CN87104122A - Soft-contact lens and manufacture method thereof - Google Patents
Soft-contact lens and manufacture method thereof Download PDFInfo
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- CN87104122A CN87104122A CN87104122.7A CN87104122A CN87104122A CN 87104122 A CN87104122 A CN 87104122A CN 87104122 A CN87104122 A CN 87104122A CN 87104122 A CN87104122 A CN 87104122A
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- pva
- contact lens
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- polyvinyl alcohol
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Abstract
Poly-vinyl alcohol solution by water and the mixed solvent that can constitute with the organic solvent of water immiscible phase prepares a kind of soft-contact lens.This solution is poured in the model with corresponding contact lens shape.This poly-vinyl alcohol solution of cooling below room temperature is owing to the polyvinyl alcohol (PVA) molecular crystallineization is made a kind of gelinite.Water exchanges out the organic solvent that contains in this gelinite, make polyvinyl alcohol (PVA) hydration contact lens, its tensile strength is not less than 10 kg/cm, and the liquid water content scope is 40% to 95% (weight), the visible transmission ratio is not less than 90%, and oxygen permeability is not less than 30 * 10
-11Cubic centimetre (standard state) mm Hg centimetre/square centimeter second.
Description
The present invention relates to the manufacture method of soft-contact lens and gelinite thereof.Specifically, the present invention relates to a kind of physical strength height, liquid water content height, the transparency is good, oxygen permeability is high polyvinyl alcohol gel rubber soft-contact lens, and relate to the manufacture method of this contact lens.
Have soft and two kinds of contact lenses of hard.The primary raw material of hard contact lens (HCL) is the polymethylmethacrylate (PMMA) with cross-linked network structure.Be widely used in the manufacturing of hard contact lens because of its transparency, molding processibility, biological stability and superior in durability, but the eyeball respiratory metabolism is required should not be worn for a long time because of its oxygen permeability is lower than, and the hard of this raw material makes patient that foreign body sensation be arranged simultaneously.
The raw material that is widely used in soft-contact lens (SCL) comprises the multipolymer of silicone elastomer and butyl acrylate (BA) and butyl methacrylate (BMA) as the hydrophobic nature raw material, and the multipolymer of polymethylacrylic acid 2-hydroxyl ethyl ester (PHEMA) and methyl methacrylate (MMA) and vinyl pyrrolidone (VP) is as the water wettability raw material.The raw material of these SCL is better than HCL aspect oxygen permeability.But the hydrophobic nature raw material has many shortcomings, as since the wettability difference of water cause wear the shortcomings such as surface fracture that sense of discomfort, significant lipid suction-operated and higher electrostatic charging cause, though and the water wettability raw material feels comfortable when wearing, the infringement of corneal is also minimum, but its manufacturing cost is very high, very strong to protein adsorption, physical strength is very low.
The somebody advises using the raw material of polyvinyl alcohol (PVA) (PVA) hydrogel as SCL, as with the PVA gel (United States Patent (USP) 3408429) of the crosslinked SCL of glyoxal with the PVA gel (day disclosure is speciallyyed permit (Tokkyo Kokai) 75111/1983) of the SCL of borate crosslinked.But because these gels are to carry out chemical crosslinking with glyoxal and borate, these soft-contact lens may make patient's cornea impaired owing to remain with unreacted compound or catabolite in gelinite.On the other hand, a kind of polyvinyl alcohol (PVA) soft-contact lens through the thermal treatment preparation (day disclosure special permission (Tokkyo Kokai) 214128/1982) is proposed, but its liquid water content and physical strength deficiency, and need carry out the process of complicated and time consumption.
In view of the above problems, the objective of the invention is to provide a kind of tensile strength to be not less than 10 kg/cm, the liquid water content scope is 40% to 95%(weight), visible transparency be not less than 90% and oxygen permeability be not less than 30 * 10
-11The PVA soft-contact lens of cubic centimetre (standard state) mm Hg centimetre/square centimeter second.By PVA being dissolved in the mixed solvent of forming by water and organic solvent, then solution is poured in the concavo-convex model corresponding to the SCL shape, make the PVA crystallization under the temperature of room temperature being lower than, can achieve the above object.
The saponification degree that is used for PVA of the present invention should be not less than the 95%(mole), to be not less than the 97%(mole) for well, be not less than 99% better.For example, be lower than the 85%(mole as the saponification degree of pectin/polyvinyl alcohol), then the physical strength of the gel of being made by PVA is not high.The viscometric degree of polymerization that is used for the polyvinyl alcohol (PVA) of the inventive method should not be lower than 1000, particularly is not less than 1700.Because the degree of polymerization reduces to make the gel strength step-down, so the commercially available degree of polymerization scope of suggestion use is 1700 to 2000 polyvinyl alcohol (PVA).The gel that intensity height, liquid water content or hot water resistance can be high if desired, then suggestion use 3000 to 10000 polyvinyl alcohol of high degree of polymerization or mainly be between with or the polyvinyl alcohol (PVA) of isotactic structure.Also the classification polyvinyl alcohol (PVA) that does not have low molecular weight fraction is used in suggestion, is come out by elution to prevent low molecular weight polyethylene alcohol.
In the present invention the organic solvent that mixes with water should with water compatible, preferably can be with any mixing ratio and water immiscible phase.The organic solvent of recommending comprise acetone, methyl alcohol, ethanol, n-propanol, isopropyl alcohol, ethylaminoethanol, phenol, tetrahydrofuran, N, dinethylformamide, glycerine, ethylene glycol, propylene glycol, triethylene glycol and dimethyl sulfoxide.In all these organic solvents, dimethyl sulfoxide is best, because it to the solubleness of polyvinyl alcohol (PVA) the highest and solidifying point descend best to the dependence of water and dimethyl sulfoxide mixing ratio, affect the physical strength and the transparency thereof of final gel to a great extent because of the mixing ratio of water and these organic solvents, so should carefully select mixing ratio according to the purposes of gel.In general, the ratio range of water and organic solvent be 90: 10 to 10: 90(weight), be preferably 70: 30 to 10: 90(weight).Even can make gel by the solution of polyvinyl alcohol (PVA) in 100% dimethyl sulfoxide, although this gel is transparent before changing solvent, after water exchange dimethyl sulfoxide, then become translucent.
For clear gel produced according to the present invention, at first compound concentration is 2% to 30%(weight) poly-vinyl alcohol solution.Liquid water content and mechanical property according to required gel are determined its concentration.Temperature or use autoclave or heating generator by under agitation raise polyvinyl alcohol (PVA) and solvent mixture are easy to prepare this extremely dense solution.
Then this poly-vinyl alcohol solution that all dissolves is cast in the concavo-convex model corresponding to the SCL shape, this solution is remained below under the temperature of room temperature.The polyvinyl alcohol (PVA) molecule carries out crystallization in this process, forms the SCL gel.Temperature is low more, and it is short more to finish the required time of crystallization.This solution should be cooled off in a temperature remains on refrigerator below-10 ℃, approximately-20 ℃ cool off better.When polyvinyl alcohol (PVA) reaches maximum crystallinity, this gel is immersed in the flowing water for a long time to remove organic solvent.Water is promptly made the polyvinyl alcohol (PVA) soft-contact lens after exchanging out organic solvent in the gel.Also can remove solvent fully, will be immersed in through the gel of super-dry again and carry out aquation in the water and produce this hydrogel with this gel drying after PVA reaches maximum crystallinity.If like this, can under atmospheric pressure, carry out gel drying simply, but, then can finish at short notice if use vacuum drying.
When preparing polyvinyl alcohol hydrogel via dry run, along with the carrying out of drying, the crystallinity of polyvinyl alcohol (PVA) will have increase slightly, thereby improve its mechanical property and light transparency.Temperature raises in the dry run, and crystallinity is raise.
In addition, in order to give this gel sterilization or to improve its mechanical property, thermotolerance and dimensional stability, can in inert gases such as nitrogen and argon gas or in de aerated water, shine this gel with ionization radial lines such as electron beam and gamma-rays down in decompression.Also chemical cross-linking agents such as glutaraldehyde, boric acid and sodium tetraborate can be used for the crosslinked of PVA gel.
Form this liquid water content height, transparent SCL that physical strength is high a kind of to seem rational mechanism explain as follows.The solution of making in the mixed solvent that the water-soluble and organic solvent of polyvinyl alcohol (PVA) is formed may be the homogeneous solution of molecular state.Along with the temperature of this homogeneous solution reduces, must make molecular motion be subjected to restriction to a certain degree and in solution, form local high segment density district.By cooling off being lower than under the temperature of room temperature, cause the formation hydrogen bond, thereby can promote to produce small crystal nucleus.Solution is long more in the following retention time of cooling condition, and the degree of polyvinyl alcohol (PVA) crystallization is high more.The crystallite that is produced plays a part crosslinked, produces a three-dimensional net structure thus.Most of hydrones certainly exist in the space of polyvinylalcohol microsphere intergranular.As a result, by means of in whole lens, forming equally distributed aperture, produce the high polyvinyl alcohol (PVA) soft-contact lens of physical strength height, transparency height and liquid water content.As sem observation at CO
2It is shown that dry resulting sample is carried out in critical point, and these apertures are not only thin but also long, and the size in hole is no more than 3 microns.Evenly and the fine and close aperture that distributes can produce atomic little variation on refractive index, thus form a kind of clear gel.For the purpose or the barrier ultraviolet ray of making up, available suitable dyestuff or pigment are coated with and dye SCL of the present invention.
More specifically narrate and explain the present invention with the following example.Should be appreciated that the present invention is not limited to these embodiment, under the condition that does not deviate from its purport and scope, can make many variations and improvement in the present invention.
Embodiment 1
To saponification degree is the 99.5%(mole), viscometric degree of polymerization is the mixed solvent shown in the interpolation table 1 in 1700 the polyethylene powder alcohol, obtains concentration polyvinyl alcohol (PVA) as shown in table 1 thus.This potpourri of heating is 2 hours in the autoclave of 110 ℃ of constant temperature, makes the homogeneous solution of polyvinyl alcohol (PVA) thus.After then this PVA solution being cooled to 50 ℃～80 ℃ temperature range, pour in the model.The one side of model is similar to protruding sphere, the radius-of-curvature (R of core
1) be 6.0 millimeters, and the another side of model is the concave ball shape of peripheral part projection, the radius-of-curvature (R of its core
2) be 6.0 millimeters, internal diameter (S) is 12 millimeters.Distance between the core on recessed ball and protruding ball surface is 0.3 millimeter.Make this model with tetrafluoraoethylene-hexafluoropropylene copolymer by the method for cutting and polishing.Remaining in-20 ℃ the refrigerator poly-vinyl alcohol solution was being kept in model 1 hour.Take out the polyvinyl alcohol gel make and this gel is immersed in 40 ℃～60 ℃ the enough water from model, water exchanges out the organic solvent in the gel.
Table 1
The embodiment mixed solvent
Sequence number prescription mixing ratio (weight) polyvinyl alcohol concentration
(%(weight))
1 water: dimethyl sulfoxide 2: 8 10
2 water: dimethyl sulfoxide 2: 8 15
3 water: ethylene glycol 4: 6 10
4 water: ethylene glycol 4: 6 15
5 water: glycerine 5: 5 10
6 water: glycerine 5: 5 15
7 water: ethylene glycol 8: 2 10
8 water: ethylene glycol 8: 2 15
Comparative example's single solvent polyvinyl alcohol concentration (%(weight))
1 water 15
2 dimethyl sulfoxides 15
3 PHEMA＊ -
* with Ethylene glycol dimethacrylate crosslinked poly-(2-hydroxyethyl methacry-late)
According to said method prepare various polyvinyl alcohol (PVA) soft-contact lens, and measure its tensile strength, elongation at break, liquid water content, visible transmission ratio and oxygen permeability according to following test condition.It the results are shown in table 2.
(tensile property)
Be under 65% the condition, to measure its tensile strength and elongation at break 20 ℃ and relative humidity (RH) with the draw speed of 100 mm/min.
(liquid water content)
Sequence number in the table 1 1～8 and comparative example's 2 gelinite is soaked after 3 days air-dry overnight in the draft chamber in 20 ℃ water.Then at room temperature further this gelinite is vacuumized dried overnight,, under 37 ℃, be placed on again in the enough water and carried out aquation in 2 days to remove the organic solvent that remains in the gelinite.Liquid water content by following formula calculated hydration polyvinyl alcohol (PVA) soft-contact lens.
Liquid water content=(hydration SCL weight-dry SCL weight)/(hydration SCL weight) * 100(%)
(visible transmission ratio)
Be soaked in the transmittance of measuring 550 nanometers SCL in the water at 25 ℃.
(oxygen permeability)
Use EMO-05SF type thin polymer film gas permeation test instrument that Japanese ESCO Denshi-Kagaku Co., Ltd. makes oxygen permeability at 35 ℃ of test PVA soft-contact lens.
Table 2
Preface tensile strength elongation at break water cut visible transmission is than oxygen permeability *
Number (kg/cm) (%) (% weight) (%)
1 24 205 79 99 41
2 32 487 74 99 32
3 16 192 87 99 53
4 27 394 83 98 50
5 13 176 88 95 54
6 21 211 82 95 47
7 19 188 84 97 49
8 20 237 76 96 38
Contrast is real
Execute routine number
1 22 218 84 68 41
2 15 185 82 61 36
3 9 140 37 98 9
* (* 10
-11Cubic centimetre (standard state) mm Hg centimetre/square centimeter second)
Embodiment 2
In nitrogen, use the soft-contact lens of electron beam irradiation sequence number 2, to improve the physical strength and the Young modulus of the polyvinyl alcohol (PVA) soft-contact lens of preparation among the embodiment 1.It the results are shown in table 3.
Table 3
Used PVA radiation dose penetration power * elongation at break 50% water cut oxygen flow
SCL sequence number (rad) (gram) is tensile force (% weight) property * * (%)
2＊＊＊ 0 110 206 53 84 51
9 3 140 165 67 81 47
10 6 194 159 85 79 44
11 9 220 116 123 77 39
* 0.2 millimeters thick
* (* 10
-11Cubic centimetre (standard state) mm Hg centimetre/square centimeter second)
The degree of polymerization of the used PVA of * * is 4800, and PVA concentration is 5%(weight)
(penetration power)
Going to insert diameter with the speed of 20 mm/min with the right cylinder of 2.0 millimeters of diameters is the sample of 12.7 millimeters (1/2 inches).Be to measure the required power of this sample that pierces through under 65% the condition 20 ℃ of following relative humidity.
(elongation at break)
Be similar to the method for embodiment 1
(50% tensile force)
50% tensile force is with stretch 50% o'clock required power of initial length of sample.Measure with being similar to the method for measuring penetration power.
(liquid water content)
Be similar to the method for embodiment 1.
(oxygen permeability)
Be similar to the method for embodiment 1.
Embodiment 3
Same quadrat method by sequence number 2 described in the embodiment 1 prepares polyvinyl alcohol gel rubber.After CO critical point drying hydrated gel body, with the surface of amplifying this gelinite of sem observation of 3000 times.Find that this gelinite has fine and close and equally distributed, size less than 3 microns elongated hole.
As mentioned above, the polyvinyl alcohol soft-contact lens by the inventive method preparation has high-tensile, high water content and good oxygen permeability. Therefore, these lens can be used for long-time intraocular and wear. And, to make simply because of it, cost is very low, and they can be used as the soft-contact lens of random use.
Claims (8)
1, a kind of tensile strength is not less than 10 kg/cm, the liquid water content scope is that 40% to 95% (weight) and oxygen permeability are not less than 30 * 10
-11The polyvinyl alcohol (PVA) soft-contact lens of cubic centimetre (standard state) mm Hg centimetre/square centimeter second.
2, the soft-contact lens of claim 1, the size that it has many holes is no more than 3 microns hole.
3, a kind of method of making the polyvinyl alcohol (PVA) soft-contact lens comprises the following steps:
(a) in the mixed solvent of water and a kind of organic solvent, prepare poly-vinyl alcohol solution,
(b) this solution is poured in the model with contact lens shape,
(c) this solution of cooling makes the polyvinyl alcohol (PVA) crystallization below room temperature,
(d) water exchanges out the organic solvent that is included in the resulting gelinite, makes the hydrated gel body.
4, the method for claim 3, wherein said organic solvent can with water immiscible phase.
5, the method for claim 3, the scope of wherein said water and organic solvent mixing ratio be 90: 10 to 10: 90(weight).
6, the method for claim 3, the concentration range of polyvinyl alcohol (PVA) is 2% to 30%(weight in the wherein said solution).
7, the method for claim 3, organic solvent wherein are dimethyl sulfoxide, glycerine, ethylene glycol, propylene glycol, triethylene glycol, N, dinethylformamide, methyl alcohol, ethanol, acetone, tetrahydrofuran, ethylaminoethanol, phenol, n-propanol or isopropyl alcohol.
8, the method for claim 3, wherein, use electron beam or gamma-rays radiation or use glyoxal, chemical cross-linking agents such as boric acid and sodium tetraborate make this hydrated gel body crosslinked.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90104979A CN1017378B (en) | 1987-06-09 | 1987-06-09 | Soft feeling lens |
| CN89103809A CN1010805B (en) | 1987-06-09 | 1987-06-09 | Soft contact lens and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89103809A CN1010805B (en) | 1987-06-09 | 1987-06-09 | Soft contact lens and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87104122A true CN87104122A (en) | 1988-12-28 |
| CN1010805B CN1010805B (en) | 1990-12-12 |
Family
ID=4814733
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90104979A Expired CN1017378B (en) | 1987-06-09 | 1987-06-09 | Soft feeling lens |
| CN89103809A Expired CN1010805B (en) | 1987-06-09 | 1987-06-09 | Soft contact lens and method of manufacturing the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90104979A Expired CN1017378B (en) | 1987-06-09 | 1987-06-09 | Soft feeling lens |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1017378B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106772728A (en) * | 2016-12-12 | 2017-05-31 | 云南科威液态金属谷研发有限公司 | Deformable minute surface |
| CN111566517A (en) * | 2018-01-30 | 2020-08-21 | 爱尔康公司 | Contact lenses having lubricious coating thereon |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3771567B2 (en) | 2003-09-02 | 2006-04-26 | 日東電工株式会社 | Filling foam composition, filled foam member and filling foam |
| CN114654636B (en) * | 2022-03-11 | 2023-08-18 | 中国海洋石油集团有限公司 | Water-soluble self-lubricating pigging and preparation method thereof |
-
1987
- 1987-06-09 CN CN90104979A patent/CN1017378B/en not_active Expired
- 1987-06-09 CN CN89103809A patent/CN1010805B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106772728A (en) * | 2016-12-12 | 2017-05-31 | 云南科威液态金属谷研发有限公司 | Deformable minute surface |
| CN106772728B (en) * | 2016-12-12 | 2019-08-27 | 云南科威液态金属谷研发有限公司 | Deformable minute surface |
| CN111566517A (en) * | 2018-01-30 | 2020-08-21 | 爱尔康公司 | Contact lenses having lubricious coating thereon |
| CN111566517B (en) * | 2018-01-30 | 2023-11-10 | 爱尔康公司 | Contact lens having a lubricious coating thereon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1010805B (en) | 1990-12-12 |
| CN1017378B (en) | 1992-07-08 |
| CN1048521A (en) | 1991-01-16 |
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