US20180196285A1

US20180196285A1 - Method for manufacturing an ophthalmic lens

Info

Publication number: US20180196285A1
Application number: US15/915,110
Authority: US
Inventors: Franco RIGATO; Glòria CASANELLAS PEÑALVER; Pau ARTÚS COLOMER; Antoni Vilajoana Mas; Juan Carlos DÜRSTELER LÓPEZ
Original assignee: Horizons Optical SL
Current assignee: Horizons Optical SL
Priority date: 2013-11-27
Filing date: 2018-03-08
Publication date: 2018-07-12
Also published as: US20170131572A2; WO2015079087A1; ES2714508T3; EP3081967B1; CA2930508A1; US9946093B2; EP3081967A1; US20150146161A1; ES2536827A1; ES2536827B1

Abstract

A method for manufacturing an ophthalmic lens including selecting a base of polymeric material and applying a multiple layer structure coating. The coating is selected by designating an interphase, a first layer (of 91-169 nm) with a refraction index higher than 1.8, a second layer (of 128-248 nm) with a refraction index lower than 1.65, a third layer (of 73-159 nm) with a refraction index higher than 1.8 and a fourth layer (of 40-138 nm) with a refraction index lower than 1.8. A total thickness of the multiple layer structure is less than 600 nm. The structure has intermediate layer(s) with intermediate refraction indices, wherein a doublet of two adjacent layers that fulfil the thicknesses above is replaced by a triplet so that the thickness and an optical thickness of the triplet differ from those of the doublet by less than 5%, respectively.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No. 14/553,428, filed Nov. 25, 2014, which claims the foreign priority benefit of Spanish Patent Application No. P201331729 filed Nov. 27, 2013, the contents of which are incorporated herein by reference.

DESCRIPTION

Field of the Invention

The invention relates to a method for manufacturing an ophthalmic lens having a base of polymeric material with a coating having an interferential multiple layer structure.

Background

The technology of multiple layer structures is known for creating interferential effects on optical surfaces.
In the field of ophthalmic lenses, it is usual to use interferential multiple layer structures to create anti-reflective or reflective surfaces of different intensities and residual colors, usually anti-reflective of green color with visible light reflection percentages lower than 2.5%, or even lower than 1.5% for each surface including a multiple layer structure.
Also known is the use of treatments for filtering a percentage of the IRA (infra-red A) or blue radiation selectively. However, the IR light filtering requires complex solutions that are not easily applicable to transparent lenses without coloring. In particular, layers of metals can be applied that absorb or help to reflect part of the IRA radiation but these materials absorb at the same time visible light, and so they do not enable obtaining high visible transmittance lenses with these features.
Interferential filters exist (for example the ones of the heat mirror type) that are used in applications for precision optics on a mineral lens, and they enable reducing the IRA radiation transmittance while maintaining a high visible transmittance: these filters have a multiple layer structure with between 40 and 100 layers and they have a total thickness over 1000 nm (nanometers), These filters are designed specifically for a certain angle of incidence of the incident radiation, and therefore if the angle varies, they display the typical effects of iridescence. Also, these treatments usually have a slight residual coloring which, in comparison with the anti-reflective lenses, makes them rather unattractive in aesthetic terms.

SUMMARY OF THE INVENTION

An object of the invention is to overcome these drawbacks. This purpose is achieved by means of an ophthalmic lens of the type indicated at the beginning wherein the multiple layer structure includes:
an interphase, orientated towards the base, of a material from the group made up of SiO_x, SiO₂, Cr, Ni/Cr, SnO₂, Al₂O₃, AlN, ZnO, SiO/Cr, SiO_x/Al₂O₃, ITO, MoO₃, with a thickness between 0 and 150 nm, preferably between 5 and 25 nm
a first high refraction index layer, of a material from the group made up of oxides, nitrides or oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index n_Dhigher than 1.8,
a second low refraction index layer, of a material from the group made up of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.65,
a third high refraction index layer made of a material from the group made up of oxides, nitrides or oxynitrides Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index n_Dhigher than 1.8,
a fourth layer, made of a material from the group made up of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.8,
where between the interphase and the first high refraction index layer there is a first intermediate layer 7 (FIG. 2) with a refraction index n_Dlower than 1.8 and with a thickness of between 0 and 160 nm,
where between the first high refraction index layer and the second low refraction index layer there is a second intermediate layer 6 (FIG. 2) with a refraction index n_Dbetween 1.65 and 1.8 and with a thickness of between 0 and 100 nm,
where between the second low refraction index layer and the third high refraction index layer there is a third intermediate layer 5 (FIG. 2) with a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between 0 and 110 nm,
where the total thickness of the multiple layer structure is at the most 600 nm, measured from the start of the interphase to the end of the fourth layer, and
where, if there is none of said intermediate layers, the thickness of said first high refraction index layer is between 91 and 169 nm, preferably between 101 and 159 nm, the thickness of said second low refraction index layer is between 128 and 248 nm, preferably between 138 and 240 nm, the thickness of said third high refraction index layer is between 73 and 159 nm, preferably between 83 and 147 nm, and the thickness of said fourth layer is between 40 and 138 nm,
and, if there is one of said intermediate layers, it holds that:
the doublet made up of the first high refraction index layer and the second low refraction index layer that fulfil said thicknesses is replaced by a triplet made up of a first intermediate layer, a first high refraction index layer and a second low refraction index layer such that the thickness of said triplet differs from the thickness of said doublet by less than 5%, and such that the optical thickness of said triplet differs from the optical thickness of said doublet by less than 5%,
and/or
the doublet made up of the first high refraction index layer and the second low refraction index layer which fulfil said thicknesses is replaced by a triplet made up of a first high refraction index layer, a second intermediate layer and a second low refraction index layer such that the thickness of said triplet differs from the thickness of said doublet by less than 5%, and such that the optical thickness of said triplet differs from the optical thickness of said doublet by less than 5%,
and/or
the doublet made up of the second low refraction index layer and the third high refraction index layer which fulfil said thicknesses is replaced by a triplet made up of a second low refraction index layer, a third intermediate layer and a third high refraction index layer such that the thickness of said triplet differs from the thickness of said doublet by less than 5%, and such that the optical thickness of said triplet differs from the optical thickness of said doublet by less than 5%.
In fact, this way a multiple layer structure is obtained that reflects a significant percentage of infra-red radiation while it maintains the anti-reflective properties in the visible, with a limited angular dispersion in the residual reflection, by adapting standard anti-reflective filter technology.
Multiple layers exist in the market for ophthalmic products, which are anti-reflective, with an infra-red filter or which limit the angular dispersion in the residual reflection, but there is no solution that groups together these four characteristics in one and the same treatment with a total thickness of less than 600 nm. This is due to the fact that each of the desired effects is achieved by including a group of layers specifically designed to fulfil the specific function in question (anti-reflective, IR filter or angular dispersion limiter in the residual reflection). This way, the total of the multiple layer structure has a plurality of layers and a high thickness. This high thickness produces secondary mechanical effects (residual stress, cracking, delamination) which, although they are maintained within acceptable values in the case of mineral precision optics lenses, they are not acceptable in the case of ophthalmic organic based lenses. Even if the amount of filtered IRA light is reduced, you still need a high overall thickness to maintain some standard anti-reflective characteristics in the visible spectrum of the ophthalmic sector.
However, it has been discovered that there is a very specific subset of thicknesses of interferential multiple layers, with an overall thickness less than 600 nm, which allows obtaining at the same time an anti-reflective treatment in the visible with low angular dispersion in the residual reflection (a visible reflection less than 5% for an incident angle of 60°, preferably less than 4%), and partially reflecting the IR-A light (an average transmission of between 780 and 1400 nm less than 76%, preferably less than 70%). The singularity of this subset of treatment layer thicknesses is revealed because when varying the thickness of each layer within a relatively small range, and without exceeding 600 nm total, some of the three desired requirements are not fulfilled.
The ranges of thicknesses that include the value “0” (for example, “from 0 to 150 nm” mean that the layer in question is optional (the value “0” is equivalent to saying that said layer is not present).
Preferably, in the event that there is none of the intermediate layers, the thickness x of the first high refraction index layer, the thickness y of the second low refraction index layer, the thickness z of the third high refraction index layer and the thickness t of the fourth layer fulfil the following relation:
$(x y z t) - (129.5 188.3 116.0 89.0) \cdot A \cdot (\begin{matrix} x - 129.5 \\ y - 188.3 \\ z - 116.0 \\ t - 89.0 \end{matrix}) \leq 1$ $where$ $A = (\begin{matrix} 8.29 \cdot 10^{4} & - 1.76 \cdot 10^{- 4}, & - 1.18 \cdot 10^{- 4} & 1.50 \cdot 10^{- 4} \\ - 1.76 \cdot 10^{- 4} & 3.34 \cdot 10^{- 4} & - 1.80 \cdot 10^{- 5} & - 3.50 \cdot 10^{- 5} \\ - 1.18 \cdot 10^{- 4} & - 1.80 \cdot 10^{- 5} & 7.16 \cdot 10^{- 4} & - 2.60 \cdot 10^{- 4} \\ 1.50 \cdot 10^{- 4} & - 3.50 \cdot 10^{- 5} & - 2.60 \cdot 10^{- 4} & 5.34 \cdot 10^{- 4} \end{matrix})$
and, if there is one of the intermediate layers, it holds that:
the doublet made up of the first high refraction index layer and the second low refraction index layer that that fulfil the relation above is replaced by a triplet made up of a first intermediate layer, a first high refraction index layer and a second low refraction index layer such that the thickness of said triplet differs from the thickness of said doublet by less than 5%, and such that the optical thickness of said triplet differs from the optical thickness of said doublet by less than 5%,
and/or
the doublet made up of the first high refraction index layer and the second low refraction index layer which fulfil the relation above is replaced by a triplet made up of a first high refraction index layer, a second intermediate layer and a second low refraction index layer such that the thickness of said triplet differs from the thickness of said doublet by less than 5%, and such that the optical thickness of said triplet differs from the optical thickness of said doublet by less than 5%,
and/or
the doublet made up of the second low refraction index layer and the third high refraction index layer which fulfil the relation above is replaced by a triplet made up of a second low refraction index layer, a third intermediate layer and a third high refraction index layer such that the thickness of said triplet differs from the thickness of said doublet by less than 5%, and such that the optical thickness of said triplet differs from the optical thickness of said doublet by less than 5%.
Advantageously the thickness x of the first high refraction index layer, the thickness y of the second low refraction index layer, the thickness z of the third high refraction index layer and the thickness t of the fourth layer fulfil the following relation:
$(x y z t) - (129.7 189.7 114.2 87.2) \cdot A \cdot (\begin{matrix} x - 129.7 \\ y - 189.7 \\ z - 114.2 \\ t - 87.2 \end{matrix}) \leq 1$ $where$ $A = (\begin{matrix} 1.53 \cdot 10^{- 3} & - 3.41 \cdot 10^{- 4} & - 1.35 \cdot 10^{- 4} & 8.99 \cdot 10^{- 5} \\ - 3.41 \cdot 10^{- 4} & {4.82}^{- 4} & - 1.86 \cdot 10^{- 5} & 9.77 \cdot 10^{- 6} \\ - 1.35 \cdot 10^{- 4} & - 1.86 \cdot 10^{- 5} & 1.12 \cdot 10^{- 3} & - 2.53 \cdot 10^{- 4} \\ 8.99 \cdot 10^{- 5} & 9.77 \cdot 10^{- 6} & - 2.53 \cdot 10^{- 4} & 8.44 \cdot 10^{- 4} \end{matrix})$
and, if there are some of the intermediate layers, preferably they fulfil the same relations above.
Preferably a simulation of the reflection and transmission curves of the multiple layer structure has the following characteristics:
a visible reflection by a light incidence angle of 15° lower than 2.5%, preferably lower than 1.5%; calculated as an average of the reflection value in the range 380-780 nm, weighted by the spectral light efficiency spectrum for day light and by the spectral distribution of the lighting D65, according to Spanish standard UNI-EN ISO 13666:1998,
a visible reflection R_visby a light incidence angle of 60° lower than 5.0%, preferably lower than 4.5%; calculated as in the case above, and
a transmission value in infra-red A T_IR-Alower than 76%, preferably lower than 70%; calculated as an average transmission value in the range 780-1400 nm according to the following formula:
$T_{IR - A} = \sum_{λ \in A} \frac{T (λ)}{14}$ $where A = {780, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400}$
In fact, the combination of these three properties within the ranges indicted makes it possible to obtain lenses with optimum results. The parameters indicated are usual in the state of the art, are clearly determined and they can be obtained in a reliable manner by following the specified standards, that include some procedures for determining the values of the parameters in question in an objective manner and common to the state of the art.
Advantageously a simulation of the reflection and transmission curves of the multiple layer structure has a blue light transmittance value T_azullower than 95%, preferably lower than 92%; calculated as the average transmission value in the range 410-460 nm according to the following formula:
$T_{azul} = \sum_{λ \in B} \frac{T (λ)}{6}$ $where B = {410, 420, 430, 440, 450, 460}$
In fact, an additional advantage is that a suitable definition of each of the layers in the multiple layer structures also allows fulfilling an additional result, which is that the (little) visible light reflected is concentrated in the blue-violet spectrum. This way the lens offers additional protection to the user, reducing the amount of blue light that reaches the user's eye.
Preferably the coating includes a layer of anti-scratching lacquer between the multiple layer structure and the base.
Advantageously the lens has a multiple layer structure both on the inner surface and on the outer surface of the lens. In fact, this way it is possible to noticeably increase the effect of the IRA radiation filtered, with an improvement also in the transmittance in visible light.
Preferably the first high refraction index layer and/or the third high refraction index layer have a refraction index n_Dhigher than 1.95.
Preferably the second low refraction index layer has a refraction index n_Dlower than 1.5.
Advantageously the fourth layer has a refraction index n_Dlower than 1.65.
Preferably the fourth layer has a refraction index n_Dbetween 1.4 and 1.6 and a thickness between 50 and 124 nm.
Advantageously the first intermediate layer has a thickness between 0 and 25 nm.
Advantageously the first high refraction index layer and/or the third high refraction index layer is made up of two high refraction index sub-layers, preferably by a first sub-layer of TiO₂and a second sub-layer of ZrO₂or vice versa. In fact, the ZrO₂has a high evaporation temperature and, as a layer of considerable thickness, can cause cracking problems due to residual stress. An alternative would be to completely replace this layer of ZrO₂with a layer of TiO₂, which has a lower evaporation temperature. However, this layer of TiO₂is less hard, therefore is scratches more easily. The solution proposed allows combining the advantages in both cases. Generally, in this specification and claims it must be understood that, when a layer is defined by indicating that the materials can be “a mixture of the above”, this includes not only the case where a layer includes a more or less homogenous mixture of said materials, but also the case where the layer is divided into sub-layers, each one of them made of one of said materials. The specific case of the two sub-layers of TiO₂and ZrO₂is an example of this. So, another advantageous solution example is when the second low refraction index layer and/or the fourth layer are made up of two low refraction index sub-layers, preferably by a first sub-layer of SiO₂and a second sub-layer of Al₂O₃or vice versa.
Advantageously on the fourth layer there is a hydrophobic outer layer.
The lenses can be both sun lenses (absorbent in the visible spectrum) and substantially transparent lenses in the visible spectrum (indoor lenses).
The application of these layers is usually done using PVD (Physical Vapor Deposition) techniques through evaporation with electron guns or thermal evaporation, although other techniques exist like Plasma enhanced Chemical Vapor Deposition (PeCVD) or the reactive Sputtering with which it is also possible to obtain this type of interferential layers.
A particularly advantageous embodiment of the invention is obtained when the multiple layer structure includes:
an interphase with a thickness between 15 and 45 nm, preferably of SiO₂,
a first high refraction index layer with a thickness between 123 and 145 nm, preferably of TiO₂,
a second low refraction index layer with a thickness between 170 and 217 nm, preferably of SiO₂,
a third high refraction index layer, divided into a first sub-layer with a thickness between 59 and 67 nm, preferably of TiO₂, and a second sub-layer with a thickness between 50 and 74 nm, preferably of ZrO₂,
a fourth layer with a thickness between 44 and 68 nm, preferably of SiO₂.

BRIEF DESCRIPTION OF THE DRAWINGS

Other advantages and characteristics of the invention are appreciated from the following description, where, in a non-limiting manner, some preferable embodiments of the invention are explained, with reference to the accompanying drawings. The figures show:

FIG. 1, a diagrammatic view of a cross section of an embodiment of a lens with a coating according to the invention.

FIG. 2, a diagrammatic view of a cross section of a multiple layer structure according to the invention.

FIGS. 3 to 15, graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation for the lenses in the respective examples.

DETAILED DESCRIPTION

FIG. 1 shows a general structure example of a lens according to the invention. The lens includes a base P of polymeric material on which there is a primer layer IM, which is optional and which usually has a thickness between 0.3 and 1.5 microns. Next there is a hardening layer E (usually with a thickness between 1 and 4 microns) on which the multiple layer structure M according to the invention is arranged. This multiple layer structure M is made up of a plurality of layers, which will be detailed later. The last layer of the structure is a hydrophobic layer H, with a thickness between 3 and 25 nm. Generally this structure can exist on the two lens surfaces or only on one of them. If present on one of them, any other conventional coating can be applied to the opposite surface.
FIG. 2 shows diagrammatically a multiple layer structure M according to the invention in greater detail.
The multiple layer structure M includes an interface IN (which is optional) of metallic material or metallic oxide, with scarce repercussion in the optical properties but critical for the mechanical properties, particularly those regarding adherence and wear, and a barrier against oxidation and diffusion. Preferably the material is one of the group made up of SiO_x, SiO₂, Cr, Ni/Cr, SnO₂, Al₂O₃, AlN, ZnO, SiO/Cr, SiO_x/Al₂O₃, ITO and MoO₃.
Next there is a first high refraction index layer 1A of metallic oxide, metallic nitride or metallic oxynitride with a refraction index n_D>1.8 (preferably >1.95) necessary for adjusting the optical properties and essential for obtaining mechanical properties resistant to scratching. It is the first high refraction index layer 1A. Preferably it is made of a material from the group made up of oxides, nitrides or oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof.
The following layer is made of a metallic oxide or fluoride with a refraction index n_D<1.65 (preferably <1.5) necessary for adjusting the optical properties and essential for obtaining the mechanical properties resistant to scratching. It forms the second low refraction index layer 2B. Preferably it is made of a material from the group made up of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof.
On the second low refraction index layer 2B there is a third high refraction index layer 3A, made of metallic oxide, metallic nitride or metallic oxynitride with a refraction index n_D>1.8 (preferably >1.95). Preferably it is made of a material from the group made up of oxides, nitrides or oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof.
On the third high refraction layer 3A there is a layer of metallic oxide or fluoride with a refraction index n_D<1.8 (preferably <1.65). It is the fourth layer 4. Preferably it is made of a material from the group made up of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof.
The total thickness of the multiple layer structure is less than 600 nm, measured from the start of the interphase to the end of the fourth layer, and preferably it is less than 500 nm.
The simulation of the reflection and transmission curves of the multiple layers is achieved using the transfer matrix method, introduced by F. Abelès (F. Abelès, J. Phys. Radium 11, 307 (1950)) and described in the state of the art (for example in H. A. Macleod, Thin-Film Optical Filters, 4^thEdition, CRC Press (2010)). It is the method applied by most of the commercial programs (see, for example, FilmStar™ (www.ftgsoftware.com) or Essential Macleod (www.thinfilmcenter.com)) on the simulation of the reflection of multiple layers, and it is used knowing the dispersion of the complex refraction indices of the materials in each layer and the substrate, in the range of 380-1400 nm, the thicknesses of each layer and the incidence angle of the light radiation.
Methods of Analyzing a Lens with a Coating According to the Invention
The analyses required to analyze a lens according to the invention can be, for example:

- Optical properties: optical transmittance and reflection spectra from 200 to 3000 nm. The reference standard will be EN1836
- Layer thickness and composition: ESCA (Electron Spectroscopy for Chemical Analysis), XPS (X-ray Photoelectron Spectroscopy), Electron Microscopy, SIMS (Secondary Ion Mass Spectroscopy).

EXAMPLES

Below are shown a series of examples wherein, in each case, the composition and thickness of the layer is indicated and the optical properties obtained.

Example 1: Minimizing the Reflection of Visible Radiation


	Layer 4	SiO₂- 81.2 nm
	Layer
3A	TiO2 - 101.8 nm
	Layer
2B	SiO2 - 169.9 nm
	Layer
1A	TiO2 - 120.8 nm
	Base	Polymer n_D= 1.6
	RV 15°	0.5%
	RV 60°	5.0%
	T IR-A	71.8%
	Total thickness	437.7 nm

FIG. 3 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Example 2: Minimizing the Transmission of IR-A Radiation


	Layer 4	SiO₂- 61.4 nm
	Layer
3A	TiO₂- 107.6 nm
	Layer
2B	SiO₂- 169.0 nm
	Layer
1A	TiO₂- 126.0 nm
	Base	Polymer n_D= 1.6
	RV 15°	1.5%
	RV 60°	5.0%
	T IR-A	69.7%
	Total thickness	463.9 nm

FIG. 4 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Example 3: Minimizing the Reflection of Radiation at 60°


	Layer 4	SiO₂- 98.0 nm
	Layer
3A	TiO₂- 117.7 nm
	Layer 28	SiO₂- 202.3 nm
	Layer
1A	TiO₂- 129.9 nm
	Base	Polymer n_D= 1.6
	RV 15°	1.5%
	RV 60°	3.0%
	T IR-A	75.3%
	Total thickness	547.8 nm

FIG. 5 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Example 4: Minimizing the Transmission of Blue Light


	Layer 4	SiO₂- 70.6 nm
	Layer
3A	TiO₂- 121.7 nm
	Layer
2B	SiO₂- 226.0 nm
	Layer
1A	TiO₂- 140.1 nm
	Base	Polymer n_D= 1.6
	RV 15°	1.5%
	RV 60°	4.4%
	T IR-A	74.3%
	Total thickness	558.2 nm

FIG. 6 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.
A 70.6% transmission of blue light is obtained.

Example 5: Minimizing the Reflection of Visible Radiation

In this Example other materials have been used to produce the layers in the multiple layer structure.


	Layer 4	MgF₂- 77.1 nm
	Layer
3A	ZrO₂- 115.8 nm
	Layer
2B	MgF₂- 189.7 nm
	Layer
1A	ZrO₂- 141.0 nm
	Base	Polymer n_D= 1.6
	RV 15°	0.4%
	RV 60°	5.0%
	T IR-A	76.0%
	Total thickness	523.7 nm

FIG. 7 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Example 6: Residual Reflection Concentrated in Green


	Layer 4	SiO₂- 100.9 nm
	Layer
3A	TiO₂- 118.5 nm
	Layer
2B	SiO₂- 188.3 nm
	Layer
1A	TiO₂- 116.9 nm
	Base	Polymer n_D= 1.6
	RV 15°	1.5%
	RV 60°	3.8%
	T IR-A	75.0%
	Total thickness	524.6 nm

FIG. 8 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Example 7: Solution According to the State of the Art

In this Example the solution that would have been obtained from the knowledge of the state of the art has been reproduced.


	Layer 6	SiO₂- 73.0 nm
	Layer 5	TiO₂- 103.3 nm
	Layer
4	SiO₂- 158.6 nm
	Layer 3	TiO₂- 100.1 nm
	Layer
2	SiO₂- 169.2 nm
	Layer
1	TiO₂- 113.2 nm
	Base	Polymer n_D= 1.6
	RV 15°	1.2%
	RV 60°	6.2%
	T IR-A	67.1%
	Total thickness	717.4 nm

As you can see, more layers are used and the thickness is greater than 600 nm.
FIG. 9 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Example 8

This Example shows how, starting with a first multiple layer structure (#8a), it is possible to improve the optical properties by including an intermediate layer 5 between the second low refraction index layer and the third high refraction index layer (#8b). It also shows another multiple layer structure (#8c) which, without the presence of the intermediate layer 5, has practically the same optical properties. The structure #8c fulfils an equivalence relation between the physical thicknesses and the optical thicknesses of the central triplet in the structure #8b (intermediate layer of Al₂O₃and its two adjacent layers) and the doublet in the structure #8c (the second low refraction index layer (SiO₂) and the third high refraction index layer (TiO₂)).


#8a	#8b	#	8c

SiO₂	84.4 nm	84.4 nm	84.4 nm
TiO₂	90.0 nm	90.0 nm	98.4 nm
Al₂O₃	0.0 nm	34.8 nm	0.0 nm
SiO₂	142.6 nm	142.6 nm	174.2 nm
TiO₂	122.5 nm	122.5 nm	122.5 nm
Base	Polymer	Polymer	Polymer
	n_D= 1.6	n_D= 1.6	n_D= 1.6
RV 15°	1.8%	0.4%	0.5%
RV 60°	11.0%	4.8%	5.0%
T IR-A	74.7%	72.9%	72.1%
Total thickness	439.6 nm	474.4 nm	479.5 nm
Thickness of the central triplet	232.6 nm	267.5 nm	272.6 nm
Optical thickness of the central triplet	388.4 nm	445.4 nm	450.6 nm

FIG. 10 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation for each of the three cases.

Example 9

In this Example, as in Example 8, it shows how, starting with a first multiple layer structure (#9a), it is possible to improve the optical properties by including an intermediate layer. In this case it is an intermediate layer 6 between the first high refraction index layer and the second low refraction index layer (#9b). It also shows another multiple layer structure (#9c) which, without the presence of the intermediate layer 6, has virtually the same optical properties. Also in this case the structure #9c fulfils an equivalence relation between the physical thicknesses and the optical thicknesses of the central triplet in the structure #9b (intermediate layer of Al2O3 and its two adjacent layers) and the doublet in the structure #9c (the first high refraction index layer (TiO2) and the second low refraction index layer (SiO2)).


#9a	#9b	#	9c

SiO₂	87.7 nm	87.7 nm	87.7 nm
TiO₂	110.8 nm	110.8 nm	110.8 nm
SiO₂	148.3 nm	148.3 nm	175.9 nm
Al₂O₃	0.0 nm	33.9 nm	0.0 nm
TiO₂	104.0 nm	104.0 nm	109.7 nm
Base	Polymer	Polymer	Polymer
	n_D= 1.6	n_D= 1.6	n_D= 1.6
RV 15°	2.9%	1.0%	1.1%
RV 60°	9.7%	4.5%	5.0%
T IR-A	74.5%	73.5%	73.0%
Total thickness	450.9 nm	484.8 nm	484.1 nm
Thickness of the triplet in contact	252.3 nm	286.3 nm	285.6 nm
with the base
Optical thickness of the triplet in	424.9 nm	480.4 nm	476.2 nm
contact with the base

FIG. 11 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation for each of the three cases.

Example 10

In this Example, the multiple layer structure has an interphase (of SiO₂and 15 nm thick), and the third high refraction index layer is sub-divided into two sub-layers (one of TiO₂and one of ZrO₂).


	Layer 4	SiO₂- 62.4 nm
	Layer
3A-2	ZrO₂- 50.0 nm
	Layer
3A-1	TiO₂- 59.3 nm
	Layer
2B	SiO₂- 175.7 nm
	Layer
1A	TiO₂- 126.5 nm
	Interphase	SiO₂- 15 nm
	Base	Polymer n_D= 1.6
	RV 15°	0.9%
	RV 60°	4.7%
	T IR-A	72.0%
	Total thickness	488.9 nm

This solution is a preferable embodiment of the invention.
FIG. 12 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Examples 11 and 12

In these Examples, as in Examples 8 and 9, it shows how, starting with a first multiple layer structure (#11a, #12a), it is possible to improve the optical properties by including an intermediate layer (an intermediate layer 5 in Example 11 and an intermediate layer 6 in Example 12). They are the structures #11 b and #12b, respectively. They also show other multiple layer structures (#11c, #12c) which, without the presence of the intermediate layer 6, has virtually the same optical properties. Also in these cases the structures #11c and #12c fulfil an equivalence relation between the physical thicknesses and the optical thicknesses of the triplet in the structures #11b and #12b and the corresponding doublets in structures #11c and #12c.


#11a	#11b	#	11c

SiO₂	85.0 nm	85.0 nm	85.0 nm
TiO₂	95.9 nm	95.9 nm	102.0 nm
Al₂O₃	0.0 nm	40.7 nm	0.0 nm
SiO₂	127.0 nm	127.0 nm	170.7 nm
TiO₂	124.3 nm	124.3 nm	124.3 nm
Base	Polymer	Polymer	Polymer
	n_D= 1.6	n_D= 1.6	n_D= 1.6
RV 15°	3.0%	0.7%	0.6%
RV 60°	11.3%	4.5%	4.8%
T IR-A	76.0%	73.6%	72.2%
Total thickness	432.2 nm	472.9 nm	481.9 nm
Thickness of the central triplet	222.9 nm	263.6 nm	272.6 nm
Optical thickness of the central triplet	377.7 nm	444.3 nm	452.9 nm

FIG. 13 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation for each one of the three cases in Example 11.


#12a	#	12b	#12c

SiO₂	78.5 nm	78.5 nm	78.5 nm
TiO₂	112.1 nm	112.1 nm	112.1 nm
SiO₂	127.0 nm	127.0 nm	160.4 nm
Al₂O₃	0.0 nm	41.2 nm	0.0 nm
TiO₂	111.3 nm	111.3 nm	122.1 nm
Base	Polymer	Polymer	Polymer
	n_D= 1.6	n_D= 1.6	n_D= 1.6
RV 15°	3.7%	1.0%	1.1%
RV 60°	10.0%	4.5%	4.7%
T IR-A	75.1%	72.9%	71.8%
Total thickness	428.9 nm	470.1 nm	473.1 nm
Thickness of the triplet in contact	238.3 nm	279.4 nm	282.4 nm
with the base
Optical thickness of the triplet in	409.0 nm	476.5 nm	478.9 nm
contact with the base

FIG. 14 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation for each one of the three cases in Example 12.

Example 13: Triplet and Doublet High Index Refraction Layers, without Interphase and with Residual Reflex Concentrated in the Green Color

- The interphase between the base and the first high refraction index layer has a thickness of 0 nm, i.e., there is no interphase layer
- The first high refraction index layer is a triplet formed by 41.8 nm ZrO₂+92.7 nm TiO₂+28.8 nm ZrO₂(total 162.9 nm), in this order, starting from the base
- The second low refraction index layer is formed by 153.4 nm of SiO₂
- The third high refraction index layer is a doublet formed by 15.0 nm ZrO₂+105.1 nm TiO₂
- The fourth layer is formed by 78.8 nm of SiO₂.

The base has a refraction index of 1.6)


	Layer 4	SiO₂- 78.8 nm
	Layer
3A-2	TiO₂- 105.1 nm
	Layer
3A-1	ZrO₂- 15.0 nm
	Layer
2B	SiO₂- 153.4 nm
	Layer
1A-3	ZrO₂- 28.4 nm
	Layer
1A-2	TiO₂- 92.7 nm
	Layer
1A-1	ZrO₂- 41.8 nm
	Base	Polymer n_D= 1.6
	RV 15°	0.8%
	RV 60°	4.6%
	T IR-A	63.6%
	Total thickness	515.1 nm

FIG. 15 shows a graph showing the reflection (in %) according to the wave length (λ, in nm) of the incident radiation.

Claims

1. A method for manufacturing an ophthalmic lens comprising the steps of:

selecting a base of polymeric material;

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of—

designating a multiple layer structure including—

an interphase, orientated towards the base and selected from the group consisting of SiO_x, SiO₂, Cr, Ni/Cr, SnO₂, Al₂O₃, AlN, ZnO, SiO/Cr, SiO_x/Al₂O₃, ITO, and MoO₃, with a thickness between 0 and 150 nm,

a first high refraction index layer selected from the group consisting of oxides, nitrides and oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index n_Dhigher than 1.8,

a second low refraction index layer selected from the group consisting of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.65,

a third high refraction index layer selected from the group consisting of oxides, nitrides and oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index n_Dhigher than 1.8,

a fourth layer selected from the group consisting of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.8,

wherein a total thickness of said multiple layer structure is at most 600 nm, measured from an outer surface of the interphase to an outer surface of the fourth layer, and

wherein, a thickness of said first high refraction index layer is between 91 and 169 nm, a thickness of said second low refraction index layer is between 128 and 248 nm, a thickness of said third high refraction index layer is between 73 and 159 nm, and a thickness of said fourth layer is between 40 and 138 nm;

substituting a doublet formed by said first high refraction index layer and said second low refraction index layer with a triplet formed by an intermediate layer, a substitute first high refraction index layer and a substitute second low refraction index layer,

wherein said intermediate layer has a refraction index nD lower than 1.8 and with a thickness between greater than 0 and 160 nm,

wherein said substitute first high refraction index layer is selected from the group consisting of oxides, nitrides and oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index nD higher than 1.8,

wherein said substitute second low refraction index layer is selected from the group consisting of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.65,

wherein said triplet has a thickness that differs from a thickness of said doublet by less than 5%, and an optical thickness of said triplet differs from an optical thickness of said doublet by less than 5%; and

applying the coating having the substituting triplet to said ophthalmic lens.

2. A method for manufacturing an ophthalmic lens comprising the steps of:

selecting a base of polymeric material

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of

designating a multiple layer structure including—

a second low refraction index layer selected from the group consisting of SiO₂, Mg F₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.65,

substituting a doublet formed by said first high refraction index layer and said second low refraction index layer with a triplet formed by a substitute first high refraction index layer, an intermediate layer and a substitute second low refraction index layer,

wherein said intermediate layer has a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between greater than 0 and 100 nm,

wherein said substitute first high refraction index layer is selected from the group consisting of oxides, nitrides and oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index n_Dhigher than 1.8,

applying the coating having the substituting triplet to said ophthalmic lens.

3. A method for manufacturing an ophthalmic lens, comprising the steps of

selecting a base of polymeric material;

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of

designating a multiple layer structure—

substituting a doublet formed by said second low refraction index layer and said third high refraction index layer with a triplet formed by a substitute second low refraction index layer, an intermediate layer and a substitute third high refraction index layer,

wherein said intermediate layer has a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between 0 and 110 nm,

wherein said substitute second low refraction index layer is selected from the group consisting of SiO₂, Mg F₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_Dlower than 1.65,

wherein said substitute third high refraction index layer is selected from the group consisting of oxides, nitrides and oxynitrides of Zr, Ti, Sb, In, Sn, Ta, Nb, Hf and mixtures thereof, with a refraction index n_Dhigher than 1.8,

applying said coating with the substituting triplet to said ophthalmic lens.

4. A method for manufacturing an ophthalmic lens comprising the steps of:

selecting a base of polymeric material;

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of—

designating a multiple layer structure including—

substituting a doublet formed by said first high refraction index layer and said second low refraction index layer with a triplet formed by said substitute first high refraction index layer, a second intermediate layer and said substitute second low refraction index layer,

wherein said second intermediate layer has a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between greater than 0 and 100 nm,

wherein any of said triplets has a thickness that differs from a thickness of said doublet by less than 5%, and an optical thickness of said triplet differs from an optical thickness of said doublet by less than 5%; and

applying the coating having the substituting triplets to said ophthalmic lens.

5. A method for manufacturing an ophthalmic lens comprising the steps of:

selecting a base of polymeric material;

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of—

designating a multiple layer structure including—

substituting a doublet formed by said second low refraction index layer and said third high refraction index layer with a triplet formed by said substitute second low refraction index layer, a second intermediate layer and a substitute third high refraction index layer,

wherein said second intermediate layer has a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between greater than 0 and 110 nm,

wherein said substitute second low refraction index layer is selected from the group consisting of SiO₂, MgF₂, Al₂O₃, LaF₃and mixtures thereof, with a refraction index n_plower than 1.65,

wherein any of said triplets has a thickness that differs from a thickness of the corresponding doublet by less than 5%, and an optical thickness of any of said triplets differs from an optical thickness of the corresponding doublet by less than 5%; and

applying the coating having the substituting triplets to said ophthalmic lens.

6. A method for manufacturing an ophthalmic lens comprising the steps of:

selecting a base of polymeric material

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of

designating a multiple layer structure including—

wherein said second intermediate layer has a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between 0 and 110 nm,

applying the coating having the substituting triplets to said ophthalmic lens.

7. A method for manufacturing an ophthalmic lens comprising the steps of:

selecting a base of polymeric material;

selecting a coating having an interferential multiple layer structure,

wherein the selecting the coating includes the steps of—

designating a multiple layer structure including—

substituting a doublet formed by said second low refraction index layer and said third high refraction index layer with a triplet formed by said substitute second low refraction index layer, a third intermediate layer and a substitute third high refraction index layer,

wherein said third intermediate layer has a refraction index n_Dbetween 1.65 and 1.8 and with a thickness between 0 and 110 nm,

applying the coating having the substituting triplets to said ophthalmic lens.

8. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein the thickness x of said first high refraction index layer, the thickness y of said second low refraction index layer, the thickness z of said third high refraction index layer and the thickness t of said fourth layer fulfil the following relation:

(x y z t) - (129.5 188.3 116.0 89.0) \cdot A \cdot (\begin{matrix} x - 129.5 \\ y - 188.3 \\ z - 116.0 \\ t - 89.0 \end{matrix}) \leq 1

where

A = (\begin{matrix} 8.29 \cdot 10^{4} & - 1.76 \cdot 10^{- 4}, & - 1.18 \cdot 10^{- 4} & 1.50 \cdot 10^{- 4} \\ - 1.76 \cdot 10^{- 4} & 3.34 \cdot 10^{- 4} & - 1.80 \cdot 10^{- 5} & - 3.50 \cdot 10^{- 5} \\ - 1.18 \cdot 10^{- 4} & - 1.80 \cdot 10^{- 5} & 7.16 \cdot 10^{- 4} & - 2.60 \cdot 10^{- 4} \\ 1.50 \cdot 10^{- 4} & - 3.50 \cdot 10^{- 5} & - 2.60 \cdot 10^{- 4} & 5.34 \cdot 10^{- 4} \end{matrix}) .

9. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein, the thickness x of said first high refraction index layer, the thickness y of said second low refraction layer, the thickness z of said third high refraction index layer and the thickness t of said fourth layer fulfil the following relation:

(x y z t) - (129.7 189.7 114.2 87.2) \cdot A \cdot (\begin{matrix} x - 129.7 \\ y - 189.7 \\ z - 114.2 \\ t - 87.2 \end{matrix}) \leq 1

where

A = (\begin{matrix} 1.53 \cdot 10^{- 3} & - 3.41 \cdot 10^{- 4} & - 1.35 \cdot 10^{- 4} & 8.99 \cdot 10^{- 5} \\ - 3.41 \cdot 10^{- 4} & {4.82}^{- 4} & - 1.86 \cdot 10^{- 5} & 9.77 \cdot 10^{- 6} \\ - 1.35 \cdot 10^{- 4} & - 1.86 \cdot 10^{- 5} & 1.12 \cdot 10^{- 3} & - 2.53 \cdot 10^{- 4} \\ 8.99 \cdot 10^{- 5} & 9.77 \cdot 10^{- 6} & - 2.53 \cdot 10^{- 4} & 8.44 \cdot 10^{- 4} \end{matrix}) .

10. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein a simulation of reflection and transmission curves of said multiple layer structure has the following characteristics:

a visible reflection R_visby a light incidence angle of 15° lower than 2.5%, calculated as an average of a reflection value in a range of 380-780 nm, weighted by an efficiency spectrum of spectral light for day light and by a spectral distribution of the illuminant D65, according to Spanish standard UNI-EN ISO 13666:1998,

a visible reflection R_visby a light incidence angle of 60° lower than 5.0%, calculated as an average of a reflection value in a range of 380-780 nm, weighted by an efficiency spectrum of spectral light for day light and by a spectral distribution of the illuminant D65, according to Spanish standard UNI-EN ISO 13666:1998, and

a transmission value in the infra-red A T_IR-Alower than 76%, calculated as an average transmission value in a range of 780-1400 nm according to the following formula:

T_{IR - A} = \sum_{λ \in A} \frac{T (λ)}{14}

where A = {780, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400} .

11. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein a simulation of reflection and transmission curves of said multiple layer structure has a blue light transmittance value T_azullower than 95%, calculated as an average transmission value in a range of 410-460 nm according to the following formula:

T_{azul} = \sum_{λ \in B} \frac{T (λ)}{6}

where B = {410, 420, 430, 440, 450, 460} .

12. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein said fourth layer has a refraction index n_Dbetween 1.4 and 1.6 and a thickness between 50 and 124 nm.

13. The method according to claim 1, wherein said intermediate layer has a thickness between greater than 0 and 25 nm.

14. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein at least one of said first high refraction index layer or said third high refraction index layer is made up of two high refraction index sub-layers.

15. The method according to any one of claim 1, 2, 3, 4, 5, 6 or 7, wherein at least one of said second low refraction index layer or said fourth layer is made up of two low refraction index sub-layers.