KR100677864B1 - a material for plastic lense blockable ultraviolet - Google Patents

Abstract

The present invention

Formula 1

40-70% by weight, where m represents an integer of 1-10

Formula 2

10-40 weight% of monomers where R 'represents 1-8 carbon atoms

Formula 3

5-30% by weight of monomers, wherein R2 is represented by 1-4 carbon atoms

Formula 4

Here, R₃ contains 1-10% by weight of monomer represented by 0-5 carbon number and 0.1-2% by weight of benzotriazole UV absorber. The present invention relates to a polymer composition and a plastic lens having UV blocking ability.

Description

Optical raw material for plastic lens with UV blocking ability {a material for plastic lense blockable ultraviolet}

The present invention relates to a composition for molding polymerization useful as an optical material capable of imparting UV blocking ability to a plastic lens and to manufacturing a plastic lens having UV blocking ability.

In general, ultraviolet rays to be blocked in optical lenses refers to a tube of 200-400nm wavelength, which is known to adversely affect the human body, especially when our eyes are overexposed to ultraviolet rays. It is known. The effect of ultraviolet rays on our eyes can be classified into three classes. The rays with wavelengths below 286 nm are mostly filtered or absorbed by the ozone layer in the atmosphere, but in the western part of western Europe due to the destruction of the ozone layer due to the recent pollution of the global environment. There is a risk of exposure. When our eyes are exposed to this wavelength, it is recognized that blindness can occur, and light with a wavelength of 286-320nm can be absorbed through the ozone layer to the eye film. And can damage the cornea. The wavelength of 320-400nm is a harmful wavelength that passes through the ozone layer, penetrates the cornea and lens of the eye and reaches the retina. When the eye is overexposed to this wavelength, it can cause yellow cataract, daylight cataract and blindness. Macular degeneration, solar retinopathy, and corneal dystrophy can be triggered. Therefore, in order to prevent the harmful wavelengths from reaching our eyes, the first method of imparting ultraviolet absorbing ability to plastic lenses is to first disperse the ultraviolet absorber in a solvent of high temperature and impregnate the molded plastic lens with the dispersion for several minutes. There is a method of manufacturing a UV blocking lens by penetrating the UV absorber into the lens, and the second method is to coat the plastic lens on the plastic lens by vacuum deposition inorganic material having ultraviolet absorbing ability. Third, the most economical method is to add a UV absorber when molding the plastic lens.

First, a method of impregnating a plastic lens into a solution in which a substance such as 2,2-dihydroxy-4,4-dimethoxybenzophenone is dissolved as an ultraviolet absorber is described in Japanese Patent No. Hei 9-269401 and Hei 1-230003. The problem is that the current lens manufacturing process, that is, the addition of an ultraviolet absorber process to the molding, hard coating, glass deposition, and the deformation of the plastic lens due to the uniformity of quality and high impregnation temperature. Second, a method of imparting UV blocking ability to a plastic lens by vacuum deposition has been introduced in Japanese Patent No. Hei 9-269401, but this method also requires no high temperature, so no specific method has been introduced. Third, a method of forming a lens by directly adding a UV absorber to the raw material of plastic, excellent in the uniformity of the compulsory force and quality has been a lot of development attempts so far. Among them, m-xylene diisocyanado, 1,2-bis [(2-mercaptoethyl) thio-3-mercaptopropane, tetrakis (mercaptomethyl) methane, dibutyl tin dilaurate as main raw materials of plastic lens Like the mixture, a urethane optical material or a mixture of styrene, bisphenol A diglycidyl ether dimethyl acrylate, polyethylene glycol di (meth) acrylate, benzyl (meth) acrylate, and the like is used. -Butyl peroxydicarbonate, di-n-propylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy pivalate, t-butylperoxy neodecanoate, Organic peroxides such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,2-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2-azobis Isobutyrate, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylbare In the case of the plastic lens manufactured using Nitrile), the UV absorber was added directly to the optical raw material to produce the plastic lens directly without severe yellowing. There is a problem that the optical raw material is dissolved. In order to solve this problem, there is a method of fixing a glass mold using a polyester tape, when using this method, there is a problem that the assembly speed of the mold is low and the lens break rate is high when the plastic is detached from the glass mold after molding.

Currently, the main raw material of the refractive index 1.55 plastic lens, which is used most frequently in Korea, is a direct injection of a UV absorber into a mixture of modified diaryl phthalate, alkylene glycol bis aryl carbonate, and diisopropyl peroxydicarbonate as a polymerization initiator. In the case of manufacturing a plastic lens by using a gasket made of polyethylene vinyl acetate copolymer, it is excellent in workability but has a problem of severe yellowing (YI value is 9.5).

An object of the present invention satisfies the physical properties such as high refractive index, thermal stability, solvent resistance, impact resistance, low specific gravity, etc. that a good plastic optical lens should have, and in particular, an optical material having excellent UV blocking property and excellent workability and colorless transparency. In providing.

In the present invention

Formula 1

40-70 wt% of monomers where m represents an integer of 1-10

Formula 2

10-40% of monomers where R 'represents 108 carbon atoms

Formula 3

5-30% by weight of monomers, where R2 is represented by 1-4 carbon atoms

Formula 4                         

It is to propose a composition of an optical raw material containing 1-10% by weight of monomer represented by 0-5 carbon number, 0.1-2% by weight of a benzotriazole-based ultraviolet absorber and a small amount of a mixture of red and blue pigments.

The resin composition for manufacturing a sunscreen plastic lens of the present invention contains the monomer (1) represented by the formula (1), the monomer (2) represented by the formula (2), and the monomer (3) represented by the formula (3) in a specific blending ratio. .

Formula 1 obtained by the transesterification reaction is difficult to control the exact molecular weight distribution, but m represents an integer of 1-15, the weight ratio of m = 0 is 10-60%, the weight ratio of m = 1-3 is 20-60 %, the weight ratio of m = 4-10 is 0-40%, and the weight ratio of m = 11 or more is 0-20%. If the weight ratio of m = 0 is lower than 10%, the viscosity is remarkably high, and a lot of bubbles are formed when the optical raw material is injected into the glass mold, and the defect rate of the lens is high. Moreover, there exists a fault which is inferior in impact resistance. If the weight ratio of m = 11 or more is 20% or more, the viscosity increases, and there is a tendency for polymerization imbalance to occur severely when molding the lens. Formula 2 is also obtained by transesterification and R 'represents an integer having 1 to 8 carbon atoms. When the carbon number is 2 or less, the impact strength of the lens tends to be low, and when the carbon number is 6 or more, the heat resistance of the lens tends to be inferior. Therefore, in order to satisfy impact strength and heat resistance, it is preferable that carbon number is 3-5. In formula (3), R₂ represents carbon number of 1-4, which puts the UV absorber directly into the optical raw material and prevents the UV-blocking lens from becoming too yellow during molding. Is excellent, but when the carbon number of R2 is 3 or more, there is a problem that the heat resistance and thermal stability of the lens is sharply dropped. In addition, when the content of Formula 3 is less than 10% by weight, it does not show a great effect on preventing yellowing of the lens. R 3 in Formula 4 represents a carbon number of 0-5, and improves weather resistance and heat resistance of the plastic lens and the secondary role of the formula 3 in preventing yellowing of the lens. The ultraviolet absorber is 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- (3-hydroxy-5-t-octylphenyl) benzotriazole, 2- [4 -[2-hydroxy-3-dodecylpropyloxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl0-1,3,5-triazine, 2- (2- Hydroxy-benzotriazole-2-phenyl) -p-cresol, 2- (2-hydroxybenzotriazole-2-phenyl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2 In -2'-hydroxy-3'-butyl-5'-methylphenyl) -5-chlorobenzotriazole,

Formula 5

The use of 2- (2'-hydroxy-3'-butyl-5'-methylphenyl) -5-chlorobenzotriazole was excellent in UV protection effect and less yellowing. The pigment was added to the monomer mixture by diluting blue pigment and red pigment in diethylene glycol bisaryl carbonate.

The monomer mixture for manufacturing the UV-blocking plastic lens of the present invention is cured to produce 2,2-azobis (2,4-dimethylbareronateyl), diisopropylperoxydicarbonate, Di-n-propyloxycarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy neodecanoate, t-butylperoxy Pival gate, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxy neodecanoate and the like Although it is possible to use, it is preferable to use 1-5 parts by weight of diisopropylperoxydicarbonate based on 100 parts by weight of the monomer composition.

The monomer mixture for manufacturing the UV blocking lens of the present invention has a low shrinkage rate during curing and has a low molding defect rate, and satisfies the physical properties of the optical raw materials such as impact resistance, heat resistance, thermal stability, and transparency, and wavelengths up to 400 nm without large yellowing. It is useful as a material for the lens that can block.

Example

Hereinafter, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited thereto.

Example 1

As the monomer (1), 55 parts by weight of the compound represented by the formula (6), 20 parts by weight of the compound represented by the formula (7) represented by the monomer (2), 20 parts by weight of the formula (8) represented by the monomer (3), and the monomer (4) Mix 5 parts by weight of the formula (9), and add 0.3 g of 2- (2'-hydroxy-3'-butyl-5'-methylphenyl) -5-chlorobenzotriazole as an ultraviolet absorber and diisopropyl as a curing catalyst. 3 g of peroxydicarbonate were mixed. The mixture was poured into a mold consisting of two glass plates and an ethylene-vinylacetate copolymer, heated at 35 ° C. in a hot air oven for 2 hours, heated at 35 ° C. to 40 ° C. for 3 hours, and heated at 40 ° C. to 85 ° C. It heated at 85 degreeC for 2 hours, after heating for 12 hours, heating up. After heat curing, the resultant was cooled to 80 ° C. to remove the cured molding from the mold, and annealing was performed at 120 ° C. for 2 hours to remove residual stress, thereby preparing an optical plastic material. The physical property evaluation of the prepared optical material was performed as follows. The monomer composition, the type and amount of ultraviolet absorber are shown in Table 1, and the results of physical property measurement are shown in Table 2.

Formula 6

(m distribution: m = 0 for 40% by weight, m = 1 for 30% by weight, m = 2 for 15% by weight, m = 3 for 7% by weight, m = 4 for 5% by weight, and m = 4 or more Weight ratio 3%)

Formula 7

(R 'is 4 carbon atoms)                     

Formula 8

(R₂ is 2 carbon atoms)

Formula 9

(R₃ has 0 carbon atoms)

Impact resistance: The lens was manufactured with a center thickness of 1.8 mm and a diameter of 80 mm, and a height of 127 cm was raised to 127 cm to drop 68 g of steel balls.

Heat resistance: The lens was kept at 130 ° C. for 2 hours, and if there was no change in deformation, cracking or yellowing, 0 was indicated as X.

Refractive index: It was measured using a 1T model of Refractometer Atacota.

Light transmittance and UV blocking rate: measured using a spectrophotometer.

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

Solvent resistance: After immersing the plastic lens in acetone and methylene chloride for 2 hours, if there is no crack or fluctuation of the plastic lens, 0 is indicated as X.

YI: Measured using a chromatic colorimeter.                     

Example 2-11

Except having used the monomer and ultraviolet absorber shown in Table 1, it manufactured similarly to Example 1, and measured the physical property of the plastic lens, and shows the physical property in Table 2.

Comparative Example 1

As the monomer (1), 80 parts by weight of the compound represented by the formula (10),

Formula 10

(distribution of m: 65% by weight of m = 0, 14% by weight of m = 1, 39% by weight of m = 3 or more) and 20 parts by weight of diethylene glycol bisaryl carbonate, where 2- 0.3 g of (2'-hydroxy-3'-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 3 g of diisopropyl peroxydicarbonate were mixed with a curing catalyst and cured in the same manner as in Example 1. And measured physical properties are shown in Table 2.

Comparative Example 2-5

Except having used the monomer and ultraviolet absorber shown in Table 1, it manufactured similarly to Example 1, and measured the physical property of the plastic lens, and shows the physical property in Table 2.

Table 1

 Monomer 1 (% by weight)  Monomer 2 (% by weight)  Monomer 3 (% by weight) Monomer 4 (% by weight) UV absorbers  Example 1    55    20    20     5 2- (2hydroxy-3-butyl-5'-methylphenyl) -5-chlorobenzotriazole  Example 2    65    20    10     5        //  Example 3    70    20     5     5        //  Example 4    60    20    20        //  Example 5    55    20    20     5 2-hydroxy-4-methoxybenzophenone  Example 6    55    20    20     5 2-hydroxy-3,5-dimylphenylbenzotriazole  Example 7    55    20    20     5 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-butyloxyphenyl) -1,3,5-triazine  Example 8    55    20    20     5 2- (3-hydroxy-5-octylphenyl) benzotriazole                                           Example 9    55    20    20     5 2- [4- (2-hydroxy-3-dodecylopropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine  Example 10    55    20    20     5 2- (2-hydroxy-benzotriazole-2-phenyl) -p-cresol  Example 11    55    20    20     5 2- (2-hydroxybenzotriazole-2-phenyl) -4,6-bis (1-methyl-1-phenylethyl) phenol  Comparative Example 1    80    20 2- (2hydroxy-3-butyl-5'-methylphenyl) -5-chlorobenzotriazole  Comparative Example 2    80    20  Comparative Example 3    80    20 2-hydroxy-4-methoxybenzophenone  Comparative Example 4    80    20 2- (3-hydroxy-5-octylphenyl) benzotriazole  Comparative Example 5    80    20 2-hydroxy-3,5-dimylphenylbenzotriazole

                    TABLE 2

 Refractive index   importance  Light transmittance Impact resistance Solvent resistance  Heat resistance UV protection rate   YI Example 1   1.55   1.28   90.1     0     0     0    96   4.0 Example 2   1.548   1.276   90.0     0     0     0    95   7.5 Example 3   1,546   1.275   89.7     0     0     0    96   8.5 Example 4   1.551   1.281   89.9     0     0     x    96   4.1 Example 5   1.55   1.28   90.2     0     0     0    74   4.7 Example 6   1.55   1.28   90.0     0     0     0    70   4.6 Example 7   1.55   1.28   89.8     0     0     0    70   4.2 Example 8   1.55   1.28   89.8     0     0     0    72   4.8 Example 9   1.55   1,28   88.9     0     0     0    74   4.5 Example 10   1.55   1.28   90.1     0     0     0    70   4.6 Example 11   1.55   1.28   90.1     0     0     0    70   4.5 Comparative Example 1   1.55   1.27   90.0     0     0     0    96   9.8 Comparative Example 2   1.55   1.27   89.9     0     0     0    65   2.7 Comparative Example 3   1.55   1.27   89.9     0     0     0    74   8.5 Comparative Example 4   1.55   1.27   90.1     0     0     0    74   8.5 Comparative Example 5   1.55   1.27   90.0     0     0     0    70   8.9

As shown in the above Examples and Comparative Examples, according to the method of the present invention, it is possible to obtain a plastic lens that can block the ultraviolet wavelength of 320-400nm (UV-A) without significant yellowing phenomenon.

Claims (3)

40-70% by weight of the polymerization component 1 of the diaryl phthalate component represented by the following formula (1), Formula 1

(Where m is an integer 1-10) 10-40% by weight of the weight component 2 represented by the following formula (2), Formula 2

(Here R₁ = 1-8 carbon number) 5-30% by weight of the polymerization component 3 represented by the following formula (3) Formula 3

(Where R₂ represents 1-4 carbon atoms) The monomer mixture for optical lenses obtained by mixing. The method of claim 1, A monomer mixture for an optical lens further comprising 1-10% by weight of the polymerization component 4 represented by the following formula (4). Formula 4

Where R₃ represents 0-5 carbon atoms The method of claim 1, A monomer mixture for an optical lens, further comprising a ultraviolet absorber consisting of 2- (2'-hydroxy-3'-butyl-5'-methylphenyl) -5-chlorobenzotriazole.