JP2002500379A - Multifocal lens that can be effectively controlled - Google Patents

Abstract

(57) [Summary] The present invention provides an effective multifocal lens. The optical lens has a first optical element that provides a first refractive index and a second optical element that provides a second refractive index. The second optical element is a volume holographic optical element, which is programmed to focus incident light. The invention further provides a crosslinkable or polymerizable optical material that is suitable for producing a biologically compatible holographic optical element. Optical materials are rapidly crosslinkable or polymerizable, changing from a fluid to a solid state within a limited period of time after exposure to a light source.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a multifocal lens including a holographic element and providing at least two indices of refraction.

Ophthalmic lenses, which are placed on or in the eye to correct visual defects
The intended products of various bifocal lenses for are available, such as contact lenses and intraocular lenses. One conventional bifocal ophthalmic lens design is a concentric simultaneous vision type. Concentric simultaneous bifocal lenses have alternating optical zones that are arranged concentrically. This concentric alternating optic zone has different radii of curvature and provides separate indices of refraction for near and far images, thus causing the near and far images to be in a common focal region. Although concentric simultaneous bifocal lenses are available in some cases, they are not widely used. This is because the image projected on the retina by the concentric simultaneous bifocal lens is composed of both near and far images, and the superimposed image does not completely clarify both near and far images. is there. For example, a distant object
When viewed through a concentric bifocal lens, an image of a near object is present at the same time and covers and covers an image of a distant object. Furthermore, since the light incident on the concentric simultaneous bifocal lens is split into two optical zones, the contrast and intensity of the focused image are sacrificed, especially in low light conditions.

[0003] Another conventional bifocal ophthalmic lens design is the diffractive simultaneous vision type. These lenses have a diffractive optical element and a refractive optical element and simultaneously project a far image and a near image on the retina using two optical compositions. As with concentric simultaneous bifocal lenses, diffractive simultaneous bifocal lenses separate light entering the eye into near and far images, and simultaneously project images onto the retina. As a result, both near and far images are not completely clear,
This causes contrast and intensity problems in low light conditions.

[0004] In addition, another conventional bifocal ophthalmic lens design is a transition type. Transition bifocal constant lenses generally follow the design of conventional bifocal lenses for eyeglasses. A transition lens has two distinct localized visual zones with different indices of refraction. The position of the bifocal lens on the eye must move from one area to another when the wearer desires to see objects located at different distances from the current focus. One major problem inherent in conventional transition bifocal lenses is that when the wearer attempts to move the lens position over the eye,
Difficulty encountered. The lens must move or move a relatively large distance on the eye to change from one visual area to another, and the movement from this one visual area to another It must be completed before vision can be obtained.

[0005] Recently, effective control attempts to provide a bifocal function in ophthalmic lenses have been proposed. A simultaneous bifocal lens with a separately applied thermal tinted coating is one example. Bifocal lenses are designed to activate the thermal tinted coating of the distant optical area of the lens as the wearer looks down to focus on nearby objects. The activated thermal tinted portion of the lens blocks light from distant optical regions, thereby preventing light covering or fogging from nearby objects. This approach is not sufficiently practical because currently available thermal coloring coating materials do not activate or deactivate quickly enough to be viable. Another approach uses a lens that changes its focal length with the help of a battery or light cell that can be opened and closed. This approach is impractical because the electronics and power supply must be small enough to fit in an ophthalmic contact lens and must be highly reliable and durable.

[0006] There remains a need for ophthalmic lenses that reliably provide a multifocal function that eliminates the disadvantages of the prior art multifocal lenses. Furthermore, there remains a need for optical materials that can be easily processed to produce holographic optical elements.

According to the present invention, there is provided a multifocal lens including a volume holographic optical element, which provides a refractive index. The lens has one or more indices of refraction, and one of the indices is effectively and selectively controlled by the wearer of the lens so that the wearer sees a clear, undamaged image. Can be This lens is suitable for various optical lenses, including contact lenses, spectacle lenses and intraocular lenses.

One embodiment of the present invention provides a multifocal lens including a first optical element and a volume holographic optical element, wherein the first optical element has a first focus at a first focus. The holographic optical element, which provides a refractive index, and in combination with the first optical element, provides a second refractive index at a second focal point. Another embodiment provides a multifocal lens having a volume holographic optical element, wherein the holographic optical element has a programmed activation angle,
The optical element then provides a first refractive index, e.g., a corrective refractive index or plane, a corrective or planar refractive index for light entering the optical element at an angle outside of the activation angle, and the activation angle. Provide a second index of refraction for light entering the optical element at an inner angle.

The present invention also provides a method for correcting a visual defect. The method includes the steps of providing a multifocal lens on the eye and moving the multifocal lens on the eye such that the appropriate focus is located on the eye recess. A multifocal lens, wherein the multifocal lens has a first optical element and a volume holographic optical element, wherein the first optical element provides a first index of refraction at a first focus; The element or the holographic optical element in combination with the first optical element can be characterized as providing a second refractive index at a second focal point. In another embodiment of the invention, the multifocal lens comprises a holographic optical element wherein the multifocal lens has a programmed activation angle, wherein the optical element is coupled to the optical element at an angle outside the activation angle. It can be characterized by providing a first index of refraction for incoming light and providing a second index of refraction for light entering the optical element at an angle inside the activation angle.

[0010] The multifocal lens of the present invention is a high efficiency corrective lens that does not have the disadvantages of simultaneous vision lenses and conventional transition lenses.

In the present invention, there is provided a biologically compatible holographic element made from a crosslinkable or polymerizable prepolymer. The prepolymer is selected from crosslinkable or polymerizable optical materials capable of forming a non-fluid or solid biologically compatible optical element within 5 minutes of irradiation of the UV source. The duration of cross-linking or polymerization was with the prepolymer placed between the bottom and top quartz slides, and a 200 watt medium pressure mercury arc lamp, with a U placed 18 cm above the top quartz slide.
It is measured by preparing a V source. The present invention also provides a hydrogel holographic device made from a prepolymer. Further, there is provided a method for manufacturing a holographic element from a prepolymer or monomeric fluid composition.

The holographic element can be used as a medical device, for example, as an optical lens and an ophthalmic lens. Optical and ophthalmic lenses having the holographic optical elements of the present invention are relatively easy to manufacture and are very suitable for correcting various non-emmetropic conditions.

The present invention provides an effective multifocal ophthalmic lens. Further, the present invention provides an effective multifocal ophthalmic lens for spectacles. Hereinafter, the term "ophthalmic lens" is used to refer to both ophthalmic and ophthalmic lenses, unless otherwise specified. The effective optical lenses of the present invention provide one or more refractive indices. More specifically, the lens has at least one index of refraction and at least one additional index of refraction that can be activated. Unlike conventional bifocal lenses, the effective multifocal lenses of the present invention provide one desired refractive index at the same time without or substantially without optical interference from other refractive indices of the lens. In this way, it can be controlled positively and selectively.

An effective optical lens includes a holographic optical element (HOE), and a suitable HOE for an effective optical lens is a transmission volume HOE. The volume HOE includes an interference fringe pattern that is programmed or recorded as a periodic change in the refractive index of the optical material. This periodic change in the index of refraction creates a plane of peak index of refraction inside the optical material, a volume grating structure. The plane of the fringe pattern in the HOE is discussed further below.

Returning to FIG. 1, this figure shows a typical effective bifocal lens 10 of the present invention. It should be noted that although the effective optical lenses of the present invention can have more than one refractive index, a bifocal lens is disclosed by reference for purposes of illustration. The lens 10 is a contact lens having the first element 12 and the HOE 14. HOE 14 is embedded or encapsulated in first optical element 12 to form a compound lens 10 in which the HOE moves in combination with lens 10. The first optical element 12 provides a first refractive index, which corrects a non-emmetropic condition, for example, myopia. Alternatively, first optical element 12 can be a planar lens that acts as a carrier for HOE 14. For a HOE, the optical element only allows the light to enter the HOE at a pre-programmed angle or within a pre-programmed angular range, ie, at an activation angle (which activates the optical element). Designed to alter the pathway. Thus, when light enters at an angle that is outside the activation angle, HOE 14 transmits the incident light completely or substantially completely without altering or substantially altering the light path. In other words, HO
E14 can act as a planar lens, except when its angle of incident light is inside a pre-programmed angle. When HOE is activated, HO
A striped or volume grating structure, programmed in E, alters the light path and provides a different refractive index from the first index of the lens 10. In addition to the activatable refractive index, the HOE provides a refractive index from the shape of the HOE 14 and the refractive index of the composition of the HOE 14. Such an additional index of refraction supplements the first optical material and provides an effective first index of the lens 10 when incident light enters the lens 10 at an angle that does not activate the HOE. As used herein, the term "activation angle" refers to the angle of incidence of the incident light (which is defined by the angle formed by the direction of travel of the incident light, and the axis perpendicular to the HOE surface; As diffracted by the grating structure,
Which satisfy Bragg's condition and are discussed further below). It should be noted that the activation angle should not be a single value, but can be a range of angles. Bragg conditions are well known in the optical arts, for example, Coupled Wave Theor
y for Thick Hologram Gratings, by H. Kogelnik., The Bell System Technica
l Journal, Vol. 48, No. 9, p. 2909-2947 (Nov. 1969). The description of the Bragg conditions disclosed herein is hereby incorporated by reference. The Bragg condition is: cos (Φ−θ) = K / 2B where K = 2π / Λ, Λ is the diffraction grating period of the interference fringes, θ is the projection angle of the incident light, and Φ is the inclination of the diffraction grating. Is the angle, and B is the average transfer constant, which is expressed as B = 2πn / λ, where n is the average refractive index and λ is the wavelength of light. When the Bragg condition is met, up to 100% of the incident light is diffracted coherently.

FIG. 2 further illustrates the function of the HOE 14 of the bifocal lens 10 of FIG. Z
The axis, which is perpendicular to the surface of the HOE, and the direction in which the incident light R travels forms a refraction angle σ. The incident light R is HO at a projection angle that is inside the activation angle of HOE 14.
Upon entering E, light R is diffracted by the pre-programmed fringe pattern of the HOE, ie, the volume grating structure, and exits the HOE as exit light S having an exit angle ρ different from the projection angle σ.

FIG. 3 shows another embodiment of an effective bifocal lens of the present invention. The bifocal active lens 16 is a compound lens having a first optical lens 17 and a HOE lens 18 (which completely covers the first optical lens 17). Alternatively, the HOE lens 18 can be sized to cover only the pupil of the eye. The first optical lens 17 and the HOE lens 18 can be manufactured separately and bonded, for example, adhesively or thermally. Alternatively, the first optical lens 17 and H
The OE lens 18 can be manufactured one continuously or simultaneously over another so that a compound lens is manufactured. This continuous or simultaneous method is particularly suitable when the first optical lens and the HOE lens are manufactured from one basic material or from two chemically compatible materials. Although the effective lens 16 is shown as a lens having an inner half first optical lens and an outer half HOE lens, other combinations of various indices of refraction can be made in accordance with the present invention.

Yet another embodiment of an effective bifocal lens is a non-composite effective HOE bifocal lens. In this embodiment, the effective HOE bifocal effective lens is H
Manufactured from optical materials that form the OE. The combination of the effective lens shape and the refractive index of the HOE material provides a first refractive index, and the programmed volume grating structure in the HOE lens provides a second refractive index. This non-composite effective HO
The E-lens embodiment is particularly suitable when the HOE material used is a biologically compatible material (and therefore does not adversely interact with ocular tissue). As used herein, the term "biologically compatible material" does not appreciably disintegrate when implanted or placed adjacent to a patient's biological tissue, resulting in a significant immune response or detrimental Given to a polymerizable material that does not induce a tissue response, such as a toxic response or significant irritation. Preferably, the biologically compatible material does not disintegrate for at least 6 months, more preferably at least 1 year, most preferably at least 10 years, and does not produce an immune or adverse tissue reaction. Suitable biologically compatible materials are highly photocrosslinkable or photopolymerizable materials. Suitable biologically compatible optical materials include derivatives and copolymers of polyvinyl alcohol, polyethylene imine, or polyvinylamine. Examples of biologically compatible materials that are particularly suitable for making the HOEs of the present invention are described in Muhlebach, US Pat.
o. 5,508,317 and Muhlebach's International Patent Application No. PCT / EP
Patents and applications disclosed in U.S. Pat. No. 96/00246, incorporated herein by reference, are discussed further below.

The HOE of the present invention is designed or programmed to have a single activation angle or range of activation angles, and the HOE directs the incident light to focus the light at a desired location. Diffract. FIGS. 4 and 5 illustrate the function of the HOE 21 of the composite effective lens 20, which includes a HOE lens element that is programmed to focus light emanating from close distances. Light 22 from a distant object is H
When entering the lens at an angle that does not activate the OE 21, the light 22 will follow the refractive index of the first optical element of the lens 20 and in combination with the refractive index of the lens of the eye (not shown), , More particularly at the focal point 24 above the depression. For example,
The first optical element 23 can have a corrective refractive index of +20 diopters to -20 diopters. It should be noted that the HOE lens 21 has a specific refractive index from the shape of the HOE lens 21 and the refractive index of the HOE composition. as a result,
The HOE lens 21 can contribute to the effective refractive index of the lens 20. Nevertheless, the inherent refractive index can be easily factored in the teachings of the present invention,
Hereinafter, in order to simplify the description of the diffraction function of the HOE lens of the present invention, the intrinsic refractive index of the HOE lens 21 is ignored. When the HOE lens 21 is not activated,
The HOE lens 21 does not interfere with the light 22 that passes through the normal refraction path provided by the first optical lens element 23. However, when the light enters the HOE lens at an angle that activates the HOE lens 21 (ie, enters inside the activation angle), the light is diffracted by the HOE lens 21. As shown in FIG. 5, the incident light is HOE
When entering the active lens 25 at an angle that activates the lens 26, the lens, in conjunction with the first optical lens 27 and the lens of the eye, collects light into the retina, and more particularly into the depression. For example, light 28 emanating from a nearby object 29 forms an image 30 above the well as the light enters the HOE lens at an angle that is inside the programmed activation angle.

For an effective bifocal lens, and more particularly for the HOE portion of the effective lens, the angle of incidence of the incident light can be varied by various means. For example, an effective lens can be tilted to change the angle of incidence of the incident light, i.e., the wearer of the lens can change the angle of light by looking at the head while looking down. Alternatively, the effective lens may have a position control mechanism that can be effectively controlled by one or more muscles of the eye by the wearer of the lens. For example, an effective lens can be shaped to have a neat ballast so that movement of the lens can be controlled by the lower eyelid. Effective lens 25 shown in FIG.
It should be noted that the activation angle of the effective lens is overestimated to more easily explain the present invention, so that the activation angle of the effective lens is not as large as the tilt angle shown in FIG. In fact, HOEs suitable for the present invention can be programmed to have a wide range of different activation angles by HOE programming methods known in the holographic arts. Thus, the degree of movement required for an effective lens to switch from one refractive index to another can easily be varied according to design criteria and the needs of the wearer of each lens.

Although the effective lenses of the present invention provide more than one index of refraction, the effective lenses form distinct images that are focused by one index of refraction at a time. As a result, the effective lens does not produce a blurred and fogged image, unlike conventional bifocal lenses, such as concentric simultaneous bifocal lenses. Returning to FIG. 5, the effective lens 25
Is positioned to view a nearby object 29 (ie, the projection angle of the light emanating from the object 29 is inside the activation angle of the HOE lens 26), the light from the object 29 is The HOE lens 26 focuses on the recess 30 in conjunction with the optical lens 27 and the lens of the eye lens. At the same time, the projection angle of light generated from a distant object is not inside the activation angle of the effective lens 25. Therefore, the path of the incident light from the distant object is not modified by the HOE lens 26, but the path of the incident light from the distant object is changed by the first optical lens 27 and the lens of the crystalline lens of the eye.
Modification, ie, refraction. Incident light from distant objects will therefore focus the image on the area 31 outside the depression. As a result, the focused images of near and far objects are not concentric or axial. The image (formed outside of the depression 31) is not clearly recognized by the wearer of the effective lens 25 and is easily ignored as the surrounding vision. As a result, the wearer of the effective lens 25 can clearly see nearby objects without contamination from light emanating from distant objects.

Similarly, when the effective lens is in a position to view a distant object (eg, as shown in FIG. 4), light 22 from the distant image will be transmitted through the lens at angles outside the activation angle of the HOE 21. to go into. Thus, the light path is not affected by the HOE 21, but only by the first optical element 27 and the lens of the eye, thereby focusing an image from an object that is far above or near the depression 24. At the same time, light emanating from nearby objects is diffracted, focused by the HOE, and projected onto the area outside the depression. Thus, the wearer of the effective lens sees distant objects clearly without noticeable interference.

The non-bleeding advantage of the active lens of the present invention is a result of the design of the active lens using the native anatomy of the eye. It is known that the concentration of retinal receptors outside the well is dramatically lower than that at the well. As a result, any image substantially focused outside the recess is not clearly recognized, since the image is not perceived by the retina as a peripheral image and is easily ignored by the wearer's brain. In fact, it has been found that the visual acuity of the human eye drops to about 20/100 at only 8 ° out of line of sight. In the above-described effective control method, the effective lens of the present invention provides a clear image from one refractive index at a time by using the unique anatomy of the eye. By using the ability to program different ranges of the retinal receptor anatomy of the eye and the activation angle at the HOE lens, the effective lenses of the present invention uniquely and selectively
It provides clear images of objects located at different distances. Compared to various simultaneous bifocal lenses, this effective lens provides clear images without obstruction, and, compared to transition bifocal lenses, this effective lens selectively selects images from different distances. It can easily be designed to require only a small movement of the lens to provide.

HOEs suitable for the present invention can be made, for example, from polymerizable or crosslinkable materials, especially fluid optical materials. Suitable polymerizable or crosslinkable HOEs are discussed further below. For purposes of explanation, the term polymerizable material is used hereinafter for polymerizable or crosslinkable materials, unless otherwise specified. An example of a method for manufacturing the HOE of the present invention is shown in FIG. The point-source target light 32 is an electromagnetic wave of the target light 32 and the reference light 3.
4 to form an interference fringe pattern (which is recorded in the polymerizable material, thereby forming a volume grating structure in the lens 33). ) And simultaneously collimated reference light 34 is projected onto the photopolymerizable HOE. The photopolymerizable HOE 33 is a photopolymerizable material that is polymerized by both the target light and the reference light. Preferably, the target light and the reference light are generated from one light source using a beam splitter. The two split parts of the light are projected onto the HOE, where the path of the target light of the split light is modified to form a point light source 32. The point light source target light 32 can be provided, for example, by arranging a conventional convex lens some distance from the photopolymerizable HOE 33 such that the light is at a distance from the HOE, ie, at the point light source position 32. . A preferred light source is a laser source, with a UV laser source being more preferred. The appropriate wavelength of the light source depends on the type of HOE used, but the preferred wavelength range is 300 nm
６００600 nm. When the photopolymerizable HOE33 is sufficiently exposed and polymerized,
The resulting HOE includes a refractive index modulation pattern, that is, a volume diffraction grating structure 35.
Further, when the fluid polymerizable optical material is used to produce a HOE, the light source converts the fluid optical material to a non-fluid or solid HOE while forming a volume grating structure. As used herein, the term "fluid" indicates that the material can flow like a fluid.

Returning to FIG. 7, when the polymerized HOE 36 enters the HOE from the opposite side of the focal point and coincides or substantially coincides with the reverse path of the collimated reference beam 34 of FIG.
It has a focal point 38 corresponding to the position of the point light source target light 32 in FIG. 6 and 7 provide an example of a method for manufacturing a HOE having a positive corrective refractive index. As will be appreciated, HOEs having a negative corrective refractive index can also be manufactured with the above-described HOE manufacturing equipment with some modifications. For example, a convergent target light source that forms a focal point on the other side of the HOE away from the light source can be used in place of a point source target light to produce a HOE having a negative corrective refractive index. According to the present invention, an effective multifocal lens having various corrective refractive indices can be easily and easily formed in various non-emmetropic states,
It can be easily and simply manufactured to correct, for example, myopia, hyperopia, presbyopia, regular astigmatism, irregular astigmatism and combinations thereof. For example, the corrective refractive index of the HOE can be changed by changing the distance, position and / or path of the target light, and the activation angle of the HOE can be changed by changing the position of the target light and the reference light. it can.

According to the present invention, suitable HOEs can be made from polymerizable or crosslinkable photomaterials that can be relatively rapidly photopolymerized or photocrosslinked. Rapidly polymerizable optical materials cause a periodic change in the refractive index created in the optical material, whereby the optical material is polymerized, forming a volume grating structure while forming a solid optical material. Preferably, suitable polymerizable and crosslinkable optical materials are selected from biologically compatible optical materials, and preferably suitable optical materials are equal to or less than 5 minutes, more preferably Is equal to or less than 3 minutes, more preferably equal to 30 seconds, or 30 minutes.
In less than a second, for example 5 to 30 seconds, it is selected from non-fluids having a defined shape by cross-linking or polymerizing, fluid-compatible optical materials forming a solidified optical element. The duration of crosslinking or polymerization is measured by placing the crosslinkable or polymerizable optical material between two quartz slides, which have the dimensions of a microscope slide and are separated by 100 im. A sufficient amount of optical material is placed on the first slide to form a circular drop having a diameter of about 14 mm, and the second slide is placed on the optical material. Alternatively, spacers can be used to prepare cylindrical spacers between slides for optical material. The optical material between the slides is illuminated with a 200 watt medium pressure mercury arc lamp located 18 cm above the quartz slide above.

A typical group of biocompatible polymerizable materials suitable for the present invention is Muller's
It is disclosed in US Pat. No. 5,508,317. A preferred group of polymerizable optical materials is U
As described in .S. Patent No. 5,508,317, it has a basic structure of 1,3-diol, in which a certain proportion of 1,3-diol units is polymerized in the 2-position. But those which have been modified to 1,3-dioxane with unpolymerized groups. The polymerizable optical material is preferably based on the number of hydroxy groups of the polyvinyl alcohol of formula (I):

[0028]

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Wherein R is lower alkylene having up to 8 carbon atoms, R ¹ is hydrogen or lower alkyl, and R ² is an olefin, preferably having up to 25 carbon atoms. From about 0.5% to about 80%, which is at least about 2%.
It is a derivative of polyvinyl alcohol having a weight average molecular weight of 2,000 and _Mw . R ² is, for example, of the formula R ³ —CO—, wherein R ³ is an olefinically unsaturated group having 2 to 24, preferably 2 to 8 and particularly preferably 2 to 4 carbon atoms. , Which is a copolymerizable group). Examples of olefinically unsaturated copolymerizable groups are ethenyl, 2-propenyl, 3-propenyl, 2-butenyl, hexenyl, octenyl and dodecenyl.

As a preferred embodiment, the group R ² has the formula (II):

[0031]

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Wherein p is 0 or 1, preferably 0; q is 0 or 1, preferably 0; R ⁴ and R ⁵ are each independently 2-8 Lower alkylene having carbon atoms, arylene having 6 to 12 carbon atoms, lower saturated divalent alicyclic group having 6 to 10 carbon atoms, arylene alkylene having 7 to 14 carbon atoms or alkylene arylene , or 13 to 16 amino is arylenealkylenearylene carbon atoms, and R ³ is a group of the same meaning as defined above).

The lower alkylene R preferably has up to 8 carbon atoms and may be straight-chain or branched. Suitable examples are octylene, hexylene, pentylene, butylene,
Includes propylene, ethylene, methylene, 2-propylene, 2-butylene and 3-pentylene. Preferably, lower alkylene R has up to 6 carbon atoms, particularly preferably up to 4 carbon atoms. Methylene and butylene are particularly preferred. R ¹ is preferably hydrogen or lower alkyl having up to 7, especially up to 4 carbon atoms, especially hydrogen.

As R ⁴ and R ⁵ , lower alkylene R ⁴ or R ⁵ preferably has 2 to 6 carbon atoms and is especially straight-chain. Suitable examples are propylene, butylene, hexylene,
It comprises dimethylethylene, and particularly preferably ethylene. Arylene R ⁴ or R ⁵ is preferably phenylene, which is unsubstituted or substituted by lower alkyl or lower alkoxy, especially 1,3-phenylene or 1,4-
It is phenylene or methyl-1,4-phenylene. The saturated divalent cycloaliphatic radical R ⁴ or R ⁵ is preferably cyclohexylene or cyclohexylene-lower alkylene, such as cyclohexylene methylene, which is unsubstituted or substituted by one or more methyl groups, For example, trimethylcyclohexylenemethylene, for example a divalent isophorone group. The arylene unit R ⁴ or R ⁵ of the alkylene arylene or arylene alkylene is preferably phenylene, which is unsubstituted or substituted by lower alkyl or lower alkoxy, and the alkylene unit is preferably Lower alkylene, for example methylene or ethylene, especially methylene. Such a group R ⁴ or R ⁵ is therefore preferably phenylenemethylene or methylenephenylene. Arylenealkylenearylene R ⁴ or R ⁵ is suitably phenylene-lower alkylene-phenylene having up to 4 carbon atoms in the alkylene unit, for example phenyleneethylenephenylene. The radicals R ⁴ and R ⁵ are each independently a lower alkylene, preferably having 2 to 6 carbon atoms, phenylene, which is unsubstituted or substituted by lower alkyl,
Cyclohexylene or cyclohexylene-lower alkylene, which is unsubstituted or substituted by lower alkyl, phenylene-lower alkylene, lower alkylene-phenylene or phenylene-lower alkylene-phenylene.

The polymerizable optical material of the formula (I) can be, for example, polyvinyl alcohol by the formula (III):

[0036]

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Wherein R, R ¹ and R ² are as defined above, and R ′ and R ″ are each independently hydrogen, lower alkyl or lower alkanoyl, such as acetyl or propionyl. And preferably about 0.5 to about 80%, more preferably about 1 to about 50%, and most preferably about 2 to 15% of the resulting polymerizable optical material. % Is replaced by compound III.

Suitable polyvinyl alcohols of the derivatized polyvinyl alcohol of the present invention have a weight average molecular weight of about 2,000 to about 1,000,000, preferably 10,000.
It has from 0 to 300,000, more preferably from 10,000 to 100,000, and most preferably from 10,000 to 50,000. Polyvinyl alcohol has less than about 50%, preferably less than about 20%, of the unhydrolyzed vinyl acetate groups. In addition, polyvinyl alcohol may comprise one or more copolymer units such as ethylene, propylene, acrylamide, methacrylamide, dimethacrylamide, hydroxylethyl methacrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl pyrrolidone, hydroxyethyl acrylate , Allyl alcohol and styrene up to about 20%, preferably up to about 5%.

The vinyl alcohol derivative is polymerized using a photocrosslinking method in a solvent, for example, using a UV laser to produce HOE. Suitable solvents are any solvents that dissolve the polyvinyl alcohol and the vinylic comonomer. Typical solvents are water, ethanol, methanol, propanol, dimethylformamide, dimethylsulfoxide and mixtures thereof. To facilitate the photocrosslinking polymerization process, a photoinitiator (
It can initiate free radical crosslinking). Typical photoinitiators suitable for the present invention include benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, Durocure® 1173 and Irgacure® photoinitiators. Preferably about 0.3 to about 2.0% of the photoinitiator is used, based on the total weight of the polymerization formulation. According to the present invention, in order to produce HOE,
A suitable concentration of polyvinyl alcohol in the solvent is preferably about 3 to about 90% by weight, more preferably about 5 to 60% by weight, especially when HOE is used as an ophthalmic lens.
It is.

A group of typical biologically compatible polymerizable optical materials suitable for the present invention is described in US Patent Application Serial No. 08 / 875,340, (Muhlebach International Patent Application No. PCT / EP96). / 00246). The description of the polymerizable optical material of the US patent application is incorporated herein by reference. Suitable optical materials are based on the number of hydroxy groups in polyvinyl alcohol or the number of imine or amine groups in polyethyleneimine or polyvinylamine, with formulas (IV) and (V):

[0041]

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Wherein R ¹ and R ² are independently of one another hydrogen, a C ₁ -C ₈ alkyl group, an aryl group or a cyclohexyl group, wherein these groups are unsubstituted Or R ³ is hydrogen or a C ₁ -C ₈ alkyl group, preferably methyl; and R ⁴ is —O— or —NH—bridge, preferably —O—. Azalactone-containing derivatives comprising polyvinyl alcohol, polyethyleneimine or polyvinylimine comprising from about 0.5% to about 80% of the units of the formula (I). Suitable polyvinyl alcohols, polyethyleneimines and polyvinylamines for the present invention are from about 2,000 to 1,
1,000,000, preferably 10,000-300,000, more preferably 10,000
It has a number average molecular weight of 000 to 100,000, most preferably 10,000 to 50,000. Particularly suitable polymerizable optical materials are methyl groups for R ₁ and R ₂ , hydrogen for R ₃ , and —O— for R ₄ , based on the number of hydroxyl groups in the polyvinyl alcohol. (I.e., an ester bond) of about 0. A water-soluble derivative of polyvinyl alcohol containing from 5 to about 80%, preferably from about 1 to about 25%, more preferably from about 1.5 to about 12%.

The polymerizable optical materials of the formulas (IV) and (V) are, for example, of the formula (VI):

[0044]

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Wherein the azalactone (wherein R ₁ , R ₂ and R ₃ are as defined above) is treated with polyvinyl alcohol, polyethyleneimine or polyvinylamine at an elevated temperature of about 55 ° C.
It can be prepared by reacting at ７５75 ° C. in a suitable solvent, optionally in the presence of a suitable catalyst. Suitable solvents are those that dissolve the polymer backbone and include aprotic solvents such as formamide, dimethylformamide, hexamethylenephosphortriamide, dimethylsulfoxide, pyridine, nitromethane, acetonitrile, nitrobenzene, chlorobenzene, trichloromethane and dioxane. Including those that are. Suitable catalysts include tertiary amines, such as triethylamine, and organotin salts, such as dibutyltin dilaurate.

In addition to the azalactone moiety, the azalactone-containing optical material can have other hydrophobic and hydrophilic vinylic comonomers, depending on the desired physical properties of the polymerized HOE. Exemplary suitable hydrophobic comonomers are, C ₁ -C ₁₈ alkyl Ruakurirato and methacrylates, C ₃ -C ₁₈ alkyl acrylamides and main Takuriruamido, acrylonitrile, methacrylonitrile, vinyl C ₁ -C ₁₈ A Rukanoato, C ₂ - C ₁₈ alkylene, styrene, vinyl alkyl ether, C ₂ -C ₁₀ perfluoroalkyl acrylates and methacrylates, C ₃ -C ₁₂ perfluoroalkylethyl thiocarbonylaminoethyl acrylate and methacrylate, acryloxy - and methacryloxy - alkyl including siloxane, N- vinylcarbazole, maleic acid, fumaric acid, a C ₁ -C ₁₂ pairs alkyl ester of itaconic acid. Typical examples of hydrophilic comonomers are hydroxyalkyl acrylates and methacrylates, acrylamides, methacrylamides, methoxylated acrylates and methacrylates, hydroxylalkylamides and methacrylamides, N-vinylpyrrolidone, N-vinylsuccinimide, N-vinylpyrrolidone , Acrylic acid, methacrylic acid and the like.

The azalactone-containing optical material is polymerized using a photocrosslinking method in a solvent, such as a UV laser, to produce a HOE. Suitable solvents are any that dissolve the polymer backbone of the optical material. Typical solvents include the aprotic solvents disclosed above in connection with azalactone modification, water, ethanol, methanol, propanol, glycol, glycerol, dimethylformamide, dimethylsulfoxide and mixtures thereof. It is desirable to add a photoinitiator, which can initiate free radical crosslinking, to facilitate the photocrosslinking polymerization step. Typical photoinitiators suitable for the present invention include benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, Durocure® 1173 and Irgacure® photoinitiators. Preferably about 0.3 to about 2.0% of the photoinitiator is used, based on the total weight of the polymerization formulation. According to the present invention, a suitable concentration of the azalactone-containing optical material in a solvent for producing the HOE is preferably about 3 to about 90% by weight, especially when the HOE is used as an ophthalmic lens. About 5-6
0%, most preferably about 10-50%.

Yet another group of biocompatible polymerizable optical materials suitable for the present invention is a functionalized copolymer of vinyl lactam and at least one additional vinyl monomer, a second vinyl monomer. is there. The copolymer is functionalized with a reactive vinyl monomer. The vinyl lactam of the present invention has the formula (VII):

[0049]

Embedded image

Wherein R _a is alkylene having 2 to 8 carbon atoms, R _b is hydrogen, alkyl, aryl, aralkyl or alkaryl, preferably hydrogen, up to 7 carbon atoms R _c is hydrogen or lower alkyl having up to 7 carbon atoms, preferably aryl having up to 14 carbon atoms, or aralkyl having up to 14 carbon atoms. Is a methyl, ethyl or propyl) lactam.

Suitable lactams of the present invention are N-vinyl-2-pyrrolidone, N-vinyl-2-
Caprolactam, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3-
Methyl-2-piperidone, N-vinyl-3-methyl-2-caprolactam, N-
Vinyl-4-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-methyl-
2-piperidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl-5-methyl-5-ethyl-2-pyrrolidone, N-vinyl-3,4,5-trimethyl-3-ethyl-2
-Pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-
Vinyl-4,4-dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3
, 5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam and mixtures thereof. Suitable vinyl lactams are heterocyclic monomers of the formula (VII) having 4 to 6 carbon atoms in the heterocycle. Further preferred vinyl lactams are heterocyclic monomers of formula (VII) having 4 carbon atoms in the complex ring and wherein R _b and R _c are independently selected from hydrogen and lower alkyl moieties. A particularly suitable vinyl lactam is N-vinyl-2-pyrrolidone.

Suitable second vinyl monomers have, in addition to the vinyl group, a functional group such as hydroxyl, amino, lower alkyl-substituted amino, carboxyl, esterified carboxyl, epoxy, or sulfo (—SO ₃ H). Contains functionalized vinyl monomers. This functional group remains when the vinyl group of the second vinyl monomer reacts with the vinyl lactam to form a polymer chain and can be used to modify or functionalize the polymer.

Suitable functionalized vinyl monomers are hydroxyl-substituted lower alkyl acrylates and methacrylates, ethoxylated acrylates and methacrylates, epoxy-lower alkyl acrylates and methacrylates, epoxycycloalkyl-
Lower alkyl acrylates and methacrylates, hydroxy-lower alkyl acrylamides and methacrylamides, hydroxy-substituted lower alkyl vinyl ethers, amino- or hydroxy-substituted styrenes, sodium ethylene sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropane Including sulfonic acid, acrylic acid, methacrylic acid, amino-lower alkyl and alkylamino-lower alkyl acrylates and methacrylates, acryloxy- and methacryloxy-lower alkylmaleimides and allyl alcohol. As used herein, the term "lower alkyl" refers to an alkyl group having up to 7 carbon atoms, preferably up to 4 carbon atoms. Particularly suitable functionalized vinyl monomers are 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, 4-aminostyrene, 3-methacryloxymethyl-7-oxa-bicyclo [4.1. 0.0] heptane, N-methacryloxyethyl-maleimide, glycidyl methacrylate, ammonium methyl methacrylate hydrochloride and ammonium propyl methacrylate hydrochloride.

The copolymer of vinyl lactam and the second vinyl monomer is prepared in a known manner in the presence or absence of a solvent. The copolymer can be a random polymer. Methods for producing random polymers are described, for example, in US Pat.
5,712,356. Suitably, the solvent dissolves the monomer and the polymer made from the monomer and is substantially inert to the monomer and the polymer made from the monomer. Typical suitable solvents are water, alcohols such as methanol, ethanol and propanol; carboxamides such as dimethylformamide and dimethylsulfoxide; ethers such as diethyl ether, THF
And diglyme; and mixtures thereof. Suitable copolymers have a weight average molecular weight of about 2,000 to about 1,000,000, preferably 10,000 to about 300.
10,000, more preferably 10,000-100,000, and most preferably 10,000.
It has a number between 00 and 50,000.

[0055] The copolymer is further modified with a reactive vinyl monomer to produce a polymer that can rapidly crosslink. Suitable reactive vinyl monomers have a reactive moiety in addition to the vinyl group, which, while retaining the vinyl group in the monomer, reacts with the functional groups present in the copolymer to form a covalent bond. Typical suitable reactive vinyl monomers are hydroxy-substituted lower alkyl acrylates and methacrylates, hydroxy-substituted lower alkyl acrylamides and methacrylamides, hydroxy-substituted lower alkyl vinyl ethers, 2-acrylamido-2-methylpropanesulfonic acid, Amino-lower alkyl and mono-lower alkylamino-lower alkyl acrylates and methacrylates, allyl alcohol, epoxy-lower alkyl acrylates and methacrylates, isocyanato-lower alkyl acrylates and methacrylates, 3 to 7 carbon atoms Vinyl-unsaturated carboxylic acids and acid chlorides and anhydrides thereof, amino-, hydroxy- or isocyanato-substituted styrenes, and epoxycycloalkyl-lower alkyl Including and methacrylates. Suitable reactive vinyl monomers are hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, isocyanatoethyl acrylate and methacrylate, acrylic acid and methacrylic acid chloride, ammonium methyl methacrylate hydrochloride, and ammonium propyl Contains methacrylate hydrochloride.

The functionalized copolymer can be crosslinked or polymerized without a solvent, but is typically crosslinked or polymerized using a photocrosslinking step in a solvent, such as a UV laser, to produce a HOE. Suitable solvents are any solvents that dissolve the polymer backbone of the polymer. Typical solvents are water, alcohols such as methanol and ethanol;
Carboxamides, such as dimethylformamide and dimethylsulfoxide; and mixtures thereof. The photocrosslinking step is performed with a photoinitiator, which can initiate free radical crosslinking. Typical photoinitiators suitable for the present invention are:
Benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, Du
rocure® 1173 and Irgacure® 2959. Preferably about 0.3 to about 2.0% of a photoinitiator is used, based on the total weight of the polymerization formulation. According to the present invention, a suitable concentration of the functionalized vinyl lactam in a solvent for producing the HOE is suitably from about 3% to about 9%, especially when the HOE is used as an ophthalmic lens.
0%, more preferably about 5% to 60%, most preferably about 10 to about 50%.

Another group of HOEs suitable for the present invention can be manufactured from conventional and other volume transmission holographic optical element recording media. As the above-mentioned polymerizable material for the HOE, the target light and the collimated reference light are simultaneously projected onto the HOE recording medium such that the electromagnetic waves of the target and the reference light form interference fringe patterns. An interference fringe pattern, a volume grating structure, is recorded in the HOE medium. When the HOE recording medium is fully exposed, the recorded HOE medium is developed by known HOE development methods. Suitable volume transmission holographic optical element recording media include commercially available holographic photographic recording materials or plates, such as dichroic gelatin. Holographic photographic recording materials are available from various manufacturers, including Polaroid Corp. Holographic media suitable for the present invention are described, for example, in International Patent Application No. P.
CT / US96 / 1 5600 to Polaroid and Nippon Paint in US Pat. No. 5,453,340. When photographic recording materials are used as HOEs, however, the toxicological effects of the material in the ocular environment should be considered. Therefore, when conventional photographic HOE materials are used, it is preferred that the HOE be packaged with a biologically compatible material. Useful biologically compatible optical materials for encapsulating the HOE include those that are suitable for the effective lenses of the present invention, and such suitable materials are discussed further below.

As is known in the ophthalmic arts, ophthalmic lenses should have a small dimensional thickness for wearer comfort. Therefore, dimensionally thin HOEs are preferred in the present invention. However, to provide a HOE with high diffraction efficiency, the HOE must be optically thick, ie, the light must be diffracted on one or more of the fringe faces. One way to provide an optically thick and dimensionally thin HOE is to program the fringe pattern in a direction tilted along the length of the HOE. Such a tilted volume grating structure causes the HOE to have a large angular deviation between the incident angle of the incident light and the exit angle of the exiting light. However, a HOE having a large angular deviation is not particularly suitable as an ophthalmic lens. For example, when such a HOE is used as an ophthalmic lens and the HOE is activated, the effective line of vision is significantly deviated from the normal straight line of vision. As a preferred embodiment of the invention, this angular limitation in the design of the HOE lens is due to the multi-layer combination HOE.
, Especially by using a two-layer HOE. FIG. 8 shows a typical multilayer HOE 40 of the present invention. To provide a dimensionally thin HOE with a smaller angle deviation, two dimensionally thin HOEs with a larger angle deviation are assembled as a combined HOE. This combination HOE 40 has a dimensionally thin first H
It has an OE42 and a second HOE44. The first HOE 42 modulates incident light such that when light enters the HOE at the activation angle α, the light exit HOE forms an exit angle β (which is greater than the projection angle α as shown in FIG. 8A). It is programmed to diffract. The first HOE preferably has a thickness from about 10 μm to about 100 μm, more preferably from about 20 μm to about 90 μm, and most preferably from 30 μm to about 50 μm. The second HOE 44 is programmed to have an activation projection angle β that matches the exit angle β of the first HOE 42. Further, the second HOE 44 is programmed to focus the incident light to the focal point 46 when the light enters inside the activation angle β. FIG. 8B shows the second HOE 44. The second HOE is preferably about 10
It has a thickness of from about μm to about 100 μm, more preferably from about 20 μm to about 90 μm, and most preferably from 30 μm to about 50 μm.

A first HOE 42 is disposed adjacent to the second HOE, and the incident light is
Outgoing light in the multilayer HOE focuses the light at the focal point 46 when directed at an angle corresponding to the activation angle α of By using a multilayer combination HOE, dimensionally thin HOEs with high diffraction efficiency and small deviation angles can be produced. In addition to high diffraction efficiency and small angular deviation, using a multilayer HOE offers other additional advantages, including correction for dispersion and chromatic aberrations. Visible light consists of the spectrum of electromagnetic waves having different wavelengths, and the difference in wavelength is the HOE
A single HOE provides an image that includes dispersion and chromatic aberration, as the light is diffracted differently. It has been found that multilayer, especially bilayer, HOEs can work in reverse to correct for those aberrations that can be produced by a single layer HOE. Therefore, the multilayer combination HOE is suitable as an element of the effective lens HOE.

According to the present invention, the HOE of the present invention preferably comprises at least about 70%, more preferably at least about 80%, of all or substantially all wavelengths of the visible spectrum of light.
, And most preferably has a diffraction efficiency of at least 95%. HO particularly suitable for the present invention
E has a diffraction efficiency of 100% of all wavelengths of the visible light spectrum. However, HOEs having lower diffraction efficiencies than specified above can also be used for the present invention. Thus, a HOE suitable for the present invention has a sharp transition angle between the activation angle and the non-activation angle, and has no gradual transition angle, thereby reducing the HOE.
Activation and deactivation of E can be achieved with a small movement of the active lens, and there is no temporary image formed by the HOE during the movement during the activation and deactivation steps, or Is the smallest.

For the first optical material of the effective lens, any optical material suitable for a hard lens, a gas permeable lens or a hydrogel lens can be used. Suitable polymerizable materials for the first optical element of an effective ophthalmic lens are hydrogel materials, gas-permeable hard materials,
And hard materials that are known to be useful in making ophthalmic lenses, such as contact lenses. Suitable hydrogel materials typically have a crosslinked hydrophilic network and retain about 35% to about 75% water, based on the total weight of the hydrogel material. Examples of suitable hydrogel materials are 2-droxyethyl methacrylate and one or more comonomers, such as 2-hydroxyacrylate, ethylacrylate, methylmethacrylate, vinylpyrrolidone, N-vinylacrylamide, hydroxypropylmethacrylate, Isobutyl methacrylate, styrene, ethoxyethyl methacrylate, methoxytriethylene glycol methacrylate, glycidyl methacrylate, diacetone acrylamide, vinyl acetate, acrylamide, hydroxy trimethylene acrylate, methoxymethyl methacrylate, acrylic acid, methacrylic acid, glyceryl Includes copolymers of methacrylate and dimethylaminoethyl acrylate. Other suitable hydrogel materials include copolymers with methylvinylcarbazole or dimethylaminoethyl methacrylate. Another group of suitable hydrogels include polymerizable materials, such as modified polyvinyl alcohol, polyethyleneimine and polyvinylamine (eg, U.S.A.).
.S. Patent No. 5,508,317 (issued to Beat Maller) and International Patent Application N
o. disclosed in PCT / EP96 / 01265). Yet another group of highly suitable hydrogel materials includes silicone copolymers (described in International Patent Application No. PCT / EP96 / 01265). Suitable gas permeable hard materials for the present invention include crosslinked siloxane polymers. The network of such polymers can be suitably cross-linked, such as N, N'-dimethylbisacrylamide, ethylene glycol diacrylate, trihydroxypropane triacrylate, pentaerythritol tetraacrylate, and other similar polyfunctional compounds. Acrylates or methacrylates or vinyl compounds such as N-methylaminodivinylcarbazole. Suitable hard materials are acrylates such as methacrylates, diacrylates and dimethacrylates, pyrrolidone, styrene, amide, acrylamide,
Includes carbonate, vinyl, acrylonitrile, nitrile, sulfone, and the like. Among suitable materials, hydrogel materials are particularly suitable for the present invention.

According to the present invention, the first optical element and the HOE are separated into thin layers when one of the multiple effective lens embodiments is implemented, or the HOE is embedded in the first optical element, Form an effective lens. Further, when the ophthalmic active lens is manufactured using a non-biologically compatible HOE, the HOE is embedded in the first optical element;
HOE does not directly contact the ocular environment because HOE may adversely affect long-term corneal health. Alternatively, as discussed above, this effective lens can produce a HOE that is biologically compatible, and the HOE can provide both the diffractive and refractive effects of an effective lens. .

FIG. 9 shows another embodiment of the present invention. The bifocal spectacle lens 50 comprises a layer of a first optical material having a first refractive index 52 (which provides a refractive index) and HO
E54, which provides the second index of refraction, is formed by dividing the layer into thin layers. The two layers are made separately and then joined, for example, thermally or adhesively. The compound lens is subsequently mechanically fitted to the spectacle frame to provide a set of bifocal glasses. The first optical material 52 is a conventional optical material for making eye glasses, for example, glass, polycarbonate, polymethyl methacrylate, and the like, and the HOE, as described above, focuses incident light. Any hologram optical material that can be programmed to Alternatively, bifocal spectacle lenses can be made from shaped HOEs, where the optical shape of the HOE provides a refractive index when the HOE is not activated, and the volume grating structure of the HOE is When it is activated, it provides diffractive power.

The multifocal optical lens of the present invention is effectively and selectively controlled, and unlike conventional bifocal lenses, one lens at a time with little or no optical interference from the multiple refractive indices of the lens. Provide the desired refractive index. In addition, the HOE-programmable properties of the effective lens make the lens highly suitable for correcting non-emmetropic conditions that cannot be easily adjusted by conventional correcting optical lenses. For example, the effective lens may be programmed to have corrective means for non-uniform and bent corneal curvature of irregular astigmatism by specifically designing the correlation position of the target light and the reference light. Can be.

The present invention is further described in the following examples. However, this example, in addition, should not be considered as limiting the invention.

[0066]

【Example】

Example 1: About 0.06 ml of the Nelfilcon A lens monomer composition is placed in the center of the female mold half and the corresponding male mold half is placed on top of the female mold half. To form a molded part of the lens. The male mold halves of the mold do not contact the female mold halves, they are separated by about 0.1 mm. The mold half of the lens is prepared from quartz and is chrome shielded except for a central circular lens portion about 15 mm in diameter. Briefly, Nelfilcon A has about 0 acrylamide crosslinker.
. Crosslinkable modified polyvinyl alcohol product containing 48 mmol / g.
Polyvinyl alcohol has an acetate content of about 7.5 mol%. Nelfilcon
A has a solids content of about 31% and contains about 0.1% of the photoinitiator, Durocure® 1173. The closed lens mold part was placed under the laser device. The laser device consists of two coherent collimated UV light having a wavelength of 351 nm.
A laser beam is provided, where one beam passes through an optically convex lens, so that the focus is formed 500 mm away from the lens mold part. The focused light is formed as point source target light. The angle formed between the path of the target light and the reference light is about 7 °. This device provides a HOE with an added corrective refractive index of 2 diopters. The lens monomer composition was exposed to a laser beam having about 0.2 watt for about 2 minutes to completely polymerize the composition and form an interference fringe pattern. Since the lens mold is shielded except for the central part, the lens monomer exposed at the circular central part of the mold is subjected to the target light and the reference light,
Polymerized. The mold part is opened to separate the lens adhering to the male half of the mold. Approximately 0.06 ml of the Nelfilcon A lens monomer composition is again placed in the center of the female mold half and the corresponding male mold half is placed on the female mold half. Was. The male and female halves of the mold are separated by about 0.2 mm. The closed mold part was exposed again to the laser device, except that the optical convex lens was moved from the target optical device. This monomer composition is
Exposure again to the laser beam for about 2 minutes allowed the composition to fully polymerize and to form a second layer of interference fringes.

The resulting compound lens has a refractive index based on the shape of the lens and the refractive index of the lens material, and a further corrective refractive index of +2 diopters that can be activated.

Example 2: 110 g of polyvinyl alcohol (Mowiol 4-88, which is available from Hoechst AG, has an 87.7% hydrolysis level and has a Mw (g / mol) of about 31,000) Was dissolved in 440 g of deionized water at 90 ° C and cooled to 22 ° C. 100.15 g of a 20.6% aqueous solution of methacrylamidoacetaldehyde, concentrated hydrochloric acid (
(377% pa, Merck) and 34.7 g of deionized water were added. The mixture was stirred at room temperature for 22 hours, then adjusted to pH 7.0 with a 5% NaOH solution. The solution was diluted with 3 liters of deionized water, filtered, and then ultrafiltered using a 1-KD-Omega membrane by Filtron. After repeating three times the sample volume, the solution was concentrated.
660 g of a 17.9% solution of methacrylamidoacetoaldehyde-1,3-acetal of polyvinyl alcohol having a viscosity of 210 cps were obtained. According to NMR studies, 11 mol% of the OH groups are acetalized, 5 mol% of the OH groups are acetylated and concentration of the aqueous polymer solution under reduced pressure gives a 30.8% solution with a viscosity of 3699 cps. Gave.

Based on the polymer content, 0.7% of Durocure® 1173 was added to the 30.8% solution. The solution was introduced into a transparent, contact lens mold of polypropylene, which had a central cavity thickness of about 100 im, and then the mold was closed. The solution was irradiated for 6 seconds from a distance of 18 cm using a 200 watt Oriel UV lamp. The mold was opened, and the transparent lens was taken out. The contact lens is biologically compatible, i.e., the lens is
It can be worn on the eye for long periods of time without causing detrimental effects on the ocular environment, and the lens modulus and flex length is 0.9 mPa and 50%.

Example 3 An azalactone-modified polyvinyl alcohol was produced as follows. 25 g of polyvinyl alcohol (Mowiol 4-98, which is available from Hoechst AG and has a 98.4% hydrolysis level and a Mw (g / mol) of about 27,000) are charged with a mechanical stirrer. Dissolved at 65 ° C. in 100 g of DMSO in a 200 ml round bottom flask. Catalyst (1,8-diazabicyclo [5.4.0] -undeca-
0.5 g of (7-ene) was added, followed by 7.14 g (0.051 mol) of 7.14 g (0.051 mol) of 2-vinyl-4,4-dimethyl-azalactone. The mixture was continuously stirred at 65 ° C. for 24 hours. The resulting modified polymer was precipitated in 1 liter of acetone with vigorous stirring. The precipitate was filtered and dried. This modified polymer has about 9 mol% of the OH groups of the polyvinyl alcohol reacted with the azalactone. The modified polymer was dissolved in DMSO to provide an approximately 30% solution, and Irgacure® 2959 was added to produce a 0.1% solution of the photoinitiator. About 0.6 ml of the modified crosslinkable polymer solution was placed on a quartz slide (which has the dimensions of a microscope) and a second quartz slide was placed on top of the solution. As a spacer, a 100 im spacer was held between slides. This crosslinkable solution, placed between the slides, was applied as described in the first recording step of Example 1
The OE recording process was performed. The selected HOE has a diffraction efficiency of about 50%. The above examples illustrate the polymerizable optical materials of the present invention, which are selected within the scope of the present invention.
Are holographic optical elements (HOEs) that can be used in a variety of applications, including optical lenses, such as multifocal contact lenses, especially biologically compatible H
This shows that OE is manufactured.

[Brief description of the drawings]

FIG. 1 shows an effective ophthalmic lens of the present invention.

FIG. 2 illustrates the diffraction function of a holographic optical element for an effective lens of the present invention.

FIG. 3 shows an effective ophthalmic lens of the present invention.

FIG. 4 shows the transmission function of the holographic optical element.

FIG. 5 shows the diffraction function of a holographic optical element when the element is activated.

FIG. 6 illustrates an exemplary method for manufacturing a holographic optical element.

FIG. 7 shows the refractive index of the holographic optical element.

FIG. 8 shows a combination holographic optical element of the present invention.

FIG. 8A illustrates a combination holographic optical element of the present invention.

FIG. 8B shows a combination holographic optical element of the present invention.

FIG. 9 shows a spectacle compound lens of the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG , KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZWF Term (Reference) 2H006 BA01 BB06 BB08 BC03 BD00 2H049 CA09 CA17 CA28 CA30 2K008 AA00 BB04 DD12 EE01 FF17

Claims (43)

[Claims] 1. A multifocal optical lens comprising a first optical element and a transmission volume holographic optical element, wherein the first optical element provides a first refractive index at a first focal point; An optical lens wherein the holographic optical element provides a second refractive index at a second focal point, wherein the first and second focal points are not axially aligned. 2. The multifocal lens according to claim 1, wherein the optical lens is an ophthalmic lens and has a stabilizing mechanism. 3. The multifocal lens according to claim 1, wherein the holographic optical element diffracts up to 100% of the incident light when the Bragg condition is met. 4. The multifocal lens of claim 1, wherein said first refractive index is selected from +10 diopters to -20 diopters. 5. The multifocal lens according to claim 4, wherein said second refractive index is a positive refractive index. 6. The multifocal lens of claim 1, wherein the lens corrects for myopia, hyperopia, presbyopia, regular and irregular astigmatism, and combinations thereof. 7. A multifocal optical lens comprising a transmission volume holographic optical element, wherein said optical element has a programmed activation angle, and wherein said optical element has an optical angle outside said activation angle. A multifocal lens that provides a first refractive index to light entering the element and a second refractive index to light entering the optical element at an angle inside the activation angle. 8. The multifocal lens according to claim 7, wherein the optical lens is an ophthalmic lens and has a stabilizing mechanism. 9. The multifocal lens according to claim 7, wherein said optical lens is a contact lens. 10. The multifocal lens according to claim 7, wherein said first refractive index is selected from +10 diopters to -20 diopters. 11. The multifocal lens according to claim 10, wherein said second refractive index is a positive refractive index. 12. The multifocal lens of claim 7, wherein said lens corrects for myopic, hyperopic, presbyopia, regular and irregular astigmatism, and combinations thereof. 13. A method for correcting non-emmetropic conditions, comprising: a) a multifocal lens for the eye, the multifocal lens including a first optical element and a transmissive volume holographic optical element. Wherein the first optical element provides a first index of refraction at a first focus and the holographic optical element or the holographic optical element in combination with the first optical element comprises a second optical element. Providing a second index of refraction at the focal point of the eye); and b) selecting the multifocal lens on the eye, where the first or second focal point is above the depression of the eye. Moving the cells so as to be arranged in a fixed manner. 14. The method of claim 13, wherein the optical lens is an ophthalmic lens and has a stabilizing mechanism that allows the lens to move stably from one position to another. 15. The method of claim 13, wherein said holographic optical element diffracts up to 100% of incident light when Bragg conditions are met. 16. The method of claim 13, wherein said non-emmetropic condition is a myopic condition, a hyperopic condition, a presbyopia condition, a regular and irregular astigmatic condition, and combinations thereof. 17. The method of claim 16, wherein said non-emmetropic condition is presbyopia, and wherein said first refractive index is selected from +10 diopters to -20 diopters. 18. A method for providing multifocal vision correction, comprising: a) a multifocal lens on the eye, the multifocal lens including a holographic optical element, wherein the optical element comprises a holographic optical element; Providing a first refractive index for light entering the optical element on the outside and providing a second refractive index for light entering the optical element at an angle inside the activation angle). And b) moving the multifocal lens on the eye such that the first focus or the second focus is selectively positioned over a depression in the eye. Features method. 19. The method of claim 18, wherein the optical lens is an ophthalmic lens and has a stabilizing mechanism that allows the lens to move stably from one position to another. 20. The method of claim 18, wherein the holographic optical element diffracts up to 100% of the incident light when the Bragg condition is met. 21. The method of claim 18, wherein said non-emmetropic condition is a myopic condition, a hyperopic condition, a presbyopia condition, a regular and irregular astigmatic condition, and combinations thereof. 22. The method of claim 21, wherein said non-emmetropic state is a myopic state, and wherein said first refractive index is selected from +10 diopters to -20 diopters. 23. A method for manufacturing a multifocal lens for correcting said non-emmetropic condition, said lens having a front curve and a base curve, a) in a mold for an optical lens. Introducing a polymerizable optical material into the mold; and b) exposing the polymerizable material in the mold to an electromagnetic wave, wherein the electromagnetic wave interferes while polymerizing the polymerizable material. Forming a striped pattern, whereby the pattern is recorded in the lens to form a volume grating structure, thereby forming a volume holographic element, wherein the pattern is disposed on, in, or in front of an eye; A method of manufacturing a multifocal lens for correcting the non-emmetropic state by diffracting light incident on the front curve of the eye when the camera is in the off state. 24. A biologically compatible holographic element made from a crosslinkable or polymerizable prepolymer, wherein the prepolymer is crosslinked or polymerized within 5 minutes of irradiation by a UV source. Forming a non-fluid biologically compatible optical element, wherein the duration of crosslinking or polymerization is such that the prepolymer is placed between a bottom and top quartz slide with a spacing of 100 im. A holographic element measured by providing a UV source, a 200 watt medium pressure mercury lamp placed 18 cm above the quartz slide on the top. 25. The prepolymer of claim 1, wherein the prepolymer is of the formula (I): Wherein R is lower alkylene having up to 8 carbon atoms, R ¹ is hydrogen or lower alkyl, and R ² is olefinically unsaturated, having up to 25 carbon atoms. 25. The biologically compatible holographic element of claim 24, comprising a derivative of polyvinyl alcohol having about 0.5% to 80% of units (which are electron-withdrawing copolymerizable groups). It is 26. R ^2, (wherein, R ³ has 2 to 2 4 carbon atoms, a copolymerizable group olefinically unsaturated) wherein R ³ -CO- olefinically unsaturated 26. The biologically compatible holographic device of claim 25, which is an acyl group of 27. The biologically compatible according to claim 26, wherein the olefinically unsaturated copolymerizable group is ethenyl, 2-propenyl, 3-propenyl, 2-butenyl, hexenyl, octenyl or dodecanyl. Holographic element. 28. The biologically compatible holographic element of claim 24, wherein said prepolymer crosslinks or polymerizes within one minute. 29. The biologically compatible holographic element of claim 24, wherein said prepolymer crosslinks or polymerizes within 30 seconds. 30. The prepolymer comprises an azalactone-containing derivative of polyvinyl alcohol, polyethyleneimine or polyvinylamine, wherein the derivative comprises a number of hydroxy groups in polyvinyl alcohol or an imine or amine in polyethyleneimine or polyvinylamine. Based on the number of groups, formulas (IV) and (V): Wherein R ₁ and R ₂ are, independently of the others, hydrogen, C ₁ -C ₈ alkyl, aryl or cyclohexyl; R ₃ is hydrogen or C ₁ -C ₈ alkyl. There, and R ₄ is, -O-, or -NH- containing about 0.5 to about 80 percent units of the bridge is a), according to claim 24 holographic element capable of biologically compatible description. 31. The prepolymer comprises a functionalized copolymer comprising a vinyl lactam and a second vinyl monomer, wherein the vinyl lactam has the formula (VII): Wherein R _a is an alkylene bridge having 2 to 8 carbon atoms, R _b is hydrogen, alkyl, aryl, aralkyl or alkaryl, preferably hydrogen, having up to 7 carbon atoms Lower alkyl, aryl having up to 14 carbon atoms, or aralkyl or alkaryl having up to 14 carbon atoms, and R _c is hydrogen or lower alkyl having up to 7 carbon atoms. 25. The biologically compatible holographic device of claim 24, which is a 5-7 membered lactam. 32. The vinyl lactam is N-vinyl-2-pyrrolidone, N-
Vinyl-2-caprolactam, N-vinyl-3-methyl-2-pyrrolidone, N-
Vinyl-3-methyl-2-piperidone, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-4-methyl-
2-caprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-
5-methyl-2-piperidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl-5-methyl-5-ethyl- 2-pyrrolidone, N-vinyl-3,4,5-trimethyl-3
-Ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4 , 4-Dimethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N
-Vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, or a mixture thereof, 32. The biologically compatible holographic element of claim 31. 33. The second vinyl monomer is a functional vinyl monomer having a vinyl group and a functional group, wherein the functional group is hydroxy, amino, lower alkyl-substituted amino, carboxyl, esterified carboxyl, alkoxycarbonyl 32. The biologically compatible holographic device of claim 31, which is an epoxy, or a sulfo. 34. The functional vinyl monomer according to claim 1, wherein the hydroxy-substituted lower alkyl acrylate and methacrylate, ethoxylated acrylate and methacrylate, epoxy-lower alkyl acrylate and methacrylate, epoxycycloalkyl-lower alkyl acrylate and methacrylate. , Hydroxy-substituted lower alkyl acrylamide and methacrylamide, hydroxy-substituted lower alkyl vinyl ether, amino- or hydroxy-substituted styrene, sodium ethylene sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid Methacrylic acid, amino-lower alkyl and alkylamino-lower alkyl acrylates and methacrylates, acryloxy and methacrylate 33. The biologically compatible holographic device of claim 32, wherein the holographic device is selected from the group consisting of riloxy-lower alkylmaleimide and allyl alcohol. 35. A biologically compatible holographic element made from a crosslinkable or polymerizable prepolymer, said copolymer being exposed to a coherent object light beam and a reference light beam. Forming a volume holographic element, wherein the prepolymer crosslinks or polymerizes within 5 minutes of irradiation by a UV source to form a non-fluid biocompatible optical element;
And the duration of crosslinking or polymerization is such that the prepolymer is placed between the bottom and top quartz slides with a spacing of 100 im and a 200 watt medium pressure mercury placed 18 cm above the top quartz slide Biologically compatible volume holographic element, measured by providing a UV source which is a lamp. 36. The biologically compatible volume holographic element of claim 35, which is a transmission holographic element. 37. The biologically compatible volume holographic element of claim 35, wherein said holographic element is used for positioning in or on an eye. 38. A holographic element made from a crosslinkable or polymerizable prepolymer, wherein the prepolymer is a fluid prepolymer and when exposed to a coherent object light beam and a reference light beam. The prepolymer forms a volume holographic element and the prepolymer crosslinks or polymerizes within 5 minutes of irradiation by a UV source to form a non-fluid, biocompatible optical element. And the duration of cross-linking or polymerization is such that the prepolymer is placed between a bottom and top quartz slide with a spacing of 100 im and a 200 watt medium pressure placed 18 cm above the top quartz slide Holographic element, measured by providing a UV source which is a mercury lamp. 39. A method for producing a holographic element, comprising: forming a crosslinkable prepolymer or a polymerizable monomer composition, wherein the prepolymer and the polymerizable monomer composition are liquid. Providing a light beam to record a holographic diffraction grating structure, wherein the fluid prepolymer or monomer is converted to a non-fluidic device within 5 minutes of irradiation of a UV source. And the duration of the conversion is to place the prepolymer between the bottom and top quartz slides, with a spacing of 100 im, 200 watt medium pressure mercury placed 18 cm above the top quartz slide A method measured by providing a UV source which is a lamp. 40. The method of claim 39, wherein said holographic grating structure is a volume holographic grating structure. 41. The prepolymer composition according to claim 1, wherein the prepolymer composition has the formula (I): Wherein R is lower alkylene having up to 8 carbon atoms, R ¹ is hydrogen or lower alkyl, and R ² is olefinically unsaturated, having up to 25 carbon atoms. 40. The method of claim 39, comprising a derivative of polyvinyl alcohol having from about 0.5% to 80% of units of (a) an electron-withdrawing copolymerizable group). 42. The prepolymer composition comprises an azalactone-containing derivative of polyvinyl alcohol, polyethylene imine or polyvinylamine, wherein the derivative comprises a number of hydroxyl groups of polyvinyl alcohol or an imine in polyethylene imine or polyvinyl amine. Based on the number of amine groups, the formula (IV
) And (V): Wherein R ₁ and R ₂ are, independently of the others, hydrogen, C ₁ -C ₈ alkyl, aryl, or cyclohexyl; R ₃ is hydrogen or C ₁ -C ₈ alkyl. There, and R ₄ comprise from about 0.5 to about 80 percent units of -O- or -NH- bridge is a)請Motomeko 39 method described. 43. The prepolymer composition comprises a functionalized copolymer comprising a vinyl lactam and a second vinyl monomer, wherein the vinyl lactam has the formula
VII): Wherein R _a is an alkylene bridge having 2 to 8 carbon atoms, R _b is hydrogen, alkyl, aryl, aralkyl or alkaryl, preferably lower alkyl having up to 7 carbon atoms. Aryl having up to 10 carbon atoms, or aralkyl or alkaryl having up to 14 carbon atoms, and R _c is hydrogen or lower alkyl having up to 7 carbon atoms. 40. The method of claim 39, wherein the method is a -7-membered lactam.