KR100741611B1 - Urethane Hydrophilic Contact Lenses Containing Silicone and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to a urethane hydrophilic contact lens comprising a silicone and a method for manufacturing the same, more particularly hydroxyethyl methacrylate, silicone-urethane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl meth The present invention relates to a hydrogel contact lens comprising a polymer composed of acrylate as a monomer and a method of manufacturing the same.

The present invention substitutes polydimethylsiloxane having high oxygen permeability to hydroxyethyl methacrylate which can be polymerized, and introduces urethane group to synthesize a material of hydrogel contact lens having better oxygen permeability and good elasticity. Can be. In addition, moisture content and light transmittance using ethylene glycol dimethacrylate as a crosslinking agent such as N-vinyl-pyrrolidone, methyl methacrylate, hydroxyethyl methacrylate, etc. You can make this good hydrogel contact lens.

Description

Urethane hydrophilic contact lens containing silicon and its manufacturing method {Urethane Contact lens containing silicone and method

Figure 1a shows the HEMA-co-Urethane synthesis process.

Figure 1b shows the synthesis process of polydimethylsiloxnae (HEMA-co-Urethane-co-PDMS).

Figure 2 shows the production route of HEMA-co-Urethane-co-PDMS.

3 shows the IR spectra of HEMA-co-Urethane-co-Polydimethylsiloxane.

Figure 4a shows the water content and diameter change of S3-E, S4-E, S5-E.

4B shows the water content and diameter change for the combination with and without EGDMA.

5 shows the light transmittance (A) of S3-E-1, the light transmittance (B) of S4-E-1, and the light transmittance (C) of S5-E-1.

The present invention relates to a urethane hydrophilic contact lens comprising a silicone and a method for manufacturing the same, more particularly hydroxyethyl methacrylate, silicone-urethane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl meth The present invention relates to a hydrogel contact lens comprising a polymer composed of acrylate as a monomer and a method of manufacturing the same.

Depending on the physical properties of the contact lens material, it can be divided into hard lens and soft lens. PMMA (polymethyl methacrylate), which is a representative material of hard lenses, has been a representative material of almost all contact lenses. Although optically transparent, there are many disadvantages such as poor wettability, no moisture content and poor oxygen permeability. In order to solve the problem of PMMA lens, contact lens hydrophilic polymer was developed by wichterle in 1960, which improved the lens fit, and many companies have been approved since Bausch & Lomb was first approved by US FDA in 1970s. Lens materials with various materials, good water content and high oxygen permeability are under development (Majecti NV & Ravi Kumar, Reactive & Functional Polymer, 46: 1-32 2000).

As the material of high oxygen permeable contact lenses, hydrogel contact lenses made of prepolymers containing silicon have been studied. This research was begun by Gaylord in 1978, and since then, Dow Corning has developed tris- (trimethylsiloxsil-) (TRIS) to begin the development of RGP (rigid gas permeability) contact lenses. In 1979, Yoyo Contact Lens of Japan began making hydrogel contact lenses with PDMS (Tanaka K. and Takahashi K., US patent 4139513, 1979).

PDMA (Polydimethylsiloxan) consists of a bonding structure of Si-O-Si. Therefore, the atom rotation is free, so it is soft, so it is excellent in wearing comfort, and the oxygen difference is possible because the difference in atomic size between Si and O is large. However, such PDMS is difficult to use by itself, so it is used by modifying a part of a molecule.

Oxygen permeability of the lens is also affected by the thickness of the lens. The thinner the lens, the better the oxygen permeability and the better the fit. However, when the thickness of the lens becomes thin, there is a problem of easy tearing. In order to eliminate this problem and make the thickness of the lens thin, there is a method of introducing a urethane group (urethane group) to the lens in order to have a good elasticity. Urethane is known to have excellent elasticity and toughness because it is composed of hard and soft groups repeatedly (Ho-Bum Park & Choon-Ki Kim, Journal of Membrane Science, 204: 257 2002).

Representative materials of soft lenses include hydroxyethyl methacrylate (HEMA), methacrylate (MA), N-vinyl-pyrrolidone (NVP), and polymers having many physical properties by polymerizing each monomer. Developed and commercialized. Contact materials using silicon monomers have the advantage of increasing oxygen permeability. A representative example is silicone contact lenses (silicone A, Dow corning Ophthalmic). However, silicone monomers have been exposed to the problem of poor wettability. In order to supplement the hydrophobicity of silicon, a lot of research has been made to make a lens by polymerizing with a material monomer of a hydrophilic hydrogel lens.

Polysiloxane is a compound composed of a structure in which [(CH ₃ ) ₂ SiO] _n is repeated. This structure is made of a Zig-Zag structure, as shown in formula (1), and has a variety of properties because the polarity and angle of Si-O consists of 104 ^o or 109 ^o . The CC bond of paraffin is a pure covalent bond with almost no polarity, whereas the Si-O bond is an intermediate state of Si ⁺ O ^- because the electrons participating in the bond are tilted to one side because of the difference in electronegativity. It's very different. In addition, the Si-O angle requires a large amount of energy even with a slight change, whereas pure ionic bonds do not have a defined atomic angle and can be bonded in any direction. Although the representative atomic angle is defined as the intermediate angle state of both, the angle can be changed even with small energy. That is, Si-O-Si can be said to be a soft bond with elasticity. Therefore, polysiloxane is an elastic bond and can be said to have properties required for contact lenses. In addition, the structure is made up of a lot of space between the molecules that can move oxygen.

<Formula 1>

On the other hand, as the prior art for the present invention, PCT / US2001 / 09072 (2001.03.22) relates to a wettable silicone hydrogel and a manufacturing method thereof, and an ophthalmic lens prepared from the silicone hydrogel, PCT / US2000 / 12952 ( 2000.05.12) relates to a plasma surface treatment method of silicon hydrogel contact lenses using a flexible carbon coating, which is different from the configuration of the present invention.

An object of the present invention is to provide a hydrogel contact lens comprising a polymer composed of hydroxyethyl methacrylate, silicone-urethane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl methacrylate as monomers. It is.

Another object of the present invention is to provide a method of manufacturing a hydrogel contact lens having good water content and light transmittance.

The present invention for achieving the above object is a hydro containing a polymer composed of hydroxyethyl methacrylate, silicone-urethane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl methacrylate as monomers. Gel contact lenses.

The content of each monomer in the polymer is based on 100 parts by weight of hydroxyethyl methacrylate 36% to 38.5%, silicone urethane 3% to 9%, N-vinyl-pyrrolidone 27% to 29%, Ethylene glycol dimethacrylate 1% to 1.1% and methyl methacrylate 27% to 29%.

The present invention comprises the steps of (1) reacting a diisocyanate with hydroxyethylene methacrylate and dibutylitine dilaurate to synthesize a copolymer of hydroxyethyl methacrylate and urethane;

(2) A copolymer of hydroxyethyl methacrylate, urethane and polymethylsiloxane was synthesized by reacting a copolymer of hydroxy-terminated polydimethylsiloxane, dibutylitine dilaurate and hydroxyethyl methacrylate with urethane. Making;

(3) polymerizing the copolymer of hydroxyethylene methacrylate, urethane and polymethylsiloxane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl methacrylate produced in (2) above; It includes a method of manufacturing a hydrogel contact lens comprising.

In the above, diisocyanate may use methylene diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.

Hereinafter, the present invention will be described in detail.

The present invention comprises the steps of synthesizing the acrylate-isocyanate prepolymer for the production of hydrogel contact lenses having good water content and light transmittance, synthesizing the acrylate-polymethylsiloxane urethane copolymer, acrylate- It consists of a method of producing a hydrogel contact lens comprising the step of polymerizing a polymethylsiloxane urethane copolymer, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl methacrylate.

First, the synthesis of the acrylate-isocyanate copolymer was prepared by adding diisocyanate to 2-hydroxyethylmethacrylate (HEMA), dibutylitine dilaurate (DBTDL) and hydroquinone. Raise the temperature to ˜65 ° C. and slowly drop HEMA for 2 hours, then raise the temperature and hold for 1 hour. The addition of hydroquinone here can prevent the polymerization of the vinyl groups of HEMA.

For the synthesis of the acrylate-polymethylsiloxane urethane copolymer, hydroxyalkyl-terminated polydimethylsiloxane having high oxygen permeability characteristics and dibutylitine dilaurate were mixed, and then the temperature was increased to 55-65 ° C. with good stirring. Up. Thereafter, the above-described HEMA-co-Urethane synthesized in the dropping funnel is slowly dropped for 2 hours, and then maintained for 2 to 3 hours with stirring.

HEMA was used to make polymerizable prepolymer, and the introduction of urethane was used to improve the elasticity and oxygen permeability. Their reaction was confirmed by FT-IR, and this polymer material can be used as a raw material for high oxygen permeability hydrogel lens.

In the above diisocyanate is methylene diisocyanate (MDI), Toluene diisocyanate (TDI), Any of hexamethylene diisocyanate (HDI) can be used.

In addition, after the silicone-urethane used as the material of the contact lens is synthesized and the polymer is used as the monomer used as the material of the hydrogel lens, the contact lens material guarantees the moisture content problem and the light transmittance of the silicon material. You can make

Many combinations using silicone-urethane polymer and ethylene glycol dimethacrylate as crosslinking agent such as N-vinyl-pyrrolidone, methyl methacrylate, hydroxyethyl methacrylate, etc. Combinations based on formulas can then be polymerized to make polymers.

      The content of each monomer in the polymer is based on 100 parts by weight of hydroxyethyl methacrylate 36% to 38.5%, silicone urethane 3% to 9%, N-vinyl-pyrrolidone 27% to 29%, It is preferable that they are 1%-1.1% of ethylene glycol dimethacrylate, and 27%-29% of methyl methacrylates.

Water content measurement and light transmittance measurement were carried out with the polymerized individual in the present invention. In the present invention, polymers pursuing transparency and water content of materials were synthesized, and their physical properties were measured.

According to the present invention, polydimethylsiloxane having high oxygen permeability was substituted with polymerizable hydroxyethyl methacrylate, and a urethane group was introduced therein to synthesize a material of hydrogel contact lens having better oxygen permeability and good elasticity. can do. In addition, moisture content and light transmittance using ethylene glycol dimethacrylate as a crosslinking agent such as N-vinyl-pyrrolidone, methyl methacrylate, hydroxyethyl methacrylate, etc. You can make this good hydrogel contact lens.

Hereinafter, the content of the present invention will be described in more detail with reference to the following examples. However, these examples are only presented to understand the content of the present invention, but the scope of the present invention is not limited to these embodiments.

Example 1 Reagent

The Acrylate reagent used was a special reagent of Aldrich, washed twice with 5% aqueous NaOH solution and twice with distilled water to remove the polymerization inhibitor, and then water was removed with anhydrous MgSO ₄ , This was used after distillation under reduced pressure. Hydroxy-terminated polydimethylsiloxane (Hydroxy-terminated Polydimethylsiloxane) was used to purchase Aldrich OH equivalent 20-21. Ethylene Glycol Dimethacrylate, Methyl Methacrylate, 2-Hydroxyethylmethacrylate, N-Vinyl-Pyrrolidon ), AIBN (Azobis2-methylpropionitrile) was used.

Example 2 HEMA-urethane copolymer (HEMA-co-Urethane) synthesis

A reflex condenser, a dropping funnel, a magnetic bar are installed in a well-dried three neck flask, and a thermostat is provided to control the temperature of the cedar flask. Then, isocyanate, DBTDL (Dibutyltindilauryate), and hydroquinone (Hydroquinone: HQ) are added to the cedar flask and hydroxyethyl methacrylate is added to the dropping funnel. Raise the flask to 60 ° C. with good stirring and slowly drop HEMA for 2 hours. At this time, the fever may occur, so be careful. After dropping is complete, hold for 2 hours and complete the reaction (FIG. 1A).

Example 3 Synthesis of HEMA-Urethane-Polydimethylsiloxane (HEMA-co-Urethane-co-PDMS) Copolymer

A well-dried cedar flask is equipped with a reflex condenser, a dropping funnel and a magnetic bar. A cedar flask is equipped with a temperature control device to control the temperature. Hydroxy-terminated polydimethylsiloxane and DBTDL (Dibutyltindilauryate) were added to the cedar flask and the temperature was raised to 60 ° C. with good stirring. Thereafter, the HEMA-urethane copolymer synthesized in Example 2 was added to the dropping funnel and then slowly dropped for 2 hours. Thereafter, the reaction is terminated after the stirring for 2 hours (FIG. 1B). 2 shows the production route of the HEMA-urethane-polydimethylsiloxane copolymer.

3 shows the IR spectra of the HEMA-urethane-polydimethylsiloxane copolymer. In the synthesis of HEMA-urethane copolymers, the reactions of HEMA's OH and diisocyanate seem to be considerably diminished by the peak of IR spectra at -OH 3300Cm ^-1 and diisocyanate peak at 2270Cm ^-1 . It was confirmed that the reaction with one of the two functional groups was completed. In the synthesis of HEMA-co-Urethane-co-Polydimethylsiloxnae, the reaction showed that the -NCO peak disappeared completely at 2270Cm ^-1 , indicating that the reaction between -OH and the remaining -NCO of PDMS was completed, and the broad range of 1000 ~ 1100Cm ^-1 was observed. The peak was Si-CH ₃ peak at Si-O-Si, 1260Cm ^-1 . And the final product is a transparent, viscous polymer.

As described above, PDMS having high oxygen permeability was substituted with polymerizable HEMA (2-hydroxyethyl-methacrylate), and a urethane group was introduced to synthesize a material of hydrogel contact lens having better oxygen permeability and good elasticity. It was.

Example 4 Preparation and Analysis Method of Contact Lens Using Silicon-Urethane

Method for manufacturing contact lens using silicone urethane:

Polymerization mixing ratio of methacrylate that satisfies light transmittance, tensile strength, etc. and silicone is a hydrophobic material, so to compensate for this, it is preferable to copolymerize with hydrophilic material to increase the high water content. Experiment. The water content and its physical properties of the polymers reacted with each raw material for 1 hour in a 70 ℃ water bath were investigated. The polymer made after the polymerization was soaked in saline for 1 day, dried in an oven at 120 ° C. for 1 hour, and weighed. The reagents were measured for their water content after polymerization using an initiator (AIBN) and polymerization of each raw material was carried out three times for reliability.

Analysis method:

IR was used for Nicolet 520P, and the moisture content was measured by swelling the made contact lens in distilled water for 24 hours, drying in 100 ℃ oven for 1 hour, and then measuring dry weight and swelling weight.

The light transmittance was measured by using visible light, UV-A, and UV-B using Toncon TM-2. For contact lens polymerization, PE Mold was used. The polymerization was carried out for 120 minutes in a 70 DEG C water bath using SJ-202W water bath.

Example 5 HEMA + NVP + SILICONE-URETHANE + MMA + EGDMA Polymerization

A contact lens material containing a hydrogel material and silicone-urethane was prepared to measure moisture content and light transmittance.

HEMA, NVP, SILICONE-URETHANE, MMA combination S3, S4, S5 by about 1% of the cross-linking agent EGDMA was added to make a combination of S3-E, S4-E, S5-E and the control combination without EGDMA. Table 1 shows the combination ratios of S3-E, S4-E, S5-E and the control combination.

Table 1.HEMA + NVP + SILICONE-URETHANE + MMA + EGDMA Compound Ratio

HEMA NVP SILICONE- URETHANE MMA EGDMA AIBN S3-E 35.94% 26.91% 8.95% 27.00% 1.11% 0.10% S4-E 37.68% 28.25% 4.68% 28.23% 1.06% 0.10% S5-E 38.35% 28.71% 2.99% 28.81% 1.05% 0.10% control 36.34% 27.21% 9.05% 27.30% 0 0.10%

As shown in Table 2, the water content of S3-E is 28.89%, which is lower than 35.09% of the combination without EGDMA. After swelling, the diameter change also increased from 12mm to 13.12 by 1.1mm, showing a smaller diameter change than the S3 combination increased by 2mm. In the case of S4-E, the water content is 25.39%, which is lower than 28.49% of the combination without EGDMA. After swelling, the diameter change was increased from 12mm to 13.12 by 1.1mm, similar to that of S4. In the case of S5-E, the moisture content is 24.30%, which is lower than 29.55% of S5, which is a combination without EGDMA. The diameter change after swelling hardly increased from 12 mm to 12.625.

Table 2.HEMA + NVP + SILICONE-URETHANE + MMA + EGDMA Polymerization Results

Raw material collection Initial diameter (mm) Diameter after swelling (mm) Dry (g) Swelling (g) Moisture content (%) S3-E One 12 13 0.0882 0.125 29.44% 2 12 13.5 0.1054 0.1495 29.50% 3 12 13 0.0693 0.0959 27.74% Average value of S3-E individuals 12 13.16667 0.087633 0.123467 28.89% S4-E One 12 13 0.0747 0.0991 24.62% 2 12 13 0.0749 0.0998 24.95% 3 12 13 0.0775 0.1027 24.54% 4 12 13.5 0.1068 0.1472 27.45% Average value of S4-E individuals 12 13.125 0.083475 0.1122 25.39% S5-E One 12 12.5 0.0779 0.103 24.37% 2 12 12.5 0.0799 0.1036 22.88% 3 12 12.5 0.0816 0.1089 25.07% 4 12 13 0.0869 0.1157 24.89% Average value of S5-E individuals 12 12.625 0.081575 0.1078 24.30% control 12 14 0.1023 0.15555 35.09%

The moisture content and diameter change rate showed that the water content decreases from S3-E to S5-E, and the diameter change rate also decreases. S5-E has a relatively low ratio of SILICONE-URETHANE, but the difference in ratio is not large and may be due to the crosslinking agent EGDMA. The change in moisture content did not show a relatively large difference. The moisture content and diameter change rate of S3-E, S4-E, and S5-E are shown in FIG. 4A.

The graph comparing the addition of EGDMA, which is a crosslinking agent, in S3 ~ S5 combination shows a tendency to decrease in water content and diameter change rate in the combination with EGDMA. In particular, the diameter change rate after the hydration of the contact lens was a significant difference and the diameter change was small. In addition, the flexibility of contact lenses was also slightly reduced. A comparison of the combination with and without the EGDMA is shown in Figure 4b.

In the light transmittance measurement results, the visible light transmittance was 91% for S3-E-1, S4-E-1, and S5-E-1. UV-B transmittance was 69% ~ 72% and UV-A was measured 87 ~ 88%. Visible light transmittance of 90% or more showed good overall transmittance. The light transmittances of S3-E-1, S4-E-1, and S5-E-1 are shown in FIG. 5.

As described above, the present invention replaces polydimethylsiloxane having high oxygen permeability with a polymerizable hydroxyethyl methacrylate, and introduces a urethane group to the hydrogel contact lens having better oxygen permeability and good elasticity. Can be synthesized. In addition, the moisture content and the light content using ethylene glycol dimethacrylate as a crosslinking agent such as N-vinyl-pyrrolidone, methyl methacrylate, hydroxyethyl methacrylate, and the like, which are used as a silicone-urethane polymer and a hydrogel material Highly transparent hydrogel contact lenses can be made.

Claims (4)

A hydrogel contact lens comprising a polymer composed of hydroxyethyl methacrylate, silicone-urethane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl methacrylate as monomers. According to claim 1, wherein the content of each monomer in the polymer is based on 100 parts by weight of hydroxyethyl methacrylate 36% to 38.5%, silicone-urethane 3% to 9%, N-vinyl-pyrrolidone Hydrogel contact lens, characterized in that 27% to 29%, ethylene glycol dimethacrylate 1% to 1.1% and methyl methacrylate 27% to 29%. (1) reacting diisocyanate with hydroxyethylene methacrylate and dibutylitine dilaurate to synthesize a copolymer of hydroxyethyl methacrylate and urethane; (2) A copolymer of hydroxyethyl methacrylate, urethane and polymethylsiloxane was synthesized by reacting a copolymer of hydroxy-terminated polydimethylsiloxane, dibutylitine dilaurate and hydroxyethyl methacrylate with urethane. Making; (3) polymerizing the copolymer of hydroxyethylene methacrylate, urethane and polymethylsiloxane, N-vinyl-pyrrolidone, ethylene glycol dimethacrylate and methyl methacrylate produced in (2) above; Method for producing a hydrogel contact lens comprising. The method of claim 3, wherein the diisocyanate is any one selected from methylene diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate.

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