CA2429150C - Cold antireflection layer deposition process - Google Patents
Cold antireflection layer deposition process Download PDFInfo
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- CA2429150C CA2429150C CA2429150A CA2429150A CA2429150C CA 2429150 C CA2429150 C CA 2429150C CA 2429150 A CA2429150 A CA 2429150A CA 2429150 A CA2429150 A CA 2429150A CA 2429150 C CA2429150 C CA 2429150C
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- 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
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
- G02B1/116—Multilayers including electrically conducting layers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0694—Halides
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- 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
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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Abstract
The invention concerns a method for making an antiglare stack by vacuum evaporation on an organic substrate (1) at a temperature lower than 150 ~C, comprising steps which consist in depositing at least a layer of material having a refractive index different from that of MgF2 (4, 4'), preparing the surface of the thus coated substrate, and depositing an outer MgF2 layer (5) without ionic assistance. The resulting antiglare stack on organic substrate exhibits good adherence and good scratch resistance. The invention is applicable to ophthalmic lenses.
Description
COLD ANTIItEFLECTION LAYER DEPOSITION PROCESS
BACKGROUND OF THE INVENTION
The present invention relates to a process for carrying out an antireflection treatment on a substrate made of an organic material, in particular an ophthalmic lens, using a technique of deposition by vacuum evaporation. Such coatings are generally produced by means of metal oxides having high and low refractive indices.
The effectiveness of an antireflection treatment depends to a great extent on the value of the refractive indices of the layers deposited. The constraints associated with the type of deposition used and the nature of the substrates to be treated restrict the materials that can be used for these treatments.
Manufacturers are being required to devise antireflection treatments of ever higher performance. For information, in the ophthalmic field, the effectiveness of such a treatinent is given in terms of reflection per face, which lies between 1.6 and
BACKGROUND OF THE INVENTION
The present invention relates to a process for carrying out an antireflection treatment on a substrate made of an organic material, in particular an ophthalmic lens, using a technique of deposition by vacuum evaporation. Such coatings are generally produced by means of metal oxides having high and low refractive indices.
The effectiveness of an antireflection treatment depends to a great extent on the value of the refractive indices of the layers deposited. The constraints associated with the type of deposition used and the nature of the substrates to be treated restrict the materials that can be used for these treatments.
Manufacturers are being required to devise antireflection treatments of ever higher performance. For information, in the ophthalmic field, the effectiveness of such a treatinent is given in terms of reflection per face, which lies between 1.6 and
2.5% for a poorly effective treatment, is between 1.0 and 1.8% for a moderately effective treatment and must nowadays be between 0.3 and 0.8% for a highly effective treatment.
These constraints mean that novel materials have to be sought, these sometimes being difficult to develop from an industrial standpoint. Another approach may consist in using materials previously reserved for substrates made of inorganic material.
To produce a highly effective antireflection treatment, it is necessary for the last layer deposited to have the lowest possible refractive index. In the case of organic substrates, Si02 is often used because of its refractive index of 1.48, its good adhesion, scratch resistance and corrosion resistance properties and its ease of deposition.
MgF2 is very widely used for substrates made of an inorganic material because of its very low refractive index, namely 1.38. A drawback of this material lies in its friability and its lack of adhesion when it is deposited at temperatures below 200 C.
In general, MgF2 is not used for organic substrates as these cannot be heated above 150 C as they undergo yellowing and deterioration.
It is therefore necessary to find a process allowing deposition of MgF2 on an organic substrate ("cold" deposition) and to find other materials which might be suitable.
JP 8-236635 (published September 13, 1996) teaches the deposition of an MgF2 layer on an organic substrate by means of the technology of sputtering.
However, the layers deposited by sputtering have particular physico-chemical characteristics. In particular, the layers deposited are generally denser, which poses an adhesion problem. The document teaches that such deposition carried out by means of vacuum evaporation results in layers having a low degree of crystallization, which entails an insufficient abrasion resistance.
A multilayer antireflection coating on an organic material in the ophthalmic field, the final layer of which is made of MgF2, is also disclosed in the document EP-A-619 504 (published October 12, 1994). That document indicates that the layers disclosed are produced by plasma-enhanced processes and within certain unspecified limits by sputtering. The most economic and most widely used deposition process is however non-plasma-enhanced vacuum evaporation. Layers obtained by plasma-enhanced evaporation furthermore have a higher density than those obtained without enhancement, but high density means that these layers are highly strained, which may result in adhesion of inferior quality.
Document JP 61250601 (published November 7, 1986) also discloses a multilayer antireflection coating on an organic substrate. According to that document, Si02 is used as the outer layer of low refractive index and preferably a multilayer coating consisting of three layers of the Y203/TiO2/SiO2 type is used.
During deposition of the multilayer coating, the interface of at least one of the layers is treated by ion bombardment. This treatment improves the adhesion of the layers.
The use of MgF2 as material having a low refractive index is neither disclosed nor suggested in that document.
Document JP 7076048 (published March 20, 1995) discloses a multilayer antireflection coating deposited on an organic substrate. This specifies that the outer layer, made of MgF2, is deposited at low temperature with ion assistance using the IAD (Ion Assisted Deposition) technique and that surface on which this layer is deposited is subjected beforehand to a cleaning treatment by ion bombardment and/or by plasma. However, it turns out that the use of the IAD technique has a number of drawbacks. This type of assistance is generally used to densify the layers deposited. But on the downside, the densest layers have lower adhesion.
Furthermore, ion assistance may make the MgF2 layer more absorbent, this being a troublesome drawback in the case of ophthalmic applications. Finally, this type of assistance makes the process more complicated and increases the production costs substantially.
SUMMARY OF THE INVENTION
The invention therefore consists in providing a process for manufacturing a multilayer antireflection coating by vacuum evaporation on an organic substrate at a temperature below 150 C, comprising the following steps: deposition of at least one layer of material of refractive index different from MgF2; preparation of the surface
These constraints mean that novel materials have to be sought, these sometimes being difficult to develop from an industrial standpoint. Another approach may consist in using materials previously reserved for substrates made of inorganic material.
To produce a highly effective antireflection treatment, it is necessary for the last layer deposited to have the lowest possible refractive index. In the case of organic substrates, Si02 is often used because of its refractive index of 1.48, its good adhesion, scratch resistance and corrosion resistance properties and its ease of deposition.
MgF2 is very widely used for substrates made of an inorganic material because of its very low refractive index, namely 1.38. A drawback of this material lies in its friability and its lack of adhesion when it is deposited at temperatures below 200 C.
In general, MgF2 is not used for organic substrates as these cannot be heated above 150 C as they undergo yellowing and deterioration.
It is therefore necessary to find a process allowing deposition of MgF2 on an organic substrate ("cold" deposition) and to find other materials which might be suitable.
JP 8-236635 (published September 13, 1996) teaches the deposition of an MgF2 layer on an organic substrate by means of the technology of sputtering.
However, the layers deposited by sputtering have particular physico-chemical characteristics. In particular, the layers deposited are generally denser, which poses an adhesion problem. The document teaches that such deposition carried out by means of vacuum evaporation results in layers having a low degree of crystallization, which entails an insufficient abrasion resistance.
A multilayer antireflection coating on an organic material in the ophthalmic field, the final layer of which is made of MgF2, is also disclosed in the document EP-A-619 504 (published October 12, 1994). That document indicates that the layers disclosed are produced by plasma-enhanced processes and within certain unspecified limits by sputtering. The most economic and most widely used deposition process is however non-plasma-enhanced vacuum evaporation. Layers obtained by plasma-enhanced evaporation furthermore have a higher density than those obtained without enhancement, but high density means that these layers are highly strained, which may result in adhesion of inferior quality.
Document JP 61250601 (published November 7, 1986) also discloses a multilayer antireflection coating on an organic substrate. According to that document, Si02 is used as the outer layer of low refractive index and preferably a multilayer coating consisting of three layers of the Y203/TiO2/SiO2 type is used.
During deposition of the multilayer coating, the interface of at least one of the layers is treated by ion bombardment. This treatment improves the adhesion of the layers.
The use of MgF2 as material having a low refractive index is neither disclosed nor suggested in that document.
Document JP 7076048 (published March 20, 1995) discloses a multilayer antireflection coating deposited on an organic substrate. This specifies that the outer layer, made of MgF2, is deposited at low temperature with ion assistance using the IAD (Ion Assisted Deposition) technique and that surface on which this layer is deposited is subjected beforehand to a cleaning treatment by ion bombardment and/or by plasma. However, it turns out that the use of the IAD technique has a number of drawbacks. This type of assistance is generally used to densify the layers deposited. But on the downside, the densest layers have lower adhesion.
Furthermore, ion assistance may make the MgF2 layer more absorbent, this being a troublesome drawback in the case of ophthalmic applications. Finally, this type of assistance makes the process more complicated and increases the production costs substantially.
SUMMARY OF THE INVENTION
The invention therefore consists in providing a process for manufacturing a multilayer antireflection coating by vacuum evaporation on an organic substrate at a temperature below 150 C, comprising the following steps: deposition of at least one layer of material of refractive index different from MgF2; preparation of the surface
3 of the substrate thus coated; and deposition of an outer layer of MgF2 without ion assistance. Preferably, the vacuum evaporation is carried out at a temperature below 100 C.
Preferably, the surface preparation is chosen from among the following treatments: ion bombardment, electron bombardment and etching carried out ex situ.
According to a preferred embodiment, said layer consists of a material having a high refractive index chosen from a group of simple or mixed oxides or mixtures of oxides of metals of groups IIIb, IVb, Vb, Vib, VIIb and lanthanides.
Preferably, the metals are chosen from the group Pr, La, Ti, Zr, Ta and Hf. Also preferred are materials having a high refractive index chosen from the group consisting of Zr02, PrTiO3, PrZ03/TiO2 mixtures, Pr60j1/Ti02 mixtures, La203/TiO2 mixtures and Zr02/Ti02 mixtures.
According to one embodiment, said layer of material of refractive index different from MgF2 is a hard coating. According to another embodiment, said layer of material of refractive index different from MgF2 is an impact-resistant layer.
According to yet another embodiment, said layer of material of refractive index different from MgF2 is an antifringe layer.
Preferably, the process comprises, before the layer of material of refractive index different from MgF2 is deposited, the prior step of depositing a layer of low refractive index. Preferably, the layer of low refractive index has a thickness of between 40 and 200 nm, preferably 60 nm.
According to one embodiment, the step of depositing the material of refractive index different from MgF2 comprises the following steps: deposition of a first layer of material of refractive index different from MgF2; deposition of a layer of material having a low refractive index; and deposition of a second layer of material of refractive index different from MgF2.
Preferably, the layer having a low refractive index is made of Si02. It is preferred for the first layer of material of refractive index different from MgF2 to have a thickness of 10 to 40 nm. It is also preferred for the layer of low refractive index to have a thickness of 10 to 100 nm, preferably 40 nm.
Advantageously, the second layer of material of refractive index different from MgF2 has a thickness of 50 to 150 nm, preferably 120 to 130 nm.
The organic substrate is preferably composed of polycarbonate.
Preferably, the outer layer of MgF2 has a thickness of 50 to 100 nm, preferably 80to90nm.
The process according to the invention preferably comprises the subsequent step of depositing a layer that modifies surface energy.
~ ,-
Preferably, the surface preparation is chosen from among the following treatments: ion bombardment, electron bombardment and etching carried out ex situ.
According to a preferred embodiment, said layer consists of a material having a high refractive index chosen from a group of simple or mixed oxides or mixtures of oxides of metals of groups IIIb, IVb, Vb, Vib, VIIb and lanthanides.
Preferably, the metals are chosen from the group Pr, La, Ti, Zr, Ta and Hf. Also preferred are materials having a high refractive index chosen from the group consisting of Zr02, PrTiO3, PrZ03/TiO2 mixtures, Pr60j1/Ti02 mixtures, La203/TiO2 mixtures and Zr02/Ti02 mixtures.
According to one embodiment, said layer of material of refractive index different from MgF2 is a hard coating. According to another embodiment, said layer of material of refractive index different from MgF2 is an impact-resistant layer.
According to yet another embodiment, said layer of material of refractive index different from MgF2 is an antifringe layer.
Preferably, the process comprises, before the layer of material of refractive index different from MgF2 is deposited, the prior step of depositing a layer of low refractive index. Preferably, the layer of low refractive index has a thickness of between 40 and 200 nm, preferably 60 nm.
According to one embodiment, the step of depositing the material of refractive index different from MgF2 comprises the following steps: deposition of a first layer of material of refractive index different from MgF2; deposition of a layer of material having a low refractive index; and deposition of a second layer of material of refractive index different from MgF2.
Preferably, the layer having a low refractive index is made of Si02. It is preferred for the first layer of material of refractive index different from MgF2 to have a thickness of 10 to 40 nm. It is also preferred for the layer of low refractive index to have a thickness of 10 to 100 nm, preferably 40 nm.
Advantageously, the second layer of material of refractive index different from MgF2 has a thickness of 50 to 150 nm, preferably 120 to 130 nm.
The organic substrate is preferably composed of polycarbonate.
Preferably, the outer layer of MgF2 has a thickness of 50 to 100 nm, preferably 80to90nm.
The process according to the invention preferably comprises the subsequent step of depositing a layer that modifies surface energy.
~ ,-
4 The invention also relates to the use of the process according to the invention to improve the adhesion of a multilayer antireflection coating that includes MgF2 on the substrate.
The invention also relates to an organic substrate coated with a multilayer antireflection coating, in particular an ophthalmic lens that can be obtained by the process according to the invention.
Further features and advantages of the invention will become apparent on reading the following description of embodiments of the invention, these being given as examples and with reference to the appended drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
The single figure, a multilayer antireflection coating obtained according to one embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The studies and trials undertaken by the Applicant in the field of MgF2 deposition on organic substrates by vacuum evaporation have resulted in the observation that, contrary to the teaching of the literature, it is possible to produce such layers by vacuum evaporation without recourse to ion assistance.
One advantage of the process according to the invention lies in the fact that it allows these layers to be deposited more economically.
Another advantage of the process according to the invention is that it makes it possible to obtain organic substrates comprising layers having the same physico-chemical characteristics as those deposited on inorganic substrates.
The invention furthermore makes it possible to obtain multilayer antireflection coatings on organic substrates which have the required characteristics, especially in terms of adhesion, but also in terms of scratch resistance.
An example of a multilayer coating that can be obtained by the process according to the invention is illustrated in the figure and described below (the refractive indices are given for a wavelength of 550 nm and the thicknesses given are physical thicknesses).
Within the context of the invention, the term "organic substrates" is understood to mean substrates made of polymer materials, in contrast with substrates made of glass. Particularly intended are substrates made of polycarbonate, polymethyl methacrylate, polythiourethane and poly(bisphenol-A-bisallyl carbonate) and in particular poly(diethylene glycol bisallyl carbonate), commercially available under the name CR39.
According to the embodiment illustrated in the figure, an organic substrate (1) is provided with a hard coating (2), also called a hard coat. This hard coating typically has a thickness of between 300 and 10,000 nm. In general, it is composed of silica or a varnish, for example an epoxide or polysiloxane varnish. It is also possible to apply a plasma polymerization layer, preferably also composed of a polysiloxane, and/or a DLC (diamond-like coating) film. However, this hard coating is not obligatory.
The invention also relates to an organic substrate coated with a multilayer antireflection coating, in particular an ophthalmic lens that can be obtained by the process according to the invention.
Further features and advantages of the invention will become apparent on reading the following description of embodiments of the invention, these being given as examples and with reference to the appended drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
The single figure, a multilayer antireflection coating obtained according to one embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The studies and trials undertaken by the Applicant in the field of MgF2 deposition on organic substrates by vacuum evaporation have resulted in the observation that, contrary to the teaching of the literature, it is possible to produce such layers by vacuum evaporation without recourse to ion assistance.
One advantage of the process according to the invention lies in the fact that it allows these layers to be deposited more economically.
Another advantage of the process according to the invention is that it makes it possible to obtain organic substrates comprising layers having the same physico-chemical characteristics as those deposited on inorganic substrates.
The invention furthermore makes it possible to obtain multilayer antireflection coatings on organic substrates which have the required characteristics, especially in terms of adhesion, but also in terms of scratch resistance.
An example of a multilayer coating that can be obtained by the process according to the invention is illustrated in the figure and described below (the refractive indices are given for a wavelength of 550 nm and the thicknesses given are physical thicknesses).
Within the context of the invention, the term "organic substrates" is understood to mean substrates made of polymer materials, in contrast with substrates made of glass. Particularly intended are substrates made of polycarbonate, polymethyl methacrylate, polythiourethane and poly(bisphenol-A-bisallyl carbonate) and in particular poly(diethylene glycol bisallyl carbonate), commercially available under the name CR39.
According to the embodiment illustrated in the figure, an organic substrate (1) is provided with a hard coating (2), also called a hard coat. This hard coating typically has a thickness of between 300 and 10,000 nm. In general, it is composed of silica or a varnish, for example an epoxide or polysiloxane varnish. It is also possible to apply a plasma polymerization layer, preferably also composed of a polysiloxane, and/or a DLC (diamond-like coating) film. However, this hard coating is not obligatory.
5 The multilayer antireflection coating deposited according to the invention includes a layer (4) of a material having a refractive index different from that of MgF2. This material may, for example, be a varnish or Si02.
According to a preferred embodiment, this layer is made of a material having a high refractive index. Within the context of the invention, the expression "material having a high refractive index" denotes materials having a refractive index greater than 1.6 and preferably from 2 to 2.6. In practice, materials of high refractive index, from 1.9 to 2.3, are usually employed for the multilayer antireflection coatings.
Such materials having a high refractive index suitable for implementing the process according to the invention are, for example, simple or mixed oxides or mixtures of oxides of metals of groups IIIb, 1Vb, Vb, Vlb, VIIb and lanthanides.
Preferably, simple or mixed oxides or mixtures of oxides of the metals Pr, La, Ti, Zr, Ta, and Hf are used, of which Zr02, PrTiO3, Pr203/TiO2 mixtures, Pr6O11/Ti02 mixtures, La203/TiO2 mixtures and Zr02/Ti02 mixtures are particularly preferred.
The layer made of material having a high refractive index may, however, itself consist of a multilayer coating comprising other layers. Thus, in the multilayer coating according to the embodiment illustrated in the figure, the layer (4) of a material having a high refractive index is divided into two layers (4) and (4') separated by a layer (3') made of a material having a low refractive index.
Advantageously, the layers (4) and (4') of material having a high refractive index may consist of the same material.
The layer (4) made of a material having a high refractive index may also be divided into a larger number of layers separated by layers of materials having a lower refractive index.
The layers (3) and (3') having a low refractive index present in the multilayer coating obtained according to the embodiment illustrated may be a material whose refractive index is less than that of the substrate, particularly less than 1.5. Such materials are, for example, Si02, or metal fluorides, Si02 being preferred.
Advantageously, the layers (3) and (3') consist of the same material.
The multilayer antireflection coating obtained according to the invention comprises an outer layer (5) of low refra.ctive index formed from MgF2. The teaching of the literature indicates that this material is difficult to deposit with satisfactory characteristics by techniques compatible with organic materials, that is to say at low temperature. However, it has been found that deposition without ion assistance on a
According to a preferred embodiment, this layer is made of a material having a high refractive index. Within the context of the invention, the expression "material having a high refractive index" denotes materials having a refractive index greater than 1.6 and preferably from 2 to 2.6. In practice, materials of high refractive index, from 1.9 to 2.3, are usually employed for the multilayer antireflection coatings.
Such materials having a high refractive index suitable for implementing the process according to the invention are, for example, simple or mixed oxides or mixtures of oxides of metals of groups IIIb, 1Vb, Vb, Vlb, VIIb and lanthanides.
Preferably, simple or mixed oxides or mixtures of oxides of the metals Pr, La, Ti, Zr, Ta, and Hf are used, of which Zr02, PrTiO3, Pr203/TiO2 mixtures, Pr6O11/Ti02 mixtures, La203/TiO2 mixtures and Zr02/Ti02 mixtures are particularly preferred.
The layer made of material having a high refractive index may, however, itself consist of a multilayer coating comprising other layers. Thus, in the multilayer coating according to the embodiment illustrated in the figure, the layer (4) of a material having a high refractive index is divided into two layers (4) and (4') separated by a layer (3') made of a material having a low refractive index.
Advantageously, the layers (4) and (4') of material having a high refractive index may consist of the same material.
The layer (4) made of a material having a high refractive index may also be divided into a larger number of layers separated by layers of materials having a lower refractive index.
The layers (3) and (3') having a low refractive index present in the multilayer coating obtained according to the embodiment illustrated may be a material whose refractive index is less than that of the substrate, particularly less than 1.5. Such materials are, for example, Si02, or metal fluorides, Si02 being preferred.
Advantageously, the layers (3) and (3') consist of the same material.
The multilayer antireflection coating obtained according to the invention comprises an outer layer (5) of low refra.ctive index formed from MgF2. The teaching of the literature indicates that this material is difficult to deposit with satisfactory characteristics by techniques compatible with organic materials, that is to say at low temperature. However, it has been found that deposition without ion assistance on a
6 lower layer that has undergone a preparation results in substrates of remarkable quality.
This preparation step according to the invention may, for example, be a treatment by ion bombardment, electron bombardment or etching carried out ex situ.
In the multilayer coating obtained according to one embodiment of the invention, the MgF2 is deposited with a thickness of 50 to 100 nm, preferably 80 to 90 nm.
It is possible to deposit, on top of the MgF2 outer layer, one or more layers for modifying the surface energy so as to facilitate cleaning and/or a layer for reducing the electrostatic effect, such as for example a conducting layer.
It has been found that the process according to the invention, especially by virtue of the step of preparing the substrate possibly already coated with other layers before the MgF2 is deposited, allows multilayer antireflection coatings to be obtained which have very satisfactory characteristics from the standpoint of adhesion, scratch resistance, resistance to chemical attack and ease of cleaning.
EXAMPLES
To characterize the multilayer antireflection coatings obtained according to the process of the invention, multilayer antireflection coatings were manufactured on organic substrates (CR39) with various materials having a high refractive index.
The substrates were coated with a mutilayer coating consisting of four layers of the SiO2/HI/SiO2/HUMgF2/top coat type (where HI denotes a material having a high refractive index).
The process according to the invention was carried out in a vacuum evaporator of the Balzers BAK 760 type.
The various HI materials used are given in the table below. The respective suppliers are indicated in brackets. For each of the materials having a high refractive index, a substrate was produced by subjecting the last layer of HI material to ion bombardment under a voltage of 100 V, a current of 1 A for 1 minute and in the presence of argon as gas, but a second substrate was not treated by ion bombardment.
Next, MgF2 was deposited by vacuum evaporation, without ion assistance.
In the examples given, the substrates were coated with a varnish based on silane hydrolysates, as described in French Patent FR 2 702 486 (published April 21, 1995) by the Applicant and more particularly described in example 3.
The outer layer, which makes cleaning easier, is a material of the hydrophobic fluoroorganosilane type. As an example, a material sold by Opton under the name OF 110 was used to produce this layer.
This preparation step according to the invention may, for example, be a treatment by ion bombardment, electron bombardment or etching carried out ex situ.
In the multilayer coating obtained according to one embodiment of the invention, the MgF2 is deposited with a thickness of 50 to 100 nm, preferably 80 to 90 nm.
It is possible to deposit, on top of the MgF2 outer layer, one or more layers for modifying the surface energy so as to facilitate cleaning and/or a layer for reducing the electrostatic effect, such as for example a conducting layer.
It has been found that the process according to the invention, especially by virtue of the step of preparing the substrate possibly already coated with other layers before the MgF2 is deposited, allows multilayer antireflection coatings to be obtained which have very satisfactory characteristics from the standpoint of adhesion, scratch resistance, resistance to chemical attack and ease of cleaning.
EXAMPLES
To characterize the multilayer antireflection coatings obtained according to the process of the invention, multilayer antireflection coatings were manufactured on organic substrates (CR39) with various materials having a high refractive index.
The substrates were coated with a mutilayer coating consisting of four layers of the SiO2/HI/SiO2/HUMgF2/top coat type (where HI denotes a material having a high refractive index).
The process according to the invention was carried out in a vacuum evaporator of the Balzers BAK 760 type.
The various HI materials used are given in the table below. The respective suppliers are indicated in brackets. For each of the materials having a high refractive index, a substrate was produced by subjecting the last layer of HI material to ion bombardment under a voltage of 100 V, a current of 1 A for 1 minute and in the presence of argon as gas, but a second substrate was not treated by ion bombardment.
Next, MgF2 was deposited by vacuum evaporation, without ion assistance.
In the examples given, the substrates were coated with a varnish based on silane hydrolysates, as described in French Patent FR 2 702 486 (published April 21, 1995) by the Applicant and more particularly described in example 3.
The outer layer, which makes cleaning easier, is a material of the hydrophobic fluoroorganosilane type. As an example, a material sold by Opton under the name OF 110 was used to produce this layer.
7 The substrates thus obtained were then subjected to a series of tests so as to evaluate their performance.
The substrates were subjected to the test called the N x 10 blows and described in the application W099/49097 (published September 30, 1999). This test stressed the adhesion of the thin layers deposited on an organic substrate. The results are given in Table 1, in which concave faces (CC) are distinguished from the convex faces (CX) of the substrates. It may be seen that the substrates manufactured according to the process of the invention give results at least comparable, and for most part superior, to materials having a high refractive index.
The substrates were also subjected to the test called the "steel wool" test.
This test was carried out using starwax No. 000 extra-fine steel wool.
Approximately 3 cm of steel wool was folded over on itself and applied to the coated substrate with a constant pressure. After making 5 to-and-fro movements, the state of the substrate was assessed visually and a rating assigned according to the following gradation:
- 1 intact substrate, no scratching or fine localized scratches present;
- 3 substrate with more intense scratches and slight tearing (white scratches);
- 5 substrate with white scratches covering almost the entire surface tested (tearing of the varnish or of the corresponding substrate). The result obtained corresponds to that of the steel wool test applied to the non-varnish CR 39.
ry.u.w.. wn.w.N, ~m õ .ui..-.. . .. d.,..iw,r~ ... .....,. .. ., .V:.rwM`h õ
a.,.r .a ., . ,....... ,v....... ........ .,.,r,- .:,n. .... . ..,.,.,.
3 n M V'~ kn kn W) VI) ~ o U
4) ~p o N M ~ N
bq +
N M M
Cl~ O =
U
cd ~".
~ U N N N N
U O~ M Ql\ M
cts n n n n U
v~
~
N N N N N
x .-+ r--q -- .-+ '-+ M Q~ M
z U n n n n n H
~
N N N N N N N N N
n n n n n n n n n U .~
v~ >
3 .~
~
N N N N N N N N N
x 1-- r-+ ~ .-+ 1-4 =-- 1'-- ~ 1--4 z v n n n n n n n n n ~ O s I==N
U ~~+ ,!C ' ==, ~ ~ ~ J
F'i ~i" = "''~'"' b !.~ - a~d ~ ~" N N .ryy Ch'J
Cd +=+ r~ ^, `^ ~ F'+ b ._^, L~i O O r~ OL, Q U N N N O N
ar Fy ~O C N '~GC O O
cd N
x a, a~a dN N~O E~ x a Substrates with a rating up to 3 were accepted, those up to 5 were rej ected.
The test was carried out for 5 to 10 substrates each time, and the average of the results is given in Table 1.
It may be seen that the results of the steel wool test are very satisfactory in the case of the substrates that have undergone the ion bombardment, whereas all of the other substrates give poor results. The PrTiO3, Pr601 >/Ti02 mixture, LaTiO3, La203/TiO2 mixture, Zr02 and ZrOZ/TiO2 mixture materials give particularly remarkable results.
In conclusion, for all of the materials tested given in the Table, the performance obtained in the N x 10 blow and steel wool tests are good and meet the Essilor standard.
It is apparent from these observations that we have identified a cold deposition process for depositing MgF2 on an organic substrate which does not require the use of IAD. This process furthermore makes it possible to deposit MgF2 layers having properties equivalent to those of layers deposited hot.
The organic substrate coated with a multilayer antireflection coating according to the invention can be used in various fields, especially in optics. It is most particularly useful in the manufacture of ophthalmic lenses.
R:\Brevers\17600\17637GB.doc - 20 janvier 2003 - 9/12
The substrates were subjected to the test called the N x 10 blows and described in the application W099/49097 (published September 30, 1999). This test stressed the adhesion of the thin layers deposited on an organic substrate. The results are given in Table 1, in which concave faces (CC) are distinguished from the convex faces (CX) of the substrates. It may be seen that the substrates manufactured according to the process of the invention give results at least comparable, and for most part superior, to materials having a high refractive index.
The substrates were also subjected to the test called the "steel wool" test.
This test was carried out using starwax No. 000 extra-fine steel wool.
Approximately 3 cm of steel wool was folded over on itself and applied to the coated substrate with a constant pressure. After making 5 to-and-fro movements, the state of the substrate was assessed visually and a rating assigned according to the following gradation:
- 1 intact substrate, no scratching or fine localized scratches present;
- 3 substrate with more intense scratches and slight tearing (white scratches);
- 5 substrate with white scratches covering almost the entire surface tested (tearing of the varnish or of the corresponding substrate). The result obtained corresponds to that of the steel wool test applied to the non-varnish CR 39.
ry.u.w.. wn.w.N, ~m õ .ui..-.. . .. d.,..iw,r~ ... .....,. .. ., .V:.rwM`h õ
a.,.r .a ., . ,....... ,v....... ........ .,.,r,- .:,n. .... . ..,.,.,.
3 n M V'~ kn kn W) VI) ~ o U
4) ~p o N M ~ N
bq +
N M M
Cl~ O =
U
cd ~".
~ U N N N N
U O~ M Ql\ M
cts n n n n U
v~
~
N N N N N
x .-+ r--q -- .-+ '-+ M Q~ M
z U n n n n n H
~
N N N N N N N N N
n n n n n n n n n U .~
v~ >
3 .~
~
N N N N N N N N N
x 1-- r-+ ~ .-+ 1-4 =-- 1'-- ~ 1--4 z v n n n n n n n n n ~ O s I==N
U ~~+ ,!C ' ==, ~ ~ ~ J
F'i ~i" = "''~'"' b !.~ - a~d ~ ~" N N .ryy Ch'J
Cd +=+ r~ ^, `^ ~ F'+ b ._^, L~i O O r~ OL, Q U N N N O N
ar Fy ~O C N '~GC O O
cd N
x a, a~a dN N~O E~ x a Substrates with a rating up to 3 were accepted, those up to 5 were rej ected.
The test was carried out for 5 to 10 substrates each time, and the average of the results is given in Table 1.
It may be seen that the results of the steel wool test are very satisfactory in the case of the substrates that have undergone the ion bombardment, whereas all of the other substrates give poor results. The PrTiO3, Pr601 >/Ti02 mixture, LaTiO3, La203/TiO2 mixture, Zr02 and ZrOZ/TiO2 mixture materials give particularly remarkable results.
In conclusion, for all of the materials tested given in the Table, the performance obtained in the N x 10 blow and steel wool tests are good and meet the Essilor standard.
It is apparent from these observations that we have identified a cold deposition process for depositing MgF2 on an organic substrate which does not require the use of IAD. This process furthermore makes it possible to deposit MgF2 layers having properties equivalent to those of layers deposited hot.
The organic substrate coated with a multilayer antireflection coating according to the invention can be used in various fields, especially in optics. It is most particularly useful in the manufacture of ophthalmic lenses.
R:\Brevers\17600\17637GB.doc - 20 janvier 2003 - 9/12
Claims (23)
1. A process for manufacturing a multilayer antireflection coating by vacuum evaporation on an organic substrate at a temperature below 150°C, comprising the following steps:
- deposition of at least one layer of material of refractive index different from MgF2;
- preparation of the surface of the substrate thus coated; and - deposition of an outer layer of MgF2 without ion assistance, the surface preparation being selected from the group consisting of ion bombardment, electron bombardment and etching carried out ex situ.
- deposition of at least one layer of material of refractive index different from MgF2;
- preparation of the surface of the substrate thus coated; and - deposition of an outer layer of MgF2 without ion assistance, the surface preparation being selected from the group consisting of ion bombardment, electron bombardment and etching carried out ex situ.
2. The process as claimed in claim 1, in which the vacuum evaporation is carried out at a temperature below 100°C.
3. The process as claimed in claim 2, in which the layer of material of refractive index different from MgF2 is made of a material having a high refractive index chosen from a group of simple or mixed oxides or mixtures of metals of groups IIIb, IVb, Vb, VIb, VIIb and lanthanides.
4. The process as claimed in one of claims 2 to 3, in which the metals are chosen from the group Pr, La, Ti, Zr, Ta and Hf.
5. The process as claimed in one of claims 2 to 4, in which the materials having a high refractive index are chosen from the group consisting of ZrO2, PrTiO3, Pr2O3/TiO2 mixtures, Pr6O11/TiO2 mixtures, La2O3/TiO2 mixtures and ZrO2/TiO2 mixtures.
6. The process as claimed in one of claims 1 to 5, characterized in that said layer of material of refractive index different from MgF2 is a hard coating.
7. The process as claimed in one of claims 1 to 6, characterized in that said layer of material of refractive index different from MgF2 is an impact-resistant layer.
8. The process as claimed in one of claims 1 to 7, characterized in that said layer of material of refractive index different from MgF2 is an antifringe layer.
9. The process as claimed in one of claims 1 to 8, comprising, before the layer of material of refractive index different from MgF2 is deposited, the prior step of depositing a layer of low refractive index.
10. The process as claimed in claim 9, in which the layer of low refractive index has a thickness of between 40 and 200 nm.
11. The process as claimed in claim 10, in which the layer of low refractive index has a thickness of 60 nm.
12. The process as claimed in one of claims 1 to 11, in which the step of depositing the material of refractive index different from MgF2 comprises the following steps:
- deposition of a first layer of material of refractive index different from MgF2;
- deposition of a layer of material having a low refractive index; and - deposition of a second layer of material of refractive index different from MgF2.
- deposition of a first layer of material of refractive index different from MgF2;
- deposition of a layer of material having a low refractive index; and - deposition of a second layer of material of refractive index different from MgF2.
13. The process as claimed in claim 12, in which the layer having a low refractive index is made of SiO2.
14. The process as claimed in either of claims 12 and 13, in which the first layer of material of refractive index different from MgF2 has a thickness of 10 to 40 nm.
15. The process as claimed in one of claims 12 to 14, in which the layer of material having a low refractive index has a thickness of 10 to 100 nm.
16. The process as claimed in claim 15, in which the layer of material having a low refractive index has a thickness of 40 nm.
17. The process as claimed in one of claims 12 to 16, in which the second layer of material of refractive index different from MgF2 has a thickness of 50 to 150 nm.
18. The process as claimed in claim 17, in which the second layer of material of refractive index different from MgF2 has a thickness of 120 to 130 nm.
19. The process as claimed in one of claims 1 to 18, in which the organic substrate is composed of polycarbonate.
20. The process as claimed in one of claims 1 to 19, in which the outer layer of MgF2 has a thickness of 50 to 100 nm.
21. The process as claimed in claim 20, in which the outer layer of MgF2 has a thickness of 80 to 90 nm.
22. The process as claimed in one of claims 1 to 21, comprising the subsequent step of depositing a layer that modifies the surface energy.
23. The use of the process as claimed in one of claims 1 to 22 to improve the adhesion of a multilayer antireflection coating that includes MgF2 on the substrate.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0015334A FR2817267B1 (en) | 2000-11-28 | 2000-11-28 | METHOD OF DEPOSITING ANTI-REFLECTIVE COLD LAYER ON ORGANIC SUBSTRATE |
FR00/15334 | 2000-11-28 | ||
PCT/FR2001/003723 WO2002044440A1 (en) | 2000-11-28 | 2001-11-26 | Method for cold process deposition of an antiglare layer |
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CA2429150A1 CA2429150A1 (en) | 2002-06-06 |
CA2429150C true CA2429150C (en) | 2010-03-30 |
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CA2429150A Expired - Fee Related CA2429150C (en) | 2000-11-28 | 2001-11-26 | Cold antireflection layer deposition process |
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US (1) | US7175878B2 (en) |
EP (1) | EP1339893B1 (en) |
JP (1) | JP2004514939A (en) |
KR (1) | KR100845244B1 (en) |
CN (1) | CN1239733C (en) |
AT (1) | ATE386830T1 (en) |
AU (2) | AU2002222043B2 (en) |
BR (1) | BR0115898B1 (en) |
CA (1) | CA2429150C (en) |
DE (1) | DE60132914T2 (en) |
ES (1) | ES2301578T3 (en) |
FR (1) | FR2817267B1 (en) |
PT (1) | PT1339893E (en) |
WO (1) | WO2002044440A1 (en) |
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JP3555844B2 (en) | 1999-04-09 | 2004-08-18 | 三宅 正二郎 | Sliding member and manufacturing method thereof |
US6969198B2 (en) | 2002-11-06 | 2005-11-29 | Nissan Motor Co., Ltd. | Low-friction sliding mechanism |
JP4863152B2 (en) | 2003-07-31 | 2012-01-25 | 日産自動車株式会社 | gear |
US7771821B2 (en) | 2003-08-21 | 2010-08-10 | Nissan Motor Co., Ltd. | Low-friction sliding member and low-friction sliding mechanism using same |
FR2861182B1 (en) * | 2003-10-16 | 2006-02-03 | Essilor Int | TRANSPARENT ORGANIC SUBSTRATE COMPRISING A TEMPERATURE RESISTANT MULTILAYER ANTIREFLECTION STACK |
JP5135753B2 (en) * | 2006-02-01 | 2013-02-06 | セイコーエプソン株式会社 | Optical article |
FR2903197B1 (en) * | 2006-06-28 | 2009-01-16 | Essilor Int | OPTICAL ARTICLE COATED WITH A TEMPERATURE-RESISTANT MULTILAYER COATED ANTI-REFLECTING COATING AND COATING, AND METHOD OF MANUFACTURING THE SAME |
US8318245B2 (en) | 2007-02-23 | 2012-11-27 | Essilor International (Compagnie Generale D'optique) | Method for producing an optical article coated with an antireflection or a reflective coating having improved adhesion and abrasion resistance properties |
FR2913116B1 (en) * | 2007-02-23 | 2009-08-28 | Essilor Int | METHOD FOR MANUFACTURING OPTICAL ARTICLE COATED WITH AN ANTI-REFLECTIVE OR REFLECTIVE COATING HAVING IMPROVED ADHESION AND ABRASION RESISTANCE PROPERTIES |
JP5308640B2 (en) * | 2007-08-06 | 2013-10-09 | Hoya株式会社 | Antireflection film and optical member using the same |
JP4693836B2 (en) * | 2007-12-17 | 2011-06-01 | 日本電波工業株式会社 | Infrared cut filter and manufacturing method thereof |
US8691331B2 (en) * | 2009-02-09 | 2014-04-08 | Prashant D. Santan | Surface modification of hydrophobic and/or oleophobic coatings |
US20110199680A1 (en) * | 2010-01-22 | 2011-08-18 | Oakley, Inc. | Eyewear with three-dimensional viewing capability |
CA2787576A1 (en) * | 2010-01-22 | 2011-07-28 | Oakley, Inc. | Lenses for 3d eyewear |
KR20130061683A (en) | 2010-04-29 | 2013-06-11 | 바텔리 메모리얼 인스티튜트 | High refractive index composition |
JP5589581B2 (en) * | 2010-06-11 | 2014-09-17 | コニカミノルタ株式会社 | Optical element and manufacturing method thereof |
FR2975507B1 (en) * | 2011-05-16 | 2014-01-10 | Essilor Int | ANTI-REFLECTIVE OPHTHALMIC LENS AND METHOD OF MANUFACTURING THE SAME |
JP5699364B2 (en) * | 2012-12-21 | 2015-04-08 | 株式会社麗光 | High hardness hard coat film |
CN103059617B (en) * | 2013-01-05 | 2015-07-22 | 江西安源光伏玻璃有限责任公司 | Preparation method for nanometer anti-reflection self-cleaning coating solution |
EP3346023A1 (en) * | 2017-01-05 | 2018-07-11 | Essilor International | Method for layer by layer optimization of a thin film |
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JPS61250601A (en) | 1985-04-30 | 1986-11-07 | Toray Ind Inc | Optical material having antireflection property and its production |
US5783299A (en) * | 1986-01-21 | 1998-07-21 | Seiko Epson Corporation | Polarizer plate with anti-stain layer |
JPS62186203A (en) * | 1986-02-12 | 1987-08-14 | Seiko Epson Corp | Antireflection film for plastic optical parts |
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US5920431A (en) * | 1996-06-27 | 1999-07-06 | Konica Corporation | Optical member having antireflection film thereon |
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-
2000
- 2000-11-28 FR FR0015334A patent/FR2817267B1/en not_active Expired - Fee Related
-
2001
- 2001-11-26 DE DE60132914T patent/DE60132914T2/en not_active Expired - Lifetime
- 2001-11-26 CA CA2429150A patent/CA2429150C/en not_active Expired - Fee Related
- 2001-11-26 ES ES01998671T patent/ES2301578T3/en not_active Expired - Lifetime
- 2001-11-26 EP EP01998671A patent/EP1339893B1/en not_active Expired - Lifetime
- 2001-11-26 AU AU2002222043A patent/AU2002222043B2/en not_active Ceased
- 2001-11-26 KR KR1020037007077A patent/KR100845244B1/en active IP Right Grant
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- 2001-11-26 CN CNB018196101A patent/CN1239733C/en not_active Expired - Fee Related
- 2001-11-26 BR BRPI0115898-8A patent/BR0115898B1/en not_active IP Right Cessation
- 2001-11-26 WO PCT/FR2001/003723 patent/WO2002044440A1/en active IP Right Grant
- 2001-11-26 AU AU2204302A patent/AU2204302A/en active Pending
- 2001-11-26 PT PT01998671T patent/PT1339893E/en unknown
- 2001-11-26 JP JP2002546785A patent/JP2004514939A/en active Pending
- 2001-11-26 US US10/432,662 patent/US7175878B2/en not_active Expired - Lifetime
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CN1478154A (en) | 2004-02-25 |
ATE386830T1 (en) | 2008-03-15 |
BR0115898A (en) | 2003-11-04 |
EP1339893A1 (en) | 2003-09-03 |
DE60132914T2 (en) | 2009-03-12 |
US7175878B2 (en) | 2007-02-13 |
CA2429150A1 (en) | 2002-06-06 |
WO2002044440A1 (en) | 2002-06-06 |
US20040067351A1 (en) | 2004-04-08 |
AU2002222043B2 (en) | 2006-10-12 |
AU2204302A (en) | 2002-06-11 |
DE60132914D1 (en) | 2008-04-03 |
KR100845244B1 (en) | 2008-07-10 |
JP2004514939A (en) | 2004-05-20 |
FR2817267B1 (en) | 2003-08-29 |
PT1339893E (en) | 2008-05-13 |
BR0115898B1 (en) | 2011-09-20 |
EP1339893B1 (en) | 2008-02-20 |
ES2301578T3 (en) | 2008-07-01 |
CN1239733C (en) | 2006-02-01 |
FR2817267A1 (en) | 2002-05-31 |
KR20030057558A (en) | 2003-07-04 |
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