KR20200137074A - Medical lens material and its moulding mould in high-functionality including silicon and metal oxide nanoparticles - Google Patents

Abstract

The present invention relates to a functional ophthalmic lens material and a forming mold thereof. The present invention, more specifically, relates to a high-functional ophthalmic lens material containing silicon and metal oxide nanoparticles and a forming mold thereof, wherein the ophthalmic lens material is a high-functional silicone hydrogel lens with high oxygen permeability, excellent antibacterial activity and wettability, and improved moisture contents, and the forming mold can mass-produce lenses in which the edge of the lens is formed with curvature.

Description

Medical lens material and its molding mold in high-functionality including silicon and metal oxide nanoparticles

The present invention relates to a functional ophthalmic medical lens material and a molding mold thereof. The ophthalmic medical lens material is a high-functional lens material with high oxygen permeability, excellent antibacterial and wettability, and improved moisture content, and the molding mold is a high-quality lens in which the edge of the lens is formed with curvature. It is configured to be able to mass-produce contact lenses of

In the case of hydroxy ethylene methacrylic acid (HEMA), which is widely used as a material for conventional hydrogel contact lenses, there is inconvenience in not supplying sufficient oxygen to the cornea through oxygen in the atmosphere, resulting in corneal edema and neovascularization. It has been found in many clinical trials that such side effects are caused.

In addition, silicone is widely used as a material for the high oxygen permeability lens, but the RGP contact lens using silicon has high oxygen permeability, but the moisture content is low, so it is inconvenient to wear it.

In addition, attempts to increase the moisture content lead to a decrease in oxygen permeability, and thus its utility is limited.

Therefore, the synthesis of a silicone hydrogel lens excellent in compatibility with other monomers by combining the advantages of the hydrogel material and the silicone material is at a very necessary time.

The present invention is to correct the inconvenience.

The present invention polymerizes a silicone material including an acrylic group and a HEMA material, and uses a PVP-based material to develop a contact lens material with high water content, excellent antibacterial and wettability, and improved related functionality, and propose a molding mold suitable therefor. By doing so, it is possible to mass-produce high quality contact lenses.

The material of the present invention has improved oxygen permeability and moisture content, good wettability, and antimicrobial properties when manufacturing contact lenses. In the molding mold of the present invention, the convex surface of the male mold is combined with the concave surface of the female mold 20 When the male and female molds are combined together, and a material of 100 to 130℃ is injected in a measured amount into the lens molding space formed in the joint space of the male and female molds, the lens material is injected and unfolded from the lens molding space and convex and concave As a result, the inner and outer surfaces of the contact lens are formed, and the outer circumferential edge of the lens collides with the surface where the annular concave groove (10f) of the male mold and the annular concave groove (20f) of the female mold come into contact with each other, and the formation is completed and molding is completed. , Since the exhausted gas is discharged to the exhaust part 20e using the gap, a lens is made in which the outer circumferential edge of the lens is molded into a curved surface, and the product can be separated by separating the male mold 10. Molding is complete.

Therefore, in the present invention, lens molding is quick, and the edge portion is molded into a curved surface to make a product that does not cause overburden, so that automatic production is possible, and mass production is possible with improved production yield, and quality of quality is improved. There is an advantage of having an advantage that can be achieved, and there is an advantage of being able to mass-produce a high-functional ophthalmic medical lens having the advantage of the developed lens material with high quality.

1 is a cross-sectional view of a water mold
2 is a cross-sectional view of an arm mold
3 is a cross-sectional view of a coupling state of a male mold and a female mold.

In the present invention, a silicone material including an acrylic group and a HEMA material are polymerized, and a PVP-based material is used to develop a contact lens material that has excellent high oxygen permeability and antibacterial properties, and has good wettability due to high water content, thereby improving related functionality. Present the molding mold.

In general, PVP (polyvinylpyrrolidone) is a water-soluble polymer, increases the dissolution rate of hydrophobic compounds, and is widely used in medical fields such as dressings and skin ulcers.

In addition, it is widely known as a polymer with little protein deposition, and has an effect of increasing the dispersion stability of nanoparticles, so it is widely used for dispersion of nanoparticles.

Research on antimicrobial and UV-blocking contact lens materials is being conducted relatively actively, but studies on the physical properties generated by nanomaterials are still insufficient. Among nanomaterials, cobalt iron oxide, a metal oxide nanoparticle, is ) Is used in the field of spectroscopy with PMMA.

Accordingly, the present invention increases the oxygen permeability of the silicon hydrogel contact lens by using cobalt iron oxide nanoparticles.

In general, the present invention uses Modified-PPMS and nanomaterials to produce a functional silicone hydrogel lens material having excellent high oxygen permeability, antibacterial properties and wettability, and improved moisture content.

Basically, the present invention is Sil-H and

DMA is synthesized in a ratio of 1:1 to 5

HEMA 10-50% by weight

PEGMEMA 1-10% by weight

0.5 to 3.0% by weight of EGDMA

It is achieved by adding 0.5 to 2.0% by weight of AIBN.

The material of the present invention prepared as described above has improved oxygen permeability and water content, good wettability and dispersion stability, and good refractive index and antibacterial properties when manufacturing a contact lens.

Measurement of oxygen permeability and moisture content

How to measure oxygen permeability

The equipment used in the experiment was Rehder single-chamber system-O2 permeometer model 201T (Rehder Development Company, Castro Valley, California, USA) and General Incubator (LIB-030M, Labtech, Korea), and ISO 18369-4:2006 , Ophthalmic optics-Contact lenses-Part 4: Physicochemical properties of contact lens materials, 4.4.3 Polarographic method. Rehder single-chamber system was used as an experimental method, and WL1000S model was used as a thermo-hygrostat (TEMP.&HUMIDITY CHAMBER) to keep the temperature and humidity constant. In addition, the thickness measurement for measuring the oxygen permeability of the lens was measured using OTG-137 of Bristol using a non-contact measurement method. The polarographic cell had a radius of curvature of 8.5 mm. The test sample was fixed in contact with the negative electrode of the sensor by a fixing device, and the front surface of the test sample was firmly pressed with a nylon mesh to be fixed. The O-ring grabbed the nylon mesh and placed the water-soluble contact lens between the polarographic cell and the nylon mesh. The entire sensor system to which the experimental contact lens was fixed was placed in a general incubator to maintain a temperature of 35°C ± 0.5°C, and the exposed surface of the test contact lens maintained a moisture saturation state with a relative humidity of 97% by weight or more in the atmosphere. Experimental contact lenses were stored in a standard saline solution (0.9 wt% sodium chloride solution) at least 24 hours before the test and allowed to equilibrate at the test temperature for at least 2 hours. Dk/t (oxygen permeability) was calculated using the following formula (1) by measuring the current value while the entire system of the sensor fixing the experimental contact lens using the Rehder single-chamber system maintained a temperature of 35°C ± 0.5°C. .

[Formula 1]

How to measure moisture content

Moisture content was measured using the gravimetric method of ISO 18369-4:2006, Ophthalmic optics-Contact lenses-Part 4: Physicochemical properties of contact lens materials. Moisture content was expressed as a percentage using the following formula in a state completely equilibrated with standard salt at room temperature.

[Formula 2]

Oxygen permeability and moisture content measurement result

Oxygen permeability (Dk), an inherent characteristic of the material, was measured as 25.79∼30.15 ×10 ^-11 (cm ² /sec) (mlO ₂ /ml×mmHg), and the moisture content was measured as 64.80∼77.69% by weight of HEMA added. It was found that the oxygen permeability and water content decreased with increasing this. However, as the amount of PEGMEMA increased, both Dk and moisture content increased slightly, and the shape and size improved. Therefore, in this study, additional addition experiments were conducted based on HAD-1 in consideration of adding additional additives.

Oxygen permeability moisture content Measurement result

ample No. Dk Water Content(%) HAD-1 One 29.83 72.61 2 30.15 76.18 3 30.11 75.91 4 29.98 77.02 5 30.07 77.28 6 29.91 77.69 Average 30.01 76.11

(%) is weight percent

In addition, in the present invention, it is possible to develop a lens material having a high refractive index by adding 2F.

The present invention, In HAD-1, the material of the silicone hydrogel contact lens, a ref. that does not contain 2F (2-fluorostyrene) and a sample containing 1.0 to 2.0% by weight of 2F are used as control and experimental groups, respectively, while maintaining oxygen permeability. An experiment to increase the refractive index was conducted. The refractive index of the manufactured lens was measured using an ABBE Refractormeter [ATAGO, DR-A1(1310)] in a hydrated state. As a result of the measurement, it was found that the ref. without 2F was 13883 and the refractive index increased as the ratio of 2F increased, as 13883 and 2F were added, and DK increased at 1 to 3 wt%. It was found that the oxygen permeability was improved by further increasing.

Mixing ratio

Sample HAD ^* HEMA PEGMEMA 2F EGDMA AIBN Sil-H DMA HAD-2 One 1-5 10-50%
(HAD standard) 1-10%
(HAD standard) 1 to 5%
(HAD standard) 0.5~3.0%
(HAD standard) 0.5~2.0%
(HAD standard)

^* (Sil-H:DMA = 1:1∼5) (%) is weight%

Refractive index and oxygen transmittance measurement result

sample No. Refractive index Dk HAD-2 One 1.4050 33.43 2 1.4013 33.38 3 1.4033 33.41 4 1.3977 34.68 5 1.4010 34.07 6 1.4024 33.91 Average 1.4018 33.81

In addition, the present invention with 2F PVP With the addition of ., it is possible to develop lens materials with high wettability and dispersion stability.

In the present invention, in order to increase the dispersion stability of the nanoparticles to be added, the contact angle was measured by adding 3 to 10% by weight of PVP to the HAD-2 combination. The experiment was conducted by measuring the contact angle of the prepared HAD-3 and selecting the optimum mixing ratio.

Mixing ratio

Sample HAD ^* HEMA PEG
MEMA 2F PVP EGDMA AIBN Sil-A DMA HAD-3 One 3 to 5 10-50%
(HAD standard) 5-10%
(HAD standard) 1 to 5%
(HAD standard) 3-10%
(HAD standard) 0.5~3.0%
(HAD standard) 0.5~2.0%
(HAD standard)

^* (Sil-A:DMA = 1:3∼5) (%) is weight%

How to measure wettability

1) Experimental contact lenses were stored in a standard saline solution (0.9 wt% sodium chloride solution) at least 24 hours before the test and allowed to equilibrate at the test temperature for at least 2 hours.

2) Experiment The contact lens was tested in a moist state, and the contact angle was measured after only removing moisture from the surface.

3) Experimental contact lens surface condition and contact angle In order to minimize the experimental error, the experiment was conducted after washing hands more than two times, and the contact angle was measured after removing moisture from the contact lens surface using KIMTECH SCIENCE Wipers, which generated less lint.

4) Use a precision screw for control the drop with syringe module to form a certain amount of water droplets at the ends of the needles using the 10mL syringe fixed to the measuring device.

5) After fixing the experimental contact lens to the lens fixing plate, use the Up/down adjustment sample stage to raise the fixing plate to make the water droplets formed on the needles contact the contact lens, and place the water droplets on the contact lens surface by gravity. Minimize spreading.

6) Use the up/down adjustment sample stage to move to the camera shooting area, use the focus adjuster to focus, and then take a picture using a digital CCD camera.

7) Using the contact angle measurement program (surfaceware7), the contact angle was checked and the record was saved. The measurement formula is as follows.

Wetability measurement result

By measuring the contact angle for wettable evaluation result of the manufactured lens, in the case of adding a combination of PVP (polyvinylpyrrolidone), that do not contain PVP Ref. The ratio of the PVP to ^o~ 90.02 60.02 ^{o o} in accordance with the addition ratio of 90.53, PVP It was found that the contact angle decreased as this increased, indicating that the wettability improved as the ratio of PVP increased. In addition, as the addition ratio of PVP increases, the dispersion stability increases, and it is believed that the dispersion of CoI (Cobalt iron oxide), a nanoparticle used in this patent, becomes easier.

In addition, the present invention 2F, With PVP Col In addition, it is possible to manufacture contact lenses with excellent antibacterial properties and oxygen permeability.

In the present invention, the sample containing the ref. that does not contain CoI (Cobalt iron oxide) in HAD-3, the material of the silicone hydrogel contact lens, and the sample containing 0.1 to 2.0% by weight of CoI as a control group and an experimental group, respectively, was used as a control group and an experimental group, respectively, and Escherichia coli ) And Staphylococcus aureus were tested for antimicrobial activity.

Mixing ratio

Sample HAD ^* HEMA PEG
MEMA 2F PVP CoI EGDMA AIBN Sil-A DMA HAD-4 One 3 to 5 10-50%
(HAD standard) 5-10%
(HAD standard) 1 to 5%
(HAD standard) 3-10%
(HAD standard) 0.1~0.3%
(HAD standard) 0.5~3.0%
(HAD standard) 0.5~2.0%
(HAD standard)

^* (Sil-A:DMA = 1:3∼5) (%) is weight%

How to measure antimicrobial activity

For the evaluation of antimicrobial activity, the sample containing 0.1 to 2.0% by weight of CoI in the base combination and the reference without CoI was used as a control group and an experimental group, respectively, to have antimicrobial activity against Escherichia coli and Staphylococcus aureus. Confirmed. For the experiment, 3M Petrifilm ^TM was used as the dry film medium, and the bacteria and lenses were put in 0.9% by weight of sodium chloride physiological saline and hydrated for 24 hours, and then water was removed. After adding a saline solution equal to 9 times the weight of the lens and a lens and shaking, 1 ml of the saline solution was taken, spread on a dry film, and incubated at 36±1° C. for 24 hours. In addition, Daewon Science's shacking incubator DS-210SL was used as an incubator for bacterial culture.

Antimicrobial and oxygen permeability measurement results

As a control group and a sample containing 0.1~0.5% by weight of CoI nanoparticles in HAD-4 selected as a basic combination, a Ref. that does not contain CoI nanoparticles and a sample containing 0.1~0.5% by weight of CoI nanoparticles were used as the control group and the experimental group, respectively, and Escherichia coli and Staphylococcus aureus), it was confirmed that the distribution of bacteria appeared in contrast. In addition, the oxygen permeability also increases with the addition of nanoparticles, so the used nanoparticles are considered to be a material capable of simultaneously improving antibacterial properties and oxygen permeability.

Final formulation decision

Finally, the combination that satisfies the physical properties of the high-functional silicone hydrogel contact lens pursued by the present invention is HEMA, PEGMEMA, 2F, PVP, CoI, crosslinking agent in a monomer (HAD) in which synthetic silicon and DMA are mixed in an appropriate ratio. It consists of a formulation in which phosphorus EGDMA and initiator AIBN are added.

If this is named as HAD-5, the mixing ratio is as follows.

Final blending ratio of the present invention

Sample HAD ^* HEMA PEG
MEMA 2F PVP CoI EGDMA AIBN Sil-A DMA HAD-5 One 3 to 5 10-50%
(HAD standard) 5-15%
(HAD standard) 1 to 5%
(HAD standard) 7-10%
(HAD standard) 0.1~0.3%
(HAD standard) 0.5~3.0%
(HAD standard) 0.5~2.0%
(HAD standard)

^* (Sil-A:DMA = 1:3∼5) (%) is weight%

As a result of measuring the optical/physical properties of the silicone hydrogel contact lens manufactured at the final blending ratio, the oxygen permeability (Dk) was 40.12×10 ^-11 (cm ² /sec) (mlO ₂ /ml×mmHg), and the moisture content was 69.11 The weight% and the contact angle were measured as 81.98 ^o , respectively. In addition, as a result of detection of Staphylococcus aureus and Escherichia coli, it was found to have excellent antibacterial properties when compared with the control group, HEMA lens-based Ref. The results on the optical/physical properties of the measured silicone hydrogel contact lenses are shown below.

Therefore, this patented product is expected to show high utilization as a material for a high-functional silicone hydrogel lens by manufacturing a contact lens with high oxygen permeability, high refractive index, high wettability, high water content, and antibacterial function.

ore· Physical properties Measurement result

sample Refractive index Contact angle( ^o ) Dk Water Content( % ) HAD-5 1.4050 81.98 40.12 69.11

(%) is weight percent

Meanwhile, the present invention discloses a molding mold suitable for manufacturing a contact lens using the developed material.

The present invention is a male mold having a convex surface for forming an inner surface of the lens in order to form a contact lens, and an female mold having a concave surface for forming the outer surface of the lens, and are combined at intervals to face the convex surface of the male mold. The contact lens molding mold is used, in which a lens material is injected and molded between the convex and concave surfaces of the male and female molds, and the contact lenses that are compression molded in the lens molding space where the male and female molds are combined are formed with a precise curved surface. Molding mold that can be quickly formed, and the outer peripheral edge of the contact lens is formed into a curved surface so that the separation of the molded product can be easily and automated, suitable for mass production, and the production yield can be improved and the quality of the product can be improved. Is selected.

The mold selected in the present invention is a male mold ( When the coupling portion 10a of 10) is coupled, the male and female molds are coupled in the vertical direction, and a concave surface 20b on which the outer surface of the contact lens is formed at the center of the bottom of the coupling portion of the female mold is formed, and the concave surface 20b The expansion part 20d is formed in the outer circumferential direction from the outer circumferential boundary part 20c so that the end of the expansion part is connected to the inner end of the coupling part 20a to form the exhaust part 20e, and the male mold 10 is the coupling part 10a. ) A convex surface 10b forming the inner surface of the contact lens is formed at the center of the lower end so that the outer circumferential inflection point 10c of the convex surface contacts the outer circumferential boundary of the concave surface 20b of the arm mold, so that between the convex surface and the concave surface The lens molding space (L) is formed, and the inclined surface (10d) is formed outward from the outer peripheral inflection point (10c) of the male mold convex surface (10b) in contact with the boundary part (20c) of the female mold concave surface (20b) In the coupling part 10a, the main wall 10e is formed to be connected to the lower end, so that the male mold 10 is coupled to the movable mold, and the female mold 20 is coupled to the fixed mold, but the male mold 10 is convex. An annular concave groove (10f) is formed between the surface (10b) outer circumferential inflection point (10c) and the inclined surface (10d), and the female mold (20) is an annular concave groove (20f) on the inner surface of the concave surface (20b) outer boundary part (20c) ) To make the outer circumferential end of the annular recessed groove (20f) of the female mold contact the inner surface of the end of the annular recessed recess (10f) of the male mold, so that the edge of the lens is formed into a curved surface. Mass production of lenses of

10: male mold 10a: male mold coupling portion
10b: convex surface 10c: outer peripheral inflection point 10d: inclined surface 10e circumferential wall
10f: annular recessed groove 20: female mold 20a: female mold coupling portion 20b: concave surface 20c: boundary portion 20d: extended portion 20e: exhaust portion 20f: annular recessed groove

Claims (2)

With Sil-H or Sil-A
In the monomer (HAD) synthesized in a ratio of 1:1 to 5 DMA
10-50% by weight of HEMA based on monomer
PEGMEMA 5-15% by weight
2F 1-5% by weight
PVP 7-10% by weight
Col 0.1~0.3% by weight
0.5 to 3.0% by weight of EGDMA
High-functional ophthalmic medical lens material containing silicon and metal oxide nanoparticles made by blending 0.5 to 2.0% by weight of AIBN
The coupling portion 10a of the male mold 10 molded from a resin selected from polyethylene terephthalate resin or polybutylene terephthalide resin is coupled to the coupling portion 20a of the female mold 20 formed of polypropylene. The mold is coupled in the vertical direction, and a concave surface 20b on which the outer surface of the contact lens is formed is formed at the center of the bottom of the coupling part of the arm mold, and the concave surface 20b is an extension part ( 20d) is formed so that the end of the extended part is connected to the inner end of the coupling part 20a to form the exhaust part 20e, and the male mold 10 is a convex surface forming the inner surface of the contact lens at the lower center of the coupling part 10a. (10b) is formed so that the outer peripheral inflection point 10c of the convex surface contacts the outer circumferential boundary of the concave surface 20b of the female mold, thereby forming a lens forming space L between the convex surface and the concave surface, and the female mold concave An inclined surface 10d is formed outward from the outer peripheral inflection point 10c of the male mold convex surface 10b in contact with the boundary part 20c of the surface 20b, so that the main wall 10e leads from the end of the inclined surface to the lower end of the coupling part 10a. By configuring to be formed, the male mold 10 is coupled to the movable mold, and the female mold 20 is coupled to the fixed mold,
The male mold 10 has a convex surface 10b, an outer circumferential inflection point 10c, and an annular concave groove 10f having a different curvature between the convex surface 10d and the start of the inclined surface 10d having a predetermined width, and the female mold 20 Is a concave surface (20b) and an annular concave groove (20f) having a different curvature on the inner surface of the outer circumferential boundary (20c) with a certain width, and the outer circumferential end of the annular concave groove (20f) of the female mold is an annular concave groove of the male mold (10f) A mold for molding a high-functional ophthalmic medical lens comprising silicon and metal oxide nanoparticles that are molded to maintain a curved surface at the outer peripheral edge of the contact lens, which is made to be in contact with the end.

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