KR20200037002A - A hydrogel lens for blocking blue light using natural material - Google Patents

Abstract

The present invention relates to a blue light-blocking silicone hydrogel lens using natural products and, specifically, to a blue light-blocking silicone hydrogel lens using natural materials including hydrophilic acrylic monomers, wetting agents, crosslinking agents, initiators, and curcumin. According to the present invention as described herein, by adding curcumin which is a natural material to a contact lens composition to prepare a lens, it is possible to prepare a contact lens that is safe when worn on the eye while having a blue light blocking function at the same time, which has been difficult to implement in a conventional contact lens.

Description

Blue light blocking hydrogel lens using natural materials. {A HYDROGEL LENS FOR BLOCKING BLUE LIGHT USING NATURAL MATERIAL}

The present invention relates to a hydrogel lens having a blue light blocking function, and more specifically, a hydrogel lens that has a blue light blocking function and is safe for eyes while manufacturing a lens by adding curcumin, a turmeric extract component as a natural material, to the lens composition. It is about.

Contact lenses are used worldwide for purposes such as vision correction and beauty. In 2016, the contact lens market is steadily growing, with the number of contact lens wearers reaching 125 million worldwide, and the use of contact lenses is becoming increasingly important. Recently, researches on contact lenses having antibacterial activity have been made, and contact lenses have been studied as a drug delivery means to treat glaucoma, and lenses with high oxygen permeability are also being released.

On the other hand, due to the development of the IT industry, a lot of blue light is emitted from light sources such as CCFL or LED used to brightly display display screens such as smartphones, tablets, computers, TVs, etc., resulting in poor vision or glare, Fatigue, headaches, etc. are increasing. Blue light, which corresponds to a short wavelength region having a short wavelength among visible rays, is generally referred to as a 380nm to 500nm region in a wavelength range. Since the wavelength is short, scattering and refractive characteristics are large. Blue light is a cause of deteriorating the quality of the image on the retina because of its large scattering property. Also, because of its large refractive index, an image is formed on the front of the retina, causing chromatic aberration, causing eye fatigue and glare, and the shorter the wavelength, the higher the energy. There is a problem that causes adverse effects on the eye cells. In the case of blue-blocking eyeglass lenses sold in Korea, it shows a minimum of 14.11% to a maximum of 41.86%, which is due to differences in the blue-blocking method such as coloring or coating method and selection of an appropriate blocking rate. As described above, various blue-blocking spectacle lenses are commercially available and used, but contact lenses aimed at blue-blocking functions are still incomplete.

Ratner BD, Buddy D. A pore way to heal and regenerate: 21st century thinking on biocompatibility. Regenerative Biomaterials. 2016; 3 (2): 107-110. Lerdvitayasakul R, Kunavisarut S. Contact lens-related microbial keratitis. J Med Assoc Thai. 2007; 90 (4): 737-743.

In order to solve the conventional problems as described above, the present invention is to reduce the transmittance of blue light passing through the contact lens by adding curcumin, a natural material capable of absorbing blue light, to the contact lens composition by preparing a blue light blocking hydrogel lens. , It aims to provide a hydrogel lens that is safe for eyes when actually worn because curcumin does not elute, while preventing glare, fatigue, and eye diseases.

In order to achieve the above object, the present invention provides a hydro-blocking hydrogel lens comprising a hydrophilic acrylic monomer, a wetting agent, a crosslinking agent, an initiator, and curcumin as a natural material.

The curcumin may be included at 0.1 to 0.8 mM in the total lens composition.

The humectant is at least one material selected from furfuryl methacrylate (FMA) and sodium hyaluronate, N-vinyl pyrrolidone (NVP) and methyl acrylate , MA).

In the case of a hydrogel contact lens in which the curcumin is contained in the total lens composition at 0.1 to 0.8 mM, oxygen of 11.26 × 10 ^-9 to 23.51 × 10 ^-9 (cm / ml O ₂ ) / (sec × ml × mmHg) Transmittance can be indicated.

According to the present invention as described above, by adding a natural product curcumin to the contact lens composition to block blue light that can cause glare, fatigue, eye disease, etc., and at the same time, to produce a hydrogel lens that is safe for eyes when worn You can.

Figure 1 shows the change in the light transmittance of the low water content hydrogel lens according to the addition of curcumin.
Figure 2 shows the change in light transmittance of the high-functional hydrogel lens according to the addition of curcumin.
3 is a result of absorbance of curcumin (FIG. 3 (a), FIG. 3 (b)) when immersing a low-functional hydrogel lens containing curcumin in PBS and a multi-purpose solution (MPS) for a week. ).
FIG. 4 shows absorbance results (FIGS. 4 (a) and 4 (b)) of curcumin released when a high-functional hydrogel lens containing curcumin is immersed in PBS and MPS for a week.
Figure 5 shows the change in water content according to the curcumin concentration of the low water content hydrogel lens containing curcumin.
6 shows the change in water content according to the curcumin concentration of the high-functional hydrogel lens containing curcumin.
Figure 7 shows the change in oxygen permeability according to the curcumin concentration of the low water content hydrogel lens containing curcumin.
8 shows a change in oxygen permeability according to the curcumin concentration of a high-functional hydrogel lens containing curcumin.
9 is a lens extraction amount according to the curcumin concentration of the low-functional hydrogel lens containing curcumin when using distilled water (FIG. 9 (a)) and a lens extraction amount according to the curcumin concentration of the low-functional hydrogel lens containing curcumin when using methanol (FIG. 9 (b)).
FIG. 10 is a lens extract amount according to curcumin concentration of a high function hydrogel lens containing curcumin when using distilled water (FIG. 10 (a)) and a lens extract amount according to curcumin concentration of a high function hydrogel lens containing curcumin when using methanol ( 10 (b)).

Hereinafter, the present invention will be described in detail.

The blue-green blocking hydrogel contact lens composition using the natural product of the present invention is characterized by comprising a hydrophilic acrylic monomer, a wetting agent, a crosslinking agent, an initiator, and curcumin. The hydrophilic acrylic monomer is 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrlate, HEMA), N, N-dimethyl acrylamide (N, N-dimethyl acrylamide, DMA), glycerol monomethacrylate (glycerol monomethacrylate, GMMA ), And one or more selected from methacrylic acid (MAA) and the like, and may be included in an amount of 42 to 95% by weight in the total lens composition. This weight percent of the hydrophilic acrylic monomer corresponds to the weight essentially required for the production of hydrogel lenses.

Among them, it is preferable to use 2-hydroxyethyl methacrylate (HEMA). Among the hydrophilic acrylic monomers, 2-hydroxyethyl methacrylate (HEMA) is the first hydrophilic monomer used in the production of soft contact lenses, and is currently the most used material for the production of hydrogel lenses and silicone hydrogel lenses. HEMA has good hydrophilicity, flexibility, and wettability, making it comfortable to use when used in contact lenses.

The crosslinking agent may be at least one selected from ethylene glycol dimethacrylate (EGDMA), diethylene glycol methacrylate (DEGMA), divinylbenzene and trimethylolpropane trimethacrylate (TMPTMA). Among them, in the case of ethylene glycol dimethacrylate (EGDMA), it is preferable to use 0.4 to 0.5% by weight of the total lens composition.

The initiators are azobisisobutyonitrile (AIBN), benzoin methyl ether (BME), 2,5-dimethyl-2,5-di- (2-ethylhexanoylperoxy) hexane and dimethoxyphenyl aceto It may be one or more selected from phenone (DMPA). For AIBN, it is preferable to use 0.45 to 2% by weight of the total lens composition.

The curcumin may be added at 0.1 to 0.8 mM in the total lens composition. When curcumin is less than 0.1mM, a blue light blocking function that is effective is not implemented, and when it exceeds 0.8mM, the blue light blocking rate is not significantly different.

The polyphenol type curcumin (diferuloymethane) is an active ingredient of the perennial herb turmeric (curcuma longa). The typical extract of turmeric has the structure I to III and contains three main components: curcumin (77%), demethoxycurcumin (17%) and bisdemethoxycurcumin (3%). Among them, I use curcumin, the I structure known to have the strongest pharmacological action.

Curcumin is known to be a substance with little physiological activity, since its solubility in hydrophilic solvents is low, so the bioavailability in aqueous solution is not high. Many studies have shown that side effects of oral administration of curcumin are mild and no toxicity has been reported. Therefore, curcumin is non-toxic and has a maximum absorption wavelength of 425 nm and absorbs the blue light region, so it can be used for manufacturing contact lenses having a blue light blocking function.

As the curcumin concentration increases, the blocking area of the blue light area increases and the color of the lens becomes darker, so it is necessary to select the appropriate concentration that matches both the light blocking rate effect and the cosmetic aspect. If the concentration of curcumin used for the actual lens polymerization does not exceed 0.8 mM, it has a blue light blocking effect and at the same time, the color of the lens due to curcumin does not appear to be yellow with a level that is clearly visible to the naked eye. It also matches.

Although curcumin is a non-toxic and low bioavailability component, the lower the concentration of curcumin emitted from the lens is, the better, to prevent various physiological effects that may occur upon release from contact lenses. In the case of the contact lens containing curcumin, which is the present invention, the curcumin component was not released from the lens when immersed in PBS and the contact lens storage solution. (1 in Measurement Example 2) Also, dipping in distilled water and heating at 70 ° C. for 24 hours Curcumin was hardly eluted in Edo (Measurement Example 7).

And when the lens containing curcumin was immersed in the lens storage solution and heated for 24 hours under the conditions of 25 ° C to 75 ° C, it was not released until 55 ° C and a very small amount was released at a temperature higher than that, but at 35 ° C, the average corneal surface temperature (2 of Measurement Example 2) Also, when a lens containing curcumin was put in PBS and heated at 35, 45, 55, 65, 75, and 121 ° C. for 24 hours, the blue light blocking rate decreased as the temperature increased. The difference in blocking rate was not great at ℃ (Measurement Example 3).

Therefore, when worn on the actual eye, there will be no problems such as safety problems of eyes or reduction of blue light blocking rate due to curcumin release from curcumin-containing hydrogel lenses.

The humectant is at least one material selected from furfuryl methacrylate (FMA) and sodium hyaluronate, N-vinyl pyrrolidone (NVP) and methyl acrylate , MA).

Of the total lens composition, furfuryl methacrylate (FMA) is 10.5% by weight, sodium hyaluronate is 0.74% by weight, and methyl acrylate (MA) is 1.48 to 25% by weight, N -Vinyl pyrrolidone (N-vinyl pyrrolidone, NVP) is preferably used in 1.48 to 20% by weight.

In the case of a hydrogel contact lens in which the curcumin is contained in the total lens composition in an amount of 0.1 to 0.8 mM, 11.26 × 10 ⁻⁹ to 23.51 * × 10 ⁻⁹ (cm / ml O ₂ ) / (sec × ml × mmHg) Oxygen permeability can be indicated. Oxygen permeability of lenses prepared by mixing curcumin to 0.1 to 0.8 mM in the total lens composition was slightly increased compared to lenses prepared without mixing actual curcumin, and when curcumin was added, the change in oxygen permeability with increasing curcumin concentration was significant. There was no difference (Measurement Example 6) and the moisture content did not significantly affect the moisture content even if the concentration of curcumin increased (Measurement Example 5) and in this case, both the oxygen permeability and water content were in accordance with the standards of the Ministry of Food and Drug Safety. It was suitable. Therefore, in the case of contact lenses containing curcumin, it protects the eyes by blocking blue light, and at the same time, it does not emit curcumin without significantly different from normal lenses without moisture and oxygen permeability, so it can be safely worn on actual eyes. It works.]

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples.

Example 1.

In order to prepare a low water content hydrogel lens, HEMA 95.4% contains MA 1.48%, NVP 1.48%, Sodium hyaluronate 0.74%, EGDMA 0.4%, and AIBN 0.45%. Co-polymerized with the addition of stars. The refractive power of the mold used in the experiment was -3.00 D, and a monomer mixed with a curvature radius of 8.6 mm and a diameter of 14.2 mm was used for the cast mold method. The low water content hydrogel lens samples were heat-polymerized at 120 ° C. for 20 minutes in an oven (Wise oven, DAIHAN scientific, Korea) to prepare contact lenses. The completed low water hydrogel lens was immersed in PBS (phosphate buffer saline) to hydrate for more than 24 hours (Table 1).

Contact lens Composition HEMA (%) MA (%) NVP (%) Sodium hyalu-
ronate (%) EGDMA
(%) AIBN (%) RB-
246 (%) Cur-
cumin (mM) LHy _0.1 95.40 1.48 1.48 0.74 0.4 0.45 1.09 0.1 LHy _0.2 95.40 1.48 1.48 0.74 0.4 0.45 1.09 0.2 LHy _0.4 95.40 1.48 1.48 0.74 0.4 0.45 1.09 0.4 LHy _0.8 95.40 1.48 1.48 0.74 0.4 0.45 1.09 0.8

HEMA: 2-hydroxyethyl methacrlate, MA: methyl acrylate, NVP: N-vinyl pyrrolidone

EGDMA: ethylene glycol dimethacrylate, AIBN: azobisiobutyonitile

Example 2.

For the production of high-functional hydrogel lenses, HEMA 42% was stirred with 25% MA, 20% NVP, 10.5% FMA, 0.50% EGDMA, and 2% AIBN, and 0 mM, 0.1, 0.2, without natural curcumin added. It was added to each concentration at 0.4 and 0.8 mM and copolymerized together. The refractive power of the mold used in the experiment was -3.00 D, and a monomer mixed with a curvature radius of 8.6 mm and a diameter of 14.2 mm was used for the cast mold method. High-functional hydrogel lens samples were heat-polymerized at 120 ° C. for 35 minutes in an oven to prepare contact lenses. The completed high-function hydrogel lens was immersed in PBS (hosphate buffer saline, pH 7.4) to hydrate for more than 2 hours (Table 2).

Contact lens Composition HEMA (%) MA (%) NVP
(%) FMA
(%) EGDMA (%) AIBN (%) Cur-
cumin (mM) HHy _0.1 42 25 20 10.5 0.5 2 0.1 HHy _0.2 42 25 20 10.5 0.5 2 0.2 HHy _0.4 42 25 20 10.5 0.5 2 0.4 HHy _0.8 42 25 20 10.5 0.5 2 0.8

HEMA: 2-hydroxyethyl methacrlate, MA: methyl acrylate, NVP: N-vinyl pyrrolidone

FMA: furfuryl methacrylate, EGDMA: ethylene glycol dimethacrylate,

AIBN: azobisiobutyonitile

Comparative Example 1.

Contact lenses were prepared in the same manner as in Example 1, except that curcumin was not added.

Comparative Example 1.

Contact lenses were prepared in the same manner as in Example 1, except that curcumin was not added.

Comparative Example 2.

Contact lenses were prepared in the same manner as in Example 2, except that curcumin was not added.

Measurement Example 1.-Blue light blocking rate according to curcumin concentration

The light blocking effect of the low water contact lens of Example 1 and the low water contact lens of Comparative Example 1 was investigated. In order to measure the light transmittance of contact lenses that have a blue light blocking effect, the lenses prepared by concentration are removed from the surface with a science wiper, and then placed on a dedicated holder and placed on a special holder to hold the UV-Vis spectrophotometer (mega-U600 UV-Vis Spectrophotometer, Scinco , Korea), the transmittance of the 300-600 nm wavelength band was measured, converted to a percentage, and the transmittance of the blue light region was displayed. The average value was used after 3 measurements for each lens.

The contact lens (comparative example 1) without curcumin polymerization in the blue light region 380 to 500 nm showed a blocking rate of 3.27 to 35.90%. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM (Example 1), the blue light blocking rates were in the range of 4.80 to 44.17, 5.43 to 49.20, 5.63 to 58.20, and 7.36 to 59.17%, respectively, and the concentration of polymerized curcumin As it was increased, the blocking rate was increased (FIG. 1, Table 3). When comparing the change of the light blocking rate according to the change in wavelength, the blocking rate increased as the wavelength decreased in the blue light region 380 to 500 nm (Table 3).

Curcumin
added
(mM
Wavelength
(nm) Blue light filtering rate (%) Comparative Example 1 Example 1 0 0.1 0.2 0.4 0.8 380 35.90 ± 5.28 44.17 ± 0.64 49.20 ± 0.70 58.20 ± 0.40 59.17 ± 0.32 400 10.27 ± 1.59 19.00 ± 0.62 19.70 ± 0.50 21.73 ± 1.37 37.53 ± 0.06 420 5.10 ± 0.95 11.53 ± 0.76 12.00 ± 0.79 15.67 ± 0.93 30.07 ± 0.15 440 4.00 ± 0.79 8.40 ± 0.79 9.13 ± 0.64 11.07 ± 1.16 24.07 ± 0.15 460 3.50 ± 0.61 6.67 ± 0.61 7.43 ± 0.67 8.37 ± 0.93 17.67 ± 0.15 480 3.47 ± 0.46 5.40 ± 0.53 6.00 ± 0.61 6.00 ± 1.06 10.57 ± 0.06 500 3.27 ± 0.46 4.80 ± 0.53 5.43 ± 0.64 5.63 ± 1.02 7.37 ± 0.21 380 ~ 500 7.19 ± 1.16 12.08 ± 0.61 13.00 ± 0.63 15.09 ± 0.97 25.16 ± 0.11

The blue light blocking effect of the high water content hydrogel lens of Example 2 and the high water content hydrogel lens of Comparative Example 2 was examined. The contact lens (comparative example 2) without curcumin polymerization in the blue light region 380 to 500 nm showed a blocking rate of 3.30 to 43.67%. When curcumin was polymerized to a concentration of 0.1, 0.2, 0.4, and 0.8 mM (Example 2), the blue light blocking rates were 3.97 to 43.50, 4.37 to 44.90, 4.40 to 53.90, and 4.77 to 63.93%, respectively, and the concentration of polymerized curcumin was It was found that the blocking rate increased as it increased (FIG. 2, Table 4). When comparing the change of the light blocking rate according to the change in wavelength, the blocking rate increased as the wavelength decreased in the blue light region 380 to 500 nm (Table 4).

Curcumin
added
(mM)
Wavelength
(nm) Blue light filtering rate (%) Comparative Example 2 Example 2 0 0.1 0.2 0.4 0.8 380 43.67 ± 0.64 43.50 ± 0.6 44.90 ± 0.2 53.90 ± 0.20 63.93 ± 0.23 400 8.93 ± 0.67 10.67 ± 0.50 15.07 ± 0.06 21.57 ± 0.98 27.03 ± 0.06 420 5.90 ± 0.66 6.90 ± 0.44 10.13 ± 0.12 14.84 ± 0.75 18.97 ± 0.06 440 4.33 ± 0.60 4.60 ± 0.36 6.50 ± 0.26 9.60 ± 0.69 12.30 ± 0.10 460 3.63 ± 0.42 4.30 ± 0.36 5.17 ± 0.25 5.87 ± 0.76 8.57 ± 0.15 480 3.47 ± 0.29 4.07 ± 0.55 4.97 ± 0.42 5.47 ± 0.76 6.27 ± 0.15 500 3.30 ± 0.26 3.97 ± 0.51 4.37 ± 0.44 4.40 ± 0.70 4.77 ± 0.15 380 ~ 500 7.24 ± 0.47 7.97 ± 0.46 10.19 ± 0.18 13.53 ± 0.61 16.92 ± 0.10

Measurement example 2.-Release amount of curcumin

1.The contact lenses of Example 1 and Comparative Example 1 have a similar osmotic pressure to the body at room temperature and buffer the PBS as a substitute for the role of tears and MPS (multi-purpose solution). And absorbance of curcumin was measured 7 days later (Figure 3 (a), Figure 3 (b)). Specifically, the contact lenses of Example 1 were placed in vials containing 5 ml of PBS and MPS, respectively, and then shaken at a speed of 50 rpm for 7 days using a shaker (Shaker, CR300, FINEPCR, Korea) to measure absorbance. The absorbance was measured at 425 nm, which is the maximum absorption wavelength of curcumin, after taking 1 ml of the solution from the vial and soaking it in a dedicated cell using a UV-Vis spectrophotometer, and the average value was used after each measurement for each lens 3 times.

As a result of confirming the amount of release in PBS and MPS, the absorbance of curcumin released from contact lenses (Comparative Example 1 and Example 1) to which curcumin concentrations of 0, 0.1, 0.2, 0.4, and 0.8 mM were added was 0.000, and curcumin was released from the lens. It can be seen that it is not released (Table 5).

Contact lens Curcumin added (mM) curcumin released (absorbance) PBS MPS _{Comparative Example 1} LHy ₀ 0 0.000 0.000 Example 1 LHy _0.1 0.1 0.000 0.000 LHy _0.2 0.2 0.000 0.000 LHy _0.4 0.4 0.000 0.000 LHy _0.8 0.8 0.000 0.000

The contact lenses of Example 2 and Comparative Example 2 had an osmotic pressure similar to that of the body at room temperature, and the buffering action was immersed in PBS and MPS, a contact lens storage solution used when storing the lenses, and absorbed curcumin after 7 days to confirm that curcumin released. (FIG. 4 (a), FIG. 4 (b)) As a result of confirming the amount of release from PBS and the contact lens storage solution, it was released from contact lenses with curcumin concentrations of 0, 0.1, 0.2, 0.4, and 0.8 mM. The absorbance of the curcumin was all 0.000, indicating that curcumin was not emitted from the lens (Table 6).

Contact lens Curcumin added (mM) curcumin released (absorbance) PBS MPS _{Comparative Example 2} HHy ₀ 0 0.000 0.000 Example 2 HHy _0.1 0.1 0.000 0.000 HHy _0.2 0.2 0.000 0.000 HHy _0.4 0.4 0.000 0.000 HHy _0.8 0.8 0.000 0.000

2. Curcumin release from hydrogel lenses containing curcumin at various temperatures.

The lenses prepared in Example 1 and Comparative Example 1 were immersed in 5 ml of a contact lens storage solution, and then heated at 25, 35, 45, 55, 65, and 75 ° C for 24 hours, respectively, and absorbance of curcumin was measured. Specifically, the prepared hydrogel lens is placed in a vial containing 5 ml of MPS, and the temperature is maintained at 25, 35, 45, 55, 65, and 75 ° C. for 24 hours, and then the curcumin contained in the lens is released for management. To do this, the absorbance was measured using a UV-Vis spectrophotometer, and the curcumin emission amount by temperature was measured using the absorbance value. The average value was used after 3 measurements for each solution.

As a result of confirming the amount of curcumin detected in the contact lens storage solution, curcumin was released at all temperatures in the low-functional hydrogel lenses to which curcumin concentrations 0 (Comparative Example 1), 0.1, 0.2, 0.4, and 0.8 mM (Example 1) were added. Did not. Table 7.

Contact lens Curcumin added (mM) curcumin released (absorbance) 25 35 45 55 65 75 _{Comparative Example 1} LHy ₀ 0 0.00 0.00 0.00 0.00 0.00 0.00 Example 1 LHy _0.1 0.1 0.00 0.00 0.00 0.00 0.00 0.00 LHy _0.2 0.2 0.00 0.00 0.00 0.00 0.00 0.00 LHy _0.4 0.4 0.000 0.000 0.000 0.000 0.002 0.003 LHy _0.8 0.8 0.000 0.000 0.000 0.000 0.002 0.003

Curcumin was not released at all tested temperatures in curcumin-containing high-functional hydrogel lenses, suggesting that curcumin would not be released not only when wearing the lens, but also at temperatures that could be exposed during lens storage or distribution (Table 8). )

Contact lens Curcumin added (mM) curcumin released (absorbance) 25 35 45 55 65 75 _{Comparative Example 2} HHy ₀ 0 0.000 0.000 0.000 0.000 0.000 0.000 Example 2 HHy _0.1 0.1 0.000 0.000 0.000 0.000 0.000 0.000 HHy _0.2 0.2 0.000 0.000 0.000 0.000 0.000 0.000 HHy _0.4 0.4 0.000 0.000 0.000 0.000 0.000 0.000 HHy _0.8 0.8 0.000 0.000 0.000 0.000 0.000 0.000

Measurement Example 3-Effect of blocking blue light according to temperature .

(1) Curcumin was mixed with a low-functional HEMA monomer, and thermally polymerized (compared by Comparative Example 1 and Example 1), and the light transmittance of the low-functional hydrogel lens exposed to heat by temperature was examined. Specifically, the curcumin contained in the soft contact lens prepared by adding 5 ml of PBS to a vial in a vial prepared for each temperature at 35, 45, 55, 65, 75, 121 ° C for 24 hours was added to the temperature. In order to confirm whether the transmittance changes by reacting, the transmittance of the 300-500 nm wavelength band was measured and expressed as a percentage. The average value was used after 3 measurements for each lens.

The 380 to 500 nm blue light blocking rate of contact lenses before exposure to heat is 3.27 to 35.90% at a concentration of 0 mM, and when the curcumin is polymerized to a concentration of 0.1, 0.2, 0.4 and 0.8 mM, the blue light blocking rate is 4 .80 to 44.17 and 5.43, respectively. The range was ~ 49.20, 5.63 ~ 58.20, 7.37 ~ 59.17%.

The 380-500 nm blue light blocking rate of the contact lens reacted at 35 ° C. for 24 hours was at a concentration of 0 mM. 3.40 ~ 40.50%. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, the blue light blocking rates ranged from 4.00 to 49.90, 5.20 to 38.60, 5.80 to 44.70, and 6.15 to 50.60%, respectively.

Curcumin concentration at 45 ℃ showed 3.00 ~ 34.30% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, it was found to be in the range of 3.80 to 40.70, 4.85 to 37.60, 5.50 to 43.50, and 5.80 to 40.24%, respectively.

Curcumin concentration at 55 ℃ showed 2.70 ~ 33.20% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, it was found to be in the range of 3.70 to 33.10, 4.60 to 38.70, 5.30 to 42.00, and 5.80 to 36.00 % , respectively.

Curcumin concentration at 65 ℃ showed 2.35 to 27.90% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, it was found to be in the range of 3.30 to 33.35, 4.40 to 39.50, 5.00 to 39.75, and 4.70 to 33.80%, respectively.

Curcumin concentration at 75 ℃ showed 2.00 to 23.30% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, the ranges were 2.97 to 29.40, 3.80 to 33.50, 4.20 to 36.90, and 4.60 to 31.60%, respectively.

Curcumin concentration at 121 ℃ showed 1.87 to 21.53% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, the ranges were 2.23 to 28.53, 2.53 to 30.00, 4.20 to 30.20, and 4.60 to 28.67%, respectively.

(2) Curcumin was mixed with a high-functional HEMA monomer, and thermally polymerized (compared to by Comparative Example 2 and Example 2), and the light transmittance of the soft contact lens exposed to heat by temperature was examined.

The 380 to 500 nm blue light blocking rate of contact lenses before exposure to heat is 3.3 to 43.67% at a concentration of 0 mM, and when the curcumin is polymerized to a concentration of 0.1, 0.2, 0.4 and 0.8 mM, the blue light blocking rate is 3.97 to 43.50, 4.37 to 44.90, respectively. , 4.40 ~ 53.90, 4.77 ~ 63.93%.

The 380 to 500 nm blue light blocking rate of the contact lens reacted at 35 ° C. for 24 hours was 3.60 to 44.40% at a concentration of 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, the blue light blocking rates ranged from 4.40 to 43.90, 4.40 to 45.20, 4.80 to 53.70, and 5.80 to 63.80%, respectively.

Curcumin concentration at 45 ℃ showed 3.10 ~ 43.20% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4 and 0.8 mM, it was found to be in the range of 3.40 to 42.00, 4.30 to 45.10, 4.50 to 45.70, and 4.60 to 57.70%, respectively.

Curcumin concentration at 55 ℃ showed 3.00 ~ 42.40% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, it was found to be in the range of 3.30 to 41.20, 3.60 to 44.60, 4.40 to 44.70, and 4.00 to 54.70%, respectively.

Curcumin concentration at 65 ℃ showed 2.70 ~ 40.00% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, it was found to be in the range of 3.30 to 39.53, 3.20 to 43.00, 4.30 to 44.40, and 3.90 to 51.60%, respectively.

Curcumin concentration at 75 ℃ showed 1.70 to 37.80% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, the ranges were 2.10 to 34.90, 2.90 to 43.00, 3.40 to 42.20, and 3.30 to 46.40%, respectively.

Curcumin concentration at 121 ℃ showed 1.60 to 33.70% at 0 mM. When curcumin was polymerized at concentrations of 0.1, 0.2, 0.4, and 0.8 mM, it was found to be in the range of 1.83 to 3.340, 2.50 to 42.80, 2.80 to 40.30, 3.10 to 44.90, and 3.10 to 45.20%, respectively.

(3) When the results of the above experiments were put together, in the case of the low water content hydrogel lens, when the difference between the blue light blocking area of the contact lens without temperature and the lens with temperature was compared, the blocking rate was decreased at 35 ° C, but there was no significant difference. It was found that the blocking rate gradually decreased as the temperature increased from 45 ° C to 75 ° C, and the difference in the blocking rate was rapidly increased at 121 ° C, the temperature at which sterilization was performed by contact lens heat sterilization. In the case of a high-function hydrogel lens, when the difference between the blue light blocking area of the contact lens without temperature and the lens with temperature was compared, the blocking rate decreased at 35 ° C, but it did not show a significant difference, and the temperature increased from 45 ° C to 75 ° C. Although the blocking rate was gradually decreased, it was found that the difference was relatively small, and the difference in blocking rate was rapidly observed at 121 ° C. It is believed that curcumin may have been decomposed by high temperature heat inside all contact lenses. As the effect of curcumin decreases as the temperature increases, the effect decreases, so it is weak for heat, but the blocking rate decreases at 35 ° C, which is similar to the temperature of the eyeball, but the difference is not large, so there is no problem in wearing it.

Measurement Example 4.-Water content

(1) Curcumin was mixed with a low water content HEMA monomer and thermally polymerized to compare the moisture content of the soft contact lens. The water content is the ratio of water to the weight of the lens. It depends on the humidity and temperature when wearing the lens, the pH of the tears, or the osmolarity. The higher the water content, the more the oxygen permeability increases and the wettability (the main factor that determines the wearability of the lens as the ability to maintain and form a tear film on the surface of the contact lens) increases, thereby improving the fit. Specifically, the water content was measured using the gravimetric method of ISO 18369-4: 2006. The prepared contact lenses were compared with the weight measured after hydrating in PBS for 24 hours and the weight of the lens dried in an oven at 65 ° C. for 24 hours or more. The average value was used after 3 measurements for each lens.

The moisture content of the contact lens (the lens prepared by Comparative Example 1) without mixing curcumin was 36.4 ± 0.3%. Curcumin concentrations of 0.1, 0.2, 0.4, and 0.8 mM (lenses prepared by Example 1) were 35.3 ± 0.2, 35.1 ± 0.2, 34.7 ± 0.2, and 34.4 ± 0.4, respectively. There was no difference (Fig. 5).

(2) Curcumin was mixed with a high water content HEMA monomer and thermally polymerized to compare the moisture content of the lens. The water content of the high-function lens (lens prepared by Comparative Example 2) without mixing curcumin was 58.8 ± 0.2. Curcumin concentrations of 0.1, 0.2, 0.4, and 0.8 mM (lenses prepared according to Example 2) were 58.5 ± 0.1, 58.4 ± 0.3, 58.9 ± 0.3, and 58.4 ± 0.3, respectively. (Fig. 6)

Measurement example 5-oxygen permeability

(1) In the case of contact lenses, if the oxygen permeability is high, it is comfortable to wear and can prevent problems such as side effects caused by hypoxia. The ability to deliver oxygen to the cornea when the lens is worn is an important element of contact lenses and is evaluated by oxygen permeability measurements. In the case of a hydrogel lens, the lens thickness and water content are the main factors determining the oxygen permeability value. Oxygen permeability was measured by a polarographic method. Put 5 ml of PBS in a 50 ml tube, immerse the contact lenses prepared by concentration, put the polarographic cell and cell mounting fixture together in a thermo-hygrostat (Wisecube, WTH-E 155, Korea, humidity 95%, temperature 35 ℃) for more than 4 hours. After maintaining the equilibrium, 15 μl of PBS was dropped on the polarographic cell, and moisture was removed from the surface of the lens with Kim Tech, and then the lens was placed on the cell. The lens was fixed with a cell mounting fixture covered with nylon mesh, and the current value was measured using a permeometer (Model 201T O ₂ permeometer, CHREATECH, USA). The central thickness of the lens was measured using an electronic thickness gauge (Model ET-3, CHREATECH, USA). The current value and the center thickness of the contact lens manufactured by concentration were repeatedly measured three times, and all methods were in accordance with the standards of the International Organization for Standardization (ISO).

(2) The oxygen permeability of the low-function soft contact lens (lens prepared by Comparative Example 1) without mixing curcumin was 11.15 ± 0.58 × 10 ⁻⁹ (cm / ml O ₂ ) / (sec × ml × mmHg). Oxygen permeability of contact lenses (lenses prepared by Example 1) in which curcumin was differently mixed at concentrations of 0.1, 0.2, 0.4, and 0.8 mM were 11.92 ± 0.96, 11.65 ± 0.01, 11.26 ± 1.68, and 11.88 ± 0.06 × 10 ^{−, respectively. 9} (cm / ml O ₂ ) / (sec × ml × mmHg), there was no statistically significant difference in the change of oxygen permeability with increasing curcumin concentration (Fig. 7).

(3) The oxygen permeability of the high-function hydrogel lens (lens prepared according to Comparative Example 2) without mixing curcumin was 22.06 ± 0.02 × 10 ^-9 (cm / ml O ₂ ) / (sec × ml × mmHg) curcumin oxygen permeability of 0.1, 0.2, 0.4, 0.8 a contact lens mixed differently in mM concentration (the lenses manufactured according to example 2) are each 23.10 ± 0.07, 22.91 ± 0.25, 23.51 ± 0.70, 23.30 ± 0.02 × 10 - ⁹ (cm / ml O ₂ ) / (sec × ml × mmHg), there was no statistically significant difference in the change of oxygen permeability with increasing curcumin concentration (Fig. 8).

(4) In the case of the oxygen permeability of low- and high-functional hydrogel lenses in which curcumin is added by concentration, the standard for oxygen permeability of the Ministry of Food and Drug Safety must be within ± 20% of the published value, but the contact lenses that do not contain curcumin The standard for oxygen permeability was ± 2.23% of the published value, so low- and high-function soft contact lenses of all concentrations met the standards of the Ministry of Food and Drug Safety.

Measurement example 6-amount of extract material

(1) Curcumin was mixed with a low water content HEMA monomer to heat polymerize, and then the amount of extraction of the lens was measured. Specifically, in the extract experiment, contact lenses prepared by concentration were measured at room temperature, and the total dry weight before extraction was used as contact lenses of 200 mg or more, and the contact lenses prepared by concentration for 24 hours were immersed in distilled water in an equilibrium state. It was made from and dried at 65 ° C. until there was no change in weight, cooled at room temperature, and then the weight of the dried lens was measured. A lens was placed in a soxhlet extraction apparatus, and approximately 70% of the flask volume was filled with pure distilled water and then extracted for at least 4 hours. After drying until there was no change in the weight of the lens, the weight was measured, and the amount of the extracted material was calculated by substituting the following equation. This process was repeated in the same manner with methanol (99.9% purity, DC chemical, Korea) instead of distilled water. All methods were evaluated in accordance with the standards of the sub-category A77030.01 Daily Wear Soft Contact Lenses published by the Korean Food and Drug Administration, "Regulations on Medical Device Items and Grades by Item", and were in accordance with the standards of ISO, the international standardization organization.

(2) The extraction amount of the hydrogel lens without mixing curcumin was 1.812% when measured with distilled water and 0.906% when measured using methanol. The extraction amount of contact lenses with curcumin concentration of 0.1 mM was 1.826% when distilled water was used and 1.185% when methanol was used. The concentration of 0.2 mM contact lens was 1.839% when distilled water was used and 1.491% when methanol was used. The extraction amount of contact lenses with a concentration of 0.4 mM was 1.888% when using distilled water and 1.540% when using methanol. The extraction amount of the contact lens at a concentration of 0.8 mM was 1.931% when using distilled water and 1.593% when using methanol (Fig. 9 (a), (b)).

(3) Curcumin was mixed with a high water content HEMA monomer, thermally polymerized, and then the amount of extraction of the lens was measured. The extraction amount of the high water content hydrogel lens without mixing curcumin was 1.389% when measured with distilled water and 0.910% when measured with methanol. The extraction amount of contact lenses with curcumin concentration of 0.1 mM was 1.904% when using distilled water and 1.172% when using methanol. The extraction amount of the concentration 0.2 mM contact lens was 2.268% when using distilled water and 2.027% when using methanol. The extraction amount of contact lenses with a concentration of 0.4 mM was 2.978% when using distilled water and 2.432% when using methanol. The extraction amount of the contact lens at a concentration of 0.8 mM was 3.744% when using distilled water and 3.498% when using methanol (Fig. 10 (a), (b)).

(4) In view of the above results, when using distilled water, the amount of extract of the high-functional hydrogel lens was higher than the amount of extract of the low-functional hydrogel lens, and the amount of extract of the high-functional hydrogel lens was also used when using methanol. There were more. In addition, it can be seen that the amount of extract material is gradually increased as the amount of extract material is increased and the curcumin concentration is increased when distilled water is used than when methanol is used.

Measurement Example 7-Eluate

(1) Curcumin was mixed with a low-functional HEMA monomer to heat-polymerize, and then a test solution was prepared using contact lenses prepared by concentration, and then experiments related to eluates were compared.

Specifically, by measuring the weight of the prepared contact lens by concentration, take 4 g or more of the contact lens, put 20 ml of pure distilled water in a 50 ml tube, immerse the contact lens, heat it at 70 ° C. for 24 hours, cool it at room temperature, and make it. A sample solution was made. Afterwards, it was confirmed that the appearance of the sample solution was colorless and transparent and free of foreign matter, and the sample solution was colored when the sample solution was boiled for 10 minutes. Then, after taking 20 ml of the sample solution and pure distilled water, add 1.0 ml of a solution of 1 g of potassium chloride (KCl, Sigma-Aldrich, USA) in 1000 ml of distilled water. Cognitive measurement. Take 10 ml of the new sample solution into a capped Erlenmeyer flask, add 0.01 ml of potassium permanganate (KMnO4, Sigma-Aldrich, USA) solution and 20 ml of diluted sulfuric acid ((H ₂ SO4, Sigma-Aldrich, USA) 1.0 ml. After boiling and cooling, 100 mg of potassium iodide (KI, Sigma-Aldrich, USA) and 5 drops of starch solution were added, and titrated with 0.01 N sodium sulphate (Na ₂ S ₂ O ₃ , Sigma-Aldrich, USA) solution. When repeating the experiment in the same manner using 10 ml, it was confirmed that the amount of sodium thiosulfate solution was 2.0 ml or less, and the absorbance of a new sample solution and distilled water was measured at a wavelength of 250 to 350 nm or less to determine whether the absorbance value was 0.10 or less.

As a result of the appearance of the sample solution, it was colorless and transparent, free of foreign matter, and was not colored when the sample solution was boiled for 10 minutes. The pH was measured by adding potassium chloride solution to distilled water and the sample solution to compare the difference. The pH of distilled water was 6.80, and the pH of 0 mM was 6.58. The pH of 0.1, 0.2, 0.4, and 0.8 mM for each concentration was 6.55, 6.55, 6.54, and 6.54, respectively. Since the difference from distilled water was 1.5 or less, it was suitable for the measured value. In a test for confirming the presence or absence of an organic or inorganic substance using potassium permanganate, which is a strong oxidizing agent, when comparing with distilled water and a test solution, distilled water consumed potassium permanganate solution was 13.55 ml. In the case of the sample solution, the consumption amounts of the potassium permanganate solutions of 0, 0.1, 0.2, 0.4, and 0.8 mM were 12.45, 12.35, 12.45, 12.45, and 12.15 ml, respectively. The difference in consumption between distilled water and sample solution was 2 ml or less, so it was suitable for the measured value. Absorbance was measured at 250-350 nm wavelength with the distilled water as a control. The absorbance of 0, 0.1, 0.2, 0.4, and 0.8 mM for each concentration was 0.011 to 0.072, 0.002 to 0.062, 0.01 to 0.064, 0.008 to 0.064, and 0.007 to 0.065, respectively.

(2) Curcumin was mixed with a high-functional HEMA monomer, thermally polymerized, and then a test solution was prepared using contact lenses prepared by concentration, and then experiments related to eluates were compared.

As a result of the appearance of the sample solution, it was colorless and transparent, free of foreign matter, and was not colored when the sample solution was boiled for 10 minutes. The pH was measured by adding potassium chloride solution to distilled water and the sample solution to compare the difference. The pH of distilled water was 6.80, and the pH of 0 mM was 6.43. The pH of 0.1, 0.2, 0.4, and 0.8 mM for each concentration was 6.41, 6.36, 6.26, and 6.35, respectively. Since the difference from distilled water was 1.5 or less, the measured value was suitable. In a test for confirming the presence or absence of an organic or inorganic substance using potassium permanganate, which is a strong oxidizing agent, when comparing with distilled water and a test solution, distilled water consumed potassium permanganate solution was 13.55 ml. In the case of the sample solution, the consumption amounts of the potassium permanganate solutions of 0, 0.1, 0.2, 0.4, and 0.8 mM for each concentration were 12.90, 12.80, 12.70, 12.70, and 12.70 ml, respectively. The difference in consumption between distilled water and sample solution was 2 ml or less, so it was suitable for the measured value. Absorbance was measured at 250-350 nm wavelength with the distilled water as a control. The absorbances of 0, 0.1, 0.2, 0.4 and 0.8 mM for each concentration were 0.019 to 0.074, 0.011 to 0.053, 0.008 to 0.051, 0.013 to 0.063, and 0.015 to 0.051, respectively.

(3) When synthesizing the results of the above experiments, both the low-function soft contact lens and the high-function soft contact lens had a colorless, transparent, and no foreign substance in the appearance, and the pH measurement was less than or equal to 1.5 at all concentrations. In the experiment to confirm the presence or absence of organic or inorganic substances, the difference in consumption of distilled water and sample solution at all concentrations was less than 2 ml. Absorbances of 250-350 nm did not exceed 0.10 at all concentrations. Therefore, curcumin hardly eluted. And this means that it is also suitable for the standard standard announced by the Korea Food and Drug Administration. It is considered that the manufactured contact lens is safe for the eyes.

As described above, specific parts of the present invention have been described in detail. For those skilled in the art, this specific technique is only a preferred embodiment, and it is obvious that the scope of the present invention is not limited thereby. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (4)

Blue light blocking hydrogel lens using natural materials including hydrophilic acrylic monomer, wetting agent, crosslinking agent, initiator, and curcumin.
According to claim 1,
The curcumin is a blue light blocking hydrogel lens using a natural material, characterized in that contained in 0.1 to 0.8 mM in the total lens composition.
According to claim 1,
The wetting agent is a substance selected from the group consisting of furfuryl methacrylate (FMA) and sodium hyaluronate, N-vinyl pyrrolidone (NVP) and methyl acrylate (methyl acrylate, MA) blue light blocking hydrogel lens using a natural material, characterized in that it comprises.
According to claim 2,
The lens is a blue-green blocking hydrogel lens using a natural material exhibiting oxygen permeability of 11.26 × 10 ^-9 to 23.51 × 10 ^-9 (cm / ml O ₂ ) / (sec × ml × mmHg).

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