CN118091981A - Lens material containing two-photon dye and preparation method and application thereof - Google Patents
Lens material containing two-photon dye and preparation method and application thereof Download PDFInfo
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- CN118091981A CN118091981A CN202211490503.2A CN202211490503A CN118091981A CN 118091981 A CN118091981 A CN 118091981A CN 202211490503 A CN202211490503 A CN 202211490503A CN 118091981 A CN118091981 A CN 118091981A
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Landscapes
- Eyeglasses (AREA)
Abstract
The application provides a lens material containing two-photon dye, a preparation method and application thereof, wherein the lens material comprises thermosetting or thermoplastic resin and two-photon dye; the two-photon dye is physically doped in thermosetting or thermoplastic resin; in the two-photon dye, the absorption wavelength of single photons is 300 nm-600 nm; the absorption wavelength of the two photons is 600 nm-1200 nm; the two-photon absorption cross section of the two-photon dye is more than 10GM. The nonlinear two-photon absorption effect of dye molecules generated at the focusing focus of the femtosecond ultrafast laser is utilized to generate a series of photochemical reactions and thermal effects, the surface or the interior of the lens can be inscribed, and the refractive index of the lens on the local micro-nano space size is changed or other optical characteristics are established to realize the personalized fine adjustment of the refractive capacity of the lens on the periphery of an optical correction area, so that the correction, prevention and control of myopia are realized when a user wears the lens for a long time.
Description
Technical Field
The application relates to the field of glasses, in particular to a lens material containing two-photon dye, and a preparation method and application thereof.
Background
Conventional framed spectacle lenses are typically mass produced using fixed molds, and even prescription spectacles purported to be individually customized can only be selected for a particular refractive index, except for the different pupil distances, pupil heights, and diameters, colors of the lenses themselves, or by plating different layers. They are not capable of fine-tuning based on the wearer's actual ocular biometric data and optical parameters, such as: the pupil diameter, peripheral eye axis length, retinal peripheral optical aberration, retinal curvature, etc. of the wearer affect the correction effect, visual perception and wearing comfort of the wearer, and the visual function of the wearer cannot be optimized if these parameters are ignored.
When wearing the myopia correcting glasses, the object image of the wearer at the central vision is projected on the retina, but the peripheral image is projected behind the retina, and the phenomenon is far vision defocus at the periphery of the retina. Teenagers are in vision development, and the peripheral hyperopic defocus state of the retina can enable the retina of the teenagers to stretch backwards to perform self-regulation, so that the eye axis is increased, and the growth of the eye axis is irreversible, and when serious, the retinal high myopia lesion is caused. However, in the prior art, the glasses for correcting the far-vision defocus phenomenon around the retina have fixed defocus amount, all adopt fixed mould pressing technology, generally cannot be individually adjusted according to each myopic patient, and especially have poor myopia control effect on teenager myopic patients, and can influence the improvement of myopia problems; moreover, if fine adjustment is to be realized, the design mode and the current processing technology of the lens are limited, the car house customization processing difficulty is high, the cost is very high, and if the mass injection molding is performed, the molding precision is insufficient, so that the expected effect is difficult to achieve. Moreover, the user cannot check and prepare the prescription on site, and the user cannot take the prescription on site and needs to wait for a period of several months.
There are currently solutions for incorporating two-photon dyes into contact lenses or intraocular lens (IOL) lenses and using laser inscription to change the refractive index of the lens, but such techniques typically require that the dye possess functional groups that can form covalent bonds with the matrix material, such as (meth) acrylic or beta-ethyl sulfone sulfate. Because contact lenses and intraocular lenses belong to three types of medical devices and are in direct contact with the aqueous tissues of the human body (cornea and vitreous body), the types and precipitation of the dyes added are severely required, and the optional materials have great limitations, so that the optimal effect cannot be achieved. In addition, the mechanism of laser inscription generally utilizes the laser photothermal effect, which is greatly compromised by the higher specific heat capacity of water, and the thermal energy converted by the dye in the hydrogel contact lens containing water after absorbing the laser energy.
Patent CN113050295A discloses a super lens and glasses with the super lens, the nano structure is set on the surface of the lens base plate by using the technical scheme of combining the femto-second laser two-photon micro-nano processing technology and photoresist, the nano structure can select photoresist (mixed liquid containing photosensitive resin), the photoresist is connected together by two-photon polymerization reaction and becomes solid, the optical phase of the lens is adjusted by adopting the mode, and the super lens is realized; however, it is only to rewrite part of the liquid laser light into a solid state on the surface of the lens, but not to rewrite the inside of the lens which is solid, and the change of the optical phase of the glasses is limited; in addition, it is necessary to have an unexposed liquid photoresist after writing, and this portion affects the optical properties of the lens, thus requiring further processing to remove the residue; furthermore, since the photoresist is positioned on the surface of the lens, the photoresist is easily worn in daily life, thereby affecting the lens, and in order to reduce the influence, a transparent protective layer is also required to be covered for protecting the lens, but the photoresist not only increases the burden of a user, but also increases the pressure and the cost of production.
Disclosure of Invention
In order to solve the technical defects in the prior art, the application provides a lens material, which is prepared by doping two-photon dye into a resin material and curing a lens monomer; the optical characteristics of diopter, contrast, aberration and the like of a control area are changed by laser inscription of the control area in the lens and by utilizing the nonlinear optical effect of the two-photon dye, and the relevant optical characteristics of a correction area are adjusted, so that the eye imaging problem of a user is improved, and the visual function of the user is in an optimal state; the adjustment is performed according to eye problems of different users, the method can be used for personalized customization, the inscription is more convenient, on-site optometry is well matched, standing and the like can be achieved, waiting time of the users is greatly reduced, and the process of matching lenses along with taking along with walking and being convenient is truly achieved. In addition, under lower laser intensity, the refractive index of the surrounding medium is changed through mechanisms such as rearrangement of chemical bonds, oxidation and the like induced by the energy level transition of electrons in the excited dye molecules absorbed simultaneously by two photons.
According to an aspect of the present application, there is provided a lens material containing a two-photon dye, the lens material including a resin material and a two-photon dye; the two-photon dye is doped in a resin material; in the two-photon dye, the absorption wavelength of single photons is 300 nm-600 nm; the absorption wavelength of the two photons is 600 nm-1200 nm; the two-photon absorption cross section of the two-photon dye is more than 10GM.
Optionally, the resin material is a thermosetting resin material and/or a thermoplastic resin material. The resin material is an optical transparent material commonly used for glasses. The resin material is preferably an optically transparent material commonly used for frame glasses.
Optionally, the absorption wavelength of the single photon is 380 nm-450 nm; the absorption wavelength of the two photons is 760 nm-900 nm.
The blue light is located in the wavelength range of 380nm to 500 nm. The visible blue region of 450nm to 500nm is believed to have a good effect on the sleep cycle of humans through modulation of melatonin (Melatonin), but where 380nm to 450nm is generally believed to be high energy visible blue light, possibly causing some damage to the photoreceptor cells. According to the laser wavelength preferential range (600 nm-1200 nm) and the most preferred range (760 nm-900 nm), the cut-off wavelength optimization range of the single photon absorption (linear absorption) of the corresponding two-photon dye designed by us is 300 nm-600 nm, the optimized wavelength is 380 nm-450 nm, and the blue light wave band harmful to human eyes is just absorbed, so that the damage to human eye cells is further weakened.
Currently, the mainstream lens materials are all hydrophobic resin materials, and under normal use conditions, the water content of the lens materials is lower than 1%, and the lens materials are basically regarded as hydrophobic materials. Because of the higher specific heat ratio of water, the addition of dye to the lens material, which is free or almost free of water, does not lose the thermal energy of the laser photothermal effect during laser lithography, compared to laser inscription in other hydrogel ophthalmic materials.
Under lower laser intensity, the refractive index of the surrounding medium is changed through mechanisms such as rearrangement, oxidization and the like of chemical bonds induced by the simultaneous absorption of two photons and the energy level transition of electrons in excited dye molecules. The wavelength of the laser used is preferably 600nm to 1200nm, more preferably 760nm to 900nm. In contrast, under the condition of single photon absorption, the dye molecules can absorb the light, and the photochemical reaction brought by the absorption effect can not be generated in a controllable narrow space; the two-photon excitation can be focused on a space focus of a micro-nano to generate high concentration of energy, the two-photon molecules only generate photochemical reaction at the focus of the laser energy reaching the excitation threshold, and no reaction exists outside the focus, so that the writing of the optical characteristics of the micro-nano in space can be realized through the control of the focus, and the writing precision is extremely high and can reach 400nm.
Alternatively, the two-photon dye must have a large two-photon absorption cross section. Increasing the conjugated chain length of the molecule, introducing electron donating groups and electron withdrawing groups, and increasing the coplanarity of the molecule is beneficial to increasing the two-photon absorption cross section of the molecule. The two-photon dye comprises at least one of pi conjugated double bond, polycyclic aromatic hydrocarbon and heterocyclic aromatic hydrocarbon containing heteroatom elements; preferably, the pi conjugated double bond molecule comprises at least one of a stilbene group, a triphenylamine group, a phenothiazine group, an azo group and a carbazole group; the polycyclic aromatic hydrocarbon can be anthraquinone and/or coumarin; the heterocyclic aromatic hydrocarbon containing heteroatom element is preferably heterocyclic aromatic hydrocarbon containing N, S element, and further can be porphyrin, phthalocyanine, polythiophene and derivatives thereof; or a structure composed of any two or more of the above. The above structure may further include an electron withdrawing group: such as cyano tertiary amine positive ion (-N +R3), nitro (-NO 2), trihalomethyl (-CX 3, X= F, cl), cyano (-CN), sulfonic acid group (-SO 3 H), formyl (-CHO), acyl (-COR), carboxyl (-COOH) and the like; or an electron donating group: electron donating groups such as oxygen anions (-O-), dialkylamino (-NR 2), alkylamino (-NHR), amino (-NH 2), hydroxy (-OH), alkoxy (-OR), etc.; or a conjugated structure (such as benzene ring, carbon-carbon double bond, nitrogen-nitrogen double bond, carbon-carbon triple bond and linkage of alternate structure thereof) containing multistage pi electrons of amide group (-NHCOR), acyloxy group (-OCOR), alkyl group (-R), carboxymethyl group (-CH 2 COOH), phenyl group (-Ph) methoxy group, halogen atom and the like. The above compounds can increase compatibility of dye molecules in lens resins by chemically designing and synthesizing functional groups that increase flexible chains or are chemically active.
Optionally, the two-photon dye may also be modified, for example, by grafting linear or branched chains containing carbon or other atoms of different lengths to the dye molecule, such as alkyl long chains, polyethylene glycol, etc.; preferably, the modifying groups are the same or similar derivatives of monomers of the resin material. The two-photon dye can be correspondingly and chemically modified according to the type of the lens resin material so as to improve the solubility of the two-photon dye in the resin material, and meanwhile, the energy transfer loss caused by the formation of aggregates due to excessively high doping is avoided.
Optionally, according to the type of the lens resin material, the two-photon dye can be correspondingly chemically modified to have a chemically active group, for example, the two-photon dye can be chemically reacted with one or more monomers of the lens resin to form a part of the resin material monomers, and then the two-photon dye is polymerized to form the resin material, so that the solubility of the two-photon dye in the resin material can be improved through covalent bond combination with the resin material monomers, and meanwhile, the energy transfer loss caused by formation of aggregates due to over-doping is avoided; for example, the dye molecule is grafted with hydroxyl, sulfhydryl or/and amino, and the resin material matched with the dye molecule is MR series.
Optionally, the above two-photon dye may be correspondingly chemically modified according to the kind of the lens resin material, and may be chemically reacted with one or more monomers of the lens resin to form a covalently bonded portion of the resin material to achieve an increase in solubility in the resin material, while avoiding energy transfer loss due to formation of aggregates caused by excessively high doping. Alternatively, the vinyl group of the polymerizable unsaturated double bond such as propenyl, methylpropenyl, etc. is grafted on the dye molecule, and the resin material matched with the vinyl group is organic glass (PMMA) or CR-39 series.
Alternatively, the two-photon dye containing distyryl groups has the general formula:
wherein n ranges from 0 to 6; r, R' is independently selected from alkyl, alkenyl, or alkynyl groups that are C 1～C18;
Optionally R, R' independently include heteroatoms; the heteroatom includes at least one of oxygen, sulfur, nitrogen, phosphorus, boron, silicon;
optionally R, R' further independently comprises at least one of-OH, -SH, -NH 2、-COOH、-COO-、-CHO、-NO2、-SO3 H, -CO-;
Preferably R, R' is independently selected from (CH 2)m-OH、(CH2)m-SH、(CH2)m-NH2 or (meth) acrylate, wherein m ranges from 1 to 18.
Optionally, the two-photon dye comprises at least one of the following compounds in the structural formula,
The maximum absorption peak of Dye 1 single photon absorption is 374nm; two-photon absorption section delta=110 GM (620 nm)
Dye 2 single photon absorption has a maximum absorption peak of 387nm, two photon absorption cross section delta=340 GM (680 nm)
Dye 3 single photon absorption peak 381nm, two photon absorption cross section δ=110gm (705 nm)
Dye 4 single photon absorption maximum peak 415nm, two photon absorption cross section delta=1300 GM (740 nm)
Optionally, the resin material includes at least one of poly allyl diglycol carbonate, polymethyl methacrylate, polyurethane, and thiopolyurethane.
The resin materials have generally higher hardness, impact resistance and refractive index, and the refractive index of the thiopolyurethane lens can reach 1.74 at most. These features are adapted to wear, ensure the integrity of the lens and make the lens thinner, but at the same time increase the difficulty of modifying the material.
Optionally, the weight percentage of the two-photon dye in the lens material is not limited, but the optimization range is 0.10% -10%, and the more optimization range is 0.5% -5%. The concentration range can be correspondingly adjusted according to the size of the two-photon absorption section of the dye, and the laser intensity and the writing speed. However, if the concentration is too low, the two-photon effect is not obvious, and the laser intensity or irradiation time is increased uniformly, so that carbonization of the material by laser may occur. Too high a concentration, too much linear optical absorption of the colored dye can affect the line of sight or the wearing aesthetic, or the dye can agglomerate, resulting in reduced two-photon efficiency or uneven inscribed optical characteristics.
The absorption of dye caused by the two-photon nonlinearity of ultrafast laser produces a series of photochemical reaction and thermal effect, so that the local adjustment of the refractive power of the lens is realized, and the dual effects of correcting myopia and further controlling the development of myopia are achieved.
The action mechanism of the two photons can carry out micro-nano fine processing in a space local area with high resolution, and the processing precision can reach submicron level. In particular, under the absorption of a material having a high two-photon absorption cross section, the absorption of laser energy can be realized only at the laser focus reaching the nonlinear absorption threshold by using a laser with a low energy density and a low repetition number.
The invention adopts an ultrafast femtosecond or picosecond pulse laser to write controllable microstructures such as gratings or micro curved surfaces into the resin plastic optical spectacle lens doped with the two-photon dye. The central optical zone of the optical lens is provided with a negative optical concave lens which is designed for general optical correction of myopia, and the microstructure writing can be carried out on the periphery of the optical lens through the scheme of the invention. On the other hand, the light scattering center can be manufactured, so that the scattering of incident light is realized, the effect of reducing the contrast of retina imaging is achieved, and the myopia control effect is further enhanced.
According to another aspect of the present application, there is provided a method for preparing a lens material as described above, comprising: (1) Mixing a two-photon dye with a resin material to obtain the lens material; or (2) mixing at least one monomer in the resin material with the two-photon dye in the presence of an initiator or in the absence of the initiator, and reacting to obtain the lens material.
Optionally, the resin material is a thermoplastic and/or thermosetting resin.
Optionally, the thermoplastic resin comprises polymethyl methacrylate (PMMA).
Optionally, the thermosetting resin comprises at least one of Polycarbonate (PADC), polyurethane, and thiopolyurethane.
Alternatively, a two-photon dye and a thermoplastic resin master batch for preparing the frame glasses, such as polymethyl methacrylate (the particle size of which is 0.1-3 mm), are heated, extruded and blended by a single screw or a double screw to prepare a master batch containing the two-photon dye, wherein the master batch can be melted and then the lens material is obtained in a mold, and the mass content of the two-photon dye is 0.1-10%.
Optionally, the two-photon dye (accounting for 0.1-10% of the weight of the lens material) is added into the active monomer for preparing the resin material, then the initiator (accounting for 0.5-1% of the weight of the active monomer) is added, and the lens material containing the two-photon dye is obtained after heating and curing for 20-24 hours at 80-120 ℃.
Optionally, the reactive monomer includes at least one of allyl diglycol dicarbonate (ADC), methyl methacrylate.
Optionally, the initiator comprises at least one of diisopropyl peroxydicarbonate, dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, and Azobisisobutyronitrile (AIBN).
Optionally, the lens material is subjected to melt compression molding according to the standard processing technology of the conventional frame glasses, and then the finished glasses are assembled by turning, polishing, cleaning and coating.
Optionally, mixing two-photon dye (accounting for 0.1-10% of the mass content of the lens material) with two active monomers (the mol ratio of the polyisocyanate compound to the polythioester compound with the polythiol group is 2:1), adding 0.2% of metal or organic catalyst, uniformly mixing for 5 hours, injecting into a completely cleaned glass mold, curing at 100 ℃ for 20 hours to 24 hours, cooling, demolding, and performing conventional turning, polishing, cleaning, coating and assembling to obtain the finished glasses.
Optionally, the amount of isocyanate in the polyisocyanate compound is greater than or equal to 2.
Alternatively, the polyisocyanate compound is a bis-isocyanate compound.
Alternatively, the bis-isocyanic acid compound is selected from at least one of m-phenylene diisocyanate, hexamethylene-1, 6-diisocyanate (HDI), 2, 4-toluene diisocyanate (2, 4 tdi), 2, 6-toluene diisocyanate (2, 6 tdi), 2,4 '-diphenylmethane diisocyanate (2, 4 MDI), 4' -diphenylmethane diisocyanate (4,4MDI), diphenylmethane diisocyanate (Polymeric MDI), 1, 6-hexamethylene diisocyanate (1, 6-HDI), hydrogenated diphenylmethane diisocyanate (H 12 MDI), isophorone diisocyanate (IPDI).
Optionally, the number of mercapto groups in the multi-mercapto thioester compound is not less than 2.
Alternatively, the multi-mercapto thio ester compound is selected from at least one of trimethylolpropane tris (3-mercaptopropionate (TMPMP), pentaerythritol tetrakis (3-mercaptopropionate) (PETMP), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 1, 4-butanediol bis (3-mercaptobutyrate), preferably pentaerythritol tetrakis (3-mercaptopropionate) (PETMP).
Optionally, adding a two-photon dye (accounting for 0.1-10% of the mass content of the lens material) into an active monomer of the resin material, adding a free radical initiator (accounting for 0.2-2% of the mass ratio of the active monomer), uniformly mixing for 5 hours, pouring the liquid mixture into a completely cleaned glass mold with an upper piece and a lower piece, packaging, and heating and curing for 20-24 hours at 95 ℃ in an oven to obtain the lens material.
Optionally, the lens material is polymethyl methacrylate (PMMA); the active monomer is methyl methacrylate; the initiator is peroxide or azo initiator such as azodiisobutyronitrile.
Optionally, the lens material is subjected to melt compression molding according to the standard processing technology of the conventional frame glasses, and then the finished glasses are assembled by turning, polishing, cleaning and coating.
According to another aspect of the present application there is provided an ophthalmic lens comprising a lens material as defined in any one of the above; and (3) carrying out two-photon laser inscription on the lens material to obtain the spectacle lens with the peripheral myopia prevention and control effect.
Optionally, after laser writing the lens material, the method further comprises the steps of pressing the lens material into a mold and slicing the lens material to obtain the lens.
Optionally, the spectacle lens comprises a correction zone and a control zone; the correcting area is positioned in the central area of the spectacle lens; the control area is positioned outside the correction area; the area diameters of the control area and the correction area are determined according to the pupil diameter of the user; the optical characteristics of the correction zone are determined according to the optical parameters of the eyes of the user; the optical characteristic value of the control zone and the optical characteristic value of the correction zone are partially or wholly different.
Optionally, the correction zone is circular; the control zone comprises at least two subareas with regular shapes or irregular shapes, and the diopter of the subareas and the diopter of the correction zone are increased, decreased or alternately changed.
Partition refers to: the optical characteristics of each zone are different, with different power. The partition structure is independent of shape, can be a symmetrical or asymmetrical structure, has the beneficial effect of synchronous vision aiming at eye movement, and can be locally adjusted according to the degree difference and sensitivity of each part of the eye.
Optionally, the partition structure is an annular area structure surrounding the correction area, or a block area structure partitioning the control area from the edge of the correction area to the edge of the control area, or a local area structure distributed outside the correction area, or any combination structure of the three.
The block-shaped area structure for partitioning the control area from the edge of the correction area to the edge of the control area is characterized in that one end of the block-shaped area structure is connected with the correction area, and the other end of the block-shaped area structure is connected with the edge of the control area; the local area structure distributed outside the correction area means that one end is not connected with the correction area, and the other end is connected with the edge of the control area, namely, one end of the local area structure is connected with the correction area, the other end is not connected with the edge of the control area, one end is not connected with the correction area, the other end is connected with the edge of the control area, is not connected with the correction area, and is not connected with the edge of the control area.
Optionally, the correction zone is circular; the control area is a ring structure positioned outside the correction area; the vision of the user wearing the myopia prevention and control lens and the myopia prevention and control effect achieved by the lens are related to the area diameters of the correction area and the prevention and control area, and the proportion of light reaching the central area and the peripheral area of the retina can be controlled according to the reasonable area sizes of the pupil, so that the user with different pupil sizes can achieve the optimal myopia prevention and control effect. Based on the principle, the diameter range of the correcting area can be 1.5-10 times of the pupil diameter of the user; the maximum width of the control zone (width being defined as the distance from the edge of the correction zone to the edge of the control zone) may be 1.5 to 15 times the diameter of the user's pupil.
Optionally, the ring structure comprises at least one or more rings. The plurality of rings may be concentric rings or non-concentric rings. The size and the optical characteristic setting of the eccentric area of the non-concentric ring can be adjusted according to the asymmetry of the retina imaging so as to ensure the optimal effect of myopia prevention and control.
Optionally, the optical features include at least one of diopters, aberrations.
The diopters of the plurality of annular structures vary along the direction from the correction zone to the control zone relative to the diopters of the correction zone.
Optionally, the diopters of the plurality of annular structures are increased, decreased or alternately varied in diopter relative to the diopter of the correction region along the direction from the correction region to the control region (i.e., lens center to lens edge). For example, the refractive power of the ring connected to the correction zone may be the greatest with the difference between the refractive power of the ring located furthest from the correction zone and the refractive power of the correction zone being the smallest among the rings of the control zone, the refractive powers of the other rings decreasing from the greatest to the least.
When the difference between the diopter of the ring connected with the correction area and the diopter of the correction area is smallest, the difference between the diopter of the ring farthest from the correction area and the diopter of the correction area in the control area is largest, and the diopter of the other rings is decreased from the minimum value to the maximum value.
Alternatively, the diopter difference may be increased or decreased, or the diopter of the odd number of rings is the same as that of the correction region, and the diopter of the other rings is different from that of the correction region, so that the diopter of the whole ring tends to be alternately changed. For example, the odd number may be one, three, five, seven, nine, or the like, and is not limited to the above-described numerical values.
For example, when two rings are present, the ring connected to the correction zone has a diopter greater or less than the diopter of the correction zone, while the ring furthest from the correction zone has the same diopter as the diopter of the correction zone; for example, when three rings are present, the diopter of the middle ring is the same as that of the correction zone, and the diopter of the other rings is different from that of the correction zone;
optionally, the zonal structure may include grating structures of different grating constants relative to the diopter of the correction zone to enhance light dispersion and enhance myopia prevention and control effects. The grating may be inscribed at different thickness positions of the lens, and the grating direction and other parameters at the different thickness positions may be the same or different.
Optionally, the zonal structures contain positive diopter values relative to the central myopia correction zone, each zonal structure being incrementally, decrementally or alternately varied with the diopter values of adjacent zonal structures.
Optionally, the diopter difference between the diopter of the area of the control zone located below the correction zone and the diopter of the correction zone is the largest.
Optionally, the difference in diopter from the correction zone is greatest when one or more block-like or local area structures are located below the correction zone. The lower side is not more than the viewing axis direction (horizontal direction).
Optionally, the block-shaped area structure is a fan-shaped or irregular shape, and the local area structure may be a fan-shaped, triangle, quadrilateral, pentagon, hexagon, star-shaped or irregular shape.
Considering the direction of the eye's line of sight when doing near work, the myopia control zone below the lens contains the maximum positive diopter relative to the myopia correction zone, thereby better reducing the lag of accommodation when doing near work while introducing peripheral myopia defocus to optimize the effect of myopia prevention and control.
Multiple levels of gratings can be written in the lens in multiple layers respectively, the gratings can be linear or spherical, and the diopter can be realized by adopting structures of micro curved surfaces (such as bulges, pits or Fresnel lens curved surfaces) and the like. The writing of the grating or the micro lens is realized by an XYZ laser three-dimensional modulation system. The spacing between layers is 1 to 100 microns, and can be 20 layers at maximum, the spacing of each grating unit is 0.1 to 1 micron, and the size of each grating unit is controlled to be 1 to 10 microns.
According to yet another aspect of the present application, there is provided a method of preparing an ophthalmic lens as defined in any one of the above, comprising: (1) detecting an ocular optical parameter of a user; (2) And according to the optical parameters, one or more laser beams are emitted by the laser writing device to locally write the laser material, so that the spectacle lens customized by the user in a personalized way is obtained.
Optionally, the ocular optical parameters include, but are not limited to, ocular axial length, diopter, corneal topography, anterior segment three-dimensional image, retinal three-dimensional topography, pupil diameter, anterior chamber depth, and the like.
Optionally, the laser writing device includes: an ultrafast laser generator XYZ scanning system; the wavelength of laser emitted by the ultrafast laser generator is 600 nm-1200 nm; the response speed of the XYZ scanning system is <100 microseconds as shown in fig. 6.
Alternatively, the XYZ scanning system can achieve inscription of fast arbitrary patterns, shapes, three-dimensional structures.
Optionally, the laser writing device further comprises a fixing device; the fixing device fixes the lens material.
Optionally, the fixing device rotates or moves at any angle in any direction.
Optionally, the securing means is an electrically controllable means.
Optionally, the fixture is movable in three directions of XYZ to facilitate the operator to adjust the inscription position of the spectacle lenses according to specific needs.
Optionally, the fixing device may also be adjusted in angle, for example, rotating about a horizontal direction (i.e., X-axis or Y-axis) and about a vertical direction (Z-axis), so that the operator can adjust the writing angle as desired.
The glasses lenses are fixed by the fastening device, the writing laser is ultrafast laser, focusing is carried out by controlling the movable lens and then the focusing lens, and then the depth of the laser writing in the lenses is controlled.
The invention provides a method for inscribing the surface and/or the inside of a lens material of an eyeglass lens by using ultra-fast laser, and can accurately inscribe any pattern, structure, micro-nano optics and texture of a myopia control area and cut and/or process the edge of the lens edge. Therefore, under lower laser intensity, the refractive index of the peripheral medium is changed through the mechanism of rearrangement, oxidization and the like of chemical bonds induced by the energy level transition of electrons in the excited dye molecules absorbed simultaneously by two photons, and the precise and personalized double customization can be performed according to the specific positions of the worn lenses, cornea and pupil after the preparation of the lenses by a user.
An ultrafast laser is used, and the central wavelength adjustment range is 600-1200nm. The resolution of the two-photon polymerization technique to produce microstructures is primarily related to the average power and exposure time of the laser. The average power of the laser directly influences the characteristic dimension of the microstructure, and the exposure time influences the photopolymerization threshold of the polymer material, so that the resolution of the microstructure prepared by the two-photon polymerization technology breaks through the optical diffraction limit by precisely controlling the average power and the exposure time of the laser. And the ultrafast laser is focused on the surface of the lens or in the lens through the XYZ three-dimensional regulating system, and the rapid two-photon inscription is realized through the two-photon effect and the three-dimensional regulating system.
According to a further aspect of the present application there is provided the use of at least one of the spectacle lenses described above for correcting ocular imaging problems.
Optionally, the ocular imaging problem includes at least one of myopia defocus, imaging hysteresis.
The technical effects are as follows:
In the hard optical lens material doped with dye molecules with high two-photon absorption cross section, such as a myopia frame spectacle lens, the application can write the surface or the inside of the lens by utilizing the effect of a series of photochemical reactions and thermal effects generated by the nonlinear two-photon absorption effect of the dye molecules generated at the focusing focus of the femtosecond ultrafast laser, and can realize the precise writing of any pattern, structure, micro-nano optics and texture of a myopia control area and the edge cutting and/or processing of the edge of the lens. The refractive index of the local micro-nano space size in the lens is changed or other optical characteristics are established, so that the individuation fine adjustment of the refractive power of the lens on the periphery of the optical correction area is realized, and the myopia correction, prevention and control are realized when the lens is worn for a long time by a user.
(1) Optical aspects: the lens is optically provided with a plurality of myopia control areas, and the increase of the eye axis is slowed down by generating myopia defocus on the peripheral retina, reducing adjustment lag when the near vision task is performed, and the like; and the zonal design of the myopia correction area is optimized to the maximum extent according to the biological parameters and the optical parameters of eyes of the wearer. The material aspect: the selected two-photon dye material can absorb blue light wave bands harmful to human eyes, and further reduces the damage to human eye cells. The dye is added into the frame lens material without water, and the thermal energy of the laser photo-thermal effect is not lost during laser lithography. Precision aspect: under lower laser intensity, the refractive index of the surrounding medium is changed through mechanisms such as rearrangement of chemical bonds, oxidation and the like induced by simultaneous absorption of two photons and energy level transition of electrons in excited dye molecules. The two-photon excitation can be focused on a space focus of a micro-nano to generate high concentration of energy, the two-photon molecules only generate photochemical reaction at the focus of the laser energy reaching the excitation threshold, and no reaction exists outside the focus, so that the writing of the optical characteristics of the micro-nano in space can be realized through the control of the focus, and the writing precision is extremely high and can reach 400nm.
(2) The precise processing capability of the two-photon nonlinear effect of the femtosecond ultrafast laser in the three-dimensional space is utilized, and rapid high-precision personalized customization can be realized. The structure of laser inscription is to be according to the actual eye biology of wearer and optical parameter data, including pupil diameter, peripheral eye axial length, retina peripheral optical aberration and retina curvature, combines the myopia control effect of clinical prediction, carries out accurate inscription to the lens, can also confirm the pose of lens according to the picture frame of wearer's selection and its face relative position, combines the specific position of wearer's self cornea, pupil to do accurate and individualized two customization again. Because the processing method is quick and convenient, the customization can be completed and implemented in a doctor's office or an eyeglass store site through a two-photon laser writing system, the method is immediately available, the practicability is high, and the method has wide application scenes.
Drawings
FIG. 1 is a schematic view of a lens having different optical characteristics according to example 4 of the present application;
FIG. 2 is a schematic view of a lens having different optical characteristics according to example 5 of the present application;
FIG. 3 is a schematic view of a lens having different optical characteristics according to example 6 of the present application;
fig. 4 is a schematic view of a lens having different optical characteristics in example 7 of the present application.
Fig. 5 is a schematic view of a lens having different optical characteristics in example 8 of the present application.
Fig. 6 is a schematic diagram of a laser writing apparatus according to the present application.
Detailed Description
The following describes specific embodiments of the present application with reference to the drawings.
In the present invention, unless otherwise indicated, scientific and technical terms used herein have the meanings commonly understood by one of ordinary skill in the art. Also, reagents, materials, and procedures used herein are reagents, materials, and conventional procedures widely used in the corresponding field. Meanwhile, in order to better understand the present invention, definitions and explanations of related terms are provided below.
Example 1
And (3) heating, extruding and blending the two-photon Dye1 and the thermoplastic material polymethacrylate by adopting a double screw to uniformly disperse the Dye, and then performing secondary processing to obtain the lens material, wherein the mass content of the two-photon Dye is 2%.
The lens material is subjected to melt compression molding, turning, polishing, cleaning and coating according to the standard processing technology of the conventional glasses to obtain the lens 1, and then inscription can be carried out.
Example 2
Adding a two-photon Dye2 into an active monomer of a resin material monomer methyl methacrylate, adding an initiator AIBN (accounting for 0.5% of the weight ratio of the active monomer), uniformly mixing for 5 hours, pouring the liquid mixture into a completely cleaned upper glass mold and a completely cleaned lower glass mold, packaging, and heating and curing for 24 hours at 95 ℃ in an oven to obtain the lens material, wherein the mass content of the two-photon Dye is 2%.
After the preparation of the lens material is completed, the mold is cooled and stripped, and then conventional turning, polishing, cleaning and coating are carried out to obtain the lens 2, and then inscription can be carried out.
Example 3
The two-photon Dye2 (accounting for 2 percent of the mass content of the lens material) is mixed with two active monomers of m-xylylene diisocyanate (CAS: 3634-83-1; from Shanghai-derived leaf Biotechnology Co., ltd.) and pentaerythritol tetra (3-mercaptopropionic acid) (PETMP; CAS:7575-23-7; from Hubei Yongkua technology Co., ltd.) (molar ratio is 2: 1) Adding catalyst DBTDL (dibutyl tin dilaurate, accounting for 0.1% of the weight of active monomer), mixing for 5 hr, injecting into completely cleaned glass mold, solidifying at 100deg.C for 20 hr, cooling, demolding, conventional turning, polishing, cleaning, coating to obtain lens 3, and inscribing.
Example 4
The pupil diameter under the light of the eye chamber of the user is 4mm, the cornea curvature is 43D, the eye axis length is 25.5mm, the eye axis curvature ratio is more than 3, and the myopia degree is-3.5D.
This example uses the lens 1 prepared in example 1, using a Ti Sapphire ultrafast laser, modulated to a characteristic center wavelength of 748nm, a repetition rate of 80MHz, a single pulse FWHM of 130fs, and an average power of 10mW.
The diameter of the optical zone of the lens 1 is 30mm, the whole lens comprises a correcting zone and a control zone, the diameter of the correcting zone is 1.5 times of the diameter of the pupil, the diameter of the correcting zone is 6mm, and the diopter is-3.5D; the control zone comprises three concentric rings numbered zone 2, zone 3, zone 4, respectively, along the direction of the correction zone to the control zone, as shown in fig. 1. Wherein the width of the area 2 is 5mm, the grating structure is included, the laser scanning speed is 20mm/sec, the laser pulse duration of the writing completion area 2 is 5 minutes, and the diopter of the writing completion area 2 relative to the correction area is +1D; zone 3 has a width of 4mm, comprising a grating structure, a laser scanning speed of 20mm/sec, and a laser pulse duration of 9 minutes to inscribe zone 3 so that its diopter relative to zone 2 is +2d; the diopter of zone 4 was the same as that of the correction zone, and no laser inscription was performed, with a width of 3mm.
According to the lens, the optical correction area and the myopia control area are arranged according to the pupil size of a wearer, the optical correction area provides clear central area vision for the wearer, and the myopia control area changes the defocus state of the periphery of the retina through positive diopter relative to the correction area, so that the purpose of guaranteeing the vision and slowing down the growth of the eye axis is achieved.
The method has the advantages of short time, great accessibility and the like from the time of obtaining the eye parameters of the user to the time of inscribing and preparing the lens, and convenience. Wherein the positive diopter of the myopia prevention and control zone relative to the correction zone is adjustable and personalized in accordance with the wearer's myopia progression rate.
If the user has too fast an eye axis growth, further accommodation is needed, i.e. design: zone 2 has a width of 5mm such that its diopter relative to the correction zone is adjustable to +2d; zone 3 has a width of 4mm such that its diopter relative to zone 2 is adjustable to +4d; the diopter of zone 4 is the same as that of the correction zone, and the width is 3mm.
Example 5
The pupil diameter under the light of the eye chamber of the user is 4mm, the cornea curvature is 43D, the eye axis length is 25.5mm, the eye axis curvature ratio is more than 3, and the myopia degree is-3.5D.
This example uses the lens 2 prepared in example 2, using a Ti Sapphire ultrafast laser, modulated with a characteristic center wavelength of 774nm, a repetition rate of 80MHz, a single pulse FWHM of 130fs, and an average power of 20mW.
The optical zone diameter of the lens is 30mm, the whole lens comprises a correction zone and a control zone, the whole lens is of concentric ring structures with different optical characteristics, the diameter of the correction zone is 6mm, the control zone comprises three concentric rings, the diopter of the correction zone is-3.5D, and the correction zone is numbered as zone 2, zone 3 and zone 4 along the direction from the correction zone to the control zone, as shown in figure 2. Wherein the width of the area 2 is 5mm, the grating structure is included, the laser scanning speed is 20mm/sec, the laser pulse duration of the writing completion area 2 is 1.5 minutes, and the diopter of the writing completion area 2 relative to the correction area is +2D; the diopter of zone 3 was the same as that of the correction zone, and no laser inscription was performed, with a width of 3mm. Zone 4 has a width of 4mm, comprising a grating structure, a laser scanning speed of 20mm/sec, and a laser pulse duration of 3 minutes to inscribe zone 4, giving a diopter of +4d with respect to zone 2.
The method has the advantages of short time, great accessibility and the like from the time of obtaining the eye parameters of the user to the time of inscribing and preparing the lens, and convenience. Wherein the positive diopter of the myopia prevention and control zone relative to the correction zone is adjustable and personalized in accordance with the wearer's myopia progression rate.
If the user has too fast an eye axis growth, further accommodation is needed, i.e. design: zone 2 has a width of 5mm such that its diopter relative to the correction zone is adjustable to +4d; the diopter of the zone 3 is the same as that of the correction zone, laser inscription is not carried out, and the width is 3mm; zone 4 has a width of 4mm such that its diopter relative to zone 2 is adjustable to +6d.
Example 6
The pupil diameter under the light of the eye chamber of the user is 4mm, the cornea curvature is 43D, the eye axis length is 25.5mm, the eye axis curvature ratio is more than 3, and the myopia degree is-3.5D.
This example uses the lens 3 prepared in example 3, using a Ti Sapphire ultrafast laser, with a characteristic center wavelength of 748nm, a repetition rate of 80MHz, a single pulse FWHM of 130fs, and an average power of 10mW.
The optic zone diameter of the lens was 30mm and the entire lens included a correction zone and a control zone, the correction zone being 6mm in diameter and containing-3.5D diopters. The control zone is a concentric ring with a ring width of 12mm. The control zone is partitioned from the edge of the correction zone to the edge of the control zone into three fan-shaped structures, as shown in fig. 3. Each sector structure comprises a grating structure, wherein a zone 2 is positioned below the correction zone, the diopter difference relative to the correction zone is the largest, the laser scanning speed during the preparation of the zone 2 is 20mm/sec, and the laser pulse duration is 9 minutes, so that the laser pulse duration is +3D relative to the correction zone; the laser scanning speed at the time of preparing zone 3 was 20mm/sec, and the laser pulse duration was 5 minutes so as to be +1D with respect to the correction zone; the laser scan at the time of preparation of zone 4 was at a speed of 20mm/sec and the laser pulse duration was 6 minutes to make it +2d with respect to the correction zone.
The method has the advantages of short time, great accessibility and the like from the time of obtaining the eye parameters of the user to the time of inscribing and preparing the lens, and convenience. Wherein the positive diopter of the myopia prevention and control zone relative to the correction zone is adjustable and personalized in accordance with the wearer's myopia progression rate.
If the user has too fast an eye axis growth, further accommodation is needed, i.e. design: zone 2 may be adjusted to +6d in diopter relative to the correction zone; zone 3 may be adjusted to +2d in diopter relative to the correction zone; the diopter of zone 4 may be adjusted to +4d relative to the diopter of the correction zone.
Example 7
The pupil diameter under the light of the eye chamber of the user is 4mm, the cornea curvature is 43D, the eye axis length is 25.5mm, the eye axis curvature ratio is more than 3, and the myopia degree is-3.5D.
The diameter of the optical area of the lens is 30mm, the whole lens comprises a correction area and a control area, the diameter of the correction area is 6mm, and the diopter is-3.5D; the control zone comprises three concentric rings numbered zone 2, zone 3, zone 4, respectively, along the direction of the correction zone to the control zone, as shown in fig. 4. Each concentric ring is provided with a laser inscribed regularly distributed microlens structure, which changes the diopter of each microlens structure by adjusting the curvature and refractive index of the microlens structure. Wherein zone 2 has a width of 5mm and each microlens structure thereof has a diopter of +1d relative to the correction zone; zone 3 has a width of 4mm and each microlens structure has a diopter of +2d with respect to the correction zone; zone 4 has a width of 3mm and each microlens structure has a refractive power of +3D relative to the correction zone.
The method has the advantages of short time, great accessibility and the like from the time of obtaining the eye parameters of the user to the time of inscribing and preparing the lens, and convenience.
Example 8
The pupil diameter under the light of the eye chamber of the user is 4mm, the cornea curvature is 43D, the eye axis length is 25.5mm, the eye axis curvature ratio is more than 3, and the myopia degree is-3.5D.
The diameter of the optical zone of the lens is 30mm, the whole lens comprises a correction zone and a control zone, the diameter of the correction zone is 6mm, and the diopter of-3.5D is contained; the control zone has a loop width of 12mm and comprises four patterns of arbitrarily shaped local areas, i.e. areas which are neither connected to the correction zone nor to the edges of the control zone, and a structure having a positive power relative to the control zone is inscribed in each pattern using a laser inscription technique, as shown in fig. 5, wherein the first quadrant of the pattern comprises a power relative to the correction zone +1d, the second quadrant of the pattern comprises a power relative to the correction zone +2d, and the third quadrant of the pattern comprises a power relative to the correction zone +3d.
The lens is convenient to write and prepare from the time of obtaining the eye parameters of the user to the time of completing the writing of the lens, and the time is short, and the like.
The pattern of the control zone in the above embodiments may also comprise structures with aberrations, or scattering patterns with light scattering effects, to further enhance the effect of myopia control.
In this document, "upper", "lower", "front", "rear", "left", "right", and the like are used merely to indicate relative positional relationships between the relevant portions, and do not limit the absolute positions of the relevant portions.
Herein, "first", "second", etc. are used only for distinguishing one another, and do not denote any order or importance, but rather denote a prerequisite of presence.
Herein, "equal," "same," etc. are not strictly mathematical and/or geometric limitations, but also include deviations that may be appreciated by those skilled in the art and allowed by fabrication or use, etc.
Unless otherwise indicated, numerical ranges herein include not only the entire range within both of its endpoints, but also the several sub-ranges contained therein.
While the preferred embodiments and examples of the present application have been described in detail with reference to the accompanying drawings, the present application is not limited to the above-described embodiments and examples, and various changes may be made within the knowledge of those skilled in the art without departing from the spirit of the present application.
Claims (10)
1. A lens material containing two-photon dye is characterized by comprising a resin material and two-photon dye;
The two-photon dye is doped in a resin material;
in the two-photon dye, the absorption wavelength of single photons is 300 nm-600 nm; the absorption wavelength of the two photons is 600 nm-1200 nm;
The two-photon absorption cross section of the two-photon dye is more than 10GM.
2. The lens material of claim 1, wherein the single photon absorption wavelength is preferably 380nm to 450nm; the absorption wavelength of the two photons is 760 nm-900 nm.
3. The lens material according to claim 1, wherein the two-photon dye is present in the lens material in an amount of 0.1% to 10% by weight;
Optionally, the two-photon dye comprises at least one of pi conjugated double bond molecules, polycyclic aromatic hydrocarbons and heterocyclic aromatic hydrocarbons containing heteroatom elements;
optionally, the pi conjugated double bond molecule comprises at least one of a distyryl group, a triphenylamine group, a phenothiazinyl group, an azo group and a carbazole group;
Alternatively, the two-photon dye containing distyryl groups has the general formula:
wherein n ranges from 0 to 6; r, R' is independently selected from alkyl, alkenyl, or alkynyl groups that are C 1～C18;
Optionally R, R' independently include heteroatoms; the heteroatom includes at least one of oxygen, sulfur, nitrogen, phosphorus, boron, silicon;
optionally R, R' further independently comprises at least one of-OH, -SH, -NH 2、-COOH、-COO-、-CHO、-NO2、-SO3 H, -CO-;
Preferably R, R' is independently selected from (CH 2)m-OH、(CH2)m-SH、(CH2)m-NH2 or (meth) acrylate, wherein m ranges from 1 to 18.
4. A method of producing a lens material according to any one of claims 1 to 3, comprising:
(1) Mixing a two-photon dye with a resin material to obtain the lens material; or alternatively, the first and second heat exchangers may be,
(2) And mixing at least one monomer in the resin material with the two-photon dye in the presence of an initiator or in the absence of the initiator, and reacting to obtain the lens material.
5. An ophthalmic lens comprising a lens material according to any one of claims 1 to 3;
And (3) carrying out two-photon laser inscription on the lens material to obtain the spectacle lens with the peripheral myopia prevention and control effect.
6. The ophthalmic lens of claim 5 wherein the ophthalmic lens comprises a correction zone and a control zone;
the correcting area is positioned in the central area of the spectacle lens;
The control area is positioned outside the correction area;
The area diameters of the control area and the correction area are determined according to the pupil diameter of a user;
the optical characteristics of the correction zone are determined according to the optical parameters of the eyes of the user;
the optical characteristic value of the control zone and the optical characteristic value of the correction zone are partially or wholly different.
7. The ophthalmic lens of claim 6 wherein the correction zone is circular; the control zone comprises at least two subareas with regular shapes or irregular shapes, and the diopter of the subareas and the diopter of the correction zone are increased, decreased or alternately changed.
8. The spectacle lens of claim 7, wherein the partition structure is an annular region structure surrounding the correction zone, a block region structure partitioning the control zone from the edge of the correction zone to the edge of the control zone, a local region structure distributed outside the correction zone, or any combination thereof.
9. The ophthalmic lens of claim 7 wherein the difference between the diopter of the area of the control zone below the correction zone and the diopter of the correction zone is greatest.
10. A method of making an ophthalmic lens according to any one of claims 5 to 9, comprising:
(1) Acquiring an eye optical parameter of a user;
(2) And according to the optical parameters, one or more laser beams are emitted by the laser writing device to carry out rapid local writing on the laser material, so that the spectacle lens customized by the user in a personalized way is obtained.
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| CN202211490503.2A CN118091981A (en) | 2022-11-25 | 2022-11-25 | Lens material containing two-photon dye and preparation method and application thereof |
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