WO2017185287A1 - High refractive index polarized spectacle lens - Google Patents

High refractive index polarized spectacle lens Download PDF

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Publication number
WO2017185287A1
WO2017185287A1 PCT/CN2016/080481 CN2016080481W WO2017185287A1 WO 2017185287 A1 WO2017185287 A1 WO 2017185287A1 CN 2016080481 W CN2016080481 W CN 2016080481W WO 2017185287 A1 WO2017185287 A1 WO 2017185287A1
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WO
WIPO (PCT)
Prior art keywords
layer
polarized
refractive index
film
adhesion
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Ceased
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PCT/CN2016/080481
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French (fr)
Inventor
Stephen Brown
Jingye LIANG
Ben Ryan
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Carl Zeiss Vision International GmbH
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Carl Zeiss Vision International GmbH
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Filing date
Publication date
Application filed by Carl Zeiss Vision International GmbH filed Critical Carl Zeiss Vision International GmbH
Priority to EP16899800.3A priority Critical patent/EP3449309B1/en
Priority to PT168998003T priority patent/PT3449309T/en
Priority to PCT/CN2016/080481 priority patent/WO2017185287A1/en
Priority to CN201680084993.2A priority patent/CN109073916A/en
Priority to CN202211366549.3A priority patent/CN115509030A/en
Priority to ES16899800T priority patent/ES2897912T3/en
Publication of WO2017185287A1 publication Critical patent/WO2017185287A1/en
Priority to US16/172,450 priority patent/US11067834B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/12—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3075—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state for use in the UV
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C2202/00—Generic optical aspects applicable to one or more of the subgroups of G02C7/00
    • G02C2202/16—Laminated or compound lenses

Definitions

  • the present invention relates to spectacle lenses for spectacles, particularly for sunglasses, the spectacle lenses being polarized lenses formed from a high refractive index substrate such as a polyurethane.
  • Spectacle lenses are those that are used in spectacles, for either outdoor or indoor use, typically providing corrective vision for wearers to accommodate for physiological errors in the human eye, but also being plano and being for aesthetic, protective or fashion purposes. Glass and plastic have both been successfully used as substrates for spectacle lenses, with plastic lenses becoming popular from the 1960’s with the advent of new plastics with improved properties.
  • Some common plastic materials used to manufacture spectacle lenses include polyethylene glycol diallyl dicarbonate (CR39 TM ) and polycarbonate.
  • CR39 TM polyethylene glycol diallyl dicarbonate
  • polycarbonate polycarbonate
  • high index plastic materials have been developed for the manufacture of spectacle lenses, and are now very popular and very successful. These “high index” materials have a higher refractive index (typically above 1.55) than other conventional plastic materials, which means that they bend light more than the conventional plastic materials.
  • refractive index lens material needs to be used to produce the same prescription than with a conventional plastic material. This desirably results in lenses that are lighter with thinner edges.
  • sunglass lenses For outdoor use, usually referred to as sunglass lenses, have traditionally been uniformly tinted so as to reduce glare and light transmission for the comfort of the wearer. However, these lenses indiscriminately filter all light whether it is aligned horizontally or vertically -glare is dampened, but not eliminated. More importantly, by filtering all components of light, visual acuity is diminished.
  • Light is made up of waves travelling in different directions.
  • Vertical light is useful to the human eye, however horizontal light commonly exists in higher proportions as glare.
  • Glare is concentrated light reflecting off a horizontal shiny surface, such as a car windscreen, sand, water, snow or asphalt roads, which reduces visibility and can make it uncomfortable, painful or even dangerous to carry on driving, cycling, skiing, etc.
  • polarized spectacle lenses were developed for outdoor use that allow the vertical component of light, which is preferred for clear vision, to pass, while eliminating the easily scattered and skewed horizontal component of light.
  • Vertically aligned light is preferred because it respects the natural tendency of the visual system to focus on the vertical component of an image.
  • polarized spectacle lenses typically include linear polarized film layers, such as polyvinyl alcohol polymer layers, having aligned dichroic dyes to extinguish the horizontal component of reflected sunlight.
  • linear polarized film layers such as polyvinyl alcohol polymer layers
  • aligned dichroic dyes to extinguish the horizontal component of reflected sunlight.
  • the components of light that are aligned with the axis of the polarizer are absorbed, allowing only the light oscillating with a wave aligned perpendicular to the axis of the polarizer to pass through the polarized film layer.
  • Such polarized film layers are however very delicate and readily absorb moisture during handling and manufacture. Accordingly, it is usual to encapsulate such polarized film layers in protective and supportive outer layers, forming a multi-layer polarizing film.
  • the present invention provides a high refractive index, polarized spectacle lens comprising a high refractive index lens substrate and a multi-layer polarized film, the multi-layer polarized film comprising at least one support layer and at least two adhesion layers, wherein at least one adhesion layers is a polarized adhesion layer.
  • the present invention further provides a process for the production of a high refractive index, polarized spectacle lens, comprising a high refractive index lens substrate and a multi-layer polarized film.
  • the present invention further discloses a spectacle comprising a high refractive index, polarized spectacle lens and the use of a high refractive index, polarized spectacle lens in a spectacle.
  • a high refractive index preferably is a refractive index of n ⁇ 1.515, particularly preferably of n ⁇ 1.520 and quite particularly preferably of n ⁇ 1.533.
  • the inventive high refractive index, polarized spectacle lenses may have vision correcting properties or not.
  • adhesion and support layers being between or adjacent to other layers, or being internal or external, this does not preclude the possibility of there being other functional layers between or adjacent those adhesion and support layers.
  • an adhesion layer could be coated with another layer which could function as a barrier layer as well as a further adhesion layer.
  • the function of such a barrier layer might be to prevent interaction of isocyanates in the lens substrate with dyes in a PVA adhesion layer, for example, during lens curing (to otherwise prevent large colour shifts) .
  • intermediate layers may be provided between adhesion layers and the support layer, such intermediate layers being provided if e.g. assistance is needed with the chemical or physical bonding of the adhesion layers to the support layer.
  • the multi-layer polarized film is protected by protective layers not necessary in the spectacle lens, but present to protect the multi-layer film against inter alia dirt, scratching or other damages during handling and prior to use.
  • the protective layers remain on the multi-layer polarized film during transportation, film cutting, handling and bending, and are removed at the point of assembly, preferably in a clean environment, to produce the inventive high refractive index polarized spectacle lens.
  • the adhesion layers preferably comprise a polyvinyl alcohol-type layer selected from one or more of the group of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , a saponified (ethylene/vinyl acetate) copolymer, or a mixture thereof.
  • An adhesion layer may be either a polarized adhesion layer or a non-polarized adhesion layer.
  • each adhesion layer adjacent to the high refractive index lens substrate has an adhesion strength between the adhesion layer and the lens substrate that is equal to or greater than 60 N/mm 2 , preferably equal to or greater than 73 N/mm 2 , further preferably equal to or greater than 86 N/mm 2 and more preferably equal to or greater than 100 N/mm 2 , in order to have sufficient resistance to lens edging during prescription frame-fitting to avoid undesirable layer separation.
  • the adhesion strength between the adhesion layer and the lens substrate is in the range of from 93 N/mm 2 to 380 N/mm 2 , preferably in the range of from 109 N/mm 2 to 355 N/mm 2 , further preferably in the range of from 121 N/mm 2 to 340 N/mm 2 , particularly preferably in the range of from 135 N/mm 2 to 322 N/mm 2 and particularly preferably in the range of from 151 N/mm 2 to 301 N/mm 2 .
  • the adhesion strength referred to here is that measured by layer separation using a universal testing machine (preferably an Instron TM twin motorised ball screw universal testing machine) .
  • At least one adhesion layer is a polarized adhesion layer, being a layer having polarizing properties by incorporating one or more dichroic dyes, iodine, or other suitable dyes into the adhesion layer, preferably a polyvinyl alcohol-type layer.
  • the adhesion layer having polarizing properties preferably a polyvinyl alcohol-type layer, may be a layer of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , a saponified (ethylene/vinyl acetate) copolymer or a blend thereof.
  • a layer of PVA is preferred as adhesion layer having polarizing properties.
  • Typical, non-limiting, examples include: C.I. Direct Blue 67, C.I. Direct Blue 90, C.I. Direct Blue 200, C.I. Direct Green 59, C.I. Direct Violet 48, C.I. Direct Red 39, C.I. Direct Red 81, C.I. Direct Red 83, C.I. Direct Red 89, C.I. Direct Orange 39, C.I. Direct Orange 72, C.I. Direct Yellow 34, C.I. Direct Green 26, C.I. Direct Green 27, C.I. Direct Green 28, C.I. Direct Green 51, C.I. Direct Black 170, and combinations thereof.
  • the multi-layer polarized film comprises two discrete adhesion layers having polarizing properties directly adjacent to each other, wherein the two layers are of a different chemical composition, e.g. a PVA layer and a PCAc layer.
  • a PVA layer e.g. a PVA layer
  • a PCAc layer e.g. a different chemical composition
  • identical or different dichroic dyes and/or iodine may be incorporated in the two layer.
  • the multi-layer polarized film comprises only one discrete adhesion layer having polarizing properties adjacent to the high refractive index substrate and/or an adhesion layer and/or a support layer.
  • the discrete adhesion layer having polarizing properties preferably comprises PVA and at least one dichroic dye and/or iodine.
  • Each adhesion layer of the multi-layer polarized film irrespective of whether the adhesion layer is polarized or not, preferably has a layer thickness ranging from about 20 micron to about 120 micron, further preferably ranging from 20 micron to 120 micron, further preferably ranging from 23 micron to 100 micron, further preferably ranging from 24 micron to 75 micron, particularly preferably ranging from 26 micron to 61 micron and quite particularly preferably ranging from 30 micron to 50 micron.
  • the multi-layer polarized film has a total thickness ranging from 70 micron to 350 micron, preferably ranging from 76 micron to 333 micron, further preferably ranging from 80 micron to 321 micron, particularly preferably ranging from 83 micron to 311 micron and quite particularly preferably ranging from 81 micron to 291 micron.
  • a polarized adhesion layer preferably a PVA layer comprising at least one dichroic dye and/or iodine, in the spectacle lens being an outer layer of the multi-layer polarized film, and thus being a layer in direct contact with the high refractive index lens substrate.
  • at least one polarized adhesion layer is in direct contact with the convex side of the high refractive index lens substrate to be positioned opposite to the wearer’eye in a spectacle.
  • the other, non-polarized adhesion layer is a layer that also bonds well to the high refractive index lens substrate, preferably to the high refractive index lens substrate on the concave side of the multi-layer film facing the wearer’s eye.
  • the non-polarized adhesion layer will be described below after the description of the preferred high refractive index lens substrates.
  • the at least one transparent support layer of the multi-layer polarized film preferably acts to provide isotropic support to the adhesion layers and thus to the multi-layer polarized film, particularly during manufacture of the film and its subsequent handling and use during the manufacture of spectacle lenses.
  • the at least one support layer preferably has a layer thickness in the range of from 60 micron to 160 micron, preferably from 70 micron to 100 micron, further preferably from 73 micron to 88 micron, particularly preferably about 80 micron and quite particularly preferably in the range of from 77 micron to 84 micron.
  • the at least one support layer preferably has a tensile strength greater than or equal to 80 N/mm 2 , more preferably greater than or equal to 95 N/mm 2
  • at least one support layer preferably has a percent elongation (also known as “elongation after fracture” ) of greater than or equal to 15%, more preferably greater than or equal to 23%. If the multi-layer polarized film comprises more than one support layer, the before mentioned values apply accordingly.
  • the at least one support layer has a tensile strength greater or equal to 83 N/mm 2 and a percent elongation of greater than or equal to 17%.
  • the at least one support layer should not be too hard and should have a similar hardness to the lens substrate.
  • the at least one support layer has a hardness in the range of 60 to 120 N/mm 2 , further preferably in the range of 71 to 116 N/mm 2 , particularly preferably in the range of 86 to 113 N/mm 2 and quite particularly preferably in the range of 100 to 110 N/mm 2 .
  • Hardness is defined as ball indentation hardness, with 30 pieces of stacked film and a measured time of 30s.
  • the at least one support layer is too hard then there can be a film separation affect during edging due to the resistance of the support layer to edging, particularly when edging equipment such as diamond composite grinding wheels are used.
  • the at least one support layer is too soft then there can occur distortions within the layer itself which appear as optical waves in the spectacle lens because the support layer is not providing sufficient rigidity to resist the influence of shrinkage and monomer flows during curing.
  • the at least one support layer may be a transparent polymer such as cellulose based polymers such as diacetylcellulose and triacetyl cellulose (TAC) , cellulose acetate butyrate (CAB) ; polycarbonate (PC) based polymers; polyester based polymers such as polyethylene terephthalate (PET) , polyethyleneterephthalate glycol (PETG) and polyethylene naphthanate; dimethyl terephthalate (DMT) ; acrylate based polymers such as polymethacrylate (PMA) , polyethylacrylate; methacrylate polymers such as polymethyl methacrylate (PMMA) , polyethyl methylacrylate; thermoplastic urethane polymers (TPU) ; polythiourethane based polymers; vinyl based polymers such polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral; styrene based polymers such as polys
  • the at least one transparent support layer will be triacetyl cellulose (TAC) , polycarbonate (PC) , cellulose acetate butyrate (CAB) , polymethyl methacrylate (PMMA) , or polyethylene terephthalate (PET) .
  • TAC triacetyl cellulose
  • PC polycarbonate
  • CAB cellulose acetate butyrate
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • the at least one transparent support layer will be TAC, PET or PC, with TAC most preferred.
  • the polymers usable as a support layer have high optical clarity and bond well with polyvinyl alcohol-type polarising layers.
  • the high refractive index lens substrate is preferably selected from one or more of the group consisting of polyurethanes, such as urethane and thiourethane polymers and copolymers, episulfides, halogen substituted derivatives of bisphenol-A, and aromatic (meth) acrylic copolymers.
  • the high refractive index lens substrate will be a polyurethane, preferably a urethane or thiourethane polymer or copolymer.
  • the high refractive index lens substrate will be a thiourethane polymer or copolymer obtained by polymerisation of isocyanate compounds and thiol compounds.
  • Suitable isocyanate compounds can be classified as aromatic compounds, aliphatic compounds and alicyclic compounds, and can be such as:
  • Suitable thiol compounds can be classified as aromatic thiol compounds, aliphatic and alicyclic thiol compounds, and can be such as:
  • Especially preferred high refractive index thiourethane lens substrates are those manufactured by Mitsui Chemicals Inc. under the MR Series brand, particularly the MR-7 TM , MR-8 TM and MR-10 TM thiourethanes.
  • the preferred material may be a polyvinyl alcohol-type layer, preferably a layer of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , or a saponified (ethylene/vinyl acetate) copolymer.
  • PVA polyvinyl alcohol
  • PVF polyvinyl formal
  • PVc polyvinyl acetate
  • saponified (ethylene/vinyl acetate) copolymer ethylene/vinyl acetate
  • the material used as non-polarized adhesion layer ideally is matched to the high refractive index lens substrate so as to be a material that bonds/adheres well to the substrate, such as for instance would be the case with a PVA adhesion layer and a thiourethane lens substrate of the type mentioned above, preferably the thiourethane obtained by polymerisation of isocyanate compounds and thiol compounds.
  • PVA adheres well to the thiourethane because PVA has –OH functional groups which bond to isocyanate functional groups in the same way as an isocyanate monomer reacts with a thiol or polyol monomer.
  • a known type of polyurethane adhesive such as a thermal or UV curable glue, a hot melt adhesive (HMA) , or a pressure sensitive adhesive (PSA) , may be used as non-polarized adhesion layer.
  • a thermal or UV curable glue such as a thermal or UV curable glue, a hot melt adhesive (HMA) , or a pressure sensitive adhesive (PSA)
  • HMA hot melt adhesive
  • PSA pressure sensitive adhesive
  • adhesion layers and/or the support layer (s) may incorporate one or more functional dyes containing active optical properties such as fashion coloured dyes, enhanced spectral coloured dyes, blue spectral absorbing dyes, UV absorbing dyes, photochromic dyes, infrared absorption dyes, narrow band absorption dyes, or combinations thereof.
  • functional dyes containing active optical properties such as fashion coloured dyes, enhanced spectral coloured dyes, blue spectral absorbing dyes, UV absorbing dyes, photochromic dyes, infrared absorption dyes, narrow band absorption dyes, or combinations thereof.
  • fixed colour dyes may be added to the second adhesion layer, being the layer of the multi-layer polarising film on the concave side, next, but not necessarily adjacent, to the substrate surface, whilst the first adhesion layer, being the layer of the multi-layer polarising film on the convex side, next, but not necessarily adjacent, to the substrate surface, already contains dichroic dyes or some other functional dyes.
  • the fixed colour dye in this case could have spectral properties that benefit the spectacle wearer by enhancing or blocking specific light wavelengths. Examples would be the addition of blue blocking dyes, UV blocking dyes or narrow wavelength colour blocking dyes.
  • Dyes could also be added to the at least one supporting layer during its manufacture. Therefore, in one embodiment of the invention, where the multi-layer polarized film includes only two adhesion layers and one support layer in-between, it is possible that each of the three layers of the multi-layer polarized film could have a different function.
  • the second adhesion layer could contain UV absorbing dyes
  • the support layer could contain a narrow wavelength fixed colour dye
  • the first adhesion layer could contain dichroic dyes for glare protection.
  • the first adhesion layer is the layer of the multi-layer polarized film which is located on the convex side, opposite to a wearer’s eye in a spectacle, whereas the second adhesion layer is located on the concave side facing a wearer’s eye in a spectacle.
  • the refractive index of the layers of the multi-layer polarized film will match the refractive index of the lens substrate.
  • PET in relation to the support layer, PET has a refractive index (1.575) that closely matches to a 1.592 refractive index lens substrate material such as the preferred MR-8 TM thiourethane material mentioned above, and thus is one preferred material for the at least one support layer.
  • TAC as support layer gives a better performance in casting, but has a refractive index of 1.47 to 1.49, which is somewhat further away from the preferred MR-8 TM thiourethane material refractive index of 1.592 mentioned above.
  • PVA usable as adhesion layer, has a refractive index of about 1.52 to 1.55.
  • the greater the difference in refractive index between the layers means that reflections (annoying to wearers of spectacle lenses) are more likely and more persistent. Also, reflected light can interfere with incoming light in such a way to cause interference fringes which manifest as bands of coloured reflections from constructive and destructive light wave interference. This is likely when the layer thicknesses are very small and close to multiples or halves of the wavelength of the incoming light. In the case of the multi-layer polarized film in the present invention, the thicknesses of the layers are preferably much larger than that required to affect interference fringes that result in coloured reflections. Therefore, the larger refractive index difference between TAC, PVA and the preferred thiourethane substrates tend not to have the effect of creating interference fringes.
  • the multi-layer polarized film may be applied on one of the surfaces of the high refractive index lens substrate, namely the convex side of the surface intended to face the wearer’s eye or the concave side of the surface intended to face the surface opposite to the wearer’s eye.
  • the multilayer polarized film is embedded in the high refractive index lens substrate.
  • the thickness of the lens substrate on concave side is preferably in the range of from 0.35 mm to 17.90 mm, further preferably in the range of from 0.36 mm to 17.00 mm, particularly preferably in the range of from 0.37 mm to 16.00 mm and particularly preferably in the range of from 0.38 mm to 15.80 mm, and the thickness of the lens substrate on the convex side is preferably in the range of from 0.41 mm to 1.19 mm, further preferably in the range of from 0.42 mm to 1.15 mm, particularly preferably in the range of from 0.43 mm to 1.13 mm and particularly preferably in the range of from 0.44 mm to 1.10 mm.
  • the present invention also provides a process for the production of the high refractive index polarized spectacle lens described above, the process including the steps of
  • a. forming a multi-layer polarized film comprising a transparent support layer between a first adhesion layer and a second adhesion layer, wherein at least one adhesion layer is a polarized adhesion layer;
  • step b stabilizing the shaped film of step b;
  • step c placing the shaped and stabilized film of step c within a lens casting assembly for the mould;
  • the shape matching of step b is achieved by taking the flat multi-layer polarized film and cutting the film to a pre-determined shape, placing the cut film onto a bending machine where it is clamped in position, applying the curved shape to the film via a mould pressing step where the press mold is heated, allowing the shape to form and stabilise, cooling and removal of the shaped film from the bending machine.
  • step c the shaped film is further stabilised by placing the shaped film between matching glass setting moulds which are then placed in an oven to set the film curve.
  • the curing step g is done by placing the filled assembly inside an air circulating oven and applying a temperature profile cure designed to provide a gentle shrinkage rate and avoid creation of bubbles and strain during the curing.
  • the shaped multi-layer polarized film is typically positioned towards the front of the lens mould, and thus the front convex side of the spectacle lens, preferably at a depth from the front surface of 0.4 mm to 1.2 mm, or at the front of the lens mould, to avoid depolarisative effects due to birefringent polymer in front of the polarized film.
  • the multi-layer polarized film is embedded in the high refractive index lens substrate in such a way that the at least one polarized adhesion layer of the multi-layer polarized film is facing the front convex side of the lens where income light passes firstly in order to block horizontally polarized light known as glare before being depolarized by bulk polymer.
  • the high refractive index, polarized spectacle lens comprises a high refractive index lens substrate and a multi-layer polarized film, wherein the multi-layer polarized film embedded in the lens substrate comprises at least:
  • a non-polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer, a polyvinyl formal (PVF) layer, a polyvinyl acetate (PVAc) layer, a saponified (ethylene/vinyl acetate) copolymer layer, a polyurethane adhesive layer, a holt melt adhesive (HMA) layer, a pressure sensitive adhesive (PSA) layer,
  • PVA polyvinyl alcohol
  • PVF polyvinyl formal
  • PVAc polyvinyl acetate
  • saponified (ethylene/vinyl acetate) copolymer layer a polyurethane adhesive layer
  • HMA holt melt adhesive
  • PSA pressure sensitive adhesive
  • a transparent support layer comprising a triacetyl cellulose (TAC) layer, a polycarbonate (PC) layer, a cellulose acetate butyrate (CAB) layer, a polymethyl methacrylate (PMMA) layer or a polyethylene terephthalate (PET) layer and
  • TAC triacetyl cellulose
  • PC polycarbonate
  • CAB cellulose acetate butyrate
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • a polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer, a polyvinyl formal (PVF) layer, a polyvinyl acetate (PVAc) layer or a saponified (ethylene/vinyl acetate) copolymer layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine,
  • PVA polyvinyl alcohol
  • PVF polyvinyl formal
  • PVAc polyvinyl acetate
  • saponified (ethylene/vinyl acetate) copolymer layer the polarized adhesion layer comprising at least one dichroic dye and/or iodine
  • the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
  • the high refractive index, polarized spectacle lens comprises a high refractive index lens substrate comprising a urethane or thiourethane polymer or copolymer and a multi-layer polarized film, wherein the multi-layer polarized film embedded in the lens substrate comprises at least:
  • a non-polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer or a polyvinyl formal (PVF) layer, having a layer thickness in the range of from 26 micron to 62 micron, preferably in the range of from 29 micron to 52 micron,
  • PVA polyvinyl alcohol
  • PVF polyvinyl formal
  • a transparent support layer comprising a triacetyl cellulose (TAC) layer, a polycarbonate (PC) layer or a polyethylene terephthalate (PET) layer, having a layer thickness in the range of from 69 micron to 89 micron, preferably in the range of from 76 micron to 86 micron, and
  • TAC triacetyl cellulose
  • PC polycarbonate
  • PET polyethylene terephthalate
  • a polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer or a polyvinyl acetate (PVAc) layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine, having a layer thickness in the range of from 23 micron to 63 micron, preferably in the range of from 24 micron to 56 micron,
  • the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
  • a non-polarized adhesion layer adjacent to the lens substrate comprising a polyvinyl alcohol (PVA) layer or a polyurethane adhesive layer,
  • PVA polyvinyl alcohol
  • a transparent support layer comprising a triacetyl cellulose (TAC) layer or a polyethylene terephthalate (PET) layer, and
  • a polarized adhesion layer adjacent to the lens substrate comprising a polyvinyl alcohol (PVA) layer or a polyvinyl formal (PVF) layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine,
  • PVA polyvinyl alcohol
  • PVF polyvinyl formal
  • the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
  • a non-polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer or a polyurethane adhesive layer,
  • a transparent support layer comprising a triacetyl cellulose (TAC) layer or a polyethylene terephthalate (PET) layer,
  • TAC triacetyl cellulose
  • PET polyethylene terephthalate
  • a non-polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer or a polyurethane adhesive layer,
  • a polarized adhesion layer adjacent to the lens substrate comprising a polyvinyl alcohol (PVA) layer or a polyvinyl formal (PVF) layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine,
  • PVA polyvinyl alcohol
  • PVF polyvinyl formal
  • the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
  • the high index, polarised ophthalmic lens is formed from a high index lens substrate and a multi-layer polarised film, the multi-layer polarised film including a transparent support layer between a first adhesion layer and a second adhesion layer, wherein one or both of the adhesion layers is a polarised layer.
  • Figure 1 is a side elevation, in cross-section, of a high refractive index, polarized spectacle lens in accordance with an embodiment of the present invention.
  • Figure 2 is a side elevation, in cross-section, of the multi-layer polarized film seen in Figure 1, prior to use in an spectacle lens, showing two protective layers for the film, the protective layers being used prior to manufacture of the spectacle lens of Figure 1.
  • FIG. 1 Illustrated in Figure 1 is a high refractive index, polarized spectacle lens 10 showing the orientation of a multi-layer polarized film 12 embedded in a high refractive index lens substrate (14a, 14b) .
  • the lens substrate is formed either side of the front side and the back side of the film 12, being the convex side 14a and the concave side 14b respectively.
  • the lens substrate is preferably a thiourethane lens substrate, further preferred the MR-8 TM thiourethane material mentioned above.
  • the multi-layer polarized film 12 has three layers, i.e. layer 12a, layer 12b and layer 12c.
  • Layer 12a is a polarized adhesion layer, being a stretched PVA layer with a layer thickness ranging from between 20 micron and 120 micron, and more preferably ranging from between 30 micron and 50 micron, and containing at least one dichroic dye.
  • Layer 12b is a support layer with a thickness ranging from between 60 micron and 160 micron, further preferably ranging from between 70 micron and 100 micron and particularly ranging from between 76 micron and 84 micron, which in this preferred embodiment is TAC.
  • This TAC support layer is characterized by a ball indentation hardness ranging from 60 to 120 N/mm 2 , a tensile strength greater than or equal to 80 N/mm 2 and a percent elongation greater than or equal to 15%.
  • Layer 12c is a non-polarized adhesion layer, whose role is essentially for adhesion purposes and is again a PVA layer, with a thickness ranging from between 20 micron and 120 micron, or more preferably ranging from between 30 micron and 50 micron.
  • PVA is ideal as an adhesion layer when the lens substrate is a polyurethane because the isocyanate functional groups in the urethane chemically bonds to the available -OH groups in the PVA during curing, providing a strong adhesion between the urethane substrate and the adhesion layer.
  • layer 12c could also be a functional adhesion layer, again being a stretched PVA layer containing dichroic dyes, photochromic dyes, broad band fixed color dyes, narrow band fixed color dyes, UV absorbing dyes, or other functional dyes. It should also be appreciated that layers 12a and 12c could have additional functional purposes, in addition to providing adhesion to a lens substrate.
  • the polarized adhesion layer 12a be positioned on the convex side of the film 12 during the formation of the film 12, in order to avoid any de-polarisation affects in the final spectacle lens.
  • the active polarizing layer is on the concave side, the light must pass through the convex side 14a of the lens, through the non-polarized adhesion layer adjacent to the substrate 14a and through the support layer before being filtered through the polarizing. The light passing through so many layers could be partially de-polarized before reaching an active polarizing layer, which can reduce the efficiency of the polarizing filter.
  • the thickness of the lens substrate on the convex side 14a of the lens will be no thicker than 1.2 mm, and will be in the range of 0.4 mm to 1.2 mm thick.
  • the thickness of the lens substrate on the concave side 14b will be no thinner than 0.3 mm, and will be in the range of 0.3 mm to 18.00 mm thick.
  • Shown in Figure 2 is the multi-layer polarized film 12 of Figure 1, prior to being embedded in a lens substrate and thus prior to the formation of an spectacle lens.
  • the layers marked as layers 20 and 22 are protective layers, present to protect the layer underneath against dirt and fluff accumulation on a surface of the film 12 from the environment, as well as protection against scratching and contact damage during handling and prior to use.
  • the protective layers thus remain on the film during transportation, film cutting, handling and bending, and are removed at the point of assembly in a clean environment thereby providing the best opportunity for the production of a clean, high quality spectacle lens.
  • Protective layers 20 and 22 can be constructed from different materials or can be of the same material. Typical materials used for the protective layers 20, 22 are polypropylene (PP) or polyethylene (PE) , which are ideally about 30 micron in thickness. In this respect, a PE protective layer is generally harder to peel away whereas a PP protective layer is easier to peel but can impart its texture to the layer underneath during lamination and bending processes. PE is thus the preferred material. For thermal resistance during the bending process, a protective layer that is a laminate combining both PE and PP can also be used.
  • the protective layers 20, 22 will be lightly held against the underlying multi-layer polarized film 12 so that the protective layers 20, 22 can be easily peeled away by hand.
  • lightly held means that the layer is not chemically bonded to a surface, but is held by weak localized static and vacuum forces.
  • no adhesive is used between the protective layers 20, 22 and the adhesion layers 12a, 12c.
  • first intermediate layer 24 that is a primer which binds chemically to the layers 12a and 12b.
  • second intermediate layer 26 can also be seen, which binds layers 12b and 12c together.
  • the intermediate layers 24, 26 can be the same or a different material, and in this embodiment are either a thermally curable or UV curable primer resin, and are ideally between about 1 micron and 4 micron in thickness.

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Abstract

A high refractive index, polarized spectacle lens (10) and a process for the production of the lens are provided. The lens (10) comprises a high refractive index lens substrate (14a,14b) and a multi-layer polarized film (12), the multi-layer polarized film (12) comprising at least one transparent support layer (12b) and at least two adhesion layers (12a,12c), wherein at least one of the adhesion layers is a polarized adhesion layer (12a).

Description

HIGH REFRACTIVE INDEX POLARIZED SPECTACLE LENS TECHNICAL FIELD
The present invention relates to spectacle lenses for spectacles, particularly for sunglasses, the spectacle lenses being polarized lenses formed from a high refractive index substrate such as a polyurethane.
BACKGROUND OF INVENTION
Spectacle lenses are those that are used in spectacles, for either outdoor or indoor use, typically providing corrective vision for wearers to accommodate for physiological errors in the human eye, but also being plano and being for aesthetic, protective or fashion purposes. Glass and plastic have both been successfully used as substrates for spectacle lenses, with plastic lenses becoming popular from the 1960’s with the advent of new plastics with improved properties.
Some common plastic materials used to manufacture spectacle lenses include polyethylene glycol diallyl dicarbonate (CR39TM) and polycarbonate. In response to a need to produce thinner lenses, a number of "high index" plastic materials have been developed for the manufacture of spectacle lenses, and are now very popular and very successful. These “high index” materials have a higher refractive index (typically above 1.55) than other conventional plastic materials, which means that they bend light more than the conventional plastic materials. As a result, less high refractive index lens material needs to be used to produce the same prescription than with a conventional plastic material. This desirably results in lenses that are lighter with thinner edges.
Spectacle lenses for outdoor use, usually referred to as sunglass lenses, have traditionally been uniformly tinted so as to reduce glare and light transmission for the comfort of the wearer. However, these lenses indiscriminately filter all light whether it is aligned horizontally or vertically -glare is dampened, but not eliminated. More importantly, by filtering all components of light, visual acuity is diminished.
Light is made up of waves travelling in different directions. Vertical light is useful to the human eye, however horizontal light commonly exists in higher proportions as glare. Glare is concentrated light reflecting off a horizontal shiny surface, such as a car windscreen, sand, water, snow or asphalt roads, which reduces visibility and can make it uncomfortable, painful or even dangerous to carry on driving, cycling, skiing, etc. Accordingly, polarized spectacle lenses were developed for outdoor use that allow the vertical component of light, which is preferred for clear vision, to pass, while eliminating the easily scattered and skewed horizontal component of light. Vertically aligned light is preferred because it respects the natural tendency of the visual system to focus on the vertical component of an image.
Typically, polarized spectacle lenses include linear polarized film layers, such as polyvinyl alcohol polymer layers, having aligned dichroic dyes to extinguish the horizontal component of reflected sunlight. In this respect, the components of light that are aligned with the axis of the polarizer are absorbed, allowing only the light oscillating with a wave aligned perpendicular to the axis of the polarizer to pass through the polarized film layer. Such polarized film layers are however very delicate and readily absorb moisture during handling and manufacture. Accordingly, it is usual to encapsulate such polarized film layers in protective and supportive outer layers, forming a multi-layer polarizing film.
With such traditional multi-layer polarizing films, it has been found that some of the more recently developed high refractive index lens substrates such as polyurethanes have difficulty bonding to the usual supportive outer layers of the multi-layer polarising film, which have been developed for the more common polyethylene glycol diallyl dicarbonate (CR39TM) and polycarbonate lens substrates. As a result, with high refractive index lens substrates, single-layer polarising films (for example having a single polyvinyl alcohol polymer layer) have been adopted, without the supportive outer layers, which have proven to be difficult to use and have thus resulted in lower take-up of high refractive index lens substrates for polarized spectacle lenses.
It is an aim of the present invention to provide a high refractive index, polarized spectacle lens, ideally for use as a sunglass lens, which is easier to manufacture.
SUMMARY OF INVENTION
The present invention provides a high refractive index, polarized spectacle lens comprising a high refractive index lens substrate and a multi-layer polarized film, the multi-layer polarized film comprising at least one support layer and at least two adhesion layers, wherein at least one adhesion layers is a polarized adhesion layer.
Preferred embodiments of the invention are given in the dependant claims 2 to 12.
The present invention further provides a process for the production of a high refractive index, polarized spectacle lens, comprising a high refractive index lens substrate and a multi-layer polarized film. The present invention further discloses a spectacle comprising a high refractive index, polarized spectacle lens and the use of a high refractive index, polarized spectacle lens in a spectacle.
Within the meaning of this application, a high refractive index preferably is a refractive index of n ≥ 1.515, particularly preferably of n ≥ 1.520 and quite particularly preferably of n ≥ 1.533.
The inventive high refractive index, polarized spectacle lenses may have vision correcting properties or not.
It will be appreciated that, throughout this specification, when reference is made to the adhesion and support layers being between or adjacent to other layers, or being internal or external, this does not preclude the possibility of there being other functional layers between or adjacent those adhesion and support layers. For example, an adhesion layer could be coated with another layer which could function as a barrier layer as well as a further adhesion layer. The function of such a barrier layer might be to prevent interaction of isocyanates in the lens substrate with dyes in  a PVA adhesion layer, for example, during lens curing (to otherwise prevent large colour shifts) . Additionally, intermediate layers may be provided between adhesion layers and the support layer, such intermediate layers being provided if e.g. assistance is needed with the chemical or physical bonding of the adhesion layers to the support layer.
In one embodiment of the invention, the multi-layer polarized film is protected by protective layers not necessary in the spectacle lens, but present to protect the multi-layer film against inter alia dirt, scratching or other damages during handling and prior to use. The protective layers remain on the multi-layer polarized film during transportation, film cutting, handling and bending, and are removed at the point of assembly, preferably in a clean environment, to produce the inventive high refractive index polarized spectacle lens.
The adhesion layers preferably comprise a polyvinyl alcohol-type layer selected from one or more of the group of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , a saponified (ethylene/vinyl acetate) copolymer, or a mixture thereof. An adhesion layer may be either a polarized adhesion layer or a non-polarized adhesion layer.
Ideally, each adhesion layer adjacent to the high refractive index lens substrate has an adhesion strength between the adhesion layer and the lens substrate that is equal to or greater than 60 N/mm2, preferably equal to or greater than 73 N/mm2, further preferably equal to or greater than 86 N/mm2 and more preferably equal to or greater than 100 N/mm2, in order to have sufficient resistance to lens edging during prescription frame-fitting to avoid undesirable layer separation. In a preferred embodiment the adhesion strength between the adhesion layer and the lens substrate is in the range of from 93 N/mm2 to 380 N/mm2, preferably in the range of from 109 N/mm2 to 355 N/mm2, further preferably in the range of from 121 N/mm2 to 340 N/mm2, particularly preferably in the range of from 135 N/mm2 to 322 N/mm2 and particularly preferably in the range of from 151 N/mm2 to 301 N/mm2. In this respect, the adhesion strength referred to here is that measured by layer separation using a universal testing machine (preferably an InstronTM twin motorised ball screw universal testing machine) .
According to the invention, at least one adhesion layer is a polarized adhesion layer, being a layer having polarizing properties by incorporating one or more dichroic dyes, iodine, or other suitable dyes into the adhesion layer, preferably a polyvinyl alcohol-type layer. The adhesion layer having polarizing properties, preferably a polyvinyl alcohol-type layer, may be a layer of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , a saponified (ethylene/vinyl acetate) copolymer or a blend thereof. A layer of PVA is preferred as adhesion layer having polarizing properties.
Typical dichroic dyes comprise at least one of the functional groups: an azo-compound bearing the functional group R-N＝N-R’, in which R and R’can be either aryl or alkyl； a naphtha-compound； or an anthraquinone compound. Typical, non-limiting, examples include: C.I. Direct Blue 67, C.I. Direct Blue 90, C.I. Direct Blue 200, C.I. Direct Green 59, C.I. Direct Violet 48, C.I. Direct Red 39, C.I. Direct Red 81, C.I. Direct Red 83, C.I. Direct Red 89, C.I. Direct Orange 39, C.I. Direct Orange 72, C.I. Direct Yellow 34, C.I. Direct Green 26, C.I. Direct Green 27, C.I. Direct Green 28, C.I. Direct Green 51, C.I. Direct Black 170, and combinations thereof.
In one embodiment of the invention, the multi-layer polarized film comprises two discrete adhesion layers having polarizing properties directly adjacent to each other, wherein the two layers are of a different chemical composition, e.g. a PVA layer and a PCAc layer. In this embodiment identical or different dichroic dyes and/or iodine may be incorporated in the two layer.
In a preferred embodiment of the invention, the multi-layer polarized film comprises only one discrete adhesion layer having polarizing properties adjacent to the high refractive index substrate and/or an adhesion layer and/or a support layer. The discrete adhesion layer having polarizing properties preferably comprises PVA and at least one dichroic dye and/or iodine.
Each adhesion layer of the multi-layer polarized film, irrespective of whether the adhesion layer is polarized or not, preferably has a layer thickness  ranging from about 20 micron to about 120 micron, further preferably ranging from 20 micron to 120 micron, further preferably ranging from 23 micron to 100 micron, further preferably ranging from 24 micron to 75 micron, particularly preferably ranging from 26 micron to 61 micron and quite particularly preferably ranging from 30 micron to 50 micron.
In one embodiment of the invention, the multi-layer polarized film has a total thickness ranging from 70 micron to 350 micron, preferably ranging from 76 micron to 333 micron, further preferably ranging from 80 micron to 321 micron, particularly preferably ranging from 83 micron to 311 micron and quite particularly preferably ranging from 81 micron to 291 micron.
PVA bonds well with high refractive index lens substrates and is thus a good choice for an adhesion layer that may be also a polarized layer. In a preferred embodiment of the present invention, a polarized adhesion layer, preferably a PVA layer comprising at least one dichroic dye and/or iodine, in the spectacle lens being an outer layer of the multi-layer polarized film, and thus being a layer in direct contact with the high refractive index lens substrate. Preferably at least one polarized adhesion layer is in direct contact with the convex side of the high refractive index lens substrate to be positioned opposite to the wearer’eye in a spectacle.
If only one of the adhesion layers of a multi-layer film consisting of two adhesion layers and one support layer is a polarized adhesion layer, then it is preferred for the other, non-polarized adhesion layer to be a layer that also bonds well to the high refractive index lens substrate, preferably to the high refractive index lens substrate on the concave side of the multi-layer film facing the wearer’s eye. For ease of understanding, preferred options for such a non-polarized adhesion layer will be described below after the description of the preferred high refractive index lens substrates.
The at least one transparent support layer of the multi-layer polarized film preferably acts to provide isotropic support to the adhesion layers and thus to the multi-layer polarized film, particularly during manufacture of the film and its subsequent handling and use during the manufacture of spectacle lenses. In the  preferred form, there is only one such support layer in the multi-layer film, and it is located between the two adhesion layers, one or both of which are the polarized layers.
The at least one support layer preferably has a layer thickness in the range of from 60 micron to 160 micron, preferably from 70 micron to 100 micron, further preferably from 73 micron to 88 micron, particularly preferably about 80 micron and quite particularly preferably in the range of from 77 micron to 84 micron. The at least one support layer preferably has a tensile strength greater than or equal to 80 N/mm2, more preferably greater than or equal to 95 N/mm2 Further, at least one support layer preferably has a percent elongation (also known as “elongation after fracture” ) of greater than or equal to 15％, more preferably greater than or equal to 23％. If the multi-layer polarized film comprises more than one support layer, the before mentioned values apply accordingly. In a preferred embodiment of the present invention, the at least one support layer has a tensile strength greater or equal to 83 N/mm2 and a percent elongation of greater than or equal to 17％.
Ideally, the at least one support layer should not be too hard and should have a similar hardness to the lens substrate. Preferably the at least one support layer has a hardness in the range of 60 to 120 N/mm2, further preferably in the range of 71 to 116 N/mm2, particularly preferably in the range of 86 to 113 N/mm2 and quite particularly preferably in the range of 100 to 110 N/mm2. Hardness is defined as ball indentation hardness, with 30 pieces of stacked film and a measured time of 30s. In this respect, if the at least one support layer is too hard then there can be a film separation affect during edging due to the resistance of the support layer to edging, particularly when edging equipment such as diamond composite grinding wheels are used. If the at least one support layer is too soft then there can occur distortions within the layer itself which appear as optical waves in the spectacle lens because the support layer is not providing sufficient rigidity to resist the influence of shrinkage and monomer flows during curing.
The at least one support layer may be a transparent polymer such as cellulose based polymers such as diacetylcellulose and triacetyl cellulose (TAC) , cellulose acetate butyrate (CAB) ； polycarbonate (PC) based polymers； polyester  based polymers such as polyethylene terephthalate (PET) , polyethyleneterephthalate glycol (PETG) and polyethylene naphthanate； dimethyl terephthalate (DMT) ； acrylate based polymers such as polymethacrylate (PMA) , polyethylacrylate； methacrylate polymers such as polymethyl methacrylate (PMMA) , polyethyl methylacrylate； thermoplastic urethane polymers (TPU) ； polythiourethane based polymers； vinyl based polymers such polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral； styrene based polymers such as polystyrene, styrene methylmethacrylate copolymers (SMMA) , styrene maleic anhydride polymers (SMA) , acrylonitrile-styrene (ANS) copolymers, acrylonitrile butadiene styrene (ABS) terpolymers, (meth) acrylate butadiene styrene (MBS) terpolymers； olefin based polymers such as polyethylene, polypropylene, polymethylpentene (PMP) , cyclic (COC) or norboraene structure-containing polyolefins, and ethylene-propylene copolymers； amide based polymers such as nylon and aromatic polyamides； imide based polymers； polyether imide based polymers； polysulfone based polymers； polyether sulfone based polymers； polyether ether ketone based polymers； polyphenylene sulfide based polymers； polyoxymethylene based polymers； and epoxy based polymers, or any blend thereof. In a preferred form, the at least one transparent support layer will be triacetyl cellulose (TAC) , polycarbonate (PC) , cellulose acetate butyrate (CAB) , polymethyl methacrylate (PMMA) , or polyethylene terephthalate (PET) . In a particularly preferred form, the at least one transparent support layer will be TAC, PET or PC, with TAC most preferred. Preferably the polymers usable as a support layer have high optical clarity and bond well with polyvinyl alcohol-type polarising layers.
The high refractive index lens substrate is preferably selected from one or more of the group consisting of polyurethanes, such as urethane and thiourethane polymers and copolymers, episulfides, halogen substituted derivatives of bisphenol-A, and aromatic (meth) acrylic copolymers. In a preferred form, the high refractive index lens substrate will be a polyurethane, preferably a urethane or thiourethane polymer or copolymer.
In a particularly preferred form, the high refractive index lens substrate will be a thiourethane polymer or copolymer obtained by polymerisation of isocyanate compounds and thiol compounds. Suitable isocyanate compounds can be classified  as aromatic compounds, aliphatic compounds and alicyclic compounds, and can be such as:
Aromatic Isocyanate Compounds
2, 4-Toluylendiisocyanate
1, 5-Naphthalenediisocyanate
4, 4'-Diphenylmethanediisocyanate
4, 4'-Diphenylsulfonediisocyanate
Aliphatic Isocyanate Compounds
Hexamethylene diisocyanate
Octamethylene diisocyanate
Bis (isocyanatoethyl) sulphide
Bis (isocyanatoethyl) disulphide
m-Xylylenediisocyanate
Alicyclic Isocyanate Compounds
Isophoronediisocyanate
4, 4'-Diisocyanatodicyclohexylmethane
1, 3-Bis (isocyanatomethyl) cyclohexane
2, 5 (6) -Bis (isocyanatemethyl) bicyclo- [2.2.1] -heptane
Suitable thiol compounds can be classified as aromatic thiol compounds, aliphatic and alicyclic thiol compounds, and can be such as:
Aromatic Thiol Compounds
1, 3-Dimercaptobenzene
1, 3, 5-Trimercaptobenzene
Bis (mercaptophenyl) sulphide
Aliphatic and Alicyclic Thiol Compounds
Pentaerythritol tetra (3-mercaptopropionate)
Pentaerythritol tetra (2-mercaptoacetate)
4-Mercaptomethy-1, 8-dimercapt-3, 6-dithiaoctane
5, 7-Dimercaptomethyl-1, 11-dimercapto-3, 6-trithiaundecane
Bis (mercaptoethyl) sulphide
2, 5-Bis (mercaptomethyl) -1, 4-dithiane
Especially preferred high refractive index thiourethane lens substrates are those manufactured by Mitsui Chemicals Inc. under the MR Series brand, particularly the MR-7TM, MR-8TM and MR-10TM thiourethanes.
Returning to a description of preferred materials for a non-polarized adhesion layer, where the multi-layer polarized film includes only one polarized adhesion layer, again the preferred material may be a polyvinyl alcohol-type layer, preferably a layer of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , or a saponified (ethylene/vinyl acetate) copolymer. In case the non-polarized adhesion layer is directly adjacent to the lens substrate, the material used as non-polarized adhesion layer ideally is matched to the high refractive index lens substrate so as to be a material that bonds/adheres well to the substrate, such as for instance would be the case with a PVA adhesion layer and a thiourethane lens substrate of the type mentioned above, preferably the thiourethane obtained by polymerisation of isocyanate compounds and thiol compounds. PVA adheres well to the thiourethane because PVA has –OH functional groups which bond to isocyanate functional groups in the same way as an isocyanate monomer reacts with a thiol or polyol monomer.
In one embodiment of the invention, alternatively to a polyvinyl alcohol-type layer, a known type of polyurethane adhesive, such as a thermal or UV curable glue, a hot melt adhesive (HMA) , or a pressure sensitive adhesive (PSA) , may be used as non-polarized adhesion layer.
It should also be noted that the adhesion layers and/or the support layer (s) may incorporate one or more functional dyes containing active optical properties such as fashion coloured dyes, enhanced spectral coloured dyes, blue spectral absorbing dyes, UV absorbing dyes, photochromic dyes, infrared absorption dyes, narrow band absorption dyes, or combinations thereof.
Indeed, in one form, where the multi-layer polarized film includes only two adhesion layers and one support layer in-between, fixed colour dyes may be added to the second adhesion layer, being the layer of the multi-layer polarising film on the concave side, next, but not necessarily adjacent, to the substrate surface, whilst the first adhesion layer, being the layer of the multi-layer polarising film on the convex side, next, but not necessarily adjacent, to the substrate surface, already contains dichroic dyes or some other functional dyes. The fixed colour dye in this case could have spectral properties that benefit the spectacle wearer by enhancing or blocking specific light wavelengths. Examples would be the addition of blue blocking dyes, UV blocking dyes or narrow wavelength colour blocking dyes.
Dyes could also be added to the at least one supporting layer during its manufacture. Therefore, in one embodiment of the invention, where the multi-layer polarized film includes only two adhesion layers and one support layer in-between, it is possible that each of the three layers of the multi-layer polarized film could have a different function. For example, the second adhesion layer could contain UV absorbing dyes, the support layer could contain a narrow wavelength fixed colour dye, whilst the first adhesion layer could contain dichroic dyes for glare protection. In this embodiment, the first adhesion layer is the layer of the multi-layer polarized film which is located on the convex side, opposite to a wearer’s eye in a spectacle, whereas the second adhesion layer is located on the concave side facing a wearer’s eye in a spectacle.
Ideally, the refractive index of the layers of the multi-layer polarized film will match the refractive index of the lens substrate. In this respect, in relation to the support layer, PET has a refractive index (1.575) that closely matches to a 1.592 refractive index lens substrate material such as the preferred MR-8TM thiourethane material mentioned above, and thus is one preferred material for the at least one support layer. However, TAC as support layer gives a better performance in casting, but has a refractive index of 1.47 to 1.49, which is somewhat further away from the preferred MR-8TM thiourethane material refractive index of 1.592 mentioned above. PVA, usable as adhesion layer, has a refractive index of about 1.52 to 1.55.
In this respect, the greater the difference in refractive index between the layers means that reflections (annoying to wearers of spectacle lenses) are more likely and more persistent. Also, reflected light can interfere with incoming light in such a way to cause interference fringes which manifest as bands of coloured reflections from constructive and destructive light wave interference. This is likely when the layer thicknesses are very small and close to multiples or halves of the wavelength of the incoming light. In the case of the multi-layer polarized film in the present invention, the thicknesses of the layers are preferably much larger than that required to affect interference fringes that result in coloured reflections. Therefore, the larger refractive index difference between TAC, PVA and the preferred thiourethane substrates tend not to have the effect of creating interference fringes.
However, general reflections are still persistent but similar to reflections from polarized lenses made using only single layer PVA polarized film where the PVA refractive index also has a large difference between it and a high refractive index substrate.
Finally, it will be appreciated that all layers in the multi-layer polarized film must be optically transparent.
In one embodiment of the invention, the multi-layer polarized film may be applied on one of the surfaces of the high refractive index lens substrate, namely the convex side of the surface intended to face the wearer’s eye or the concave side of the surface intended to face the surface opposite to the wearer’s eye.
In a preferred embodiment of the invention, the multilayer polarized film is embedded in the high refractive index lens substrate. In this preferred embodiment, the thickness of the lens substrate on concave side is preferably in the range of from 0.35 mm to 17.90 mm, further preferably in the range of from 0.36 mm to 17.00 mm, particularly preferably in the range of from 0.37 mm to 16.00 mm and particularly preferably in the range of from 0.38 mm to 15.80 mm, and the thickness of the lens substrate on the convex side is preferably in the range of from 0.41 mm to 1.19 mm, further preferably in the range of from 0.42 mm to 1.15 mm, particularly preferably in  the range of from 0.43 mm to 1.13 mm and particularly preferably in the range of from 0.44 mm to 1.10 mm.
The present invention also provides a process for the production of the high refractive index polarized spectacle lens described above, the process including the steps of
a. forming a multi-layer polarized film comprising a transparent support layer between a first adhesion layer and a second adhesion layer, wherein at least one adhesion layer is a polarized adhesion layer；
b. matching the shape of the polarized film to the shape of the front surface of an spectacle lens mould；
c. stabilizing the shaped film of step b；
d. placing the shaped and stabilized film of step c within a lens casting assembly for the mould；
e. holding the shaped polarized film close to the front mould surface by a gasket；
f. injecting a high refractive index lens substrate liquid monomer into the lens casting assembly via a filling port whereby the monomer is able to flow around the shaped polarized film covering both sides of the film to completely fill the assembly, and
g. curing the lens substrate around the polarized film to form an spectacle lens.
Preferably, the shape matching of step b is achieved by taking the flat multi-layer polarized film and cutting the film to a pre-determined shape, placing the cut film onto a bending machine where it is clamped in position, applying the curved shape to the film via a mould pressing step where the press mold is heated, allowing the shape to form and stabilise, cooling and removal of the shaped film from the bending machine.
Further preferably, in step c the shaped film is further stabilised by placing the shaped film between matching glass setting moulds which are then placed in an oven to set the film curve.
Further preferably, the curing step g is done by placing the filled assembly inside an air circulating oven and applying a temperature profile cure designed to  provide a gentle shrinkage rate and avoid creation of bubbles and strain during the curing.
In a preferred form, the shaped multi-layer polarized film is typically positioned towards the front of the lens mould, and thus the front convex side of the spectacle lens, preferably at a depth from the front surface of 0.4 mm to 1.2 mm, or at the front of the lens mould, to avoid depolarisative effects due to birefringent polymer in front of the polarized film. Preferably the multi-layer polarized film is embedded in the high refractive index lens substrate in such a way that the at least one polarized adhesion layer of the multi-layer polarized film is facing the front convex side of the lens where income light passes firstly in order to block horizontally polarized light known as glare before being depolarized by bulk polymer.
In a preferred embodiment of the invention, the high refractive index, polarized spectacle lens comprises a high refractive index lens substrate and a multi-layer polarized film, wherein the multi-layer polarized film embedded in the lens substrate comprises at least:
a) a non-polarized adhesion layer, comprising a polyvinyl alcohol (PVA) layer, a polyvinyl formal (PVF) layer, a polyvinyl acetate (PVAc) layer, a saponified (ethylene/vinyl acetate) copolymer layer, a polyurethane adhesive layer, a holt melt adhesive (HMA) layer, a pressure sensitive adhesive (PSA) layer,
b) a transparent support layer, comprising a triacetyl cellulose (TAC) layer, a polycarbonate (PC) layer, a cellulose acetate butyrate (CAB) layer, a polymethyl methacrylate (PMMA) layer or a polyethylene terephthalate (PET) layer and
c) a polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer, a polyvinyl formal (PVF) layer, a polyvinyl acetate (PVAc) layer or a saponified (ethylene/vinyl acetate) copolymer layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine,
wherein the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
In a further preferred embodiment of the invention, the high refractive index, polarized spectacle lens comprises a high refractive index lens substrate comprising a urethane or thiourethane polymer or copolymer and a multi-layer  polarized film, wherein the multi-layer polarized film embedded in the lens substrate comprises at least:
a) a non-polarized adhesion layer, comprising a polyvinyl alcohol (PVA) layer or a polyvinyl formal (PVF) layer, having a layer thickness in the range of from 26 micron to 62 micron, preferably in the range of from 29 micron to 52 micron,
b) a transparent support layer, comprising a triacetyl cellulose (TAC) layer, a polycarbonate (PC) layer or a polyethylene terephthalate (PET) layer, having a layer thickness in the range of from 69 micron to 89 micron, preferably in the range of from 76 micron to 86 micron, and
c) a polarized adhesion layer comprising a polyvinyl alcohol (PVA) layer or a polyvinyl acetate (PVAc) layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine, having a layer thickness in the range of from 23 micron to 63 micron, preferably in the range of from 24 micron to 56 micron,
wherein the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
In a particularly preferred embodiment of the invention, the high refractive index, polarized spectacle lens comprises a high refractive index lens substrate comprising a thiourethane polymer or copolymer having a refractive index n ＝ 1.5 bis 1.7, preferably n ＝ 1.592, and a multi-layer polarized film, wherein the multi-layer polarized film is preferably embedded in the lens substrate and comprises at least:
a) a non-polarized adhesion layer adjacent to the lens substrate, comprising a polyvinyl alcohol (PVA) layer or a polyurethane adhesive layer,
b) a transparent support layer, comprising a triacetyl cellulose (TAC) layer or a polyethylene terephthalate (PET) layer, and
c) a polarized adhesion layer adjacent to the lens substrate, comprising a polyvinyl alcohol (PVA) layer or a polyvinyl formal (PVF) layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine,
wherein the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
In a further embodiment of the invention, the high refractive index, polarized spectacle lens comprises a high refractive index lens substrate comprising a thiourethane polymer or copolymer having a refractive index n ＝ 1.5 bis 1.7,  preferably n ＝ 1.592, and a multi-layer polarized film, wherein the multi-layer polarized film is preferably embedded in the lens substrate and comprises at least:
a) a non-polarized adhesion layer, comprising a polyvinyl alcohol (PVA) layer or a polyurethane adhesive layer,
b) a transparent support layer, comprising a triacetyl cellulose (TAC) layer or a polyethylene terephthalate (PET) layer,
c) a non-polarized adhesion layer, comprising a polyvinyl alcohol (PVA) layer or a polyurethane adhesive layer,
d) a polarized adhesion layer adjacent to the lens substrate, comprising a polyvinyl alcohol (PVA) layer or a polyvinyl formal (PVF) layer, the polarized adhesion layer comprising at least one dichroic dye and/or iodine,
wherein the at least one polarized adhesion layer of the multi-layer polarized film is facing the lens substrate on the convex side opposite to a wearer’s eye.
In a further embodiment of the invention, the high index, polarised ophthalmic lens is formed from a high index lens substrate and a multi-layer polarised film, the multi-layer polarised film including a transparent support layer between a first adhesion layer and a second adhesion layer, wherein one or both of the adhesion layers is a polarised layer.
BRIEF DESCRIPTION OF DRAWINGS
Having briefly described the general concepts involved with the present invention, a preferred embodiment of a polarized spectacle lens will now be described that is in accordance with the present invention. However, it is to be understood that the following description is not to limit the generality of the above description.
In the drawings:
Figure 1 is a side elevation, in cross-section, of a high refractive index, polarized spectacle lens in accordance with an embodiment of the present invention； and
Figure 2 is a side elevation, in cross-section, of the multi-layer polarized film seen in Figure 1, prior to use in an spectacle lens, showing two protective layers for the film, the protective layers being used prior to manufacture of the spectacle lens of Figure 1.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
Illustrated in Figure 1 is a high refractive index, polarized spectacle lens 10 showing the orientation of a multi-layer polarized film 12 embedded in a high refractive index lens substrate (14a, 14b) . The lens substrate is formed either side of the front side and the back side of the film 12, being the convex side 14a and the concave side 14b respectively. In this embodiment, the lens substrate is preferably a thiourethane lens substrate, further preferred the MR-8TM thiourethane material mentioned above.
In a preferred embodiment of the invention, the multi-layer polarized film 12 has three layers, i.e. layer 12a, layer 12b and layer 12c. Layer 12a is a polarized adhesion layer, being a stretched PVA layer with a layer thickness ranging from between 20 micron and 120 micron, and more preferably ranging from between 30 micron and 50 micron, and containing at least one dichroic dye.
Layer 12b is a support layer with a thickness ranging from between 60 micron and 160 micron, further preferably ranging from between 70 micron and 100 micron and particularly ranging from between 76 micron and 84 micron, which in this preferred embodiment is TAC. This TAC support layer is characterized by a ball indentation hardness ranging from 60 to 120 N/mm2, a tensile strength greater than or equal to 80 N/mm2 and a percent elongation greater than or equal to 15％.
Layer 12c is a non-polarized adhesion layer, whose role is essentially for adhesion purposes and is again a PVA layer, with a thickness ranging from between 20 micron and 120 micron, or more preferably ranging from between 30 micron and 50 micron. PVA is ideal as an adhesion layer when the lens substrate is a polyurethane because the isocyanate functional groups in the urethane chemically  bonds to the available -OH groups in the PVA during curing, providing a strong adhesion between the urethane substrate and the adhesion layer.
As mentioned above, layer 12c could also be a functional adhesion layer, again being a stretched PVA layer containing dichroic dyes, photochromic dyes, broad band fixed color dyes, narrow band fixed color dyes, UV absorbing dyes, or other functional dyes. It should also be appreciated that  layers  12a and 12c could have additional functional purposes, in addition to providing adhesion to a lens substrate.
When configured for a polarized spectacle lens, it is preferred that the polarized adhesion layer 12a be positioned on the convex side of the film 12 during the formation of the film 12, in order to avoid any de-polarisation affects in the final spectacle lens. In this respect, if, in this embodiment, the active polarizing layer is on the concave side, the light must pass through the convex side 14a of the lens, through the non-polarized adhesion layer adjacent to the substrate 14a and through the support layer before being filtered through the polarizing. The light passing through so many layers could be partially de-polarized before reaching an active polarizing layer, which can reduce the efficiency of the polarizing filter.
In a further preferred embodiment of the invention, the thickness of the lens substrate on the convex side 14a of the lens will be no thicker than 1.2 mm, and will be in the range of 0.4 mm to 1.2 mm thick. The thickness of the lens substrate on the concave side 14b will be no thinner than 0.3 mm, and will be in the range of 0.3 mm to 18.00 mm thick.
Shown in Figure 2 is the multi-layer polarized film 12 of Figure 1, prior to being embedded in a lens substrate and thus prior to the formation of an spectacle lens. The layers marked as  layers  20 and 22 are protective layers, present to protect the layer underneath against dirt and fluff accumulation on a surface of the film 12 from the environment, as well as protection against scratching and contact damage during handling and prior to use. The protective layers thus remain on the film during transportation, film cutting, handling and bending, and are removed at the point of  assembly in a clean environment thereby providing the best opportunity for the production of a clean, high quality spectacle lens.
This is not possible with conventional PVA polarized films because they are too delicate, and conventional PVA polarized films also require any protective layers to be removed before bending. Indeed, in these conventional forms, if protective layers are allowed to remain on the polarized film during bending, it is nearly impossible to remove from a PVA layer after bending without damaging the PVA layer. This means that such conventional PVA polarized film is limited in its use and ultimately the quality of lenses made using such conventional PVA polarized film is lower, or the production yield is lower, which significantly increases cost.
Protective layers  20 and 22 can be constructed from different materials or can be of the same material. Typical materials used for the  protective layers  20, 22 are polypropylene (PP) or polyethylene (PE) , which are ideally about 30 micron in thickness. In this respect, a PE protective layer is generally harder to peel away whereas a PP protective layer is easier to peel but can impart its texture to the layer underneath during lamination and bending processes. PE is thus the preferred material. For thermal resistance during the bending process, a protective layer that is a laminate combining both PE and PP can also be used.
Generally the  protective layers  20, 22 will be lightly held against the underlying multi-layer polarized film 12 so that the  protective layers  20, 22 can be easily peeled away by hand. In this respect, “lightly held” means that the layer is not chemically bonded to a surface, but is held by weak localized static and vacuum forces. In this embodiment, no adhesive is used between the  protective layers  20, 22 and the  adhesion layers  12a, 12c.
Finally, in Figure 2 there can be seen a first intermediate layer 24 that is a primer which binds chemically to the  layers  12a and 12b. Similarly, a second intermediate layer 26 can also be seen, which binds  layers  12b and 12c together. The  intermediate layers  24, 26 can be the same or a different material, and in this embodiment are either a thermally curable or UV curable primer resin, and are ideally between about 1 micron and 4 micron in thickness.
It will be appreciated that there may be other variations and modifications not described herein that are also within the scope of the present invention.

Claims (15)

  1. A high refractive index, polarized spectacle lens comprising a high refractive index lens substrate and a multi-layer polarized film, the multi-layer polarized film comprising at least one transparent support layer and at least two adhesion layers, wherein at least one of the adhesion layers is a polarized adhesion layer.
  2. A polarized spectacle lens according to claim 1, wherein the adhesion layer adjacent to the lens substrate has an adhesion strength between the adhesion layer and the lens substrate that is equal to or greater than 60 N/mm2.
  3. A polarized spectacle lens according to any one of the preceding claims, wherein each adhesion layer has a layer thickness ranging from 20 micron to 120 micron.
  4. A polarized spectacle lens according to any one of the preceding claims, wherein at least one of the at least two adhesion layers is a polarized adhesion layer and at least one of the at least two adhesion layers is a non-polarized adhesion layer.
  5. A polarized spectacle lens according to any one of the preceding claims, wherein the at least one non-polarized adhesion layer comprises at least one of the group of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , a saponified (ethylene/vinyl acetate) copolymer, a polyurethane adhesive, a holt melt adhesive (HMA) , a pressure sensitive adhesive (PSA) , or a mixture thereof and the at least one polarized adhesion layer comprises a polyvinyl alcohol-type layer selected from at least one of the group of polyvinyl alcohol (PVA) , polyvinyl formal (PVF) , polyvinyl acetate (PVAc) , a saponified (ethylene/vinyl acetate) copolymer, or a mixture thereof and at least one dichroic dye and/or iodine.
  6. A polarized spectacle lens according to any one of the preceding claims, wherein the at least one support layer has a layer thickness in the range of from 60 micron to 160 micron.
  7. A polarized spectacle lens according to any one of the preceding claims, wherein the at least one support layer has a ball indentation hardness in the range of 60 N/mm2 to 120 N/mm2.
  8. A polarized spectacle lens according to any one of the preceding claims, wherein the at least one support layer has a tensile strength greater than or equal to 80 N/mm2.
  9. A polarized spectacle lens according to any one of the preceding claims, wherein the at least one support layer has a percent elongation greater than or equal to 15％.
  10. A polarized spectacle lens according to any one of the preceding claims, wherein the support layer comprises at least one transparent polymer selected from the group comprising cellulose based polymers, polycarbonate (PC) based polymers； polyester based polymers； acrylate based polymers； methacrylate polymers； polythiourethane based polymers； vinyl based polymers； styrene based polymers； olefin based polymers； amide based polymers； polyether imide based polymers； polysulfone based polymers； polyether sulfone based polymers； polyether ether ketone based polymers； polyphenylene sulfide based polymers； polyoxymethylene based polymers； and epoxy based polymers, or any blend thereof.
  11. A polarized spectacle lens according to any one of the preceding claims, wherein the high refractive index lens substrate is selected from one or more of the group of polyurethanes, episulfides, halogen substituted derivatives of bisphenol-A, aromatic (meth) acrylic copolymers, or any blend thereof.
  12. A polarized spectacle lens according to any one of the preceding claims, wherein the adhesion layers and/or the support layer (s) comprise (s) one or more functional dyes selected from one or more of the group of fashion coloured dyes, enhanced spectral coloured dyes, blue spectral absorbing dyes, UV absorbing dyes, photochromic dyes, infrared absorption dyes, narrow band absorption dyes, or combinations thereof.
  13. A process for the production of a high refractive index, polarized spectacle lens, comprising a high refractive index lens substrate and a multi-layer polarized film, wherein the process includes the steps of:
    a. forming a multi-layer polarized film comprising a transparent support layer between a first adhesion layer and a second adhesion layer, wherein at least one of the adhesion layers is a polarized adhesion layer；
    b. matching the shape of the polarized film to the shape of the front surface of an spectacle lens mould and placing the shaped polarized film within a lens casting assembly for the mould；
    c. stabilizing the shaped film of step b；
    d. placing the shaped and stabilized film of step c within a lens casting assembly for the mould；
    e. holding the shaped polarized film close to the front mould surface by a gasket；
    f. injecting a high refractive index lens substrate liquid monomer into the lens casting assembly via a filling port whereby the monomer is able to flow around the shaped polarized film covering both sides of the film to completely fill the assembly, and
    g. curing the lens substrate around the polarized film to form an spectacle lens.
  14. Spectacle comprising high refractive index, polarized spectacle lens, wherein the spectacle lens comprises a high refractive index lens substrate and a multi-layer polarized film.
  15. Use of a high refractive index, polarized spectacle lens comprising a high refractive index lens substrate and a multi-layer polarized film in a spectacle.
PCT/CN2016/080481 2016-04-28 2016-04-28 High refractive index polarized spectacle lens Ceased WO2017185287A1 (en)

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EP16899800.3A EP3449309B1 (en) 2016-04-28 2016-04-28 High refractive index polarized spectacle lens
PT168998003T PT3449309T (en) 2016-04-28 2016-04-28 High refractive index polarized spectacle lens
PCT/CN2016/080481 WO2017185287A1 (en) 2016-04-28 2016-04-28 High refractive index polarized spectacle lens
CN201680084993.2A CN109073916A (en) 2016-04-28 2016-04-28 High Refractive Index Polarized Spectacle Lenses
CN202211366549.3A CN115509030A (en) 2016-04-28 2016-04-28 High refractive index polarized glasses lens
ES16899800T ES2897912T3 (en) 2016-04-28 2016-04-28 Polarized lens for high refractive index glasses
US16/172,450 US11067834B2 (en) 2016-04-28 2018-10-26 High refractive index polarized spectacle lens

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PCT/CN2016/080481 WO2017185287A1 (en) 2016-04-28 2016-04-28 High refractive index polarized spectacle lens

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JP7357051B2 (en) * 2019-06-28 2023-10-05 ホヤ レンズ タイランド リミテッド Polarized lens manufacturing method, polarized film and polarized lens
WO2020262400A1 (en) * 2019-06-28 2020-12-30 ホヤ レンズ タイランド リミテッド Polarizing lens
TWI733193B (en) * 2019-09-17 2021-07-11 朱啓賢 Lens composition having light filtration, rapid color change and recovery and manufacturing method thereof
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CN115509030A (en) 2022-12-23
EP3449309A1 (en) 2019-03-06
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EP3449309B1 (en) 2021-09-22
CN109073916A (en) 2018-12-21
PT3449309T (en) 2021-11-05
US11067834B2 (en) 2021-07-20
US20190064549A1 (en) 2019-02-28
EP3449309A4 (en) 2019-03-27

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