WO2012165050A1

WO2012165050A1 - Anti-glare optical element

Info

Publication number: WO2012165050A1
Application number: PCT/JP2012/059623
Authority: WO
Inventors: 正和本多; 小田　博文; 佳苗宮澤; 加藤　裕久; 武洋清水
Original assignee: 伊藤光学工業株式会社
Priority date: 2011-06-02
Filing date: 2012-04-09
Publication date: 2012-12-06
Also published as: JP5985167B2; JP2013011840A

Abstract

Provided is an anti-glare optical element that has superior anti-glare performance, is superior from the viewpoint of protecting the eyes, and assures visibility when used in lenses for eyeglasses, etc. This optical element is formed from a transparent base material and is a single layer or multiple layers having a polarizing element. The transparent base material contains a pigment that absorbs specific wavelengths along with an ultraviolet ray absorbing agent. In a transmittance curve measured using a spectrophotometer ("transmittance curve" in the following), the transmittance curve provides a first valley minimum and a second valley minimum in the wavelength regions of 450 - 500 nm and 550 - 630 nm, respectively. Furthermore, the overall average transmittance in the wavelength region of 400 - 700 nm is 35% or greater. The transmittance for each of the first and second valley minimums is 60% or less, and the difference from the transmittance for each of the adjacent maximums is 20% or greater. Furthermore, the average difference in transmittance at each minimum wavelength ± 20 nm from the transmittance at each of the first and second valley minimums is in a range of 10 - 50%.

Description

Anti-glare optical element

The present invention relates to an antiglare optical element. In particular, it relates to an invention suitable as a plastic lens for spectacles.

Here, a plastic lens will be described as an example, but the present invention is not limited to this.

That is, the antiglare optical element according to the present invention is not limited to a plastic lens, but an inorganic glass lens, a sun visor, ski goggles, window glass for automobiles and houses, airplane and motorcycle windshield glass, display filter cover, lighting equipment It can be applied to a cover for an automobile.

When used as spectacles, for outdoor use such as golf, cycling, fishing, hitchhiking, walking, driving, shopping, laundry washing, etc., for visual glare and blocking harmful rays, when viewing PCs and mobile screens, and before going to bed It is suitable for indoor use.

The meaning of each term in the present specification and claims is as follows.

“Transmittance curve”: Waveform curve of transmittance corresponding to the wavelength measured with a spectrophotometer,
“Valley”: A relatively large valley that is an element of the overall waveform of the transmission curve; from the short wavelength side to the first, second, and third valleys,
“Adjacent maximum wavelength”: the wavelength corresponding to the first maximum on the left side of the valley,
“Adjacent maximum transmittance”: Transmittance at the adjacent maximum wavelength.

The human eye perceives brightest light around 555 nm (center wavelength of the standard relative luminous sensitivity curve) (510-600 nm) in light-adapted vision (photopic vision), and dark-adapted vision (dark vision) ), The light around 507 nm (472 to 542 nm) is felt brightest. Therefore, the light in the above-mentioned wavelength range feels dazzling to human eyes.

Therefore, in order to prevent glare, light having the above-described wavelength may be cut.

However, in order to prevent glare on summer beaches and winter ski resorts, generally wear glasses with colored lenses such as sunglasses. In such a colored lens, there is a problem that light in all wavelength regions is cut uniformly, resulting in insufficient light amount (dark field of view).

By the way, when a specific wavelength absorbing dye is used, only a particularly strong wavelength range (570 to 600 nm) can be selectively absorbed in a wavelength range that is dazzling to human eyes.

Therefore, a prescription for imparting a so-called anti-glare property to the spectacle lens is applied using this characteristic. The main prescription is to selectively shield as much as possible the wavelength range that tends to give glare, and it is effective to contain a rare earth element compound such as a neodymium compound that can actually absorb visible light in the vicinity of 585 nm in a highly wavelength selective manner. Anti-glare performance can be obtained (cited from Patent Document 1, paragraph 0002).

However, these rare earth metal compounds are very expensive and cannot be mixed and coated into a coating film without losing the transparency of the transparent resin.

That is, the method of blending a specific organic rare earth metal complex with the resin material has various disadvantageous problems.

Firstly, depending on the lens material, the selection of the organic portion of the organic rare earth metal complex is greatly limited, so it is often limited to expensive compounds. For example, in a thiourethane lens system, a normal organic rare earth metal complex has problems such as solubility and dispersibility in a resin, undesirable reactivity with a lens resin, and storage stability in the environment.

Secondly, in order to achieve the low light transmittance (high light shielding property) required in the wavelength region near 585 nm, the amount of the organic rare earth metal complex is usually required to be about 5% by weight. In addition to the inconvenience of using a large amount of expensive organic rare earth metal complex, it is often forced to balance with deterioration of mechanical properties of the lens. (Cited from Patent Document 1, paragraph 0005).

In order to solve the above problems, Patent Documents 1 and 2 propose a plastic spectacle lens containing an organic specific wavelength absorbing dye and having an antiglare property equivalent to that of a neodymium compound-containing plastic.

That is, Patent Document 1 has a main absorption valley (minimum peak) in the wavelength region of 565 to 605 nm (preferably 580 to 590 nm) in the visible light absorption spectrum (spectral transmittance curve). 2) A desirable specific wavelength absorbing dye is a tetraazaporphine compound represented by the following formula (1) (Claim 4 etc.).

[In the formula (1), A1 to A8 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a straight chain or branched chain having 1 to 20 carbon atoms. Or a cyclic alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, or 7 to 7 carbon atoms Represents a dialkylamino group having 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and a linking group A ring other than an aromatic ring may be formed through M, and M represents two hydrogen atoms, a divalent metal atom, a divalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom. Represents. ]
In Patent Document 2, as a synthetic resin base material, the transmittance curve has a minimum (valley) in the wavelength range of 550 to 585 nm, and the average transmittance in the wavelength range of 470 to 550 nm is 10% or more. The specific wavelength-absorbing dye is a squarylium compound represented by the following formula (2) (claim 1 and the like).

JP 2008-134618 A Japanese Patent Laid-Open No. 2003-107412

However, in recent years, from the viewpoint of eye health, in addition to improving anti-glare performance, cuts in the blue and blue wavelengths (400 to 500 nm) have been required.

In fact, the intensity in the blue wavelength range of 400 to 500 nm in clear weather is much higher than in other wavelength ranges (see Fig. 1). FIG. 1 shows the relative intensity (%) measured by the applicant's employee under the following conditions and based on a standard where the maximum value on a sunny day is 1 with respect to the wavelength.

Measurement date: September 22, 2010 (sunny), September 24, 2010 (cloudy)
Measuring place: Toyohashi, Aichi Measuring instrument: Spectroradiometer FieldSpec3 (ASD, USA)
Measurement method: Measure from the north window toward the sky
The following problems have been reported in the media regarding the effect of blue light of 400 to 500 nm on the eyes (so-called blue hazard).

1. I feel glare. Blue light retina injury ⇒ Eye damage Awakening effect ⇒ Wake up in the morning. Inhibition of sleeping substances ⇒ Can't sleep at night The body clock is delayed ⇒The clock is out of sync because it cannot sleep. The image appears blurred ⇒ Because of chromatic aberration, blue light is emitted from sunlight, personal computers (PCs), mobile phones, TVs, LED lighting, etc. There is an adverse effect.

List of Sources: Journal of the Illuminating Sciences of Japan, April 2010 "LED Lighting Issues (Biological Safety)"
Weekly Bunharu July 1, 2010 issue "Blue light erodes mind and body" Japanese and US experts urgently warrant "Kiichi Kawasaki Improvement of anti-glare can be achieved by combining a thin polarizing plate and a transparent substrate it can. (Patent Document 2, paragraph 0021, Examples 4 and 6: both polarizing spectacle lenses).

However, in Example 4 of Patent Document 2, as shown in FIG. 6 of the same document, a visible light region (400 to 550 nm) shorter than 550 nm (hereinafter referred to as “the visible light region”) (hereinafter referred to as “blue light absorber”) In the “short wavelength side visible light region”), the average transmittance is 50% or more, which is high. In Example 6, as shown in FIG. 8 of the same reference, the average transmittance is 20% or less, but the transmittance is sharp at the approximate median value (480 nm) of the blue wavelength (450 to 495 nm). Has a maximum.

However, when FIG. 8 according to the sixth embodiment is compared with FIG. 6 according to the fourth embodiment, the data itself is questionable. The only difference between the two is the presence or absence of an infrared absorber. Although it can be understood that the transmittance decreases at the upper limit of the visible light range (760 nm) due to the inclusion of the infrared absorber, such an extreme difference occurs in the short wavelength side of the visible light range (400 to 550 nm). Hard to think.

Incidentally, in other examples having no polarizing element in the same document, the transmittance in the vicinity of 500 nm exceeds an average value of 30% or more (the same applies to Example 4 having a polarizing element). Most of them have a sharp maximum (near 500 nm) in the short wavelength side visible light region (400 to 550 nm) (the same applies to Example 6 having a polarizing element).

Also, in the transmittance curve in Patent Document 1, the transmittance is 50% or more or 20% or more in the short wavelength side visible light region (400 to 550 nm).

Therefore, the eyeglass lenses for Patent Documents 1 and 2 do not intend to actively cut (block) the short wavelength side visible light region (400 to 550 nm) including blue light together with ultraviolet rays. Absent.

Further, in Patent Documents 1 and 2, the visible light region on the long wavelength side exceeding 550 nm (hereinafter, “long wavelength visible region”) corresponds to the valley long wavelength side (minimum) in the present invention. The minimum value is approximately 25% or less in transmittance, and the valley is sharp.

Thus, the antiglare performance is improved by lowering the transmittance in the wavelength region where glare is likely to be imparted. However, if the valley transmittance is too low or the valley is sharp, the illuminance difference between the emission color of the valley minimum wavelength and the emission color of the nearby wavelength increases, making it difficult to recognize the emission color of the valley minimum wavelength. Or when the emission color is an illumination color, the field of view may be darkened.

For example, the center wavelength of yellow light is 580 nm, whereas the center wavelength of yellow-red (orange) light is 600 nm (Katsuhiro Saito, “Bluebacks: Science of Light and Color” 2010, Kodansha, p96, Fig. 4-3. ). For this reason, if the transmittance of yellow light is lowered in order to enhance the antiglare effect, the transmittance of orange decreases accordingly, and the central wavelength (589 nm) of the sodium lamp illumination does not pass through the lens, and the field of view is reduced. There is a risk of darkening (see Patent Document 2, paragraph 0003).

In view of the above, it is an object of the present invention to provide an anti-glare optical element that is excellent in terms of eye protection when it is applied to a spectacle lens and the like, and is easy to secure visibility. And

Another object of the present invention is to provide an anti-glare optical element that can cut the short wavelength side visible light region (400 to 550 nm) and is desirable from the viewpoint of eye health.

As a result of diligent development efforts to solve the above-mentioned problems, the present inventors have conceived optical elements having the following configurations.

(1) A single layer or multiple layer optical element comprising a transparent substrate and having a polarizing element,
In the transparent substrate, a specific wavelength absorbing dye is contained together with an ultraviolet absorber,
In the transmission curve,
A first valley minimum and a second valley minimum are provided in each wavelength region of 450 to 500 nm and 550 to 630 nm of the transmittance curve,
The overall average transmittance in the wavelength region of 400 to 700 nm is 35% or more,
Each transmittance of the first and second valley minimums is 60% or less, and has a difference of 20% or more from each adjacent maximum transmittance,
Each transmittance of the first and second valley minimums and a transmittance difference average at each minimum wavelength ± 20 nm are in the range of 10 to 50%.

(2) A single-layer or multi-layer optical element comprising a transparent substrate and having a polarizing element,
In the transparent substrate, a specific wavelength absorbing dye is contained together with an ultraviolet absorber,
In the transmittance curve measured with a spectrophotometer,
A first valley minimum at 450 to 500 nm, a second and a third valley minimum each having a transmittance of 25% or more shallower than the first valley minimum in each wavelength region of 550 to 630 nm and 650 to 700 nm,
The overall average transmittance from 400 to 700 nm is 30% or more,
The transmittance of the first valley minimum is 30% or less, and the difference from the adjacent maximum transmittance is 25% or more,
Each transmittance of the second and third valley minimums is 55% or less, the difference from the adjacent maximum transmittance is 10% or more,
The transmittances of the second and third valley minimums and the average difference in transmittance at each minimum wavelength ± 20 nm are in the range of 10 to 40%.

(3) A single-layer or multi-layer optical element comprising a transparent substrate and having a polarizing element,
The transparent substrate contains an ultraviolet absorber together with a specific wavelength absorbing dye,
In the transmittance curve measured with a spectrophotometer,
A first valley minimum at 450 to 500 nm, a second and a third valley minimum each having a transmittance of 25% or more shallower than the first valley minimum in each wavelength region of 550 to 630 nm and 650 to 700 nm,
The overall average transmittance in the wavelength region of 400 to 700 nm is 30% or more,
The transmittance of the first valley minimum is 30% or less, and the difference from the adjacent maximum transmittance is 25% or more,
Each transmittance of the second and third valley minimums is 55% or less, the difference from the adjacent maximum transmittance is 5% or more,
Each transmittance of the first and third valley minimums and the average transmittance difference at each minimum wavelength ± 20 nm are in the range of 10 to 40%, and the transmittance of the second valley minimum and each minimum wavelength ± 20 nm The average transmittance difference is in the range of 3 to 10%.

It is a light-intensity spectrum figure of the day of fine weather and cloudy in the beginning of autumn. It is a schematic sectional drawing which shows an example of the polarizing lens which can apply this invention. It is sectional drawing for description of the casting molding method of the lens to which this invention is applied. 2 is a graph showing the transmittance of an antiglare lens prepared in Example 1. FIG. 6 is a graph of transmittance of an antiglare lens prepared in Example 2. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 3. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 4. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 5. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 6. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 7. FIG. 6 is a graph of the transmittance of the ultraviolet cut lens prepared in Comparative Example 1. FIG. 6 is a graph of the transmittance of the polarizing lens prepared in Comparative Example 2. FIG. 6 is a graph of the transmittance of the polarizing lens prepared in Comparative Example 3. FIG. It is a graph of the transmittance | permeability of the polarizing lens of Example 6 (reference example) which concerns on the prior application of this invention. 6 is a graph of the transmittance of an antiglare lens prepared in Example 8. FIG. 10 is a graph of the transmittance of an antiglare lens prepared in Example 9. FIG. 6 is a graph of transmittance of an antiglare lens prepared in Example 10. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 11. FIG. 6 is a graph of the transmittance of an antiglare lens prepared in Example 12. FIG. 14 is a graph of transmittance of the antiglare lens prepared in Example 13. FIG. It is a graph of the transmittance | permeability of the anti-glare lens prepared in Example 14.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Here, the case where the anti-glare lens as an optical element without a polarizing element is formed of a transparent synthetic resin material (organic glass: transparent plastic) which is a lens base material is taken as an example.

Naturally, the present invention can also be applied to a polarizing lens 11 having a multilayer structure having a transparent base layer 15 on one or both sides of a thin plate-like polarizing element 13 as shown in FIG. The anti-glare lens may use inorganic glass as a lens base material.

The anti-glare lens of this embodiment is molded by an injection molding method or a casting molding method as shown in FIG.

And as a transparent synthetic resin material as a transparent base material which is an antiglare lens forming material, for example, episulfide resin, thiourethane resin, urethane resin, thiourea resin, urea polymer composition, epoxy resin, It is appropriately selected from acrylic resin, nylon resin, polycarbonate resin, polyamide resin, sulfide resin, and the like.

When a high refractive index is required for the antiglare lens, a sulfur-containing resin such as the following thiourethane resin (polythiourethane) (a) or episulfide resin (b) is used as the polymerizable liquid material. In particular, polythiourethane makes it easy to obtain a high refractive index in the lens, and a thin lens can be manufactured.

(A) Polythiourethane is a polymer (resin) having a bond (—NHCOS—, —NHCSO—, —NHCSS—) in which at least one oxygen atom of a polyurethane bond (—NHCOO—) is replaced with a sulfur atom. In other words, a known material composed of one or two or more polyisocyanate components selected from polyisocyanate, polyisothiocyanate, polyisocyanatothioisocyanate and a polythiol component can be suitably used (Japanese Patent Laid-Open 8-208792 etc.).

Here, as isocyanate components, aliphatic, alicyclic, aromatic, and derivatives thereof, and sulfide, polysulfide, and thiocarbonyl (thioketone) derivatives in which sulfur is introduced into a part of their carbon chains are parent compounds. Can be mentioned. Among these, from the viewpoint of yellowing resistance, an aliphatic or alicyclic one is desirable.

In addition, as the polyol component, aliphatic, alicyclic, aromatic, and derivatives thereof, and sulfides, polysulfides, and polythioethers in which sulfur is introduced into a part of their carbon chains are used as base compounds. Things can be mentioned. Among these, from the viewpoint of yellowing resistance, an aliphatic type or an alicyclic type is also desirable.

Specifically, it is desirable that the polythioether represented by the following chemical formula (3) consists or is mainly composed of a base compound.

As the other polyol component, a fully substituted ester of a ω-mercapto aliphatic carboxylic acid of a branched hydrocarbon polyhydric alcohol can be suitably used.

Specifically, trimethylolpropane tris (2-mercaptoglycolate), pentaerythritol tetrakis (2-mercaptoglycolate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropioate) Nate) and the like.

(B) The episulfide resin means a polymer (resin) obtained by reacting a dithioepoxy compound, a curing agent, and another polymerizable compound, and is represented by the following chemical formula (4), for example. A known curing agent for curing the linear alkyl sulfide type dithioepoxy compound can be used (Japanese Patent Application Laid-Open Nos. 9-1107979, 10-114764, etc.).

As the curing agent, amines, organic acids, and inorganic acids, which are ordinary epoxy resin curing agents, can be used.

As the acrylic resin, a general-purpose commercially available polymer material for lenses can be used.

When producing the anti-glare lens (plastic lens) of the present invention by casting, various additives such as dyes, bluing agents, internal mold release agents, anti-molding agents are added to the polymerizable liquid material that is the material of the lens substrate. An odorant, an antioxidant, a stabilizer, a polymerization initiator and the like may be added as necessary. The resin curing (polymerization) is performed by thermosetting polymerization, ultraviolet curing polymerization, or the like.

Also, it is desirable that the surface of the plastic lens of the present invention is subjected to a modification process such as hardness by forming a hard coat which is generally performed.

The hard coat is formed with a general-purpose silicone paint. In general, it is desirable that the hard coat is provided with a primer layer.

The primer layer is preferably formed of a paint based on a urethane-based or ester-based thermoplastic elastomer, and is usually used by increasing the refractive index by adding metal oxide fine particles or the like.

The hard coat and primer layer are leveled with UV absorbers such as benzophenone, benzotriazole, and phenol, and silicone surfactants and fluorine surfactants to improve the smoothness of the coating film. Agents and other modifiers can also be added.

The coating method is selected from known methods such as dipping and spin coating.

Further, surface treatment such as anti-fogging treatment, antireflection treatment, water repellent treatment, antistatic treatment, dyeing, etc. may be applied.

As the inorganic material for forming the antireflection film, metal oxides such as silica, titania (IV), tantalum oxide (V), antimony (III) oxide, zirconia, and alumina, and metal fluorides such as magnesium fluoride are preferably used. Can be used.

In the antiglare optical element (antiglare lens) having the above-described configuration, it is a prerequisite that the transparent substrate contains a specific wavelength absorbing dye together with an ultraviolet absorber.

One aspect of the present invention is characterized in that, in the above preconditions, the following characteristics are provided.

1) A first valley minimum and a second valley minimum are provided in each wavelength region of 450 to 500 nm (preferably 460 to 490 nm) and 550 to 630 nm (preferably 560 to 620), respectively.

2) The overall average transmittance in the wavelength region of 400 to 700 nm is 35% or more (preferably 40% or more).

3) Each transmittance of the first and second valley minimums is 60% or less (desirably 40% or less) and has a difference of 20% or more (desirably 25% or more) from each adjacent maximum transmittance. The transmittance difference between the first and second valley minimums is usually 20% or less (preferably 15% or less). If the transmittance difference is large, the white balance of the transmitted light color is shifted, and the transmitted light color and the lens itself may be colored.

4) Each transmittance of the first and second valley minimums and the average difference in transmittance at each minimum wavelength ± 20 nm is in the range of 10 to 50% (preferably 20 to 45%).

By synergizing these characteristics, it is easy to ensure various visibility (visibility such as green, visibility in cloudy weather, visibility in the distance) as well as improving the antiglare property of the present invention.

That is, by the above 1) and 3), it is possible to cut near the blue wavelength range (550 nm) that is a hazard color and the standard relative luminous sensitivity central wavelength (555 nm) that feels glare, and in 4) above, It is presumed that it is easy to ensure the visibility as well as the antiglare property by providing the shape with an appropriate curvature and area (with an appropriate absorption band width). Furthermore, it is estimated that by setting the overall average transmittance of 2) to be equal to or higher than a predetermined value, it is easy to ensure the visibility at the time of cloudy weather and the distance. This is supported by Examples 5, 6 and 7 having a low average transmittance of 50% or less because the visibility in cloudy weather is not so good.

Furthermore, the intermediate waveform between the first and second valleys is a plateau shape with a gentle top surface (20 ° or less, preferably 10 ° or less) or a continuous peak with a transmittance difference of 15% or less (preferably 10% or less). It is desirable to have multiple micro maxima (see Tables 2-3-1 and 2-3-2).

By adopting such a configuration, it is estimated that the transmittance tends to decrease toward the wavelength range of 555 nm, which is the maximum wavelength of the specific visibility curve, and contributes to further improvement of the antiglare property.

As these specific wavelength absorbing dyes, for example, one or more tetraazaporphyrin compounds, squarylium compounds, azomethyl-based, and indole-based ones can be selected and used.

More specifically, examples of the tetraazaporphyrin compound include those represented by the above structural formula (1) described in Patent Document 1 and the following structural formula (5) described in Japanese Patent Application Laid-Open No. 2003-21847. Can be suitably used.

[Wherein, rings A, B, C, D, A ′, B ′, C ′, D ′ each independently represent a fused aromatic ring formed at two β-positions of the pyrrole ring, You may have. M represents a trivalent metal atom and one hydrogen atom or a tetravalent metal atom. Each substituent of each ring of ring A, B, C, D is connected to each substituent of each ring of ring A, B, C, D and / or rings A ′, B ′, C ′, D via a linking group. It may be bonded to each substituent of each ring of '. ]
Moreover, as a squarylium compound, what is shown by above-mentioned structural formula (2) of patent document 2 can be used conveniently.

Further, as the ultraviolet absorber, a conventional one can be used. Examples thereof include benzophenone-based, phenyl acrylate-based, sterically hindered amine-based, salicylic acid ester-based, benzotriazole-based, hydroxybenzoate-based, cyanoacrylate-based, hydroxyphenyltriazine-based, and the like.

Of these, benzotriazole-based compounds represented by the following structural formula (6) and derivatives thereof are desirable.

It was confirmed that the ultraviolet absorber represented by the structural formula (6), when mixed in a large amount, exhibited not only an ultraviolet absorption effect but also a blue cut function (relative decrease in transmittance) as shown in the examples described later. (Example 1 and Example 3).

And the compounding prescription of the specific wavelength absorbing dye and the ultraviolet absorber is as follows.

1) Specific wavelength absorbing dye: 0.5 × 10 ⁻⁴ to 5.0 × 10 ⁻³ parts (preferably 0.8 × 10 ⁻⁴ to 3.5 × 10 ⁻³ parts) with respect to 100 parts of resin raw material ). When the blending amount of the specific wavelength absorbing dye is too small, it is difficult to secure antiglare properties and it is difficult to secure visibility such as green and distant visibility. On the other hand, if the amount is excessive, the overall transmittance becomes low, and it becomes difficult to ensure visibility.

2) UV absorber: 0.1 to 6 parts (preferably 1 to 4 parts) per 100 parts of resin raw material. When the blending amount of the UV absorber is too small, it is difficult to cut UV rays. On the other hand, if the amount is excessive, the overall transmittance becomes low, and it becomes difficult to ensure visibility.

In the above description, the polarizing element-less is taken as an example. However, when a polarizing element is used, it is desirable to use a polarizing element having a polarization degree of 80% or less (preferably 70% or less). It has been confirmed in an earlier application (Japanese Patent Application No. 2011-38468) by the applicant of the present application that a valley disappears when a polarizing element having a high degree of polarization is used.

FIG. 14 (FIG. 11 attached to the prior application) shows a transmittance curve using a polarizing element having a polarization degree of 99.6% in the same formulation (Example: Prior Application Example 5) as Example 2 of the present invention.

Another aspect of the present invention is substantially the same as the above invention, but the waveform characteristics of the transmittance curve are slightly different as follows.

1) First valley minimum at 450 to 500 nm, and second and third valley minimums each having a minimum transmittance of 25% or more shallower than the first valley minimum in each wavelength region of 550 to 630 nm and 650 to 700 nm. ing.

2) The overall average transmittance at 400 to 700 nm is 30% or more (preferably 35% or more).

3) The transmittance of the first valley minimum is 30% or less (preferably 10% or less), and the difference from the adjacent maximum transmittance is 25% or more.

4) Each transmittance of the second and third valley minimums is 55% or less (preferably 50% or less), and the difference from the adjacent maximum transmittance is 10% or more.

5) The transmittance of each of the first, second and third valley minimums and the average transmittance difference at each minimum wavelength ± 20 nm are in the range of 10 to 40% (preferably 15 to 30%).

The difference between the above invention and the above invention is that the second and third valleys shallower than the first valley appear in the transmittance curve.

The action and effect are the same as in the above invention, but since the transmittance is relatively low, the antiglare property is excellent in fine weather, but the visibility is poor in cloudy weather or rainy weather.

Still another one of the present invention is substantially the same as the above invention, but the waveform characteristics of the transmittance curve are slightly different as follows.

4) Each transmittance of the second and third valley minimums is 55% or less (preferably 50% or less), and the difference from the adjacent maximum transmittance is 5% or more.

5) Each transmittance of the first and third valley minimums and the average transmittance difference at each minimum wavelength ± 20 nm are in the range of 10 to 40% (preferably 15 to 30%). The transmittance and the average difference in transmittance at each minimum wavelength ± 20 nm are in the range of 3 to 10% (preferably 5 to 8%).

The operational effect is the same as that of the above invention, but the second valley minimum valley in the wavelength range of 550 to 630 nm with high visibility is shallower than the above, so that the eyes can easily feel the brightness, and compared with the above. Visibility is improved.

Hereinafter, examples carried out together with comparative examples in order to confirm the effects of the present invention will be described. In the following description, “parts” indicating the number of blending parts means “parts by mass”.

<Ultraviolet absorber>
Commercial products having the following compound names were used.

UV-01 2- (4-Ethoxy-2-hydroxyphenyl) -2H-benzotriazole UV-02 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl ) Phenol UV-03 2- (2-Hydroxy-5-t-butylphenyl) -2H-benzotriazole <Specific wavelength absorbing dye>
Commercial products of the following respective compounds having the following specific absorption peak wavelengths were used.

C-01 tetraazaporphyrin-based metal complex compound, absorption peak wavelength 480 nm
C-02 Tetraazaporphyrin-based metal complex compound, absorption peak wavelength 595 nm
C-03 Ferrocyanine metal complex compound, absorption peak wavelength 760 nm
C-04 Tetraazaporphyrin-based metal complex compound, absorption peak wavelength 590 nm
Tables 1-1 and 2 summarize the materials (materials) used in Examples and Comparative Examples and the amounts added.

<Examples 1 to 3, 5 to 6, 8 to 10, 12 to 13>
(1) Preparation of polymerizable liquid material 100 parts of m-xylylene diisocyanate, 0.1 part of dibutyltin dichloride as a curing agent, 0.5 part of an alkyl phosphate (alcohol C8 to C12) salt as an internal release agent, aromatic As an imparting agent, 0.2 parts of ethyl caproate, an ultraviolet absorber shown in Table 1 and a specific wavelength absorbing dye were added, respectively, and the mixture was sufficiently stirred for 1 hour at a liquid temperature of 15 ° C. in a nitrogen gas atmosphere.

Thereafter, 100 parts of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol was added, and the mixture was sufficiently stirred for 1 hour at a liquid temperature of 15 ° C. in a nitrogen gas atmosphere.

Then, after deaeration for 1 hour with stirring at a liquid temperature of 15 ° C. and 133 Pa using a vacuum pump, the mixture is filtered through a 1 μm filter, and a polythiourethane lens raw material liquid having a refractive index (nd) of 1.67 (polymerizable liquid material). ) Was prepared.

(2) Lens molding A cavity 25 is formed in the peripheral openings of the first and

second molds

17 and 19 made of glass to form a mold 27, and the cavity 25 of the mold 27 is inserted into the cavity 25 via a liquid material inlet 23a. Then, a polymerizable liquid material is injected and polymerized or crosslinked and cured by means such as thermosetting polymerization or ultraviolet curing (photo) polymerization.

First mold (made of glass, outer shape 80 mm, used surface curvature 66.16 mm, center thickness 4.0 mm) 17, second mold (made of glass, outer shape 80 mm, used surface curvature 65.59 mm, center thickness 4.0 mm) 19 A molding die 27 was prepared by being held by a plastic gasket 23 so that the center distance was 2.0 mm (see FIG. 3).

After injecting the polymerizable liquid material into the above mold, the lens was molded by heating and polymerizing under the following temperature conditions. After the polymerization, the mold release step for removing from the mold was physically (mechanically) performed with a wedge-shaped tool.

“35 ° C. × 5 hours → 35 ° C. to 60 ° C. over 5 hours → 60 ° C. to 100 ° C. over 2 hours → 100 ° C. to 120 ° C. over 1 hour → 120 ° C. × 3 Time → cool from 120 ° C. to 40 ° C. over 4 hours. ”
(3) Lens Color Adjustment For Example 5, the lens produced using the above polymerized liquid material was dissolved in warm water heated to 90 ° C. by DystarDianix Red E-FB (manufactured by Dystar Japan Co., Ltd.). The sample was dipped in a container for 30 seconds to adjust the appearance color and the transmittance.

<Examples 4, 7, 11, and 14>
(1) Preparation of dye-kneaded resin pellet for injection molding The specific wavelength-absorbing dye and addition amount shown in Table 1 were mixed in Iupilon CLS-3400 (Mitsubishi Engineering Plastics Co., Ltd .; polycarbonate masterbatch containing UV absorber). Thus, resin pellets for injection molding were produced.

(2) Injection molding of lens A mold for molding a lens having an outer shape of 75 mm and a center thickness of 2.1 mm is attached to an electric hybrid vertical injection molding machine TR100VR manufactured by Sodick Co., Ltd.
This is injection molded with the specific wavelength absorbing dye-mixed resin pellets.

<Comparative Example 1>
On the base material of the lens base material formed by using a polythiourethane lens resin having a refractive index (ne) of 1.60 as the base material, a silicone-based impact-resistant coat in order from the base material side, a silicone type A hard coat and an inorganic antireflection film were formed, and a fluorine-based water repellent film was formed as the outermost surface layer.

<Comparative Example 2>
A dye-based PVAL polarizing film “Brown-30” (polarization degree: 99.2%) is sandwiched between polythiourethane-based lens resins having a refractive index (ne) of 1.60 and formed on a lens base material. Then, a silicone-based impact-resistant coat, a silicone-based hard coat, and an inorganic antireflection film were formed in this order from the substrate side, and a fluorine-based water-repellent film was formed as the outermost surface layer.

<Comparative Example 3>
A dye-based PVAL polarizing film “Gray-30” (polarization degree 99.5%) is sandwiched between polythiourethane-based lens resins having a refractive index (ne) of 1.60 and formed on a lens base material. A silicone-based impact-resistant coating, a silicone-based hard coat, and an inorganic antireflection film were formed in this order from the substrate side, and a fluorine-based water-repellent film was formed as the outermost surface layer.

<Test methods and results>
With respect to the optical elements of the examples and comparative examples prepared above, the transmittance was measured according to the transmittance measuring method shown in JIS-T7333.

Measurement was performed using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.) under the conditions of a measurement wavelength of 380 to 780 nm, a scan speed of 600 nm / min, a sampling interval of 1 nm, and a slit of 5 nm.

The transmittance curves of the test results are shown in FIGS. 4 to 13 and FIGS. 15 to 21.

In any of the examples, there is one clear short wavelength side valley and one long wavelength side valley (Examples 1 to 4, 8 to 11) or a plurality (two) (Examples 5 to 7, 12 to 14) Appears. Note that the intermediate waveform (1) of Examples 8 to 11 has no maximum / minimum transmittance, and Examples 12 to 14 have substantial maximum / minimum transmission in the intermediate waveforms (1) to (2). Has no rate.

On the other hand, none of the comparative examples has such a valley.

Also, from the following tables showing the characteristics in the transmittance curves of each example and comparative example, it can be seen that each example satisfies the constituent requirements (invention specific matter) of the present invention.

The luminous transmittance is relatively higher in the former in Examples 1 to 4 and the corresponding Examples 8 to 11 in which the long wavelength side valley is one.

Also, in Examples 5 to 7 and corresponding Examples 12 to 14 in which the long wavelength side valley is two, the former and the latter have substantially the same luminous transmittance with the former being slightly lower.

In <Table 2-1A> and <Table 2-1B>, (1) Average transmittance (400 to 700 nm), (2) Minimum transmittance of the first and second valleys, and the difference between these transmittances, ( 3) Difference between adjacent maximum wavelength and transmittance and minimum transmittance of the first and second valleys, and (4) luminous transmittance.

<Table 2-2-1A>, <Table 2-2-2A> and <Table 2-2-3A>, and <Table 2-2-1B>, <Table 2-2-2B> and <Table 2 -2-3B> shows the transmittance difference average value (intermediate value) between the transmittance at each minimum wavelength ± 20 nm and the minimum transmittance in the first, second, and third valleys.

<Table 2-3-1> and <Table 2-3-2> show the maximum and minimum transmittances and transmittance differences of the intermediate waveforms (1) and (2) (Examples 5 to 7 only), respectively.

Furthermore, the following evaluations (a) to (d) were performed using the lenses of the respective examples and comparative examples (excluding Examples 8 to 14).

Specifically, performance evaluation was performed according to the following evaluation criteria, with 10 people playing golf on a daily basis as panelists (monitors).

Positive evaluation 8 or more: ◎, 5-7: ○, 2-4: △, 1 or less: ×
The evaluation results are shown in Table 3.

Then, ◎: 3 points, ○: 2 points, Δ: 1 point, x: 0 points, and as a comprehensive evaluation, 10 points or more: ◎, 8 points or more: ○, 6 points or more: Δ: 5 Below the point: x.

(a) Compared to the case without a lens, the visibility of turf (green) and undulation (undulations on the course such as fairways and greens) at golf courses will be improved. Evaluation (b) Evaluate whether or not the dazzle reduction effect can be obtained with respect to the brightness of the lens when playing golf in fine weather (c) The brightness of the lens when playing golf in cloudy weather is dark Evaluate whether visibility is good without becoming too much (d) Evaluate whether it is easy to see trees etc. when looking at a distant mountain compared to when no lens is attached From the results, it was confirmed that the effects of improving the visibility of turf and the like were obtained for each example in golf.

Claims

A single-layer or multilayer optical element comprising a transparent substrate and having a polarizing element,
In the transparent substrate, a specific wavelength absorbing dye is contained together with an ultraviolet absorber,
In the transmittance curve (hereinafter referred to as “transmittance curve”) measured with a spectrophotometer,
A first valley minimum and a second valley minimum are provided in each wavelength region of 450 to 500 nm and 550 to 630 nm of the transmittance curve,
The overall average transmittance in the wavelength region of 400 to 700 nm is 35% or more,
Each transmittance of the first and second valley minimums is 60% or less, and has a difference of 20% or more from each adjacent maximum transmittance,
Each transmittance of the first and second valley minimums and a transmittance difference average at each minimum wavelength ± 20 nm are in the range of 10 to 50%.
An anti-glare optical element characterized by that.
The anti-glare optical element according to claim 1, wherein a difference in transmittance between the first valley minimum and the second valley minimum is 20% or less.
A single-layer or multilayer optical element comprising a transparent substrate and having a polarizing element,
The transparent substrate contains an ultraviolet absorber together with a specific wavelength absorbing dye,
In the transmittance curve (hereinafter referred to as “transmittance curve”) measured with a spectrophotometer,
A first valley minimum at 450 to 500 nm, a second and a third valley minimum each having a transmittance of 25% or more shallower than the first valley minimum in each wavelength region of 550 to 630 nm and 650 to 700 nm,
The overall average transmittance in the wavelength region of 400 to 700 nm is 30% or more,
The transmittance of the first valley minimum is 30% or less, and the difference from the adjacent maximum transmittance is 25% or more,
Each transmittance of the second and third valley minimums is 55% or less, the difference from the adjacent maximum transmittance is 10% or more,
Each transmittance of the first, second, and third valley minimums and the average transmittance difference at each minimum wavelength ± 20 nm are in the range of 10 to 40%.
An anti-glare optical element characterized by that.
A single-layer or multilayer optical element comprising a transparent substrate and having a polarizing element,
The transparent substrate contains an ultraviolet absorber together with a specific wavelength absorbing dye,
In the transmittance curve (hereinafter referred to as “transmittance curve”) measured with a spectrophotometer,
A first valley minimum at 450 to 500 nm, a second and a third valley minimum each having a transmittance of 25% or more shallower than the first valley minimum in each wavelength region of 550 to 630 nm and 650 to 700 nm,
The overall average transmittance in the wavelength region of 400 to 700 nm is 30% or more,
The transmittance of the first valley minimum is 30% or less, and the difference from the adjacent maximum transmittance is 25% or more,
Each transmittance of the second and third valley minimums is 55% or less, the difference from the adjacent maximum transmittance is 5% or more,
Each transmittance of the first and third valley minimums and the average transmittance difference at each minimum wavelength ± 20 nm are in the range of 10 to 40%, and the transmittance of the second valley minimum and each minimum wavelength ± 20 nm The average transmittance difference is in the range of 3 to 10%.
An anti-glare optical element characterized by that.
The transparent substrate is formed of a transparent synthetic resin layer containing a specific wavelength absorbing dye together with an ultraviolet absorber, and the blending amount of the specific wavelength absorbing dye with respect to 100 parts of the resin raw material is 0.5 × 10 −4 to 5.0. with a × 10 -3 parts, amount relative to 100 parts of the resin material of the UV absorber, according to claim 1 to 4, antiglare optical element according to any one, wherein 0.1 to 6 parts.
6. The antiglare optical element according to claim 5, wherein the blending amount of the specific wavelength absorbing dye with respect to 100 parts of the resin raw material is 0.8 × 10 −4 to 3.5 × 10 −3 parts.
The antiglare optical element according to any one of claims 1 to 6, wherein the polarization degree of the polarizing element is 80% or less.