Coated container and method for preparing the same

Abstract

A coated glass container comprising a glass container coated with a protective layer based on tin-doped titanium dioxide.

Description

[Technical Field]

[0001] The present invention relates to a coated glass container and a method for preparing a coated glass container.

[0002] In many applications, glass containers are required to be reusable. Bottles for milk, soft drinks, and beer have long been part of a closed-loop use-return-wash-refill-reuse cycle. These bottles need to withstand the demands of these cycles while maintaining their aesthetic appeal for consumers. In particular, bottles are susceptible to scratches and other surface damage that can occur during movement on conveyors and during transportation.

[0003] To mitigate such abrasions, a "cold-end" coating has routinely been applied to containers after annealing at temperatures of approximately 21-80°C. Examples include stearate, oleic acid, and polyethylene coatings. While these coatings are suitable for single-use bottles, they are easily washed away during the cleaning and refilling processes of reusable bottles. As a result, abrasions occur at any contact point.

[0004] To reduce scratches on reusable bottles, "hot-end" coatings such as titanium dioxide have been used. These coatings are applied at approximately 450-600°C after the bottles have been molded and before the cooling annealing step.

[0005] However, titanium dioxide coatings have been found to still exhibit scratching issues as a result of container cleaning cycles. Therefore, it is beneficial to provide coated glass containers that mitigate these problems.

[0006] According to a first aspect of the present invention, a coated glass container is provided, comprising a glass container coated with a protective layer based on tin-doped titanium oxide.

[0007] The inventors were surprised to find that the composition of the protective layer imparted excellent durability to the coated glass container in abrasion and caustic cleaning cycle tests.

[0008] In the context of the present invention, a layer said to be "based on" one or more specific materials means that it consists primarily of the one or more corresponding materials, and usually means that it comprises at least 50 at.% of the one or more materials.

[0009] In the following description of the present invention, unless otherwise specified, if an alternative value for the upper or lower limit of the tolerance range of a parameter is disclosed and it is shown that one of these values ​​is preferable to the other, it should be implicitly understood that each of the intermediate values ​​of the parameter, which lies between the preferred and unpreferred alternative values, is preferable to the unpreferred value, is preferable in itself to the unpreferred value, and is preferable to each of the values ​​between the unpreferred value and the intermediate value.

[0010] Throughout this specification, the terms “composed of” or “containing” mean “containing the specified components but not excluding the presence of other components.” The terms “substantially consisting of” or “substantially consisting of” mean “containing the specified components but excluding other components, with the exception of materials present as impurities, materials inevitably present as a result of processes used to provide the components, and components added for purposes other than achieving the technical effects of the present invention.” Typically, when referring to a composition, a composition consisting substantially of a specific group of components contains less than 5% by weight of non-specified components, typically less than 3% by weight, and more typically less than 1% by weight.

[0011] The terms "consisting of" or "consisting of" mean that a specified component is included, while other components are excluded.

[0012] When appropriate to the context, the use of the terms "to be equipped" or "to be equipped" may be interpreted to include the meaning of "substantially consisting of" or "substantially consisting of," as well as the meaning of "consisting of" or "consisting of."

[0013] In this specification, phrases such as "in the range of x to y" are interpreted as meaning "x to y" and therefore including the values ​​of x and y.

[0014] In the context of the present invention, a transparent material or transparent container is a material or container that transmits visible light so that an object or image located on the other side or behind the material can be clearly seen through the material or container.

[0015] In the context of the present invention, the "thickness" of a layer is expressed as the distance traversing the layer in the minimum dimension direction of the layer, from any predetermined position on the surface of the layer to a position on the opposite surface of the layer.

[0016] In the context of this invention, "derivative" refers to a chemical substance that is structurally related to another chemical substance and theoretically derived from it.

[0017] In the context of the present invention, "container" refers, in particular, to a device suitable for containing liquids, powders, gels, etc.

[0018] For example, when a container is completely filled with liquid, only a portion of its surface comes into contact with the liquid. In the context of this invention, the "inner surface" of the container refers to the portion of the container surface that comes into contact with the liquid when the container is completely filled. In contrast, the remaining portion of the container surface that does not come into contact with the liquid when the container is completely filled is called the "outer surface."

[0019] Preferably, the glass container is a bottle, vial, tube, canister, or jar.

[0020] Preferably, the protective layer is disposed on the outer surface of the container. In some embodiments, the protective layer may cover the entire outer surface of the container. In another embodiment, the protective layer may cover a part of the outer surface of the container. Preferably, the protective layer covers at least 70%, more preferably at least 80%, still more preferably at least 90%, and most preferably at least 95% of the outer surface of the container.

[0021] The glass container preferably comprises a closed bottom located at a first end of the glass container. Preferably, the glass container further comprises a body extending from the closed bottom and closed in the circumferential direction. Preferably, the glass container further comprises an opening (commonly referred to as a "finish"). Preferably, the opening is located at a second end of the glass container. The second end of the glass container is preferably the end on the opposite side (i.e., the farthest side) from the first end of the glass container. Preferably, the body extends axially from the bottom.

[0022] Preferably, the glass container further comprises a neck extending from the body and terminating at the opening. Preferably, the neck extends axially from the body. Preferably, the neck is generally conical in shape.

[0023] Preferably, the protective layer does not cover the opening. This configuration reduces the possibility of problems caused by the contact between the substance and the protective layer when the glass container is filled with the substance. Preferably, the protective layer covers the entire outer surface of the container except for a region at least 0.5 cm, more preferably at least 1 cm, still more preferably at least 1.5 cm, and most preferably at least 2 cm away from the opening, but preferably within a range of up to 4 cm, more preferably up to 3.5 cm, and still more preferably up to 3 cm from the opening.

[0024] Preferably, the protective layer consists of substantially tin-doped titanium dioxide. More preferably, the protective layer consists of tin-doped titanium dioxide.

[0025] Preferably, the protective layer has a bulk tin concentration of 0.01 to 8 at%, more preferably 0.1 to 6 at%, still more preferably 0.1 to 5 at%, and most preferably 0.2 to 4.5 at%. In the context of the present invention, the term "bulk" means a portion at least 2 nm away from the surface of the protective layer in the direction of the minimum dimension of the protective layer.

[0026] Preferably, the protective layer has a bulk tin dioxide concentration of less than 1 at%, more preferably less than 0.5 at%, still more preferably less than 0.1 at%, and even more preferably less than 0.01 at%. Most preferably, the bulk of the protective layer does not contain tin dioxide. Preferably, the entire protective layer has a tin dioxide concentration of less than 1 at%, more preferably less than 0.5 at%, still more preferably less than 0.1 at%, and even more preferably less than 0.01 at%. Most preferably, the entire protective layer does not contain tin dioxide.

[0027] Preferably, the surface of the protective layer shows a water droplet contact angle of at least 55°, more preferably at least 65°, still more preferably at least 70°, but preferably a maximum of 90°, more preferably a maximum of 80°, and still more preferably a maximum of 75°. The contact angle is measured using a 5 microliter drop.

[0028] Preferably, the protective layer is based on tin-doped titanium dioxide in which tin is present in a tetravalent oxidation state.

[0029] Preferably, the protective layer is at least 5 nm, more preferably at least 15 nm, still more preferably at least 20 nm, and most preferably at least 25 nm, but preferably has a physical thickness of a maximum of 200 nm, more preferably a maximum of 150 nm, still more preferably a maximum of 100 nm, and most preferably a maximum of 70 nm.

[0030] Preferably, the protective layer is thermally decomposable. As used herein, "thermally decomposable" refers to a coating or layer chemically bonded to a glass container.

[0031] Preferably, the protective layer consists of substantially tin-doped titanium dioxide with a bulk tin concentration of 0.1 to 5 at%, and the surface of the protective layer exhibits a water droplet contact angle of at least 60° but up to 90°, the contact angle of which is measured using a 5 microliter droplet.

[0032] Preferably, the glass container is transparent. The glass container may be colorless or colored. The glass container may be a metal oxide glass container. The glass container may be colorless or colored. A typical soda-lime silicate glass composition (by weight) is SiO2 69-74%, Al2O3 0-3%, Na2O 10-16%, K2O 0-5%, MgO 0-6%, CaO 5-14%, SO3 0-2%, and Fe2O3 0.005-2%. The glass composition may contain other additives, such as refining aids, which are usually present in amounts of up to 2%. Colorless float glass means glass having the composition defined in BS EN 572-1 and BS EN 572-2 (2004). In the case of colorless float glass, the weight ratio of Fe2O3 is usually 0.11%. Float glass with an Fe2O3 content of less than approximately 0.05% is usually called low-iron float glass. Such glass typically has the same basic composition of other component oxides; that is, low-iron float glass is soda-lime silicate glass, just like colorless float glass. Typically, colored float glass has at least 0.5% by weight of Fe2O3, for example, 1.0% by weight of Fe2O3. Alternatively, the glass container may be a borosilicate glass container, an alkali aluminosilicate glass container, or an aluminum oxide crystal glass container.

[0033] The protective layer may come into direct contact with the surface of the glass container. Alternatively, the protective layer may come into indirect contact with the surface of the glass container; that is, the protective layer may be deposited on top of one or more previously deposited layers.

[0034] According to a second aspect of the present invention, a method for preparing a coated glass container according to the first aspect is provided. This method is (a) The step of preparing a glass container, (b) The steps of supplying the titanium-containing precursor and the tin-containing precursor to the surface of the glass container or to a location adjacent to the surface of the glass container, (c) The step of reacting the titanium-containing precursor and the tin-containing precursor to precipitate a protective layer based on tin-doped titanium dioxide on the surface of a glass container, and so on.

[0035] Preferably, the protective layer is deposited by chemical vapor deposition (CVD). Alternatively, the coating may be deposited by physical vapor deposition methods such as sputtering or pulsed laser deposition, or by sol-gel methods or other solution processes.

[0036] When the protective layer is deposited by CVD, the vessel is preferably at a temperature of 400°C to 700°C, more preferably 450°C to 650°C, and even more preferably 500°C to 650°C. This temperature is readily supplied by the residual heat from casting the glass vessel when the method is incorporated into a continuous manufacturing process for the glass vessel. Therefore, the method is preferably incorporated into a continuous manufacturing process for the glass vessel, and more preferably the temperature of the glass vessel is supplied by the residual heat from casting the glass vessel.

[0037] Preferably, the titanium-containing precursor comprises one or more of the following: titanium alkoxide, titanium acetylacetonate, titanium acetate such as titanium tetraacetate, and titanium alkyl. Preferably, the titanium-containing precursor comprises titanium alkoxide. The titanium alkoxide can be selected from one or more of the following: titanium tetraisopropoxide (TTIP), titanium ethoxide (TET), titanium n-butoxide, titanium t-butoxide, di(isopropoxide)bis(2,2,6,6-tetramethyl-3,5-heptanesionate)titanium(IV), pentamethylcyclopentadienyltitanium trimethoxide, titanium(di-isopropoxide)bis(acetylacetonate), and derivatives thereof. Preferably, the titanium alkoxide is titanium tetraisopropoxide (TTIP). TTIP is advantageous in terms of volatility and stability at relatively high temperatures. It also has the advantage of being readily available and low-cost.

[0038] Preferably, the tin-containing precursor comprises one or more of the following: tin alkoxides such as tin isopropoxide, tin acetylacetonate, tin diacetate, tin tetraacetate, methyl tin diacetate, or tin acetate such as dibutyl tin diacetate (DBTA), tetramethyltin, tetraethyltin, tetraisobutyltin, and their derivatives. The tin alkoxide can be selected from one or more of the following: tin methoxide, tin ethoxide, tin n-butoxide, tin t-butoxide, tin n-propoxide, tin isopropoxide, and their derivatives. Preferably, the tin alkoxide is tin isopropoxide. Preferably, the tin-containing precursor comprises DBTA.

[0039] Preferably, step (b) comprises generating one or more gases and / or gas mixtures, more preferably by heating titanium-containing precursors and tin-containing precursors. The precursor compounds may be liquid or solid at some point, but may be volatile and therefore can be vaporized or sublimated for use as a gas mixture. Once in a gaseous state, the precursor compounds can be contained in a gas stream and utilized in the CVD process. Preferably, the generation of gases and / or gas mixtures comprises heating titanium-containing precursors, tin-containing precursors and / or other precursor compounds using a bubbler system or a thin-film evaporator system. Thin-film evaporator systems are particularly suitable for production-scale processes.

[0040] The gas mixture may further comprise one or more oxygen-containing precursors distinct from the titanium-containing precursors and the tin-containing precursors. Preferably, the oxygen-containing precursors are selected from one or more organic oxygen-containing compounds or inorganic oxygen-containing compounds. Preferably, one or more oxygen-containing precursors are one or more organic oxygen-containing compounds.

[0041] The organic oxygen-containing compound may be one or more carbonyl compounds. Preferably, the carbonyl compound is an ester. More preferably, the carbonyl compound is an ester having an alkyl group having a β-hydrogen. Alkyl groups having 2 to 10 carbon atoms and containing a β-hydrogen are preferred. Preferably, the ester is selected from one or more of ethyl acetate (EtoAc), ethyl formate, ethyl propionate, isopropyl formate, isopropyl acetate, n-butyl acetate, and t-butyl acetate. Most preferably, the one or more oxygen-containing compounds are a mixture of both t-butyl acetate and ethyl acetate.

[0042] In another embodiment, the oxygen-containing precursor may be supplied as part of a gaseous composition such as air. Alternatively, the oxygen may be supplied in a substantially purified form. In either of these two embodiments, the oxygen is supplied in molecular oxygen form. The inorganic oxygen-containing compound may be selected from one or more of the following: water (H2O), carbon dioxide (CO2), nitric oxide (NO), nitrogen dioxide (NO2), and nitrous oxide (N2O).

[0043] The gas mixture may further comprise one or more carrier gases or diluent gases, such as nitrogen, air, and / or helium, preferably nitrogen. Thus, the method may include providing a source of one or more carrier gases or diluent gases from which separate supply lines may extend.

[0044] Preferably, the gas mixture is supplied to the coating apparatus. In certain embodiments, the gas mixture is supplied through the coating apparatus and discharged from the coating apparatus using one or more gas distribution beams before the protective layer is deposited. In certain embodiments, the gas mixture is formed before being supplied to the coating apparatus. For example, a titanium-containing precursor, a tin-containing precursor, and a carrier gas or diluent gas, preferably nitrogen, may be mixed in a supply line connected to the inlet of the coating apparatus. In other embodiments, the gas mixture may be formed within the coating apparatus. In preferred embodiments, the titanium-containing precursor and the tin-containing precursor are held separately until they are supplied to the surface of the glass container or a location adjacent to the surface of the glass container.

[0045] The method is preferably a dynamic process in which the glass container moves in steps (b) and (c). Preferably, the container moves at a predetermined speed of, for example, more than 3 m / min, more preferably 3 m / min to 20 m / min.

[0046] Preferably, CVD is carried out during the continuous manufacturing process of the glass vessel, preferably at substantially atmospheric pressure (APCVD). Alternatively, CVD may be carried out using low-pressure CVD or ultra-high vacuum CVD. CVD may be carried out using aerosol-assisted CVD or direct liquid injection CVD. Furthermore, CVD may be carried out using microwave plasma-assisted CVD, plasma-enhanced CVD, remote plasma-enhanced CVD, atomic layer CVD, combustion CVD (flame pyrolysis), hot-wire CVD, metal-organic CVD, rapid thermal CVD, gas-phase epitaxy, or photo-initiated CVD.

[0047] Preferably, the method is Before step (a), a tunnel is provided on the conveyor belt so that the conveyor belt transports the glass containers from the upstream end, where the glass containers enter the tunnel, to the downstream end, where the glass containers exit the tunnel. The tunnel has an upper and first and second side walls, and has one or more nozzles located on at least one side wall, the nozzles supplying gas jets across the path of glass containers being transported within the tunnel, further comprising: The titanium-containing precursor and the tin-containing precursor are supplied in the form of a gas jet to the surface of the glass container or to a location adjacent to the surface of the glass container.

[0048] Preferably, a linear arrangement of nozzles is located on at least one side wall of the tunnel. Preferably, at least one exhaust port is located on the side wall, and more preferably, the exhaust port is located closer to the downstream end than the nozzles. Preferably, the tunnel further comprises means for applying negative pressure to the exhaust port, such as an exhaust fan. Preferably, the tunnel further comprises an evaporator, and more preferably the evaporator comprises a heatable tube. Preferably, a carrier gas flow is led through the evaporator to one or more nozzles. Preferably, titanium-containing precursors and tin-containing precursors are introduced into the carrier gas flow within the evaporator. Preferably, a diluent gas is introduced into the carrier gas flow, preferably after leaving the evaporator and before reaching one or more nozzles.

[0049] A third aspect of the present invention provides the use of a protective layer based on tin-doped titanium dioxide for improving the durability of a glass container.

[0050] Any features described above in relation to the first and second aspects of the present invention may also be used in relation to other aspects of the present invention. Any invention described herein may be combined with any features of other inventions described herein as necessary. Any necessary features applicable to one aspect of the present invention may be used in any combination and in any number. Furthermore, they may be used in any combination and in any number with other aspects of the present invention. This includes, but is not limited to, cases where a dependent claim of any claim is used as a dependent claim of another claim of this application.

[0051] The reader's attention is directed to all documents and papers filed concurrently or previously in connection with this application and published together with this specification. The contents of all such documents and papers are incorporated herein by reference.

[0052] All features disclosed herein (including the attached claims, abstract and drawings), and / or all steps of any disclosed method or process, can be combined in any combination, except for at least some combinations in which such features and / or steps are mutually exclusive.

[0053] Each feature disclosed herein (including the attached claims, abstract, and drawings) may be replaced by alternative features having the same, equivalent, or similar purpose unless expressly stated otherwise. Accordingly, unless expressly stated otherwise, each disclosed feature is merely an example of a general series of equivalent or similar features.

[0054] The present invention will be further described by the following specific embodiments, which are illustrative and not limiting, with reference to the accompanying drawings. [Brief explanation of the drawing]

[0055] [Figure 1] This is a schematic diagram of the APCVD system used to prepare a sample according to the present invention. [Figure 2] These images show the water contact angle before and after caustic cleaning treatment for a sample and a comparative sample according to the present invention. [Examples]

[0056] A comparative sample ("Sample B") was prepared using the custom-made APCVD system 1 shown in Figure 1. The two precursors, detailed below, were housed in separate stainless steel bubblers 2 and 3 and subsequently heated to generate the vapor pressure necessary for transport through system 1 to the mixing chamber 4. The gas flow through system 1 was controlled by stainless steel pipe 5 connected to the mixing chamber 4, and by stainless steel valves (6=2-way valve, 7=3-way valve) fitted to the sections of bubblers 2 and 3 and pipe 5. All components of CVD system 1 (e.g., pipe 5, mixing chamber 4, bubblers 2 and 3) were connected to RS k-type thermocouples to measure the temperature of each part of system 1, and further connected to a Eurotherm® temperature controller. The vapor generated from the precursors was transported through the system at various flow rates by oxygen-free N2 gas (BOC® 99.99%) 8. A flow meter was fitted to each pipe 5 to control the flow rate of the carrier gas 8 before it reached system 1. The gas was transported from the mixing chamber 4 to the quartz tube reactor 9 via a double baffle manifold. The substrate 10 was housed in the reactor 9 and heated on a graphite block (320 mm in length) 11 containing three Whatman® heater cartridges. An exhaust pipe 12 was fitted to the reactor 9 to discharge by-products generated during film formation. Furthermore, an exhaust pipe 13 was indirectly connected to the bubblers 2, 3 and the mixing chamber 4. The preparation of the sample according to the present invention ("Sample A") was carried out using the same method, except that the two precursors were transported to two separate mixing chambers before being combined in the reactor.

[0057] Using the APCVD system described above, the Sn-doped TiO2 ("A" sample) and a comparative mixed titania:tin oxide film ("B" sample) according to the present invention were coated onto uncoated standard soda-lime silicate glass (80 × 225 × 3.2 mm). 3 The film was deposited on the glass substrate, effectively mimicking a portion of the container glass. The glass substrate was washed with acetone (99%), isopropanol (99.9%), and distilled water before coating to prevent environmental or handling contamination, and then dried in a furnace. Titanium(IV) isopropoxide (TTIP, 97%, Sigma-Aldrich™) was used as the single-source precursor for titanium and oxygen. Dibutyltin diacetate (DBTDA, 99.5%, Sigma-Aldrich™) was used as the tin source along with TTIP. The selection of precursors was primarily based on industrial relevance. In the glass bottle industry, non-chlorinated titanium precursors are preferred to reduce the impact of the chemical washing process, which is part of the Na+ transfer and recycling process from the glass substrate.

[0058] The temperature of the bubbler for TTIP was set to 110°C to achieve the desired vapor pressure, while the bubbler containing DBTDA was set to 130°C. The temperature of the mixing chamber was set to 200°C, and the TTIP and DBTDA lines were heated to 180°C. All samples were deposited using a deposition time of 60-180 seconds, a substrate temperature of 550°C, and a total gas flow rate of 18.5 L / min. -1It was prepared. In normal film formation, all parts of the system were heated to an appropriate temperature and stabilized under a steady flow of carrier gas. The carbon block containing the glass substrate was heated to the target temperature for film formation. The precursor was transported by an appropriate N2 flow rate and released from the bubbler at a sufficient vapor pressure to reach the mixing chamber and the reactor. After the film formation time elapsed, the precursor flow was switched to the exhaust path and then closed. The sample was cooled to room temperature under a N2 carrier gas flow, taken out of the reactor, and further handled and stored in the atmosphere. After coating, the sample was cut into a size of 30×30 mm for property evaluation. The samples used for analysis were selected from similar regions in the reactor so that the gas flow and temperature at the evaluation site were constant throughout.

[0059] (Characterization of Samples) (Raman Spectroscopy Measurement) The optical properties of the samples were investigated using a double-beam double-chromator Perkin Elmer Lambda 950 UV / Vis / NIR spectrophotometer. Transmission spectra were recorded in the wavelength range of 0 to 2500 nm for all target samples. All measurements were carried out with 60 seconds per scan and a total of 10 scans.

[0060] (X-ray Photoelectron Spectroscopy (XPS) Measurement) Untreated and Sn-doped titanium dioxide (20×20 mm 2Selected thin film samples were analyzed using a Thermo Scientific K-α spectrometer with monochromatic Al Kα rays and a dual-beam charge compensation system. Spectra were recorded with a constant pass energy of 50 eV and a spot size of 400 μm. To optimize peak definition and reduce background-induced errors, 100 scans were combined and measured with a 25-second acquisition time. The instrument outputs binding energy values ​​with an error of less than ±0.2 eV. Both surface and depth profiles were acquired for the samples. For the latter, the etching time was set to 500 seconds for all samples. All investigated spectra were recorded in the range of 0 to 1200 eV. High-resolution profiles were acquired for both surface and depth profile scans for the Ti 2p (449-475 eV), Sn 3d (480-500 eV), O 1s (526-545 eV), and C 1s (280-299 eV) orbitals. After recording, the entire spectrum was calibrated using the standard value of 284.8 eV, relative to the C 1s orbital. The peaks were further modeled using XPSCasa software to account for different environments and to calculate the film composition. This was achieved by dividing the area under the peaks by the respective relative sensitivity factor (RSF) (NIST database), corresponding to the relative concentrations of elements in the material.

[0061] (Water contact angle (WCA) measurement) The hydrophilicity of the samples was investigated by WCA measurements in multiple regions of each sample. This was achieved using an FTA (First Ten Angstroms Inc.) 1000B surface analyzer. The droplet size in all measurements was 5 μL. For all samples, 40 images of the water droplet in contact with the sample surface were accumulated and recorded.

[0062] (Raman spectroscopy) Raman spectra were recorded for four samples ("Sample A") according to the present invention, each comprising a tin-doped titania membrane with a bulk tin concentration in the range of 0.1 to 5 at% Sn. For all four samples, the wavelength was approximately 143 cm⁻¹. -1 , 199cm -1 , 398cm -1, 518 cm -1 , 640 cm -1 A distinct vibration band was observed at -1 and -1 , which is consistent with the space group of the anatase phase of TiO2, suggesting that the deposited film is mainly in the anatase phase. Furthermore, in samples with a relatively high bulk tin concentration (more than 3 at.% Sn), weaker vibration modes were observed at 250 cm -1 , 325 cm -1 , 366 cm -1 , which is consistent with the minor presence of the brookite phase in previous studies of Sn-doped TiO2 films prepared by the sol-gel method. There was no detection of SnO2 via Raman spectroscopy, suggesting that Sn 4+ ions are incorporated substitutionally. The shift in the Raman frequency and full width at half maximum (FWHM) of the main anatase Raman peak at about 143 cm -1 was confirmed as a trend with increasing bulk tin concentration, consistent with previous studies of similar materials and shown as a result of the general trend in the case of doped thin films. [[ID=十五]] [[ID=十六]]

[0063] [[ID=十七]] Raman spectra were also recorded for five comparative samples ("B" samples) with bulk tin concentrations of 8 - 17 at.% Sn in mixed titania:tin oxide films. Across all spectra, a peak characteristic of anatase at a frequency of about 143 cm -1 was shown, but the peaks corresponding to the other five fundamental vibrations of anatase were significantly weaker. No other titanium dioxide phases were observed, suggesting that no phase transition occurred due to the increasing bulk tin concentration. A peak characteristic of the vibration mode of SnO2 was observed at 636 cm -1 . These results suggest that the incorporation of Sn 4+ into the film was in the form of SnO2. The overall weak spectral features suggest the presence of SnO2 rather than tin-doped titania, as SnO2 is known to have low Raman scattering ability. The absence of a shift in the Raman frequency of the main anatase Raman peak with increasing bulk tin concentration also indicates that Sn 4+This further supports the idea that tin is incorporated into the material in the form of SnO2 rather than as a dopant, forming a composite film of anatase and tin oxide. Furthermore, increasing the bulk tin concentration did not result in a significant change in the calculated FWHM value. This finding further suggests that the anatase structure of sample B was not disturbed by the presence of tin. Consequently, the characteristic anatase Ramann features were weaker compared to sample A, which is consistent with the presence of a multiphase material.

[0064] (X-ray photoelectron spectroscopy (XPS) analysis) (Surface scan of tin 3D orbitals) (Sample A) Table 1 shows the bond energies corresponding to the Sn3d doublet. The error associated with these values ​​is ±0.2 eV. All values, within their error range, correspond only to Sn in the oxidized state 4+.

[0065] [Table 1]

[0066] Table 1 shows that for both components of the 3d binot, a tendency for the binding energy to decrease with increasing Sn surface concentration can be observed. This further supports the idea that the in-film environment changes due to tin incorporation.

[0067] (Sample B) Table 2 shows the bond energies corresponding to the Sn3d doublet. The error associated with these values ​​is ±0.2 eV. All values, within their error range, correspond only to Sn in the oxidized state 4+. There is no change in bond energies across the table, indicating that no changes are induced by the range of tin concentrations. This further suggests that tin oxides are incorporated into the sample in a form rather than as dopants.

[0068] [Table 2]

[0069] (Concentration calculation from XPS profile) For the range of sample A, the relative concentrations of Sn versus Ti were calculated in both surface and bulk XPS profiles. This was achieved by converting the raw area of ​​the target peak to an effective area using the relative sensitivity factor (RSF). The RSF values ​​used for the Ti2p and Sn3d orbitals were 7.81 and 25.1, respectively. The relative concentrations of Sn and Ti were obtained, and thus the proposed ternary oxide formula Sn x Ti 1-x Different values ​​of x were determined for O2. At the surface, x ranged from 0.35 to 0.50, while in the bulk, this decreased significantly, dropping to 0.03.

[0070] (Abrasion resistance and caustic cleaning cycle tests) The film integrity of the samples was tested by simulating the industrial cleaning process of recycled glass bottles. The film thickness of all tested samples ranged from 30 to 150 nm. The samples were subjected to a 15-minute cycle in a 2% NaOH solution at 80°C. Between each cycle, the film surface was polished with 150-grit sandpaper. Sample A maintained its film integrity without developing scratches after 10 cycles of caustic cleaning.

[0071] In contrast, sample B showed scratches on the polished areas after 5 cycles, and these effects became more pronounced after 7 cycles. The integrity of the film in areas where no scratches were visible was not affected visually.

[0072] Therefore, Sample A, which had a tin-doped titania film, performed far better in these tests than Comparative Sample B, which had a mixed titania:tin oxide film.

[0073] The water contact angle (WCA) was measured before and after the caustic washing test. Sample A had an average contact angle of 70–75° before caustic treatment, while comparative sample B showed a lower average WCA of approximately 50–55°. This further indicates that the films in the two sets have different compositions. WCA measurements were performed for all samples after five caustic washing cycles. The film of sample A showed almost no change in WCA (see Figure 2a, the top row shows water droplet images on the sample 5 cycles before, and the bottom row shows similar images 5 cycles after). In contrast, sample B showed a tendency for WCA to decrease after caustic treatment (see Figure 2b, the top and bottom rows show images before and after).

[0074] The present invention is not limited to the details of the embodiments described above. The present invention also extends to novel features or novel combinations thereof, or novel methods or steps of processes or novel combinations thereof, disclosed herein (including the appended claims, abstract, and drawings).

Claims

1. Glass container coated with a protective layer based on tin-doped titanium dioxide, A coated glass container equipped with the following features.

2. The coated glass container according to claim 1, wherein the protective layer is substantially made of tin-doped titanium dioxide, and preferably the protective layer is made of tin-doped titanium dioxide.

3. The coated glass container according to claim 1 or 2, wherein the protective layer has a bulk tin concentration of 0.01 to 8 at%, preferably 0.1 to 6 at%, more preferably 0.1 to 5 at%, and most preferably 0.2 to 4.5 at%.

4. The coated glass container according to any one of claims 1 to 3, wherein the entire protective layer has a bulk tin dioxide concentration of less than 1 at%, preferably less than 0.5 at%, more preferably less than 0.1 at%, and even more preferably less than 0.01 at%.

5. The coated glass container according to any one of claims 1 to 4, wherein the entire protective layer has a tin dioxide concentration of less than 1 at%, preferably less than 0.5 at%, more preferably less than 0.1 at%, and even more preferably less than 0.01 at%.

6. The coated glass container according to any one of claims 1 to 5, wherein the entire protective layer does not contain tin dioxide.

7. The coated glass container according to any one of claims 1 to 6, wherein the surface of the protective layer exhibits a water droplet contact angle of at least 55°, preferably at least 65°, more preferably at least 70°, but up to 90°, preferably up to 80°, more preferably up to 75°, the contact angle being measured using 5 microliters of water droplets.

8. The coated glass container according to any one of claims 1 to 7, wherein the protective layer has a physical thickness of at least 5 nm, preferably at least 15 nm, more preferably at least 20 nm, most preferably at least 25 nm, but up to 200 nm, preferably up to 150 nm, more preferably up to 100 nm, most preferably up to 70 nm.

9. The coated glass container according to any one of claims 1 to 8, wherein the protective layer is thermally decomposable.

10. The coated glass container according to any one of claims 1 to 9, wherein the protective layer comprises substantially tin-doped titanium dioxide and has a bulk tin concentration of 0.1 to 5 at%, and the surface of the protective layer exhibits a water droplet contact angle of at least 60° but up to 90°, the contact angle being measured using 5 microliters of water droplets.

11. (a) The step of preparing a glass container, (b) The step of supplying the titanium-containing precursor and the tin-containing precursor to the surface of the glass container or to a position adjacent to the surface of the glass container, (c) The step of reacting the titanium-containing precursor and the tin-containing precursor to precipitate a protective layer based on tin-doped titanium dioxide on the surface of the glass container, A method for preparing a coated glass container according to any one of claims 1 to 10, comprising the steps of:

12. The method according to claim 11, wherein the protective layer is deposited by chemical vapor deposition (CVD), and the titanium-containing precursor and the tin-containing precursor are kept separate until they are supplied to the surface of the glass container or a position adjacent to the surface of the glass container.

13. The method according to claim 12, wherein the container is at a temperature of 400°C to 700°C, preferably 450°C to 650°C, and more preferably 500°C to 650°C.

14. The method according to any one of claims 11 to 13, wherein the titanium-containing precursor comprises one or more of titanium alkoxides, titanium acetylacetonate, titanium acetates such as titanium tetraacetate, and titanium alkyls, preferably comprising a titanium alkoxide, and more preferably the titanium alkoxide being titanium tetraisopropoxide (TTIP).

15. The method according to any one of claims 11 to 14, wherein the tin-containing precursor comprises one or more tin alkoxides such as tin isopropoxide, tin acetylacetonate, tin diacetate, tin tetraacetate, methyl tin diacetate or tin diacetate (DBTA) or other tin acetates, tetramethyltin, tetraethyltin, tetraisobutyltin and its derivatives, preferably comprising a tin alkoxide, and more preferably DBTA.

16. Use of a protective layer based on tin-doped titanium dioxide to improve the durability of glass containers.

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