CN116102699A - Closely-distributed microlens-based anti-near control lens substrate and preparation method and application thereof - Google Patents

Abstract

The invention discloses an anti-proximity control lens base material densely distributed with microlenses and its preparation method and application. The base material is composed of the following materials: polyol containing episulfide groups, isocyanate, catalyst, solvent and chain extender ; The ratio of the molar fraction of polyols containing episulfide groups to isocyanates is 1: (1.0‑1.1); the amount of catalyst accounts for 0.5‑1.2% of the total mass of polyols containing episulfide groups and isocyanates; the amount of solvent accounts for 50‑120% of the total mass of polyols and isocyanates in the group; the amount of chain extender is 2‑8% of the mass of isocyanate. The episulfide group of the present invention effectively increases the refractive index and Abbe number of the polymer, and improves its impact strength and toughness as a lens substrate; the processing technology avoids the excessive performance requirements of traditional mechanical processing on the microlens substrate , and at the same time meet the processing accuracy of the microlens lens.

Description

Anti-proximity control lens base material densely distributed with microlenses and its preparation method and application

technical field

The invention relates to an anti-proximity control lens base material densely distributed with microlenses, a preparation method and application thereof, and belongs to the technical field of microlens anti-proximity control lens materials.

Background technique

Polymer optical materials have been widely used in recent years because of their light weight, cheap price, and easy processing and molding. They have replaced inorganic optical glass and other materials in many aspects. They are widely used in the field of lens materials. According to statistics, the popularity of resin lenses rate increases year by year. The working principle of traditional myopia lenses is to add a concave lens in front of the eyes, so that the points that cannot be imaged on the retina are moved to the retina, so that our eyes can see objects clearly. However, because people's retina is an arc similar to the internal structure of a sphere, rather than a plane, this makes the image of the part beyond the imaging focus behind the retina, and the eye axis will be slowly elongated to adapt to this change. Over time Vision will be deepened.

By controlling the growth rate of the eye axis, it can effectively delay the progression of myopia. Based on the above reasons, there are many ways to prevent the progression of myopia, and the most widely used methods are as follows: The first is the peripheral defocusing technology, which prevents the growth of the eye axis by reducing the degree around the lens. The second is to add microlenses to the lens, depending on the distribution, structural design and number of microlenses, to achieve different anti-proximity control effects, such as allowing the light at the lens to be imaged in front of the retina, so that the light forms a non-focus in front of the retina The beam belt, etc., can slow down or prevent the eye axis from being stretched, thereby slowing down the progress of myopia. Overall, the effect of preventing myopia through microlenses is better, because microlenses can be finely adjusted in fine optics according to the difference in vision, which is more targeted. But on the other hand, this also increases the requirements for the microlens array and its lens material and processing technology. There are also some patents on microlens arrays, such as patent CN 202210623672.2 which discloses a multi-focal lens with a wave structure and a microlens structure, and CN202210599054.9 which discloses a spectacle lens with ring-shaped micro-toricular lens array and its design method etc. Although these arrays are designed from different angles of diopter, the microlens arrays are mostly limited to circular areas. In fact, this is not in line with the characteristics of human vision and observation habits. This design will somewhat cause visual fatigue and reduce the clarity of vision. Therefore, it is necessary to further design the microlens array according to the characteristics of human vision.

In terms of microlens processing, the processing technologies reported in the literature include direct and indirect methods, such as inkjet printing, laser direct writing, screen printing, photolithography, photopolymerization, hot melt reflow technology, and vapor phase chemical deposition. There are also methods that use traditional mechanical methods to cooperate with optical and control technologies, such as compression molding. However, when it comes to the processing technology of micro-lenses based on lenses, it is necessary to consider that the number of known micro-lenses ranges from hundreds to thousands. In this case, the technology used is not only the refinement of the processing technology At the same time, there are also high requirements for the performance of lens materials. Patent CN201911073459.3 proposes that the lens microlens can be processed by CNC lathe and 3D printed, or the spectacle lens can be selected from soft transparent plastic polymer materials, and can be formed by centrifugal casting, cutting and grinding, or direct molding. Regardless of the method, the size of the microlens needs to be at the millimeter level, and the processing accuracy is limited. In terms of material selection, a soft transparent plastic polymer material is required, but there is no specific description of what kind of polymer material to use. Traditional vision correction lenses mainly use CR-39, PMMA and PC, which are brittle and difficult to process. From these two perspectives, we can see the importance of material selection to the function realization and practical application of the lens. Therefore, how to ensure the coordination between the performance of the lens material and the processing technology is an important issue in the development of the microlens anti-proximity control field. Therefore, there is an urgent need for a processable, densely distributed anti-proximity lens substrate with microlenses and its preparation method and application.

Contents of the invention

In order to solve the problem of coordination between the lens material and the processing technology, and further solve the requirements of the strength and toughness of the base material of the anti-proximity control lens densely distributed with microlenses, the present invention provides an anti-proximity control lens with densely distributed microlenses Substrate.

At the same time, the present invention provides an anti-proximity control lens base material densely distributed with microlenses and a preparation method thereof. The method adopts a near-infrared femtosecond laser pulse two-photon polymerization process to further avoid traditional mechanical processing on densely distributed microlenses. The performance requirements of the lens base material are too high, and at the same time, the processing accuracy of the microlens lens is satisfied.

At the same time, the invention provides an application of the anti-proximity control lens base material with densely distributed microlenses.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

The anti-proximity control lens substrate with densely distributed microlenses is composed of the following materials: polyols containing episulfide groups, isocyanates, catalysts, solvents and chain extenders;

The ratio of mole fractions of polyols containing episulfide groups to isocyanates is 1: (1.0-1.1);

The amount of catalyst accounts for 0.5-1.2% of the total mass of polyols and isocyanates containing episulfide groups;

The amount of solvent accounts for 50-120% of the total mass of polyols and isocyanates containing episulfide groups;

The amount of chain extender is 2-8% of the mass of isocyanate.

Polyols containing episulfide groups are diols or triols with one of the following structures:

Among them, R ₁ is one of alkyl, alkenyl, and aromatic ring groups containing 2-10 carbons, and there can only be one -OH on the same carbon atom; R ₂ is an alkyl group containing 3-9 carbons One of alkyl group, alkenyl group and aromatic ring group, and there can be at most one -OH on the same carbon atom.

Polyols containing episulfide groups have one of the following structures:

The isocyanate is one or more of isophorone diisocyanate IPDI, diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, and dicyclohexylmethane diisocyanate HMDI.

The catalyst is one of diethanolamine DEOA and dibutyltin dilaurate DBTDL;

The solvent is one of 1,3,5-trimethylbenzene and acetone;

The chain extender is one or more of ethylene glycol and 1,4-butanediol.

The preparation method of the anti-proximity control lens base material densely distributed with microlenses comprises the following steps:

Step 1: Prepolymerization reaction, first add polyols and catalysts containing episulfide groups into the reaction vessel, then add isocyanate, heat and react at 55-65°C for 1-3 hours, then add solvent to dilute to obtain prepolymerization mixture ;

Step 2: chain extension reaction, adding a chain extender to the prepolymerization mixture, mechanically stirring at 70-90°C, continuing the reaction for 1-3 hours, and then cooling to room temperature to obtain sulfur-containing polyurethane;

Step 3: Processing and molding to obtain a sulfur-containing polyurethane resin system, and after the sulfur-containing polyurethane resin system is processed by two-photon polymerization, an anti-proximity lens with densely distributed microlenses is obtained;

The two-photon polymerization process is as follows: inject the sulfur-containing polyurethane resin system into the lens mold, irradiate the near-infrared femtosecond laser pulse to the position of the microlens on the surface of the resin system, and obtain the microlens array through two-photon polymerization on the part of the irradiated resin system , the center wavelength of the near-infrared femtosecond laser pulse is 760nm, the pulse width is 80fs, the repetition frequency is 75MHz, the maximum output power is 5W, the excitation power is 5.5mW, the scanning step of x and y axis is 0.15-0.35μm, and the scanning step of z axis is 0.45-0.65μm, after the microlens array is obtained, the unirradiated part of the resin system undergoes free radical polymerization under the irradiation of ultraviolet light. The wavelength of ultraviolet light is 365nm, the power is 350W, and the irradiation time is 1-5min. Finally, dense Anti-proximity lens distributed with microlenses.

On the anti-proximity control lens, the number of microlenses is between 1000-2600, and the microlenses are in a circular structure with a diameter of 80-500 μm, and all the microlenses form an elliptical array.

The structure of the elliptical array is as follows: the center line of the innermost microlens close to the center of the anti-proximity lens forms an elliptical area. The line connecting the center of the outermost microlens forms a larger ellipse, and the centers of all ellipses are in the center of the anti-close-control lens. The number is between 5-15 circles, the distance between the centers of two adjacent microlenses on the same elliptical ring is 0.618-1.236 times the diameter of the circular microlens, and the distance between two adjacent elliptical rings is 1.000 times the diameter of the circular microlens -1.854 times.

The application of the anti-proximity control lens substrate with densely distributed microlenses in the anti-proximity control lens, the refractive index of the anti-proximity control lens is greater than 1.712, the Abbe number is greater than 41, the impact strength is greater than 36.6kJ/m ² , and the tensile strength Greater than 40MPa.

An anti-proximity control lens, comprising an anti-proximity control lens substrate densely distributed with microlenses.

Beneficial effects of the present invention:

(1) Improve the refractive index of polyurethane substrates as optical materials by introducing episulfide groups, reduce dispersion, increase the Abbe number, and synergize with other polyol groups such as aromatic ring groups to improve the impact strength of polyurethane substrates and toughness.

(2) While improving the impact strength and flexibility of the resin monomer, by optimizing and adopting the two-photon polymerization process to process microlenses for lenses, on the premise of ensuring that the optical requirements are met, further avoiding traditional mechanical processing on the substrate Strict performance requirements, while meeting the processing accuracy of microlens lenses.

(3) The circular microlenses are concentrically distributed on the lens in an elliptical shape, which abandons the design of the traditional anti-proximity lens with a circular or polygonal area in the center. The imaging is more in line with human visual characteristics, and the processed glasses are comfortable to wear. The field of view is clear, especially suitable for teenagers and children who focus on using their eyes or look around at a high frequency, with reduced fatigue and good prevention and control effects.

(4) The processing technology based on the microlens for lens of the present invention further avoids the excessive performance requirement of the microlens base material in traditional mechanical processing, and at the same time satisfies the processing accuracy of the microlens lens. The invention also provides a distribution mode of the microlens array, and the processed glasses are comfortable to wear and have a good effect of preventing close-up.

(5) The sulfur-containing polyurethane resin of the present invention has a refractive index of at least 1.712, an Abbe number of 42, high impact strength and toughness, and is especially suitable for densely distributed materials based on 3D internal carving and two-photon polymerization processing. Anti-proximity lenses with microlenses.

Description of drawings

Fig. 1 is the schematic diagram of the anti-proximity control lens densely distributed with microlenses of the present invention;

Fig. 2 is a schematic diagram of the relationship between the microlenses on the anti-proximity control lens of the present invention.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. The specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Example 1

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

Epithiodiol 19.6g

Isophorone diisocyanate 23.5g

Diethanolamine 0.38g

Acetone 38g

Ethylene glycol 0.9g

Wherein, epithio dihydric alcohol has following structure (formula I):

The present invention makes the anti-proximity control lens through the following steps:

Step 1: Prepolymerization reaction, first add 19.6g of epithiodiol and 0.38g of catalyst diethanolamine into the reaction vessel according to the above material ratio, and then add 23.5g of isophorone diisocyanate, at 65°C Under heating reaction 1.5 hours, add the acetone dilution of 38g again, obtain prepolymerized mixture;

Step 2: chain extension reaction, add 0.9 g of chain extender ethylene glycol to the prepolymerization mixture obtained in step 1, mechanically stir at 85 ° C, continue the reaction for 1.5 hours, and then cool to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

The two-photon polymerization process is as follows: the sulfur-containing polyurethane resin system is injected into the lens mold, and under the control of the system program, the near-infrared femtosecond laser pulse is irradiated on the surface of the resin system, and the irradiated part is obtained by two-photon polymerization to obtain a microlens array. The near-infrared femtosecond laser pulse is generated by a titanium sapphire femtosecond laser with a center wavelength of 760nm, a pulse width of 80fs, a repetition rate of 75MHz, a maximum output power of 5W, an excitation power of 5.5mW, a scanning step of 0.15μm in x and y axes, and a scanning step of 0.15μm in the z axis. The scanning step is 0.45 μm, and the other lens parts (that is, the part of the resin system that has not been irradiated by the near-infrared femtosecond laser pulse) undergo radical polymerization under the irradiation of ultraviolet light. The ultraviolet light is generated by a high-pressure mercury lamp with a wavelength of 365nm and a power of The irradiation time is 350W, and the irradiation time is 1min, and finally a resin-based anti-proximity control lens with densely distributed microlenses is obtained. As shown in Figures 1 to 2, the anti-proximity control lens of the present embodiment is densely distributed with microlenses, the number of microlenses is between 1000-2600, and the microlenses are in a circular structure with a diameter of 80 μm, close to the lens The line connecting the center of the innermost microlens in the center forms an elliptical area, the long axis of the ellipse is in the horizontal direction, and the length is 1.1cm, and the line connecting the center of the outermost microlens away from the center of the lens forms a larger ellipse. The center of the ellipse is in the center of the lens, and other microlenses are arranged in turn between the inner and outer microlenses to form an elliptical ring. The number of elliptical rings is 6 circles, and the distance between the centers of two adjacent microlenses on the same elliptical ring is a circle. 0.618-1.236 times the diameter of the circular microlens (this size is not fixed, some are denser, some are sparser), and the distance between two adjacent elliptical rings is 1.4 times the diameter of the circular microlens.

Application of an anti-proximity control lens base material densely distributed with microlenses in an anti-proximity control lens.

An anti-proximity control lens, comprising the anti-proximity control lens substrate in this embodiment densely distributed with microlenses.

Example 2

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

Epithio trihydric alcohol 15.8g

Diphenylmethane diisocyanate 25g

Dibutyltin dilaurate 0.45g

Acetone 45g

1,4-Butanediol 0.6g

Wherein, epithio trihydric alcohol has following structure (formula II):

The present invention makes the anti-proximity control lens through the following steps:

Step 1: prepolymerization reaction, add the epithiol trihydric alcohol of 15.8g, the catalyst dibutyltin dilaurate of 0.45g in the reaction vessel earlier according to the above-mentioned material ratio, then add the diphenylmethane diisocyanate of 25g, in Heating and reacting at 55°C for 2.5 hours, then adding 45g of acetone for dilution to obtain a prepolymerized mixture;

Step 2: chain extension reaction, add 0.6g of chain extender 1,4-butanediol to the prepolymerization mixture obtained in step 1, mechanically stir at 90°C, continue the reaction for 1.0 hour, and then cool to room temperature to obtain sulfur polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

The two-photon polymerization process is as follows: the sulfur-containing polyurethane resin system is injected into the lens mold, and under the control of the system program, the near-infrared femtosecond laser pulse is irradiated on the surface of the resin system, and the irradiated part is obtained by two-photon polymerization to obtain a microlens array. The near-infrared femtosecond laser pulse is generated by a titanium sapphire femtosecond laser, with a center wavelength of 760nm, a pulse width of 80fs, a repetition rate of 75MHz, a maximum output power of 5W, an excitation power of 5.5mW, a scanning step of 0.35μm on the x and y axes, and a scanning step of 0.35μm on the z axis. The scanning step is 0.65 μm, and the other lens parts undergo free radical polymerization under the irradiation of ultraviolet light. The ultraviolet light is generated by a high-pressure mercury lamp with a wavelength of 365nm, a power of 350W, and an irradiation time of 5 minutes. Finally, a densely distributed microlens is obtained. Resin-based anti-proximity lenses.

The anti-proximity control lens of the present embodiment is densely distributed with microlenses, the number of microlenses is between 1000-2600, the microlenses are in a circular structure, the diameter is 500 μm, and the innermost microlens center line near the center of the lens An elliptical area is formed, the long axis of the ellipse is in the horizontal direction, and the length is 2.3cm. The line connecting the center of the outermost microlens away from the center of the lens forms a larger ellipse, and the centers of all ellipses are in the center of the lens. The other microlenses are arranged in turn between the inner and outer microlenses to form an elliptical ring, the number of elliptical rings is 15, and the distance between the centers of two adjacent microlenses on the same elliptical ring is 0.618-1.236 times the diameter of the circular microlens , the distance between two adjacent elliptical rings is 1.854 times the diameter of the circular microlens.

Application of an anti-proximity control lens base material densely distributed with microlenses in an anti-proximity control lens.

An anti-proximity control lens, comprising the anti-proximity control lens substrate in this embodiment densely distributed with microlenses.

Comparative example 1

The difference between this comparative example and embodiment 1 is only:

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

2,3-dithio(2-mercapto)-1-propanethiol 26g

Isophorone diisocyanate 23.5g

Diethanolamine 0.4g

Acetone 40g

Ethylene glycol 1.2g

This comparative example makes the anti-proximity control lens through the following steps:

Step 1: prepolymerization reaction, first add 26g of 2,3-dithio(2-mercapto)-1-propanethiol and 0.4g of catalyst into the reaction vessel according to the above material ratio, and then add 23.5g of iso Phortone diisocyanate was heated and reacted at 65°C for 1.5 hours, and then diluted with 40g of acetone to obtain a prepolymerized mixture;

Step 2: chain extension reaction, add 1.2 g of chain extender to the prepolymerization mixture obtained in step 1, mechanically stir at 85°C, continue the reaction for 1.5 hours, and then cool to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

Comparative example 2

The difference between this comparative example and embodiment 1 is only:

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

Epithio trihydric alcohol 21.6g

Diphenylmethane diisocyanate 25g

Dibutyltin dilaurate 0.45g

Acetone 45g

1,4-Butanediol 0.6g

Wherein, epithio trihydric alcohol has following structure:

The present invention makes the anti-proximity control lens through the following steps:

Step 1: prepolymerization reaction, first the epithiol trihydric alcohol of 21.6g, the catalyst dibutyltin dilaurate of 0.45g are added in the reaction vessel according to the above-mentioned material ratio, then add the diphenylmethane diisocyanate of 25g, in Heating and reacting at 55°C for 2.5 hours, then adding 45g of acetone for dilution to obtain a prepolymerized mixture;

Step 2: chain extension reaction, add 0.6g of chain extender 1,4-butanediol to the prepolymerization mixture obtained in step 1, mechanically stir at 90°C, continue the reaction for 1.0 hour, and then cool to room temperature to obtain sulfur polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

Comparative example 3

The difference between this comparative example and embodiment 1 is only:

A myopia lens base material is prepared from the following materials:

Polyether polyol 16.4g

Isophorone diisocyanate 23.5g

Diethanolamine 0.32g

Acetone 32g

Ethylene glycol 0.75g

The present invention makes the anti-proximity control lens through the following steps:

Step 1: Prepolymerization reaction, first add 16.4g of polyether polyol and 0.32g of catalyst diethanolamine into the reaction vessel according to the above material ratio, then add 23.5g of isophorone diisocyanate, and heat at 65°C React for 1.5 hours, then add 32g of acetone for dilution to obtain a prepolymer mixture;

Step 2: chain extension reaction, add 0.75 g of chain extender to the prepolymerization mixture obtained in step 1, mechanically stir at 85 ° C, continue the reaction for 1.5 hours, and then cool to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

Comparative example 4

A myopia lens base material is prepared from the following materials:

2,3-dithio(2-mercapto)-1-propanethiol 26g

Isophorone diisocyanate 23.5g

Diethanolamine 0.4g

Acetone 40g

Ethylene glycol 1.2g

The present invention makes the anti-proximity control lens through the following steps:

Step 1: Prepolymerization reaction, first add 26g of 2,3-dithio(2-mercapto)-1-propanethiol and 0.4g of catalyst diethanolamine into the reaction vessel according to the above material ratio, and then add 23.5g The isophorone diisocyanate was heated and reacted at 65° C. for 1.5 hours, and then diluted with 40 g of acetone to obtain a prepolymerized mixture;

Step 2: chain extension reaction, add 1.2 g of chain extender ethylene glycol to the prepolymerization mixture obtained in step 1, mechanically stir at 85 ° C, continue the reaction for 1.5 hours, and then cool to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, the sulfur-containing polyurethane described in step 2 is hot-pressed into a certain mold, and after the release agent is released from the mold, the anti-proximity lens is obtained.

The performance tests of the resins or lenses obtained in the various examples and comparative examples were carried out by the following methods, and the results are shown in Table 1.

(1) Measurement of light transmittance

According to the method of ISO 8980-3-2005 standard, the light transmittance is related to the thickness of the sample, so the light transmittance is converted into the corresponding value of the standard thickness (0.2mm).

(2) Determination of Refractive Index

The refractive index of the material was measured using an Abbe refractometer.

(3) Impact strength

The notched impact strength of the material was tested using a pendulum impact testing machine.

(4) Tensile strength

A universal testing machine is used to perform a tensile test on the material to obtain the tensile strength of the material.

(4) Aging resistance

According to the ISO 11985 standard method, the aging test of ultraviolet and visible light radiation is carried out.

Table 1 performance test result table

As can be seen from the test results, the light transmittance of embodiment 1-embodiment 2 is all above 99%, the refractive index is all above 1.712, the Abbe number is above 41, and the impact strength is all above 36.6kJ/ ^m2 . The tensile strength is higher than 40MPa, so that lenses with densely distributed microlenses can be produced, and the vision after wearing is clearer, more comfortable to wear, and has a good effect of preventing myopia. Comparative Example 1 uses polyols containing other sulfides, and the properties of all aspects are reduced. Comparative Example 2 uses epithiopolyols with a large number of carbons, which has little impact on optical properties, but the impact strength and The tensile strength drops more, and the processing and performance of the lens are affected. Comparative example 3 uses polyether polyols that have not been vulcanized and modified, and the obtained polyurethane substrate has a low refractive index and Abbe number, and the light transmittance is relatively low. The rate is only up to 93%, which basically belongs to the situation that the transmittance and the refractive index cannot be improved at the same time, and other properties are also average. Comparative example 4 is a polymer lens material made by a hot pressing molding process, and its impact toughness and tensile strength Compared with Example 1-Example 2, it is significantly lower, and even lower than other comparative examples, and cannot meet the performance requirements of lens processing with densely distributed microlenses. The traditional lenses made by it can meet the vision requirements , but the effect of preventing myopia in young people is not good.

Example 3

The difference between this embodiment and embodiment 1 is only:

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

Epithio dihydric alcohol (formula I) 19.6g

Toluene diisocyanate 23.5g

Diethanolamine 0.216g

1,3,5-Trimethylbenzene 21.6g

Ethylene glycol 0.47g

The present invention makes the anti-proximity control lens through the following steps:

Step 1: Prepolymerization reaction, first add 19.6g of epithiodiol and 0.216g of catalyst diethanolamine into the reaction vessel according to the above material ratio, then add 23.5g of toluene diisocyanate, and heat the reaction at 60°C After 1 hour, add 21.6 g of 1,3,5-trimethylbenzene for dilution to obtain a prepolymerized mixture;

Step 2: chain extension reaction, add 0.47g of chain extender ethylene glycol to the prepolymerization mixture obtained in step 1, mechanically stir at 70°C, continue the reaction for 3 hours, and then cool to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

In this embodiment, the number of elliptical rings in the microlens array is five, and the distance between two adjacent elliptical rings is 1.000 times the diameter of the circular microlens.

Example 4

The difference between this embodiment and embodiment 1 is only:

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

Epithio dihydric alcohol (formula I) 19.6g

Dicyclohexylmethane diisocyanate 23.5g

Diethanolamine 0.517g

1,3,5-Trimethylbenzene 51.7g

Ethylene glycol 1.88g

The present invention makes the anti-proximity control lens through the following steps:

Step 1: Prepolymerization reaction, first add 19.6g of epithiodiol and 0.517g of catalyst diethanolamine into the reaction vessel according to the above material ratio, and then add 23.5g of dicyclohexylmethane diisocyanate, at 60°C Heated and reacted for 3 hours, then added 51.7g of 1,3,5-trimethylbenzene for dilution to obtain a prepolymerized mixture;

Step 2: chain extension reaction, add 1.88 g of chain extender ethylene glycol to the prepolymerization mixture obtained in step 1, mechanically stir at 80 ° C, continue the reaction for 3 hours, and then cool to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

Example 5

The difference between this embodiment and embodiment 1 is only:

An anti-proximity control lens base material densely distributed with microlenses, prepared from the following materials:

Epithio dihydric alcohol (formula I) 19.6g

Isophorone diisocyanate 12.0g

Toluene diisocyanate 11.5g

Diethanolamine 0.431g

Acetone 43.1g

Ethylene glycol 0.47g

1,4-Butanediol 0.705g

The present invention makes the anti-proximity control lens through the following steps:

Step 1: Prepolymerization reaction, first add 19.6g of epithiodiol and 0.431g of catalyst diethanolamine into the reaction vessel according to the above material ratio, then add 12.0g of isophorone diisocyanate and 11.5g of Toluene diisocyanate was heated and reacted at 60° C. for 2 hours, and then diluted with 43.1 g of acetone to obtain a prepolymerized mixture;

Step 2: Chain extension reaction, add 0.47g of chain extender ethylene glycol and 0.705g of chain extender 1,4-butanediol to the prepolymerization mixture obtained in step 1, stir mechanically at 75°C, and continue the reaction 2 hours, then cooled to room temperature to obtain sulfur-containing polyurethane;

Step 3: processing and molding, after the sulfur-containing polyurethane described in step 2 is subjected to two-photon polymerization processing, an anti-proximity control lens with densely distributed microlenses is obtained.

It should be appreciated that in the above description of exemplary embodiments of the invention, in order to streamline this disclosure and to facilitate understanding of one or more of the various inventive aspects, various features of the invention are sometimes grouped together in a single embodiment, figure, or in its description. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, inventive aspects lie in less than all features of the foregoing disclosed embodiments, as the claims reflect. Thus, the claims following the Detailed Description are hereby expressly incorporated into this Detailed Description, with each claim standing on its own as a separate embodiment of this invention.

While the invention has been described in terms of a limited number of embodiments, it will be apparent to a person skilled in the art having the benefit of the above description that other embodiments are conceivable within the scope of the invention thus described. In addition, it should be noted that the language used in the specification has been chosen primarily for the purpose of readability and instruction rather than to explain or define the inventive subject matter. Accordingly, many modifications and alterations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the appended claims. With respect to the scope of the present invention, the disclosure of the present invention is intended to be illustrative rather than restrictive, and the scope of the present invention is defined by the appended claims.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also possible. It should be regarded as the protection scope of the present invention.

Claims (10)

1. The closely-distributed anti-close control lens base material with the microlenses is characterized by comprising the following materials: a polyol containing an episulfide group, an isocyanate, a catalyst, a solvent and a chain extender;

the mole fraction ratio of the polyol containing the cyclic sulfur group to the isocyanate is 1: (1.0-1.1);

the catalyst amount is 0.5-1.2% of the total mass of the polyalcohol containing the cyclic sulfur group and the isocyanate;

the solvent amount is 50-120% of the total mass of the polyalcohol containing the cyclic sulfur group and the isocyanate;

the chain extender is used in an amount of 2-8% by mass of the isocyanate.

2. The closely spaced microlens anti-proximity lens substrate of claim 1 wherein the polyol containing an episulfide group is a diol or triol having one of the following structures:

wherein R is ₁ Is alkyl, alkenyl or aryl containing 2-10 carbonsOne of the ring groups and at most one-OH group on the same carbon atom; r is R ₂ Is one of alkyl, alkenyl and aryl groups containing 3-9 carbons, and at most only one-OH can be contained on the same carbon atom.

3. The close-up prevention lens substrate with densely packed microlenses according to claim 2, wherein the episulfide group-containing polyol has one of the following structures:

4. the closely spaced microlens-based anti-proximity lens substrate of claim 1 wherein the isocyanate is one or more of isophorone diisocyanate IPDI, diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, dicyclohexylmethane diisocyanate HMDI.

5. The closely spaced microlens anti-proximity lens substrate of claim 1 wherein the catalyst is one of diethanolamine DEOA, dibutyltin dilaurate DBTDL;

the solvent is one of 1,3, 5-trimethylbenzene and acetone;

the chain extender is one or more of ethylene glycol and 1, 4-butanediol.

6. The method for preparing a closely-distributed microlens-based material for preventing near control according to any one of claims 1 to 5, comprising the steps of:

step 1: the preparation method comprises the steps of (1) pre-polymerizing, namely adding polyalcohol containing an episulfide group and a catalyst into a reaction container, then adding isocyanate, heating at 55-65 ℃ for reaction for 1-3 hours, and then adding a solvent for dilution to obtain a pre-polymerizing mixture;

step 2: chain extension reaction, adding a chain extender into the prepolymer mixture, mechanically stirring at 70-90 ℃, continuing to react for 1-3 hours, and cooling to room temperature to obtain sulfur-containing polyurethane;

step 3: processing and forming to obtain a sulfur-containing polyurethane resin system, and carrying out two-photon polymerization processing on the sulfur-containing polyurethane resin system to obtain a near control prevention lens densely distributed with microlenses;

the two-photon polymerization processing technology comprises the following steps: injecting a sulfur-containing polyurethane resin system into a lens mold, irradiating near infrared femtosecond laser pulses to the positions of micro lenses on the surface of the resin system, obtaining a micro lens array by two-photon polymerization of the irradiated resin system, wherein the central wavelength of the near infrared femtosecond laser pulses is 760nm, the pulse width is 80fs, the repetition frequency is 75MHz, the maximum output power is 5W, the excitation power is 5.5mW, the x-axis scanning step distance is 0.15-0.35 mu m, the z-axis scanning step distance is 0.45-0.65 mu m, and after obtaining the micro lens array, the non-irradiated resin system is subjected to free radical polymerization under ultraviolet irradiation, the wavelength of ultraviolet light is 365nm, the power is 350W, the irradiation time is 1-5min, thus obtaining the near control lens densely distributed with micro lenses.

7. The method for preparing a near control lens substrate densely distributed with micro lenses according to claim 6, wherein the number of the micro lenses on the near control lens is 1000-2600, the micro lenses are in a circular structure, the diameter is 80-500 μm, and all the micro lenses form an elliptical array.

8. The method for preparing a closely spaced microlens array for preventing and controlling a lens substrate according to claim 8, wherein the elliptical array has the structure: the center connecting line of the innermost micro lens close to the center of the anti-close control lens encloses an elliptical area, the long axis of the ellipse is in the horizontal direction, the length of the ellipse is 1.1-2.3cm, the center connecting line of the outermost micro lens far away from the center of the anti-close control lens encloses a larger ellipse, all the centers of the ellipses are located at the center of the anti-close control lens, other micro lenses are sequentially arranged between the inner micro lens and the outer micro lens and form elliptical rings, the number of the elliptical rings is 5-15 circles, the center distance between two adjacent micro lenses on the same elliptical ring is 0.618-1.236 times of the diameter of the circular micro lens, and the distance between two adjacent elliptical rings is 1.000-1.854 times of the diameter of the circular micro lens.

9. Use of a close-up preventing lens substrate densely populated with microlenses according to any of claims 1-5, in which the refractive index of the close-up preventing lens is greater than 1.712, the abbe number is greater than 41, and the impact strength is greater than 36.6kJ/m ² The tensile strength is more than 40MPa.

10. A proximity control lens comprising a proximity control lens substrate according to any one of claims 1 to 5 densely populated with microlenses.

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