JP7350280B2 - plastic eyeglass lenses and glasses - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act (1) Meeting name: 59th Academic Conference of the Japanese Society of Neurology (2) Date: May 23, 2018

The present invention relates to plastic eyeglass lenses (including sunglass lenses) and eyeglasses (including sunglasses) using the plastic eyeglass lenses.

As described in Japanese Patent No. 5807237 (Patent Document 1 below), light-shielding glasses are known that prevent photophobia by blocking light at a wavelength of 485 nm (nanometers), which is the light absorption peak of melanopsin.
These light-shielding glasses reduce the transmittance of light in a wavelength range of 485 nm or including this by, for example, forming an optical multilayer film, introducing a volume phase hologram, or incorporating fine metal particles.

Patent No. 5807237

Recently, regarding endogenous photosensitive retinal ganglion cells (ipRGCs) containing melanopsin in the retina of the eye, it has been found that headaches worsen under light irradiation in visually impaired migraine patients, suggesting that ipRGCs are involved in headaches. (Noseda R. et al., Nature Neurosci., 2010).
Furthermore, a comparison was made between electroretinograms and visual evoked potential measurements in migraine patients with normal vision without visual impairment, and it was found that cones and rods are involved in headaches accompanied by photosensitivity. (Noseda R. et al., Brain., 2015).
Furthermore, in DIN SPEC 5031-100 2015 August, melanopic effects, which are the effects of light on physiological and psychological processes in the human body via ipRGC in the retina, were defined. An effect function indicating the relative degree of melanopic effect is shown in FIG. This action function is based on a 32-year-old standard observer, and the action intensity for light with a wavelength of 485 nm has a peak (relative intensity 1), and the action intensity for light of about 440 nm and 540 nm is half the peak (relative intensity 1). 0.5).
In this way, people (particularly migraine patients) who receive stimulation of the ipRGC in the retina with light in the wavelength range centered on 485 nm may feel a headache or its worsening, but the possibility of this is reduced. That is, no glasses have been proposed for preventing or alleviating headaches.
Therefore, the main object of the present invention is to provide plastic eyeglass lenses and eyeglasses that can suppress light stimulation of ipRGC and prevent and alleviate headaches.

In order to achieve the above object, the invention according to claim 1 is a plastic eyeglass lens having a base material made of plastic, wherein the thickness of the base material is 4 mm or less, and the base material has a wavelength of 505 nm. A monoazo nickel complex dye and a merocyanine dye, which have a maximum value of absorption distribution, are added in a total amount of 0.05 wt% or more and 0.8 wt% or less based on the weight of the polymerizable compound of the base material. In addition, an ultraviolet absorber with an absorption peak wavelength of less than 380 nm and at least one of a blue dye and a violet dye for mitigating yellow color are added to both sides of the base material to prevent reflection of visible light. An optical multilayer film is formed for this purpose, and is characterized by a transmittance of 70% or more in a wavelength range of 410 nm or more and 430 nm or less.
According to a second aspect of the invention , in the above invention, the base material contains a thiourethane resin.
According to a third aspect of the present invention , in the above-mentioned invention, the base material contains an episulfide resin.
According to a fourth aspect of the present invention , in the above-mentioned invention, the base material contains a thermoplastic resin.
The invention according to claim 5 is a pair of eyeglasses, characterized in that the plastic eyeglass lens of the above invention is used.

The main effect of the present invention is to provide plastic eyeglass lenses and eyeglasses that can suppress light stimulation of ipRGC and prevent and alleviate headaches.

3 is a graph showing the spectral transmittance distribution of Examples 1 to 3 in the visible range. 2 is a graph showing (a) the average number of headache days and (b) the average number of medication days related to the evaluation of Example 1 of the present invention. 3 is a graph showing the degree of headache according to the evaluation of Example 1. 1 is a graph showing a melanopic action spectrum.

Examples of embodiments according to the present invention will be described below. The present invention is not limited to the following forms.

The plastic eyeglass lens according to the present invention includes at least a plastic base material.
A thermosetting resin is preferably used as the resin formed by polymerizing a monomer (polymerizable compound), which is the main material (material exceeding the majority in weight ratio) at the time of completion of polymerization (composition) of the base material, For example, polyurethane resins, thiourethane resins, urethane-urea resins, episulfide resins, polycarbonate resins, polyester resins, acrylic resins, polyethersulfone resins, poly4-methylpentene-1 resins, diethylene glycol bisallyl carbonate resins, or combinations thereof. is used. Further, a thermoplastic resin may be used as the main material of the base material.
Furthermore, if at least one of a thiourethane resin and an episulfide resin is used as the material for the base material, the refractive index of the base material will be relatively high, and it will be easy to reduce the thickness during vision correction.
On the other hand, if a thermoplastic resin is used as the material for the base material, a durable base material can be easily formed.

The monoazo nickel complex dye is added to the base material in a weight ratio of 0.05 wt% or more and 0.6 wt% or less with respect to the main materials (total weight of polymerizable compounds). A monoazo nickel complex dye is a coordination compound formed by a coordination bond between a monoazo dye, which is a yellow dye, and a nickel ion. Here, among the monoazo-based nickel complex dyes, those whose absorption distribution has a maximum value in a wavelength range of 480 nm or more and 520 nm or less are used.
Alternatively, the merocyanine dye is added to the base material in a weight ratio of 0.05 wt% or more and 0.8 wt% or less based on the main materials (total weight of polymerizable compounds). Merocyanine dyes are synthetic dyes belonging to polymethine, such as merocyanine I, merocyanine 540, or a mixture thereof. Here, among merocyanine dyes, those whose absorbance distribution has a maximum value in a wavelength range of 480 nm or more and 520 nm or less are used.
Alternatively, the base material contains a monoazo nickel complex dye and a merocyanine dye, and the ratio of their combined weight to the weight of the main materials (total weight of polymerizable compounds) is 0.05 wt% or more and 0.8 wt% or less. They are added together in such a way that Preferably, the weight ratios of the monoazo nickel complex dye and the merocyanine dye do not deviate from the above-mentioned ranges.
By adding at least one of the monoazo nickel complex dye and the merocyanine dye, light in the wavelength range of 480 nm or more and 520 nm or less is absorbed, and light stimulation to ipRGC can be simply suppressed, thereby preventing and alleviating headaches. This can be achieved easily.
That is, a plastic eyeglass lens containing such a base material becomes a light-shielding lens that blocks light in a wavelength range of 480 nm or more and 520 nm or less. Light blocking includes those that reduce transmittance.

If the weight ratio is below the lower limit of each weight ratio mentioned above, the absorption of light in the wavelength range of 480 nm or more and 520 nm or less will be reduced, and the yellowish color will be suppressed, which is advantageous in terms of visibility and aesthetic appearance. The suppression of light stimulation to ipRGC due to the absorption of light in the wavelength range becomes relatively insufficient, and the effect of preventing and alleviating headache becomes relatively insufficient.
When the above-mentioned upper limits of each weight ratio are exceeded, the light stimulation to ipRGC due to the absorption of light in the wavelength range of 480 nm or more and 520 nm or less is sufficiently suppressed, and the effect of preventing and alleviating headaches is sufficiently exhibited; The yellow tint becomes too strong, and the visibility and aesthetic appearance are relatively poor (the color when viewed through glasses with a strong yellow tint is strongly perceived as unnatural, and the appearance of the glasses is avoided).

Further, from the viewpoint of protecting the eyes while ensuring visibility and further preventing lens deterioration, preferably an ultraviolet absorber is added to the base material, and more preferably an ultraviolet absorber having an absorption peak wavelength of less than 380 nm. is added. The amount of such ultraviolet absorber added is adjusted from the above-mentioned viewpoint.
The thickness of the base material is not particularly limited, but it is preferably 4 mm (millimeters) or less, since the internal transmittance increases proportionally as the thickness increases, and the appearance and weight of the eyeglass lens are relatively poor. It is said that

A plastic eyeglass lens may be composed only of a base material, but a hard coat film may be formed on at least one side of the base material.
The hard coat film is preferably formed by uniformly applying a hard coat liquid onto the surface of the base material.
Further, as the hard coat film, preferably an organosiloxane resin containing inorganic oxide fine particles can be used. The organosiloxane resin is preferably one obtained by hydrolyzing and condensing an alkoxysilane. Further, specific examples of the organosiloxane resin include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, methyltrimethoxysilane, ethylsilicate, or a combination thereof. These hydrolyzed condensates of alkoxysilanes are produced by hydrolyzing the alkoxysilane compounds or a combination thereof with an acidic aqueous solution such as hydrochloric acid.
On the other hand, specific examples of materials for inorganic oxide fine particles include zinc oxide, silicon dioxide (silica fine particles), aluminum oxide, titanium oxide (titania fine particles), zirconium oxide (zirconia fine particles), tin oxide, beryllium oxide, antimony oxide, Examples include tungsten and cerium oxide sols used alone or in a mixed crystal of two or more of them. From the viewpoint of ensuring transparency of the hard coat film, the diameter of the inorganic oxide fine particles is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less. In addition, the blending amount (concentration) of the inorganic oxide fine particles is 40% by weight or more (weight percent) of the total components of the hard coat film, from the viewpoint of ensuring an appropriate degree of hardness and toughness in the hard coat film. It is preferable that it accounts for less than % by weight. In addition, at least one of acetylacetone metal salt and ethylenediaminetetraacetic acid metal salt can be added to the hard coating liquid as a curing catalyst, and furthermore, it can ensure adhesion to the base material, facilitate formation, and provide desired (half-metal) properties. ) A surfactant, a coloring agent, a solvent, etc. can be added as necessary to impart a transparent color.
The inorganic oxide (metal oxide) in the inorganic oxide fine particles is selected to have as little absorption in the visible range as possible to ensure high transmittance over the entire visible range, and to ensure that colors visible to the naked eye are visible when wearing lenses. From the viewpoint of ensuring a state with very little difference in color, it is preferable to use an oxide of one or more metals other than Ti and Ce. Since Ti (titanium) oxides and Ce (cerium) oxides absorb in the visible region (particularly on the short wavelength side), they are excluded from preferred metal oxides. Examples of such preferable metal oxides include Sb (antimony), Zr (zinc), Sn (tin), Si (silicon), Al (aluminum), Ta (tantalum), La (lanthanum), and Fe (iron). , Zn (zinc), W (tungsten), Zr (zirconium), In (indium), or a combination thereof.
The physical thickness of the hard coat film is preferably 0.5 μm (micrometer) or more and 4.0 μm or less. The lower limit of this film thickness range is determined because it is difficult to obtain sufficient hardness if the film is thinner than this range. On the other hand, regarding the upper limit, if it is thicker than this, the possibility of problems with physical properties such as the occurrence of cracks and brittleness increases dramatically, and the influence of absorption (reduction in transmittance) in the visible range by inorganic oxide fine particles increases. It is determined by increasing.
Furthermore, a primer film may be added between the hard coat film and the substrate surface from the viewpoint of improving the adhesion of the hard coat film. Examples of the material of the primer film include polyurethane resin, acrylic resin, methacrylic resin, organosilicon resin, or a combination thereof. The primer film is preferably formed by uniformly applying a primer liquid to the surface of the base material. The primer liquid is a liquid in which the above resin material and inorganic oxide fine particles are mixed in water or an alcohol-based solvent.

An optical multilayer film may be added to the plastic eyeglass lens. The optical multilayer film may be formed on a base material, but is preferably formed on a hard coat film. The optical multilayer film is formed on at least one side of the base material, and when formed on both sides, preferably both films have the same laminated structure.
From the viewpoint of ensuring antireflection function (antireflection film), the optical multilayer film is preferably formed to have a flat and high transmittance distribution over the entire visible range.
From the viewpoint of ensuring antireflection function, the optical multilayer film is preferably formed by alternately laminating low refractive index layers and high refractive index layers, and preferably has an odd number of layers as a whole (5 layers in total, 7 layers in total). etc.). More preferably, when the layer closest to the substrate (the layer closest to the substrate) is the first layer, the odd-numbered layers are low refractive index layers and the even-numbered layers are high refractive index layers.
The low refractive index layer and the high refractive index layer are formed by a vacuum deposition method, an ion-assisted deposition method, an ion plating method, a sputtering method, or the like.

In the plastic eyeglass lens of the present invention, an intermediate film other than a hard coat film or another type of antifouling film (water repellent film/oil repellent film) etc. is provided between the optical multilayer film and the base material and at least on the surface of the optical multilayer film. When forming an optical multilayer film on both sides, the types of different films added may be changed, or the presence or absence of the film may be changed.

Furthermore, at least one of a blue pigment and a purple pigment may be added to the plastic eyeglass lens in order to alleviate or cancel out the yellow color mainly caused by the addition of at least one of a monoazo nickel complex pigment and a merocyanine pigment. .

Furthermore, by using the plastic eyeglass lenses described above, eyeglasses can be produced that can simply suppress light stimulation of ipRGC and can easily prevent and alleviate headaches.
These glasses are light-shielding glasses that use light-shielding lenses.

Next, Examples 1 to 3 of the present invention will be explained using appropriate drawings. Note that the present invention is not limited to the following examples. Furthermore, depending on how the present invention is perceived, the examples may become comparative examples that do not belong to the present invention.

Examples 1 to 3 are all plastic eyeglass lenses, and their base materials are all made of thermosetting resin for eyeglasses, and have a circular shape with a standard size for plastic eyeglass lenses.
In Examples 1 to 3, different base materials (first to third base materials) were formed.

The first base material was formed as follows.
That is, first, the following solution A was prepared in advance. That is, as liquid A, 0.05 g (gram) of a dye containing 99% or more of a monoazo nickel complex (YAZ-28 manufactured by Yamada Chemical Co., Ltd.) was mixed with 2,5 bis(isocyanatomethyl)-bicyclo[2, A mixture of 2,1]heptane and 2,6bis(isocyanatomethyl)-bicyclo[2,2,1]heptane dissolved in 50 g at room temperature was prepared. The monoazo nickel complex-containing dye has a maximum value of its absorption distribution at a wavelength of 505 nm.
In addition, Solution B for alleviating the yellow color was prepared in the same manner as Solution A. That is, as liquid B, 0.05 g (gram) of a blue pigment (TAP-18 manufactured by Yamada Chemical Industry Co., Ltd.) was mixed with 2,5 bis(isocyanatomethyl)-bicyclo[2,2,1]heptane and 2, A mixture of 6bis(isocyanatomethyl)-bicyclo[2,2,1]heptane dissolved in 50 g at room temperature was prepared.
Next, 2.0 g of liquid A, 0.2 g of liquid B, 0.1 g of Stefan Zerec UN, and 0.04 g of dibutyltin dichloride were added to 2,5 bis(isocyanatomethyl)-bicyclo[2,2,1]heptane. and 50.8 g of a mixture of 2,6 bis(isocyanatomethyl)-bicyclo[2,2,1]heptane and stirred at 25° C. for 1 hour to completely dissolve.
Subsequently, 22.4 g of pentaerythritol tetrakis (3-mercaptopropionate) and 26.8 g of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane were added to this mixed solution, The mixture was prepared by stirring at 25°C for 30 minutes.
This preparation was defoamed for 1 hour at 0.3 mmHg or less, filtered through a 5 μm (micrometer) PTFE (polytetrafluoroethylene) filter, and poured into a mold. The mold includes a flat glass mold whose inner space has a center thickness of 2.0 mm and a diameter of 80 mm, and a tape.
The temperature of the mold into which the liquid preparation was poured was gradually raised from 25°C to 130°C, kept at 130°C for 2 hours, and then cooled to room temperature. The time from the start of temperature rise to the completion of cooling of the mold was 18 hours. By heating and cooling the mold as described above, the monomer was polymerized within the mold, and a molded article that became a plastic eyeglass lens was formed. After the polymerization was completed, the molded body was released from the mold and placed in a 130° C. environment for 2 hours for annealing.
The dye containing 99% or more of the monoazo nickel complex in the first base material (Example 1) accounts for 0.18 wt% with respect to the total weight of the polymerizable compounds of the base material (base material raw material).

Further, on both sides of the first base material, an optical multilayer film (antireflection film) for preventing reflection, which has the same structure and has a common structure, was formed by vacuum deposition, and was referred to as Example 1. . Here, the antireflection film has a total five-layer structure in which the layer closest to the base material is the first layer, the odd-numbered layers are low refractive index layers (SiO ₂ ), and the even-numbered layers are high refractive index layers (ZrO ₂ ). It was said that
Note that at least one of the addition of the blue pigment and the provision of the antireflection film may be omitted. Further, the antireflection film may have a structure other than the above-mentioned total five-layer structure, the front surface and the back surface may have different structures, or one of the front surface and the back surface may be omitted. Also good. Furthermore, an intermediate film may be disposed between the anti-reflection film and the base material, an antifouling film or the like may be applied to the surface of the anti-reflection film, or another film may be used instead of the anti-reflection film. May be granted.

On the other hand, the second base material was formed as follows.
That is, first, the following solution C was prepared in advance. That is, as liquid C, 0.05 g (gram) of merocyanine dye (DAA-95, manufactured by Yamada Chemical Co., Ltd.) containing 99% or more of merocyanine was mixed with 2,5 bis(isocyanatomethyl)-bicyclo[2,2, 1] Heptane and 2,6 bis(isocyanatomethyl)-bicyclo[2,2,1]heptane dissolved in 50 g of a mixture at room temperature was prepared. Merocyanine dye has a maximum value in its absorption distribution at a wavelength of 505 nm.
Next, 4.0 g of liquid C, 2.0 g of ultraviolet absorber (T-53 manufactured by Daiwa Kasei Co., Ltd.), 0.1 g of Zerec UN manufactured by Stefan, and 0.04 g of dibutyltin dichloride were added to 2,5 bis(isocyanatomethyl). - Bicyclo[2,2,1]heptane and 2,6bis(isocyanatomethyl)-bicyclo[2,2,1]heptane were placed in a container together with 50.8g of the mixture and stirred for 1 hour at 25°C until complete. dissolved in.
Then, in the same manner as the first base material, this liquid mixture was prepared, cast, heated, cooled, and annealed to form a second base material. No antireflection film or the like was applied to the second base material, and the second base material was used as Example 2 as it was.
The merocyanine dye in the second base material (Example 2) occupies 0.45 wt% with respect to the total weight of the polymerizable compounds of the base material (base material raw material).
In addition, in Example 2, the addition of the ultraviolet absorber may be omitted, and in Example 1, the addition of the ultraviolet absorber may be made. Further, in Example 2, other films such as an antireflection film may be applied.

On the other hand, the third base material was formed as follows.
That is, 2.0 g of liquid A, 2.0 g of liquid C, 2.0 g of ultraviolet absorber (T-53 manufactured by Daiwa Kasei Co., Ltd.), 0.1 g of Zerec UN manufactured by Stefan, and 0.04 g of dibutyltin dichloride were mixed into 2.5 g of liquid C. was placed in a container with 50.8 g of a mixture of bis(isocyanatomethyl)-bicyclo[2,2,1]heptane and 2,6bis(isocyanatomethyl)-bicyclo[2,2,1]heptane at 25°C. It was stirred for 1 hour to ensure complete dissolution.
Then, in the same manner as the first base material, this liquid mixture was prepared, further cast, heated, cooled, and annealed to form a third base material. No antireflection film or the like was applied to the third base material, and the third base material was used as Example 3 as it was.
Note that the third embodiment also includes modifications similar to the first and second embodiments.

FIG. 1 shows the spectral transmittance distributions of Examples 1 to 3 in the visible range (wavelengths from 380 nm to 780 nm). Note that the visible range may be set in various ways, such as a lower limit of 400 nm or an upper limit of 750 nm.
In Examples 1 to 3, the minimum value of the transmittance distribution, ie, the maximum value of the absorption distribution, exists at a wavelength of 505 nm, which is within the wavelength range of 480 nm or more and 520 nm or less. The minimum value of the transmittance distribution is about 38% in Example 1, about 25% in Example 2, and about 17% in Example 3. Note that absorption rate (%) = 100 - transmittance (%) - reflectance (%), but the reflectance in the visible range is at most 3%, and in Example 1, anti-reflection was performed. Therefore, it is within 1% and can be ignored, that is, absorption rate (%)≈100−transmittance (%).
In addition, in Examples 1 to 3, a transmittance of 70% or more was ensured in the short wavelength range of 410 nm or more and 430 nm or less, and a transmittance of about 90% was ensured in the long wavelength range of 510 nm or more and 780 nm or less, Visibility is ensured while cutting (suppressing) transmitted light in the wavelength range of 480 nm or more and 520 nm or less.
The wavelengths to which the half values between the maximum value and the minimum value (505 nm) on the short wavelength side of Examples 1, 2, and 3 belong are approximately 462, 471, and 460 nm in order, and the long wavelengths of Examples 1, 2, and 3 The wavelengths to which the half values between the local minimum value and the adjacent maximum value belong are approximately 518, 521, and 521 nm in this order.

According to the transmittance distribution of Examples 1 to 3, the transmittance can be suppressed to correspond to the relative value of the action intensity in the melanopic action spectrum shown in FIG.
Therefore, when glasses using the spectacle lenses of Examples 1 to 3 are worn, the wearer is protected from light stimulation to ipRGC, and headaches can be easily prevented and alleviated.

2 and 3 show the results of evaluation of eyeglasses using the eyeglass lens of Example 1.
In this evaluation, 10 migraine patients were asked to wear the glasses according to Example 1 for 4 weeks while driving a car at night, and the average number of headache days (Figure 2 (a) We investigated the average number of days on medication (Figure 2 (b), ``While wearing''), the number of days on which medication was taken to alleviate headaches (Figure 2 (b) ``While wearing''), and the degree of headache (Figure 3 ``While wearing'' 3 types) It was done by. Each time a headache occurs, subjects are asked to rate the severity of their headache in three stages: severe, moderate, and mild. 3 points are given if the headache is severe, and 3 points are given if the headache is moderate. It was evaluated by adding 2 points for severe symptoms and 1 point for mild symptoms.
Furthermore, a similar survey was conducted for 4 weeks on the same 10 migraine patients without wearing the glasses according to Example 1 ("before wearing" in FIGS. 2 and 3). In FIG. 3, the degree of headache is shown by averaging the total points for 1/3 day for each of the 10 patients.
The average night driving time was 38 minutes before and 34 minutes after installation.

As shown in Figure 2(a), the number of headache days significantly decreased from 8.7 days before wearing the glasses according to Example 1 to 7.0 days while wearing them (p value < 0.05 ).
Moreover, as shown in FIG. 2(a), the number of days taken for taking the medication decreased from 5.4 days before wearing the glasses according to Example 1 to 4.5 days while wearing them.
Furthermore, as shown in Figure 3, the degree of headache decreased from 4.3 in the morning before wearing to 4.1 while wearing it, to 95.3% of the level before wearing, and in the afternoon it decreased to 4.3% of the level before wearing. It dropped from 9 to 4.3 while wearing it, to 87.8% of before wearing it, and at night, it significantly decreased from 5.3 before wearing it to 3.2 while wearing it, to 60.4% of before wearing it.
According to such evaluation, it can be said that Example 1 was able to suppress headaches.
In addition, in Examples 2 and 3, which have the same transmittance distribution as Example 1 and have slightly lower transmittance over the entire visible range than Example 1, although the visibility when worn is slightly inferior to Example 1, A headache suppressing effect equivalent to or higher than that of Example 1 is fully exhibited.

Claims (5)

A plastic eyeglass lens having a plastic base material,
The thickness of the base material is 4 mm or less,
The monoazo nickel complex dye and the merocyanine dye, which have a maximum absorption distribution at a wavelength of 505 nm, are added to the base material in a total amount of 0.05 wt% or more based on the weight of the polymerizable compound of the base material. 8 wt% or less, and an ultraviolet absorber with an absorption peak wavelength of less than 380 nm, and at least one of a blue pigment and a violet pigment for mitigating yellow color, are added.
An optical multilayer film for preventing reflection of visible light is formed on both sides of the base material,
A plastic eyeglass lens characterized by having a transmittance of 70% or more in a wavelength range of 410 nm or more and 430 nm or less. The plastic eyeglass lens according to claim 1 , wherein the base material includes a thiourethane resin. The plastic eyeglass lens according to claim 1 or 2, wherein the base material contains an episulfide resin. The plastic eyeglass lens according to claim 1 , wherein the base material includes a thermoplastic resin. Eyeglasses characterized in that the plastic eyeglass lens according to any one of claims 1 to 4 is used.

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