WO2006087502A1 - Couche dlc antisalissure - Google Patents
Couche dlc antisalissure Download PDFInfo
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- WO2006087502A1 WO2006087502A1 PCT/FR2006/050153 FR2006050153W WO2006087502A1 WO 2006087502 A1 WO2006087502 A1 WO 2006087502A1 FR 2006050153 W FR2006050153 W FR 2006050153W WO 2006087502 A1 WO2006087502 A1 WO 2006087502A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J65/00—Lamps without any electrode inside the vessel; Lamps with at least one main electrode outside the vessel
- H01J65/04—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels
- H01J65/042—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels by an external electromagnetic field
- H01J65/046—Lamps in which a gas filling is excited to luminesce by an external electromagnetic field or by external corpuscular radiation, e.g. for indicating plasma display panels by an external electromagnetic field the field being produced by using capacitive means around the vessel
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
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- G02B1/105—
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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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/30—Vessels; Containers
- H01J61/305—Flat vessels or containers
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31—Surface property or characteristic of web, sheet or block
Definitions
- the present invention relates to a substrate comprising a surface-treated antireflection coating whose optical properties are not very sensitive to soiling and which are easy to clean.
- Anti-reflective coatings are particularly used in the field of ophthalmic lenses, in particular spectacle lenses. It is generally mono or multilayer coating generally obtained by vacuum deposition of metal oxides.
- the soil has two major effects, firstly it alters the visual perception of the wearer, by degrading the transmission transmitted transmitted light beams perceived by the wearer and, on the other hand, it causes unsightly effects, by modifying locally on the surface of the glass the intensity and the color of the reflection perceived by an outside observer.
- hydrophobic and / or oleophobic coatings are obtained by applying, on the surface of the antireflection coating, compounds that reduce the surface energy.
- Such compounds have been widely described in the prior art, for example in patents US4410563, EP0203730, EP749021, EP844265, EP933377.
- Silane compounds bearing fluorinated groups in particular perfluorocarbon or perfluoropolyether group (s), are most often used.
- silazane, polysilazane or silicone compounds comprising one or more fluorinated group (s) such as those mentioned above.
- a particularly effective known method consists in depositing on the antireflection coating compounds carrying fluorinated groups and Si-R groups, R representing an OH group or a precursor thereof, preferably an alkoxy group.
- R representing an OH group or a precursor thereof, preferably an alkoxy group.
- conventional hydrophobic and / or oleophobic coatings have a thickness of less than 10 nm and give a surface energy of less than 20 mJ (millijoules) / m 2 and less than 15 mJ / m 2 for the most efficient ones. These coatings give satisfaction to a large number of carriers.
- the substrates comprise an intermediate layer interposed between the substrate and a substantially optically transparent DLC outer layer deposited by evaporation.
- stacks of layers deposited from the substrate are described, in this order: a first interlayer, a second interlayer, a DLC layer, another interlayer, an outer layer of the DLC type.
- the thicknesses of these different layers may be chosen to minimize or maximize the reflection of light in a predetermined wavelength range.
- WO92 / 05951 indicates that the advantage of these stacks is to have superior abrasion resistance compared to conventional optical coatings.
- the DLC deposit is preferably carried out by deposition by means of an ion gun from a hydrocarbon gas, in particular methane, or carbon vapor.
- the thickness of the DLC layer may vary from 10 Angstroms to 10 microns, preferably at least 200 Angstroms.
- Example Q describes reflective stacks deposited in this order from the surface of the mineral glass substrate SiO 2 (75 nm) /
- the substrate thus coated can be used as a sunglass lens and has a blue-yellow reflection.
- US Pat. No. 5,190,807 describes stacks of the same type on an organic substrate itself coated with a layer of polysiloxane. one or more intermediate layers, which may comprise metal oxides or metal nitrides.
- the substrates are sunglass lenses and are essentially made of polycarbonate.
- the abrasion resistance of the final stack and its durability are the main characteristics mentioned for these products.
- US 6077569 discloses a method for producing antireflection coatings and mirror effect on lenses such as ophthalmic lenses, especially for sunglass lenses.
- the dielectric materials used include DLC materials.
- This material can be used as a component of one of the layers of the stack, or can be used as the top or outer layer of the stack, in which case the DLC layer provides additional protection against abrasion, good strength chemical.
- the patent states that the high atomic density of the DLC layer, its hydrophobic nature, its hardness, and its low coefficient of friction lead to a stack having a longer life, better abrasion resistance and cleaning ability. .
- the first coating of the stack is a composite transparent coating having a high degree of abrasion resistance.
- This abrasion resistant coating preferably 5 to 20 microns is obtained by ion assisted deposition from an organosilane plasma or organosilazane.
- the DLC layer is used for its conventional properties, and essentially to increase the abrasion resistance and shelf life of the products on which it is deposited.
- the thickness of the DLC layer is at least 20 nm.
- the document WO92 / 05951 indicates in particular that, to increase the abrasion resistance of the stack, it is preferable to provide a plurality of DLC layers forming an integral part of the stack, which makes it possible to increase the total thickness of the stack. DLC filed.
- One of the objectives of the invention is to provide a substrate comprising an antireflection stack whose optical properties, particularly in transmission, are not, or very little affected by soiling, including fingerprints.
- Another object of the invention is to obtain a substrate comprising an antireflection coating that is not very sensitive to soiling and that can be easily cleaned from a conventional stack, without the need to modify the structure and the materials constituting this stack.
- Another objective of the invention is to provide an anti-reflective stack that is not very sensitive to soiling, without significantly affecting the performance of the antireflection stack.
- Another object of the invention is to obtain a substrate having an antireflection and having a high optical transmission, despite the presence of dirt on the surface thereof.
- a substrate having two main faces, at least one of which comprises an antireflection coating on which is deposited an outer layer in contact with the air, of thickness less than or equal to 10 nm, of which surface energy is less than 60 mJ / m 2 and the surface has a contact angle with oleic acid of less than 70 °.
- the inventors have found that by depositing on the surface of an antireflection stack an ultrafine layer of an oleophilic material with a low surface energy, the optical properties in transmission of the substrate coated with the antireflection stack were almost not affected by the stains deposited on the antireflection stack, unlike anti-reflective coatings bearing hydrophobic and oleophobic top coats conventionally used and described above. In practice, this means, in the case where the substrate is an ophthalmic lens of a spectacle lens, that the wearer does not have his or her vision affected, or very little, by the soiling.
- the deposition of a soiling has the effect of locally adding an additional layer of a fatty material on the antireflection stack, which has the effect of disrupt the optical properties of the latter, by affecting on the one hand the transmission incident light rays and, on the other hand, the reflection of these same rays.
- the color of the residual reflection is generally modified locally in the area where the soil is located.
- the inventors have found that the stain deposited on hydrophobic and oleophobic top coats currently used as an outer layer deposited on antireflection stacks matches microgoutlets which are easy to remove from the surface due to the low surface energy. but which diffuse the light.
- the preferred outer layers are those having a contact angle with oleic acid of less than or equal to 40 °, more preferably less than or equal to 30 °, more preferably less than or equal to 20 °, and optimally less than or equal to 15 ° .
- the outer layer will be chosen with the lowest possible surface energy, while retaining the oleophilic properties described above.
- the surface energy of said outer layer is less than 55 mJ / m 2 , more preferably less than 50 mJ / m 2 , more preferably less than 45 mJ / m 2 , and optimally less than 30 mJ / m 2 .
- the surface energies are calculated according to the OwensWendt method described in the following reference: "Estimation of the surface force energy of polymers” W. D. W., Wendt R. G. (1969) J. APPL POLYM.SCI, 13, 1741-1747.
- any type of material or mixture of materials can be used leading to the required oleophilic and surface energy properties.
- DLC layers containing silicon and fluorine DLC layers containing silicon and fluorine. Such layers are described, for example, in the article "M. Grishke (1998) Diamond and Relaled Materials, 7, 454-458". These layers are obtained by plasma methods from, (for example) HMDSO (hexamethyldisiloxane) or TMS (trimethylsilane) for the silicon films and CF 4 for the fluorinated layers.
- HMDSO hexamethyldisiloxane
- TMS trimethylsilane
- a material particularly suitable for the implementation of the invention is a DLC material.
- DLC materials have been widely described in the literature and can be defined as a metastable form of amorphous carbon containing a significant fraction of CC sp 3 bonds. It can be materials comprising only carbon or hydrogenated alloys designated aC: H.
- DLC layers The properties of the DLC layers and the processes for obtaining them are described in particular in the article "Diamond-like amorphous carbon”; J.Robertson; Materials science and engineering R37 (2002) 129-181.
- the DLC material comprises an ⁇ -C: H material. Layers of this material are relatively hydrophobic
- This type of material can be defined as hybrid sp 2 carbon clusters, mostly aromatic, dispersed in a matrix having hybridized carbon-carbon bonds sp 3 , more or less hydrogenated.
- the layer comprising the ⁇ -C: H material is chemically deposited in the plasma-assisted vapor phase.
- the plasma-assisted chemical vapor deposition method involves obtaining, by the application of a voltage, a condensation reaction at the surface of the sample between a reactive gas and this surface, the reactive gas being at least partially ionized in the form of a plasma.
- the plasma is obtained by at least partial ionization of a gas comprising a hydrocarbon, such as CH 4 , C 2 H 2 , C 2 H 4 and C ⁇ H ⁇ , preferably methane CH 4 .
- a gas comprising a hydrocarbon, such as CH 4 , C 2 H 2 , C 2 H 4 and C ⁇ H ⁇ , preferably methane CH 4 .
- CH 3 + , C 2 H 5 + , H + ions are formed which will bombard the substrate.
- the plasma also comprises CH 3 , C 2 H 5 and H radicals.
- the substrate is in contact with a cathode coupled to a radiofrequency generator.
- An important parameter that makes it possible to define the structural state of the DLC films, and in particular a-C: H obtained, is the self-biasing voltage applied between the substrate-carrier electrode (cathode) and the plasma.
- the hydrogen concentration decreases when the self-bias voltage at the cathode increases in absolute value.
- H of the deposited layer are small in size and dispersed in a highly hydrogenated sp 3 matrix.
- the mechanical properties of this layer are similar to those of a polymer and are relatively weak.
- a self-bias voltage, in absolute value of 150 volts
- the sp 3 matrix is less hydrogenated and a maximum sp 3 carbon-carbon hybridization and good mechanical properties are obtained.
- high self-bias voltages in absolute value of the order of 400 volts, the size of the graphitic clusters increases, the layer becomes more absorbent and less hard.
- the ⁇ -C: H material used in the context of the present invention generally comprises a hydrogen atom atomic percentage of 30 to 55%, and more preferably greater than 43%.
- ⁇ -C H materials are deposited by imposing generally on the cathode a self-biasing voltage of 0 to -400 volts, preferably 0 to -150 volts, and more preferably -10 to -50 volts.
- the gas pressure typically ranges from 10 "2 mbar to 10" 1 mbar.
- the refractive index at 25 ° C. and 630 nm of said outer layer varies from 1.58 to 2.15, preferably from 1.60 to 2.10.
- the thickness of said outer layer varies from more than 2 nm to 10 nm, and better still from 3 to 8 nm. At these reduced thicknesses, the absorption of the DLC layer remains low. As indicated above, it is moreover possible to minimize this absorption by operating, during the deposition of this layer, to low self-bias voltages, in absolute value, of the cathode.
- Self-biasing voltages from 0 to -50 volts are particularly recommended, preferably from -10 to -50 volts, this latter range of voltages making it possible to combine a low extinction coefficient with satisfactory mechanical properties (hardness).
- ⁇ C: H materials which have an extinction coefficient at 400 nm of less than 0.20, preferably less than 0.15. .
- the antireflection coating on which the layer is deposited may be an antireflection coating conventionally known in the state of the art.
- the antireflection coating may consist of a mono- or multilayer film, of dielectric material such as SiO, SiO 2 , Si 3 N 4 , TiO 2 , ZrO 2 , Al 2 O 3 , MgF 2 or Ta 2 O 5 , or mixtures thereof.
- This anti-reflection coating is generally applied by vacuum deposition according to one of the following techniques:
- the antireflection coating is a multilayer coating, it is an alternating stack of layers of high refractive index material and low refractive index material.
- high index n% ⁇ 1.55 preferentially> 1.60; low index " ⁇ (1, 50, preferentially ⁇ 1, 45.
- the reflection coefficient Rm (mean of reflection over the wavelength range 400-800 nm) of the substrate face coated with said antireflection coating and said outer layer is less than 2.5%.
- the reflection coefficient Rm of the coated face is less than 2%, better still less than 1, 5% and better still less than 1%.
- the antireflection coating generally has a physical thickness of less than 700 nm, preferably less than 500 nm.
- the antireflection coating is a multilayer coating.
- the material with a high refractive index of the antireflection coating is preferably chosen from metal oxides.
- the material with a low refractive index is preferably chosen from silicon oxides, in particular SiO 2.
- the antireflection coating is preferably deposited by evaporation.
- the antireflection stack may comprise one or more DLC layers, but preferentially, the antireflection coating does not comprise a layer comprising a DLC material.
- the outer layer in contact with the air, with a thickness of less than or equal to 10 nm, whose surface energy is less than 60 mJ / m 2 and the surface has an angle of contact with oleic acid of less than 70 ° is preferably deposited on a low refractive index layer comprising a silicon oxide and constituting the layer of the antireflection coating furthest from the substrate.
- Anti-reflective coatings may be deposited on any suitable organic or inorganic glass substrate, for example ophthalmic lenses, in particular spectacle lenses, these substrates possibly being bare or optionally coated with one or more coatings, preferably an abrasion-resistant coating. , itself preferably deposited on an anti-shock primer and / or an adhesion primer.
- the antireflection coating is deposited on an anti-abrasion coating.
- an underlayer or foundation layer may be deposited between the abrasion-resistant coating and the anti-reflection coating.
- silica-based underlays which can reach more than 100 nm in thickness, or Cr-based or niobium-based sublayers or their generally finer oxides. typically less than 10 nm thick.
- the anti-abrasion coating is a polysiloxane or methacrylate coating. It is preferably obtained by deposition and hardening of a sol prepared from at least one alkoxysilane such as an epoxysilane, preferably trifunctional, and / or a hydrolyzate thereof, obtained for example by hydrolysis with a solution of hydrochloric acid HCl. After the hydrolysis step, the duration of which is generally between 2 h and 24 h, preferably between 2 h and 6 h, catalysts are optionally added. A surfactant compound is also preferably added to promote the optical quality of the deposit.
- the preferred epoxyalkoxysilanes comprise an epoxy group and three alkoxy groups, the latter being directly bonded to the silicon atom.
- a preferred epoxyalkoxysilane may be an alkoxysilane bearing a ⁇ - (3,4-epoxycyclohexyl) group, such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- Particularly preferred epoxyalkoxysilanes have formula (I):
- R 1 is an alkyl group of 1 to 6 carbon atoms, preferably a methyl or ethyl group
- R 2 is a methyl group or a hydrogen atom
- a is an integer from 1 to 6
- b is 0, 1 or 2.
- epoxysilanes are ⁇ -glycidoxypropyltriethoxysilane or ⁇ -glycidoxypropyltrimethoxysilane.
- ⁇ -glycidoxypropyltrimethoxysilane is used.
- epoxydialkoxysilanes such as ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane and ⁇ -glycidoxyethoxypropylmethyldimethoxysilane can also be used.
- epoxydialkoxysilanes are preferably used at lower levels than the epoxytrialkoxysilanes mentioned above.
- R 3 and R 4 are chosen from substituted or unsubstituted alkyl, methacryloxyalkyl, alkenyl and aryl groups (examples of substituted alkyl groups are halogenated alkyls, in particular chlorinated or fluorinated alkyls);
- Z is an alkoxy, alkoxyalkoxy or acyloxy group;
- c and d represent 0, 1 or 2, respectively; and
- c + d represents 0, 1 or 2.
- This formula includes the following compounds: (1) tetraalkoxysilanes, such as methylsilicate, ethylsilicate, n-propylsilicate, isopropylsilicate, n-butylsilicate, sec-butylsilicate, and t-butylsilicate, and / or (2) trialkoxysilanes, trialkoxyalkoxylsilanes or triacyloxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vi ny Itriéthoxysi lane, vi ny Itri may bethoxyéthoxysi lane, vi ny Itriacétoxysi lane, phenyltrimethoxysilane, phenyltriethoxysilane, v-chloropropyl trimethoxysilane, ⁇ -trifluoropropyltrimethoxys
- the silane hydrolyzate is prepared, for example, by adding water or a solution of hydrochloric acid or sulfuric acid to the silane (s) in the presence of a solvent. It is also possible to carry out the hydrolysis without adding solvents and simply by using the alcohol or carboxylic acid formed during the reaction between the water and the alkoxysilane (s). these solvents by other solvents, such as alcohols, ketones, alkyl chlorides, and aromatic solvents.
- the solution may also comprise particles of inorganic materials such as metal oxide or oxyhydroxide particles, or silica.
- Such particles are silica particles, or particles of high refractive index such as titanium oxide or zirconium particles.
- the sol / gel composition preferably comprises at least one hardening catalyst.
- curing catalysts examples include aluminum compounds, and in particular aluminum compounds chosen from:
- R is a linear or branched chain alkyl group of 1 to 10 carbon atoms, a phenyl group, a group
- n is an integer of 1 to 3.
- an aluminum chelate is a compound formed by reacting an alcoholate or an aluminum acylate with nitrogen and sulfur-free sequestering agents containing oxygen as a coordination atom.
- the aluminum chelate is preferably chosen from the compounds of formula (V):
- X is a group OL in which L is an alkyl group of 1 to 10 carbon atoms
- Y is at least one ligand produced from a compound of formula (1) or (2):
- M 1 , M 2 , M 3 and M 4 are alkyl groups of 1 to 10 carbon atoms, and v is 0.1 or 2.
- Examples of compounds of formula (V) that may be mentioned are aluminum acetylacetonate, aluminum ethylacetoacetate bisacetylacetonate, aluminum bisethylacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate and diisopropoxide monohydrate. aluminum methylacetoacetate.
- anti-abrasion coating compositions may also comprise one or more additives, such as pigments, UV absorbers, photochromic dyes, anti-yellow agents, antioxidants.
- the anti-abrasion coating compositions may further comprise an organic solvent, preferably boiling point, at atmospheric pressure, between 70 and 140 ° C.
- organic solvent usable according to the invention there may be mentioned alcohols, esters, ketones, tetrahydropyran, tetrahydrofuran and mixtures thereof.
- the alcohols are preferably chosen from lower alcohols (in CrC ⁇ ), such as methanol, ethanol and isopropanol.
- the esters are preferably chosen from acetates and, in particular, ethyl acetate.
- the composition may also comprise one or more surfactants, in particular fluorinated or fluorosilicone surfactants, generally in a proportion of 0.001 to 1% by weight, preferably 0.01 to 1% by weight, relative to the total weight of the composition.
- surfactants include the FLUORAD ® FC430 marketed by 3M, the
- the theoretical solids content of the coating composition preferably comprises from 1 to 50% by weight of mineral colloids, better still from 3 to 35% by weight, and more preferably from 10 to 35% by weight.
- the theoretical dry weight (TE) is the calculated total weight of solids from the various constituents of the final coating composition.
- weight of solids derived from silanes is meant the weight calculated in units Qk Si O (4-k) / 2 in which Q is an organic group directly bonded to the silicon atom via an Si-C and Qk bond
- SiO (4-k) / 2 is derived from Qk Si R '"(4-k) or Si-R'" generates SiOH by hydrolytic treatment, and k denotes 0, 1 or 2.
- Any conventional deposition process may be used to deposit the abrasion-resistant coating layer.
- dip coating a technique according to which the substrate to be coated is immersed in a bath of the composition, or the deposit by centrifugation.
- the sol is deposited preferentially by "spin coating", that is to say by centrifugation, on substrates, for example an ORMA® substrate, of Essilor, based on poly (diethylene glycol bisallyl carbonate).
- substrates for example an ORMA® substrate, of Essilor, based on poly (diethylene glycol bisallyl carbonate).
- the deposition rate is between 100 rpm and 3000 rpm, preferably between 200 rpm and 2000 rpm.
- the varnishes are then cured, preferably by heat treatment in an oven for a period of 1 to 5 hours, typically 3 hours at a temperature between 80 ° C. and 120 ° C.
- the thicknesses of the anti-abrasion coating layer vary from 1 to 10 microns, preferably from 3 to 8 microns.
- anti-shock primer layer it is possible to use any anti-shock primer layers conventionally used for articles made of transparent polymeric material, such as ophthalmic lenses.
- Preferred primer compositions include thermoplastic polyurethane compositions, such as those described in Japanese Patents 63-141001 and 63-87223, poly (meth) acrylic primary compositions, such as those described herein. in US Pat. No. 5,015,523, compositions based on thermosetting polyurethanes, such as those described in Patent EP-0404111, and compositions based on poly (meth) acrylic latexes and polyurethane latex, such as those described in US Pat. in US 5,316,791, EP-0680492.
- Preferred primary compositions are polyurethane-based compositions and latex-based compositions, particularly polyurethane latices.
- the poly (meth) acrylic latices are copolymer latices consisting mainly of a (meth) acrylate, such as, for example, ethyl or butyl, methoxy or ethoxyethyl (meth) acrylate, with a generally minor proportion of at least one other comonomer, such as for example styrene.
- a (meth) acrylate such as, for example, ethyl or butyl, methoxy or ethoxyethyl (meth) acrylate
- at least one other comonomer such as for example styrene.
- Preferred poly (meth) acrylic latices are acrylate-styrene copolymer latices.
- Such latexes of acrylate-styrene copolymers are commercially available from Zeneca Resins under the name Neocryl ®.
- Polyurethane latices are also known and commercially available.
- polyurethane latices containing polyester units such latexes are also marketed by Zeneca Resins under the name ® and NEOREZ by Baxenden Chemical Company under the name WITCOBOND ®. Mixtures of these latices, in particular polyurethane latex and poly (meth) acrylic latex, can also be used in the primer compositions.
- primer compositions may be deposited on the faces of the optical article by dipping or centrifugation and then dried at a temperature of at least 70 ° C. and up to 100 ° C., preferably of the order of 90 ° C., for a period of 2 minutes to 2 hours, generally of the order of 15 minutes, to form primer layers having thicknesses, after curing, of 0.2 to 2.5 ⁇ m, preferably 0, 5 to 1, 5 ⁇ m.
- organic glass substrates suitable for optical articles according to the invention mention may be made of polycarbonate substrates and those obtained by polymerization of alkyl methacrylates, in particular C 1 -C 4 alkyl methacrylates, such as methyl (meth) acrylate and ethyl (meth) acrylate, polyethoxylated aromatic (meth) acrylates such as polyethoxylated bisphenolates di methacrylates, allyl derivatives such as aliphatic or aromatic polyol allyl carbonates, linear or branched, thio (meth) acrylic, substrates polythiurethane, polycarbonate (PC) and polyepisulfide.
- alkyl methacrylates such as methyl (meth) acrylate and ethyl (meth) acrylate
- polyethoxylated aromatic (meth) acrylates such as polyethoxylated bisphenolates di methacrylates
- allyl derivatives such as aliphatic or aromatic polyol
- substrates obtained by polymerization of the allyl carbonates of polyols among which may be mentioned ethylene glycol bis allyl carbonate, diethylene glycol bis 2-methyl carbonate, diethylene glycol bis (allyl carbonate), ethylene glycol bis (2-chloro allyl carbonate), triethylene glycol bis (allyl carbonate), 1,3-propanediol bis (allyl carbonate), propylene glycol bis (2-ethyl allyl carbonate), 1,3-butylenediol bis (allyl) carbonate), 1,4-butenediol bis (2-bromo allyl carbonate), dipropylene glycol bis (allyl carbonate), trimethylene glycol bis (2-ethyl allyl carbonate), pentamethylene glycol bis (allyl carbonate), isopropylene bis phenol -A bis (allyl carbonate).
- ethylene glycol bis allyl carbonate diethylene glycol bis 2-methyl carbonate
- diethylene glycol bis (allyl carbonate) ethylene glyco
- substrates obtained by polymerization of diethylene glycol bis allyl carbonate sold under the trade name CR 39 ® by PPG Industrie (ORMA lens ® ESSILOR).
- substrates obtained by polymerization of the thio (meth) acrylic monomers such as those described in the French patent application FR-A-2 734 827.
- the substrates can be obtained by polymerization of mixtures of the above monomers.
- the surface of the substrate Before deposition, it is possible to activate the surface of the substrate by appropriate treatment, such as a plasma or corona treatment, or treatment with an acidic or basic aqueous solution, so as to create reactive sites that will allow better adhesion with the anti-abrasion coating composition.
- appropriate treatment such as a plasma or corona treatment, or treatment with an acidic or basic aqueous solution, so as to create reactive sites that will allow better adhesion with the anti-abrasion coating composition.
- the deposition chamber comprises two electrodes essential for obtaining the plasma and for producing the deposit. These are two metal discs with a radius of 10 cm. The first is solid and has a thickness of 4 mm: it is used during deposits on silicon substrate. The second 1 cm thick has three circular holes 6.5 cm radius and 4 mm thick in which are placed ophthalmic glasses of power "-2", or "0" (glass without power). Prior to deposition, the substrate-holder electrode is placed in an airlock where a primary vacuum is produced. The electrode is then automatically routed to the deposition chamber. The use of an airlock makes it possible to always keep the deposit chamber empty between two experiments.
- the power is applied to the substrate holder electrode, which is then self-biased.
- the variation of the applied power leads to the variation of the autopolarization voltage and therefore acts on the energy of the ions bombarding the surface during the growth of the layer.
- Two powers 40 and 85W were applied which correspond to two self-bias voltages -35V and -150V and -150V.
- the self-bias voltage is normally negative, but is sometimes mentioned in absolute value.
- the electrode automatically switches to the deposition chamber.
- the argon flow is adjusted to 20 cm 3 / s and the argon inlet valve is opened.
- An "applied power" incident power of 50 W corresponding to a substrate self-biasing voltage is selected.
- the deposit time is set to one minute.
- the argon inlet valve is closed, the throttle valve is opened, and the hot cathode gauge is turned on.
- the deposition time is set to 1 hour 20 to achieve a deposit of about 100 nm, 5 minutes for a thickness of about 6 nm and
- the "unload” button is pressed to return the substrate electrode to the airlock before an air release operation is performed automatically.
- the substrate-carrier electrode is removed from the reactor.
- An 85 W (applied power) incident power corresponding to a platform voltages voltage of -150 V is selected.
- the deposition time is set over 40 minutes to achieve a deposition of about 100 nm, 2 minutes for a thickness of about 6 nm and 1 minute for a thickness of about 3 nm.
- the power is applied to the target electrode, then self-biased.
- the changes in structure and optical properties of the layers are mainly governed by ion energy incidents and since with this mode, the substrate is still grounded, a single power (85W) has been applied.
- the cathode sputter operating mode is selected.
- the deposition time is set to 30 minutes to achieve a deposition of about 100 nm, 1 minute 44 for a thickness of about 6 nm and 52 seconds for a thickness of about 3 nm.
- Figure 1 a graph showing the values of the surface energies and contact angles of substrates coated or not by a layer a-C: H according to the invention as a function of the thickness of the layer a-C: H;
- FIG. 2 is a graph showing the values of the surface energies and the contact angles of substrates coated or not with an ⁇ -C: H layer according to the invention as a function of the self-biasing voltage;
- FIG. 3 is a graph representing the values of the surface energies and the contact angles of substrates coated with an ⁇ -C: H layer according to the invention or with hydrophobic and / or oleophobic coatings of the prior art.
- the contact angle measurements are static contact angle measurements and were made from the DIGIDROP apparatus distributed by GBX. It allows the estimation of a contact angle from a photograph taken at a given moment (3000 ms) after the deposition of a drop of different liquids: water, diiodomethane, formamide and oleic acid.
- the determination of the surface energy of the ⁇ -C: H material was carried out by the Owens-Wendt method.
- a cleaning test used consists in depositing a stain spot of 20 mm in diameter (it is an artificial sebum, consisting mainly of oleic acid) on an ophthalmic glass and reproducibly perform wiping in a movement back and forth (a return and corresponding corresponding, by definition two wiping); with a cotton fabric (from the company Berkshire) with a load of 750 g.
- a second cleaning test was performed with fingerprint deposits from three operators. Each operator deposited on three glasses two contiguous prints for each test series. The results are therefore the average of 9 visibility measures. The operator passed his finger on the forehead before applying it to a new glass.
- Wiping is then done following the same protocol as in test A.
- a visual inspection by transmission inspection against a light source is performed at each step of the test. (After 0, 2, 10, 20, 70, 150, 200 wiping). The state of cleanliness of the glass is noted on a scale with 3 levels:
- Substrates coated with aC H layers made with constant self-biasing voltage (-150V) having different thicknesses (3, 6 and 100 nm) as well as substrates coated with aC: H layers produced at different self-biasing voltages (0, -35 V and -150 V), having the same thickness (100 nm) were obtained following the protocols defined above.
- the aC: H layers keep the same surface energies. Thus, 3 nm is enough for give the layer the characteristic contact angle behavior of the material aC: H.
- Figure 3 shows that the glasses treated with an Optron top coat OF110 are hydrophobic and fairly strongly oleophobic.
- glasses without top coats where the second silica layer of the antireflection is in contact with the air display a hydrophilic and oleophilic character.
- the glasses coated with the aC: H layer show a relative hydrophobicity and a strong oleophilicity.
- Example 3- Cleaning test results
- test A A first series of cleanability experiments was carried out (test A described previously).
- Antireflection glasses were tested as described in Example 2 and covered with a 6 nm ⁇ C: H (-150 V) layer and then identical anti-reflection glasses coated with 3 nm treatments: different self-polarization, (-150 V, -35 V, 0 V).
- the cleaning test behavior of the ⁇ -C: H treated glasses appears to be the same as the carbon layer is 6 or 3 nm (Table 1).
- Table 1 also indicates that, whatever the self-biasing voltages (-150 V, -35 V, OV), the cleanability behavior remains the same.
- Test B A second series of cleaning tests was carried out.
- test A The results confirm the tests carried out with application of artificial sebum stain.
- EP 947 601 Bayer, iron straw was carried out on anti-reflective glasses coated with a layer a-C: H (-35 V, 3 nm) deposited on an antireflection coating.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06726191A EP1856563A1 (fr) | 2005-02-21 | 2006-02-21 | Couche dlc antisalissure |
JP2007555679A JP2008532792A (ja) | 2005-02-21 | 2006-02-21 | 耐汚染性dlc皮膜層 |
US10/571,743 US20070178301A1 (en) | 2005-02-21 | 2006-02-21 | Antisoiling dlc layer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0550479A FR2882443B1 (fr) | 2005-02-21 | 2005-02-21 | Couche dlc antisalissure |
FR0550479 | 2005-02-21 |
Publications (1)
Publication Number | Publication Date |
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WO2006087502A1 true WO2006087502A1 (fr) | 2006-08-24 |
Family
ID=34954565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2006/050153 WO2006087502A1 (fr) | 2005-02-21 | 2006-02-21 | Couche dlc antisalissure |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070178301A1 (fr) |
EP (1) | EP1856563A1 (fr) |
JP (1) | JP2008532792A (fr) |
FR (1) | FR2882443B1 (fr) |
WO (1) | WO2006087502A1 (fr) |
Cited By (1)
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US20220314588A1 (en) * | 2021-04-05 | 2022-10-06 | Japan Aviation Electronics Industry, Limited | Laminated body and display device provided with the same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6049979B2 (ja) * | 2009-07-03 | 2016-12-21 | ソニー株式会社 | 光学素子、および表示装置 |
WO2015115399A1 (fr) * | 2014-01-28 | 2015-08-06 | 太陽化学工業株式会社 | Structure ayant un film de carbone et procédé de formation d'un film carboné |
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WO2000031569A1 (fr) * | 1998-11-20 | 2000-06-02 | Sola International Holdings Ltd. | Lentille portant un revetement de façon a reduire la perception des taches |
JP2003098305A (ja) * | 2001-09-19 | 2003-04-03 | Sumitomo Metal Mining Co Ltd | 反射防止フィルム |
FR2847346A1 (fr) * | 2002-11-15 | 2004-05-21 | Essilor Int | Procede d'obtention d'un marquage sur une lentille ophtalmique a basse energie de surface |
US20040257525A1 (en) * | 2003-06-20 | 2004-12-23 | Vision-Ease Lens, Inc. | Ophthalmic lens with graded interference coating |
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JPS53111336A (en) * | 1977-03-11 | 1978-09-28 | Toray Ind Inc | Coating composition |
DE3019355A1 (de) * | 1980-05-21 | 1981-12-03 | Hoechst Ag, 6000 Frankfurt | Verfahren und vorrichtung zum trennen von stoffgemischen in fluessiger phase |
US5171607A (en) * | 1990-01-29 | 1992-12-15 | Bausch & Lomb Incorporated | Method of depositing diamond-like carbon film onto a substrate having a low melting temperature |
US5135808A (en) * | 1990-09-27 | 1992-08-04 | Diamonex, Incorporated | Abrasion wear resistant coated substrate product |
US5190807A (en) * | 1990-10-18 | 1993-03-02 | Diamonex, Incorporated | Abrasion wear resistant polymeric substrate product |
US5846649A (en) * | 1994-03-03 | 1998-12-08 | Monsanto Company | Highly durable and abrasion-resistant dielectric coatings for lenses |
JP3760528B2 (ja) * | 1996-11-07 | 2006-03-29 | ソニー株式会社 | 表示素子用フィルター |
US6335086B1 (en) * | 1999-05-03 | 2002-01-01 | Guardian Industries Corporation | Hydrophobic coating including DLC on substrate |
JP2001141903A (ja) * | 1999-11-15 | 2001-05-25 | Sony Corp | 反射防止フィルム |
JP2002194547A (ja) * | 2000-06-08 | 2002-07-10 | Applied Materials Inc | アモルファスカーボン層の堆積方法 |
JP2003248102A (ja) * | 2002-02-25 | 2003-09-05 | Hitachi Maxell Ltd | 多層構造の反射防止膜 |
JP4517590B2 (ja) * | 2003-06-05 | 2010-08-04 | 三菱化学株式会社 | 耐汚染性付与剤及びそれを用いた耐汚染性物品 |
US20090243011A1 (en) * | 2008-03-26 | 2009-10-01 | Texas Instruments Incorporated | Manufacturing Optical MEMS with Thin-Film Anti-Reflective Layers |
-
2005
- 2005-02-21 FR FR0550479A patent/FR2882443B1/fr not_active Expired - Fee Related
-
2006
- 2006-02-21 EP EP06726191A patent/EP1856563A1/fr not_active Withdrawn
- 2006-02-21 JP JP2007555679A patent/JP2008532792A/ja active Pending
- 2006-02-21 WO PCT/FR2006/050153 patent/WO2006087502A1/fr active Application Filing
- 2006-02-21 US US10/571,743 patent/US20070178301A1/en not_active Abandoned
Patent Citations (4)
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WO2000031569A1 (fr) * | 1998-11-20 | 2000-06-02 | Sola International Holdings Ltd. | Lentille portant un revetement de façon a reduire la perception des taches |
JP2003098305A (ja) * | 2001-09-19 | 2003-04-03 | Sumitomo Metal Mining Co Ltd | 反射防止フィルム |
FR2847346A1 (fr) * | 2002-11-15 | 2004-05-21 | Essilor Int | Procede d'obtention d'un marquage sur une lentille ophtalmique a basse energie de surface |
US20040257525A1 (en) * | 2003-06-20 | 2004-12-23 | Vision-Ease Lens, Inc. | Ophthalmic lens with graded interference coating |
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US20220314588A1 (en) * | 2021-04-05 | 2022-10-06 | Japan Aviation Electronics Industry, Limited | Laminated body and display device provided with the same |
Also Published As
Publication number | Publication date |
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EP1856563A1 (fr) | 2007-11-21 |
FR2882443B1 (fr) | 2007-04-13 |
JP2008532792A (ja) | 2008-08-21 |
FR2882443A1 (fr) | 2006-08-25 |
US20070178301A1 (en) | 2007-08-02 |
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