3 moles of ethylene oxide. A resin composition for an optical lens selected from the group consisting of a tyrol triacrylate, a trimethol triacrylate added with 6 moles of ethylene oxide, a trimethol triacrylate added with 10 moles of ethylene oxide, and a mixture thereof. The method of claim 1, wherein the (C) aromatic allyl compound is styrene, alphamethylstyrene, alphamethylstyrene dimer, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, m-diisopropenylbenzene And a mixture thereof. The optical lens manufactured by radically polymerizing the resin composition for optical lenses of any one of Claims 1-3.