JP5824218B2 - Anti-glare optical element - Google Patents

Description

  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, a polarized window glass for automobiles and houses, a polarized windshield glass for airplanes and motorcycles, and a filter cover for display. It can also be applied to lighting equipment covers.

  When used as eyeglasses, for outdoor use such as cycling, fishing, walking, driving, shopping, washing clothes, etc., and for indoor use at the time of visual recognition of personal computers and mobile screens and before going to bed, for the purpose of preventing glare and harmful rays Is preferred.

  The human eye feels the brightest light in the vicinity of 555 nm (center wavelength of the standard relative luminous sensitivity curve) (510 to 600 nm) in the light-adapted vision (photopic vision).

Therefore, in order to prevent glare, light near the wavelength described above may be cut.
However, in order to prevent glare on summer beaches and winter ski resorts, glasses with colored lenses such as sunglasses are generally worn. Such a colored lens has a problem that the light in the entire wavelength region 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 the vicinity of the wavelength range that is dazzling to human eyes.

  Therefore, a prescription for imparting a so-called anti-glare performance 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 in fact, organic rare earths with rare earth elements such as neodymium as the central atom that can absorb visible light in the vicinity of 585 nm in a highly wavelength selective manner. When an element complex is contained, an effective antiglare performance can be obtained (cited from Patent Document 1, paragraph 0002).

  However, these organic rare earth element complexes are very expensive, and cannot be mixed or coated into a coating film without impairing the transparency of the transparent resin.

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

  First, depending on the lens material, the selection of the organic portion of the organic rare earth element complex is greatly limited and is often limited to expensive compounds. For example, in a thiourethane lens system, a normal organic rare earth element 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 vicinity of the wavelength range of 585 nm, the amount of the organic rare earth element complex is usually required to be about 5% by weight, Not only is the inconvenience of using a large amount of expensive organic rare earth element complex, but often the mechanical properties of the lens are reduced and balanced. (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, in Patent Document 1, in a visible light absorption spectrum (spectral transmittance curve: hereinafter referred to as “transmittance curve”), a main absorption valley (minimum peak) is observed in a wavelength region of 565 to 605 nm (preferably 580 to 590 nm). (Claims 1 and 2), and a desirable specific wavelength absorbing dye is a tetraazaporphyrin 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 linear 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, and 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. ]

  Moreover, in patent document 2, it has the minimum (valley) of a transmittance curve in the wavelength range 550-585 nm of a transmittance curve as a synthetic resin base material, and the average transmittance in a wavelength region 470-550 nm shows 10% or more. The specific wavelength absorbing dye is a squarylium compound represented by the following formula (2) (Claim 1 etc.).

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 the antiglare performance, a cut in a purple / blue blue wavelength range (400 to 500 nm) has been required.

  In fact, the intensity in the blue wavelength range in clear weather is much higher than in other wavelength ranges (see FIG. 1). FIG. 1 shows the relative intensity (%) displayed by the applicant's employee on the basis of the measurement under the following conditions, with the maximum value on a sunny day being 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 points have been reported in the media regarding the effect of the blue wavelength range on the eyes (so-called “blue hazard”).
1. I feel dazzling. 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 heart and body" Japanese and US experts urgently warn "Kawasaki Kiichi

  Further, the improvement in antiglare performance can be achieved by combining a thin plate-shaped polarizing element and a transparent substrate (Patent Document 2, paragraph 0021, Examples 4 and 6).

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

  However, when FIG. 8 of the sixth embodiment is compared with FIG. 6 of 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 on the upper side 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 visible light region (400 to 550 nm). Hard to think.

  Incidentally, in another example having no polarizing element in the same document, the transmittance in the vicinity of the polarizing element 500 nm exceeds an average value of 30% or more (the same applies to Example 4 having a polarizing element). And most 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).

  Moreover, also in the transmittance curve in Patent Document 1, in the short wavelength side visible light region (400 to 550 nm), the transmittance has a maximum value of 50% or more or 20% or more.

  Therefore, the description in Patent Documents 1 and 2 does not intend to positively cut (block) the short wavelength side visible light region (400 to 550 nm) including blue light together with ultraviolet rays.

  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 a wavelength range where glare is easily imparted. However, if the valley transmittance is too low or the valley is sharp, the illuminance difference between the emission color of the valley wavelength and the emission color of the nearby wavelength becomes large, and it becomes difficult to recognize the emission color of the valley wavelength. If the emission color is an illumination color, the field of view may be darkened.

  For example, when light with a wavelength range of 550 to 600 nm is cut, the center wavelength of yellow light is 580 nm, whereas the center wavelength of yellow red light is 600 nm, which is close to the author (Katsuhiro Saito, “Blue Backs: Science of Light and Color 2010, Kodansha, p96, Fig. 4-3), the visibility of yellow light is reduced, and the illumination light (center wavelength: 589 nm) of the sodium lamp does not pass through the lens, which may darken the field of view (patent) Reference 2 paragraph 0003).

  In view of the above, the present invention provides an antiglare optical element that has excellent antiglare performance when applied to a spectacle lens and the like, is excellent from the viewpoint of eye protection, and easily ensures visibility. With the goal.

  Another object of the present invention is to further absorb light in the blue wavelength range (400 to 500 nm), which is considered harmful to the eyes, and to cut ultraviolet rays, which is desirable from the viewpoint of eye health. The purpose is to provide elements.

  As a result of diligent development to solve the above-mentioned problems, the present inventors have come up with an optical element having the following configuration.

The present invention is an optical element having a transparent base material layer on at least one surface of a thin plate-like polarizing element, and a multilayer of two or more layers composed of the polarizing element and the transparent base material layer,
The ultraviolet absorber is contained in at least one layer in the multilayer, and a specific wavelength absorbing dye is contained in at least one layer that is the same as or different from the layer containing the ultraviolet absorber,
In the transmittance curve (hereinafter referred to as “transmittance curve”) measured with a spectrophotometer,
1) It has at least one valley long wavelength side and valley short wavelength side in the wavelength range of 550 nm to 605 nm or less and the wavelength range of 450 to 550 nm,
The valley long wavelength side, the each of the case where there exist a plurality, with the minimum value is 25 percent, the minimum value for the maximum value of transparently rate value in the wavelength range of ± 20 nm of the valley wavelength The ratio of 0.5 to 0.9,
Overall average transmittance in the wave length range 450 to 550 nm (integrated average) is 30% or less,
Or
2) having at least one valley length wavelength side in the wavelength range of more than 550 nm to 605 nm or less,
The valley long wavelength side, the each of the case where there exist a plurality, with the minimum value is 25 percent, the minimum value for the maximum value of transparently rate value in the wavelength range of ± 20 nm of the valley wavelength The ratio of 0.5 to 0.9,
There is no transmittance peak in the wavelength range of 450 to 550 nm, and
The overall average transmittance (integrated average) in the wavelength region of 450 to 550 nm is 30% or less,
It is characterized by this.

By setting it as the said structure, since it has a valley (minimum) long wavelength side in the center wavelength vicinity of the standard relative visibility curve which is the cause of glare, anti-glare performance can be improved combined with a polarizing element. In addition, since it has other valleys in the wavelength range of 450 to 550 nm (blue and strong intensity range) or does not have a sharp transmittance peak, it can further increase the antiglare effect and reduce blue hazard. Contributing to eye health conservation can be expected. Furthermore, if it is assumed that have a valley in the short-wavelength-side visible light region as a specific wavelength absorbing dye, without blending the ultraviolet absorber, it is possible to UV (new knowledge). Further, it has been found that even when the minimum value on the valley long wavelength side exceeds 25%, antiglare performance can be exhibited when combined with a polarizing element. It was also found that if a polarizing element having a low degree of polarization is used, valleys clearly appear on both the long wavelength side and the short wavelength side (Examples 6 and 7).

In each of the above configurations, the overall average transmittance (integrated average) in the wavelength region of 450 to 550 nm is more preferably 30% or less. Reduction of blue hazard is more certain. In addition, those having an overall average transmittance (integral average) of 30% or less in the wavelength range of 450 to 550 nm of the above configuration can be easily obtained by using a polarizing element having a degree of polarization of 90% or more, or appropriately coloring. Can be achieved.

  In the above configuration, the minimum value of the valley is set to 5% or more, and the valley long wavelength side and the short wavelength side are usually minimum with respect to the maximum value of the luminous transmittance value within the wavelength range of ± 20 nm of the wavelength of the valley value. It is desirable that the value ratio is 0.5 to 0.9.

  Moreover, it becomes easy to ensure the visibility of the light of a specific wavelength that the minimum value by the side of a valley long wavelength shall be 25% or more.

  If the curvature of the valley is too large (flat, dull), it is difficult to cut the wavelength due to the valley. Conversely, if the valley curvature is small (sharp), the difference in emission illuminance near both sides of the valley wavelength becomes large, and the visibility of the emission color at the valley wavelength may be reduced. Further, by setting the minimum value of the valley to 5% or more, it is possible to ensure the transmission of light of the wavelength, and there is no possibility that it is difficult to visually recognize the emission color of the wavelength.

  In each of the above-described configurations, it is desirable that the overall average transmittance (integrated average) in the wavelength range of more than 605 nm and 780 nm is more than 30%. This is to secure the field of view at night and in the tunnel.

  Furthermore, harmful ultraviolet rays can be cut by providing a spectral transmittance of 1% or less at a wavelength of 400 nm and a spectral transmittance of 20% or less at a wavelength of 410 nm.

Further, when the antiglare optical element is formed of a degree of polarization, a transparent substrate layer made of a transparent synthetic resin layer containing a specific wavelength absorbing dye and an ultraviolet absorber, 100 parts of a resin material of the specific wavelength absorbing dye and the ultraviolet absorber It is achieved by setting the blending amount to the former: 0.5 × 10 ^{−5 to} 1.5 × 10 ⁻² parts and the latter: 0.5 to 5 parts (preferably 1.5 to 5 parts). Easy to do.

That is, the present inventors have found that the incorporation of a large amount of an ultraviolet absorber is effective not only for ultraviolet rays cut but also for cutting the short wavelength side visible light region including blue light. The compounding amount of the specific wavelength-absorbing dye is within the scope of the present invention at the example level of the conventional cited documents 1 and 2, etc. (cited document 1: 1.0 × 10 ⁻⁵ or cited document 2: 2. 0 × 10 ⁻⁵ ), and the blending amount of the ultraviolet absorber is outside the range below the lower limit of the present invention (cited document 1: 0.05 part, cited document 2: 0.4 part).

  The anti-glare performance is further improved by synergizing the cut of light in a specific direction by the polarizing lens and the cut of visible light short wavelength (blue light), and the image is not blurred because the chromatic aberration is reduced. Improve (visible).

As in the present invention, when a desired color tone is obtained by mixing other dyes while maintaining selective light absorption characteristics in a specific visible light wavelength region, in a wavelength region other than the necessary selective light wavelength region. If there are as few light absorption factors as possible (the valley is clear and has an appropriate curvature and the transmittance curve is flat ) , that is, the number of valleys is smaller, the color mixing combination method becomes simpler. In addition, it is easy to adopt a wider range of target color tone and to obtain a color tone with less blur.

  In other words, the anti-glare optical element of the present invention is an average that selectively cuts the blue short wavelength side visible light region together with the strong long wavelength side visible light region or does not have a sharp maximum in the transmittance curve. The anti-glare performance can be obtained by making it special.

It is a light-intensity spectrum figure of the day of fine weather and cloudy in the beginning of autumn. It is one model sectional drawing of the polarizing lens to which this invention is applied. It is sectional drawing for description of the casting molding method of the polarizing lens of the tape winding system using the 1st, 2nd mold. It is sectional drawing for description of the casting molding method of the polarizing lens of a gasket seal system similarly. 2 is a graph of the transmittance of the antiglare optical element prepared in Example 1. FIG. 4 is a graph of the transmittance of an antiglare optical element prepared in Example 2. FIG. 6 is a graph of the transmittance of the antiglare optical element prepared in Example 3. FIG. 6 is a graph showing the transmittance of the optical element (polarizing lens) prepared in Comparative Example 1. FIG. 6 is a graph of the transmittance of the optical element (polarizing lens) prepared in Comparative Example 2. FIG. 6 is a graph showing the transmittance of the optical element (polarizing lens) prepared in Example 4. FIG. 6 is a graph showing the transmittance of the optical element (polarizing lens) prepared in Example 5. FIG. 6 is a graph showing the transmittance of the optical element (polarizing lens) prepared in Example 6. FIG. FIG. 10 is a graph showing the transmittance of the optical element (polarizing lens) prepared in Example 7. 10 is a graph of the transmittance of the optical element (polarizing lens) prepared in Example 8. FIG. 10 is a graph of the transmittance of the optical element (polarizing lens) prepared in Example 9. FIG. 6 is a graph of transmittance of an optical element (polarizing lens) prepared in Comparative Example 3. FIG. It is a graph of the transmittance | permeability of the optical element (polarizing lens) prepared in the comparative example 4. FIG. 11 is a graph showing the transmittance of the optical element (polarizing lens) prepared in Example 10. 10 is a graph of the transmittance of the optical element (polarizing lens) prepared in Example 11. FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  The optical element (polarizing lens) 11 of the present embodiment is basically a transparent synthetic resin layer (lens layer) cast-molded using a polymerizable liquid material on both surfaces of a polarizing element (polarizing film or polarizing sheet) 13. ) 15 and 15 (see FIG. 2).

  Next, as a casting molding method of the polarizing lens of this embodiment, any of the following (1) tape winding method (FIG. 3) and (2) gasket seal method (FIG. 4) may be used. In FIG. 3, a lens layer is formed on one side.

  Basically, a polarizing lens 11 having lens layers 15 and 15 on both surfaces of a polarizing element (polarizing film or polarizing sheet) 13 and a pair of first and second molds (usually made of glass) 17 and 19 are used. The shaping polarizing element 13 is floated on the first mold 17 while the first mold 17 is held substantially horizontally, and the second mold 19 is shaped. The peripheral openings of the first and second molds 17 and 19 are formed by winding the tape 21 in a state where the polarizing element 13 is set with a predetermined gap, or the cavity is formed by a plastic gasket 23. 25 is prepared, a mold 27 is prepared, a polymerizable liquid material is injected into the cavity 25 of the mold 27, and polymerized or crosslinked and cured by means such as thermosetting polymerization or ultraviolet curing polymerization. To form Te.

  The first and second molds 17 and 19 have at least one (both in the illustrated example) a positioning member 30 for positioning the polarizing element 13 at a predetermined position.

  The gasket 23 is formed with a polymer material inlet 23a as shown in FIG.

  As the gasket material, an ethylene copolymer, an olefin-based thermoplastic elastomer, or the like that has elasticity and can prevent leakage of the polymerizable liquid material is preferable.

  Hereinafter, the manufacturing method of the polarizing lens of this embodiment using the casting method will be described.

  First, the polarizing element (polarizing film or polarizing sheet) 13 is bent by a known method such as vacuum bending or hot pressing in accordance with the curvature of the first mold 17.

It does not specifically limit as a polarizing film used here, For example, the following can be used.
A polarizing film obtained by impregnating polyvinyl alcohol (PVAL) with a water-soluble dichroic dye,
A polarizing film obtained by impregnating iodine in a PVAL uniaxially oriented film,
A polarizing film obtained by impregnating a PVAL uniaxially oriented film with a water-soluble dichroic dye,
-A polyvinylene polarizing film having a polyene structure as the molecular structure such as PVAL,
A polarizing film in which a water-insoluble dye containing at least one dichroic dye is added to a polyester resin,
・ Polyvinylene polarizing film that dehydrates the PVAL film itself into a conjugated double bond and has dichroism,

  The polarizing sheet is a sheet in which a protective resin layer is formed by attaching a transparent protective sheet to one or both surfaces of the polarizing film 13. Examples of the transparent protective sheet include a cellulose sheet, a polyester sheet, an acrylic sheet, a polycarbonate sheet, and a polyamide sheet.

  These polarizing elements (polarizing film or polarizing sheet) 13 are cut into a mold shape by a punching press or laser processing, and are subjected to bending processing (shaped processing). After the shaping process, drying annealing is appropriately performed depending on the material of the polarizing element and the state of deformation. Conditions for this drying annealing are appropriately selected from the range of 20 to 120 ° C. × 5 minutes to 25 hours depending on the type of polarizing element.

The adhesive layer 14 is formed by applying an adhesive to the polarizing element after the shaping by a known method such as dipping or spin coating, and solidifying by normal temperature and heat drying.
The conditions for room temperature and heat drying are appropriately selected from the range of 20 to 120 ° C. × 5 minutes to 10 hours depending on the material of the adhesive and the type of the polarizing element.

  The adhesive is not particularly limited as long as the adhesive layer has rubber-like elasticity. Usually, what is called an elastomer adhesive is used, and desirably, the adhesive layer exhibits M200: 0.1 to 1.0 MPa in a tensile test (JIS K 6251).

  Specifically, (1) ester-based TPE, (2) urethane-based TPE, and (3) two-component / one-component curable polyurethane, etc. are diluted or dispersed in organic solvents, water, etc. A type of adhesive can be used.

  The method for applying the adhesive can be appropriately selected from known methods such as dipping and spin coating.

  A polarizing plastic lens having a lens layer on both surfaces of a polarizing element having an adhesive layer formed thereon after the shaping process as described above, using the pair of first and second molds, the above-described tape winding method or gasket Molded by the seal method.

  A transparent plastic material is used as the lens material. For example, episulfide resin, thiourethane resin, urethane resin, thiourea resin, urea polymer composition, epoxy resin, acrylic resin, nylon resin, polycarbonate resin, polyamide resin, sulfide resin, etc. To select as appropriate.

  If the polarizing lens requires high refraction, 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 material, 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, and polyisocyanatothioisocyanate, and a polythiol component can be preferably used (Japanese Patent Laid-Open No. 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) is composed of 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. Known compounds that cure a linear alkyl sulfide type dithioepoxy compound can be used (Japanese Patent Laid-Open Nos. 9-1110979 and 10-114764).

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

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

  When the plastic lens (polarizing lens) that is the optical element of the present invention is manufactured by casting, various additives such as a dye, a bluing agent, and the like are added to the polymerizable liquid material that is a lens material. You may add a mold release agent, a deodorizer, antioxidant, a stabilizer, a polymerization initiator, etc. as needed. The resin curing (polymerization) is performed by thermosetting polymerization, ultraviolet curing polymerization, or the like.

  In addition, it is desirable to apply a commonly used reinforced coating (hard coat) to the surface of the plastic lens of the present invention and to modify the hardness or the like.

  The hard coat is formed of a general-purpose silicone coating film. The hard coat is usually via a primer layer.

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

  The cured film and primer film of the present invention include ultraviolet absorbers such as benzophenone-based, benzotriazole-based, and phenol-based materials, silicone-based surfactants, fluorine-based surfactants, etc. for improving the smoothness of the coating film. Leveling agents and other modifiers can also be added.

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

  Furthermore, surface treatments such as antifogging treatment, antireflection treatment, water repellent treatment, antistatic treatment, and dyeing 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.

  The present invention relates to a multilayer optical element (glasses lens) having a polarizing function provided by a thin-plate-shaped polarizing element having the above-described structure, and a specific wavelength absorbing dye together with an ultraviolet absorber in any one layer or another layer. It is a characteristic requirement to contain.

  The specific wavelength absorbing dye is particularly limited as long as it has at least one valley long wavelength side and valley short wavelength side in the wavelength range of 550 nm to 605 nm or less and the wavelength range of 50 to 550 nm (desirably, the wavelength range of 470 to 510 nm). Not.

  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 structural formula (1) described in Patent Document 1 and the following structural formula (5) described in JP-A 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.

  Moreover, a conventional thing can be used as a ultraviolet absorber. Examples include benzophenone, diphenyl acrylate, sterically hindered amine, salicylic acid ester, benzotriazole, hydroxybenzoate, cyanoacrylate, and hydroxyphenyl triazine.

Of these, benzotriazole derivatives are desirable.
The benzotriazole-based UV absorber efficiently cuts the wavelength range of 380 to 450 nm that overlaps the blue wavelength range (400 to 500 nm), while other types of UV absorbers cut the wavelength range of 380 nm or more. The amount is small. For this reason, when a large amount of a triazole-based ultraviolet absorber is blended in the optical element (lens) within a limit that does not cause yellowing or white turbidity, a blue wavelength band cut function is also achieved.

  Examples carried out together with comparative examples to confirm the effects of the present invention will be described below.

  The polarizing element, the ultraviolet absorber and the specific wavelength absorbing dye used in this example are as follows.

<Polarizing element>
Commercial products with the following specifications were used.
F-01; Dye-based PVAL polarizing film “Gray-30”, polarization degree 99.5%
F-02: Dye-based PVAL polarizing film “Brown-30”, polarization degree 99.2%
F-03; iodine-based PVAL polarizing film “Brown-41”, degree of polarization 95.1%
F-04; Dye-based PVAL polarizing film “Rose Brown-24”, polarization degree 95.8%
F-05: Dye-based PVAL polarizing film “Ruby-15”, polarization degree 99.6%
F-06; iodine-based PVAL polarizing film “Gray-60”, degree of polarization 45.8%
F-07: Dye-based PVAL polarizing film “Gray-45”, polarization degree 77.3%
F-08: Dye-based PVAL polarizing film “Gray-12G”, polarization degree 99.9%
F-09: Dye-based PVAL polarizing film “Marron-20”, polarization degree 99.8%
F-10: Dye-based PVAL polarizing film “Gray-28”, polarization degree 98.3%
S-01: Dye-type polycarbonate polarizing sheet for sunglasses "Gray-15", polarization degree 99.8%
S-02: Dye-type polycarbonate polarizing sheet for sunglasses "Gray-12", polarization degree 99.8%

<Ultraviolet absorber>
Each commercial product having the following compound name was used.
UV-01; 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol UV-02; 2- (2-hydroxy-5-t-butylphenyl) ) -2H-benzotriazole UV-03; 2- (4-butoxy-2-hydroxyphenyl) -2H-benzotriazole UV-04; 2- (4-ethoxy-2-hydroxyphenyl) -2H-benzotriazole UV- 05; 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1 dimethylethyl) -4-methylphenol

<Specific wavelength absorbing dye>
Each commercial product having the following specifications was used.
C-01: Tetraazaporphyrin-based vanadium complex compound isomer mixture, absorption peak wavelength 595 nm
C-02: Tetraazaporphyrin-based copper complex compound isomer mixture, absorption peak wavelength 585 nm
C-03; tetraazaporphyrin-based europium complex compound isomer mixture, absorption peak wavelength 481 nm
C-04; isomer mixture of tetraazaporphyrin-based vanadium complex compound, absorption peak wavelength 497 nm
C-05; squarylium compound, absorption peak wavelength 594 nm
C-06; pyromethene compound, absorption peak wavelength 497 nm
C-07; cyanine compound, absorption peak wavelength 500 nm

  Table 1 shows a summary of the materials (raw materials) and addition amounts used in Examples and Comparative Examples.

<Test group I: Examples 1-3>
1) Preparation of adhesive for polarizing film The mixture of the following formulation was stirred until it was in a uniform state.
Water-based emulsion ester-based thermoplastic elastomer “Pesresin A-160P” (Takamatsu Yushi Co., Ltd., water-dispersed emulsion, solid content 27%) 100 parts Methyl alcohol 900 parts Silicone surfactant “SILWET L-77” (Momentive Performance・ Materials Japan LLC

2) Bending process of polarizing film and application of adhesive The polarizing film was humidified according to the curvature of 66.16 mm of the first mold and then bent by a hot press.

  This was cut into a circular shape having an outer diameter of 80 mm with a laser processing machine to produce a polarizing film having a curvature.

The above-prepared adhesive was applied to a polarizing film having this curvature.
The coating method was performed by dipping at an adhesive solution temperature of 15 ° C., an immersion time of 30 seconds, and a lifting speed of 200 mm / min.

  Then, it dried at 50 degreeC for 30 minutes with the hot-air circulation furnace.

3) Preparation of polymerizable liquid material 90 parts of bis (2,3-epithiopropyl) disulfide, 10 parts of 4,7-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol Mixing and stirring for 30 minutes while adjusting the temperature to 15 ° C. in a gas atmosphere, 0.3 part of N, N-dimethylcyclohexylamine as a curing catalyst, isopulegol as a fragrance imparting agent, ultraviolet absorbers shown in Table 1 and specific wavelengths Each absorbing dye was added, and the mixture was further mixed and stirred for 30 minutes while adjusting the temperature to 15 ° C. in a nitrogen gas atmosphere.

4) Molding of Polarizing Lens The above-mentioned shaped polarizing film or polarizing sheet (Examples 1 to 4 and Comparative Examples 1 to 4) is formed from the first mold (made of glass, outer diameter 80 mm, surface usage curvature 66.16 mm, center thickness 4 0.0mm), second mold (made of glass, outer diameter 80mm, working surface curvature 65.59mm, center thickness 4.0mm) After setting between two sets, attach the adhesive tape so that the center spacing is 3.0mm A mold was prepared by winding.

  As the adhesive tape, a 6263-50 adhesive tape manufactured by Sliontec Co., Ltd., in which a silicone adhesive was applied on a 38 μm thick PET film, was used.

  After injecting a polymerizable liquid material into the molding die, heating was performed under the following temperature conditions to polymerize and cure, thereby performing polarizing lens molding. After the polymerization, the mold release step for removing from the mold was physically (mechanically) performed with a wedge-shaped tool.

  “30 ° C. × 10 hours → 30 ° C. to 50 ° C. over 5 hours → 50 ° C. to 100 ° C. over 2 hours → 100 ° C. to 120 ° C. over 1 hour → 120 ° C. × 2 Time → cool from 120 ° C. to 40 ° C. over 4 hours. ”

<Test Group II: Examples 4-6, Comparative Examples 1-2>
In this Test Group II, the polythiourethane lens resin having a refractive index (ne) of 1.67 can provide sufficient adhesion between the lens resin and the polarizing film even without the adhesive, so the preparation and application of the adhesive Do not do.

1) Bending process of polarizing film or polarizing sheet The polarizing film shown in Table 1 was prepared, the polarizing film was humidified according to the curvature of 66.16 mm of the first mold, and then bent by a hot press.

  This was cut into a circular shape having an outer diameter of 80 mm with a laser processing machine to produce a polarizing film having a curvature.

  Then, in order to remove the humidified water | moisture content, it dried at 60 degreeC for 80 minute (s) with the hot air circulation furnace.

2) 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 alkyl phosphate ester (alcohol C8 to C12) salt as an internal mold 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 at a liquid temperature of 15 ° C. in a nitrogen gas atmosphere for 1 hour.

  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, it is filtered through a 1 μm filter, and a polythiourethane lens raw material liquid having a refractive index (n _D ²⁵ ) of 1.67 (polymerizability). Liquid material) was prepared.

3) Molding of Polarizing Lens The above-mentioned shaped polarizing film or polarizing sheet (Examples 1 to 4 and Comparative Examples 1 to 4) was made into the first mold (made of glass, outer diameter 80 mm, surface curvature 66.16 mm, center thickness 4 0.0mm), second mold (made of glass, outer diameter 80mm, working surface curvature 65.59mm, center thickness 4.0mm) After setting between two sets, attach the adhesive tape so that the center spacing is 3.0mm A mold was prepared by winding.

  As the adhesive tape, a 6263-50 adhesive tape manufactured by Sliontec Co., Ltd., in which a silicone adhesive was applied on a 38 μm thick PET film, was used.

  After injecting a polymerizable liquid material into the molding die, heating was performed under the following temperature conditions to polymerize and cure, thereby performing polarizing lens molding.

  “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. ”

<Test Group III: Examples 6-9, Comparative Examples 3-4>
Similar to Test Example Group II, the polythiourethane lens resin having a refractive index (ne) of 1.60 provides sufficient adhesion between the lens resin and the polarizing film even without an adhesive. Do not do.

1) Bending process of polarizing film or polarizing element It carried out like Test example group II.

2) Preparation of polymerizable liquid material 100 parts of 2,5-bicyclo [2,2,1] heptanebis (methyl isocyanate), 0.1 part of dibutyltin dichloride as a curing agent, alkyl phosphate ester (alcohol as an internal mold release agent) C8-C12) 0.3 parts of salt, 0.2 parts of ethyl caproate as fragrance imparting agent, UV absorber and specific wavelength absorbing dye shown in Table 1 were added, respectively, liquid temperature 25 ° C., nitrogen gas atmosphere Stir well for 1 hour.

  Thereafter, 50 parts of pentaerythritol tetrakis (3-mercaptopropionate) and 50 parts of 4,7-bis (mercaptomethyl) -3,6,9-trithia-1.11-undecanedithiol were added, and the liquid temperature The mixture was sufficiently stirred at 25 ° C. in a nitrogen gas atmosphere for 1 hour.

3) Molding of polarizing lens The above-mentioned shaped polarizing film or polarizing sheet (Examples 1 to 4 and Comparative Examples 1 to 4) was formed into a first mold (made of glass, outer diameter 90 mm, surface curvature 66.16 mm, center thickness 4 .0mm), second mold (made of glass, outer diameter 90mm, working surface curvature 65.59mm, center thickness 4.0mm) After being set between two sheets, injection molding is performed so that the center distance is 2.5mm. A built-in mold was prepared in the gasket.

  As the gasket, Miralastomer No. 6010 resin manufactured by Mitsui Chemicals, Inc. was injection-molded and used.

<Test group IV: Examples 10 and 11>
1) A polarizing film shown in Table 1 was prepared, and a polarizing sheet having a curvature was prepared by cutting into a circular shape having an outer diameter of 80 mm with a laser processing machine. Further, the polarizing sheet was bent by a hot press in accordance with the curvature of the hot press mold of 66.5 mm.

2) Preparation of dye-embedded resin pellets for injection molding The specific wavelength-absorbing dyes shown in Table 1 and the addition amount are “Iupilon CLS-3400” (registered trademark of Mitsubishi Engineering Plastics, Inc .; polycarbonate masterbatch containing UV absorber) To produce resin pellets for injection molding.

3) Injection molding of polarized lens A mold for molding a polarized lens having an outer diameter 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.
A bent polarizing sheet is attached thereto, and injection molding is performed using the specific wavelength absorbing dye mixed resin pellet.

<Test methods and results>
The transmittance of each of the optical elements (polarizing lenses) of Examples and Comparative Examples prepared above was measured according to the following method.
The transmittance value of the polarizing lens was measured using non-polarized light, as shown in “Specimen Specification and Test Method of Refractive Correction Eyeglass Lens” of JIS T-7333. Alternatively, it was calculated as an average value of transmittance values measured in two directions perpendicular to each other on the polarization plane of the sample. The measurement was performed using a “Hitachi spectrophotometer U-4100” under the conditions of a measurement wavelength of 350 to 850 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. 5 to 19 and Tables 2 and 3 summarize the items of the invention-specific items of the present invention obtained from the respective drawings.

  From the results shown in Table 2, it can be seen that each example satisfies all of the invention-specific matters of the present invention. On the other hand, it can be seen that each comparative example has items that do not satisfy the invention-specific matters of the present invention.

  Further, monitor glasses were prepared by putting two polarizing lenses of each example and comparative example in a spectacle frame.

  When the monitor glasses are used and the scenery in the following weather is viewed indoors or outdoors in the following weather during the summer (from early July 2010 to late August of the same year) It was recognized that there was anti-glare property when there were more than 8 conditions when it was reduced or clearly visible. The determination criteria were as follows based on the number of people who were recognized as having anti-glare properties.

◎: 9 or more, ○: 7-8, △: 5-6, ×: 4 or less From Table 4 showing the UV-cutting properties and the results thereof, the optical element of the present invention (glasses lens) is It was confirmed that the film was excellent in UV-cutting properties, and antiglare performance and visual performance were sufficient.

11 Optical elements (polarizing lenses)
13 Polarizing element (polarizing film or polarizing sheet)
15 Lens layer

Claims (6)

An optical element having a transparent base material layer on at least one surface of a thin plate-like polarizing element, and having two or more layers composed of the polarizing element and the transparent base material layer,
The ultraviolet absorber is contained in at least one layer in the multilayer, and a specific wavelength absorbing dye is contained in at least one layer that is the same as or different from the layer containing the ultraviolet absorber,
In the transmittance curve (hereinafter referred to as “transmittance curve”) measured with a spectrophotometer,
Having at least one valley long wavelength side and valley short wavelength side in a wavelength range of more than 550 nm to 605 nm or less and a wavelength range of 450 to 550 nm,
It said valley long wavelength side, the each of the case where there exist a plurality, with the minimum value is 25 percent, the minimum value for the maximum value of transparently rate value in the wavelength range of ± 20 nm of the valley wavelength The ratio of 0.5 to 0.9,
Overall average transmittance in the wave length range 450 to 550 nm (integrated average) is 30% or less,
An anti-glare optical element characterized by that. An optical element having a transparent base material layer on at least one surface of a thin plate-like polarizing element, and having two or more layers composed of the polarizing element and the transparent base material layer,
The ultraviolet absorber is contained in at least one layer in the multilayer, and a specific wavelength absorbing dye is contained in at least one layer that is the same as or different from the layer containing the ultraviolet absorber,
In the transmission curve,
Having at least one valley length wavelength side in the wavelength range from 550 nm to 605 nm,
The valley long wavelength side, the each of the case where there exist a plurality, with the minimum value is 25 percent, the minimum value for the maximum value of transparently rate value in the wavelength range of ± 20 nm of the valley wavelength The ratio of 0.5 to 0.9,
There is no transmittance peak in the wavelength range of 450 to 550 nm, and
The overall average transmittance (integrated average) in the wavelength region of 450 to 550 nm is 30% or less,
An anti-glare optical element characterized by that. Minimum the Valley short wavelength side, are each in the case of multiple presence, der minimum value of 5% or more Rutotomoni, the maximum value of transparently rate value in the wavelength range of ± 20 nm of the valley wavelength 2. The antiglare optical element according to claim 1, wherein a ratio of the values is 0.5 to 0.9. The antiglare optical element according to any one of claims 1 to 3, wherein an overall average transmittance (integral average) in a wavelength range of more than 605 nm and not more than 780 nm is more than 30%. The antiglare optical element according to any one of claims 1 to 4, which exhibits a spectral transmittance of 1% or less at a wavelength of 400 nm and a spectral transmittance of 20% or less at a wavelength of 410 nm. The transparent substrate layer is formed of a transparent synthetic resin layer containing a specific wavelength absorbing dye and an ultraviolet absorber, and the blending amount of the specific wavelength absorbing dye and the ultraviolet absorber with respect to 100 parts of the resin raw material is 0.5: × 10 ^-5 ~1.5 × 10 ^-3 parts of the latter: antiglare optical element according to any one of claims 1-5, characterized in that 0.5 to 5 parts.

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