JP3084309B2 - Method of manufacturing lens for correcting vision - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a contact lens or an intraocular lens.

[0002]

BACKGROUND OF THE INVENTION It is well known that contact lenses and intraocular lenses are currently used for the purpose of correcting vision, and that the number of users, particularly those of contact lenses, will continue to increase. Seem. It should be noted that the number of users of myopia contact lenses in the young age group is larger than in other age groups. By the way, as the age of these young people increases, the demand for presbyopia contact lenses is thought to increase, but presbyopia contact lenses are not currently provided.

The reason for this is that presbyopic contact lenses are required to be able to correct vision for hyperopia and myopia with a single lens, and such requirements have been fulfilled for contact lenses. This was because it was extremely difficult to do so. That is, the spectacle lens is actually provided as a bifocal lens such as a multifocal lens due to its large size. However, the technology of the spectacle lens is directly applied to a small contact lens. It is extremely difficult. In addition, there have been proposals to change the radius of curvature of a part of the lens to make it a contact lens for presbyopia for bifocal use, and a proposal to form a diffraction grating on the contact lens to make it bifocal, but changed the curvature. In this case, the interface at the portion having a different curvature is clear, and there is a problem that the image shape changes such that the image suddenly becomes large or small at this interface. However, it has not reached the practical stage due to various causes such as difficulty in cleaning, difficulty in attaching dirt to grooves in the diffraction grating portion, and difficulty in cleaning.

[0004] Next, as for an intraocular lens, an intraocular lens having a near vision region in the center using a plurality of curvatures is currently being clinically applied, but refraction at a boundary having a different curvature. There are problems such as blurring due to a jump in the rate and poor eyesight correction due to poor processing. Also, an intraocular lens having a bifocal point using a diffraction grating is being developed. However, the absorption of biological components such as fibrin into the lattice portion occurs, and the amount of light in a necessary focal region is reduced by half by dividing light into two. For this reason, there is a problem that visual acuity does not appear in a dark place, and conversely, there is a problem that a rainbow-like image is generated by a prism phenomenon in a place of strong light.

Further, a technique has been proposed in which a cylindrical preform having a refractive index distribution is formed by utilizing the reactivity of a monomer, and this is cut and polished to obtain a contact lens for presbyopia. It has been pointed out that the distribution changes over time or becomes cloudy. As another method, a method has been reported in which a gel is first prepared and a monomer having a different refractive index is diffused into the gel to form a refractive index distribution.However, in this method, the gel state is kept constant. In particular, it is difficult to accurately form regions having different focal points in the central portion, and thus it is difficult to form a presbyopic contact lens or an intraocular lens.

[0006]

DISCLOSURE OF THE INVENTION As a result of the inventor's intense research on refractive index distribution type materials, it has been found that a refractive index can be obtained without using a monomer reactivity ratio at all and without using copolymerization of two or more monomers. It has been found that it is possible to form a platonic material with a rate distribution.

For example, a cylindrical polymerization tube is made of polymethyl methacrylate (PMMA), and a mixed monomer solution of a polymerizable monomer, methyl methacrylate (MMA), and a non-polymerizable monomer, bromobenzene (BrB), is formed in a cylindrical shape. PMM
Filled in A tube. Then, the PMMA tube swells with the mixed monomer solution of MMA and BrB, and a swelling layer is formed on the inner wall of the PMMA tube. And, in the swelling layer, MMA and BrB
Is mixed, but the BrB molecule is MM
Since it is much larger than the A molecule, it is difficult to enter the swelling layer, and MMA is small and enters the swelling layer preferentially. That is, the ratio of diffusion into the gel layer is MMA and Br.
B and MMA remaining outside the swollen layer and B
Ratio of rB and MMA and BrB penetrating into the swollen layer
Will be different from the ratio. Then, when heating or UV irradiation from around the PMMA tube, the gel effect is mainly induced in the swelling layer, so that polymerization starts earlier than any other portion in the PMMA tube. In other words, MMA polymer mainly precipitates from around the PMMA pipe, and this gradually
Proceed from the inner wall of tube A toward the center, and finally PMM
The polymerization of MMA having a high BrB ratio occurs near the center of the tube A, and the polymerization of the entire system is completed. In this way PM
It has become possible to form a transparent cured product having a refractive index distribution from the center to the periphery of the MA tube.

That is, since most plastic materials swell with ordinary monomers, a swelling layer can be easily formed on the plastic surface. Next, a mixture of two types of monomers (polymerizable monomer and non-polymerizable compound) or a mixture of monomer and oligomer, or monomer and polymer is diffused into the swelling layer. And / or performing selective diffusion depending on the compatibility or the size with the oligomer or polymer to form a swollen layer having a monomer composition distribution.
Also, dissolution of the plastic material swelled and dissolved in the mixture layer,
Diffusion takes place. When the swelling layer was polymerized while maintaining the composition distribution, a plastic material having a refractive index distribution according to the composition distribution could be formed. In other words, a polymerizable monomer and a non-polymerizable compound, or a polymerizable monomer and an oligomer, or a polymerizable monomer and a polymer are injected into a transparent polymerization tube, and the monomer molecules are diffused. By polymerizing, a plastic material having a refractive index distribution according to the composition distribution could be formed.

The present invention has been accomplished on the basis of the above findings, and an object of the present invention is to provide a multifocal (for example, a contact lens or an intraocular lens, particularly a presbyopic multifocal) having excellent transparency. Near vision area in the center, far vision area in the periphery,
Or, conversely, a contact lens or an intraocular lens having a far vision area at the center and a near vision area at the periphery is provided simply.

It is an object of the present invention to provide at least one polymerizable monomer and at least one non-polymerizable compound in a hole or a recess of a plastic material .
(A non-polymerizable compound) , and a step of diffusing the monomer molecules and performing a polymerization treatment. A step of injecting at least one polymerizable monomer and at least one non-polymerizable compound (however, a non-polymerizable compound other than the polymerization initiator) into the holes or recesses of the plastic material; And performing a polymerization process.

Further, the method comprises the steps of disposing at least one polymerizable monomer and at least one non-polymerizable compound around a plastic material, and performing a polymerization treatment by diffusing the monomer molecules. This is achieved by a method for producing a contact lens. In addition, the method includes a step of arranging at least one polymerizable monomer and at least one non-polymerizable compound around a plastic material, and a step of performing a polymerization treatment by diffusing the monomer molecules. Is achieved by a method for manufacturing an intraocular lens.

Further, the method is characterized by comprising a step of injecting at least one kind of polymerizable monomer and oligomer into a hole or a concave portion of the plastic material, and a step of performing a polymerization treatment by diffusing the monomer molecules. This is achieved by a method of manufacturing a contact lens. An intraocular lens comprising: a step of injecting at least one kind of polymerizable monomer and oligomer into a hole or a concave portion of a plastic material; and a step of performing a polymerization treatment by diffusing the monomer molecules. Is achieved.

A contact lens comprising a step of arranging at least one kind of polymerizable monomer and oligomer around a plastic material, and a step of performing a polymerization treatment by diffusing the monomer molecules. Is achieved. Further, a method for manufacturing an intraocular lens, comprising: a step of arranging at least one kind of polymerizable monomer and oligomer around a plastic material; and a step of performing a polymerization treatment by diffusing the monomer molecules. Achieved by the method.

Further, the method is characterized by comprising a step of injecting at least one kind of polymerizable monomer and polymer into a hole or a concave portion of the plastic material, and a step of performing a polymerization treatment by diffusing the monomer molecules. This is achieved by a method of manufacturing a contact lens. In addition, a step of injecting at least one polymerizable monomer and polymer into the holes or recesses of the plastic material, and allowing the monomer molecules to diffuse,
And a polymerization process.

A step of arranging at least one polymerizable monomer and a polymer around the plastic material;
A process of diffusing the monomer molecules and performing a polymerization treatment. Also, a method for manufacturing an intraocular lens, comprising: a step of arranging at least one kind of polymerizable monomer and polymer around a plastic material; and a step of diffusing and polymerizing the monomer molecules. Achieved by the method.

Here, the plastic material constituting the peripheral portion or the central portion of the vision correcting lens may be any material which swells in a polymerizable monomer and forms a swelling layer on the surface. And those used as intraocular lens materials. For example, an acrylic resin, a styrene resin, a silicone resin, an acrylic breathable material containing silicone or a fluorine atom, a cellulose resin, a urethane resin, and the like can be given. Of course, it is possible to use contact lens materials and intraocular lens materials that have been proposed so far, and it is also possible to use contact lens materials and intraocular lens materials that will be proposed in the future. is there.

Examples of the polymerizable monomer to be filled in the holes or recesses of the plastic material or disposed around the plastic material include acrylic monomers and styrene monomers. Of course, it is not limited to these. Further, the same monomer as the resin raw material (monomer) constituting the plastic material may be used, or a different monomer may be used.

The non-polymerizable compound used together with the polymerizable monomer ensures transparency when the non-polymerizable compound is dispersed in a polymer obtained by polymerizing the polymerizable monomer or in the plastic material. It is sufficient that a gradient is formed in the refractive index due to the difference in the dispersion rate. For example, n-hexane, benzene, toluene,
Bromobenzene, α-bromonaphthalene, β-bromonaphthalene, di (n-butyl) phthalate, benzyl n-butyl phthalate, cholesterol linoleate, squalene and the like can be mentioned. Of course, it is not limited to these.

The oligomer used together with the polymerizable monomer has, for example, a molecular weight of about 1,000 to 10,000, which may or may not have a polymerizable group. For example, silicone acrylic-modified oligomer, silicone methacryl-modified oligomer, polyethylene glycol monoacrylate-based oligomer, polyethylene glycol monomethacrylate-based oligomer, polyethylene glycol diacrylate-based oligomer, polyethylene glycol dimethacrylate-based oligomer, epoxy acrylate-based oligomer, epoxy methacrylate-based Oligomer, polyester acrylate oligomer, polyester methacrylate oligomer and the like can be mentioned. Of course, it is not limited to these.

Examples of the polymer used together with the polymerizable monomer include PMMA and benzyl methacrylate polymer (poly-BzMA). Of course, the material is not limited to these, and materials used as a contact lens material or an intraocular lens material can be used. The polymerizable monomers and non-polymerizable compounds, oligomers and polymers that are filled in the pores or recesses of the plastic material or placed around the plastic material are swellable to the plastic material or the product obtained after the polymerization treatment. What is necessary is just to select in consideration of a refractive index distribution and transparency. That is, as described above, when a PMMA tube is used as a plastic material, MMA is used as a polymerizable monomer filled in the tube.
However, if BrB having a high refractive index is selected as the non-polymerizable monomer, the obtained product has a higher refractive index in the central part than in the peripheral part. In addition, regarding the mixing ratio of the polymerizable monomer and the non-polymerizable compound, oligomer or polymer, the refractive index distribution of the product obtained after the polymerization treatment and whether or not the product has a hardness capable of mechanical processing are considered. It should just be selected. For example, the ratio of the former to the latter is 99 to 5
1 to 50 parts by weight, more specifically 95 to 100 parts by weight
It is used in a ratio of 5 to 30 parts by weight with respect to 70 parts by weight.

Hereinafter, the present invention will be described in detail with reference to specific examples. In the following, a description will be given by filling a mixture of a polymerizable monomer and a non-polymerizable compound, an oligomer or a polymer into a cylindrical polymerization tube and polymerizing the mixture. It is not necessary to place a transparent plastic polymer inside, and during this time, a mixture of a polymerizable monomer and a non-polymerizable compound, oligomer or polymer is filled and polymerized, so that the surroundings of the plastic material A mixture of a polymerizable monomer and a non-polymerizable compound, oligomer or polymer can be disposed in the same manner, and the same can be implemented. Further, the embodiment of the contact lens can be diverted to the embodiment of the intraocular lens by changing the shape.

[0022]

【Example】

[Example 1] A mixed solution of MMA and BrB (weight ratio: 5:
1) 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (P
H3M) was added to the center hole of a cylindrical tube made of PMMA having an inner diameter of 2 mm and an outer diameter of 10 mm by adding 0.5 wt% of n-butyl mercaptan and 0.15 wt% of n-butyl mercaptan,
Then, while rotating this at a speed of 100 rpm, while selectively diffusing and permeating the monomer mixture into a cylindrical tube, the mixture is kept at 95 ° C. for 24 hours to perform a polymerization reaction, and a transparent plastic round bar having a refractive index distribution is obtained. Obtained.

The round bar was processed into a flat plate having a diameter of 9.5 mm and a thickness of 0.2 mm by a usual cutting and polishing method.
The refractive index of the portion from the center to 3.0 mm from the center was measured by using an interferometer with an interference phase-inspection microscope manufactured by rl Zeissaus Jena. As a result, it was observed that the refractive index decreased from the center to the vicinity of 1.0 mm as the distance from the center increased, and the center and the radius of 2.0 m were observed.
There was a difference of about 0.05 in the refractive index from the position of m.

The above-mentioned round bar is 9.5 mm in diameter and 4.0 in thickness.
mm, and the rear surface has a radius of curvature of 7.40 mm and the front surface has a radius of curvature of 8.1 by a normal cutting and polishing method.
0mm, central part thickness 0.40mm, size 9.5mm
Into contact lenses. With respect to this contact lens, the vertex refractive index was calculated up to a position of 3.00 mm from the center based on the method described below. The result is -4.75 diopters from about 1.00 mm from the center, and -6.75 diopters from about 1.00 mm from the center to 3.00 mm, which is bifocal. It is a type of contact lens.

[Method of Calculating Apex Refraction] A laser beam parallel to the optical axis of the contact lens is made incident on a position of radius r, and the ray traces the distance Z ₁ from the lens in the optical axis direction. The shift distance X ₁ and the shift distance X ₂ from the optical axis when the distance Z ₂ further advances in the optical axis direction are measured, and the focal length Y is calculated from the following equation (1), and the equation (1) 2)
To calculate the vertex refractive index D (diopter).

Y = Z ₁ − (Z ₂ −Z ₁ ) / (X ₂ −X ₁ ) × X ₁ (1) D = 1 / Y (2) [Example 2] Instead of BrB in Example 1, Α-
The same procedure was carried out using bromonaphthalene to obtain a transparent plastic round bar having a refractive index distribution, which was processed into a flat plate having a diameter of 9.5 mm and a thickness of 0.2 mm by a normal cutting and polishing method to obtain a refractive index. As a result of measurement, 1.0 mm from the center
It is observed that the refractive index decreases with distance from the center to the vicinity, and the refractive index is about 0.06 between the center and the position with a radius of 1.0 mm. There was a difference.

The above-mentioned round bar was 9.5 mm in diameter and 4.0 in thickness.
mm, and the rear surface has a radius of curvature of 7.40 mm and the front surface has a radius of curvature of 8.1 by a normal cutting and polishing method.
0mm, center thickness 0.40mm, size 9.0mm
Into contact lenses. With respect to this contact lens, the vertex refractive index was calculated up to a position of 3.00 mm from the center. The result is -4.25 diopters from the center to about 1.00 mm, and -6.7 from about 1.00 mm to 3.00 mm from the center.
5 diopters, which are bifocal type contact lenses.

Example 3 A transparent plastic round bar having a refractive index distribution was obtained in the same manner as in Example 1 except that n-butyl benzyl phthalate was used instead of BrB.
This was processed into a flat plate having a diameter of 9.5 mm and a thickness of 0.2 mm by a normal cutting and polishing method, and the refractive index was measured.
It was observed that the refractive index decreased from the center to the vicinity of 1.0 mm as the distance from the center increased, and the refractive index between the center and a position having a radius of 1.0 mm was observed. Had a difference of about 0.07.

The above-mentioned round bar is 9.5 mm in diameter and 4.0 in thickness.
mm, and the rear surface has a radius of curvature of 7.40 mm and the front surface has a radius of curvature of 8.1 by a normal cutting and polishing method.
0mm, center thickness 0.40mm, size 9.0mm
Into contact lenses. With respect to this contact lens, the vertex refractive index was calculated up to a position of 3.00 mm from the center. The result is -3.75 diopters from about 1.00 mm from the center and -6.7 from 3.00 mm from about 1.00 mm from the center.
5 diopters, which are bifocal type contact lenses.

[Embodiment 4] In Embodiment 1, the PMMA
Instead of a cylindrical tube, a cross-linked PMMA-ED polymer containing 5% by weight of bifunctional ethylene glycol dimethacrylate (ED) is 2.6 mm in inner diameter and 10 mm in outer diameter.
MM instead of MMA and BrB
A and poly-BzMA (weight ratio 9: 1), and di-t-butyl peroxide (PB-
D) was used in an amount of 0.5% by weight, the polymerization temperature was set to 105 ° C., and the same procedure was carried out to obtain a transparent plastic round bar having a refractive index distribution.
As a result of processing into a flat plate having a thickness of 0.2 mm and a thickness of 0.2 mm, and measuring the refractive index, it has a distribution in which the refractive index decreases from the center to about 1.3 mm as the distance from the center increases. Is observed, and the center and radius 1.3
There was a difference of about 0.03 in the refractive index from the position of mm.

The above round bar is 9.5 mm in diameter and 4.0 in thickness.
mm, and the rear surface has a radius of curvature of 7.40 mm and the front surface has a radius of curvature of 8.1 by a normal cutting and polishing method.
0mm, center thickness 0.40mm, size 9.0mm
Into contact lenses. With respect to this contact lens, the vertex refractive index was calculated up to a position of 3.00 mm from the center. The result is -5.75 diopters from about 1.30 mm from the center and -6.7 from about 1.30 mm from the center to 3.00 mm.
5 diopters, which are bifocal type contact lenses.

Example 5 In Example 4, the crosslinked P
A cylindrical tube of MMA-ED polymer having an inner diameter of 3.0 mm and an outer diameter of 10 mm was used, and MMA and a polyester acrylate oligomer represented by the following Chemical Formula 1 (weight ratio 3:
Using 2), the same procedure was repeated except that the polymerization was performed at a rotation speed of a cylindrical tube of 200 rpm and a polymerization temperature of 110 ° C., thereby obtaining a transparent plastic round bar having a refractive index distribution, which was obtained by a normal cutting and polishing method to a diameter of 9 mm. It was processed into a flat plate having a thickness of 0.5 mm and a thickness of 0.2 mm, and the refractive index was measured.
It has been observed that the refractive index has a distribution in which the refractive index decreases as the distance from the center increases, and the refractive index is about 0.045 between the center and a position having a radius of 1.5 mm. There was a difference.

The above-mentioned round bar is 9.5 mm in diameter and 4.0 in thickness.
mm, and the rear surface has a radius of curvature of 7.40 mm and the front surface has a radius of curvature of 8.1 by a normal cutting and polishing method.
0mm, center thickness 0.40mm, size 9.0mm
Into contact lenses. With respect to this contact lens, the vertex refractive index was calculated up to a position of 3.00 mm from the center. The result is -5.25 diopters from about 1.50 mm from the center and -6.7 from about 1.50 mm from the center to 3.00 mm.
5 diopters, which are bifocal type contact lenses.

[0034]

Embedded image

[Embodiment 6] In Embodiment 4, 2, 2,
50% by weight of 2-trifluoroethyl methacrylate (3FMA), 45% by weight of MMA, 5% by weight of EDMA
Cross-linked fluorine-containing polymer (P3F
M-MMA-ED) using a cylindrical tube having an inner diameter of 3.0 mm and an outer diameter of 10 mm, and the same procedure as above except that the polymerization temperature was set to 105 ° C. to obtain a transparent plastic round bar having a refractive index distribution. This is 9.5 mm in diameter by a normal cutting and polishing method,
It was processed into a flat plate with a thickness of 0.2 mm, and the refractive index was measured.As a result, it was found that the material had a distribution in which the refractive index became smaller as the distance from the center increased to around 1.5 mm from the center. Observed and 1.5mm radius with center
There was a difference of about 0.07 in the refractive index between the positions.

The above round bar was 9.5 mm in diameter and 4.0 in thickness.
mm, and the rear surface has a radius of curvature of 7.40 mm and the front surface has a radius of curvature of 8.1 by a normal cutting and polishing method.
0mm, center thickness 0.40mm, size 9.0mm
Into contact lenses. [Example 7] In Example 1, a cylindrical tube made of PMMA having an inner diameter of 3.8 mm and an outer diameter of 10 mm was used, and MMA and BrB (5: 1 by weight) and 0.5% by weight as a filling mixture were used. A transparent plastic round bar having a refractive index distribution was obtained in the same manner as above except that PH3M was used, and this was processed into a flat plate having a diameter of 9.5 mm and a thickness of 0.2 mm by a normal cutting and polishing method. As a result of measuring the rate, 1.9 m from the center
It is observed that the refractive index has a distribution in which the refractive index decreases as the distance from the center increases until near m,
Then, there was a difference of about 0.05 in the refractive index between the center and the position having a radius of 1.9 mm.

The above-mentioned round bar was 9.5 mm in diameter and 4.0 in thickness.
After being formed into a block shape of mm, the rear surface was formed into a flat plate, the front surface had a radius of curvature of 7.80 mm, the center portion had a thickness of 0.90 mm, and the size was 6.0 mm by an ordinary cutting and polishing method. The result of measuring the apex refraction of this intraocular lens was +23.0 diopters from a position about 1.89 mm from the center, and +19.0 diopters from a position about 1.91 mm from the center to the periphery. And
This is a bifocal type.

──────────────────────────────────────────────────続 き Continued from the front page (72) Inventor Masamitsu Kuriaki 3-10 Yoshihoncho, Nakagawa-ku, Nagoya, Aichi Prefecture Inside Japan Contact Lens Co., Ltd. (72) Inventor Kanichi Nakamura 3- Yoshimotocho, Nakagawa-ku, Nagoya, Aichi Prefecture In Japan Contact Lens Co., Ltd. (72) Inventor Naokatsu Tanahashi 3-10 Yoshihoncho, Nakagawa-ku, Nagoya City, Aichi Prefecture In Japan Contact Lens Co., Ltd. (56) References JP-A-62-222203 (JP, A) JP-A-5-96553 (JP, A) JP-A-62-89901 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02C 1/00-13/00 G02B 3/00

Claims (12)

(57) [Claims] At least one polymerizable monomer and at least one non-polymerizable compound (a non-polymerizable compound other than a polymerization initiator) in a hole or a concave portion of a plastic material.
And the step of injecting and diffusing the monomer molecules,
A method of producing a contact lens. 2. At least one polymerizable monomer and at least one non-polymerizable compound (however, a non-polymerizable compound other than a polymerization initiator) in a hole or a concave portion of a plastic material.
And the step of injecting and diffusing the monomer molecules,
A method of producing an intraocular lens, comprising a step of performing a polymerization treatment. 3. A method comprising: arranging at least one polymerizable monomer and at least one non-polymerizable compound around a plastic material; and performing a polymerization treatment by diffusing the monomer molecules. A method for producing a contact lens, comprising: 4. A method comprising: arranging at least one polymerizable monomer and at least one non-polymerizable compound around a plastic material; and performing a polymerization treatment by diffusing the monomer molecules. A method for producing an intraocular lens, characterized in that: 5. A method comprising the steps of: injecting at least one kind of polymerizable monomer and oligomer into holes or recesses of a plastic material; and performing a polymerization treatment by diffusing the monomer molecules. Method of manufacturing contact lenses. 6. A method comprising: injecting at least one polymerizable monomer and oligomer into a hole or a concave portion of a plastic material; and performing a polymerization treatment by diffusing the monomer molecules. A method for manufacturing an intraocular lens. 7. arranging at least one polymerizable monomer and oligomer around the plastic material;
A process of diffusing the monomer molecules and performing a polymerization treatment. 8. arranging at least one polymerizable monomer and oligomer around the plastic material;
Diffusing the monomer molecules and performing a polymerization treatment. 9. A method comprising: injecting at least one polymerizable monomer and polymer into a hole or a concave portion of a plastic material; and performing a polymerization treatment by diffusing the monomer molecules. Method of manufacturing contact lenses. 10. A method comprising the steps of: injecting at least one polymerizable monomer and polymer into a hole or a concave portion of a plastic material; and performing a polymerization treatment by diffusing the monomer molecules. A method for manufacturing an intraocular lens. 11. arranging at least one polymerizable monomer and polymer around the plastic material;
A process of diffusing the monomer molecules and performing a polymerization treatment. 12. arranging at least one polymerizable monomer and polymer around the plastic material;
Diffusing the monomer molecules and performing a polymerization treatment.